Showcasing a review from Prof.

Haoshen Zhous As featured in:

Energy Interface Technology Group at the National
Institute of Advanced Industrial Science and
Technology (AIST), Japan.

Title: Towards sustainable and versatile energy storage devices:

an overview on organic electrode materials

Electroactive organics are promising high performance electrode

materials, towards sustainable and versatile energy storage devices
beyond Li-ion batteries. The image depicts the cycle life of a green
battery based on organic electrode materials in the future and its
peculiar applications. See Song & Zhou,
Energy Environ. Sci., 2013, 6, 2280.

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Towards sustainable and versatile energy storage

devices: an overview of organic electrode materials
Cite this: Energy Environ. Sci., 2013, 6,
2280
Zhiping Song*a and Haoshen Zhou*ab

As an alternative to conventional inorganic intercalation electrode materials, organic electrode materials

are promising candidates for the next generation of sustainable and versatile energy storage devices. In
this paper we provide an overview of organic electrode materials, including their fundamental
Published on 10 May 2013. Downloaded on 22/07/2013 10:08:57.

Received 1st March 2013
Accepted 8th May 2013
DOI: 10.1039/c3ee40709h
www.rsc.org/ees
knowledge, development history and perspective applications. Based on dierent organics including n-
type, p-type and bipolar, we rstly analyzed their working principles, reaction mechanisms,
electrochemical performances, advantages and challenges. To understand the development history and
trends in organic electrode materials, we elaborate in detail various organics with dierent structures,
including conducting polymers, organodisuldes, thioethers, nitroxyl radical polymers and conjugated
carbonyl compounds. The high electrochemical performance, in addition with the unique features of
organics such as exibility, processability and structure diversity, provide them great perspective in
various energy storage devices, including rechargeable Li/Na batteries, supercapacitors, thin lm
batteries, aqueous rechargeable batteries, redox ow batteries and even all-organic batteries. It is
expected that organic electrode materials will show their talents in the post Li-ion battery era,
towards cheap, green, sustainable and versatile energy storage devices.

Broader context
State-of-the-art Li-ion batteries recently met their development bottleneck because of the energy-density limitation of inorganic intercalation cathodes, in
addition to the resources and environmental issues brought about by large-scale use of transitional metal based electrode materials. As an alternative, organic
electrode materials have attracted more-and-more interest in recent years due to their high electrochemical performance, resource sustainability, environmental
friendliness, structure diversity, exibility and so on. Since 1969, a many organic electrode materials with various structures have been investigated as cathodes
or anodes for various energy storage devices including Liorganic batteries. The previous researches indicate that conducting polymers, nitroxyl radical
polymers and conjugated carbonyl compounds are promising organic electrode candidates for the next generation of cheap, green, sustainable and versatile
energy storage devices beyond conventional Li-ion batteries.

1 Introduction supercapacitors in the aspect of not only charge/discharge

In the 21st century, energy and environmental issues are
recognized as two major challenges to human beings. In order
to meet the desire for an ecient and clean power source tting
the development of peoples' daily life and production, scientists
have never given up trying to improve the electrochemical
performance of existing battery techniques and seek novel
battery techniques.1,2 Currently, in the rapid development of
consumer electronics, electric vehicles and energy storage
stations, the relatively poor battery performance becomes the
major bottleneck. They put forward higher requirements on the
state-of-the-art rechargeable lithium batteries and
a
Energy Technology Research Institute (ETRI), National Institute of Advanced
Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki
305-8568, Japan. E-mail: son-zp@aist.go.jp; hs.zhou@aist.go.jp
b
National Laboratory of Solid State Microstructures & Department of Energy Science
and Engineering, Nanjing University, Nanjing 210093, China
performance, but also safety, cost, sustainability and environ-
mental friendliness,3 which provide great opportunities and
challenges to the research and application of novel electrode
materials and battery techniques.
In the past two decades, Li-ion batteries have achieved great
successes due to their superior comprehensive battery perfor-
mance, compared to leadacid, NiCd and NiMH battery.
However, like the previous battery techniques, its development
has also met a bottleneck recently. First, the conventional
inorganic cathode materials (e.g., LiCoO2 and LiFePO4) for Li-
ion batteries are restricted by their theoretical specic capacity
and structure stability, making it dicult to improve further
their energy density. Second, the large-scale production and use
of transition metal (e.g., Mn, Fe, Co, Ni) based cathode mate-
rials, causes more and more concern for resources and envi-
ronmental issues. Therefore, while most researchers in this
eld are still seeking high capacity cathodes (e.g.,
xLi2MnO3$(1
x)LiMO2)4 and anodes (e.g., Si)5 for conventional

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Review
Li-ion batteries, more-and-more researchers shi their atten-
tion to other alternative battery techniques, such as LiS, LiO2
(ref. 6) and Liorganic batteries.7
As an alternative to inorganic electrode materials involving
intercalation reactions (e.g., LiCoO2, LiFePO4, graphite,
Li4Ti5O12 and Si) or conversion reactions (e.g., transition metal
oxides and suldes),8 the electroactive organics or polymers
involving reversible redox reactions are promising candidates
as electrode materials for the new generation of green lithium
batteries because of their higher theoretical capacity, safety,
sustainability, environmental friendliness and potential low
cost.3,7 Not only that, as the charge compensation function of
Li+ can be substituted by other ions in electrochemical
redox reactions of many organic electrode materials, and
they have many distinct merits over inorganic electrode
materials in reaction kinetics, structure diversity, exibility
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and processability, they will also show great signicance in
many other battery techniques, such as rechargeable sodium
batteries, supercapacitors, thin lm batteries (e.g., exible,
printable or even transparent), aqueous rechargeable batteries,
redox ow batteries, and even all-organic batteries (see
Section 4).
For a long time, organic electrode materials have received
much less attention compared to inorganic electrode materials,
mainly because of their relatively poor electrochemical perfor-
mance and the great success of inorganic electrode materials in
either research or application. Like LiS and LiO2 batteries,6
Liorganic batteries are not a new concept that have appeared
recently, their history can be traced back to 1969,9 almost the
same time as the birth of lithium batteries.10 During the past
decades, the research on organic electrode materials has never
stopped and a lot of dierent organic structures and redox
mechanisms have been tried for higher electrochemical
performance to compete with inorganic materials. In the 1980s
and 1990s, conducting polymers and organodisuldes were
Zhiping Song received his BSc
and PhD degrees from the
Department of Chemistry,
Wuhan University, China, in
2006 and 2011 respectively. In
20102011, he spent more than
one year working as a visiting
PhD student in Dr Donghai
Wang's group at the Pennsylva-
nia State University, USA. He is
currently a postdoctoral fellow
in Prof. Haoshen Zhou's group
at the Energy Technology
Research Institute (ETRI), National Institute of Advanced Indus-
trial Science and Technology (AIST), Japan. His research interests
mainly focus on developing novel organic electrode materials and
their applications in various energy storage devices including
rechargeable lithium batteries.
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intensively studied as electrode materials for rechargeable
lithium batteries,11 but their battery performance is still far
from practical use. Thus aer 2000, researchers gradually shif-
ted their interest towards nitroxyl radical polymers and conju-
gated carbonyl compounds, and achieved great progress in this
eld.7 Nowadays, the comprehensive electrochemical perfor-
mance of some organic cathode materials, including energy
density, power density and cycling stability, are comparable or
even superior to the conventional inorganic cathodes. However,
compared to inorganic electrode materials, the research on
organic electrode materials is still in its early stages, and may be
not familiar to many researchers. Although there are already a
few reviews7,11 involving almost all the published papers on this
topic, we think there is still a lack of a review paper that intro-
duces systematically and simply the basic knowledge of organic
electrode materials. So we venture to write this review, as a brief
introduction of the fundamentals, development and prospec-
tives of organic electrode materials, aiming to cause more
interest and innovation in this eld.
2 Fundamentals of organic electrode
materials
2.1 Working principles and cell congurations
The basic requirement for a cathode or anode active material
(either inorganic or organic) for a rechargeable battery is that it
can undergo a reversible electrochemical redox reaction, at least
from the chemical species aspect. Thus, besides the transition-
metal (e.g., Ti, V, Mn, Fe, Co, Ni) based inorganic electrode
materials,12 there are also many other elemental substances
(e.g., Li, Na, Mg, C, O2, Si, P (ref. 13), S, Sn, I2 (ref. 14)) and
electroactive organics that can be used as electrodes for
rechargeable batteries. For inorganics, the redox reaction is
related to the valence change of the transition-metal or
elemental substance, while for organics, the redox reaction is
Haoshen Zhou graduated from
the Department of Physics,
Nanjing University, China, in
1985. He received his PhD
degree from the Department of
Chemical Engineering, the
University of Tokyo, Japan, in
1994. He is now a prime senior
researcher of the Energy Tech-
nology Research Institute (ETRI)
and leading the Energy Interface
Technology Group, in National
Institute of Advanced Industrial
Science and Technology (AIST), Japan. He is also a guest professor
in both the University of Tokyo and Nanjing University. His
research interests include the synthesis of functional materials and
their applications in Li-ion batteries, metalair batteries, new type
batteries/cells, fuel cells, dye sensitized solar cells, hydrophobic/
hydrophilic surfaces and electrochemical sensors.
Energy Environ. Sci., 2013, 6, 22802301 | 2281

