Journal of Power Sources 292 (2015) 87e94

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Preparation of a cost-effective, scalable and energy efficient all-copper

redox flow battery
David Lloyd*, Eva Magdalena, Laura Sanz, Lasse Murtoma
€ki, Kyo
€ sti Kontturi
Aalto University, Department of Chemistry, Kemistintie 1, 02150 Espoo, Finland

h i g h l i g h t s

97% current efficiency is demonstrated over forty chargeedischarge cycles.

Energy efficient operation at currents up to 75 mA cm2 is reported.

A stack design which can achieve 72% energy efficiency is shown.

The cost-effective design yields a capital cost for the stack of 200e1250 $/kWh.

a r t i c l e i n f o a b s t r a c t

Article history: A design for the all-copper redox flow battery based on readily available, cost-effective construction
Received 2 February 2015 materials is presented. The design results in a stack cost of between 70 and 300 $/m2, with the electrolyte
Received in revised form costing 60 $/kWh. The area specific resistance of the cell is 1.5 U cm2.
15 April 2015
A maximum round trip energy efficiency of 72% occurs at a current density of 40 mA cm2, this is
Accepted 29 April 2015
Available online xxx
similar to values reported for zincebromine redox flow batteries. The two major loss processes are
attributable to permeation of Cu2þ through the microporous separator at current densities below
50 mA cm2 and excessive electrode overpotentials at current densities greater than 75 mA cm2.
Keywords:
Redox flow battery
Two methods to characterise the current efficiency of the electrochemical processes in the cell are
Chlorocopper complexes reported. A round trip current efficiency of 98% is consistently found when cycling the all-copper battery
All-copper at a current density of 150 mA cm2.
Microporous separator © 2015 Elsevier B.V. All rights reserved.
Expanded graphite foil

1. Introduction states of copper: Cu, Cuþ and Cu2þ, where Cuþ and Cu2þ are dis-
solved species and Cu is metallic copper. The Cuþ redox state is
In this paper we will demonstrate that it is possible to develop a typically unstable in solution and requires the use of suitable li-
redox flow battery (RFB) with a technically useful energy efficiency gands to form a complex which is stable against disproportion-
of 72% using cost-effective and abundant materials: namely a ation, with both chloride [3e6] and acetonitrile [7e9] having been
microporous separator, expanded graphite foil electrodes and an shown to be suitable. The three redox states are connected by the
electrolyte based on copper and hydrochloric acid. Copper is reactions shown in Equations (1) and (2).
currently produced at an annual rate of around 20 million tonnes
[1] and typically has a purity of at least 99.994% [2], which is suf- discharge
Negative electrode : Cu ) * Cuþ þ e (1)
ficient for application in an RFB. For this reason, copper is one of charge
only a handful of elements that are immediately suited to the task
of building the stationary battery capacity required to balance the
many gigawatts of intermittent renewable electricity which are charge
Positive electrode : Cuþ ) * Cu2þ þ e (2)
expected to come on line globally within the next five to ten years. discharge
RFBs based on copper electrochemistry employ the three redox
The use of only three redox states, one of which is an insoluble
solid, makes preparation of the electrolytes a simple process as the
* Corresponding author. electrolytes in both half-cells at the initial 0% state-of-charge (SOC)
E-mail address: david.lloyd@aalto.fi (D. Lloyd). are identical solutions of pure Cuþ. This is an important

http://dx.doi.org/10.1016/j.jpowsour.2015.04.176
0378-7753/© 2015 Elsevier B.V. All rights reserved.
88 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94

simplification over other RFB electrochemistries based on a single
element, such as the ubiquitous vanadium RFB (VRFB). An elec-
trolyte in this starting condition can be easily prepared using a one-
pot synthesis by dissolving either the Cuþ or Cu2þ salt in the sup-
porting electrolyte and then adding Cu and mixing. Any Cu2þ pre-
sent is spontaneously converted to Cuþ by the comproportionation
reaction, shown in Equation (3).
Comproportionation reaction : Cu2þ þ Cu/2Cuþ
water. This electrolyte inevitably contains traces of Cu2þ, either
through contamination of the original CuCl salt or the ingress of
oxygen during preparation. It is possible to eliminate this
contamination prior to loading the electrolyte in to the cell by
adding a small amount of copper powder (99%, British Drug House)
and shaking the flask for around a minute, at which point the
electrolyte should be colourless. The electrolyte is carefully dec-
anted from the volumetric flask during filling of the electro-
(3) chemical cell to prevent any copper powder from being transferred.

