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Design Considerations for Unconventional Electrochemical

REVIEW
Energy Storage Architectures

Alexandru Vlad,* Neelam Singh, Charudatta Galande, and Pulickel M. Ajayan*

all need to be used in conjugation with an


Batteries have become fundamental building blocks for the mobility of energy storage system to provide smooth
modern society. Continuous development of novel battery chemistries and power leveling. Currently, electrochem-
electrode materials has nourished progress in building better batteries. ical energy storage systems are by far the
most optimal solutions for powering a
Simultaneously, novel device form factors and designs with multi-functional
broad range of technologies, expanding
components have been proposed, requiring batteries to not only integrate from compact and light-weighted port-
seamlessly to these devices, but to also be a multi-functional component for a able electronic devices to stationary grid-
multitude of applications. Thus, in the past decade, along with developments scale energy storage applications.[3–6]
in the component materials, the focus has been shifting more and more These energy storage devices (batteries
and supercapacitors) store the available
towards novel fabrication processes, unconventional configurations, and
electrical energy in the form of chemical
additional functionalities. This work attempts to critically review the develop- energy and release it whenever needed,
ments with respect to emerging electrochemical energy storage configura- by simply reversing the electrochemical
tions, including, amongst others, paintable, transparent, flexible, wire or cable reaction.[7–11] Among various available
shaped, ultra-thin and ultra-thick configurations, as well as hybrid energy battery chemistries, lithium batteries and
storage-conversion, or graphene-incorporated batteries and supercapacitors. supercapacitors are the most promising
technologies.[7,9–20]
The performance requirements are elaborated together with the advantages,
Ever since the realization of the first
but also the limitations, with respect to established electrochemical energy electrochemical energy storage cell by
storage technologies. Finally, challenges in developing novel materials with Alessandro Volta (end of 17th century),
tailored properties that would allow such configurations, and in designing the working principle and its function
easier manufacturing techniques that can be widely adopted are considered. has changed very little.[21,22] Basically, two
redox couples (or charge storage elec-
trodes), electrically and physically sepa-
rated, are bridged by an ion conducting
1. Introduction medium to constitute an electrochemical cell. This holds
true also for modern Li-ion batteries, although the chemistry
Sustainable energy development for a low-carbon footprint involved is much more complex. During operation, the elec-
triggered major changes in our society, compelling us to think trons are transferred through an external circuit while ions
twice on how we use, store and dispense energy resources.[1,2] shuttle through the electrolyte to counterbalance the depleted
With fossil fuels still providing the highest specific energy, charge at the electrodes.[23] So far, much of the effort has been
given their fast depletion, replacement solutions are eagerly directed towards improvement of the energy and power charac-
required. Several solutions exist for sustainable energy har- teristics by downsizing the active components, re-engineering
vesting including solar, wind, and geothermal. However, they the current collectors and separators, as well as fine-tuning the

Dr. A. Vlad Dr. N. Singh, Dr. C. Galande, Prof. P. M. Ajayan


Institute of Information and Communication Technologies Department of Materials Science and NanoEngineering
Electronics and Applied Mathematics Rice University
Electrical Engineering Houston, TX 77005, USA
Université catholique de Louvain E-mail: ajayan@rice.edu
Louvain-la-Neuve B-1348, Belgium Dr. N. Singh, Dr. C. Galande
E-mail: alexandru.vlad@uclouvain.be Big Delta Systems LLC
Dr. A. Vlad Houston, TX 77005, USA
Institute of Condensed Matter and Nanosciences
Bio- and Soft Matter
Université catholique de Louvain
Louvain-la-Neuve B-1348, Belgium

DOI: 10.1002/aenm.201402115

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physico-chemistry of binders, conductive additives and of ion


REVIEW

conducting media.[15,24–31] Continuous novelty has been further Alexandru Vlad received his
introduced in the battery technology by intelligently designing Ph.D. in Applied Sciences,
devices and tailoring material properties.[32,33] However, para- Electrical Engineering from
digm changes are required to move a step forward from cut- Universite catholique de
ting-edge science towards practical implementation.[34–36] So Louvain (Belgium) in 2009.
far, the improvement of battery technology has been slow when After a postdoctoral stay
compared, for example, to the microelectronics industry. This at Rice University he was
is evident from the incremental increase in the energy den- awarded a research fellowship
sity of commercialized batteries (average increase per year of from the National Research
≈7% in specific energy and ≈10% in energy density over the Foundation (Belgium).
past 20 years), and not much has changed in the terms of used Currently, he is pursing an
materials and form-factors of these devices.[19,37] Essentially, academic career at Universite
the materials and fabrication process has mostly remained catholique de Louvain. His research interests cover the
the same as 20 years ago.[19] Thus, ongoing materials innova- area of materials science, nanotechnology and applied
tion needs to be complimented by the design, fabrication and electrochemistry, with a focus on studies of charge and
assembly process of these energy storage devices. matter transport through nanostructured materials for
The emergence of novel multitasking electronic device con- energy storage and harvesting applications.
figurations such as curved cell phones, flexible and transparent
displays, smart cloths etc., does not require a mere energy
storage device (classical batteries or supercapacitors), but a Neelam Singh received her
power source that can be seamlessly integrated with these novel Ph.D. in Materials Science
device configurations and can additionally be a structural com- and Engineering from Rice
ponent of the device as well. These ambitious requirements University in 2014. Her
have triggered active interest over the past years resulting in primary research interests
many breakthrough scientific advances in device configura- include designing and
tions and fabrication process of energy storage devices (as will developing novel electrode
be broadly debated in Section 4). The broad spectrum of the architectures for Li-ion bat-
emergent configurations includes, amongst others, paintable, teries and ultracapacitors
transparent, flexible, cable-type, and ultrathin configurations, with a focus on developing
as well as hybrid or graphene-incorporated lithium batteries efficient coating/manufac-
and super-capacitors. While being straightforward in operation, turing processes. Currently,
these designs became possible only through ingenious material she is working as a Chief Technology Officer at Big Delta
design and assembly approaches. Systems, Inc.—a Rice University spin out based on her
Here, we highlight recent advances with respect to uncon- work on paintable batteries.
ventional technologies and designs for electrochemical energy
storage with a main emphasis on assembly or manufacturing
techniques, devices with additional functionalities, and hybrid Pulickel Ajayan received his
energy harvesting–storage systems. A critical view is presented, Ph.D. in Materials Science
primarily emphasizing the offered benefits, together with a and Engineering from
depiction of some intrinsic drawbacks and potential solutions, Northwestern University in
where applicable. The correlation with conventional engineering 1989. After post-doctoral
is also given. This Review is organized into five Sections. After work at NEC Corporation
a brief introduction in Section 1, we discuss why Li-ion bat- (Japan), the Laboratoire de
teries and supercapacitors are important to us in Section 2. We Physique des Solides, Orsay
briefly recall the standard battery manufacturing approaches (France) as a Humboldt
and configurations in Section 3. The main purpose of this sec- fellow at the Max-Planck-
tion is to give an overview of the established and commercial- Institut für Metallforschung,
ized configurations and protocols, and thus identify the design Stuttgart (Germany), he
principles and materials development challenges related to joined the Materials Science and Engineering faculty
unconventional electrochemical energy storage manufacturing at Rensselaer Polytechnic Institute. Currently he is the
approaches and configurations. Next, an exhaustive overview of Benjamin M. and Mary Greenwood Anderson Professor
these disruptive battery approaches is given. Within this context, in Engineering at Rice University and is Professor and
the cell configurations and manufacturing methods that are, for Founding Chair of the Department of Materials Science
the moment, laboratory prototypes, or currently under industrial and Nanoengineering. His research interests are focused
development and not yet commercially available are the main on functional nanostructured materials for a variety of
considerations.[8,19,38,39] Flow,[40] dialytic,[41,42] semi-solid[43] or applications.
molten-form batteries[44,45] (i.e., that are based on non-solid form
electrodes) are not critically considered here (except in some

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special configurations, for instance, stretchable configurations by intercalation compounds during the late 70s through to the

REVIEW
that use liquid-form electrode materials, as discussed further). beginning of 80s.[22] The same period was also marked by the
Section 4 is divided into six sub-sections describing the main discovery of transition metal oxides (LiMO2 with M typically
directions identified so far: flexible configurations; ultra-thin and being Co, Ni, Mn) capable of reversibly de-intercalating/interca-
ultra-thick batteries;paintable and printable approaches; optically lating Li+ ions within a crystalline lattice.[46] Sony first commer-
active schemes; graphene and all-carbon based systems; and cialized the Li-ion batteries developed by Asahi Chemicals in
hybrid devices. Finally, given the broad spectrum of proposed 1991. The newly born Li-ion (or rocking chair) technology era
technologies and configurations, a question arises: what should has monotonically progressed since then until recently, when it
we expect next? The trends in the field are analyzed and some showed up a revolutionary interest primarily due to the world-
potential developments are also discussed. wide energy problems requiring urgent solutions.[1,9,17]
The field of smart battery devices is young, yet flourishing Although electrochemical energy storage devices have been
and with huge potential. Present and future developments will used in portable electronics for a while, their massive use for
certainly consolidate this direction and the day when these bat- other applications has emerged recently.[5,17] As shown in
teries will power-up our e-papers, smart clothes, driverless pla- Figure 1, whereas the market for portable lithium-ion batteries
toons or make our houses energy self-contained may not be so (LIB) is predicted to follow a steady-state growth, automotive
far away. One thing is clear, visionary ideas and advanced mate- Li-ion batteries are anticipated to be a much faster growing
rials knowledge is the key to success. market, given the worldwide demand for electric vehicles. It is
being largely accepted that the production and use of automo-
tive electric vehicles will help alleviate the worldwide depend-
2. Why Lithium Batteries and Supercapacitors? ence on oil, and has the potential to mitigate future climate
change. Nonetheless, the environmental impact of the large-
Amongst the known electrochemical energy storage chem- scale generation of renewable energy, and the consequently rap-
istries, lithium chemistry has attracted most of the attention. idly developing and expanding battery industry is also debated,
While lead–acid, NiCd, NiMH, Zinc and alkaline batteries have especially when it comes to manufacturing processes, avail-
eclipsed the battery industry for decades, lithium cells have ability of raw materials, as well as end-of-life battery disposal
rapidly gained their place and are presently largely dominating and recycling.[47–49] As can be also noticed in Figure 1, NiCd
the demand (Figure 1).[17] The rapid growth of Li-ion battery and NiMH battery demand is expected to decrease below 5%
technology is noteworthy. Just in a decade, Li-ion batteries have by 2020, and eventually vanish in the upcoming 10 to 15 years,
occupied the majority of the battery market and their demand with LIB largely dominating the field. At present, the market
is still increasing. Now, these batteries are not only used in potential of the unconventional energy storage sources configu-
portable electronics, but also in electrical vehicles, aerospace, ration (as those covered by this Review) is not known and not
defense, and medical devices. included in Figure 1. The huge investments and expected ben-
There are several reasons for this interest. Lithium is the efits—a sustainable energy management as well as various gov-
lightest metal and the least dense solid element: equivalent ernmental programs—are the primary driving forces behind
weight 6.94 g mol−1, and specific gravity 0.53 g cm−3; as such this evolution.
it offers the highest specific capacity of 3860 mAh g−1. Li is But probably more exciting and challenging aspects for the
also the most electropositive element: –3.04 V versus standard scientific community are the abundance of various available
hydrogen electrode. With an energy density of 11.7 kWh kg−1, chemistries when dealing with Li-ion or more generally, Li-
Li comes very close to the hydrocarbons (gasoline constituents). chemistry based electrochemical cells.[19,39,50] Whereas lead–
Eventually, the high reactivity, as well as issues associated to the acid, NiCd, NiMH, Zinc and alkaline cells rely primarily on
dendrite growth of the metallic lithium, forced its replacement conversion-type redox reactions, Li-based cells make use of
conversion, alloying, and intercalation reactions.[8,38] The large
variety of developed batteries can be further divided by the cell
configuration: heterogeneous solid–liquid–gas (such as Li–O2,
Li–CO2, Li–SO2, etc cells), solid–liquid (regular cells) or all
solid-state phase, semi-liquid or all-liquid redox-flow configura-
tions, and probably other to be proposed.[38] Furthermore, the
library of chemical compounds known or tested so far as poten-
tial active materials in Li-ion cells is enormous and continu-
ously evolving.[19,22,38,39] Add to this the major improvements
made by active material nanostructuring, functional coating,
and additives, as well as electrolyte enhancement, and the
potential that Lithium technology can provide is almost infinite.
This is why Li-ion cells are probably the most versatile energy
storage sources capable of fulfilling the requirements of a broad
Figure 1. Worldwide rechargeable battery market predictions. A steady-
range of applications. As a matter of fact, Li-ion technology can
state growth for LIB market is expected in the upcoming years. The major
demand is predicted to come from the automotive industry. Abbrevia- cover a broad range of power and energy requirement, as shown
tions: NiMH: nickel-metal hydride; LIB: lithium battery; NiCd: nickel-cad- in Figure 2A. Some cell configurations approach the power per-
mium. Reproduced with permission.[17] Copyright 2013, US EPA. formances of the supercapacitor devices whereas, on the other

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techniques and is primarily intended to give


REVIEW

readers a better view on the innovations


provided by the disruptive approaches. Spe-
cific manufacturing details and technical
specifications of available battery formats
are thoroughly reviewed in specialized litera-
ture,[8,19,22,38,39] and are beyond the scope of
this Review. Although different in operation
mechanism and constituent chemistry, the
manufacturing procedures and cell construc-
tion of capacitors and batteries (including
Li-ion) are similar to a certain extent[56,57] and
for simplicity, only the production chain for
Li-ion batteries is discussed here.
The battery chemistry, manufacturing,
and packaging has continuously evolved over
time.[19,22] The main components of a Li-ion
battery (also applies to other types of bat-
teries as well as to supercapacitors) are: i) a
pair of electrodes with terminals to connect
to the external circuitry; ii) a separator that
electrically and physically separates the elec-
trodes preventing electrical shorting; iii) the
electrolyte that carries the charged ions to the
electrodes; and iv) the housing to contain the
electrodes and chemicals in place and avoid
chemical exchange with the environment.[58]
The electrodes are furthermore comprised of
active material coating and metal foil current
collector; aluminum and copper foil being
most commonly used for positive and nega-
tive electrodes respectively.
Figure 2. Power, energy and applications. A) Specific power vs. energy for different battery
The separator is typically made of a
chemistries. When optimized for both, energy and power density, Li-ion technology outper-
[5 ]
forms other chemistries. Source: Johnson Control – SAFT 2005 and 2007. B) Application microporous polymer film (polyethylene,
requirements function of battery power and energy. Li-ion technology can fulfill the demands polypropylene, polyethylene/polypropylene
of a broad range of applications. Reproduced with permission.[51] Copyright 2015, Panasonic. blends, etc).[22,59] Certain configurations may
also comprise a gel of liquid electrolyte and
extreme, these can also be designed to achieve the highest spe- polymer(s), or a solid-state electrolyte that
cific energy amongst electrochemical storage devices. Of course, acts simultaneously as separator and ion conduction matrix.[8]
Li-S8 and Li-O2 systems go beyond this and challenge the energy Since there have been many recent developments dealing with
density of gasoline.[52–55] Unfortunately, these systems still novel electrolyte compositions, types and formulations, a short
require further developments. Figure 2A gives a broad perspec- classification is provided to help further understand the electro-
tive of the specific power and energy delivered by various electro- lyte integration limitations.[8,60–65]
chemical storage sources. A different view is given in Figure 2B
where application requirements for battery power and capacity • Liquid electrolytes.[66,67] These are made of a Li salt dissolved
are represented.[51] Only Li-ion technology can fulfill the specific into an organic solvent. They are used in conjunction with a
requirements of a broad range of applications. Li-ion technology thin and porous film, typically made of non-swellable poly-
already dominates the small and medium load power market: mers. These polymer separator films can be a multilayered
18650-type batteries, portable electronics, UPS systems, small structure such as Celgard separators.[19] Recent reports detail
size driving solutions, etc. Nonetheless, there might be some as well the use of pure inorganic separators for lithium-ion
more work needed to largely adopt them for high power driving batteries.[68] Since liquids have no mechanical integrity, the
applications and high-energy grid-scale implementation. thickness limit and the mechanical properties of electrolyte
are determined here by the separator film.
• Ionic-liquid (ILs) electrolytes.[69,70] These consist of a salt in
3. Conventional Cell Configurations and its liquid state at a temperature below 100 °C. Mechanical
properties and processing requirements are similar to those
Manufacturing Methods
of liquid electrolytes. Most of the ILs have wider electrochem-
This Section gives a short description of conventional bat- ical stability windows and lower vapor pressure compared to
tery fabrication methods and commercially implemented liquid electrolytes, which makes them very attractive for safer

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Li-ion batteries. Recent developments include ionogels or require a high vacuum physical vapor deposition line. How-

REVIEW
surface grafted poly-ionic liquids that enhance the retention ever, most fabrication facilities nowadays use organic solvent
of ionic liquids within a solid matrix to avoid possible leak- based liquid electrolytes in combination with Celgard type
age.[71–74] separators.
• Gel-polymer electrolytes. These are typically composed of a The composition of Li-ion batteries is complex and the
polymer matrix, solvent, and lithium salt.[8,75–77] The manu- chemistry inside is even more complicated when these cells
facturing usually implies thermal processing of a mixture of are being cycled. The composition and structure of commercial
monomer, polymer precursor or directly the polymer with the Li-ion cells is outlined in Figure 3.[88] Materials that are already
Li-salt containing electrolyte. Although it has enhanced safety in use, as well as some new chemistries that are under develop-
properties due to a better retention of the liquid electrolyte, ment are highlighted.[19,38] Supercapacitors have a slightly sim-
the mechanical stability is sometimes not sufficient enough pler chemical composition, relying primarily on high surface
to allow utilization of only gel-polymer electrolyte. A porous area carbon at both electrodes (symmetrical supercapacitors).
separator membrane may be required to ensure integrity.[78] The chemistry is also less complicated, with a lower extent of
• Swelled membrane electrolytes. While similar in composi- parasitic side reactions explaining the better cycle lifetime per-
tion to gel-type electrolytes, the fabrication procedure is dif- formances seen in this kind of devices.[56] Yet the low specific
ferent and the swelled membrane electrolytes can display bet- capacitance attained in supercapacitor devices calls for new
ter structural integrity.[8,76,79] As defined by their name, these material developments that may eventually lead to systems
membranes are made by swelling a polymer film with a Li- that are as sophisticated as current Li-ion batteries.[13,89] As can
salt electrolyte. The mechanical integrity is maintained and be observed from Figure 3, the constituents of Li-ion batteries
the membranes can be used without the porous separator. span many chemistry sub-disciplines (including organic, inor-
These membranes should not be confused with the micropo- ganic, materials, transition metal, solid-state, as well as polymer
rous, non-swellable polymer membranes (separators) soaked chemistry) with at least 20 compounds with distinct function-
in the electrolyte as the liquid solvent retention mechanism ality being require for a typical Li-ion cell assembly. Addition-
is different. ally, the chemistry of Li-ion cell becomes even more complex as
• Solid-state electrolytes. Liquid free electrolytes comprise soon as it starts cycling. The listed constituents start reacting,
two main classes: glassy ceramic inorganic Li-conducting altering dramatically their physico-chemical properties. Fur-
frameworks, and solid (dry) polymer electrolytes. The Li+ thermore, new species (for instance, solid electrolyte inter-
conduction is purely in the solid phase and displays better phase and the complex chemistry associated to its formation)
mechanical properties compared to other electrolytes. It can are being generated that will eventually participate in or impede
be molded to arbitrary shapes and dimensions. The main charge and ion exchange.[8] Gaseous and soluble species are
limitations of this technology are low ionic conduction at being also generated, requiring further special attention when
room temperature, as well as poor interfacing and structural designing Li-ion cells. In short, a perfect synergy is required
rigidity of ceramic-type electrolytes, being suitable for certain between all of the components and even a minor change of one
battery configurations (see Section 4.3). Polymer electrolytes of the constituents may considerably affect the overall efficient
have better mechanical properties, yet the ionic conductivity functioning. This is one of the reasons why the battery devel-
at room temperature is still unsatisfactory for practical appli- opment has displayed little advance over the past years (when
cations. Block-copolymer solid-state electrolytes have the po- compared to other technologies, for example, to the microelec-
tential to overcome the 10−4 S cm−1 conductivity barrier; and tronics industry).[19] And this has to be seriously considered for
further developments are being demanded to endow both novel unconventional developments as well. Unfortunately, for
high ionic transport and good mechanical stability.[80–83] Re- the moment, there is no magic solution to this.
cent developments further demonstrate liquid-like conduc- The value chain for the production of Li-ion cells based on
tivities in super-ionic glass-ceramic Li-ion and Na-ion elec- organic liquid electrolytes is schematized in Figure 4A.[91] The
trolytes, Li10GeP2S12 and Na3PS4 respectively, while hybrid first step in the manufacturing process is preparing the elec-
polymer–ceramic electrolytes are being explored to alleviate trode slurry by mixing constituent materials. The electrodes
mechanical issues.[84–86] comprise (see also Figure 3) active materials (for example
LiCoO2, LiMn2O4, LiNi1/3Mn1/3Co1/3O2, LiNi0.8Co0.15Al0.05O2,
Particular attention should be given to the solid-state and gel LiFePO4) at the positive terminal and graphite-based com-
electrolytes. The latter may have the consistency and appear- pounds (recently, also with inclusion of tin or silicon) at the neg-
ance of a solid material, yet it is different from solid-state ionic ative terminal, conductive carbon additives (typically acetylene
conductors, especially with regards to the mechanism of ionic black and conductive graphite) and a polymer binder (polyvi-
conduction, composition, and preparation methods, as well nylidene difluoride homo- and copolymers, polytertrafluoroeth-
as limitations in the operating conditions.[8,19] Gel-electrolyte ylene, styrene butadiene rubbers or carboxymethylcellulose).[19]
based energy storage devices are sometimes presented as solid- These constituents are dispersed and dissolved in a solvent or
state supercapacitors or batteries. Yet a true solid-state superca- in water, depending on the binder class, to form viscous slur-
pacitor (i.e. liquid organic, ionic liquid or aqueous electrolyte ries. Additives or thickening agents are also occasionally added.
free) may be power limited if not designed as an electrostatic The formed slurry is then coated at a predefined thickness on
capacitor.[87] Finally, it should be noted that the choice of elec- metallic current collector foils to form the electrodes. The nature
trolyte significantly affects the Li-ion manufacturing line. For of the metal foil current collector closely depends on the elec-
example, solid-state battery manufacturing would additionally trode polarity and cell chemistry.[92] Depending on the final cell

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Figure 3. Li-Ion batteries: composition and structure of conventional cells. A) Constituents composition of Li-ion batteries. Underlined components—
well established and commercially available chemistries; italic— some foreseen chemistries. Adapted with permission from.[90] Copyright 2012, Mac-
millan Publishers Limited. B) Cross-section of an 18650 cell: low magnification and high magnification highlighting the compact and dense structure
with well-defined interfaces. Copyright 2015, ZEISS Microscopy.[88] Abbreviations: polyvinylidene fluoride homo- and co-polymers (PVDF), polytetra-
fluoroethylene (PTFE), styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), polyethylene (PE), polypropylene (PP), polymethylmethacrylate
(PMMA), polyacrylonitrile (PAN).

Figure 4. Conventional battery manufacturing technology. A) The value chain for the production of Li-ion cells. Reproduced with permission.[91] Copy-
right 2012, Springer B) Cross-section overview within the layer structure of a Li-ion battery. The red square delimits the “compositional unit cell” of the
battery stack. Copyright 2015, ZEISS Microscopy.[93] C) Photograph of a free-standing electrode film composed of high tap density SnO2 particles and
carboxymethyl cellulose binder with Super-P Li (SP-Li) conductive carbon, formed from an aqueous slurry cast by doctor-blading. The free-standing film
spontaneously evolved via delamination from the substrate as the slurry solvent evaporated. Reproduced with permission.[94] Copyright 2014, Royal Society
of Chemistry. D) Photograph of a self-standing, 30 um-thick battery electrode delaminated from the Al foil current collector. The composition is: 88%
LiCoO2, 6% acetylene black and 6%PVDF. The membrane is self-supported, flexible, can be folded and can support reversible stretching to a certain degree.