Energy & Environmental Science
based on the charge state change of the electroactive organic
group or moiety.
Generally, we can divide organic electrode materials into
three types according to their dierent redox reactions (Fig. 1).
For n-type organics, the reaction is between the neutral state (N)
and the negatively charged state (N
), while for p-type organics,
the reaction is between the neutral state (P) and the positively
charged state (P+). There is also another type called bipolar
organics, for which the neutral state (B) can be either reduced to
a negatively charged state (B
) or oxidized to a positively
charged state (B+), but it can be also regarded as N or P because
only half of the reaction occurs on one electrode in most cases.
In the electrochemical reduction reaction of N or oxidation
reaction of P, cation (Li+) or anion (A
) are, respectively,
necessary to neutralize the negative charge of N
or the positive
charge of P+. In the reverse redox process, Li+ or A
will migrate
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back from the electrode to the electrolyte. For many n-type
organics, Li+ can be substituted by other alkali metals (e.g., Na+
and K+) or even H+, which will not aect signicantly the elec-
trochemical behavior of the material. This is greatly dierent
from inorganic intercalation compounds, which are very
sensitive to the radius of the cation. For p-type organics, a lot of
anions can be used as A
, such as ClO4
, PF6
, BF4
and TFSI

in non-aqueous electrolyte, or Cl
and NO3
in aqueous
electrolyte.
To assemble a rechargeable battery, we need to match the
cathode with an anode. First, there must be a voltage gap large
enough for practical use between a cathode with higher redox
potential and an anode with lower redox potential. But that is
not enough; we should also consider the redox state of the active
material in both the cathode and anode. For instance, if the
anode is in its reduced state in a fresh cell, it should be rstly
oxidized. Meanwhile, there must be a reduction reaction on the
cathode because the electron is transported from the anode to
the cathode though the external circuit, thus the cathode must
be in its oxidation state in the fresh cell. Vice versa, if the anode
is in its oxidation state initially, the cathode must be in its
reduction state.
Based on the above considerations, we demonstrate four
types of possible cell conguration for rechargeable lithium
batteries (Fig. 2). If the anode is in a reduced state and the
Fig. 1 The redox reaction of three types of electroactive organics: (a) n-type; (b)
p-type; (c) bipolar. A
means anion of the electrolyte and Li+ can be replaced by
other alkali ions.
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cathode is in an oxidised state in a fresh cell, the rst step of
charge/discharge cycling is discharging (Fig. 2a and c). In the
reversed situation, the rst step is charging (Fig. 2b and d).
Whatever the cell conguration, each organic electrode material
can nd its role. Theoretically, n-type organics may exist in the
N or Li+N
form, while p-type organics may exist in the P or P+A

form, and all these four forms can be applied as either the
anode or cathode, according to their redox potential. But in fact,
Li+N
is always unstable in an ambient atmosphere because of
the spontaneous hydrolysis reaction and oxidation reaction,
especially when the N/N
redox potential is lower than 2.5 V vs.
Li+/Li, so it is unlikely that Li+N
can be used as an anode. For p-
type organics, the P+/P redox potential is always higher than 2.5
V vs. Li+/Li, so either P or P+A
is unlikely to be usable as an
anode. In another word, organics prefer to be applied as the
cathode in rechargeable batteries with dierent forms, such as
N, Li+N
, P+A
and P in Fig. 2ad, respectively. We only consider
the situation of N as organic anode, (Fig. 2b and d) because it is
stable in an ambient atmosphere and has the possibility to
possess a relatively low redox potential. For bipolar organic B
(Fig. 1c), we can treat it as N or P according to the actual redox
reaction occurring on the electrode.
Among the four cell congurations in Fig. 2, (a) and (b) are
two most common cases to researchers, in which Li+ is the
deposition or insertion ion for both the anode and cathode. The
rst generation of rechargeable lithium batteries belongs to
conguration a, which involves Li metal or alloy as the anode
and Li source. Layered TiS2 was the best intercalation cathode at
that time.1 This type of battery was eliminated from the market
because of the serious safety issue caused by Li dendrite.
However, because Li metal possesses the highest theoretical
capacity (3680 mA h g
1) and it can match with many high
capacity cathodes, such as S and O2, the study of the Li anode
has never stopped. For an n-type organic cathode, this is also
the most favored conguration, and most of the literature on
organic electrode materials has to adopt this conguration,
since the Li+N
form is usually dicult to synthesize and store.
Fig. 2b shows the cell conguration of an Li-ion battery,
consisting of a reduction state cathode as the Li source such as
LiCoO2 and LiFePO4, and an oxidation state anode such as
graphite, Li4Ti5O12 and Si. Li metal can be also applied as the
anode in this system, which is widely used as a half-cell in
research, but it plays the role of a substrate and current collector
instead of the active material. In this conguration, the n-type
organic can nd its role as either the anode or cathode. N with a
lower redox potential can be applied as the anode, which has
been realized in a few researches (see Section 4.2). Although we
have mentioned that Li+N
is dicult to synthesize and store, it
is not a unsolvable problem if we really want to use it as cathode
to match with a Li-free anode. Especially when the N/N
redox
potential is relatively high (>3.0 V vs. Li+/Li), Li+N
will not be
easily oxidized in the ambient atmosphere and we just need to
prevent it from hydrolysis. Although there is still no reported
example of an Li+N
cathode as far as we know, there have been
a few similar attempts on Li2S (ref. 15) and Li2O2 (ref. 16)
cathodes as an alternative to an LiS and LiO2 battery, which
are more dicult to realize.
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Fig. 2 The cell congurations and charge transfer processes of various types of rechargeable batteries. Bipolar organic B can be regarded as N or P in these
congurations, according to the actual electrode reaction.

Fig. 2c and d present the two possible cell congurations for 2.2 Structures and redox mechanisms
p-type organics. In these two cases, A
has to transport
In the above discussion, we have listed the abstract redox
between the cathode and the electrolyte, while Li+ has to
reactions of dierent electroactive organics, (Fig. 1) but that is
transport between the anode and the electrolyte, which causes
not enough for us seeking for new organic electrode materials.
the concentration change of the electrolyte. In Fig. 2a and b, We must gure out what kind of organic structures and redox
the electrolyte just plays the role of cation conductor, and we
mechanisms can be applied in electrode materials. In Table 1,
usually try to use as little electrolyte as possible to improve the
we categorize them into seven types, which cover most of the
energy density of the whole cell. However, in Fig. 2d, we must
researches on organic electrode materials in the past decades.
add enough electrolyte to provide sucient Li+ and A
for
Among the seven types of structures, organodisulde and
electrode reactions and meanwhile ensure the ion conduc-
conjugated carbonyl belong to n-type organics, conjugated
tivity. In Fig. 2c, although it is unnecessary to add excess
amine and conjugated thioether belong to p-type organics,
electrolyte, we should conrm that the electrolyte and P+A

while conjugated hydrocarbon and nitroxyl radical belong to
cathode contain the same anion A
, otherwise this may aect bipolar organics. It is may be controversial to list thioether (4e)
the electrochemical performance. Another thing that should be
as one type, because the redox mechanism does not belonging
noted is that when calculating the specic capacity of p-type
to any type in Fig. 1 and has not been clearly veried, but we still
organics, we must specify whether it is based on the mass of P
take it into account to show the possibility of multi-electron
or P+A
, because A
always takes up a big part of the molecular
reactions of organic electrode materials. Another thing that
weight.

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Table 1 The structure and redox mechanism of various types of organic electrode materials

Structure Redox mechanism Examples References

Conjugated hydrocarbon 3234

Conjugated amine 3538

Conjugated thioether 39,40 and 129

Organodisulde 58 and 64
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Thioether (4e) 67 and 68

Nitroxyl radical 7072

Conjugated carbonyl 107 and 99

Fig. 3 The redox voltage and specic capacity of typical inorganic and organic
electrode materials for rechargeable lithium batteries. The structure of each
organic can be found in Table 1, Fig. 12, Table 3 and Fig. 16.

should be noted is that although nitroxyl radicals are bipolar, Fig. 4 Simplied cycle life of sustainable rechargeable batteries. Reprinted with
permission from ref. 25. Copyright 2008 WILEY-VCH.
they are always regarded as p-type organics in practical use to
obtain stable electrochemical performance (see Section 3.4).

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Table 2 Some electrochemical parameters of typical conducting polymers

Doping level Theoretical capacity/ Redox potential

Name Structure (xmax) mA h g
1 (V vs. Li+/Li)

02.0 (n)
Polyacetylene (PAc) 0.07 144 3.54.0 (p)

01.0 (n)
Polyparaphenylene (PPP) 0.4 141 4.04.5 (p)

Polyaniline (PAn) 1.0 295 3.04.0

Polypyrrole (PPy) 0.33 136 3.04.0

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Polythiophene (PTh) 0.25 82 3.04.2

Fig. 5 Typical electrochemical redox process of p-type conducting polymer.