Completion of this reaction is also simple to observe as the pure

2.2. Preparation of 50% state-of-charge electrolytes
Cuþ electrolyte is clear and colourless, whereas solutions contain-
ing a mixture of both the Cuþ and Cu2þ complex are dark brown, in
In certain experiments it was desirable to initialize the system
the case of the chloride ligand. Previously, we reported the use of
using electrolytes that simulate conditions at 50% state-of-charge
mixtures of HCl and CaCl2 as supporting electrolytes and as a source
(SOC). In the case of the negative half-cell electrolyte, or cath-
of chloride ligands [10]. We have also previously demonstrated the
olyte, this was achieved by preparing a solution using the same
excellent kinetics of the two redox reactions shown in Equations (1)
method described in Section 2.1, however the CuCl concentration
and (2) [3,10]. Zhao et al. [5] have studied similar electrolytes and
was reduced to 1 M. In the case of the positive half-cell electrolyte,
shown that stripping of metallic copper to form the monovalent
or anolyte, the concentration of CuCl was similarly reduced to 1 M
copper chlorocomplex, the forward reaction in Equation (1), is a €en, purum) was added,
and an additional 1 M of CuCl2 (Riedel de Ha
two-step process involving the formation of an intermediate CuCl
resulting in a solution that is equimolar in Cu2þ and Cuþ. When
deposit followed by dissolution in the form of a [CuCl2] complex.
preparing anolyte at 50% SOC the reaction with copper powder was
They recommend operating at increased temperature and high
not performed to prevent reduction of Cu2þ to Cuþ.
concentrations of free chloride to increase the rate of CuCl disso-
lution, thereby preventing passivation of the negative electrode
2.3. Evaluation of the current efficiency of the negative electrode
during stripping. These operating conditions have also been shown
reaction
to allow high solute concentrations [10,6] and appreciable cell
potentials [11], which are critical to achieve useful energy and
As suggested by the recent work by Zhao et al. [5], beyond a
power density and efficient operation.
certain current density the speed at which copper can strip be-
Since the cost of the supporting electrolytes used is relatively
comes the rate limiting step in the reactions taking place at the
trivial and the preparation method simple the electrolyte cost is
negative electrode, with a passivating CuCl layer formed on the
dominated by the price of copper. We therefore estimate the
surface of the electrode. To independently study the efficiency of
electrolyte cost to be around 60 $/kWh. This value compares
the deposition and stripping reaction a thermostatted and air-tight
extremely favourably with the electrolyte cost in a VRFB, which is
glass cell was filled with the Cuþ electrolyte described in Section
estimated to be at least 200 $/kWh [12].
2.1. This cell was used to perform three electrode measurements,
We have also recently shown that due to the high reagent
the working electrode was a rotating disc electrode (RDE) tip (5 mm
concentrations used an energy density as high as 26 Wh l1 can be
active electrode area, Pine instruments, no rotation was used,
achieved for the cell chemistry reported here [6], with a value of
platinum or glassy carbon active electrode material) and the quasi-
19.6 Wh l1 being realistically achievable. These values are com-
reference and counter electrodes were both 2 mm diameter grade-
parable to values reported for a range of RFB chemistries reported
A copper wires. The electrolyte was stirred vigorously to ensure a
earlier, including the all-vanadium system [13].
continuous supply of fresh electrolyte to the surface of the working
In our previous paper, where we introduced the aqueous all-
electrode. A small amount of copper turnings (>99.0%, Fluka) were
copper concept, we were only able to report useful energy effi-
added to the bottom of this cell to ensure that any Cu2þ formed, for
ciencies at low current densities of 10e20 mA cm2 [10]. In the
instance due to oxygen permeation, was converted to Cuþ. A
current paper we will demonstrate a cell design costing only 70 to
completely colourless electrolyte was typically achieved after
300 $/m2 and an alternative electrolyte formulation which allow us
15 min of commencing stirring.
to also attain meaningful energy efficiencies at current densities up
The current efficiency of the deposition and stripping process
to 75 mA cm2. In addition, we present a range of techniques to
was evaluated by galvanostatically depositing and then stripping
independently study the various subprocesses that occur in the cell,
copper from the working electrode using an Autolab PGSTAT12
for instance the rate of crossover of Cu2þ through the microporous
potentiostat. The potential of the electrode was monitored during
separator, the efficiency of deposition and stability of the copper
stripping and in the event that the potential rose above 0.45 V the
deposit and the effect of temperature and current density on the
stripping process was aborted. In the event of incomplete stripping
rate at which the copper electrode passivates during stripping. We
of the copper deposit due to passivation the electrode was restored
also demonstrate that the possible side reactions, namely hydrogen
to the original pristine condition by repeatedly applying a constant
and chlorine evolution, are entirely avoided due to the nobility of
potential of 0.3 V for a period of 1 min until the open circuit po-
metallic copper and the small cell potential of 0.65 V.
tential (OCP) returned to a value higher than 0.3 V. This is essen-
tially the same technique as previously used to study the efficiency
2. Experimental of the zinc deposition and stripping process in a ZinceCerium RFB
[14].
2.1. Preparation of 0% state-of-charge electrolyte
2.4. Evaluation of current efficiency losses due to permeation of
Sufficient anhydrous CuCl (anhydrous copper(I)chloride pow- Cu2þ
der, 97%, Alfa Aesa) and fuming HCl (37%, Merck) to achieve con-
centrations of 2 M and 8 M respectively are weighed in to a To develop an RFB that is cost effective it would appear to be
volumetric flask and made up to the intended volume with distilled imperative to replace costly perfluorinated ion-exchange
 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94 89