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configuration, the electrodes can be either single- or double-side paper, cloth or skin-compatible electronics running on metal-

REVIEW
coated. The coated electrodes are then calendered and dried. It polymer encased prismatic or cylindrical cells filled with cor-
should be noted here that only active materials contribute to rosive and flammable liquid electrolyte. Breakthrough battery
the stored charge, and maximizing their content increases the advances are required to follow up with the forthcoming elec-
gravimetric capacity of the battery. The amount of carbon and tronic industry revolution.
polymer additives is of paramount importance as well. While
carbon helps in establishing a good electrical interface with the
active material, improving the charge collection and rate perfor- 4. Unconventional Techniques and Configurations
mance, the polymer binder holds in place the these constituents
and endows mechanical properties to the electrode. Further, Thus, the advent of smart electronic technologies in recent
during the tailoring step, the electrodes and the separator are years triggered vivid research on smart power sources.[96,98–100]
cut to size to fit the dimensions of the finished cells. While up to now the primary function of a battery was basi-
The next step, cell stacking, defines the size and the shape cally the energy storage and release on demand, the emerging
of the finished cell. There are several types of cell stacking direction of smart power sources explores as well the new
processes for Li-ion battery assembly: single sheet stacking, functionalities that could be integrated into or with a battery to
Z-folding or Z-folding with single electrodes, and flat winding. create a multifunctional power source, such as structural bat-
Flat winding can be used to make both prismatic and cylindrical teries. Simplifying or re-designing the battery manufacturing
(jelly roll) cells, whereas the rest of the processes are designed and assembly protocols that enables seamless battery integra-
for prismatic cell production. Curious to note, it is presumed tion into arbitrary configurations and shape is also a part of this
that the cell quality and performance depends significantly on progress. The plethora of emerging smart battery technology
the cell stacking process. For example, in Asia, the most applied includes, amongst others, flexible, metal-foil current collector-
process is flat winding, whereas Europe favors production sys- free, ultra-thin and ultra-thick, paintable and printable, gra-
tems based on a single sheet stacking process. However, none phene enabled and all-carbon, as well as optically active and
of these processes has been subjected to a methodic compar- integrated hybrid configurations. This progress was enabled
ison.[91] Cell finishing includes welding of conductors to the by our advanced knowledge on materials properties and pro-
current collectors, drying, electrolyte filling, sealing, as well cessing, and is certainly expected to progress further, reaching
as cell formation, venting and charge–discharge testing prior levels where man-made energy managing devices will compete
to the commercialization. Manufacturing of Li-ion cells as we or even outperform the ability of biological systems to comply,
know is a well-established, mature industry.[19,22] convert, harvest, store and deliver energy.
The commercial cells are highly compact, being optimized The smart battery field (based on unconventional configu-
for high volumetric energy performance. The current collector rations, assembly and fabrication techniques) has emerged
foils, active materials coatings and separator are typically ≈10, not as an independent direction, but rather as a necessity cre-
50 and 10 µm thick; with current collectors being coated on ated by the recent technological progress, especially in the
both sides to elevate the gravimetric energy (Figure 4B).[93] electronic industry. Fabricating Li-ion batteries to comply with
Even without the current collector metal foil the battery elec- these requirements has necessitated complete rethinking of
trodes already display good mechanical properties, being self- the battery manufacturing and assembly protocols, sometimes
supported, flexible and foldable (Figure 4C and 4D, see also dis- resulting in major technological breakthroughs. The main chal-
cussion in Section 4.1). The metallic or plastic housing is used lenge involved in realizing the multifunctional, flexible, light
to entrap the liquid electrolyte, avoid any leakage and ensure weight battery with unconventional form factor is the possi-
mechanical strength when operated in real-life conditions. The bility of mass manufacturing without involving a huge capital
electrochemical performances are excellent: the commercial- investment in the current manufacturing facilities i.e. easy
ized LIBs having a granted life-time of more than 500 cycles adaptability of new assembly and fabrication techniques. A
with reasonable charging/discharging time of less than 2 hours further technological challenge in keeping up with the power
when optimized for high power. requirements of future electronic devices, and eventually the
All these being said, a question arises: why do we need to transportation industry, is the achievement of high energy den-
replace something that works well? First, building higher sity and gravimetric capacity without compromising the safety
energy density batteries and capacitors is highly desirable as it and cost of the batteries.
may allow wider adoption of some still exploratory directions Most of the approaches described in the following sections
like driving or stationary type applications (Figure 2B). Another are intended to simplify the manufacturing and incorporate
perspective is on the applications or devices that will use these additional functionalities. Unfortunately, the penalty is that the
batteries. Up to now, the end users were satisfied by the energy energy storage capacity (either gravimetric, volumetric, or per
storage–delivery functionality of batteries. Size, weight, shape unit area) is usually lower than that of commercially available
and mechanical properties of the power storage device were systems, based on the same cell chemistry and cell volume or
not as critical as today. However, recent technological break- mass.[89] Although this is not straightforward when consid-
throughs use non-conventional materials and approaches ering only separate battery elements such as the electrodes,
to design and build tomorrow's electronic and bio-medical the electrolyte or the current collectors, the balance sheet is not
devices.[95–97] If one also targets the portability of these devices, so optimistic anymore when analyzing those elements at the
batteries must comply with engineering and aesthetic require- cell level.[58] The cell encapsulation and wiring, as well as the
ments as well. It can be rather difficult to conceive plastic, security and construction elements, account for a considerable

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mass and occupy a non-negligible volume in the cell.[19] If and subsequent integration of all these constituents within
REVIEW

novel active component architectures and manufacturing pro- a functional cell. Proper synergy of all three elements is cru-
tocols are to be used they must to take into consideration these cial (see also Figure 3). For instance, taking the example of
aspects as well. Otherwise, the performance metrics may be the highly sought Li-O2 battery, while many novel chemistries
under-estimated.[89] and designs have been successfully synthesized and tested,
It is worth noting once again that the “primary function” of only solutions to particular issues have been provided, and the
a battery or a supercapacitor remains the energy storage, and whole puzzle still awaits practical solutions.[52] Adding to this
whenever an additional functionality is included, it should not issues in finding adequate anode configuration, cell stacking,
severely affect the charge storage properties, i.e., it should not and finishing (including proper packaging and sealing), as well
dramatically diminish the gravimetric or volumetric capaci- as integration of additional elements (such as O2 containers or
ties as well as the power capability. Otherwise, the device selective gas permeation membranes) highlights the crucial
may lose its energy storage purpose. Safety concerns of the importance of system-level considerations.[103–105]
devices, although very important, are beyond the scope of this The same applies to the unconventional battery configura-
work, andsince safety primarily relates to a complex interplay tion and manufacturing approaches (as will be detailed in sub-
between the cell chemistry, energy density and encapsulation sequent sections). While at the separate element level the esti-
(or housing) type, it is difficult to assess this parameter given mations look appealing, the balance sheet at an operational cell
the early-stage development of these technologies.[58,101,102] level is not always so optimistic.[106] Most of the time, when extra
Finally, the associated materials and manufacturing processes functionality is added (for example, enhancing the mechanical
costs are also not critically considered here. Again, since most or aesthetic properties, or making hybrid functions), the energy
of the disruptive technologies described here are laboratory pro- storage functionality (energy and power density) is diminished
totypes and based on emerging materials, further scale-up can while costs are potentially increased. Alas, the spinning wheel
be envisioned to make them commercially attractive. of the non-trivial processes is not always progressing towards
The balance between the energy storage functionality and the increasing the basic energy storage performances (Figure 5).
added extra functionalities is rather complex, and sometimes it However, this should not discourage further work. Quite the
is difficult to discern in between. Figure 5 depicts the interplay opposite; it shows that more effort is being requested to move
between these values. The inner core highlights the primary a leap forward towards commercially and economically viable
metrics for the energy storage advancement, namely: increased systems. Furthermore, one must note that the performance
safety, energy, and power density, as well as lifetime, at minimal metrics as depicted in Figure 5 are especially critical for applica-
costs.[9] The envelope that drives this progress is founded on tions where mass, volume and price are crucial for the adoption
three main development directions: synthesis of novel mate- of the electrical energy storage, as is mostly the case for EVs
rials, their efficient assembly within the device structural units (electrical vehicles) or grid storage (Figure 2). Other applica-
tions may be less stringent with this respect, and notions such
as aesthetics and cloth-integrated or arbitrary form factors may
be of higher priority than the cost or the energy density.
Thus, in the context of this Section, we consider disruptive
or unconventional all cell configurations, assembly techniques,
and fabrication processes which fall outside the conventional
technology as described in Section 3 (see also Figure 4). In
other words, we analyze cell configurations and manufacturing
methods that are, for the moment, laboratory prototypes or cur-
rently under industrial development and not yet commercially
available.[4,19,22]
These advances can be broadly sorted into (but are not lim-
ited to) the following classes, depending on their target func-
tionality or application:

• Mechanical: batteries and supercapacitors endowed with spe-


cial mechanical properties such as flexible, stretchable, bend-
able, rollable, and foldable configurations.
• Device configuration and structure: functionalities or im-
Figure 5. Spinning wheel of energy storage technology. The main func- provements primarily originating from configuration of de-
tion of a battery remains energy storage and delivery on demand. Inno- vice components and their integration to form the structure
vation in material synthesis, components assembly, and integration of a device. It includes, among others, monolithic superca-
drive further progress by reducing the costs and increasing the safety, pacitors or batteries, ultra- thin/thick batteries, paper and
lifetime, and energy, as well as power density. Complementary, disruptive textile systems. It also includes the architecture of current
approaches have been proposed to incorporate additional functionalities
collectors: current collector-free devices or active material in-
into the energy storage devices or facilitate their seamless integration
into electronic devices, cloths or common household objects. However, tegrated with nano/micro structured current collectors.
these innovations may come at the expense of the stored energy (energy • Form factor: functionalities or improvements primarily
or power density). originating from the free form factor design of the battery.

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Includes, among others, paintable and printable fabrication, mechanical properties, being highly resistant to wear and tear,

REVIEW
cable type, and textile integrated, as well as any other process flexible, foldable, and rollable although it measures only 30µm
capable of arbitrary shape manufacturing and packaging. in thickness and contains 6 wt% of PVDF binder (Figure 4D).
• Optically active: batteries endowed with optical properties. In- Klavetter et al. have recently shown that a 5 µm thick electrodes
cludes, among others, transparent and electrochromic batteries. made of high tap density SnO2 particles and carboxymethyl cel-
• Hybrid systems: (co)-integrated energy storage –harvesting– lulose binder with Super-P Li (SP-Li) conductive carbon can be
conversion devices. easily handled, flexed, and folded without the support substrate
• Graphene incorporated systems. Includes batteries and ca- (Figure 4C). The authors particularly highlighted that by using
pacitors where incorporation of graphene (either as active CNT, the electrode strength at break, as well as the electronic
charge storage component or as conductive additive or me- conductivity, could be increased and the cycling performance
chanical scaffold) was found to modify the manufacturing of electrodes made using the low-cost SP-Li carbon exceeded
approach and improve the electrochemical performances. that of the electrodes made with the orders-of-magnitude more
expensive 1D carbon.[94]
It is however difficult to rigorously differentiate these tech- However, to produce high energy capacity cells, a number
nologies as many related developments are interdisciplinary of such flexible components are stacked (see for example
and fit into more than one of the described classes. Thus, a Figure 4) leading to a cell with reduced flexibility and finally,
given technique or configuration was primarily assigned to one the type of safety packaging renders the final cell rigid or with
of these classes based on the identified major advance or spe- very limited compliant properties. Furthermore, it is generally
cific application. Since neat classification was not always pos- reckoned that the mechanical resistance of the separator layer
sible, especially whenever strong similarities were identified, is the most important for the safe operation of the battery.[19]
many of the cited technologies and advances are cross-refer- Consequently, mechanical attributes such as flexible or fold-
enced in different sections. able are probably not the most appropriate metrics to describe
the performance of some of the proposed disruptive batteries
designs. There are other attributes, far more important than
4.1. Flexible Configurations the mechanical dimensions, such as current collector-free
or embedded and functionalized electrodes, single-phase or
Flexible batteries are gaining huge interest due to the current monolith structures, and batteries built on value added prod-
surge in flexible electronics.[107–109] Various configurations ucts like paper, plastics, cables, textiles, etc. Yet, for the sake of
based on a multitude of chemistries and different supporting clarity and consistency with the literature they will be further
backbones have been proposed and tested so far.[107,110,111] named as flexible.
Enhanced mechanical properties are the main attributes The most straightforward approach for flexible electrodes
assigned to these batteries. As mentioned in previous sections, fabrication is done by growing, functionalizing, or embedding
next generation electronic devices are expected to be less rigid active materials onto or within a flexible conductive scaffold
and bulky than they are presently. Flexible, stretchable, foldable, that works as a current collector.[108,109,112–126] Given the large
rollable, or a combination of these are some of the features that availability and unique electrochemical properties, most of the
are needed for the battery units as well, in order to achieve a methods exploit carbon-based scaffolds such as woven fibers
seamless integration of the energy storage device. In this sec- mats, nanotube forests, carbon cloth, Bucky papers, and others.
tion, we detail how these characteristics have been possible to The light weight of carbon element is an added advantage
attain with Li-ion batteries and supercapacitors by changing which could result in higher gravimetric capacity of cells.[127–155]
the composition, structure, and assembly protocol. After briefly The active material integration within these scaffolds can as
outlining some similarities with the standard battery configu- well be done in various ways, such as electrochemical or chem-
rations, we will discuss the achievements made so far with ical growth and deposition, heterogeneous mixing, impregna-
respect to the enhancement of mechanical properties, as well as tion, or post-assembly carbon growth. A figurative example is
unconventional form factors of batteries and supercapacitors. given by the work of Bao et al. (Figure 6A).[137] The authors have
Mechanical flexibility is defined as the ability of a material to used a hierarchical woven carbon cloth to grow Zn2SnO4/MnO2
yield with applied external force. Although much effort is being core/shell nanowires for high performance supercapacitor
directed towards the development of flexible batteries it should electrodes. The woven carbon cloth is flexible and has a high
be noted that the components of commercially available Li-ion exposed surface capable of accommodating more Zn2SnO4
batteries and supercapacitors (as well as other types of energy per unit area. The structural hierarchy was confirmed by SEM
storage cells) are flexible individually. As a matter of fact, the inspection: the cloth is made by weaved large ropes composed
electrode coating and stacking protocols as described in Figure 4 of carbon microfibers whereas subsequent 2-step growth deco-
involve individual components that are flexible and foldable, as rated each microfiber with conductive Zn2SnO4 core and MnO2
well as the fact that cell winding process relies on rollable com- active material. Enhanced specific capacitance, energy density,
ponents. A single Li-ion cell stack is relatively thin (see red high- power density and long lifetime were attained using this config-
lighted area in Figure 4B). It measures approximately 150 µm, uration. Liu et al. have used a similar approach to grow ZnCo2O4
including the metal foil current collectors, two electrodes, nanowire arrays on carbon cloth for binder-free (and current
and the separator. It can be easily manipulated and exposed collector free as well) anodes for Li-ion batteries (Figure 6B).[140]
to extreme mechanical constraints. Even the active material The hierarchical electrodes exhibited high capacity, and good
coating without the metal foil current collector has exceptional cycling stability as well as rate capability.

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Figure 6. Flexible configurations—(non-)woven fabrics, CNTs, and mats based. A) SEM images of Zn2SnO4 nanowires grown radially on woven carbon
microfibers at different magnification, evidencing the structural hierarchy. Reproduced with permission.[137] Copyright 2011, American Chemical Society.
B) FESEM images and rate performance of the ZnCo2O4 nanowire arrays grown on carbon cloth. Reproduced with permission.[140] Copyright 2012,
American Chemical Society. C) SEM images of the CNT fabric before and after coating with Si via a LPCVD process. Reproduced with permission.[143]
Copyright 2012, American Chemical Society. D) SEM image of a LiCoO2/Super-Aligned-CNT composite. Rate performance of the composite cathodes
for various amounts of CNTs. Reproduced with permission.[156]

Carbon nanotubes (CNT) have been also extensively used Li-ion positive materials based on oxide compounds: LiCoO2,
for the realization of flexible electrodes for batteries and LiMn2O4, LiNixCoyMn1–x–yO2, etc.; requiring high temperature
supercapacitors.[125,127,131,134,145,149,157–171] Here, depending on annealing in air or oxygen. Post-synthesis carbon growth is also
the assembly approach, higher mass loading can be achieved incompatible, as CNT synthesis implies a reducing atmosphere
without compromising the mechanical resistance of the com- that may irreversibly degrade the mixed oxide cathode. These
posite electrodes. Evanoff et al. used a CNT-based, electrically issues have been solved in an elegant way by simply incorpo-
conductive nonwoven fabric coated with silicon to build a mul- rating synthesized active material particles into nonwoven CNT
tifunctional Li-ion battery anode (Figure 6C).[143] The authors fabrics. Several fabrication approaches have been developed;
have achieved a high mass loading of Si of approximately 50% the most commonly used technique is based on heterogeneous
by weight, displaying high specific capacity and stable electro- mixing of both components in a solvent followed by filtration,
chemical performance. Moreover, given that CNTs also dis- sedimentation or dry-coating.[141,171–176] The CNTs mainly dic-
play an electrochemical response at low voltages, below 1 V tate the mechanical and electrical properties and when mixed
vs. Li/Li+, the CNT@Si configuration could be considered as with positive electrode materials, they do not contribute to the
a paradigm change in the electrode design and operation. Not stored charge as previously detailed. The content, and hence the
only does the CNT scaffold replace the metal foil current col- inactive mass, can be precisely controlled here and depending
lector in the cell, but it also works as an active material to store on the CNT physico-chemical properties, positive electrodes
energy, reducing the overall inactive weight and volume inside with extremely low CNT content have been fabricated. For
the battery. example, Luo et al. mixed super-aligned CNT (SACNT) with
The CNT/active material core/shell configuration might not commercially available LiCoO2 or LiMn2O4 particles to build
be possible to realize for all of the materials of interest for Li-ion binder-free (as well as metal foil current collector-free) com-
batteries. Synthesis requiring high temperature annealing posite electrodes with enhanced electrochemical performance
in oxidizing atmosphere can irreversibly damage the CNTs while retaining the mechanical characteristics, even at low CNT
structure with negative impact on the electrical and mechan- contents.[156] They have fabricated robust and mechanically
ical properties. This is especially the case for commonly used stable composite electrodes with only 1% by weight SACNT.

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They have assigned the properties enhancement to the con- and minimize the possibility of generating an insulating SEI

REVIEW
tinuous and three-dimensional SACNT network rendering layer in between conductive carbon and active material parti-
well-developed porous structure, high mechanical strength, and cles. This effect is even more accentuated when dealing with
superior flexibility of the composite. The sheet resistivity of the high capacity alloying anodes where continuous and uncon-
SACNT composite has been found to be orders of magnitude trolled SEI formation is the major degradation mechanism of
lower than of composites prepared in a classical way composed the electrodes.[180–182] Certainly, eliminating binders will slightly
of carbon black and PVDF binder. Also, the rate performance increase the gravimetric capacity but this may require addi-
and the cycle lifetime were found to be considerably enhanced tional surface passivation processing as well as incorporation of
as compared to standard electrodes (Figure 6D). material to endow wear and tear resistance. Furthermore, for
One possible advantage of these configurations is the industrial implementation, there are still questions that remain
absence of metal foil current collectors that can account for unanswered such as longer cycle lifetime, high power capa-
some 10–25 wt% of the total electrode mass.[58] The lack of bility, as well as economical aspects related to the synthesis and
metal foil current collector can also simplify the assembly pro- assembly of such batteries.
cess since there will be only three layers to be processed and Another major search direction in the field of flexible energy
laminated as well as avoid any issues related to the adhesion, storage sources is the paper-based batteries and supercapaci-
delamination, and contact resistance at the current collector tors.[183–196] Whereas the realization of carbon-based fabrics,
interface. Nevertheless, the impact of this new electrode con- mats and cloths type electrodes enables the integration of active
figuration assembly step on the energy and power density materials into the current collector, the paper-based electrodes
of the cell as well as on the battery manufacture value chain allow for further progress, enabling the integration of the bat-
remains an open question. Increasing further the active mate- tery separator unit as well.[197–199] Although the cellulose paper
rial loading and decreasing the processing costs may eventu- has lower performance than the commercially implemented
ally result in commercially competitive products. Rather than microporous polymer separators it is considered that its inte-
disruptive overhaul, incremental redesign of conventional gration into the Li-ion battery value chain will lower the produc-
methods seems the best option for the moment. Park et al. suc- tion costs and make the manufacturing process environmen-
ceeded in assembling flexible high-energy Li-ion batteries with tally benign.[200,201] At the same time, the hygroscopic nature
fast charging capability by using honey-comb patterned Cu and of cellulose based paper, the absence of a thermal shutdown
Al current collectors to achieve maximum adhesion in the elec- effect and need of thicker paper to avoid dendrites growth
trodes.[177] The assembled Li-ion cells exhibited excellent power through the large pores of the paper are some of the issues
and energy performance along with stable cycling stability up to that must be solved before targeting large scale industrial
200 cycles in an in situ bending test. implementation.[200]
Most of the flexible battery and supercapacitor configura- Cellulose papers have been already proposed as a building
tions built so far were based on liquid electrolyte or polymer-gel material for energy storage devices, especially in aqueous cells,
formulations. Such configurations are known to poses safety where hygroscopicity is beneficial for the cell operation.[202] It
issues if not properly manipulated. To overcome this and build was primarily tested as a replacement solution for the electro-
bendable, yet all-solid-state lithium batteries, Nam et al. have lyte soaked separators.[200] Their integration into Li-ion battery
recently proposed the use of solution processable thin sulfide technology remained, however, limited until recent years. One
solid electrolyte films reinforced with a mechanically compliant ingenious way of cellulose integration into Li-ion batteries was
poly(paraphenylene terephthalamide) fiber nonwoven scaf- provided by Pushparaj et al. (Figure 7A).[203] The authors inte-
folds.[178] Cell stacking, superior power performances as well grated the electrode, separator and electrolyte into single con-
as structural and electrochemical integrity upon bending were tiguous nanocomposite that was used as a building block for
attained compared to those of conventional cells without the a variety of thin mechanically flexible energy storage devices:
nonwoven polymer scaffold. The next big thing to expect could supercapacitor, battery, and hybrid dual-storage battery-in-
be thus the realization of all-solid-state stretchable lithium supercapacitor devices. This was done by embedding aligned
batteries. CNTs into nanoporous cellulose paper. Different electrolytes
Flexible battery configurations can potentially eliminate were tested displaying remarkable electrochemical perfor-
the use of polymeric binders for the electrode manufacturing. mances. Nystrom et al. used polypyrrole coated cellulose fibers
This seems to be a promising approach to further increase the extracted from Cladophora species algae.[204] In their study,
gravimetric capacity at the cell level. Yet, the elimination of the individual nanofibers were conformally wrapped with a 50 nm
binder may be detrimental for battery operation. The polymeric thin layer of polypyrrole. Coating was done by oxidative poly-
binders are not intended only to ensure structural stability and merization of the pyrrole monomer at the surface of the fiber.
adhesion to the current collector, they also play the role of cohe- The plastic laminated cell showed high charging rates and dis-
sion elements between the electrode constituents.[38,179] Weak played good cycling stability, delivering 25 mAh g−1 at a current
physical contact between the active material components and density of 600 mA cm−2 for more than 100 cycles (Figure 7B).
conductive additives may be lost during battery operation and As stated by the authors, although the cell was limited in
handling. Another problem is the formation of electrically insu- delivered potential as compared with Li-ion batteries, the poly-
lating solid-electrolyte interphase (SEI) at the surface of the pyrrole–cellulose composite electrodes could be highly suitable
active particles and conductive carbon that will lower the charge for the next generation energy storage systems. Printing energy
collection efficiency and degrade the battery performance. The storage components or functional devices on paper has been
polymeric binders also contribute to the surface passivation also proposed and already shown impressive progress.[205–207]

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Figure 7. Paper based energy storage devices. A) Cross-sectional SEM image of the nanocomposite paper showing MWCNT protruding from the
ionic liquid infiltrated cellulose thin films. Cyclic voltammograms (acquired at a scan rate of 50 mV/s) of the nanocomposite supercapacitor devices
with various electrolytes. Reproduced with permission.[203] Copyright 2007, National Academy of Sciences, U.S.A. B) Cycling behavior of the cellulose/
polypyrrole composite cell at a current density of 600 mA cm−2. Reproduced with permission.[204] Copyright 2009, American Chemical Society. C)
Schematic illustration of the polyaniline/CNT nanocomposite electrodes and SEM side view of the ultrathin gel polymer electrolyte device. Discharge
capacity of the paperlike polymer supercapacitor when operated with different electrolytes. Reproduced with permission.[135] Copyright 2010, American
Chemical Society. D) Conductive composite fabricated by dipping the textile into an aqueous SWCNT. Reproduced with permission.[208] Copyright
2010, American Chemical Society. E) Paper battery lamination process. The paper is used as both the separator and the substrate. Reproduced with
permission.[132] Copyright 2010, American Chemical Society. F) Conductive paper electrode fabrication by simple drawing with a graphite pencil on
Xerox paper. Areal and gravimetric capacitances of the supercapacitor at different current densities are also shown. Reproduced with permission.[209]
Copyright 2011, Royal Society of Chemistry.