Generally, a reversible redox reaction usually occurs on an

organic group or moiety with conjugated structure and atoms
with lone pair electrons, such as N, O and S. This is reasonable,
because a conjugated structure is benecial to the electron
transportation in the reaction and charge delocalization of the
redox product, and lone pair electrons usually have a higher
reaction activity. We will discuss each type of structure in detail
when we introduce the development the history of organic Fig. 6 (a) Photograph and (b) cross-section SEM image of PAn/graphene
electrode materials in Section 3. composite thin lm. Adapted with permission from ref. 50. Copyright 2010
American Chemical Society.

2.3 Requirements for electrochemical performance

Roughly speaking, every organic molecule that can undergo a
reversible electrochemical redox reaction, either a small organic
molecule or polymer, is a possible candidate electrode material
for energy storage. Based on each structure listed in Table 1, we
can design and synthesise large amount of organics. What
kinds of organics, then, are worth further research? We
summarise some basic requirements for these organic candi-
dates, mainly on electrochemical performance.
(a) Reaction reversibility: here reversibility means not only
chemical reversibility, but also thermodynamic reversibility. It

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Fig. 7 Typical organodisuldes and their theoretical capacity: tetraethylthiuram disulde (TETD),53 poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT),5762 poly(2,20 -
dithiodianiline) (PDTDA),63 poly(5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene) (PDTTA).64 The capacity of PDTDA is based on the assumption that each aniline unit
can contribute 0.5 e and ignores the mass of A
.
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Fig. 8 Typical nitroxyl radical polymers and their theoretical capacity:

poly(2,2,6,6-tetramethylpiperidine-1-oxyl-4-yl methacrylate) (PTMA),69,73,74,8385
poly(2,2,6,6-tetramethylpiperidine-1-oxyl-4-yl vinyl ether) (PTVE),22,75,76 poly-
(TEMPO-substituted norbornene) (PTN),77,80,81 poly(2,2,5,5-tetramethylpyrroli-
dine-1-oxyl-3-yl ethylene oxide) (PTEO).82

is an important factor determining the electrochemical polari-

zation and rate capability of the electrode material. The
dierent reaction mechanisms in Table 1 show huge dierences
in reaction kinetics. For example, organodisulde and thioether
(4e) always show very slow reaction kinetics, because the bond
breaking/forming of the SS or S]O bond needs a high acti-
vation energy. On the contrary, all other redox reactions show
fast kinetics. Especially, nitroxyl radical presents the highest
reaction kinetics and always leads to excellent high rate
performance.
(b) Redox potential: like the reaction reversibility, it is also
mainly determined by the electroactive organic group or
moiety. Dierent structures in Table 1 show huge dierence in
charge/discharge plateau or average charge/discharge voltage.
In Fig. 3, we can compare the redox potentials of some typical
organic electrode materials. As we mentioned above, organics
prefer to be applied as the cathode rather than the anode,
since their redox potentials are usually between 2.0 and 4.0 V
vs. Li+/Li, and much lower than inorganic intercalation cath-
odes. Usually, p-type organics possess a higher redox potential
than n-type organics. For instance, nitroxyl radical TEMPO
(only TEMPO+/TEMPO couple is utilized) and conducting
polymer PAn always show a similar average charge/discharge
voltage of about 3.5 V, while organodisulde PDMcT and most
conjugated carbonyl compounds including quinones (e.g. BQ, Fig. 9 (a) Typical charge/discharge curves and (b) cycling and rate performance
of PTMA as the cathode material for a rechargeable lithium battery. Reprinted
NQ and AQ) and dianhydrides (e.g. PMDA, NTCDA and PTCDA)
with permission from ref. 74. Copyright 2006 Elsevier. (c) The electron transfer
show redox potentials below 3.0 V. Beside the functional group process in a radical polymer electrode. Reprinted with permission from ref. 70.
or moiety, the adjacent electron-withdrawing group (e.g., Cl, Copyright 2009 WILEY-VCH.
F, CN and NO2) or electron-donating group (e.g., OH, NH2

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Fig. 10 Typical electrochemical redox mechanism of quinone and dianhydride.
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Fig. 11 (a) Cyclic voltammogram of 2 mM AQ in 0.1 M TBAP/CH3CN electrolyte
at a scan rate of 100 mV s
1. Adapted with permission from ref. 86. Copyright
2005 American Chemical Society. (b) Chargedischarge curve of AQ electrode
(AQ : C : PTFE 6 : 3 : 1) in 1 M LiTFSI/DOL + DME electrolyte at a current rate of
0.2 C.
and OCH3) can also elevate or lower the redox potential
respectively, which can be forecast by theoretical chemical
calculation.17,18
(c) Theoretical capacity: the theoretical specic capacity of an
organic electrode material can be calculated by the following
formula:
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n  F C mol
1
Ct mA h g
1
Mw g mol
1
n  96 485 C n  96 485 A s
Mw g Mw g
n  96 485  1000=3600 mA h
Mw g
26 801  n

mA h g
1
Mw
in the formula, Ct, n, F and Mw respectively mean the theoretical
specic capacity, the transferred electron number in each
structural unit, the Faraday constant and the molecular weight
of the structural unit. According to this formula, there are two
ways to improve the theoretical capacity: one is adopting multi-
electron reactions and another is reducing the molecular weight
of the structural unit. For a certain reaction mechanism, n is
always specied, so the most ecient approach is to simplify
the structure, reducing unnecessary groups or moieties as much
as possible. There is also a huge dierence in the theoretical
capacity between dierent types of organic electrode materials
(Fig. 3). For example, TEMPO polymers can only achieve a
theoretical specic capacity below 140 mA h g
1 because the
monomer molecular weight is large, and only one electron
(TEMPO+/TEMPO) can be reversibly transferred-in per struc-
tural unit. In contrast, conjugated carbonyl based
materials present a large capacity range from 100 mA h g
1 to
600 mA h g
1.
(d) Solubility: one major problem of organic electrode
materials is the dissolution of the active material in the elec-
trolyte, which aects signicantly its cycling stability. Generally,
small organic molecules cannot avoid dissolution in the elec-
trolyte, either aqueous or non-aqueous, so they always show low
discharge capacity and poor cycling performance. In contrast,
polymers are always insoluble in the electrolyte, and likely to
obtain good cycling performance.
(e) Synthesis and cost: it is much easier to design an organic
electrode material than to synthesize it, and some organics
with optimal structure are very dicult or even impossible to
synthesize. As a result, a compromise must sometimes be
made between structure optimization and synthesis simpli-
cation. Since the research on organic electrode materials is still
in its early stage, we usually do not care about the cost of the
raw material and synthesis. However, if they come to the
application stage in the future, cost is an important factor to
consider. In other words, it is better to investigate those
organics with simple structures, cheap raw materials and easy
synthesis.
In summary, the above ve factors are the basic require-
ments guiding us to design and evaluate organic electrode
materials. It is necessary to take all these factors into account
before experiments. For dierent applications, we usually
emphasize one or two factors. For example, we should choose
structures with high reaction reversibility for high power
density electrodes, and structures with both high redox poten-
tial and high theoretical capacity for high energy density
cathodes.
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Fig. 12 Typical small organic molecules based on conjugated carbonyl groups and their theoretical capacity. (a) Simple quinones: benzoquinone (BQ),21,87 naph-
thoquinone (NQ), anthraquinone (AQ),86,88,89 phenanthraquinone (PQ).90 (b) Quinone derivatives: 2,5-dimethoxy-1,4-benzoquinone (DMBQ),21,91 2,3,5,6-tetrachloro-
1,4-benzoquinone (chloranil),87,92,93 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ),87,90,94 1,2,4-trihydroxyanthraquinone (purpurin).24 (c) Multi-carbonyl quinones:
5,7,12,14-pentacenetetrone (PT),95 nonylbenzohexaquinone (NBHQ).96,97 (d) Simple dianhydrides: pyromellitic anhydride (PMDA),98 1,4,5,8-naphthalenetetracarboxylic
dianhydride (NTCDA),99,100 3,4,9,10-perylentetracarboxylic dianhydride (PTCDA).99 (e) Other conjugated carbonyl compounds: dichloroisocyanuric acid (DCA),9 N,N0 -
diallyl-2,3,5,6-tetraketopiperazine (AP),101 5,50 -indigodisulfonic acid sodium salt (indigo carmine).102 The theoretical capacity is calculated based on the carbonyl group
number except dianhydrides and AP.