membranes with more cost-effective materials, such as micropo-

rous separators, which have at least an order of magnitude lower
unit-cost [12]. These materials are non-selective and therefore Cu2þ
ions present in the positive half-cell electrolyte will inevitably
diffuse through the separator and react with the copper present in
the negative half-cell leading to self-discharge of the battery, which
is the reaction shown in Equation (3). In this paper we report re-
sults obtained using a commercial lead acid battery separator
which has previously been used in RFB studies, namely Daramic
(0.5 mm plain microporous polyethylene) [15].
To study permeation we have employed permeability cells,
which are typically used to study similar parasitic processes in fuel
cell membranes, for instance methanol permeation through Nafion
in direct methanol fuel cells [16].
As described previously [9,17,18], the two electrodes, which are
not typically used in fuel-cell permeability experiments, transform
the permeability cells in to an extremely simple and reliable
miniature RFB with an electrolyte volume of only 5 ml. This system
also has precise temperature control over a range up to 95  C and
minimal corrosion problems. In these experiments the area of each
graphite electrode (Faber-Castell TK 9071, 2 mm, graphite com-
posite) is close to that of the separator, being 0.6 cm2 and 0.5 cm2 Fig. 1. Construction of single-cell RFB. Each half-cell is assembled in the descending
respectively. This is similar to the conditions in the larger cell order shown above. A 2 mm stainless steel endplate (6), is placed on a 6 mm PVC sheet
fitted with inlet and outlet connectors (5). This is aligned above the manifold layer (4),
described in Section 2.5 which, due to the deposition of copper, fast
which is placed over the electrode (3). This assembly is placed on the separator (1),
kinetics and excellent mass transport in the electrolyte, does not with a gasket (2) placed in-between to form the half-cell chamber.
require the use of felt electrodes.
The rate at which Cu2þ permeates through the separators is
assessed by filling the negative and positive half-cells with the Cuþ Table 1
and mixed CuþeCu2þ electrolytes described in Section 2.2 respec- Estimated bill-of-materials for a stack containing 100 cells in series based on the
materials considered in this work. The electrodes are assumed to operate in a bipolar
tively, which simulates a system with both electrolytes at 50% SOC.
configuration. The endplates are assumed to be 1 cm thick 316 stainless steel which
This cell is then cycled over a range of current densities from 5 to are protected from the electrolytes with a 1 cm thick PVC lining.
200 mA cm2 with an initial charging step of 200 s followed by
Component Price/$ m2
discharge. Ten measurements were performed at each current
density to allow the system to reach equilibrium conditions before Low High Typical
proceeding to the next current density. The electrolytes were not Bipolar electrode [19] 50 200 100
replaced during these measurements. Separator [20] 1 15 2 [21]
Gaskets [22] 9 40 10
Endplates [23,24] 10 40 15
2.5. Construction and operation of a single-cell RFB Total 70 295 127