Meng et al. have used similar approaches and built a paper- all one-dimensional electrospun nanofibers,[211] whereas Lei-
like polymer supercapacitor by embedding two polyaniline jonmarck established a paper-making process based on nano-
coated intertwined CNT networks in a polyvinyl alcohol – fibrillated cellulose to build single-paper flexible Li-ion battery
H2SO4 gel electrolyte.[135] The composite device had a contin- cells.[186]
uous gel polymer phase (Figure 7C). The monolith configura- Regular cellulose based materials i.e., paper, cotton textiles,
tion is expected to have enhanced mechanical properties, espe- cellophane (also called “transparent nanopaper”), and rayon are
cially when dealing with shear and tear loads as the delamina- intrinsically electrically insulating, justifying their application
tion of layers is prohibited by the continuous polymer phase. as battery separator. However, their use is extended beyond the
The integrated device also displayed superior electrochemical separator function by making these materials electrically con-
characteristics while being twisted, showing high specific ductive. Electrically conductive paper and textiles have been pri-
capacitance retention of 350 F g−1 for more than 1000 cycles marily used as supercapacitor electrodes or as current collectors
with a very low leak current. A different approach was imple- for Li-ion batteries.[208,212] To render these substrates electrically
mented by Hu et al. to build a secondary Li-ion paper bat- conductive, simple solution based approaches have been pro-
tery.[132] The authors laminated free-standing thin films of posed. For example, Hu et al. fabricated conductive textile with a
LiCoO2/CNT and Li4Ti5O12/CNT on two sides of a paper sheet simple dipping and drying process using CNT inks (Figure 7D).
(Figure 7E). To enhance the adhesion of films to the paper, The composite textile preserves the mechanical properties of
they first applied a thin layer of PVDF solution on the paper. the pristine material while being endowed with electrical con-
The lamination was done while the PVDF coated paper was ductivity properties. This kind of conducting composites can
still wet, so that the solution penetrates the electrodes and be used either as electrode in supercapacitor devices or as cur-
glues them to the paper. This configuration could be also con- rent collector for Li-ion batteries. An original idea was proposed
sidered as a continuous polymer phase battery although it was by Zheng et al. who fabricated conductive paper electrode by
not specified to what extent the polymer penetrates into the simple drawing with a graphite pencil on a sheet of Xerox
electrodes. Other devices with paperlike characteristics or mor- paper.[209] It is well known that tiny graphite fragments and gra-
phology have been further proposed. Gaikwad et al. proposed phene sheets are obtained whenever graphite is abraded on a
a technique to reinforce arbitrary battery electrodes by sup- surface, such as drawing with a pencil on a sheet of paper. The
porting them with mechanically tough, low-cost fibrous mem- sheet resistance for a three-step coating was found to be as high
branes.[210] An ingenious design was proposed by Aravindan as 223 Ω cm−1. By coating both sides of the paper and impreg-
et al. by building a LiMn2O4 | PVdF-HFP | TiO2 cell comprising nating with an appropriate electrolyte, the authors made a

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supercapacitor device integrated into a single piece of paper dis- techniques are almost unlimited, solutions to alleviate these

REVIEW
playing high areal capacitance and excellent long term cycling problems will certainly be provided.
performance (Figure 7F). As mentioned, one of the advantages provided by the flex-
From this overview it is clear that the field has progressed ible battery assembly route is the possibility to entirely elimi-
rapidly in only a couple of years. Driven by the advent of the nate the use of metal foil current collectors. Aluminum and
field of paper electronics,[99,213] many configurations have been copper foils have the merits of enhancing the mechanical sta-
proposed and many more materials have been tested, either as bility of the electrode coatings as well as of ensuring efficient
active redox materials or as passive, conducting or binding com- current collection in high area Li-ion batteries configurations
ponents.[134,192,214] However, there are still many problems left (jellyroll, wound and folded type batteries). Nevertheless, they
to be solved before these technologies compete with products induce certain mechanical constraints. For instance, stretch-
existing on the market. First of all, it is noticeable that mainly able energy storage and conversion devices[215,216] are needed
supercapacitor device configurations have been explored. for a soft future:[217] smart clothing, wearable electronics, e-skin
This is not surprising as supercapacitors have less stringent and humanoids.[97,218,219] While the electrode coatings and the
requirements for assembly and especially for safe and long- microporous polymer separators could be reversibly stretched
term operation as compared to Li-ion batteries. And although and compressed to a certain degree, bulk metal foils will con-
supercapacitors have high power density characteristics, their strain this movement and eventually, will be irreversibly dam-
energy density remains low for many portable power applica- aged. Various solutions for building stretchable energy storage
tions. Furthermore, the attained gravimetric and volumetric devices have been proposed so far.[208,220–237]
energy densities are problematic. The thickness of one battery Back in 2009, Yu et al. proposed the use of a buckled CNT
stack (Figure 4B) measures approximately 150 µm with the macrofilms to build stretchable supercapacitors.[238] To enable
separator layer having a thickness of 10 µm. For comparison, this, the authors uniaxially pre-strained a PDMS film on top of
regular printer paper is about 100µm thick. Integrating such which they deposited the CNT macrofilm (Figure 8A). Upon
elements into Li-ion cells will considerably lower the volumetric relaxation, a buckled CNT film was obtained. The supercapac-
capacity. Whereas much thinner paper sheets are conceivable, itor device showed little performance change when subjected to
their mechanical properties as well as Li dendrite penetration mechanical stress. The authors used a filter paper soaked in the
may be problematic. Clearly, there are further improvements to electrolyte in between the stretchable electrode that may hinder
be made with respect to this, but since the opportunities pro- the stretching ability of the two-electrode supercapacitor config-
vided by the disruptive battery assembly and manufacturing uration. Although the stretching ability was only unidirectional

Figure 8. Stretchable energy storage devices. A) SEM image of a buckled SWNT macrofilm electrode fabricated on pre-strained elastomeric substrate.
Device performance remained unaltered even after being exposed to mechanical strain. Reproduced with permission.[238] B) Schematic view of a com-
pliant Zn–MnO2 gel electrolyte cell. Photographs of two cells in series powering a LED while subjected to uniaxial and biaxial stretching. Reproduced
with permission.[239] C) A self-similar, serpentine interconnect battery powering a red LED while biaxially stretched to 300%. Top-right: galvanostatic
charge –discharge curves of the battery electrodes without (black) and with 300% uniaxial strain (red). Bottom-right: output power as a function of
applied biaxial strain. Reproduced with permission.[240] Copyright 2013, Macmillan Publishers Limited. D) Cross-section image of the MnO2-Zn stretch-
able battery built on a silver fabric under 0% and 100% strain. EIS and discharge curves at 0, 50 and 100% strain. Reproduced with permission.[241]

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this work pioneered the development of stretchable power by wrapping two layers of CNT sheets, serving as the two elec-
REVIEW

sources. trodes, on an elastic fiber.[243]


A slightly different approach was proposed by Kaltenb- Another recent technological trend is the integra-
runner et al[239] to fabricate stretchable energy storage devices. tion of electronic devices into fabrics to achieve smart clot
The authors built a compliant Zn–MnO2 gel-electrolyte cell hing.[19,37,96,100,244–248] To realize this and to achieve seamless
by enclosing gel pastes of active materials with PDMS elas- integration we would need electronics devices and their power
tomer (Figure 8B). As the entire device was made of elastomer units to possess mechanical, structural and aesthetic proper-
building blocks and gel (liquid) pastes, the structure supported ties similar to cloth (Figure 9A). The human body and the sur-
ultrahigh strain (up to 100%) in both, uniaxial and biaxial rounding environment comprise many energy sources, such as
stretching modes without affecting the electrochemical perfor- sunlight, body heat, and movements, or ambient radio frequen-
mance. Since a gel or a liquid paste has infinite strain response, cies. Many energy-harvesting designs that can be integrated
the stretch limits of this type of devices are intrinsically set by with cloth have been proposed, for example textiles integrated
the elastomer enclosures. This configuration holds great prom- with harvesters that capture energy based on solar cells,[249,250]
ises as it allows for relatively high gravimetric and volumetric RF antennas, thermoelectric pile, or piezoelectric devices.[251–260]
energy densities. Nevertheless, the large separation between However, development of energy storage for smart garments
the positive and negative electrodes as well as the safety issues remains a challenge in terms of safety, comfort and aesthetics
related to the flowing nature of the constituents still have to be vs. energy and power density.[248,261,262] Energy density as well
solved. A similar design, based on a non-liquid component,was as outstanding mechanical characteristics (including fatigue
proposed by Gaikwad et al.[241] Instead of using liquid pastes lifetime) are additional limiting factors.
of Zn and MnO2, the authors used a stretchable silver fabric The most intuitive way of integrating energy storage devices
loaded with active materials (Figure 8D). The stretchable elec- or power sources into fabrics is to mimic the textile micro-
trodes and the aqueous gel electrolyte composed of 6M KOH, structure, i.e. fabricate the power fibers and then weave them
0.4M ZnO powder and 1.6% polyacrilic acid were subsequently to get a cloth. Fiber, cable or naturally roll-type batteries can
assembled in an elastomer casing prior to testing. The batteries be the most appropriate type of energy storage device for this
have shown a high mechanical flexibility being able to support purpose. This technology is relatively young (the first scientific
up to 150% strain while being twisted by 90°, with little impact articles being published in 2011) yet, more than a dozen of
on the electrochemical performance. Stretchable silver–zinc bat- publications can be accounted already whereas patent applica-
teries based on silver nanowires embedded in elastomer matrix tions are probably in the pending application stage.[268] Again,
have been proposed by Yan et al.[242] The dual functionality was given the simplicity and less stringent requirements for man-
maintained even in highly stretched states (80% strain). ufacturing and especially for safe operation, mainly superca-
A self-similar interconnect battery design was proposed pacitor power fibers have been explored,[227,243,248,269–296] the
by Xu et al.[240] The authors ‘broke down’ a Li-ion battery into Li-ion technology integration being still challenging yet with
smaller-scale storage components which were electrically wired strong efforts undertaken leading recently to valuable develop-
via deformable electrical interconnects in specialized, ‘self- ments.[221,233,260,263–265,297–303] Chemistries other than Li-ion are
similar’ geometries (Figure 8C). An evenly dispersed polymer being explored as well, with flexible fiber-type zinc-carbon and
gel electrolyte was injected into the electrodes gap to close the zinc-air batteries being recently demonstrated.[147,304] Further-
power cell circuit. The LiCoO2/Li4Ti5O12 couple delivered a more, a few attempts to build integrated energy harvest/storage
constant power at the expected voltage of 2.3 V vs. Li/Li+ even power fibers have already been successfully realized; the energy
when strained up to 300%. The authors have also designed a device hybridization techniques are detailed in Section 4.5.
stretchable wireless RF power transmission system and inte- Clearly there is a huge interest behind this technology given its
grated both devices to demonstrate battery charging without high-end applications.
direct physical contact. This configuration is of huge interest The very first technology report found dealing with power
for biomedical applications where non-invasive control (for fibers originates from ITN Energy Systems Inc back to 2003
instance, battery charging) is being targeted. (the report actually states that the PowerFiber was practi-
Stretchable energy storage configuration will intrinsically cally implemented earlier, in 2001).[263] Neudecker and his
possesses lower areal and volumetric energy densities. To com- team developed solid-state thin-film rechargeable batteries on
plement the low areal coverage of active material, thicker elec- fibrous substrates (Figure 9B). The fabrication was done using
trodes could be designed, although this may have a detrimental a custom designed rotational shadow mask system that allowed
effect on the rate performance of the battery. For example, Xu et them to sequentially deposit the thin-film battery layers via
al. achieved load capacities of 1.1 mAh cm−2 in their segmented physical vapor deposition techniques. As detailed in the report,
layout.[240] When compared to commercial systems, displaying complex multilayer structures (up to 8 functional battery layers)
3–10 mAh cm−2, the value is not so low, whereas the stretching have been tested on a variety of substrates (alumina, copper,
functionality is unique.[38] Further technological aspects need stainless steel, Inconel, sapphire and carbon fibers). The Power-
to be addressed, such as mechanical fatigue degradation of Fibers were electrochemically cycled under ambient conditions
interconnects, battery elements, or encapsulating enclosures. and found to retain more than half of the initial capacity after
Ideally, the fatigue lifetime should be comparable to the cycle 2,000 cycles. They have also made power composites containing
lifetime of the cell. These aspects may be less critical for gel multiple PowerFibers. These composites have the advantage of
paste based cells.[239] Finally, a hybrid stretchable fiber-shaped considerably increasing the specific area (and thus, the specific
supercapacitor design was also proposed recently by Yang et al. surface capacity): three layers of 17 µm diameter PowerFibers

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REVIEW
Figure 9. Fiber, cable and roll-type energy storage devices. A) Design concept for cloth integrated energy storage, harvesting and electronic device
components. This design intends to power textiles to store the energy. Reproduced with permission.[248] Copyright 2013, Royal Society of Chemistry.
B) Cross-sectional SEM image of a Li metal-free PowerFiber fabricated on sapphire substrate. Inset: image of a PowerFiber fabricated onto 33 µm in
diameter carbon fiber substrate comprising 8 functional battery layers. Bottom: PowerComposite consisting of 10 individual PowerFibers integrated into
a flexible PET shell. Copyright 2003, ITN Energy Systems.[263] C) Cross-section image and schematic view of the cable battery containing a hollow-helix
anode with multiple-helix structure. The spring-like structure enables mechanical flexibility and ensures efficient electrolyte transport to the electrodes.
Typical charge and discharge profiles of the cable batteries. Reproduced with permission.[264] D) Rate performance of a roll-up, lithium polymer silicon
nanowire battery with different anode configurations. The polymer monolith configuration ensures good mechanical stability when the battery stack is
subjected to extreme mechanical loading, whereas the porous metal-shell configuration enhances the electrochemical properties of the silicon nanowire
anode. Reproduced with permission.[265] Copyright 2012, National Academy of Sciences, U.S.A. E). Schematics of the hybrid organic/inorganic self-
wound capacitor based on rolled-up nanomembranes altogether with cross-sectional view of a capacitor comprising 13 windings and rolled from a 600
µm long planar capacitor. Reproduced with permission.[266] Copyright 2010, American Chemical Society. F). SEM image of a microtube rolled-up from
SiOx/SiOy bilayer nanomembranes, together with TEM bright-field image from the cross section of a single tube highlighting the interface between the
silicon-rich and oxygen-rich layers. Reproduced with permission.[267]

composite have 371% more specific surface than a double-side battery components during repeated flexing as well as safety
coated foil of the same area. Further lowering the fiber diam- issues must be optimized before this product hits the market.
eter can significantly increase the specific area and thus spe- Nevertheless, it remains one of the pioneering examples of
cific capacity (ultimate downscaling, towards the micron-scale the cable- or fiber-type battery. Further progress was very fast,
coaxial battery, is considered as part of the nanobattery research with a dozens of reports over the past year.[268] Carbon based
direction that will be detailed in the next section). For now, it is supercapacitors with single-fiber coaxial[273,276,279] and two-fiber
clear that the fiber Li-ion battery has been well established, pro- twinned[227,272,275,278] have been fabricated. Other configura-
totypes or even real products being probably already in use. Yet, tions, including twined polypyrrole/MnO2/CNT cotton threads
the nature of the project probably prohibited large media atten- supercapacitors,[277] Zn/MnO2 fiber batteries,[147] as well as inte-
tion and the report triggered little attention from the academia. grated power fibers for energy harvesting and conversion,[274]
The first academic research reports appeared some 10 years have been proposed. A very recent study proposed the integra-
later. Kwon et al. have developed a cable-type flexible Li-ion tion of energy storage functionality into the electrical cables by
battery based on hollow multi-helix electrodes.[264] The cable- building a supercapacitor on a metal wire inner core.[305,306]
battery design was based on Ni-Sn anode strands coiled into The coaxial configuration is seemingly harder to achieve, yet
a hollow spiral core surrounded by a tubular outer LiCoO2 it is highly desirable due to lower mechanical constrains and
cathode (Figure 9C). A poly(ethylene terephthalate) non-woven the higher gravimetric capacitance provided. Precise sequential
film was wrapped around the anode and used as separator coating of battery or supercapacitor layers is difficult to achieve,
and the cell was activated by injecting a standard carbonate especially when dealing with solution based processing. The
based liquid organic electrolyte in the hollow space of the main problem lies in defect-free conformal coating with pre-
structure. A thermal shrinkwrap tubing was used to package cise thickness of the electrolyte-separator layer. One way of
and seal the finalized device. The cable-battery displayed out- achieving the coaxial configuration could involve first the
standing mechanical and electrochemical properties due to fabrication of a planar cell stack on a sacrificial substrate fol-
its unique structural features yet, strongly dependent on the lowed by chemical or mechanical delamination and controlled
morphology of the anode core (hollow anode was found to be roll-up of the delaminated stack around a support fiber. The
better than the non-hollow anode). As stated by the authors, planar configuration (described in detail in the following Sec-
the fatigue behavior and the structural disintegration of the tion) can be much easier to manufacture (either by physical

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vapor deposition of by using solution coating) and allows for a battery performances similar to those of commercial cells. And
REVIEW

better control over the thickness and morphology of the battery why not, filling the hollow inner section with a conductive wire
layers. There are several examples in the literature that have or other extra elements. Of course, it will make a 18mm diam-
approached this fabrication. Vlad et al. have used a sequential eter cable (based on a 18650 cell) with probably reduced flex-
silicon nanowire polymer infiltration–gel-polymer coating– ibility given the multi-layer composition and rigid encapsula-
cathode slurry coating followed by mechanical delamination tion. The structural flexibility could be increased by reducing
to build a rolled Li-ion battery (Figure 9D).[265] To stabilize the the number of wound layers and by replacing the metallic can
fragile silicon nanowire configuration, the authors have devel- with a flexible polymer one. Seemingly simple in realization,
oped an electroless plating process to apply a thin conformal yet with very few developments reported in this direction.[309]
copper layer around each nanowire. The silicon core–copper Kim et al. got inspiration from the structure of commercial bat-
shell structure was also found to exhibit enhanced rate perfor- teries and designed ribbon-type Li-ion batteries for textile appli-
mance as compare to bare nanowire configuration. This design cations.[310] The authors achieved this by sequentially stacking
requires further optimization, especially regarding the mechan- 2-mm-wide ribbon electrodes made by coating the active battery
ical delamination step that was found to be responsible for material on metal foils stripes using conventional processing
damaging the silicon nanowires, resulting in rather large initial methods. The separator membrane was Z-folded while sequen-
capacity drop. Further development also revealed that metallic tially integrating in between the electrode ribbons. Competitive
surface layers severely affect the swelling and fracture behavior electrochemical and mechanical performances were attained
of silicon nanowires during lithiation.[307] using these ribbon-type batteries and the potential for the tex-
Other roll-type processes have been also developed. Bufon et al. tile and cloth type rechargeable batteries is highlighted. But
examined the self-assembly of hybrid nanomembranes and probably most important is the striking similarity with the con-
fabricated ultra-compact energy storage elements (Figure 9E). ventional battery manufacturing approaches, yet with markedly
Being two orders of magnitude smaller than their planar coun- different final product design that could enable much faster
terparts yet, exhibiting capacitances per footprint area of around technology transfer protocols.
200 µF cm−2 the authors established new performance records To shortly summarize, this section has reviewed advances
at that time.[266] Using similar sacrificial layer techniques, with respect to manufacturing, processing and operation of
Zhang et al. fabricated multi-layer Si-based coiled nanomem- compliant, paper-based, stretchable as well as wire and fiber
branes and found them suitable for negative electrode for integrated batteries and supercapacitors. Altogether, these sys-
lithium batteries (Figure 9F).[267] Ji et al. made Swiss roll mem- tems are generally depicted in the literature as flexible energy
branes as small as 5 µm in diameter and characterized their storage sources given their ability to comply with any desired
supercapacitive behavior.[280] Similarly, Sharma et al. designed shape. It is clear that only the tip of the iceberg has been
large area, rolled-up nanomembrane-based capacitor arrays by explored and there are still many opportunities at the bottom,
combining bottom-up and top-down fabrication methods.[308] either to improve the existing designs or to design new con-
Considerable scale-up was achieved, enabling parallel fabri- figurations. Although their electrochemical performance, and
cation of more than 1600 devices on a 4-inch wafer. As men- probably the manufacturing price, still hardly compete with the
tioned by the authors, the fabricated electrostatic rolled-up commercially available batteries, they have shown that disrup-
ultra-compact energy-storage elements have a large potential tive changes are possible and it is a matter of time before we
in powering various autonomous microsystems. These systems see them powering our portable flexible electronics.
could be also explored as microscale power sources and can
provide insight into the charge transfer at the electrolyte/elec-
trode interface. But the rolling approach could be also explored 4.2. Ultra-Thin and Ultra-Thick Batteries
to build power fibers by coiling up the delaminated membranes
around support fibers. This could be further applied in a con- This Section discusses two antipodal battery configurations:
tinuous or segmented layout. If one recalls the composition of ultra-thin and ultra-thick electrode-based, that are particularly
a commercial cylindrical Li-ion cell (Figure 4), the structure is designed to deliver high power and high energy, respectively.
the result of winding battery constituents around a supporting Whereas the chemistry of these batteries can be similar, the
core. The quest would be then to drastically diminish the char- fabrication methods, performance, and structural details, as
acteristics dimensions of all battery layers (the topic of the fol- well as their applicability, are radically different. Thin and ultra-
lowing Section) and find adequate winding protocols, as well thin film batteries are targeted for those applications where
as scale-up and control the fabrication of the thin-film electro- high power and low energy is needed e.g. sensors, RFID card
chemical cells. readers etc. Ultra-thick counterparts are in turn primarily con-
Noticeably, most of the above-mentioned flexible, paper- ceived for low-power and high-energy applications. The pri-
based, and fiber or wire shaped batteries have been realized by mary difference comes from the characteristic dimension of
developing new manufacturing methods for the integration of the constituents (also when compared to commercial battery
active battery and supercapacitor materials. Curiously, not so configurations). To recall Figure 4B, the typical thicknesses of
many developments are inspired by conventional battery manu- the battery constituents are as follows: Cu and Al metal foils
facturing, although there is much to learn from that. Recalling are ≈10–15 µm thick, the separator ranges from 10 to 20 µm,
the structure of a commercial Li-ion cell (Figure 3B) one can whereas the electrodes are each ≈50 µm thick. In the following,
imagine that by axially extending the multilayered structure, batteries in which these dimensions are orders of magnitude
one can end up as well with a cable-type configuration, yet with different will de detailed.