2.4 Advantages and challenges commercial LiCoO2 (550 W h kg
1) and potential
In recent years, we nd a tendency in the development of various xLi2MnO3$(1
x)LiMO2 (1000 W h kg
1).4
(b) High power density: since many organic redox mecha-
photoelectric materials in that organics are replacing inorganics.
nisms intrinsically have much faster reaction kinetics than
A lot of organic photoelectric materials19,20 have actually already
inorganic intercalation cathodes, organic materials based on
been applied in photoelectric devices such as organic light-
these reactions are potentially high-power electrode candidates.
emitting diodes (OLEDs), photovoltaic (PV) devices and eld-
In Table 1, except organodisulde and thioether (4e), it is
eect transistors (FETs). This is because on one hand the
possible for all other organic structures to achieve high rate
performance of organics is comparable or even superior to
conventional inorganics, on the other hand organics have many performance. For example, nitroxyl radical polymer22 can retain
incomparable advantages to inorganics. For energy storage 97% of its theoretical capacity even at a charge rate of 1200 C
and discharge rate of 60 C in aqueous electrolyte.
devices, we believe this tendency is also applicable based on the
(c) Structure diversity: although there have been tremendous
following advantages of organic electrode materials.
researches on inorganic cathode materials, most of them focus
(a) High energy density: in Fig. 3, it is found that the relatively
on a few materials. At present, it becomes more and more
lower redox potential of organic cathodes can be oset by their
dicult to nd new types of inorganic cathodes and make a
much higher theoretical capacity, thus it is still possible for
breakthrough in battery performance. But for organic cathodes,
them to obtain high energy density. For instance, benzoquinone
(BQ)21 possesses a theoretical energy density of about 1400 W h there are huge possibilities in both the structures and proper-
kg
1, calculated from its redox potential of 2.8 V and theoretical ties. Besides the structures listed in Table 1, there are still many
other structures and redox mechanisms to be discovered.
capacity of 496 mA h g
1. This is much higher than that of

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Fig. 13 Typical polymer electrode materials based on conjugated carbonyl
groups and their theoretical capacity: polymeric quinone (PQ),104 poly(5-amino-
1,4-naphthoquinone) (PANQ),105 poly(2,5-dihydroxy-1,4-benzoquinone-3,6-
methylene) (PDBM),106,107 poly(anthraquinonyl sulde) (PAQS),108,109,113 poly(2-
vinylanthraquinone) (PVAQ),110 polymer-bound pyrene-4,5,9,10-tetraone
(PPYT),111 polyimide (PI-2 and PI-5).112,113 The theoretical capacity is calculated
based on the carbonyl group number, except for PI-2 and PI-5.
Fig. 14 (a) Cycling performance and (b) rate performance of PPYT. The cathode
(PYT or PPYT : AB : PVDF 3 : 8 : 2) is tested in LiTFSI/tetraglyme electrolyte at 45

C. For (a) PYT is tested at 0.2 C while PPYT is tested at 1 C. Reprinted with
permission from ref. 111. Copyright 2012 American Chemical Society.
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Fig. 15 Comparison between the electrochemical performance of AQ and PAQS
as cathode materials for rechargeable lithium batteries. The cathode (AQ or
PAQS : C : PTFE 6 : 3 : 1) is tested in 1 M LiTFSI/DOL + DME electrolyte at a
current rate of 0.2 C.
(d) Flexibility: recently there is a tendency of making devices
thinner, smaller, exible and wearable. In this respect, organic
materials show inherent advantages compared to inorganics.
Besides the conventional way of making electrode, there may be
many other methods to fabricate organic electrodes including
casting, printing and vapor deposition, due to their character-
istics of solubility, lm-forming ability and sublimability.
(e) Sustainability: the large-scale use of transition metal based
electrode materials is somewhat of an unsustainable route
towards the devolvement of energy storage devices, because of
resource limitations, environmental pollution and large energy
consumption in both synthesis and recycling.3 Ideally, organic
electrode materials could be extracted directly23,24 or eventually
synthesized26,27 from biomass and recycled through carbon
dioxide cycling (Fig. 4). In the whole process, there is no addi-
tional CO2 produced and much less energy is consumed during
chemosynthesis and thermal recycling.
In above discussion, we have summarized the main merits of
organic electrode materials. However, many of them have not
been realized at present and it is also full of challenges in the
research and commercialization of organic electrode materials.
(a) Low mass density: as we know, organics usually have a
much lower mass density than inorganics because of their
dierent elements and crystalline state. This is not a problem
when we are just concerned about the gravimetric energy
density. However, for energy storage devices emphasizing the
volumetric energy density, such as rechargeable lithium
batteries used in mobile phones and electric vehicles, this is a
big drawback and only those organics with much higher gravi-
metric energy density are competitive.
(b) Low electronic conductivity: except conducting polymers,
almost all other organic electrode materials are electrical
insulators, which seriously hinder the full utilization and high
rate performance of the active materials. Just like the
approaches for the LiFePO4 and S cathode, adding sucient
conductive carbon through a proper method can signicantly
improve the electron transport in the electrode and ensure a
high utilization ratio of the active material. However, compared
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Table 3 Typical organic salts based on conjugated carbonyl and their electrochemical parameters. Note that the practical capacity is usually approximate

Redox potential Theoretical capacity/ Practical capacity/

Formula Structure (V vs. Li+/Li) mA h g
1 mA h g
1 Reference

Li2C6H2O4 1.72.5 353 176 114

Li2C6O6 1.53.5 589 500 26

Li4C6O6 1.62.0 274 200 115

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Li2C14H6O4 1.52.5 213 126 116

Li2C6H4O4 1.31.5 348 150 117

Li2C8H4O4 0.71.0 301 300 117

Na2C8H4O4 0.20.6 V vs. Na+/Na 255 250 118120

Li2C16H8O4 0.60.7 193 200 121

Li2C18H12O8 1.62.0 145 (2e) 125 122

Li2C10H2N2O4 1.52.0 235 (2e) 200 123

Li2C14H4N2O4 1.82.8 193 (2e) 140 124

to inorganic cathodes, a much larger amount of conductive
carbon should be used due to their low mass density and high
surface area, thus the mass ratio of active material in the whole
electrode is only 2070% in previous researches. The best
approach to overcome this drawback is adopting organics with a
large conjugated structure, or mix active materials with excel-
lent conductive carbon (e.g., CNT or graphene) on a molecular
level (see Section 4.3).
(c) Dissolution: as mentioned above, the unwanted dissolu-
tion of active materials in the electrolyte is a major problem for
organic electrode materials over a long period. For many small
organic molecules, the dissolution is very serious and the
shuttle eect makes the cell unrechargeable. The most ecient
strategy to solve this problem is to design and synthesise
organic polymers with a stable skeleton and a highly electro-
active moiety, since they are always insoluble in commonly used
electrolytes for batteries. There is also another type of polymer,
the coordination polymers, which connect electroactive moie-
ties with coordination bonds between the metal ions and N, O
or S atoms. The coordination bond can hinder the dissolution
of electroactive moieties but essentially cannot avoid this
problem (see Section 3.5.3).

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Fig. 16 Other organic electrode materials and their theoretical capacity: poly-
triphenylamine (PTPAn),125 triquinoxalinylene,126 poly(N-vinylcarbazole) (PVK),127
triazine,128,129 sulfur-linked tetrathionaphthalene polymer [poly(S-TTN)],130 poly-
(vinylferrocene),131 tetracyanoquinodimethane (TCNQ),90,132 poly-
(galvinoxylstyrene),81 polymeric 2,5-di-t-butyl-1,4-dialkoxybenzene (PDBDAB).133
Fig. 17 Redox reaction and charge/discharge curves of Na2C8H4O4 anodes for
Na-ion batteries. Adapted with permission from ref. 118. Copyright 2012
WILEY-VCH.
(d) Li metal anode: for the majority of organic electrode
materials, especially n-type organics, Li metals or alloys must be
applied as the anode and lithium source, which brings about
serious safety issue in practical use.10 Since LiS and LiO2
batteries also face this problem, there have been many attempts
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Fig. 18 (a) TEM image of PAQS/graphene composite synthesized by in situ
polymerization. (b) Voltage proles of PAQS/graphene composite (PAQS :
graphene 74 : 26) at dierent C-rates. The capacity is calculated based on the
mass of the whole composite. Reprinted with permission from ref. 113. Copyright
2012 American Chemical Society.
at Li surface protection28 or lithium powder/carbon composite
anodes.29,30 It is expected that this problem will be nally
resolved to realize high energy density batteries with Li metal
anodes.
3 Development history of organic electrode
materials
We have discussed a lot of fundamental knowledge on organic
electrode materials, but it is still necessary to elaborate the
dierent types of organic electrode materials in detail. Since the
main organic structures and redox mechanisms have been
divided into seven types in Table 1, the elaboration is approxi-
mately according to this classication and roughly in a chro-
nological order. Note that the rst three types of conjugated
structures (Table 1), including hydrocarbons, amines and thi-
oethers, are all attributed to conducting polymers, because they
mostly exist in this form and demonstrate many similar prop-
erties. Another thing that should be noted is the chronological
order is based on the period when one type of organic electrode
material is intensively studied, which is more appropriate for us
to understand their development history and tendencies. Since
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Fig. 19 (a) Possible exible thin lm battery based on n-type organic as cathode and carbon (CNT or graphene) paper as current collector. (b) Possible all-solid thin lm
battery based on n-type organic as cathode and solid Li-ion conductor as electrolyte. (c) Photograph of exible graphene paper. Reprinted with permission from ref. 52.
Copyright 2013 Royal Society of Chemistry. (d) Photograph of a exible, transparent and conductive CNT thin lm on a plastic substrate. Reprinted with permission
from ref. 142. Copyright 2011 WILEY-VCH. (e) Photograph of transparent PTN thin lm on an ITO-PET substrate prepared by a photocrosslinking approach. Reprinted
with permission from ref. 77. Copyright 2007 Royal Society of Chemistry. (f) Photograph of ink-jet printed supercapacitor on Xerox paper. Reprinted from ref. 145.
Copyright 2010 American Institute of Physics.