A single-cell RFB with an electrode surface area of 18 cm2 was

prepared from cost-effective and widely available materials using
and 300 $/m2. Due to the relatively low price of the Daramic
the simple methods described below. The same microporous
separator and the absence of felts the stack cost is dominated by the
separator material described in Section 2.4 was compressed be-
cost of the graphite fluoropolymer composite bipolar plate. A full
tween two expanded graphite foil electrodes (SGL Group, 0.6 mm
estimate of the stack cost would require knowledge of the
SIGRACELL TF6), with frame shaped gaskets (Silicone rubber, 2 mm,
manufacturing cost for a stack based on this combination of ma-
Hexamer OY, Finland) inserted between the separator and foils to
terials and construction technique. This is currently lacking, but it is
create the cell chambers. Electrolyte was introduced and with-
worth noting that at industrial scale the expanded graphite foils,
drawn from the ends of these chambers by two lines of small
gaskets and microporous separators can be sourced in roll format.
openings punched in to the electrodes at the top and bottom of
In principle this makes the design well suited to efficient imple-
each cell chamber. These holes allow liquid to pass to and from the
mentation in a process with a low tooling cost, for instance based
manifolds behind the electrode, which are formed by cutting two
on flatbed die cutting.
large rectangular apertures in a rubber sheet (Silicone rubber,
4 mm, Hexamer OY, Finland). These apertures span the top or
bottom line of openings respectively and are positioned directly 3. Results
underneath the inlet and outlet connectors of each half-cell.
This construction method, shown in Fig. 1, is similar to that used 3.1. Efficiency of the deposition and stripping reaction
in the commercial Electrocell device we previously reported [10].
The reservoirs were two air-tight and thermostatted glass vessels The dependency between current efficiency and current density
each filled with 80 ml of the electrolyte described in Section 2.1. The for the deposition and stripping of copper on a Pt RDE tip in a three
electrolytes were circulated by means of two speed programmable electrode cell is shown in Fig. 2A. At current densities between 20
centrifugal pumps (Iwaki, RD-12TE24-N1V12) operating at their and 125 mA cm2 the round trip current efficiency for the depo-
lowest flow rate (0.22 l/min, which is 2% of maximum flow rate). sition and stripping reaction, hi,cathode, is relatively constant with a
An estimate of the bill-of-materials for a stack based on this value of 98 ± 3%. At current densities beyond 125 mA cm2 the
design is shown in Table 1. This estimate suggests that at com- electrode passivates during stripping and the current efficiency
mercial scale a stack based on these materials will cost between 70 drops sharply. This correlates strongly with the OCP values
90 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94

the inert electrode and the growth of localized copper islands. At

low current densities there are far fewer nucleation sites generated
and since these have a smaller surface area than the geometric
electrode surface they become more easily passivated during the
stripping process. As is shown in Section 3.2, when longer depo-
sition times are used carbon materials can deliver equally good
current efficiency as platinum.
The three electrode cell was also used to perform measurements
where a charging current density of 100 mA cm2 was applied for
60 s and the platinum electrode was then held at 0 current density,
i.e. OCP, for varying periods of time prior to stripping of the copper
deposit. This method simulates the effect of the negative electrode
of the battery being charged and then left in an idle state before
discharge. The correlation between current efficiency and rest time
is shown in Fig. 3. The drop in efficiency indicates there is a slow
corrosion process occurring at the copper electrode, equivalent to a
parasitic current of around 0.1 mA cm2. This relatively negligible
effect may also be attributable to permeation of oxygen in to the
cell, although hydrogen evolution cannot be entirely ruled out at
this point. This result shows that the copper deposit formed is
extremely stable in the electrolyte used, when compared to values
reported previously for zinc or iron based RFBs [14,25].