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Thin-film batteries originated from the requirement of more stringent requirements regarding the morphology, thick-

REVIEW
integrating power sources into electronic circuitry at the com- ness and electrochemical properties of the solid-state electrolyte
ponent (chip) level to achieve a distributed power system layer, especially when targeting nanometer-scale thicknesses.
inside the electronic devices. Subsequently, a progressive One of the thinnest Li-ion battery ever reported was real-
shift from planar 2D thin-film battery configurations towards ized in 2012 by Ruzmetov et al.[338] The authors used sequen-
3D integrated micro-batteries (and lately, nano-batteries) was tial physical vapor deposition of various materials on silicon
observed.[311] This change was motivated by the need for higher nanowires, targeting primarily 3D coaxial nano-batteries. They
stored energy per unit area. Simultaneously, ultra-thin film bat- also built planar structures on flat Si/SiO2 as control specimens
teries have emerged, in part due to their striking similarity with (Figure 10A). The structure shown in Figure 10A is less than
3D nano-batteries but also due to their very unique physical and 1.5 µm thick with 444 nm-thick LiCoO2 cathode; 364 nm-thick
electrochemical properties. Furthermore, these systems proved LiPON (N-doped Li3PO4) solid-state electrolyte; and, 80 nm-
to be irreplaceable prototypes for better understanding of elec- thick n-doped silicon anode. Anode and cathode current collec-
trochemical phenomena at the nanoscale.[312] It is beyond the tors, adhesive and encapsulating layers made of Ti and Pt mul-
scope of this section to review all thin-film or 3D battery con- tilayers were ≈200 nm thick. Thinner electrodes have been also
figurations. The interested reader is referred to existing litera- designed and tested. Unfortunately, below 110 nm thick elec-
ture reports and reviews highlighting the background, achieve- trolyte films, the batteries were found to rapidly self-discharge
ments, and challenges in the field.[87,313–319] Here, configura- and structural characterization revealed irreversible damages at
tions in which all of the battery layers are ultimately scaled the SSEI interface indicative of electrical and chemical break-
down, approaching the few-nanometer scale, are discussed. down. The lower limit for the reliable operation of the battery
These configurations should not be confused with ultrathin, 3D was found for ≈180 nm thick LIPON layer. As demonstrated by
battery, or planar interdigitated electrodes comprising one or the authors, in thin film batteries, the electrolyte thickness and
two functional nanostructured battery layers.[320–337] Although stability set the length scales for the device.
there is potential to further coat or functionalize these archi- Similar findings, although with different materials and
tectures with the electrolyte and the opposite electrode mate- with much thicker electrode and electrolyte layers, have been
rials, for some configurations this integration may still be chal- previously reported by Brazier et al.,[350] Sakuda et al.,[354] and
lenging, as is detailed in the following. recently by Santhanagopalan et al.[355] These studies revealed
Similar to the standard configuration, ultra-thin film bat- drastic chemical and structural changes upon cycling. The
teries comprise five functional layers: the two couples of posi- SSEI was characterized by severe damaging and void forma-
tive/negative current collectors and electrodes separated by an tion as well as pronounced migration of the chemical elements
electronically insulating ion conducting layer.[19] However, reali- between the anode/cathode and the electrolyte layers. The
zation of ultra-thin batteries with the conventional slurry based initially well-defined interface was no more preserved upon
coating process is almost impossible due to its limited capa- cycling, presenting cavities within the electrolyte film and low
bility in terms of scaling down the components to nanometer wetting points between the solid-electrolyte and negative elec-
range. Researchers in the battery field have realized this fun- trodes. The faulty regions were found to extend for several
damental problem and recognized as well that one of the fun- hundreds of nanometers. It should be noted that these findings
damental limitations of the ultrathin-film configuration is the impose severe constrains and require careful consideration
solid-state electrolyte.[338] So far, only the solid-state electrolytes when targeting thin-film as well as 3D nano-battery designs.[356]
comply with the electrochemical and electrical requirements for Koo et al.[352] have used thicker electrodes in their thin film
the realization of sub-micron electrolyte layers in the ultra-thin batteries. The authors sequentially deposited LiCoO2/LiPON/Li-
film battery configuration. Ultra-high vacuum deposition tech- metal on mica substrates for a total battery thickness of ≈5 µm
niques have been primarily used to coat the solid electrolyte as (excluding the encapsulation layer). The mica was used as a
well as the entire multi-layered thin film battery. Although tech- sacrificial substrate and the entire battery was subsequently
niques such as sol–gel deposition can also produce thin films transferred onto and encapsulated with flexible PDMS films
of Li-ion battery materials, precise morphological and thickness (Figure 10B). The developed universal transfer approach could
control is rather challenging.[178,339–341] Atomic layer deposition in principle enable the realization of diverse, ultra thin-film
(ALD) allows for atomic precision thickness control and has flexible LIBs regardless of the battery chemistry. The study
been also used to fabricate thin film battery components.[342,343] also concluded that thin-film LIBs are more stable on flex-
Nonetheless, whereas the anode and cathode active materials ible substrates than on rigid brittle substrates. Furthermore,
synthesized using ALD display good electrochemical perfor- an all-in-one flexible LED-LIB system was built by integrating
mances, the solid-state electrolytes grown by ALD are still a flexible organic light-emitting source. Recently, Zhu et al.
poorly performing.[344–346] Finally, it should be noted that even reported an ultra-thin film battery.[353] The authors have stacked
if soft techniques exist for structuring solid-state electrolytes by LiNi0.33Co0.33Mn0.33O2/LiPON/TiO2 on a Ti substrate using
using lithium conducting polymers,[81,347–349] their integration magnetron sputtering techniques (Figure 10C). Again, although
into ultra-thin film Li-ion technology remains challenging and the main purpose of the work was not the realization of the
rather questionable, given the harsh mechanical and electro- thinnest LIB, the authors have achieved a record thickness of
chemical changes at the solid-state electrolyte interphase (SSEI) 2 µm (no current collector and encapsulating layers) with
during cycling.[350,351] Clearly, the solid-state electrolyte remains LiPON layer accounting for more than half of the thickness.
the primary bottleneck of this technology. Not only are the dep- There are several fundamental advantages provided by the
osition techniques less well established, but there are also far thin-film configuration (Figure 11). First of all, the ultra-thin

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Figure 10. Ultra-thin batteries. A) SEM and TEM cross-section view of an ultra-thin film LIB. The thickness of the entire battery is less than 1.5 µm
Charge–discharge curves at 10−7 A for an ultra-thin film LIB with 0.007 cm2 active area. Reproduced with permission.[338] Copyright 2012, American
Chemical Society. B) Cross-sectional SEM view showing the stacked layers in a thin-film LIB. Left-bottom: Picture of an all-in-one flexible LED system
integrated with a bendable LIB. Right-bottom: Induced stress function of applied bending force. Reproduced with permission.[352] Copyright 2012,
American Chemical Society. C) FIB cross-sectional image of a 2µm thick solid-state battery. The thickness comprises only the anode/electrolyte/cathode
stack. Reproduced with permission.[353] Copyright 2013, American Chemical Society.

film LIB configuration provides an irreplaceable platform for in data interpretation. Furthermore, as already demonstrated,
the investigation of solid-state bulk and interfacial electrochem- these systems could be also fashioned to enable in-situ visu-
ical processes at the nanoscale.[312] The simplified chemical alization of the electrochemical processes at the nanoscale.[357]
composition (as compared to commercial systems, see Figure 4) Ultra-thin-film batteries are intrinsically flexible and contain
can allow for a sharper understanding of the electrochemical no liquid components so they are inherently safer to operate
solid-state processes and limiting factors. The drawback is that because there are no issues related to leakage or boiling of sol-
SSEI becomes a major constituent and may induce incertitude vents during thermal or mechanical abuse conditions. Thin-
film batteries are also capable of delivering
high currents in a very short time due to the
faster kinetics of the electrochemical reac-
tion (since the rate of reaction is not limited
by the diffusion due to the extremely short
length scales). There is a niche of applica-
tions where compact, flexible, high power
and safe LIBs are required such as sensors,
biomedical devices and smart cards etc.
Optical transparency could be also ren-
dered in these batteries. Although the used
materials are rather opaque and downscaling
to thicknesses that may no longer operate
properly is required to make the entire stack
transparent, other approaches could be
applied. For instance, the thin film could be
patterned to have open windows and render
an optical illusion of transparency (Figure 11;
see Section 4.4 for experimental implementa-
Figure 11. Thin film battery potential. By virtue of their reduced thickness, the thin-film bat-
tion).[358] Another way of building transparent
teries are intrinsically flexible (not taking into account the supporting substrate and encap-
sulation box), can be made transparent (either by realizing openings or by using transparent batteries could be by using naturally trans-
materials,) and are an ideal study platform for the implementation of 3D micro-/nano-battery parent battery materials. However, there are
configuration. not so many materials complying with these

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specifications. Optically transparent current collector electrodes developments will reveal the ultimate physical limit in ultra-

REVIEW
can be made by means of nanostructuring[359,360] and polymer thin film batteries. Nonetheless, the developments made so far
thin-film electrolytes are intrinsically transparent. The main in the field are encouraging, opening the possibility for many
problem lies in the development of transparent anode and interesting applications and setting the scaling laws for the 3D
cathode materials. For negative electrodes, an elegant solution nano-battery realm.
exists: single- or few-layer graphene; and several thin film bat- Finally, it is worth mentioning that the 3D nanostructured
tery configurations based on this extraordinary material have configuration was found especially useful for the realization of
already been realized.[323,361,362] Other possible candidates are electrostatic capacitors where the device capacitance scaled lin-
TiO2, SnO2 or SiOx. The retention of the optical transparency early with the active surface.[87,368] Ultra-thin film electrostatic
upon lithiation is however challenging.[363] For cathode mate- capacitors provide the ultimate high-power density tool with
rials there are even fewer possibilities. Lithium vanadates charge/discharge speed being limited by the external RC cir-
(LixVOy) and copper sulfates (CuSO4) are known to be colored cuit. The tradeoff is extremely low energy stored because the
yet transparent, and show reversible redox chemistry.[364] The charge is stored only at the surface and the specific surface of
solution may be provided by the electroactive polymers known these devices is low. Banerjee et al. proposed a solution for this
to be intrinsically transparent, with some classes showing high by designing coaxial metal–insulator–metal capacitors using
redox potentials with competitive storage capacities.[365] More alumina templates.[87] Again, the dielectric material (equivalent
details on optically transparent batteries can be found in Sec- of the separator or electrolyte for LIBs and supercapacitors)
tion 4.4. is the primary issue when dealing with such devices. Higher
Inevitably, there has to be a trade-off for these outstanding dielectric constant and high voltage breakdown are the key
qualities. The main disadvantage of the thin film configura- parameters for building performing electrostatic energy storage
tion is the low areal capacitance (typically of the order of tens devices.[369–372]
of µA cm−2). In most of the above described configurations, the On the opposite side of the ultra-thin film battery spectrum
anode and cathode materials occupy ≈1/3 of the battery volume are the ultra-thick or ultra-high energy cells that rely on high
and have a similar gravimetric fraction contribution. The capacity electrodes characterized by extremely thick electrodes.
energy density is even lower if one considers the substrate and Probably the easiest way to the fruition of ultra-high energy cells
the encapsulation materials. Designing better solid-state elec- is to increase the amount of active material by increasing the
trolytes that could be fabricated and reliably operated at some thickness of the electrodes. Recalling Figure 4B, the electrodes
50 nm thickness, or even lower, will considerably diminish the occupy approximately 65% volume of the entire battery stack,
gravimetric and volumetric contribution of the electrolyte layer. whereas the active materials typically represent 50% volume
Making thicker electrodes can increase the areal capacity, yet at of the battery. The gravimetric contribution of the active mate-
the expense of high power performances. Proper balance may rials is also diminished by the weight of current collector foils
be difficult to find and probably the most sought approach for as well as of the encapsulating can, thus reducing the energy
increasing the areal and gravimetric energy density of these bat- density of the cell. The straightforward approach to change this
teries is the realization of a 3D configuration that can be seen balance in favor of active cathode and anode materials is simply
as the rolled variant of the thin-film configuration (see also Sec- to increase the thickness of the respective layers. Though this
tion 4.1 regarding the rolled-up energy storage configurations). can be realized relatively easily, the battery operation will be
If one considers the thinnest functional battery films reported significantly affected. Ultra-thick electrodes suffer from high
in,[338] made of 180nm-thick LIPON, 180nm-thick LiCoO2, polarization due to high ohmic resistance, lower ionic conduc-
35 nm thick-Si and some 200 nm for the enclosing metallic tion through the thick electrode, less efficient current collection
layers, the thinnest battery ever made actually barely measures and thus, limited power performances.[373] Thicker electrodes
600 nm; a true breakthrough in the field! And, if considering also suffer from low thermal conductivity that can raise serious
these dimensions in a coaxial configuration (Figure 11), the concerns regarding the safety of the device due to slow heat
smallest 3D nanobattery that can be built using this technology dissipation through the electrode thickness. Ensuring safety,
is little bigger than 1µm in diameter. And a question arises: is efficient ionic transport and current collection in thick elec-
it possible to make thinner or smaller batteries? In theory it can trodes are the main challenges, especially as the target current
be possible, for example by diminishing the thickness of the density increases. Furthermore, increasing the battery stack
anode, cathode and enclosing metallic layers. Another option is thickness significantly diminishes the ability to fold or roll the
to reduce the number of battery layers, and as such, the entire components. It should be noted here that the fabrication of
battery thickness. For example, Yada et al. proposed a very ultra-thick electrodes is rather difficult using conventional roll-
ingenious concept and built a battery simply by sandwiching to-roll slurry based processes (Figure 4) due to electrode drying,
a Li2O–Al2O3–TiO2–P2O5 glass–ceramic solid electrolyte in component segregation and delamination issues. Slot-die, knife
between metallic Cu and Mn films.[366] The three-layer stack edge or reverse roll thick coatings are prone to cracks due to the
became a 0.5 V all-solid-state lithium-ion battery after applying higher stress developed during drying and results in mechani-
a d.c. voltage of 16 V, thus greatly simplifying the assembly cally unstable electrodes that are not easy to manipulate.
protocol for an otherwise complicated battery configuration. For example, Aboulaich et al. have explored all-inorganic
Nonetheless, the thickness as well as the electrochemical and monolithic LIBs.[374,375] The authors built symmetrical
dielectric properties of the electrolyte layer will ultimately deter- Li3V2(PO4)3–Li1.5Al0.5Ge1.5(PO4)3–Li3V2(PO4)3 and asymmet-
mine the scaling limit for ultra-thin and 3D nano-batteries.[367] rical LiFePO4–Li1.5Al0.5Ge1.5(PO4)3–Li3V2(PO4)3 solid state cells
Whether this is possible remains an open question and future using a spark plasma sintering procedure (Figure 12A). The

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Figure 12. Ultra-thick batteries. A) Galvanostatic charge–discharge curves for an all-inorganic Li3V2(PO4)3/Li1.5Al0.5Ge1.5(PO4)3/Li3V2(PO4)3 solid-state
cell. The thickness of the battery stack is 1 mm. Reproduced with permission.[374] B) SEM image of a 660 µm-thick, sintered monolithic cathode (inset)
and cross section of a 74% dense sintered cathode. Volumetric energy density versus battery volume as compared to selected commercially available
technologies. Reproduced with permission.[376] C) Cross section SEM image of the dual-scale porosity battery electrode. The electrode is more than
1 mm-thick and has aligned channels of ≈ 6 µm in diameter spanning throughout the entire thickness (inset), with an average channel spacing of
17 µm. Rate performance of the fabricated dual-scale porosity battery electrodes. Reproduced with permission.[377]

configuration actually resembles the thin-film LIB design, would eventually lead to irreversible fracture of the monolith.
although, given the thickness of the electrodes, some funda- The authors accredit as well the semiconducting properties of
mental changes have been implemented. A unique feature of LixCoO2 for the successful operation this battery as well. Par-
the LIB in ref.[374] is the continuous solid-electrolyte (Li1.5Al0.5 tially de-lithiated LiCoO2 displays reasonable electronic con-
Ge1.5(PO4)3) phase expanding through the entire battery thick- ductivities (<10−3 S cm−1 in the fully lithiated state, x = 1; and
ness. The authors actually chose an adequate name for their >1 S cm−1 upon delithiation, x > 0.06).[378] Increase in the elec-
LIB: monolith solid-state LIB; the Stone-Age revisited. Con- tronic conductivity allows faster charge transfer even in the
sidering that the battery had a thickness of 1 mm, including a thicker LiCoO2 electrode and results in better utilization of the
200 µm solid-state thick electrolyte, the cell actually performed active material. The electrode capacity at a compaction density
very well, even if cycled at a temperature of 80 °C it delivered a of 74% and at ≈0.4 mm thickness is as much as 20 mAh cm−2
capacity of up to 10 mAh cm−2. Super-ion conductor type elec- (considering that only 80% of capacity was retained).
trolytes and better solid-state electrolyte–electrode interfaces The same group has further refined the technology and pro-
could potentially enhance further the cycling performances. vided a hierarchical porous configuration to allow for an effi-
An ultra-thick monolith cathode electrode made entirely of cient ionic transport and improve the power density of these
LiCoO2 was realized by Lai et al.[376] The authors achieved cubic batteries.[377] Diffusion and conduction in percolating sys-
millimeter scale lithium rechargeable batteries with energy den- tems, characterized by tortuosity, is an important parameter
sities orders of magnitude higher than those normally achieved for describing transport phenomena in multi-phase systems.
using standard manufacturing procedures (Figure 12B). They In very thick battery electrodes this can be very detrimental,
discovered that densely sintered electrodes made of lithium limiting the electrochemical performances (assuming that
intercalation oxides could be actually cycled very well. This the electronic conductivity and charge collection are not the
finding was contrary to the general belief that the bulk mate- rate-limiting steps).[379–381] The authors have introduced dual-
rial would result in electrochemical grinding due the stress scale porosity in cathodes through repeated co-extrusion of
induced during the insertion and de-insertion of Li-ions and coaxial LiCoO2–carbon/binder fibers. After the 3rd generation

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extrusion and sample burnout, regular aligned channels of manufacturing. Recalling Figure 4, the first step in battery

REVIEW
≈6 µm spanning through the entire electrode thickness were manufacturing is the slurry coating on metal-foil current collec-
obtained (Figure 12C). The influence of the electrode mor- tors. The coating process requires precision and accuracy and is
phology on the output performance was clearly evidenced by considered to be the critical element in ensuring high reliability
the enhanced rate performance with the increased number of product. Poor quality coatings will results in battery malfunc-
extrusion passes. tion or failure. Typical industrial scale coating processes are slot
Other solutions have been also proposed to increase ionic con- die, extrusion, reverse roll coating and knife-over-roll or doctor
ductivity by increasing the specific surface area of the LIB elec- blade coating.[8,19,38] Lab-scale processes are usually limited to
trodes. Evanoff et al. have used aligned CNT carpets coated with doctor blade, bar, and screen coating. Although these coating
silicon to build mm-thick LIB anodes.[382] The active material techniques are established as standard tools for battery elec-
loading is expected to be very high. Thermal dissipation in thick trodes fabrications, there are several limitations related to these
electrodes is always a concern and crucial for the safety of batteries. techniques that oriented the research to develop other coating
In their study, authors also showed that the ultra-thick Si-CNT or electrode fabrication schemes. For instance, most of these
composite has a thermal conductivity of 400 W m−1 K−1, which conventional methods are restricted to metal-foil current collec-
exceeds the thermal dissipation of powder-based electrodes by an tors. Coating current collector materials on non-conducting flex-
order of magnitude. Vlad et al. have reported core-shell silicon– ible or rigid substrates could be an alternative for replacing the
copper nanowire electrodes with a mass loading of 2–3 mgSi cm−2 metal foils. Also, conventional coating processes limit the thick-
corresponding to a specific capacity of 10 mAh cm−2, whereas ness of electrodes that can be fabricated without compromising
Mazouzi et al. went a leap further and managed to achieve up to the mechanical properties of the electrodes. Thus, the current
10 mgSi cm−2 using 3D copper foams.[383] High areal mass elec- coating process limits the capacity of cells that can be produced.
trode loading was also realized by solution infiltration and filtra- The conventional battery manufacturing is also limited to the
tion of porous CNT and textile networks as well as other pro- economic production of batteries with limited form factors,
cesses.[384–386] Integrating such high active material loaded anodes i.e., cylindrical or rectangular shaped batteries. However, the
with the ultra-thick cathodes presented in previous paragraph will emerging electronic devices are moving towards unconventional
result in batteries with extremely high gravimetric and volumetric or more arbitrary shapes and these devices require unconven-
energy densities, even when considering the packaging elements. tional shaped batteries as well. With the current manufacturing
Power density, thermal management as well as multiple layers process, it is very costly and time consuming to produce bat-
integration remains challenging, however. teries with arbitrary form-factors. Making a round-shaped bat-
To shortly summarize, this section highlighted the recent tery (for example to fit into your smart-phone) requires slot
advances with respect to realization, integration and charac- cutting and soldering of prismatic cells of different sizes[387]
terization of ultra-thin film and ultra-thick Li-ion batteries. or complex handling of non-rectangular battery layers.[388] A
Both technologies have their advantages and drawbacks and fabrication process capable of making batteries with any given
are intended for some specific niche applications. Whereas footprint will considerably simplify the process. This can be
ultra-thin film configurations are suitable for flexible, all solid- enabled by direct coating of all of the battery components into
state applications, they inherently suffer from very low specific the desired shape either through a mask or by subsequent cut-
areal capacities. Their energy density decreases drastically due ting. Furthermore, direct coating also implies a monolith-type
to the fact that the major constituent of the cell becomes the structure with little delamination of layers, making possible the
packaging. Increasing their surface area, in other words, redi- integration of such devices into flexible substrates. Not least,
recting the technology towards 3D micro-/nano-batteries can this enables battery integration on a variety of substrates, pro-
increase the specific energy, yet this direction is still explora- cesses difficult to realize otherwise.[90] It should be noted that
tory and requires further work before having this technology the fabrication of most of the flexible-type LIB and supercapac-
implemented into real-life batteries. Nevertheless, it is the itor configurations described in Section 4.1 is actually based on
ultimate downscaling platform to study the battery operation variations of printing and painting approaches.
at the nanoscale and set the scaling laws for the coaxial 3D Coating the “separator–electrolyte” layer has been so far the
micro-/nano-batteries realization. On the opposite, the ultra- most challenging. The problem comes from stringent require-
thick batteries have high energy but have limited mechanical ments for its proper functionality. First of all, it requires good
characteristics, and may become unpractical when high power mechanical strength: rigid enough to sustain any mechanical
is required. Nevertheless, these examples show how broad and shock or tear and flexible enough to be able to bend or fold.[19,38]
generous the field of electrochemical energy storage can be: Polymer-gel or swelled membranes are the most suited, given
scaling the device dimensions not only scales the energy and that solid-state electrolyte technology is still exploratory and the
power, it also requires entire rethinking of the assembly and common ionic conductivities remain low for practical appli-
proper functioning scheme, chemical and physical properties cations. In order to be applied as a coating, the polymer-type
of active, ion and electron conductive components. electrolyte needs good mechanical properties and conformal
coverage to avoid shorting between layers when applying the
next layer or when operating the battery. It should also display
4.3. Paintable and Printed Approaches a certain degree of porosity and be able to uptake appropriate
amounts of liquid electrolyte. Not least, it has to be adherent
This section is intended to give an overview of the recent to the surrounding electrode layers to avoid delamination and
advances in the coating protocols for energy storage devices maintain structural integrity.