Fig. 21 Comparison of the comprehensive electrochemical performance

between dierent types of organic electrode materials. Note that this is only a
rough estimation and it is not suitable to compare specic organics.

conjugated carbonyl compounds (Section 3.5) are not only the

earliest type of organic electrode materials, but also the most
Fig. 20 A possible all-organic battery based on conjugated carbonyl cathode
and anode. attractive and fruitful research eld at present, we will pay more
attention to this part.

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3.1 Conducting polymers (1981) pristine state. Because of the low doping level of PAc, PPP, PPy
31 and PTh, their theoretical capacity is less than 150 mA h g
1 and
Since the discovery of conducting polymers in 1977, scientists
the practical capacity is much lower than this value. It is
found that they can achieve not only the electronic conductivity
possible for PAn to achieve a full-oxidation state (xmax 1) in
of semiconductors or even metals, but also the redox activity of
non-aqueous electrolyte and thus it has the highest theoretical
electrode materials. Thus there have appeared a lot of
capacity of 295 mA h g
1, but it is dicult for the practical
researches on conducting polymers as electrode materials for
capacity based on the total mass of P and A
in the pristine state
rechargeable batteries since 1981.32 Among various conducting
polymers studied in the past decades, there are ve typical ones to exceed 150 mA h g
1.
including polyacetylene (PAc),32,33 polyparaphenylene (PPP),33,34 As previously mentioned, p-type organics always present
relatively higher redox potential than n-type organics. For the
polyaniline (PAn),35,36 polypyrrole (PPy)37,38 and polythiophene
conducting polymers listed in Table 2, the redox potentials are
(PTh)39,40 (Table 2). Although in Table 1 we attribute them to
all above 3.0 V. For PPP, the redox potential (4.04.5 V) is even
three types of structures, they actually show many similar
higher than most inorganic electrode materials. However,
electrochemical behaviors.
because of the much lower specic capacity, the energy density
Among the ve typical conducting polymers, PAn, PPy and PTh
of conducting polymers is not comparable to inorganics.
are regarded as p-type organics, while PAc and PPP are belong to
Another critical drawback of conducting polymers is their poor
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bipolar organics (Fig. 1). When used as cathode, PAc and PPP can
be also attributed to p-type organics. Unlike other p-type organics,
conducting polymers always exist in the p-doping state instead of
the electroneutralization state. It is well known that electroneutral
polymers are absolute insulators and only doped polymers show
greatly improved electronic conductivity, which was the rst
discovery in conducting polymers.31 Except for PAc, all other
conducting polymers are pristinely in the p-doped state, synthe-
sized by either chemical36 or electrochemical41 oxidation poly-
merization. The ratio of doped units to all structural units is
dened as the doping level or doping degree, expressed as x in
(Px+$xA
)n (0 # x # 1). P means the structural unit in the con-
ducting polymer, which is equal to CH for PAc.
In Fig. 5, we demonstrate the typical electrochemical redox
process of a p-type conducting polymer as cathode material. The
open circuit voltage (OCV) of the cathode material strongly
depends on the doping level, thus the gradient of the voltage
prole is very sloping. Since the as-synthesized conducting poly-
mer is in an intermediate state (B point), it can be rstly either
discharged to the full-reduction state (A point) or charged to a
semi-oxidation state (C point) when using Li metal as the anode
(Fig. 2c and d). However, it is unlikely to charge to the full-
oxidation state (D point). For most conducting polymers, the full-
oxidation state is very unstable and it begins to decompose
(usually involving reaction with the electrolyte) aer the C point,
due to the serious charge repulsion interaction between structural
units. We dene Vmax as the highest cuto voltage for conducting
polymers to achieve both large capacity and acceptable cycling
performance, accordingly the highest doping level is xmax.
The xmax is an important factor to estimate the theoretical
capacity of a conducting polymer. However, even for a specied
conducting polymer, xmax was greatly dierent in previous
researches. This is because xmax is strongly depends on the
synthesis conditions, anion type and electrochemical test
conditions. In order to compare the electrochemical perfor-
mance between dierent conducting polymers, we adopt the
highest reliable xmax values in the literature11 and calculate their
theoretical capacity based on these values (Table 2). Note that
the theoretical capacity is based on the molecular weight of only
the P unit in (Px+$xA
)n, while the experimental specic capacity
is mostly based on the molecular weight of Px+$xA
in the
cycling stability, especially when increasing the cuto voltage
for higher capacity. This is mainly because the irreversible
overoxidation reaction at high voltage makes more-and-more
structural units inactive during charge/discharge cycling. In
addition, the low Coulombic eciency and self-discharge
phenomenon are also two negative factors hindering the prac-
tical application of conducting polymers in rechargeable
lithium batteries.
In spite of the above disadvantages, the greatest strength of
conducting polymers is their high electronic conductivity.
Therefore the most appropriate application for energy storage is
as a cathode for supercapacitors42,43 or as a conductive additive
in composite cathode materials.44,45 PAn and PPy are two of the
most promising in these applications due to their simple
synthesis, relatively high energy density and cycling stability.
The pseudocapacitor based on a conducting polymer cathode
can undergo a fast redox reaction in the bulk of the material, so
it can obtain a much superior capacitance compared to
conventional electrochemical double-layer capacitors (EDLC)
based on carbon electrodes.43 Since their electrochemical
performance can be promoted by improving the surface area,
electronic conductivity and ion conductivity, recently there has
been a lot of research work on the synthesis of nanostructured
conducting polymers,46,47 as well as nanocomposites of con-
ducting polymers with CNT48 or graphene.4952 Especially for
PAn, there have been many attempts to prepare PAn/graphene
composite paper or thin lms,4952 which can obtain both high
electrochemical performance and high exibility (Fig. 6).
3.2 Organodisuldes (1988)
It is known that SS bond can be reversibly broken and rebuilt,
and the two-electron redox reaction (Table 1) can provide a
much larger capacity than the doping/undoping reaction of
conducting polymers. Therefore there has appeared a large
amount of research on organodisulde (Fig. 7) cathode mate-
rials since 1988,53 most of which was done by S. J. Visco et al.5356
and N. Oyama et al.5762 In order to clearly understand the
electrochemical behavior of organodisulde cathode materials,
we divide their development history into the following three
stages.