3.2. Effect of Cu2þ permeation through the separator on current

efficiency

The extent to which Cu2þ permeation through the separator

impacts the current efficiency of the cell, hi, was tested using the
miniature RFB described in Section 2.4. Fig. 4 shows that the
dominant cause of poor current efficiency at current densities
below 50 mA cm2 is the permeation of Cu2þ through the separator,
since hi monotonously increases towards an asymptote of 98% at
higher current densities. At current densities of 40, 100 and
250 mA cm2 hi of the miniature RFB was 85.7, 94.0 and 96.9%
Fig. 2. Current efficiency of the copper deposition and stripping reaction at a platinum respectively. A complication in this analysis is that the rate of Cu2þ
(A) or glassy carbon electrode (B) as a function of current density and temperature. permeation will depend on the concentration of Cu2þ in the posi-
Deposition time was 100 s.
tive half-cell and hence also the state-of-charge of the cell. In
principal, it is necessary to repeat these experiments at different
observed after the cycling process, with the electrode showing a states-of-charge.
negligible potential difference versus the copper wire quasi refer- The experimental data was fitted to a simple model based on the
ence electrode at current densities above 125 mA cm2. This in- results presented in Section 3.1, which indicate a maximum current
dicates incomplete stripping of the copper deposit. When the efficiency for the deposition and stripping of copper, hi,cathode of
stripping process is reactivated at a lower current density it com- 98%. The permeation of Cu2þ from the PHC to the NHC introduces a
pletes successfully and the surface of the electrode is restored to the parasitic current at the negative electrode during charging, due to
original pristine state.
Based on these observations it would appear a current density of
125 mA cm2 is the maximum value supported by the negative
electrode surface reaction. This is confirmed when the duration of
the deposition and stripping processes is varied at a current density
of 125 mA cm2, with the system showing a steady current effi-
ciency of 98 ± 1% over a range of deposition times up to 30 min.
These measurements demonstrate that the problem of hydrogen
evolution is largely avoided in the all-copper system and that the
desired negative electrode reactions take place with good efficiency
over a broad range of current densities from 20 to 125 mA cm2.
This compares particularly favourably with the results previously
reported for RFBs based on zinc deposition, where the current ef-
ficiency drops from 95% to 80% at current densities below
50 mA cm2 [14].
The results at the glassy carbon electrode, shown in Fig. 2B,
demonstrate much poorer efficiency at low current densities, in
stark contrast to the platinum electrode. This is due to the low rate
of copper nucleation on this material which, because of the short Fig. 3. Dependency of current efficiency, hi, on rest time, trest, between deposition and
duration of the deposition step, results in incomplete coverage of stripping, the deposition time was 1 min and the current density was 100 mA cm2.
 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94 91

Fig. 4. The relation between current efficiency, hi, and current density, j, for a minia- Fig. 5. Galvanostatic polarisation curves acquired at 60  C during charging ( )
ture RFB employing a 0.5 mm daramic separator, the cell was initialized at 50% SOC. and discharging (-) of the single-cell RFB described in Section 2.5. The potential was
The squares are experimentally observed values obtained at 60  C. The solid line shows taken after holding the cell at each current density for 30 s.
simulated current efficiency values based on Equation (4) described in Section 3.2.

processes, was observed at frequencies between 1000 and 25 Hz.

the preferential conversion of Cu2þ to Cuþ. During discharging a
parasitic process still occurs, as Cu2þ present at the cathode will
spontaneously react with metallic copper according to the reaction
shown in Equation (3). The permeation of Cu2þ can therefore be
thought of as a constant self-discharge current, jsd, and the impact
this has on the current efficiency of the cell, hi, will be proportional
to the current density, j, as predicted by Equation (4).