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So far, various coating processes have been developed, all developed by Gao et al.[393] In this study the laser power was
REVIEW

of them relying on solution-based processing. Direct, ink-jet, used to drive a chemical reaction instead of a physical process:
screen or laser printing and brush or spray painting are the photothermal reduction of graphene oxide to reduced graphene
most representative of this class. Each technique was found oxide (a more detailed description is given in Section 4.5).
to be suitable for different applications, classification being Considering the huge growth of the printed microelectronic
primarily done by the process scale at which it can be imple- industry, lots of efforts have been devoted towards the devel-
mented. For example, laser writing is suitable for micro-scale opment of printable power sources. Printing has emerged as
power sources; printing, for inch-scale and painting, for meter- a powerful tool for flexible substrate and organic materials
scale. Hence the ability to print or paint the electrolyte–sepa- integration.[99,396,397] Printing the power sources has become a
rator layer remained the bottleneck, mainly separate layers and necessity for thin and low power portable autonomous devices,
in some cases, up to two co-integrated layers were typically for example RFID cards.[398] Within this respect, screen printing
implemented. The potential of fully painted–printed battery and ink-jet printing are the most preferred techniques. Ink-jet
remained unfeasible until recently.[90] printing works by propelling droplets of ink onto the target sub-
Direct laser writing (DLW) has been extensively used for strate. If the ink is replaced with the battery materials slurry, a
the realization of micro-batteries. The process relies on laser- printed electrode is obtained after drying. With computer con-
induced forward transfer of battery inks onto metal foil cur- trol, specific and intricate patterns can be designed. Commer-
rent collectors. The current collector metal foils are also usu- cial tools are capable of very high speed printing; some tools
ally micro-machined to desired dimensions, usually few square are capable of printing up to 30 inch wide at a speed of 200 m
mm. The printable inks are pre-deposited on transparent rib- per minute. Furthermore, sub-micron level resolution can be
bons and have composition of typical battery slurries. Wartena achieved using modern ink-jet printers. In screen-printing,
et al. have used graphitic carbon/binder and LiCoO2/carbon/ the ink is applied directly to the surface and the deposited
binder inks for printing negative and positive electrodes on film thickness can be set using a blade that moves across the
micro-structured metal current collectors with 4 mm × 4 mm receiving substrate (screen). It can be used with or without a
footprints.[389] Ollinger et al. have laser printed ionic liquid stencil mask. Doctor blade and bar coating are techniques
swelled polymer membranes and used them in combination derived from the screen-printing approach.
with laser printed LiCoO2 films.[390] Both components were Screen printing has been applied for the fabrication of posi-
separately made through laser printing so it required further tive and negative electrodes for LIBs and supercapacitors. The
sandwiching of these layers to form the device. Kim et al. fab- technique is suitable for thin as well as for thick film electrode
ricated thick film LiCoO2/gel-polymer electrolyte/carbon LIBs deposition and the lateral resolution is limited by the stencil
using similar protocols.[391,392] Each layer was ≈50µm thick mask.[206,399–403] Keskinen et al. have used a bar-coater approach
(Figure 13A) and the battery demonstrated better performances to print environment friendly symmetric activated carbon
than the equivalent configurations made by sputter deposi- supercapacitors. The supercapacitors were designed to work
tion thin-film techniques. Here again, separate electrodes were as a hybrid power source for printed electronic applications.
printed and subsequently sandwiched with a porous polymer The whole design was done to achieve a printed supercapacitor
separator impregnated with a liquid electrolyte. An ingenious that is non-toxic, recyclable and easily incinerable.[404] First,
DLW protocol for the fabrication of micro-supercapacitors was silver and graphite inks were used to define the current collec-
tors on a recyclable paperboard followed by
screen-printing of the water based activated
carbon slurry to form the symmetrical elec-
trodes. The activated carbon slurry was based
on non-toxic water-soluble chitosan binder.
Again, given that no printing approach for
the separator–electrolyte layer was available,
the electrodes and current collectors were
simply sandwiched with different polymer
and paper based separators to build the
supercapacitor. Gaikwad et al. have printed
arrays of high potential Zn-MnO2 alkaline
cells (10 connected in series to give an open
circuit potential of 14 V) and interfaced the
Figure 13. Printed batteries. A) Schematic diagram of the direct laser write technique and cells with printed organic semiconductor ring
[405] The authors have used
cross-sectional SEM image of a printed Li-ion microbattery. The layers visible (from top to oscillator circuit.
bottom) are: 1) Cu foil current collector, 2) carbon anode, 3) GPE soaked separator, 4) LiCoO2 commercially available polyvinyl alcohol/cel-
cathode, and 5) Al foil current collector. Reproduced with permission.[391] Copyright 2007, lulose wet-laid membranes, serving as sepa-
Elsevier. B) Imprintable composite gel-polymer electrolyte (c-GPE). Charge/discharge profiles rator and support for the electrodes.
of a cell comprising a 3D Si anode/c-GPE/lithium metal (C/2 rate) and SEM surface view
Economic fabrication of printed electronics
of inversely-replicated c-GPE. Reproduced with permission.[394] C) Thin film supercapacitor
realized using sprayed SWCNT films on PET as electrodes sandwiching a PVA/H3PO4 based was mostly possible due the use of inkjet
polymer electrolyte-separator. Reproduced with permission.[395] Copyright 2009, American printers. Inkjet printing has the advantage
Chemical Society. of lower lateral resolution, but suffers from

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serial-type processing and limited deposit thickness in a single of CNT in diluted H2SO4 on both sides of the membrane.

REVIEW
run. Again, one or two integrated layers have been deposited, Upon drying, sulfuric acid concentrated, doping the Nafion
the separator/electrolyte layer being again the technology bot- membrane and resulting in direct activation of H+ within the
tleneck. An inkjet printer can be easily used to print variety of ion-conducting membrane. Metallic copper foils have been
electrode materials. It is not restricted to one particular type of attached further to both ends to achieve high power output.
electrode. It was easily applied for the realization of thin-film One advantage of these approaches is that CNTs films can be
SnO2[406] and Li4Ti5O12[407] anodes, and LiMn2O4 cathodes,[408] in principle used as both, charge collection and storage layers,
as well as organic radical battery electrodes,[409,410] or graphene/ simplifying the manufacturing process. Nevertheless, this
polyaniline supercapacitor electrodes.[411] CNT film preparation approach is limited to supercapacitor-type devices, knowing to
using inkjet printing was extensively studied, and not only for have rather low energy densities. Spray processing of battery
energy applications, given their potential for various high-tech electrodes has been also proposed. Wu et al. proposed a novel
applications including displays, electrical interconnects, actua- flexible thin-film electrode design by introducing the functional
tors.[412,413] Printed CNT films have been recently reported for electrode material in a CNT skeleton using a one-step spray-
use as current collectors or electrodes in supercapacitor and painting approach.[122] The huge interest comes from the fact
LIB applications.[414] Solution processed copper and aluminum that spray painting is one of the techniques that can enable
based inks have been also developed[415,416] and could be useful larger-scale processing, well beyond the A4 print paper format.
for printing the current collectors for printed batteries and The technique is also suitable for coating large surfaces of
supercapacitors. A 3D printing technique was recently pro- various shapes displaying complex geometries. Scaling up can
posed by Sun et al.[417] In this study, the authors deposited be easily implemented, room-size facilities (spraying booths)
highly concentrated, viscous, and fast hardening suspensions being already in use by the automotive industry. For instance,
through 30 µm nozzles to achieve layer-by-layer sequential Beneventi et al. recently demonstrated a pilot paper machine
printing of interdigited 3D micro-batteries. The compact and by spray coating for processing Li ion cells operated at a paper
high aspect ratio design (30 µm wide, 300 µm tall digits with a sheet speed of 15meters perminute.[423]
pitch of 50 µm) enabled high areal density of 9.7 J cm−2 with a The above-mentioned developments are based on printing
power density of 2.7 mW cm−2 one or maximum two layers followed by lamination. During
Many other ink-type deposition approaches have been fur- the assembly step the separator–electrolyte layer is incorporated
ther proposed. Kil et al. have designed and imprinted a shape- in between the two printed or painted layers. The lamination
conformable and mechanically flexible electrolyte material.[394] usually requires mechanical and hot pressing or use of liquid
The composite gel polymer electrolyte was composed of UV- swelled layers to enable intimate contact and promote infiltra-
curable polymer matrix, liquid electrolyte (1 M LiPF6 in ethylene tion. Sequential stacking also limits the battery integration into
carbonate/propylene carbonate) and alumina nanoparticle arbitrary shaped substrates with complex geometries. Further-
fillers. The authors used the liquid mixture to mold (followed by more, additional positioning and alignment steps may also
crosslinking) various 3D electrode configurations (Figure 13B). be required. The ability to print the porous separator–electro-
Electrochemical properties of these electrolytes were also tested lyte could greatly simplify the process and provide a truly full
and found to compete with standard electrolyte (high stability printed battery or supercapacitor. The solution was provided by
window, up to 5.5 V vs. Li/Li+; good cycling stability when used Singh et al. in 2012.[90]
in conjunction with LiCoO2 cathode and silicon anode). Towards Authors formulated paints for all the components of a Li-ion
a fully printed battery approach was proposed by Fenton et al. battery and were able to sequentially deposit the five layers by
in 2009.[418] The authors have used a robocasting technique to using solely spray deposition technique (Figure 14). Since each
print the electrodes and focused their study on LiFePO4 based battery layer was painted (out of a liquid suspension) instead
electrodes. Although not realized at that time, the authors have of being stacked, an intimate and conformal contact was
foreseen that the ability to print every layer of the battery will established at every interface within the cell (Figure 14, SEM
enable ultimate design flexibility in the application of printed cross-section image). Consequently, the interfacial resistance is
or painted type batteries. Redox active organic materials can be diminished, helping in a more efficient charge collection and
readily processed through solution-based approaches and could ionic transport. Probably the most important technological
provide a solution for all-printed or painted energy storage achievement of this work was the unique ability to coat the gel-
sources. There are already many organic compounds known to polymer electrolyte, as seemingly, this was the bottleneck of
have redox activity both as positive and negative electrodes and the print or paint-based battery fabrication. Using this method
further progress could enrich this library.[410,419–421] and developed formulations, the authors have fabricated LIBs
Kampgen et al. fabricated single-walled CNTs thin film on various substrates including glass, plastic foil, ceramic tiles.
supercapacitors by spray coating aqueous dispersions on var- They fabricated Li-ion batteries not only on the flat surfaces
ious substrates.[395] The CNT thin films served as both, current of various materials but also on the curved surfaces, opening
collectors and charge storage electrodes. The authors have used unlimited opportunities for integration of batteries/supercapac-
a printable gel electrolyte and built symmetrical supercapacitors itors with various materials and objects. The authors also dem-
by sandwiching the CNT networks and the gel-polymer electro- onstrated that with this new fabrication technique it is possible
lyte (Figure 13C). Recently, Huang et al. designed high power to manufacture batteries with arbitrary foot prints, for example
supercapacitors using one-step spraying of CNT-based inks.[422] they fabricated a battery spelling “RICE” on the curved surface
The authors have used Nafion membranes as mechanical sup- of a beer mug. Virtually, there are no limitation regarding the
port and porous separator and sprayed aqueous suspensions type, shape and morphology of the substrates. At a thickness of

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polymer electrolytes. One of the major advan-


REVIEW

tages in using printing or painting technique


remains the ability to design batteries into
arbitrary shapes with virtually no limitations
regarding the substrate type. Efficient bat-
tery integration into confined spaces of the
modern ultra-compact electronic devices,
integration of energy storage sources into
various outdoor objects or just simply minia-
ture battery realization for smart-card applica-
tions by printing are some of the short-term
applications being targeted. Whereas many
other could be envisioned given the flexibili-
ties of these processes and infinite possibili-
ties of using these techniques to integrate
and design batteries in unconventional ways.

4.4. Optically Active Schemes/Configurations

A recent trend in the microelectronics


industry is the realization of transparent
electronic devices making us dream for the
analogue of the mythical Avatar movie “trans-
Figure 14. Paintable battery. Paradigm change in battery fabrication achieved by spray-painting
parent and portable screens.”[424] At CES
all of the battery components into a monolith structure. The authors have used CNT-based
paints for the cathode current collector, LiCoO2 paint for cathode layer, a PVDF based micropo- tradeshow 2010, Samsung presented a trans-
rous gel-polymer separator, a Li4Ti5O12 paint for anode layer and finally, a Cu nanoparticle ink parent laptop showing us that the directors
for the anode current collector layer. SEM cross-section showing intimate contact between the visions of the near future can be become a
sprayed layers. Voltage profiles for a LiCoO2/Li4Ti5O12 spray painted battery. Reproduced with technological reality. The futuristic device was
permission.[90] Copyright 2012, Macmillan Publishers Limited. composed of a fully transparent screen based
on AMOLED technology attached while the
approximately 0.5 mm, the painted battery had an areal energy rest of the computer relying on more standard technology. The
density of 6 Wh m−2. Increasing further the energy could be next big thing we will expect is a fully transparent smart phone
done by making thicker active layers; compaction being pro- or tablet computer. But is this possible with the present tech-
hibited here. Although the areal energy density is still probably nology? We can design and fabricate transparent displays, touch
low, the technique can be potentially applied to large, outdoor panel functionality as well as constituent electronics (micropro-
surfaces, compensating the low energy by the high surface area. cessors, memory, expansion cards, storage disk, mother board
While some safety issues must be solved before applying these and communication ports) could be also realized using trans-
batteries to the walls or roofing of our houses, the implementa- parent, all-organic technology (although, at lower performances
tion solution is provided and there are other interesting applica- using the state-of-the-art knowledge).[425–427] And of course,
tions that are being presently developed. Further improvements a transparent energy storage unit will be required that might
are mainly related to the safety and may imply integration of be the most ambitious part to realize. In part, this difficulty is
solid-state electrolytes, use of less harmful battery chemistries given by the intrinsic properties of known battery materials i.e.
(aqueous batteries for instance) or development of a paintable of being strongly light absorbing (opaque). At the same time,
encapsulation formulation capable to prevent the transport of the stored capacity scales linearly with the amount of the active
oxygen or water into or liquid electrolyte out of the cell. material; in other words, more material means more capacity
As highlighted in this Section, there has been noticeable pro- but also more absorption (or less transparency). Nevertheless,
gress in the design and manufacturing process of Li-ion bat- researchers have proposed ingenious solutions to overcome
teries and supercapacitors by printing or painting. Although this hurdle and there are already several operational transparent
seemingly simple in realization, entirely printing or painting a battery concepts. This section is devoted to the advances with
battery came out to be a complex interdisciplinary task and was respect to optically active energy storage schemes. The main
achieved only recently. Notably, similar to the battery designs emphasis is put on the development of transparent devices
presented in previous sections (ultra-thin and thick, flexible, whereas electrochromic configurations are also highlighted as
stretchable, etc) the separator/electrolyte layer seems to be again they can involve simultaneously certain degree of transparency
the technology limiting component. Probably, once the solid- as well as color changes induced by the redox processes taking
state electrolytes will compete or eventually outperform the place at the electrodes. Electrochromic energy storage units are
standard electrolyte and separator formulations (electrochemi- being considered as another intelligent human-machine inter-
cally and mechanically) we may assist to a broader implementa- face where the state of charge or health of the battery could be
tion yet, till then, we must deal with and improve the gel-type simply visually assessed by the user.

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In order to make a fully transparent battery, all of the five con- optical transmission (single layer graphene absorbs only 2.3%

REVIEW
stituents layers must be transparent (the enclosure unit is not of the visible spectrum) while still preserving the good electrical
discussed here but could be also transparent, if, for instance, conductivity and the electrochemical properties are very similar
using glass or plastic materials). Similar to transparent all- to CNTs. Since the next Section is entirely devoted to graphene
organic electronics,[426] all-organic batteries could be also devel- enhanced energy storage, much of the discussions will be pre-
oped in a transparent form.[419,428] The main difference is that sented therein. Here, we will be limited to transparent electrode
organic electronics relies on thin-film technology and even if applications for energy storage devices. Graphene and CNT
the active materials are light absorbing in the bulk state, they based transparent electrodes have been extensively tested so far
can be rendered transparent or semi-transparent if applied in for photovoltaic and light-emitting applications.[434–437] It is how-
thin-film form. Applying the same to an all-organic battery, the ever intriguing why such films have been so far only modestly
device will store unpractical low amounts of energy, most prob- explored for the realization of transparent batteries or capaci-
ably not even enough to power an electronic device of the same tors.[438–440] Probably because the main hurdle with this respect
areal footprint. Increasing the thickness could enhance the remains the realization of transparent battery electrodes?
energy density yet, result in loss of transparency and degrada- Since most of the active battery materials are opaque, there
tion of charge collection requiring addition of highly absorbing are basically two options left to make a transparent battery out
conductive carbons. The integration of inorganic material will of opaque materials. Either by thinning the thickness of the
eventually further exacerbate the problem. absorbing layers down to the point where part of the light is
Making a transparent separator–electrolyte is probably the being transmitted or by applying structuring and rendering an
easiest task. Most of the gel and swollen polymer membrane optical illusion of transparent battery. As already discussed, the
electrolyte are already (semi)transparent even at thicknesses first option (see also the discussion on ultra-thin film batteries
above hundreds of micrometers.[8,76] Solid-state polymer elec- detailed in Section 4.2) is technologically less appealing due
trolytes are also majorly transparent and could become valuable to very low areal energy density provided. The second route, if
candidates if the ionic conductivity is improved.[29] Nonetheless, properly designed, can become technologically relevant. The
the optical transparency changes might occur at the interfaces simplest way of creating an optical illusion of transparency is
and need to be considered. Making transparent current collec- the implementation of grid-like electrodes. If the filling ratio
tors becomes more complicated, as the materials must comply is low enough and the grid feature dimensions are smaller or
with the harsh electrochemical environment when operating comparable to the resolution of the human eye, the structured
the battery and have low sheet resistance. Traditionally, trans- sheet can become indistinguishable from the transparent sub-
parent electrodes for microelectronics industry were made of strate. Yang et al. have successfully explored this approach and
conducting oxides (SnO2, In2O3, TiO2, ZnO) while recent nano- were the first to create a fully transparent Li-ion battery.[358] The
technology progress has provided alternatives based on CNTs authors developed a microfluidic-assisted deposition technique
or nanowire networks, regular metallic meshes and single- or to pattern grid-like LiCoO2 and Li4Ti5O12 electrodes. Grid-
few-layer graphene.[359,360,429–433] If applied as current collectors patterned Au film electrodes served as the current collector
in Li-ion batteries or supercapacitors, electrochemical stability whereas a sheet of transparent gel electrolyte was inserted in-
must be considered first. Metal oxides are probably not the best between the two electrode to finalize the transparent battery
candidates for negative electrodes due to possible irreversible (Figure 15A).
conversion reactions, although pioneering studies within this A packaged full cell provided an energy density of 10 Wh L−1
respect are being already undertaken,[363] whereas most of the while showing a transparency of 60% in the visible spectrum
metallic structures are not suitable for positive electrodes due range. Naturally, the energy density is inversely proportional to
to high oxidizing potentials that will corrode the material. For the transparency and this could be adjusted by varying the width
example, transparent copper nanowires arrays[430,432] could and spacing of the grid electrodes: 30, 60 and 78% transparency
be used as anode current collectors but may require surface corresponded to 20, 10 and 5 Wh L−1 respectively. Although the
coatings to withstand cathode potentials (for example, nickel specific areal energy density is low, of approximately 1 Wh m−2
coated, could be stable up to 4 V vs. Li/Li+).[92,360] Noble metal per one cell stack, the energy could be increased by stacking
nanowires are stable at high cathode potentials nevertheless, several cells or by increasing the thickness of the active mate-
manufacturing and raw materials costs could become impor- rials. Furthermore, transparent batteries could be in prin-
tant for large-scale implementation. ciple integrated into glass windows without severely affecting
CNTs have a very large electrochemical window. At low their aesthetical aspect while providing an added value to the
anodic potentials reversible Li+ intercalation or surface reac- window. For example, covering Willis Tower in Chicago with
tions can take place without severely affecting their electronic battery windows could back-up some 40kWh of energy. Fur-
properties whereas CNTs are also known to be chemically thermore, co-integration of transparent energy harvesting
stable even at high oxidizing potentials, up to 5.5 V vs. Li/Li+. sources could be also envisioned. Recent progress has shown
For equivalent sheet resistance, some CNT based films exhibit that visibly transparent polymer solar cells produced by solu-
optical transmittance comparable or even superior to that of tion processing could be integrated into glass substrates as well
commercial ITO. Moreover, simple synthesis and assembly (Figure 15B).[441,444] A stacked transparent battery and solar cell
methods and rather cheap and abundant raw materials make device (for example, considering device shown in Figure 15A
CNTs valuable candidates for the realization of transparent stacked on top the one shown in Figure 15B) will absorb
electrodes.[413,429] Graphene derivatives are also interesting can- some 50% of light and could operate as a stand-alone energy
didates since under certain conditions they present very high source, powering and storing the energy for the building. If

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Figure 15. Transparent energy storage and harvesting devices. A) Schematic view of a transparent battery with staked grid-like patterned electrodes.
Right: SEM image of the battery electrode and the UV–vis spectrum of gel electrolyte, a single electrode, and a full battery. Reproduced with permis-
sion.[358] Copyright 2011, National Academy of Sciences, USA B) Visibly transparent polymer solar cells produced by solution processing. Reproduced
with permission.[441] Copyright 2012, American Chemical Society. Pilling-up a transparent battery with a transparent solar cell could lead to a trans-
parent, standalone energy capture-storage device. C) Schematic diagram, optical transparency and electrochemical performance of an interdigitated
electrode based transparent capacitor. Reproduced with permission.[442] Copyright 2013, American Chemical Society. D) Transmittance spectra for
PTMA (dotted curve), glass substrate (thin solid curve) as well as of PTMA/SWNT (4 wt%) composite with 100 nm (dashed curve), and 580 nm film
thickness (thick solid curve). Inset: a photograph of the PTMA/SWNT composite (1200 nm) on a glass substrate. Right: transmittance at 550 nm during
charge/discharge cycles. Reproduced with permission.[443]

6% efficient window PVs were used to entirely cover the same transparency although, other issues related to ionic and elec-
Willis Tower, it would generate nearly 5.3 GWh of energy per tronic diffusion could interfere. Techniques like ink-jet printing,
year.[445] Smarter window composites could be further inte- self-assembly, nanowire decorated surface-enhanced metallic
grated for a more efficient light and energy conversion manage- electrodes and large-scale soft-lithography protocols could be
ment.[446,447] Certainly, the energy balance of the Willis Tower is further configured to precisely structure grid-like or interdigit
far more important than what could smart windows store and electrodes for superior performance transparent energy storage
harvest, yet this could be part of the smart-building venture, sources.[409,453–459]
combined with other energy efficient solutions.[448] Various forms of transparent electrodes have been also pro-
Other grid-like transparent energy conversion devices have posed in the literature. Even if a transparent full cell was not
been subsequently proposed.[449] Li et al. have designed semi- always realized, the developments on separate components
transparent transparent devices by means of interdigit elec- could serve as a basis for building-up transparent full cells. As
trodes.[442] Using this approach, the authors have fabricated mentioned, graphene and CNTs have been already considered
dye-sensitized solar cells and supercapacitors, the later having for the realization of transparent energy storage sources. Thin-
a carbon-carbon symmetrical configuration (Figure 15C). The film composites made of graphene or CNTs have been used
in-plane electrode configuration allows also for good mechan- either as transparent electrodes or as current collectors for the
ical properties without inducing short-circuits while bending realization of LIBs and supercapacitor devices. Yu et al. pre-
the device yet, may result in poor delivered power density given pared ultra-thin transparent graphene films and used them in
long diffusion paths between the electrodes. Nam et al. have supercapacitor applications.[460] The optical transparency of the
also designed flexible and transparent interdigit supercapaci- films was found to linearly decrease with thickness increase in
tors.[450] The device was built on a PET substrate by means of accordance with Beer–Lambert’s law (20% and 60% absorption
photolithography and physical vapor deposition. To close the for 25 nm and 100 nm thick films respectively). At a scan rate
power circuit, the symmetrical MnO2/MnO2 supercapacitor was of 10 mV s−1, a capacitance of 100 F g−1 was obtained for var-
activated with a PVA/H3PO4 gel membrane. The encapsulated ious thickness films with good capacitance retention at higher
device showed 50% optical transmission in the visible range. scan rates. Transparent, nitrogen-doped few-layer graphene
In principle, any grid-like structure could be rendered trans- was found to deliver almost double the capacity of pristine
parent if properly dimensioned. Higher areal energy density at graphene when cycled as a Lithium anode.[323] Graphene films
the expense of transparency could be obtained by increasing were also found suitable as transparent electrodes for electro-
the electrode depth and width, while reducing the pitch.[451] If chromic devices. Ko et al. have electrodeposited Prussian Blue
using transparent materials, like graphene or CNT based cur- nanoparticles on transparent graphene films and demonstrated
rent collectors, polymer based active materials, or transparent electrochromism with response times as fast as 4 seconds.[461]
oxides for supercapacitor applications,[452] the scaling up could Choi et al. have combined the transparency of thin CNT films
be done more easily, without compromising too much the with good optical transmission of a radical battery polymer,

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poly(2,2,6,6-tetramethylpiperidine-1-oxy-4-yl methacrylate) (PTMA) electrode(s). If a redox process is involved, the electrochromic

REVIEW
to build a transparent charge-storage material.[443] The authors device then can be also considered as a charge storage unit.
have wrapped PTMA around CNT and achieved good electro- The electrode chemistry however was not optimized so far for
chemical performances for a low carbon content (4 wt% CNT). storage applications (i.e., the optical contrast far more impor-
This also translated into good optical transmission even at tant than the energy or power density). Recent efforts however
elevated film thicknesses. The transmittance of a 580 nm thick tackled such hybridization schemes by exploring materials that
film was found to be close to 90% and even thick films of more show at the same time optical transformations (color change or
than 1 µm showed good optical transmission (Figure 15D). The reversible inter-conversion between opaque and transparent)
optical properties were unaltered even after extended cycling, and can store relevant amount of energy.[469] One possible appli-
over 500 charge–discharge cycles. Hence PTMA (as well as cation of such devices is the realization of smart battery devices
other polymer-based battery materials) can be solution pro- where the state of charge or depth of discharge could be moni-
cessed, the production scale-up could be envisioned using tradi- tored by simple visual inspection.
tional printing schemes or by exploring emerging self-assembly CNTs proved again their versatility. Yanagi et al. were able
opportunities.[113,409,462,463] to realize electrochromic all-carbon electrodes using metallic
Energy storage devices with a smart human-machine inter- single walled CNTs.[470] The color change was enabled in
face can be obtained by further incorporating electrochromic carbon films without ITO electrodes, single walled CNTs acting
materials into battery electrodes. Electrochromism is the phe- as both electrochromic components and electrodes (interest-
nomenon of reversible color or more generally, optical prop- ingly, the same rationale is applied when designing all-CNTs
erties change, in response to an applied voltage.[464,465] The supercapacitors). The mechanism of optical absorption change
market and research are in continuous expansion although the in CNTs proceeds through filling and depletion of electronic
applications are rather focused, smart windows and electro- states (electron or hole doping), process known as Van Hove
chromic glass. Traditionally, electrochromic active components singularity, modifying the optical transitions between states
were based on transition metal compounds (most commononly, in CNTs. The films displayed very clear, stable and reversible
oxides of Ag, Ni, Ir, Nb, W), polymer or organic redox materials, color changes exhibiting various colors function of applied
liquid crystals and particle suspensions integrated with liquid voltage and diameter of nanotubes (Figure 16A). The capaci-
electrolyte redox cells.[465–467] A recent trend is the development tance of the electrochromic films was not measured but it may
of all-solid-state devices—mirrors and electrochromic win- be presumed that the electrodes display similar capacitance
dows— the main hurdle being here again the development of values as classic CNT based supercapacitor electrodes making
a suitable solid-state electrolyte.[468] The electrochromism may this device function simultaneously as an electrochromic and
be or not accompanied by a redox reaction taking place at the charge storage unit.