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(a) Dimeric organodisuldes: in 1988, S. J. Visco et al. rstly
introduced TETD as a cathode material for a high temperature
sodium battery.53 Later they studied some other dimeric orga-
nodisuldes and the reaction kinetics of the RSSR/2RS
reac-
tion.54 Due to the high solubility of RSSR and RS
in organic
electrolytes, it is unlikely that these kind of organodisuldes
can be applied in rechargeable lithium batteries.
(b) Polymeric organodisuldes with SS bonds in the main
chain: This kind of polymer is mainly synthesized from dimer-
captan or multimercaptan by oxidation polymerization.55,56 The
most typical example is PDMcT,5762 which has attracted the
most attention among all organodisuldes due to its high
theoretical specic capacity (362 mA h g
1). Note that although
the oxidised state of PDMcT is polymer, the discharged product
DMcT2
is a small organic molecule, and sometimes DMcT is
directly used as the active material in the reduced state. Due to
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the serious dissolution of small organic molecules in the elec-
trolyte, the cycling stability of this kind of polymer cathode is
still very poor. Another critical problem is the slow reaction
kinetics of the SS bond, which results in low utilization of
active material at ambient temperature. In 1995, N. Oyama et al.
discovered the electrocatalysis eect of PAn for the redox reac-
tion of DMcT.58 Later, they also found that the addition of Cu2+
can further improve the battery performance of DMcT due to its
electrocatalysis and stabilization eect.59 From then on, there
appeared a lot of researches on DMcT/PAn and DMcT/PAn/Cu(II)
composite materials.6062 However, the battery performance is
still far from practical use because of intrinsic dissolution
problem and slow kinetics.
(c) Polymeric organodisuldes with SS bonds in the side chain:
This kind of polymer consists of conducting polymer as the
main chain and SS bonds in the side chain, two typical
examples of which are PDTDA63 and PDTTA.64 Although PDTDA
contains an insoluble and electronically conductive main chain,
the cycling performance is still poor because the dislocation of
the two main chains aer discharging hinders the rebuilding of
the SS bond. Therefore, researchers proposed another type of
polymer with SS bonds on the side of the same chain, such as
PDTTA. This design can solve both the dissolution problem and
dislocation problem, but the electrochemical performance of
PDTTA is still unsatisfactory mainly due to the slow kinetics.
In summary, organodisuldes were recognized as promising
organic cathode materials for rechargeable lithium batteries in
the 1990s. In order to overcome the problem of dissolution and
slow kinetics, scientists have made huge eorts in optimizing
the polymer structure and incorporating electrocatalytic addi-
tives. However, the intrinsic drawbacks are dicult to overcome
completely, and the electrochemical performance of organo-
disuldes is unlikely to be improved to an acceptable level for
practical use. Therefore, the research on this topic has almost
disappeared in recent years.
3.3 Thioethers (20072009)
In the research of organosulde cathode materials, C. Zhan
et al.6568 found that sometimes the material can deliver a much
higher capacity than its theoretical value when certain
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electrolytes (e.g., LiTFSI/DOL + DME) and a high cuto voltage
(e.g., >4.2 V) is applied. They speculated this is related to the
four-electron reaction of thioethersulfoxidesulphone (Table
1) Therefore they tested several thioethers as cathode materials,
either conjugated66,67 or unconjugated.65,68 For instance,
poly(3,4-ethylenedioxythiophene) (PEDOT)67 and poly-
(tetrahydrobenzodithiophene) (PDBDT)68 (Table 1) can achieve
a discharge capacity of as high as 500800 mA h g
1, with a
discharge voltage between 1.5 and 2.5 V. In spite of the high
energy density, the reaction polarization is too large and the
cycling performance is very unstable. Moreover, the cells cannot
avoid becoming dead aer dozens of charge/discharge cycles.
This is probably due to the unusual reaction mechanism, in
which the electrolyte plays an important role in providing O
atoms to form sulfoxide and sulphone groups. Since the
detailed reaction mechanism is still unknown yet, and the poor
cycling stability is far from practical use, this type of thioether
cathode materials has no practical signicance except showing
the possibility for multi-electron reaction of organics.
3.4 Nitroxyl radical polymers (2002)
In 2002, K. Nakahara et al.69 rstly proposed a stable nitroxyl
radical polymer, namely PTMA (Fig. 8), as cathode material for
rechargeable lithium batteries. Aer 2007, there appeared a lot
of researches on radical polymer electrode materials,7072 mostly
based on nitroxyl radicals, such as 2,2,6,6-tetramethylpiper-
idine-1-oxyl (TEMPO) and 2,2,5,5-tetramethylpyrrolidine-1-oxyl
(PROXYL) (Table 1). The majority of research works on this topic
were done by K. Nakahara et al.69,7376 and H. Nishide
et al.22,70,71,7783 Although in previous reviews7072 other radicals
were also categorized as radical polymer electrode materials,
and those batteries were dened as organic radical batteries
(ORBs), only nitroxyl radical polymers are discussed here; but
other radical polymers will be also mentioned in Section 3.6.
In Table 1, the reaction mechanism of nitroxyl radical indi-
cates it is a bipolar organic, but there is little research on its two-
electron reaction.78,85 In most cases, they are used as p-type
polymers in order to obtain high discharge voltage and stable
cycling performance. Thus, conguration d in Fig. 2 must be
adopted for a nitroxyl radical polymer to assemble a cell. In spite
of the A
consumed from the electrolyte, the theoretical capacity
of nitroxyl radical polymers is strictly limited by the one-electron
reaction and their large molecular weight. In Fig. 8, we list the
structures and theoretical capacities of some typical examples,
including PTMA, PTVE, PTN and PTEO. The highest theoretical
capacity of these polymers is only 147 mA h g
1 and it is unlikely
to be further improved by structure optimization.
Fig. 9a and b show the typical battery performance of PTMA,74
which is the most studied among various nitroxyl radical poly-
mers due to its sucient stability and relative high capacity. The
charge/discharge plateau is very at at 3.5 V and the utilization
ratio is close to 100%. The cycling and rate performance of PTMA
are also excellent due to the stable polymer structure and fast
reaction kinetics of the radical. Other TEMPO based polymers
always show similar electrochemical behavior but dierent
specic capacity. The greatest strength of nitroxyl radical
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polymers is their high rate performance. If the electrode is well
fabricated, TEMPO based polymers can easily sustain a current
rate of 20 C or 50 C. This arises mainly from the fast electron self-
exchange reaction between adjacent TEMPO units (Fig. 9c),70
which result in the ecient electron transfer despite the insu-
lating polymer main chain.
3.5 Conjugated carbonyl compounds (1969)
Quinone is a type of well-known organic with good electro-
activity. The redox mechanism can be generalized as an enoli-
zation reaction and a reverse reaction of the carbonyl group,
which can be promoted by a conjugated structure (Table 1). In
fact, besides quinone, many other conjugated carbonyl
compounds can also undergo a similar electrochemical redox
reaction. Based on their high theoretical capacity, fast reaction
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kinetics, as well as their structural diversity, we believe they are
the most promising type of organic electrode materials so far.
In Fig. 10, we take AQ and NTCDA as examples, to show the
typical redox reaction of quinone and dianhydride, the two most
famous kinds of structural units among conjugated carbonyl
compounds. For a dilute AQ solution, its two-step reversible
redox mechanism involving a radical anion (AQ_
) as transition
state has been widely reported (Fig. 11a).86 However, when used
as electrode materials for rechargeable batteries, there is prob-
ably only one at charge/discharge plateau (Fig. 11b). This is may
be because AQ_
is more unstable in the solid-electrode-con-
taining conductive carbon than in the solution, thus the second
reduction step (AQ_
/AQ2
) occurs very fast and the voltage gap
between the two steps is too small to distinguish the plateaus.
This phenomenon has been also discovered for many other
conjugated carbonyl compounds with a two-electron reaction.
For NTCDA, although it has four carbonyl groups, it is
unlikely to fully utilize all of them. In order to obtain high
reversibility and cycling stability, a two-electron reaction is
usually adopted for rechargeable batteries (Fig. 10). Although
lowering the cuto voltage can further reduce NTCDA and
obtain higher discharge capacity, the structure may be
destroyed due to the serious charge repulsion interaction,
which is similar to what happened in conducting polymers at
high charging voltage. The charge repulsion interaction signif-
icantly restricts the practical capacity of electrode materials
with high carbonyl group density or multi-electron reaction.
In the above discussion we introduced briey the general
electrochemical behavior of conjugated carbonyl compounds.
In the past decades, a large amount of such materials have been
investigated as electrode materials. In order to clearly elaborate
their development history and features, we divided them into
three types: small organic molecules, organic polymers and
organic salts.
3.5.1 Small organic molecules (1969). In 1969, D. L. Wil-
liams et al.9 reported a primary lithium battery using dichlor-
oisocyanuric acid (DCA) as cathode. This is probably the rst
report on organic electrode materials. From then on, many
scientists attempted to use small organic molecules as cathodes
to assembly rechargeable batteries, with either an aqueous or
non-aqueous electrolyte. In Fig. 12, we list the typical structures
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and their theoretical capacity, mostly based on quinone and
dianhydride. Although many of them can achieve high
discharge capacity and high energy density, they all suered
from the dissolution problem and cannot obtain acceptable
cycling performance.
In order to solve the dissolution problem, researchers have
tried several approaches in recent years. On one hand, increasing
the content of conductive carbon89 or incorporating mesoporous
carbon88 can strengthen the immobilization and prevent the
active material from dissolving. On the other hand, using a solid
electrolyte (e.g., LISICON)21 or polymer electrolyte (e.g., LiTFSI/
PEO)94 can completely prevent dissolution. However, so far there
has been no satisfactory result reported. The immobilization
method cannot essentially avoid the dissolving and may probably
reduce the capacity of the whole electrode. A solid electrolyte or
polymer electrolyte will bring about low ion conductivity at
ambient temperature and large interface resistance. Although
using a liquid21 or quasi-solid94 electrode can reduce the interface
resistance, it will greatly reduce the energy density of the whole
battery. A very recent work shows that a high-salt-concentration
electrolyte is helpful in inhibiting the dissolution of polysuldes
for LiS batteries,103 which is probably also a useful strategy for
many organic electrode materials.
3.5.2 Organic polymers (1986). In 1986, J. S. Foos et al.104
attempted to synthesize polymeric quinone (PQ) from electro-
chemically synthesized poly(l,4-dimethoxybenzene) and tested
its electrochemical performance as a cathode for lithium
batteries. PQ looks like a perfect structure for polymer cathode
based on conjugated carbonyl, because of its relatively high
discharge voltage (2.53.0 V vs. Li+/Li), high theoretical capacity
(505 mA h g
1), as well as its insolubility. Unfortunately,
however, the practical discharge capacity was only about one
fourth of the theoretical value, and the cycling performance was
very poor, due to the imperfect synthesis and unoptimized test
conditions at that time.
Aer 1999, researchers have synthesized and tested many
other polymer electrode materials based on quinone and dia-
nhydride105113 (Fig. 13). Especially in recent years, many poly-
mers (e.g., PAQS,108 PVAQ,110 PPYT111 and PI-5 (ref. 112)) have
shown excellent comprehensive electrochemical performance
compared to previous results, including high capacity close to
the theoretical value, high cycling stability and high Coulombic
eciency, as well as high rate capability. For instance, PPYT can
retain 83% of its initial capacity aer 500 cycles, or 90% of its
capacity at 30 C as compared to 1 C (Fig. 14).111
Compared to monomer, polymer is always completely
insoluble in the electrolyte, either aqueous or non-aqueous.
Therefore the best way to solve the dissolution problem is by
constructing polymer electrode materials with a stable and
inactive skeleton, as well as highly electroactive organic group
or moiety. However, it will also bring about many drawbacks,
including reduced theoretical specic capacity, enlarged elec-
trochemical polarization and slow ion/electron transportation
in the electrode. For example, compared to AQ, PAQS can attain
signicantly improved cycling stability with slightly reduced
capacity (Fig. 15), but the charge/discharge curve becomes more
sloping, with slightly reduced average discharge voltage. This is
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probably related to the charge repulsion interaction between AQ
units in the polymer chain, in addition to the electronic insu-
lation of the polymer. Sometimes there is a capacity increasing
stage for the polymer electrode, identied as the activation
process (Fig. 15). We attribute this phenomenon to insucient
contact between the polymer and the electrolyte, which will be
gradually improved during the charge/discharge process.
Another major problem is the low electronic conductivity,
because most polymers are insulators. In order to fully utilize
the active material, a large amount of conductive carbon (e.g.,
3060%) is usually added during the fabrication of the elec-
trode. An alternative approach is optimizing the mixing of active
material with conductive carbon, for example, by in situ poly-
merization (Fig. 18).113 If the electrode is well fabricated,
conjugated carbonyl based polymers are likely to achieve good
high rate performance due to the fast reaction kinetics.
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3.5.3 Organic salts (2008). Since 2008, there has appeared
a new type of conjugated carbonyl compound as electrode
materials, namely organic salts or coordination polymers
(Table 3). These organic salts include Li or Na salts of hydroxyl
quinone,26,114116 conjugated dicarboxylates117121 and dianhydride
derivatives.122124 The majority of the works were done by
M. Armand, J.-M. Tarascon and P. Poizot.26,115,117,121123. The
advantage of these type of organics is that the coordination bond
such as O/Li/O can connect the small organic molecules and
partially solve the dissolution problem. Therefore they can ach-
ieve much better cycling stability compared to small organic
molecules, but are still unsatisfactory in long-term cycling.
Although these organics already contain Li ions, they are still in
the oxidation state of n-type organics. This is because the CO