j  jsd
hi ¼ hi;cathode
j þ jsd
This assumes the current applied to the cell is equal at all times.
If differing current densities are applied during charging and dis-
charging, jcharge and jdischarge respectively, then the expression
shown in Equation (5) is appropriate. Equations (4) and (5) assume
the reaction at the anode, shown in Equation (2), has 100% current
efficiency. This assumption is validated by the results for a complete
RFB system, which are reported later in Section 3.4.
0   1
jdischarge jcharge  jsd
hi ¼ hi;cathode @  A
jcharge jdischarge þ jsd
Fig. 4 shows that Equation (4) is capable of describing the
observed behaviour excellently at all useful values of current effi-
ciency and indicates that jsd is 3.0 mA cm2 under the conditions
tested, it also confirms the value of 98% determined for hi,cathode in
Section 3.1.
Below 25 Hz the signal exhibited significant noise and no reliable
data could be obtained. Fitting of these distorted impedance
spectra results to a typical Randle's circuit connected in series with
an inductor yielded impedance values of 1.12 U cm2 for the solution
resistance and between 0.15 and 1.5 U cm2 for the charge transfer
resistance. The sum of these values is comparable to those observed
using DC methods and suggests that the solution resistance
(including that of the separator) is responsible for around half of
(4) the ASR. However, further significant improvement of the EIS
measurement system used and better experiment design will be
required to allow precise characterisation of the various processes
which contribute to the cell impedance.
Based on the overpotentials observed, hV can be estimated for
the optimized RFB, this is shown in Fig. 6. These results can be
combined with the current efficiency measurements reported in
Section 3.2 to determine round trip energy efficiency, hE, this is also
shown in Fig. 6.
Based on the high conductivity of the electrolyte described in
Section 2.1 at 60  C, which is 957 mS cm1, the ASR due to Ohmic
(5) losses is estimated to be 0.35 U cm2, therefore a significant fraction
of the overpotentials observed must be attributable to concentra-
tion or activation overpotentials at the electrodes or additional

3.3. Voltage efficiency of the all-copper battery

The voltage efficiency, hV, of a realistic all-copper RFB was

studied using the optimized cell design described in Section 2.5. A
typical polarization curve is shown in Fig. 5.
The relation between potential and current density during both
charging and discharging is highly linear and yields an area specific
resistance (ASR) of 1.4e1.5 U cm2.
The impedance of this cell was also investigated using electro-
chemical impedance spectroscopy in the vicinity of the OCP for a
cell that had been charged to 30% SOC. The first problem encoun-
tered was a relatively large stray inductance, which was noticeable
at frequencies above 1 kHz. In addition, since two electrode pro-
cesses were being studied simultaneously a relatively distorted Fig. 6. Round-trip voltage (A), current () and energy (-) efficiencies for the all-
semicircle, possibly attributable to the two charge transfer copper RFB at 60  C.
92 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94