Figure 16. Electrochromic energy devices. A) Optical absorption spectra and photographs of color change in films of metallic SWCNTs with diam-
eters of 0.84, 1.0, and 1.4 nm, as a function of applied potential. Reproduced with permission.[470] Copyright 2011, Wiley VCH. B) Photographs of
the V2O5-based electrochromic supercapacitor device displaying color change upon charge and discharge. Contrasted color variation was observed
during chronopotentiometry experiments. Reproduced with permission.[471] Copyright 2012, American Chemical Society. C) Color change of thin-film
electrodes of the Prussian blue analogues (Li,Na)4y–2M[Fe(CN)6]y zH2O in the charge and discharge states for different M. Reproduced with permis-
sion.[472] Copyright 2012, IOP Science.

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Conjugated redox polymers are also suited for electrochromic periodic structure. Morphologically, these architectures are very
REVIEW

energy storage devices.[420,473] Chen et al. designed smart and appealing for energy storage applications as they are character-
stretchable supercapacitors by coating thin transparent films ized by a 3D bi-continuous network, display high specific sur-
of CNTs followed by electrochromic polyaniline.[230] A hybrid faces while preserving a high free volume for the electrolyte
polymer (polyaniline) – transition metal oxide (W18O49) has uptake and electrode volume expansion upon cycling. While
been also proposed recently with smart energy level indicating there are many explored hard templating techniques offering
functionality (i.e., electrochromic response).[474] Nanostructured high structural ordering,[481] colloidal self-assembly lithog-
metallic oxides have been explored by Wei and Scherer for the raphy is seemingly the preferred approach due simplicity in
realization of electrochromic ultracapacitors.[471,475] To increase implementation and large variety of size and colloid chemis-
the surface to volume ratio and enhance the ion-intercalation tries. Numerous colloidal crystal template electrode materials
processes the authors used a self-assembled block-copolymer including anode,[327,482–487] cathode,[326,482,488,489] separators and
patterning approach to structure the V2O5 and NiO active mate- electrolytes,[490] mesoporous carbon for supercapacitor appli-
rials into ordered bicontinuous double-gyroid networks. The cations,[491] as well as more complex electrochemical superca-
symmetric V2O5–V2O5 supercapacitor exhibited high specific pacitors and full-cell architectures[492,493] have been realized and
capacitance of 155 F g−1 as well as high power densities due tested so far. Electrochemical properties of the so-formed nano-
to short ion diffusion lengths, good electronic transport and composites were found to be superior to their bulk counterpart
large surface area enabling fast Li+ insertion/extraction.[471] The owing to peculiar morphology.
color change between the charged–discharged states explored Their application as photonic components is however less
the rich color palette provided by vanadium compounds in dif- acknowledged. The optical response of photonic structures is
ferent redox states (Figure 16B). Similarly, NiO was structured very sensitive to small changes in refractive index or surface
and found to display enhanced electrochromism properties.[475] environment changes. Bulk or surface redox reactions taking
For both materials, higher coloration contrast with higher col- place in battery or supercapacitor electrodes are accompa-
oration efficiency and faster response time was obtained when nied by variation of the dielectric constant of the constituent
compared to planar non-structured devices. material (as well as considerable volume and shape modifi-
Many transition metal compounds display compositional cation) and could induce important changes of the optical
colors and most of them retain this optical property within a response.[484,494–497] Photonic crystal structures could be
lithium-rich framework. Some of these materials also show designed to enhance the optical transmission and render ‘trans-
significant optical appearance change upon lithium insertion/ parent’ materials that are otherwise opaque or could be used
extraction, most prominent being the vanadium based mate- to implement other type of visual illusion effects like diffracted
rials.[476] Electrochromism in LiCoO2 has been known for more color change upon charge–discharge cycling. And all this sup-
than two decades. Wei et al. prepared thin films of lithium plemented by enhanced electrochemical performances due to
cobalt oxide by RF-sputtering from powdered LiCoO2.[477] These hierarchical micro-, nano-, meso-porous electrode framework.
films changed in color from pale amber to dark brown trans- Strong light absorptions presented by most of battery materials
parent states upon reversible electrolytic removal of lithium are prohibiting for the moment devices with such futurist fea-
ions.[786] However, it might be difficult to maintain these prop- tures. Nevertheless, the structural basis exists and upon further
erties in bulk electrodes containing acetylene black as conduc- optimization and novel material implementation, this approach
tive additives. Thin film configuration might be more appro- could become a reality.
priate yet, suffers from low specific energy provided (see also This Section provided an overview of the recent achieve-
Section 4.2). ments with respect to the integration of optical functionality
Prussian blue analogues, with a generic formula of into the energy storage sources. For the realization of trans-
AxM[Fe(CN)6]y (where A and M are alkali and transition parent batteries, two options seem to be most promising: grid-
metals, respectively) have been known for a long time as effi- like electrode batteries and use of intrinsically transparent
cient electrochromic materials. These compounds have been or semi-transparent electrode materials. The latter option is
also known for a while to reversibly intercalate/extract lithium interesting because scaling-up to reach technologically rel-
making of them potential candidate electrode materials for evant energy storage densities is possible yet, it is limited to
Li-ion batteries.[478–480] Moritomo et al. have studied thin film few materials that can maintain transparency in both, charged
electrodes of various Prussian blue analogues (M = Ni, Co, Mn and discharged states. Grid-like or interdigit transparent elec-
and Cd) and found that these compounds display a rapid Li+ trodes are more versatile as there are virtually no limitations
intercalation behavior (more than 60% capacity retention at a with respect to used materials. Nevertheless, the technique
rate of 100 C).[472] Moreover, the thin film electrode displayed has intrinsic transparency limitations function of the available
contrasted color differences between charged and discharged energy density dictated by the electrode specific dimensions.
states making of these compounds valuable candidates for high Increasing the specific energy of the grid-like electrodes could
energy density and high performance electrochromic devices be done by using thicker electrodes or special electrode designs
(Figure 16C). whereas surface enhanced electrodes could be used to boost the
Finally, although not demonstrated yet, photonic crystal capacity of the interdigit configuration.[328,498–501]
structures as basis for electrochemical cells could be also Portable energy sources incorporating electrochromic ele-
used to integrate the optical functionality into energy storage ments have been also reviewed. The technological problems are
sources. Photonic structures show distinctive optical proper- also related to finding suitable materials to display contrasted
ties, different from bulk material characteristics, due to their color changes under reversible redox cycling. Such devices

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could establish the human–battery interface of the future, From this short survey it is rather clear that carbon-based

REVIEW
communicating to the user in a friendly way the state-of-charge/ materials play an important role in the design and reliable func-
discharge of the battery. Besides applications in transparent tioning of batteries and supercapacitors. Historically, the car-
high-tech electronics, transparent batteries are also undeniable bons were first used as low-voltage lithium-intercalation com-
tools for scientific research. Non-invasive optical spectroscopy pounds and electronically conductive additives. Subsequently,
methods (Rama and Fourier-transform infrared (FTIR) spec- the discovery of new allotropic forms and acquirements of new
troscopy) could be applied to insitu investigations of redox pro- insight into the chemistry and electrochemistry of nanostruc-
cesses taking place at the electrodes and interfaces, monitoring tured carbons have extended the range of applications up to the
the degradation of liquid or solid electrolyte.[358] There are many point that presently we have the knowledge to build an entire
possibilities offered and many to be discovered. The future all-carbon battery or supercapacitor.[518,519] There has been tre-
looks bright! mendous work on the implementation and improvements
of carbon additives and active components for energy storage
devices. Reviewing every aspect of carbon-based materials
4.5. Graphene-Inside Batteries and Capacitors development and integration into batteries or supercapacitors is
beyond the scope of this section and many featured articles are
Carbon is ubiquitous for a reliable functioning of most known available in the literature treating this topic.[21,504,516] Graphene
energy storage devices. Ever since the invention and commer- integration is not fully explored and there are many ingen-
cialization of LIBs and supercapacitors, carbon, in its various ious opportunities provided by this wonder material for the
allotropic forms, has played an irreplaceable role, considerably improvement or realization of new energy storage cells. This
enhancing the power and energy density.[21,502–506] For example, Section highlights recent advances with respect to novel carbon
graphitic carbon, has been and will probably remain the main nanomaterials integration into LIBs and supercapacitors with a
component of the Li-ion negative electrode.[8] Recent develop- special emphasis on graphene-enabled new configurations.
ments on high capacity anode materials shed some doubts The reason why various allotropes of carbon have been
onto the future of the carbon-based anodes[340,507] although, widely adopted in electrochemical energy storage devices is
practical solutions for reliable cycling of Si, Sn, Al or Ge their abundance, low price, affordable manufacturing indus-
composed anodes is still missing. Eventually, high capacity trialization, and. especially, their outstanding physico-chem-
carbon composite anodes providing stable cycling for sev- ical properties.[503,520] Large electrochemical stability window
eral hundreds of cycles at approximately 1200 mAh g−1 have (0–5.5 V vs. Li/Li+), high conductivity, good mechanical proper-
the potential to reshape the negative electrode materials land- ties, high specific surface area and low tap density as well as
scape.[181,182,508–512] One has to know that above this limit, the enhanced chemical and thermal stability are the primary attrib-
contribution of the anode to the total capacity of the battery utes of the carbon material used in battery technology. As a
levels-off and higher values may not be justified while working matter of fact, not many known materials can comply to these
with ≈200mAh g−1 cathode materials.[15,513] Finally, since most requirement as well as carbons do. As highlighted throughout
supercapacitor devices are based on carbonaceous electrodes, it previous sections, CNTs and other carbon nanostructures
is clear that the carbon era in energy storage is far from being have been extensively exploited to integrate novel functionali-
finished.[514,515] ties and build disruptive battery architectures.[163,164,413] CNTs,
So far, many carbon allotropes can be identified in commer- carbon fibers and fabrics as well as carbon and graphite inks
cial as well as prototype Li-ion batteries and supercapacitors are irreplaceable when targeting flexible and stretchable, cur-
(see also Figure 3). By composition and function, they can be rent collector integrated, paper and textile-based architectures
divided as follows:[503,504,516,517] (see Section 4.1). Ultra-thin and ultra-thick film electrodes and
batteries have been also possible throughout the use of special
• Supercapacitors. Function: active charge storage material or CNT, carbon fibers and graphene-based composites (see details
electrically conductive additive in both, positive and negative in Section 4.2). Painting or printing positive and negative elec-
electrodes. Composition: CNTs, high specific area carbons, trodes or current collectors was possible using nanostructured
acetylene and/or carbon black, mesoporous carbons, single- carbons based inks (see details in Section 4.3) whereas thin
layer or few-layer graphene (SLG, FLG). CNT films as well as SLG and FLG successfully enabled optical
• Li-ion battery anode. Active charge storage component: gra- functionality integration into LIBs and supercapacitors (see
phitic, mesoporous carbons, CNTs, SLG, FLG. Conductive details in Section 4.4). It is pointless to stress again at which
additive: carbon black, CNTs, SLG, FLG. point these materials have become ubiquitous throughout
• Lithium battery cathode. Active charge storage component: energy storage technology.
perfluorinated carbons (primary batteries). Conductive addi- Since the discovery of the wonder material, graphene, many
tive: carbon black, CNTs, SLG, FLG. applications have been envisioned incorporating graphene into
• Li-ion battery and supercapacitor additives. mechanical scaf- their core.[361,521,522] Energy applications have not passed by.
fold, replacement for binders. Impermeable coatings, O2 and Transparent electrodes for solar harvesting,[523–525] conductive
H2O protection, inhibitor for shuttling effect (for example, scaffolds for photoelectrochemical water splitting,[526–530] addi-
in Li-S batteries). Graphene oxide, electrolyte/separator upon tives and active materials for batteries, supercapacitors and fuel
adequate activation,thermal conductivity enhancement. cells,[531–537] as well as many others[538–543] have shown signifi-
• Current collectors. Replacement for Cu or Al metal foils: car- cant performance enhancement upon graphene incorporation.
bon black polymer composites, CNTs, SLG, FLG. Since carbons played a primordial role in the development

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of batteries and supercapacitors the arrival of graphene has with respect to nature and type of active components. In this
REVIEW

marked a turn point in these technologies: replacement of tra- method, the active material is blended with rGO, with or
ditional carbon materials by graphene. As such, in a very short without the binder and subsequently casted, precipitated or fil-
period of time, graphene and its analogues have been success- tered to obtain the electrode. The disadvantages are the rather
fully tested as current collectors, electrode materials, conductive weak bonding as well as low and non-uniform coverage of the
additives, replacement for binders, electrolytes, and many other. graphene matrix and consequently, low current collection effi-
But what makes graphene so special for energy storage appli- ciency and possible detachment of the active material from the
cations? It is its electronic, optical, thermal and mechanical graphene. In some cases, surface functionalization was found
properties that enable a series of configurations that were dif- to lead to improved graphene–active material interface.[555–558]
ficult or even impossible to realize previously. Graphene is a Several Li-ion battery materials have been tested using this
two-dimensional, one-carbon atom thick material and as simple fabrication approach and displayed improved cycling perfor-
as it may look, it offered/s probably the richest physics, chem- mances upon graphene incorporation.[129,133,559–564]
istry and materials science background to date. The theoretical In situ synthesis or growth of active battery materials in
value of the room temperature mobility is 200 000 cm2 V−1s−1 presence of graphene has been found to provide better results
at a carrier density of 1012 cm−2 corresponding to a resistivity in terms of power delivery and long-term cycling. Using this
of 10−6 Ω cm.[544] As such, the graphene is less resistive than approach, a better dispersion and enhanced adhesion of gra-
any known metal. Although the practical values are much lower phene sheets within the active materials is obtained. This also
due to substrate scattering, it still retains high conductivities allows the use of lower amounts of graphene as compared to
with mobilities in excess of 20 000 cm2 V−1 s−1. Graphene also other methods. Various electrode materials have tested so far,
has a very high thermal conductivity, 5000 W m−1 K−1 at room generally being made via solution-based synthesis or vapor-
temperature[545] whereas mechanically, it is considered as one phase deposition. In the first method, the graphene sheets
of the strongest and rigid materials ever tested. The tensile are first homogeneously dispersed into the active material
modulus is of 1 TPa[546] while at the same time being very light, precursor solution followed by subsequent chemical, solvo-
with a surface density of approximately 0.77 mg per square thermal or thermal processing to synthesize the active mate-
meter (or conversely, 1 g SLG will expose a high surface area of rial.[410,458,565–579] In the vapor-phase route, the active material
2600 square meters). Such extraordinary properties could only is usually deposited at high temperature on pre-assembled gra-
provide exceptional battery and supercapacitor performances. phene sheets.[580,581] The amount and the morphology of the
Indeed, incorporating graphene into energy storage sources synthesized materials can be precisely controlled by the applied
brings clear benefits owing to these outstanding properties. chemistry. For example, Wang et al. have grown LiMn1–xFexPO4
High electrical conductivity enhances the power performance nanorods on graphene and tested them as cathode material in
while thermal conductivity dissipates the heat generated due LIBs.[582] The authors have solvothermally converted selectively
to Joule heating when high current densities are applied. The grown Fe-doped Mn3O4 on the surface of graphene sheets and
mechanical properties are more than adequate to use graphene obtained LiMn1–xFexPO4 with crystal shape and morphology
as a replacement for polymer binders. Furthermore, the low suitable for fast Li+ diffusion along the radial[010] direction of
surface and volume density allows the incorporation of only the nanorods (Figure 17A). At a total carbon content of 26 wt%
small amounts of graphene as compared to standard carbon (including both, rGO and conductive carbon additive) the com-
additives while maintaining or outperforming the electrochem- posite electrode showed superior rate performances with more
ical and mechanical performances. Supercapacitor technology than 65 mAh g−1 retained capacity at a cycling rate of 100 C.
was also boosted by graphene due to the extremely high sur- Most of the tested materials displayed graphene enabled supe-
face area to mass ratio, elevated electronic conductivity and rior electrochemical properties. The process has however some
large electrochemical stability window. The interested reader is intrinsic limitations. For example, conformal graphene wrap-
referred to recent review articles focusing on specific improve- ping is difficult to realize and the synthesis approach is limited
ments enabled by graphene incorporation into energy devices to controlled atmosphere synthesis conditions.
as well as on the electrochemistry of graphene and related Graphene-incorporated organic cathodes have been also
compounds.[506,531,547–552] investigated. These composite are of great interest for a sus-
The most simple and straightforward implementation of tainable energy storage technology, hence these electrodes
graphene into batteries or supercapacitor is by realizing uni- are all-carbon systems with no heavy-metal content. Much
form mixtures of graphene and active materials components interest has been shown for this alternative as it can reduce
(graphene as well if capacitor devices are being targeted). For the carbon footprint of the energy technology by integrating
industrial scalability, rGO (reduced graphene oxide) typically the entire battery cycle-life into the/a carbon processing loop:
made by chemical reduction of GO is employed. GO in turn is use and recycle–incinerate–carbon biosynthesis–battery manu-
obtained from graphite through various thermal, chemical and facturing.[410,584–586] Surprisingly, the synthesis of graphene–
electrochemical processes, the Hummers method being widely organic redox systems remains less explored for the moment,
adopted.[553,554] Similar to techniques described in Section 4.1, only few results being reported so far.[587] Direct synthesis of
several approaches have been developed so far, each of them composites made of CNT or other nanocarbons and organic
with intrinsic advantages and disadvantages: i) direct blending redox units for LIBs also remain rather poorly explored,
or mixing; ii) active material growth or synthesis on graphene; although they hold great promises.[158,160,410,588–592] In the case of
and iii) graphene growth on the active material matrix. The insulating organic materials, intimate dispersion of conductive
first option is the simplest to realize and has no limitations agent is crucial for proper functioning and given the graphene’s

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REVIEW
Figure 17. Graphene enabled energy storage. A) TEM image and discharge profiles at various cycling rates for LiMn0.75Fe0.25PO4/rGO composite.
Reproduced with permission.[582] B) Rate performance of poly(anthraquinonyl sulfide) composites with different amounts of graphene and CNTs.
Cross-section TEM image of poly(anthraquinonyl sulfide)/graphene composite demonstrated highly uniform dispersion of graphene within the polymer
matrix. Reproduced with permission.[583] Copyright 2012, American Chemical Society. C) Photograph of a bent, graphene foam (GF) based battery
encapsulated by PDMS; charge discharge performance of a flexible LTO/GF//LFP/GF full battery in the flat configuration. Reproduced with permis-
sion.[142] Copyright 2012, National Academy of Sciences USA D) Free-standing, lightweight, and highly conductive ultrathin graphene foam, loaded with
lithium iron phosphate, showing enhanced rate performance. Reproduced with permission.[386] Copyright 2012, American Chemical Society.

high electrical conductivity as well as its high surface area, it structural integrity and avoid dissolution of active species. Mild
has been again identified as a “hardly to replace” material. Fur- chemistries for carbon nanosheets growth have been recently
thermore, since most of these materials are swollen by the bat- proposed and although this can be realized even at room tem-
tery electrolyte, there is no solid-state ion diffusion limitation, perature, defect free application of such versatile coatings
the rate performance being majorly dictated by the electronic remains the subject of further developments.[596]
conductivity of the composite electrode.[18,410,420] For instance, Graphene has been also used as an encapsulation material
Song et al. have prepared a series of graphene–electroactive for lithium–sulfur (Li–S) batteries.[597] Li–S (alongside with Li–
polymer composites based on poly(anthraquinonyl sulfide) and O2) battery is considered as one of the future energy storage
polyimide through a simple in situ polymerization process.[583] systems given the very high specific energy and energy density
The highly dispersed polymer–graphene composite was found it can provide: 2567 Wh/kg and 2199 Wh l−1, respectively.[52] A
to sustain ultrafast charging and discharging, delivering more major issue in Li–S cell operation is the solubility of polysulfide
than 100 mAh g−1 at a cycling rate of 100 C (Figure 17B). The intermediates Li2S3–6, (also known as the polysulfide shuttle
authors demonstrated that at a similar mass loading of conduc- effect) resulting in rapid capacity fading.[598] Several methods
tive additive (graphene or CNT at 6 wt%), the graphene com- have been proposed over decades to delay or to block the disso-
posite displayed one order of magnitude higher electronic con- lution yet, the Li–S battery has still not reached mass commer-
ductivity, higher surface area and electrode utilization ratio as cialization.[4,599,600] Graphene could be again the wonder solu-
well as enhanced rate performance. This clearly demonstrated tion here. The single atom thick material is known to be highly
the improvement of the electrode performances upon graphene impermeable, even helium gas was shown to be blocked by
incorporation. graphene.[601] Surprisingly, He-leak-tight membranes made of
Graphitic (also being called graphene-like) growth has been GO have been found to allow unimpeded permeation of water
also applied on some battery materials.[593] The technique is molecules, explained by the low-friction flow of a monolayer of
however limited given the high processing temperature as well water through GO laminates.[602,603] Consequently, graphene
as inert or reducing atmosphere required for growth. More- could effectively block for the polysulfides dissolution while
over, graphene growth is known to be surface catalyzed only by still allowing a sufficient Li+ flux and electron transport.[604,605]
some materials further limiting the applicability.[594,595] Never- Several successful implementations have been already provided
theless, graphene growth on active battery materials remains with respect to this and graphene coatings have been found to
highly desirable as it can ensure highly intimate and conformal effectively retard the sulfur shuttling effect.[606–612] The tech-
contact, create a stable passivation layer as well as keep the nique however requires further improvements. Assembling