group connected to Li+ cannot be utilized to contribute to the
capacity, otherwise the crystal structure will be irreversibly
broken down, resulting in poor cycling performance.
Because of the existence of the CO
group, the charge
repulsion interaction will lower the redox potential of the mate-
rial. For instance, Li2C6H2O4 (ref. 114) and Li2C14H6O4 (ref. 116)
show much lower discharge voltage than BQ and AQ, respectively.
Especially, conjugated dicarboxylates117121 always show a much
lower redox potential (e.g., 0.51.5 V vs. Li+/Li) than other
conjugated carbonyl compounds, thus they are rare organic
anode candidates for rechargeable lithium or sodium batteries.
For example, aer lithium terephthalate (Li2C8H4O4) was repor-
ted,117 there were many attempts on sodium terephthalate
(Na2C8H4O4)118120 as the anode for Na-ion battery, due to its
appropriate redox potential and relatively high capacity.
3.6 Other organic electrode materials
Except for the above-mentioned ve types of organic electrode
materials, there have also appeared many other novel struc-
tures in recent years, as listed in Fig. 16. Among them, triazine
is a bipolar organic, TCNQ and poly(galvinoxylstyrene) belong
to the n-type organics, while the others are all of the p-type.
PTPAn, triquinoxalinylene and PVK all have a conjugated
amine structure, so their redox mechanism is similar to that of
PAn and PPy (Table 1). In spite of the low theoretical capacity
of PTPAn,125 it shows excellent rate capability at 20 C and
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cycling stability over 1000 cycles, mainly beneting from its
structural specicity. Triazine128,129 is another conjugated
amine structure, but unlike others, its bipolar property can
provide it with a much larger reversible capacity between 1.5
and 4.5 V vs. Li+/Li. Poly(S-TTN)130 contains both the structure
of SS bond and thianthrene (TA), but its reaction mechanism
is dierent from other organodisuldes when tested between
2.8 and 4.4 V. It is similar to the p-type reaction of PTh
(Table 1), but with much higher specic capacity and cycling
stability. Poly(vinylferrocene)131 is a rare example of an organ-
ometallic electrode material, involving the well-known ferro-
cene redox moiety. It shows a redox potential of about 3.5 V
and a specic capacity closed to the theoretical value (126 mA
h g
1). Although the present result is not so satisfactory, it is
expected to be a high power cathode candidate because of the
fast reaction kinetics of the ferrocene unit. It also inspires us
that organometallic electrode material may be another
important development direction besides organics and inor-
ganics. TCNQ90,132 has similar electrochemical behavior to
quinone, with an even higher redox potential (2.83.2 V) than
BQ, due to the strong electron-withdrawing eect of four CN
groups. Besides the nitroxyl radical, there are still many other
kinds of stable radicals that have been investigated as elec-
trode materials, such as poly(galvinoxylstyrene)81 and
PDBDAB.133 Galvinoxyl is a n-type radical with a redox potential
of about 3.0 V, while dialkoxyaryl is a p-type organic with a
redox potential of about 4.0 V. Like the nitroxyl radical
polymers, the greatest strength and weakness of poly-
(galvinoxylstyrene) and PDBDAB is, respectively, the fast reac-
tion kinetics and the low theoretical capacity. Although many
of these organics are inappropriate for practical use due to
their low energy density, they indicate the great structural
diversity of organic electrode materials. Some structures can
also inspire and encourage us to design and investigate new
electrode materials with higher electrochemical performance.
4 Perspective applications of organic
electrode materials
The high electrochemical performance, in addition with the
unique properties of organics such as exibility, processability
and structure diversity, provide organic electrode materials with
great opportunities to be applied in various types of energy
storage devices, as either cathodes or anodes, with either
aqueous or non-aqueous electrolytes, in either the bulk or thin-
lm forms. Note that the following classications are according
to dierent standards, so sometimes they may overlap
each other.
4.1 Cathodes for Liorganic or Naorganic batteries
In previous researches, almost all organic electrode materials
were investigated in a half-cell with Li metal as the anode and
sucient non-aqueous electrolyte, because it is compatible with
either n-type or p-type organics, with ether high or low redox
potential (Fig. 2). However, in practical use, n-type organics are
more appropriate than p-type organics because they do not
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consume electrolyte during the charge/discharge process. Since
the Li+N
cathode is dicult to synthesise and store in an
ambient environment, n-type organic cathode materials are
unlikely to replace inorganic cathodes in conventional Li-ion
batteries with graphite as the anode. Thus the best choice for
the organic cathode to be used in a rechargeable lithium battery
is conguration a in Fig. 2. We dene it as an Liorganic battery,
following the denition of the LiS battery and LiO2 batteries. ion diusion kinetics in the bulk inorganic particles. Con-
As discussed in Section 2.4, the safety issue of an Li metal anode
is a common challenge faced by LiS, LiO2 and Liorganic
batteries. Beyond that, although Liorganic battery cannot
achieve as high an energy density as the LiS and LiO2 battery,
it does not suer from their insurmountable problems, such as
unavoidable dissolution and large reaction polarization. In
particular, many polymer cathode materials have already shown
excellent comprehensive battery performance comparable to
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LiCoO2 and LiFePO4. Therefore, the Liorganic battery is
somewhat closer to practical use than the LiS and LiO2
battery, in spite of the cost and the safety issues of the Li anode.
At present, however, it is still necessary to develop novel poly-
mer cathodes with higher energy density and the possibility of
large-scale production.
Rechargeable sodium batteries134136 have been recognized
recently as an alternative to rechargeable lithium batteries
because of the much lower cost of sodium. However, the
migration of the typical inorganic cathode materials of lithium
batteries to sodium batteries has mostly failed, because the
crystalline structure is very sensitive to the insertion ion radius.
In contrast, the ion radius has very little eect on the electro-
chemical performance of n-type organics, mainly due to their
so structure. Therefore, the cathode material for an Li equipment.138140 According to their dierent type of electro-
organic battery can be directly used as the cathode for an Na
organic battery. The discharge voltage is expected to be about
0.3 V lower because of the voltage gap between the Li+/Li and
Na+/Na couple.
4.2 Anodes for Li-ion or Na-ion batteries
Since it is possible for n-type organics to possess a relatively low
redox potential (e.g., 01.5 V vs. Li+/Li), they may be also appli-
cable as anodes for non-aqueous Li-ion or Na-ion batteries, as
illustrated in Fig. 2b. Up to now, there have been very few
reports on organic anode materials, including bipolar con-
ducting polymers (PAc33 and PPP33,34) and conjugated dicar-
boxylates.117121 Due to the low capacity of the conducting
polymer, it is more appropriate to develop conjugated carbonyl
compounds as anode materials. Compared to Li-ion batteries,
an organic anode is better suited for Na-ion batteries, because
of the lack of an applicable anode for Na-ion batteries, as well as
the relatively lower redox potential vs. Na+/Na. For instance,
Fig. 17 shows the redox reaction and charge/discharge curves of
disodium terephthalate (Na2C8H4O4)118 as anode for Na-ion
battery. The relative low redox potential (0.20.6 V vs. Na+/Na)
and at voltage plateau give important insights into developing
novel organic anode materials, but the large irreversible
capacity in the initial cycle is another challenge faced by organic
anodes.
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4.3 High power electrodes for supercapacitors or batteries
In order to satisfy the demands of electric vehicles for both high
energy density and high power density, it is necessary to develop
electrode materials with extremely high rate performance (e.g.,
releasing all their energy within several seconds). As previously
mentioned, one major strength of organic electrode materials is
their inherent fast reaction kinetics, compared to the slow Li-
ducting polymers, nitroxyl radical polymers and conjugated
carbonyl compounds are all promising candidates for high
power electrodes. For instance, there are already a lot of inves-
tigations on PAn/C composite cathodes for pseudocapaci-
tors4852 (Fig. 6). Recently, there have also been some attempts to
modify carbonyl groups on the surface of CNT137 or graphene,29