Ohmic losses in the separator. Nonetheless, an ASR of 1.5 U cm2

compares favourably with the value of 4.5e5.4 U cm2 obtained
during initial development work on the all-vanadium RFB (VRFB)
by the group of Skyllas-Kazacos et al., where they employed non-
activated commercial felt electrodes [26]. For highly-optimized
VRFBs, employing compressed carbon papers, values as low as 0.6
to 0.9 U cm2 have been reported [27]. An ASR less than 1 U cm2 is
unlikely to be achievable for the system presented here without the
use of high surface area electrodes.
A peak in hE of 72% occurs at a current density of around
30e40 mA cm2, the drop in hE at higher current densities is
relatively small and doubling of the current density to 70 mA cm2
results in a relatively modest decrease of hE to only 67%. By com-
parison, in the widely reported zincebromine RFBs typical opera-
tional current density and hE are 20 mA cm2 and 75% respectively
[28]. A value of 75% for the hE is also not uncommon for the VRFB
[27]. Therefore the peak hE value of 72% observed for the all-copper
RFB appears to be reasonable at this relatively early stage of tech-
nical development.
When the all-copper battery is operated at 70 mA cm2 a power
density of 37 mW/cm2 is achieved during discharge. This is the
same power density achieved in the zincebromine RFB when
operated at typical conditions of 20 mA cm2. This suggests that the
low cell potential in the all-copper RFB is balanced by relatively low
Ohmic losses, high deposition efficiency and facile reaction kinetics.
Based on the stack cost estimate reported in Section 2.5 we predict
a cost of between 200 and 1250 $/kW for the stack, with the wide
variation resulting from the choice of which side of the energy ef-
ficiency peak in Fig. 6 the system is designed for and significant
uncertainty regarding cell construction costs. This range of values
lies within the 1500 $/kW capital cost target set by the U.S.
Department of Energy for grid-storage applications [29], with a cost
estimate in the middle of the range leaving significant resources for
other capital costs which will inevitably be incurred.
Fig. 7. (A) Current efficiency ( , hi) and variation in the SOC of the cell between the
charged and discharge state (, DSOC) for 43 cycles of operation. (B) OCP of cell after
3.4. Cycling experiments with a single-cell RFB charging completes ( ) and after discharging completes ( ) during the same cycling
experiment. The current density was 150 mA cm2.
To demonstrate that the all-copper battery can be effectively
cycled over longer periods, the miniature RFB described in Section
2.4 was loaded with the electrolyte described in Section 2.1, i.e. 2 M system was initialised at 50% SOC, the OCP was typically 0.68 V after
in CuCl and at 0% SOC. The system was then left to cycle at a current cycling completed.
density of 150 mA cm2, with monitoring of the cell potential to When regular cycling with the larger RFB described in Section
prevent overcharging. The potential cut-off limits used for charging 2.5 was attempted at a current density of 50 mA cm2 the capacity
and discharging were 0.9 and 0.3 V respectively. A full char- of the battery was observed to rapidly fade from an initial 58% of
geedischarge cycle over the entire theoretical SOC range of the cell the theoretical value to only 3% within 9 h. This appears to be due to
would require 4 h under these conditions. oxygen permeation through the flexible silicone tubing used to
Fig. 7a shows that the depth of charging was higher during the plumb the system.
first two cycles and correlated with a poor hi, this indicates that the
system is not able to fully discharge to 0% SOC at the high current 3.5. Energy storage cost estimates for an all-copper RFB
density applied. Presumably, this is due to the concentration of
Cu2þ becoming too low to sustain the discharge process at low SOC. The unit cost of energy storage for the all-copper battery is
After the second cycle the SOC range accessible during cycling shown in Fig. 8. Note that only the electrolyte and stack material
showed a gentle rise to a maximum of 57% by the 26th cycle. During costs are considered, the cost of the remaining balance-of-plant is
the last 13 cycles it dropped relatively rapidly to 46% by the last not considered and can be significant given the relatively low en-
cycle. After the first two initial cycles hi was a steady 98.6 ± 2.1% ergy density of the electrolyte.
until cycling was manually terminated after the 43rd cycle. For the system with a 1:1 power to energy ratio the combined
Fig. 7b shows that the open circuit potential, OCP, after charging cost is completely dominated by the stack cost and is virtually
dropped monotonously from 0.73 to 0.68 V. The OCP after discharge identical to the $ kW1 cost. The apparent asymptotic behaviour
initially rose from 0.57 to 0.59 V during the first two cycles, which shown for the 1:1 ratio is due to the drop in the cell voltage as the
correlates well with the poor value of hi observed, before slowly current density is increased, which reduces the rate at which power
dropping back to 0.57 V by the 30th cycle, at which point it rose density increases. By contrast, for the 1:5 and 1:10 ratios the
again to 0.58 V during the remaining cycles applied. Average OCP asymptotic behaviour is related to the cost of the electrolyte
observed using this battery was 0.63 V, which is close to the becoming relatively dominant at high current densities. It is worth