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graphene flakes patches around sulfur nanoparticles inevi- binder and the conductive carbon additives, at a lower mass
REVIEW

tably present defects, susceptible to provide pathways for the content while preserving or outperforming the electrochemical
polysulfide leakage. Infiltration approaches come with intrinsic characteristics. Designing a self-supported 3D graphene back-
limitations: if sulfur can be infused inside, the polysulfides will bone requires however special approaches. So far, the use of
inevitably diffuse out at some point. Hollow shells, like carbon 3D macroporous catalytic support for the graphene growth has
onions[613,614] or vesicular particles,[615] incorporating sulfur been explored with this respect, the Ni foam being the most
could become a better alternative although the realization used given its commercial availability. Originally developed
seems elaborated and structural defects must be further mini- for Ni-MH batteries, Ni foams can be available in various for-
mized as to increase the cycle life-time. Following the same mats, including but not limited to: 0.6–10 mm in thickness,
rationale, graphene conformal coating could be also applied to bulk density 0.25–0.65 g cm−3, porosity ≈85–95%, areal den-
suppress excessive electrolyte decomposition and uncontrolled sity ≈320 g m−2; typical size of the Ni struts is in the order of
SEI formation on battery materials. 100 µm. Hence metallic Ni was shown to be an efficient cata-
Hence the lithiated carbons have low negative electrochem- lyst,[640,641] Ni foam has been broadly explored as 3D scaffold
ical potentials, graphene has been also found suitable as anode templates for the CVD growth of graphene. The net advantage
materials in Li-ion (but also Na-ion) batteries.[504,531,532,616–622] of this configuration over the assembled structures of chemi-
Distinct from graphite anodes, where Li+ intercalates at edge cally derived graphene sheets is better electrical conductivity
planes, no such reaction is possible in the case of SLG. In prin- due to lower inter-sheet junction contact resistance.[642] After
ciple, FLG or restacked SLG could display graphite intercalation graphene growth and nickel dissolution, a graphene foam is
behavior given that the graphitic crystal structure is restored. being obtained perfectly reproducing the original morphology
Graphene-based anodes show excessively high lithiation capaci- of the Ni foam yet, being much lighter, bearing a hollow struts
ties, far above the theoretical 372 mAh g−1 for C6Li.[621,623] The interior and much higher mechanical flexibility.
high Li+ uptake capability is assigned to higher specific surface Hence graphene foams are electrically conductive, light-
area combined with excess Li+ uptake at the surface and edge weighted, mechanically stable and display high porosity as well
defects as well as conversion reactions of various functional as surface area, these scaffolds have been found again as excel-
groups.[323,624–630] The low volumetric energy density and Cou- lent platforms to disrupt the battery and supercapacitor tech-
lombic efficiency at the first cycle as well as higher operating nologies.[150] The active battery materials can be grown inside
potential have to be addressed before broadly accepting this or on the graphene walls or just infiltrated in the empty space
material as Li-ion battery anode.[631] of the foam. As compared to pristine Ni foam, the power capa-
Although much explored as anode materials in Li-ion bat- bility of the battery electrode is decreased due to lower electrical
teries, carbon materials and derivatives are also suitable as posi- conductivity yet, the gravimetric capacity is severely increased
tive electrode materials and the same rationale could be applied (<5 mg cm−3 density and more than 99.5% porosity for the gra-
to graphene. Fluorinated graphites and CNTs have been known phene foam).[642] Furthermore, these electrodes have enhanced
for a while as 3 V materials for primary lithium batteries with mechanical properties supporting also reversible stretching
high specific capacity, of more than 500mAh g−1.[632–636] Fluori- and folding modes. Li et al. designed a flexible battery using
nated graphene however, has been only recently tested as posi- graphene foam at both electrodes.[142] At the anode, the gra-
tive electrode material.[637,638] Lithium borocarbide has been phene scaffold was surface-decorated with Li4Ti5O12 nanocrys-
theoretically predicted as a unique material for LIBs.[639] With tals while the positive electrode consisted in nanocrystalline
an intercalation potential of 2.3–2.4 V vs. Li/Li+, a specific LiFePO4 grown as well on graphene foam. No metal current
energy density of 1088 W h kg−1, a volumetric energy density collectors, conducting additives, or binders have been used.
of 2463 W h L−1 and volume changes lower than 3% upon Competing electrochemical performances were obtained in
insertion/extraction it looks indeed like a promising material. original flat and mechanically stressed states owing to rapid
A dual-graphite chemistry has been also proposed recently.[519] electron and ion transport within the porous framework as well
The reversible dual-graphite intercalation chemistry with simul- as mechanical rigidity of the graphene framework (Figure 17C).
taneous accommodation of Li+ and PF6− in graphitic structures Ji et al. have also explored graphene foam–LiFePO4 composite
was enabled by a high voltage electrolyte. The system, based on electrodes, yet prepared via infiltration methods.[386] The 3D
a fluorinated solvent and additive, demonstrated high cycling interpenetrated structure was found to support higher charge/
efficiencies at 5.2 V, thus enabling all-graphite storage batteries. discharge currents than the trivial configuration: LFP coated on
Hence high voltage operation was ascribed to anion intercala- Al-foil electrode (Figure 17D). The net gravimetric capacity gain
tion into graphite, alike functioning of a graphene-based device was considerable, 23% and 170% higher than that of the Al/
is to be explored. Graphetizing these approaches could incor- LFP and Ni-foam/LFP cathode, respectively. Furthermore, the
porate the graphene's exceptional benefits and result in battery authors highlighted the higher electrochemical stability window
cathodes with further extraordinary properties. The direction is, of graphene as compared to that of Al and Ni foils, which
however, still poorly explored and awaits its pioneers. are generally used as positive current collector in lithium ion
Alongside the chemical and electrochemical benefits, the batteries.
mechanical properties of graphene architectures have been also From the above presented, it is clear that graphene has the
explored. Being very rigid but at the same time very light, gra- power to disrupt the lithium-ion battery technology. What is
phene can be also used as a mechanical reinforcement scaffold more certain is that graphene is already reshaping the super-
to keep the structural integrity of the battery electrode. Being capacitor technology road map.[643] The elevated specific area,
also electronically conductive, it can actually replace both, the high electron conduction as well as simpler composition and

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less stringent assembly and operation requirements makes of The pores were 0.6 to 5 nanometers wide and uniformly dis-

REVIEW
graphene the primary candidate for the future ultracapacitor tributed across the carbon walls. High capacitance values
technologies.[89,293,644–649] The electrical double layer (super) were obtained with the activated graphene oxide electrodes
capacitors (EDLCs) reversibly store the energy by virtue of approaching 200 F g−1. Unexpectedly, the obtained capacitance
electrical double layer of electrolyte ions at the surface of elec- values were close to other graphene or activated carbon based
trodes.[13,516,650–653] The absence of Faradaic reaction at the elec- capacitors displaying lower specific surface area.[57]
trodes and the surface storage mechanism are at the origin of The miscorrelation between the measured capacitances and
the extremely fast charge absorption and delivery. There are specific surface area was attributed to graphene sheet restacking
also rate-limiting factors such as electrode ohmic contribu- directed by the hydrogen bonding interactions of residual inter-
tion or diffusion constraints although less significant than in calated water molecules.[658–661] As such, the graphene's mate-
batteries. The tradeoff is the low energy density of the EDLC rial identity and the high surface area advantages are lost. At
devices. As a consequence, the main focus on today's EDLCs a specific area of 2630 m2 g−1, the affordable capacitance of
research is increasing their energy density. And the primary graphene was reported to be as high as 550 F g−1.[662] Conse-
way of doing this is by increasing the surface area of the elec- quently, one would expect capacitance values of 400 F g−1for
trodes. Once again, graphene is being considered as the key graphene electrodes with typical surface areas of 2000 m2 g−1.
material for advancing this technology. Of course, surface functionality, pore morphology and acces-
Standard activated carbon materials presently used in EDLCs sibility are accounted for the observed lower values however,
have a specific surface area around 2000 m2 g−1.[57] The theo- graphene restacking is considered as being the major limiting
retical value for graphene is already 2630 m2g−1. Chemical mechanism.[663–667] If the process is however totally or partially
activation has been found to further increase the specific sur- suppressed, ultrahigh, close to predicted, capacitance values are
face area. Carbon activation with KOH is a well-known process being obtained: 210 F g−1for 1000 m2 g−1.[668,669] Clearly there
generating nanoscale pores in the carbon matrix and has been is huge potential behind this technology as capacitance values
applied on various types of carbons to improve their porosity as high as 1000 F g−1 and energy densities comparably higher
and capacitance.[172,654,655] Zhu et al. have used KOH activation than those of lead-acid (50–100 Wh L−1) batteries are physically
of microwave exfoliated graphene oxide and achieved a record possible. Technical solutions must be provided first. Covalently
surface area of 3100 m2 g−1.[656] The obtained carbon displayed bonded 3D CNTs and graphene nanonetworks could be a solu-
a dense and continuous 3D nanometer scale porous network tion as restacking would be sterically and mechanically not
of highly curved, single carbon atom-thick sheets (Figure 18A). favored and the charge transfer considerably improved. Design
and realization of such structures is con-
tinuously progressing and efficient fabrica-
tion and integration routes are being already
developed.[670–677]
Graphene materials provide further pos-
sibilities for super-EDLCs technology. For
instance, GO is an electronically insulating
material that is capable to absorb and hold
substantial amounts of water. Gao et al. have
found that the trapped water amount inside
the GO membranes is sufficient enough to
allow the membrane to function as an ionic
conductor while the insulating property of
the GO, allows it to serve as an electrode sep-
arator.[393] The authors have explored the pho-
tothermal reduction of GO into rGO[678,679]
to construct rGO–GO–rGO supercapacitor
devices with in-plane and sandwich struc-
ture, in a single processing step (Figure 18B).
For example, a ≈22 µm thick GO film of
was laser patterned on both sides to achieve
≈1 µm thick RGO layers on both sides of
the GO film. RGO regions worked as a high
Figure 18. Graphene enhanced supercapacitors. A) High-resolution TEM image showing the surface area carbon electrodes whereas the
presence of a dense network of nanoscale pores in the activated microwave exfoliated graphene remained RGO acted as an electrolyte–sepa-
oxide chunk. Reproduced with permission.[656] Copyright 2011, AAAS. B) Laser-patterning of rator. Absorbed water from the atmosphere
free-standing hydrated GO films resulted into RGO–GO–RGO supercapacitors. Histogram activated the ion conduction and Nafion-like
comparison of areal capacitance density of a sandwich-type device with different electrolytes
as well as the corresponding volumetric energy density versus power density. Reproduced with
proton conduction was proposed in hydrated
permission.[393] Copyright 2011, Macmillan Publishers Limited. C) Volumetric stack capacitance GO films. Excess water or other types of elec-
of a laser scribed graphene capacitor compared to a commercial activated carbon electro- trolytes have been found to further enhance
chemical capacitor. Reproduced with permission.[657] Copyright 2012, AAAS. the specific capacitance. Subsequently, more

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work has been devoted to photothermal reduction of GO for capacitances of individual components.[688] Thus, despite
REVIEW

example, by using DVD optical drives[657] or by using the photo- announced great potential, it is still unclear if graphene and its
flash of a simple digital camera.[626] Higher capacitance values derivatives will revolutionize the energy storage field or eventu-
and better power capabilities were obtained with respect to ally find niche applications.[689,690]
standard activated carbon electrodes (Figure 18C) yet, still lower
than the theoretical 550 Fg−1 for SLG. Recently, Hu et al. pro-
posed an ingenious protocol to fabricate all-in-one fiber super- 4.6. Hybrid Devices
capacitor through region specific reduction of a GO fiber
through laser irradiation.[286] An energy storage system naturally requires a power source
As an epilogue to this section, it is clear that carbon allotropes for repeated function. Except primary cells (that are already
have been, are and will be the key components for pushing in the charged state after assembly), all rechargeable electrical
the envelope limit of the energy storage technology. Amongst energy storage systems require external electrical energy input
all of them, graphene arises as the ultimate material, capable to restore the delivered charge. Charging source, wiring and
of fulfilling many functionalities simultaneously. If properly storage units are indispensable elements for the stationary or
designed and assembled, graphene can effectively substitute mobile electric infrastructure. Whereas for most of the appli-
the binder and the conductive carbon additives in lithium-ion cations this configuration is complete, requiring grid optimi-
batteries. Furthermore, chemical functionalization induces rad- zation and better energy distribution management, emerging
ical changes in the electrochemical response, being possible to electronic technologies demand for disruptive energy har-
use graphene derivatives as anode, cathode and electrolyte/sep- vest– deliver–store configurations. A mobile electronic device
arator material. As a matter of fact, using present knowledge, remains “mobile” as far as the battery is charged. Once docked
a fully graphene based LIB can be potentially built: graphene for the recharge it becomes a ‘stationary’ device and even if
as anode, swollen GO as electrolyte/separator, fluorinated gra- the recharge time can be drastically diminished the mobility
phene as cathode, and why not (semi)-impermeable graphene is still limited by the requirements of a recharge infrastruc-
or GO films as encapsulation materials.[518,680] Of course, there ture. The solution, at least conceptually, is straightforward –
are still some technical and material related challenges to be integration of energy harvest and store elements within the
handle before reaching a practical implementation. Regardless device framework. Small-scale solutions have been known for
whether such batteries will be available tomorrow or in a couple a while: tabletop personal calculators powered simultaneously
of years, graphene is already disrupting the supercapacitor by photovoltaic cells and batteries (eventually rechargeable)
technology. With an exceedingly high theoretical capacitance of are being commercialized since late 80s. The energy require-
550 F g−1 for the single layer graphene, there are big chances to ments of modern electronic devices however became far too
increase the energy density of supercapacitors up to the point to important to be fulfilled by this technology forcing the scien-
replace the lead-acid batteries with graphene EDLCs. tists to pave the way for a new research direction: hybridiza-
Nevertheless, the full potential of graphene is still far from tion of energy storage–harvesting–conversion devices. The
being completely explored in both, Lithium-ion batteries and hybridization of different energy storage materials and tech-
supercapacitors. Restacking remains a big problem for the effi- nologies is beyond the scope of this section and the inter-
cient utilization of high surface area displayed by graphene. ested reader is referred to several recent publications on this
Graphene composites suffer from rather low inter-sheet contact topic.[18,691–693]
resistance, penalizing again the intrinsic ultra-high conduc- Over the time, there have been many solutions proposed
tivity within the graphene sheets. Graphene foams or 3D gra- for the hybrid energy device technology. Three primary classes
phene–CNT composites hold great promises for solving most can be ascribed depending on the structure and the way the
of these issues hence they maintain covalent bonding and as active units are assembled. The most intuitive resumes to the
such, high electron conductivities. Restacking can be sterically realization of separate portable energy storage and harvesting
impeded and the mechanical properties will be those of pristine modules interfaced by electrical wiring and charging control
graphene. Yet, presently designed graphene foams suffers from modules. The technology is mature, applicable at small and
macroscopic dimensions and a severe miniaturization (by at large scale, and many solutions are being already commercial-
least two orders of magnitude) may be required to truly benefit ized (solar chargers for phones, media players, tablets as well
from the wonder properties of graphene.[536,675,681–683] as large scale solar battery banks for back-up systems and off-
Finally, it should be mentioned that caution must be exer- grid antenna powering). Although simple in realization and
cised with respect to utilizing graphene or graphene analogues efficient for high energy applications, miniaturization is how-
derivatives for energy storage or other electrochemical devices ever non-convenient. Both, energy storage and harvesting units
and applications.[684,685] Radich et al. have recently demon- necessitate their own frame and packing modules and external
strated that rGO is not suitable platform for TiO2 based pho- wiring is required. This increases the overall mass and reduces
tocatalysis.[686] The authors demosntrated that rGO is vulner- the overall maneuverability. Integrating both types of devices
able to photogenerated OH• radical attack and raised concerns and the electrical wiring within the same frame would greatly
of its use in many applications where OH• or other oxidizing enhance the handiness and significantly reduce the mass of the
radical species (such as O2•− in Li-O2 batteries) are likely to be device. With this respect, many developments have been pro-
formed.[687] Buglione et al. demonstrated that no synergistic posed, namely by integrating solar power units with batteries or
effect or enhanced capacitance is obtained in a graphene – CNT other energy storage systems and the commercialization seems
composite, the total capacitance being just the sum of specific eminent.[90,694]

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A disruptive breakthrough however has been marked by the for paintable solar cells are known.[704–707] Nonetheless, inter-

REVIEW
co-integration of energy devices within the same structural plat- structural/device hybridization seems to offer more venues
form. More gravimetric energy gain can be achieved in this way namely, possibility of miniaturization and free-form manufac-
as the co-integrated configuration eliminates the need of elec- turing; lower dead-mass components and less energy losses;
trical wiring (and consequently, reduced ohmic losses), uses the well-defined interfaces and better energy transfer efficiency.
same encapsulation unit and eventually, has shared constitu- Although huge progress has been achieved so far with this
ents (for instance, electrodes) playing a dual, yet definite role in respect, there are also some fundamental, intrinsic to device
both types of energy devices. There are clear benefits provided limitations that must be considered carefully and these aspects
by such technology not only with respect to the handiness in are being discussed in the following.
use and more efficient device realization but also with respect The first photorechargeable energy storage cells date back
to gravimetric energy density improvements and presumably, to early 70’s and were based on the photochemistry of Ag/Ag+
a more efficient charge transfer and utilization due to shared redox couple. Theodorou and Payne explored the photodisso-
interfaces and constituents. However, like for the all previously ciation of Ag2O into metallic silver and gaseous oxygen (that
mentioned disruptive technologies, here as well some techno- could be also regarded as a sort of metal–oxygen battery). To
logical issue must be solved first. More important, there are allow the reverse reaction, one electrode was made porous so
also fundamental, intrinsic to materials and device physics lim- that oxygen from the ambient air can diffuse and re-oxidize the
itations that may be not so easy to address. This Section over- silver electrode.[708] Bayard designed a more complicated set-up:
views the realizations done so far with respect to the co-inte- glass-F/SnO2/V2O5/AgBr/Ag0.35V2O5/Ag, and exploited the dif-
gration and hybridization of energy devices detailing especially fusion property of photodissociated Ag+ (from AgBr) through
on solar to electrical power conversion – electrochemical energy ion conducting Ag0.35V2O5 layer, to charge the system.[709] De
storage configurations while other configurations are being also Schuster explored AgCl photodissociated in contact to a liquid
highlighted. electrolyte containing KCl.[710] Licht et al. designed photoelec-
The solar system Sun is the Earth's infinite source of energy. trochemical polysulfide solar devices based on n-CdSe0.65Te0.35 ||
The Earth receives an astronomically high amount of energy CoS/aqueous CsSx/SnS cells, operating at 11.3% efficiency, and
from the Sun, 100 000 TW. The annual worldwide energy con- able to sustain a constant load current, insensitive to daily fluc-
sumption is actually provided by the sun in just more than one tuations in solar radiation, through a 1.5 kΩ load.[711] Probably,
hour.[695] Even if the amount of solar radiation for practical end since at that time the energy was not a big society concern,
is less than 1/100th of the total amount of received energy, it these pioneering efforts did not received much further atten-
still remains the major renewable energy source.[2] Henceforth, tion only until recently.
it is not surprising the interest that this technology received Over past few years the reports on photovoltaic charged bat-
over the past years, further fostered by the worldwide energy teries have multiplied rapidly.[712–715] While different chemis-
crisis and excessive depletion of fossil energy resources. There tries have been used to design the solar cell and energy storage
are several well-established techniques for industrial scale har- unit they have similar structural and operation features.[716] In a
vesting. Solar thermal energy technology is the oldest, most simplified representation, the photocharge is generated within
established and widely used for various applications such as the photovoltaic layer and separated carriers are being collected
water processing (heating, disinfection, desalination), thermal at the battery electrodes: one electrode by direct contact and
building management (cooling and ventilation) as well as elec- the opposite through external circuitry wiring (Figure 19A).
tricity and fuel production (photovoltaics, photoelectrochemical Two different types of photocharged energy storage cells are
water splitting and solar power concentrators).[696–699] Amongst, distinguished, depending on the structure of the hybridized
only photovoltaic systems allow direct conversion of solar electrode: two- and three-electrode configurations (Figure 19B).
into electrical energy. Furthermore, this technology is also the In the first case, the photovoltaic layer is directly interfaced
most compact, requires less maintenance, posses high power or incorporated into charge-storage layer. The three-electrode
efficiency (already approaching the theoretical 34% efficiency) configuration has an internal bi-functional electrode operating
and presently, is being manufactured at rather low costs (less as cathode of the photovoltaic cell and anode for the storage
than 1 $ W−1 p−1). It is quite natural that photovoltaics has been cell.[716] Depending on the storage cell type (Coulombic or Fara-
already integrated into various electronic platforms and it is daic), as well as on the electrode and electrolyte chemistry, the
considered as the main power source for future portable, stand- charging is realized in open- or in close-circuit configurations.
alone electronics. One of the most studied configurations is based on various
Direct integration, and hybridization of solar cells with or dye-sensitized solar cells operated in iodine-based liquid elec-
within energy storage cells (batteries, supercapacitors and trolytes. The I3−/I− has a redox potential of 0.53 V vs. hydrogen
other) has attracted great attention recently.[700,701] Extra- and and operates through a shuttle effect between both electrodes
intra-structural device integration, as discussed above, is easier For example, Hauch et al. have designed a WO3 | LiWO3 ||
to realize yet, presents some intrinsic drawbacks.[694,702,703] The LiI | LiI3 cell having a dye-sensitized TiO2 cell incorporated at
potential of constructing one of the two devices on top of the the anodic site and a catalytic Pt film at the cathodic site.[717]
other, has been recently demonstrated by painting a LIB on Under illumination, the photons absorbed by the photovoltaic
top of prefabricated solar cells.[90] Both devices could share the layer generated an electron-hole pair triggering a redox reac-
same encapsulation system and wiring connections are mini- tion at the shared electrode as well as in the electrolyte: 3I−/
mized. The reverse assembly sequence as well as a fully paint- I3−–WO3/WO3−. During discharge I3− is reduced at Pt elec-
able configuration could be hence envisioned, as techniques trode involving the use of liquid electrolytes to allow ionic

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Solid-state cells are more desired due to plethora of advan-