to achieve both high energy density and high power density by
combining the redox reaction with the double-layer capacitance
of high surface-area carbon. An alternative approach to over-
come the low carbonyl density and complicated synthesis is to
prepare polymer/carbon nanocomposites through in situ poly-
merization. For example, a PAQS/graphene nanocomposite113
can deliver a discharge capacity of more than 100 mA h g
1
within 16 seconds (Fig. 18). Anyway, once the electrode has been
fabricated so as to suciently mix organics and conductive
carbon, it will be much easier for organics to achieve higher rate
performance than inorganics.
4.4 Thin lm batteries or all-solid batteries
Thin lm batteries are useful in many applications such as IC
cards, sensors, microelectronics and bendable electronic
lytes, they can be divided into polymer thin lm batteries with
polymer or gel electrolytes (Fig. 19a), and all-solid thin lm
batteries with inorganic solid electrolytes (Fig. 19b). When a
polymer electrolyte (e.g., LiTFSI/PEO) or solid electrolyte (e.g.
LISICON) is applied in the battery, there is a great opportunity
for small organic molecules to be utilized because of the elim-
ination of the dissolution problem. Recently, there have been
many attempts to use carbon paper (a thin lm of CNT or gra-
phene, Fig. 19c and d) as a current collector to assemble exible
or transparent thin lm batteries.141,142 Compared to inorganic
cathode materials,141 the compatibility of organics with CNT or
graphene is helpful to reduce the interface resistance between
the carbon paper and organic cathode, or to synthesize an
organic/carbon nanocomposite4852,113 as cathode, therefore
organics are more appropriate for the fabrication of a exible
thin lm battery140,143 (Fig. 19a). Some polymers, for example
photocrosslinked PTN77 (Fig. 19e), can form a transparent thin
lm, which is signicant for the assembly of transparent energy
storage devices.142,144 Moreover, many novel electrode fabrica-
tion techniques such as casting,52 patterning,144 printing145
(Fig. 19f) and vapor deposition could be used to assemble thin
lm batteries, based on the special properties of organics
including solubility, lm-forming ability and sublimability. In
one word, organic electrode materials bring about great
opportunities to make energy storage devices thinner, smaller,
exible, printable and even transparent.
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4.5 Aqueous rechargeable batteries
Although aqueous rechargeable batteries have a much lower
energy density than non-aqueous Li-ion batteries due to the
working voltage limitation, they still attract much attention
because of their low cost, high safety and high power density.
However, previous investigations on aqueous rechargeable
lithium batteries (ARLBs)146148 indicate that most inorganic
intercalation compounds show much poorer electrochemical
performance in an aqueous electrolyte than in a non-aqueous
electrolyte, mainly due to harmful side reactions and dissolu-
tion during the charge/discharge process. In contrast, polymer
electrode materials do not suer from these problems if the
charge/discharge voltage range is within the electrochemical
window of the aqueous electrolyte. Many polymers have already
shown excellent electrochemical performance in an aqueous
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electrolyte, including conducting polymer (PAn),43 nitroxyl
radical polymer (PTVE)22 and conjugated carbonyl polymer
(PVAQ).110 Rather than in non-aqueous electrolyte, they can
suciently show their ultra-fast charge/discharge ability in
aqueous electrolyte due to the much higher ion conductivity.
Among these polymers, conducting polymers and nitroxyl
radical polymers are more appropriate for cathodes, while
conjugated carbonyl polymers should be applied as anodes
because of their much lower redox potential (2.03.0 V vs.
Li+/Li). Since the cation type has little eect on the electro-
chemical performance of conjugated carbonyl polymers,
besides ARLBs, aqueous rechargeable sodium batteries (ARSBs)
or even proton batteries are also realizable in the future.
4.6 Redox ow batteries
Since the dissolution problem of small organic molecules is
dicult to overcome in common rechargeable batteries, there is
an alternative strategy of using them in solution phase with an ion
exchange membrane as separator. In order to fully utilize the
organic active materials in solution, the redox ow battery (RFB)149
is a good choice. Compared to previous RFBs, for example, all
vanadium ow batteries and RFBs based on organic cathodes
and/or anodes are more environmentally friendly.93,150152 The
structure diversity of organic electrode materials provides huge
numbers of candidates for the cathode and anode. The redox
potential and solubility of the specied organics can be also
modied by introducing other functional groups. In order to
improve the solubility of organic active materials, a non-aqueous
electrolyte may be also used in the RFB,150152 which will signi-
cantly enlarge the working voltage of the battery.
4.7 All-organic batteries
An all-organic battery constitutes both an organic cathode and an
organic anode. Usually, except for current collectors and Li-ions
(or Na-ions) in the electrolyte, there are no other metal elements.
They have attracted much interest in recent years because of their
exibility, sustainability and environmental friendliness. At
present, the attempts on all-organic battery have mainly focused
on matching a p-type cathode with an n-type anode (Fig. 2d). For
instance, the p-type radical cathode PTN is matched with an n-
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type radical anode poly(galvinoxylstyrene) to assemble a high
power all-organic battery.81 Another example is thr bipolar con-
ducting polymer PPP,34 which was used as both cathode and
anode, beneting from the large voltage gap between its p-type
reaction and n-type reaction (Table 2). In spite of the low energy
density, these systems are far from practical use due to the
consumption of the electrolyte in the charging process. Therefore
we proposed a novel type of all-organic battery, with n-type
organics as both the cathode and anode (conguration b in
Fig. 2b). More specically, the battery constitutes conjugated
carbonyl compound N with a low redox potential as the anode
and conjugated carbonyl compound M+N0
with high redox
potential as the cathode (Fig. 20). This system can be operated in
either an aqueous or non-aqueous electrolyte, with various
cations. It is expected this system can obtain a working voltage of
about 2.02.5 V in a non-aqueous electrolyte, or around 1.0 V in
an aqueous electrolyte. In an aqueous electrolyte, a proton may
be used as a substitute for Li+ or Na+, thus a metal-free all-organic
battery could be realized, which could be also dened as proton
battery.2 To achieve this goal, there are a lot of challenges to face
in developing high performance organic cathodes and anodes
based on conjugated carbonyls.
5 Conclusions
In summary, we provide an overview of organic electrode
materials, including their fundamental knowledge, develop-
ment history and perspective applications. Generally, the
development of organic electrode materials is still in its infant
stage, aer more than 40 years' research. Fortunately, they are
now meeting great opportunities because of increasing
concerns on resources and environmental issues, the energy
density limitation of inorganic cathode materials, as well as
the electrochemical performance breakthrough of organic
electrodes in recent years. Among dierent types of organics,
we believe conjugated carbonyl compounds are the most
promising type at present, because only they have the potential
to achieve simultaneously high energy density, high cycling
stability and high power density (Fig. 21). Moreover, its n-type
reaction mechanism and structural diversity provide it with
broad application prospects, compared to p-type conducting
polymers and nitroxyl radical polymers. Of course, there are
still a lot of new structures and new reaction mechanisms to be
discovered, which can be inspired by other organic functional
materials such as organic photoelectric materials.19,20 Anyway,
there is still a great deal of room to improve the electro-
chemical performance of organic electrode materials. Another
important research direction is extending the application of
organic electrode materials. The unique features of organics
including exibility, processability, structure diversity and fast
kinetics provide organic electrode materials many perspective
applications besides Liorganic batteries, such as exible thin
lm batteries and all-organic batteries. Besides LiS and LiO2
batteries, it is also expected that organic electrode materials
will show their talents in the development of sustainable and
versatile energy storage devices beyond Li-ion batteries.
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