theoretical cell potential of 0.65 V reported by Lundstro €m [11]. By noting that at a 1:5 and 1:10 power to energy ratio the thickness of
contrast, for the experiments reported in Section 3.2, where the the copper deposit attainable before the negative half-cell becomes
 D. Lloyd et al. / Journal of Power Sources 292 (2015) 87e94
Fig. 8. Dependency of the combined stack and electrolyte cost on current density for
power to energy ratios of 1:1(A), 1:5() and 1:10(-) kW kWh1 respectively.
completely full is a limiting factor, with 75 and 40 mA cm2 being
realistic limits for the 1:5 and 1:10 ratios respectively.
For 1:5 and 1:10 power to energy ratios, the low cost of the
electrolyte is more noticeable and the cost of energy storage drops
to within the range typical for lead-acid batteries at relatively low
current densities. Within a 30e40 mA cm2 current density range,
where energy efficiency is maximised, the combined costs are be-
tween 103 and 191 $ kWh1 for 1:10 and 1:5 power to energy ratios
respectively.
4. Conclusions
In this work we have conclusively demonstrated outstanding
current efficiency for both electrode processes, even under extreme
conditions of high current density and acidity. However, good ef-
ficiency of the negative electrode reaction clearly requires opera-
tion at elevated temperatures, with 50  C being the lowest value
appropriate to avoid passivation of the copper deposit during
discharge. This requirement does not appear to be incompatible
with the target application, since significant engineering effort and
cost is typically required to prevent overheating in VRFBs. By
contrast, the all-copper RFB benefits from increased operating
temperatures.
The daramic separator used in this work yields a useful current
efficiency of at least 90% only when the system is operated at a
current density greater than 60 mA cm2. A sustained current ef-
ficiency of 98% was demonstrated when operating a single-cell RFB
at 150 mA cm2 for 40 cycles. This proves that provided suitable
electrode reactions and operating conditions are selected, a
microporous separator can be used to good effect in RFB
applications.
The voltage efficiency has been shown to be improved by a
suitable stack design. The ASR observed was around 1.5 U cm2,
which is significantly lower than the values reported during initial
development work on the VRFB.
A technically useful round trip energy efficiency of 72% was
demonstrated. This is comparable to values reported for typical
systems, such as ZneBr RFBs or the VRFB. Further improvement in
the energy efficiency of the all-copper RFB can be achieved either
by substituting daramic with a separator that is less permeable to
Cu2þ or further reduction in the ASR of the cell. The second option,
reduction of the ASR, is the obvious route to pursue, since this will
allow improved operation at high current and power densities.
However, this approach will likely require the use of structured,
high surface area electrodes. The traditional strategy of using
93
compressed carbon felts or papers to achieve a high surface area
electrode does not appear to be compatible with hybrid RFBs where
metal deposition occurs and therefore alternative strategies will
need to be developed.
In the short term the exploration of alternative separator ma-
terials appears to be the simplest approach to rapidly improve
energy efficiency. In this work we have demonstrated a simple
experimental methodology to quantify separator performance in
this context. One of the key benefits of the all-copper RFB is that
only one species in solution, namely Cu2þ, is responsible for current
efficiency losses due to permeation through the separator. By
comparison, in the VRFB all four vanadium species can permeate
through the separator. This not only increases the rate of self-
discharge, but also makes it harder to analyse separator perfor-
mance and select improved materials, since all four species require
simultaneous targeting.
A major objective in future work will be to demonstrate appli-
cation of the same cost-effective cell materials and design in a
scaled-up multicell configuration. An additional problem requiring
attention is the elimination of oxygen ingress, which can easily
degrade both current efficiency and battery life in laboratory scale
systems.
The major conclusion which can be drawn from the work pre-
sented here is that a small cell potential of 0.65 V in no way renders
the all-copper battery ineffective as a means to efficiently store
energy, only the energy density is obviously compromised. The low
cell potential clearly benefits the current efficiency of the system,
with little tendency for parasitic electrode reactions to occur at high
current densities. The avoidance of highly reactive electrochemical
species in the positive half-cell, such as Br2, Ce4þ or V5þ also ap-
pears to reduce the problem of corrosion of cell materials, which
can enable the use of more cost-effective construction materials. It
would appear that significant theoretical work is still required to
develop a realistic understanding of the complex relationship be-
tween system performance and cost when adjusting the many
parameters which can be optimised in redox flow batteries.
Acknowledgements
SGL Group and Daramic are gratefully acknowledged for
providing the materials used in this study.
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