REVIEW

tages provided (see also previous Sections). Hence both, solid-


state solar cell and energy storage devices exists, solid-state
hybridized cells have been envisioned. Nevertheless, given that
only solid-state photovoltaic technology is mature enough com-
pared to solid-state electrochemical energy storage, that still
requires improvements, there are only few solid cells designs,
most of them being composed of solid solar cells combined
with liquid electrolyte batteries. Chakrapani et al. explored the
possibility of hybridizing multijunction silicon solar cells with a
LiCoO2/Si nanowire LIB with a shared contact integrating both,
Si nanowires for Li-ion battery and Si multijuntion solar cell on
the opposite sides.[733] A TiN barrier layer was found to efficiently
block excessive Li+ diffusion into the photovoltaic layer that
could degrade solar conversion performance. Another important
issue addressed by the respective study was direct charging of a
4 V LIB using a single element solar cell. Hence single junction
photovoltaics have an output voltage of 0.6–1 V, direct charging
of a 4 V cell cannot be realized. Several other solutions have been
proposed and will be discussed later in this section.
As pointed out above, solid cells are high desirable for
many applications including miniaturization as well as flex-
ible and cloth integration. Although direct hybridization of
classical configuration solid-state batteries and solar cells is
appealing, practical implementation is rather challenging and
Figure 19. A) Schematics of charge generation, transfer and storage made researchers look for other, simpler solutions. Of course,
mechanism in a photo rechargeable battery. B) Schematic and circuit let's not forget about the Bayard's solar batteries[709] that were
diagram for the two- and three-electrodes type hybrid photovoltaic charge already solid-state and for some reasons, got lost in oblivion.
storage cells. By introducing an internal bi-functional electrode that oper- For example, Pandey et al. have built solid-state, two-electrode
ates as cathode of the photovoltaic cell and anode of the storage cell, the
photobatteries and studied the charge creation and storage
three-electrode configuration achieves higher charging voltage. Repro-
duced with permission.[716] Copyright 2007, Chemical Society of Japan. abilities of cyanine-based materials, and found that they can
be recharged simply through exposure to white light.[734] The
simple to realize devices consisted in active cyanine layers
mobility. The cell delivered 1.8 C cm−2 in dark after being illu- sandwiched between ITO/PEDOT:PSS and Al electrodes. The
minated at 1000 W m−2 for 1 h. Other photorechargeable cells authors found that the molecular structure of the dendrimer as
based on I−/I3− redox-electrolytes have been explored making well as the nature of anion strongly affected the photo-gener-
use of polypyrrole redox electrodes,[718] CNT-polyaniline ated charge storage efficiency (Figure 20A). The mechanism of
composite electrodes,[719] symmetric activated carbon,[720,721] the photo-charge storage was attributed to charge trapping sites
TiO2/poly(3,4-ethylenedioxythiophene)-polypyrrole polymeric within the bulk of the film, created through internal charge
storage electrodes,[722] poly(3,4-ethylenedioxythiophene),[723] transfer from the balancing anion to the cationic cyanine.
and poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]diox- There were no shared electrodes or interfaces (a polyimide layer
epine)[724] supercapacitor electrodes, interdigitated comb-like being used to isolate the cells) and external wiring was used to
electrodes,[725] electrocatalytic mesh supported TiN nano- connect the cells.
tube arrays[726] as well as for the realization of LIB–solar cells Much effort has been directed so far for the realization of
power pack,[727] integrated energy wires,[274,728] as well as wire-type energy devices (the wire or cable type energy storage
hybrid harvest–store–sense devices.[729] Clearly this technology configurations are detailed in Section 4.1) and of course, the
has developed fast and provided valuable results. Nonethe- hybridization of energy harvesting and store units within a
less, there are some drawbacks related to use of soluble redox wire configuration has been envisioned as well.[735–738] Whereas
active components namely, redox shuttle, responsible for self- solid-state configuration would greatly simplify the assembly
discharge phenomenon. Furthermore, use of liquid electro- and device integration (into cloths, fabrics or mats) protocols,
lyte hinders the device form factor as discussed in previous the manufacturing complexity constrained the realization so
Sections. Gel-type electrolytes partially solve these limita- far to liquid electrolyte based configurations. Wire-shaped
tions whereas solid-state cells are the most suited. Based on dye-sensitized solar cells,[739–742] nanowire based piezoelectric
natural photosynthetic system with pigmented bilayer lipid energy scavengers[251,743] as well as supercapacitor and bat-
membrane semiconductor-septum solar cells have been devel- teries[269,281,298] (see Section 4.1 for a thorough description) have
oped that use ion-blocking materials (typically metal foils) to been actively developed over the past few years in view of their
avoid electrolyte migration and limit the self-discharge.[730–732] integration into smart cloth and wearable electronics. Hybrid-
Still, liquid electrolytes are being employed in both electrode ization of these technologies was a logic continuation of this
compartments. effort. Alas, this research direction is still exploratory, probably

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Figure 20. Hybrid energy storage–harvesting devices. A) Discharge current obtained for different cyanine-based photo-rechargeable materials (the
reader is referred to the original article for the molecular structure visualization). Inset shows the device structure. Reproduced with permission.[734]
B) Schematic illustration and the circuit connection during charging and discharging of an “energy wire” and corresponding photocharge–discharge
curve. Reproduced with permission.[728] C) Schematic and circuit illustration of a printable photo-supercapacitor during (left) the charging process
and (right) galvanostatic discharge. The corresponding voltage and current profiles vs. time are shown below each scheme. Reproduced with permis-
sion.[401] Copyright 2011, Royal Society of Chemistry. D) Three discharge/charge cycling performances of a hybrid dye-sensitized solar cell–lithium ion
battery. Reproduced with permission.[727] Copyright 2012, American Chemical Society.

due to technological complexity, with only few results being storage efficiency of about 1.5%. As also noted by the authors,
reported so far. the realization of the novel wire structure enables unique and
Bae et al. were amongst the first to prototype hybrid promising applications, with potential for smart electronic tex-
energy converters and storage devices integrated into a single tiles and self-powering systems for portable electronic devices
microfiber using ZnO nanowires and graphene as building and equipment yet, further developments are required to reach
blocks.[270] The authors used the same platform, ZnO nanow- a mature technological level.
ires grown on Au coated thin plastic wire, to build 3 types of A three-electrode printable supercapacitor was designed and
energy devices: a piezoelectric generator (graphene/ZnO), a tested by Wee et al.[401] The solar cell unit consisted of a ITO/
supercapacitor (graphene/PVA-H3PO4–H2O gel electrolyte/ PEDOT:PSS/P3HT:PCBM/Al-CNT network. The Al-CNT layer
ZnO) and a dye sensitized solar cell (graphene/ZnO nanow- also shared the role of charge storage electrode in the sym-
ires/dye/electrolyte/Au). The authors achieved good perfor- metric CNT–CNT supercapacitor integrated into the structure
mances for each of the energy harvesters and storage devices (Figure 20C). The hybrid device required circuit commutations
demonstrating that simultaneous harvesting of solar and when charged and operated through an external load. The entire
mechanical energies as well electrochemical storage is pos- architecture operated at a voltage of 0.6 V and yielded a capacity
sible. Nonetheless, simultaneous integration and operation of of 28 F g−1 after being illuminated for 70s at 100 mW cm−2.
the hybridized devices was not presented. A hybrid operational The authors went a leap further and connected in series two
bi-functional energy wire was demonstrated by Chen et al.[728] solar cells, raising the working voltage of the supercapacitor
The photoelectric part was fabricated by twisting a TiO2/dye and the entire device to almost 1 V. Obviously, more cells could
decorated Ti wire with a CNT fiber achieving an energy conver- be stacked to increase further the voltage.
sion efficiency as high as 2.2% for a prototype configuration. It is worth mentioning here some intrinsic limitations and
The supercapacitor part was made as well by twisting a Ti wire challenges of this recently reborn technology. Most of the solar
with a CNT fiber with a PVA/H3PO4 gel electrolyte in between cells have a typical open circuit voltage of 0.6–1V. Whereas this
displaying high electrochemical stability and capacitance values is not a limitation for supercapacitor devices (due to their linear
(length and areal values of 0.024 mF cm−1 and 0.6 mF cm−2, voltage–current response) driving a >1 V redox reaction is dif-
respectively). The photocharging and discharging of the energy ficult. Hence most of the currently used batteries require more
wire required different circuit connections with distinctive pho- than 1 V for charging, a technological problem exists: direct
tocharge and discharge characteristics (Figure 20B). The energy interfacing is prohibited. For Li-ion batteries, usually oper-
efficiency of the supercapacitor unit approached the 69%, the ating at 4 V, photocharging can be achieved by using either a
hybrid devices operating at a total photoelectric conversion and DC-to-DC energy converter, a stacked single-junction cell or

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a multi-junction photovoltaic device. The first option is to be


REVIEW

excluded in the present context as it introduces extra wiring and


electronic circuitry. Multi-junction photovoltaic device integra-
tion has been proposed and some design requirements detailed
yet, practical implementation is lacking for the moment.[733]
a-Si thin-film solar cells have higher open-circuit and have been
explored to charge a thin-film Nb2O5/LiPON/LiMn2O4 battery
deposited on top of a prefabricated and encapsulated a-Si thin-
film solar cell.[744] Guo et al. have also attempted this realm and
fabricated an integrated power pack by incorporating a series-
wound dye sensitized solar cell and a Li-ion battery on a Ti foil
bearing double-sided TiO2 nanotube arrays.[727] Three tandem
solar cells based on TiO2 nanorod and nanotube arrays, pro-
vided an open-circuit voltage of 3.39 V and a short-circuit cur-
rent density of 1.01 mA cm−2, sufficient to charge the LiCoO2/
TiO2 cell under solar irradiation (Figure 20D). The cells shared
the same Ti substrate and operated at a total energy and storage
efficiency of 0.82%.
Other types of environment energy scavenger devices have
been hybridized with charge storage units as well. Piezoelectric
generators convert mechanical energy into electrical energy and
have been explored to charge capacitors and batteries. Xue et al.
have merged the two processes into one hybrid device.[745] The
authors replaced the polyethylene separator used in conven-
tional LIBs with a piezoelectric poly(vinylidene fluoride) film
acting simultaneously as battery separator, swollen polymer
electrolyte and energy source (Figure 21A). The piezoelectric
potential generated from the poly(vinylidene fluoride) film
upon mechanical straining acts as a charge pump to drive Li+
ions to migrate from the cathode to the anode accompanying
charging reactions at electrodes. The mechanical energy was
directly converted and simultaneously stored as electrochemical
energy without going through the intermediate step of first con-
verting into electricity. By attaching a power cell to the bottom
of a shoe, the authors also demonstrated that the compres-
sive energy generated by walking can be converted and stored
directly by the self-charging power cell.
A CuO/PVDF nanocomposite anode was also found suitable Figure 21. Hybrid devices: mechanical and thermal power harvesting.
for a piezo-driven self-charging battery.[747] The stored capacity A) Cross-sectional SEM structure design and real-life implementation of a
and energy of the integrated devices within 240 s (applied force self-charging power cell by hybridizing a piezoelectric nanogenerator and
of 18 N at 1 Hz) was 0.0247 µA h and 6.12 µJ, respectively. a Li-ion battery. Self-charging and discharge cycles of the hybrid power cell
Huang et al. implemented energy storage in a polyvinylidene under different forces and frequencies, respectively. Reproduced with per-
fluoride dielectric layer coated on the counter-electrode of a mission.[745] Copyright 2012, American Chemical Society. B) Schematic
diagram of the hybrid energy cell based on ZnO nanowire array grown
dye-sensitized solar cell.[748] Although such self-charging power
on an ITO/PET substrate. Output voltage of the hybrid pyroelectric and
cells hold great promises for harvesting and storing mechanical integrated six solar cells for harvesting thermal and solar energies. Repro-
energy in our living environment the same limitation as for duced with permission.[746] Copyright 2012, American Chemical Society.
solar rechargeable batteries are being faced. The output voltage
is not sufficient to drive redox reactions at the electrodes when A flexible hybrid energy cell for simultaneously harvesting
high voltage batteries are being integrated, the charge storage thermal, mechanical, and solar energy was reported recently
mechanism being primarily of Faradaic type rather than Cou- by Yang et al.[746] The device was composed of Ag/PVDF/
lombic. Furthermore, the piezoelectric efficiency of PVDF Ag/P3HT/ZnO/ITO sandwich structure and showed prom-
membranes may be irreversibly affected by the liquid electrolyte ising performance with respect to harvesting the three type
uptake, necessitating further improvements, electrolyte insensi- of energies (Figure 21B). Co-hybridizing such architectures
tive piezoelectric or solid-state configuration integration. Nev- with energy storage cells is of huge interest for example for
ertheless, these pioneering examples demonstrated the possi- wearable electronics as it can harvest and store energy from
bility of such hybridization and could be further integrated with thermal and body motion as well as from surrounding light
other energy harvesting elements including solid-state flexible sources while delivering the charge whenever such stimulus
nanocoposite generators,[749] thermoelectric cells,[750] triboelec- are interrupted.[248] A different research strategy for hybrid
tric nanogenerators,[751–753] or hybrid solar-piezoelectric.[754] solar harvesting and capacitive storage was proposed by Xia

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et al. exploring both oxidative and reductive energies at a designs have shown the potential for breakthrough techno-

REVIEW
single electrode.[755] The integrated photoelectrochemical logical advances in the field, the primary metrics that drive the
device with simultaneous supercapacitor and hydrogen evo- commercial implementation still remain the price per kilowatt
lution functions was based on TiO2/Ni(OH)2 oxides core/ ($ kW−1), specific energy (or kilowatts per kilogram, kW kg−1)
shell nanorod arrays. The charge/discharge processes in the and energy density (or kilowatts per liter, kWh L−1).[764] One
solar hydrogen generation and supercapacitor hybrid was also should recall that the fundamentals of battery and capacitor
accompanied by photochromism (reversible color changes, technologies were paved more than 40 years ago and have
see also Section 4.4). already been on the market for over 20 years. And although
Finally, some hybrid grid-scale technologies are shortly there has been fervent research ongoing recently, we still
mentioned here. For instance, known for a very long time,[41] majorly rely for our mobile applications on Co/Mn/Ni (or
renewable energy generation from water solutions of different alike)[787]–graphite cell chemistries packed in jelly-roll type
salinity, like river and sea water, has recently attracted attention cells.[8,19,22,38] Nonetheless, the pioneering achievements show
and not only for sustainable power generation but also for fresh the potential provided by disrupting trivial technologies and
water production.[756,757] In fact, this approach can be regarded pave the way for future smart energy systems.
as hybridization between of energy storage and water treatment Given the broad spectrum of proposed and developed tech-
technologies, although these hybrid architectures have a dif- nologies as well as of device configurations described in pre-
ferent functionality and operate at much larger scale than the vious sections, a natural question arises: what should we expect
previously mentioned hybrid energy systems. Various systems next? We can either look at improving these technologies by
have been proposed so far based on surface capacitive[758–760] or increasing their performance metrics or start looking at new
bulk redox[761,762] desalination, all of them proving their versa- realms. Both alternatives seem highly attractive and can offer
tility and with promising energy efficiencies.[763] lot of potential from many perspectives, novel chemistry devel-
Clearly there has been huge progress in field of hybridized opments, materials science and engineering as well as techno-
energy technologies. Solar energy, one of the most promising logical and commercial ventures.
renewable energy source of the future, can be now directly Certainly, most of the mentioned designs and technolo-
stored as the chemical energy at the supercapacitor or bat- gies are not well developed enough and the next evident step
tery electrodes. Pezoelectric, pyroelectric as well as thermo- will be ameliorating and maturating the techniques to make
electric energy harvesters are being also studied as possible them competitive for commercial applications. For instance,
embedded power sources for electrochemical storage units. increasing the volumetric energy density by efficiently com-
Providing simple integration protocols, enabling practical uti- pacting the components, utilizing less inactive material (espe-
lisation and achieving efficient charge transfer between the cially for flexible, conductive scaffold-based approaches) to
hybridized elements are the main focus directions. Their suc- increase the gravimetric capacity or switching to new battery
cessful implementation is expected to mark a turn point for chemistries are only some approaches could be implemented
many technologies, the portable electronics being probably to ameliorate the energy storage performances. Some devel-
the mostly affected, as it will enable true stand-alone energy opment directions have been already pointed throughout
systems. While the opportunities are endless, there are also this article. In this section, other potential developments are
some engineering and materials related challenges awaiting briefed, with an emphasis on disruptive architectures based
ingenious solutions. The output voltage of most of the energy on new chemistries (such as Li–O2 and Li–S systems) and
harvesting and conversion devices is still too low to allow bio-derived, bio-inspired or bio-interfaced energy storage
direct interfacing with 4 V Li-ion batteries, requiring mul- sources.
tiple cells connected in series. Seamless integration, although As already mentioned, one of the primary drawbacks of
highly desirable, may be also problematic. Proper functioning these technologies is the relatively low gravimetric as well as
of photovoltaic cells requires well-defined semiconducting volumetric energy density. Compaction, and proper electrode
interfaces with precise doping levels. Battery operation how- engineering could only partly overcome this issue and the gain
ever is accompanied by ion and dopants diffusion. Shared in energy could be at the expense of fabrications costs and com-
electrodes or interfaces configurations may be thus prohibited plications as well as lower power density (for example, by opti-
unless proper ion diffusion barrier materials can be found mizing the conductive scaffold configuration, composition and
and efficiently integrated. Such configurations may be more mass as detailed in Section 4.1). Whereas new electrode mate-
appropriate for now for hybridization with supercapacitors rial innovations are expected to provide major technological
materials. The challenges are big, yet the expected outcome is improvements and are irreplaceable for certain technologies,
even greater providing many opportunities for material scien- high energy density Li–O2 and Li–S batteries are considered
tists and engineers for interdisciplinary research and develop- as key-stone systems for massive adoption of electrochemical
ment ventures. energy storage devices.[52] So why not build flexible, stretch-
able, transparent, ultra-thin or thick, as well as cable-type bat-
teries using these chemistries? The problem is that unlike
5. What’s Next? commercialized intercalation cathodes, these technologies are
still in the stage of research because of high polarization, low
Energy storage research has been driven for many years by energy efficiency, poor capacity retention as well as cycling
applied technology needs.[104] And although recent funda- stability.[16,52,104] Deciphering first the fundamental flaws is
mental electrochemistry understanding and innovative material required before moving to the next stage.

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Developing disruptive batteries based on novel chemistries bioelectrical energy storage, harvesting and conversion units.
REVIEW

such as Li–O2 and Li–S systems can also provide more than An interesting approach was proposed by Kim et al.[773] The
only higher energy density. For example, sulfur was recently authors designed self-deployable current sources fabricated
shown to be processable as a macromolecular material with pol- from edible materials built to disappear. The developed
ymer-like chemical and mechanical properties while retaining energy sources were powered by onboard sodium ion elec-
its sulfur electrochemical activity in a lithium cell.[765,766] Poly- trochemical cells providing output potentials of up to 0.6 V
mers provide many manufacturing opportunities and could and currents in the range of 5–20 µA. Yin et al. fabricated
enable Li–S configurations that were difficult to achieve previ- recently a fully biodegradable primary batteries making use
ously, such as thin-film processing, room-temperature solution of bioresorbable building blocks[774] whereas a biodegradable
infiltration or gel–polymer formulations. Furthermore, the syn- gel electrolyte for flexible supercapacitors was proposed by
thesized sulfur block-copolymers are intrinsically transparent Moon.[775] Berchmans et al. were the first to report the fab-
and if properly choosing the conductive scaffold composition rication of a rechargeable, benign, skin-worn Ag/Zn-based
and design this could lead to the development of next genera- tattoo battery by making use of unconventional materials,
tion transparent Li-ion batteries with much higher energy den- such as screen printed electrodes, temporary tattoo paper,
sities. Within the same perspective, some of the reactants and alkaline gel electrolytes and a PDMS cover for sealing the
discharge products in a Li–O2 cell are as well optically clear battery.[776]
and non-absorbing materials that could further boost the trans- Although several advances have been made towards this
parent battery technology. end, the route yet is long before naturally powering up a Li-ion
Another very inspiring route to follow is bio-derived and battery.[777–779] For example, Kim et al. have fabricated a redox-
integrated energy storage sources. Nature has been refining capacitor made of chitosan and a redox-active catechol.[780] Not
this technology for billions of years and there are models to only did they find that the fabricated films can be rapidly and
take inspiration from. Citric acid cycle or photosynthesis in repeatedly cycled electrochemically, but they also demonstrated
chloroplasts are some examples that store high energy in the reliable charging and discharging under bio-relevant condi-
chemical bonds of adenosine triphosphate, nicotinamide or tions. The authors have implemented an enzymatic charging
flavin cofactor. Subsequent harnessing for various biological protocol in which electrons are transfer from glucose to the film
processes implies multiply coupled, stepwise redox reactions via an NADPH-mediated redox-cycling mechanism offering the
of these high energy carrying molecules. Furthermore, these unique capability of inter-converting biochemical into electro-
processes are characterized by high energy efficiency and chemical energy. Further progress has been proposed by Lee
especially, by their ultimate catalytic selectivity. It would be et al. by demonstrating the possibility of exploring the energy
thus highly advantageous to get inspiration from biomimetic storage mechanism of flavin redox cycling in mitochondria
protocols to build better energy storage systems, and why not to lithium rechargeable batteries (Figure 22).[781] The flavin-
build hybrid bio-interfaced batteries, supercapacitors and other based electrodes were found to reversibly store and release two
energy devices.[767,768] lithium ions and two electrons per formula unit. By further
Direct interfacing is hardly conceivable because of incom- molecular engineering, the authors have designed architectures
patible chemistries involved in both type of systems. Yet pio- with enhanced electrochemical performances including higher
neering advances are being already provided, for example, working potential di-chloro derivatives (7,8dichloro-10-ribityl-
towards implantable bio-supercapacitors.[769] Another issue isoalloxazine) and specific capacities as high as 180 mAh g−1 in
is the relatively low specific energy (high molecular weight lumiflavine. Clearly these reports have shown not only that the
and low working potentials) that can be stored in such bio- biological energy transduction mechanism can provide guide-
molecular systems. However, interfacing such technolo- lines for the realization of man-made energy storage system
gies with the human body to draw, store and deliver elec-
trical energy when needed for example, to
power a wearable electronic device, via a
tattooed or skin integrated devices could
be regarded now as a science fiction vision
although the potential and interest are
massive.[218] Selective molecular and ion
membranes could be adapted as to allow
passage of only active energy bearing bio-
molecules from the human body to the bat-
tery unit to draw the electrical energy for
the connected devices while subsequently
sending back the reduced species into the
bio-environment for their energy resto-
ration.[770] Although great advances have
Figure 22. Bio-inspired systems: Energy transduction in mitochondria (left panel) where flavins
been made towards permanent and tran- work as redox centers to store energy from nutrients into high-energy ATP. For synthetic energy
sient form electronic devices grafted onto device applications (right panel), flavins serve as an active material that reversibly takes up and
or into the human body,[98,218,771,772] further releases electrons and lithium ions during electrochemical energy storage. Reproduced with
work is required to also include efficient permission.[781]

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but also realized the first steps towards their hybridization and Seeing the advances presented in this Review, the moment

REVIEW
co-integration. when the high-end R&D developments of disruptive energy
Further natural inspiration could lead also to complex self- storage architectures will no more be part of science-fiction
healing batteries, supercapacitors and microelectronics.[782,783] prospects but real-life devices is probably not so distant. Tack-
The very first steps are being already paved. Wang et al. dem- ling these aspects from the lab–scale in order to demonstrate
onstrated that by building a CNT-based supercapacitor on their potential as practical devices holds on some key mate-
self-healing substrate, damage repairing properties could be rials and technological challenges. But this should only further
also incorporated into energy storage sources.[784] A very inter- motivate the scientific and engineering community to seek for
esting concept of air-rechargeable Li-organic cell was proposed better performances and ingenious designs. The time to come
by Renault et al.[785] By exploring the peculiar redox properties will reveal which of the described technologies will have an
of dilithium (2,5-dilithium-oxy)-terephthalate salt, they discov- impact on our life and which are prone to the oblivion. Ulti-
ered that this active battery material behaves also like an oxygen mately, developments will only be restrained by the conceptual
scavenger. This enabled the self-recharging of the respective Li bottlenecks lying between man's unlimited imagination and
cell by opening it to air, operating as a sort of hybrid “Li/O2 fuel genuine device implementation. One thing is sure, the future
cell”. looks powered.
It is clear that there is plenty of room for technological and
material innovations for further progress in these directions.
And although much effort in the literature is directed towards Acknowledgements
the development of current collector and electrode materials
and configurations, separator and/or the electrolyte layers seem A.V. acknowledges National Fund for Scientific Research (F.R.S. – FNRS,
to be the main limiting components that lie in between our Belgium) and SPW-DG06 BATWAL 1117494 project for financial support.
unlimited imagination and real device implementation. Indeed, Received: November 25, 2014
all way through Section 4, these battery constituents have been Published online:
pointed as being the weakest elements in designing architec-
tures with better energy performances. So, probably, the first
step towards the next generation disruptive energy technology
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