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DOI: 10.1002/cssc.201200962

A Solar Rechargeable Flow Battery Based on

Photoregeneration of Two Soluble Redox Couples
Ping Liu,[a] Yu-liang Cao,[a] Guo-Ran Li,[b] Xue-Ping Gao,*[b] Xin-Ping Ai,[a] and Han-Xi Yang*[a]
Growing concerns regarding climate change and the future
energy crisis drive us to explore alternative clean and renewable energy sources, among which solar energy is the most
viable to meet the global energy demand. With increasing
penetration of solar electricity in the global energy markets,
we need to suppress the effects caused by the intermittent
nature of solar irradiation on the reliability and stability of the
grid system. A practical solution is to develop affordable storage technologies that can effectively store solar electricity[1] or
convert photovoltaic power into dispatchable fuels.[2]
Although many types of rechargeable batteries have been
suggested for use in solar electricity storage, large scale applications are difficult because of limits on resources, cost, and
power.[35] In recent years, a number of photorechargeable
electrochemical cells have been described for the in situ conversion of solar energy to electricity and chemical energy.
An accessorial electrode was introduced into a dye-sensitized
solar cell (DSSC) for storing photogenerated charges; therefore,
functioning as a combined DSSC and electrochemical cell or
capacitor.[610] Photorechargeable cells have an electrical storage capacity proportional to the size of the DSSC and loading
of the electroactive material; therefore, for practical applications, they suffer from similar restrictions to conventional batteries, that is, solid material resources and cost. Conversely,
redox flow batteries (RFBs), which utilize a pair of soluble
redox couples, have a number of advantages, such as flexible
design, long lifetimes, high reliability, as well as acceptable operation and maintenance costs, which are particularly suitable
for large-scale electrical energy storage.[1113] If a RFB can be regenerated under solar illumination, it could lead to a significant
breakthrough in the efficient and affordable storage of solar
energy.
Herein, a mechanism for the conversion of solar energy to
chemical energy is proposed, which can regenerate redox species discharged from a RFB by flowing through a DSSC; the
redox-active species can then be stored in tanks until required
for RFB applications. The feasibility of convenient solar energy

[a] P. Liu, Y.-l. Cao, X.-P. Ai, Prof. H.-X. Yang

College of Chemistry and Molecular Science
Wuhan University
Wuhan 430072 (PR China)
E-mail: hxyang@whu.edu.cn
[b] G.-R. Li, X.-P. Gao
Institute of New Energy Material Chemistry
Nankai University
Tianjin 300071 (PR China)
E-mail: xpgao@nankai.edu.cn
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201200962.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

conversion and storage is investigated for fabricating a RFB

system that can store solar energy.
The configuration and working mechanism of a RFB that can
store solar energy is shown in Scheme 1. This system consists
of a DSSC and a RFB, which are connected through two elec-

Scheme 1. Schematic representation of the working principle of a RFB

system that can store solar energy. O1/R1 and O2/R2 denote the oxidized/reduced states of the two redox couples.

trolyte circuit loops that allow two soluble redox couples to

separately enter the RFB for electrochemical discharge, and
then to pump the discharged redox couples into the DSSC for
photoregeneration. Following photoregeneration, the two
redox couples can be stored in two individual reservoirs for
subsequent RFB applications. The two cells are separated by
a lithium-ionic conducting glass ceramic membrane to prevent
the crossover of the redox couples between the anodic and
cathodic compartments; charge balance is maintained as only
the transport of nonreactive electrolyte cations can occur.
A critical challenge is to find two pairs of redox couples with
sufficient solubility, electrochemical reversibility, and suitable
redox potentials. As displayed in Scheme 1, the O1/R1 redox
couple requires a redox potential that is sufficiently higher
than the O2/R2 couple. In addition, the O1/R1 redox couple requires a slightly lower potential than the oxidation potential of
the dye so that it is regenerated when passing through the
DSSC. As an anode-active material, the O2/R2 couple of the RFB
must have a redox potential considerably lower than that of
the O1/R1 couple and it should be slightly lower than the Femi
level of the TiO2 photoanode. This is necessary so that the oxidized species from the anodic compartment of the RFB can be
reduced at the counter electrode by receiving photogenerated
electrons from the TiO2 photoanode in the DSSC.
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In our proof-of-concept experiment, redox-active I3/I and

[Fe(C10H15)2] + /Fe(C10H15)2 (denoted hereafter as DMFc + /DMFc)
were selected as the two redox couples because of their electrochemical reversibility and suitable redox potentials.
As shown in Figure 1, the redox potential of the I3/I couple

The discharged products (I and DMFc + ) could also be

stored in two separate storage reservoirs for subsequent
photoregeneration by recirculating them through the DSSC,
according to Equations (1)(3). Therefore, based on the above
experimental results and reaction mechanism analysis, the
design of such a rechargeable solar powered RFB system is
feasible.
To verify the feasibility of the rechargeable solar-powered
RFB system, the fabricated battery was photocharged by using
Xe lamp illumination with 40 mW cm2 irradiation for 2400 s at
a flow rate of 2 mL s1. The RFB was then discharged in the
dark at a constant current of 30 mA and a constant flow rate of
5 mL s1. According to Figure 2 a, the photocharge voltage of

Figure 1. Cyclic voltammograms of the soluble redox couples on platinum

electrodes at a scan rate of 10 mV s1 for I2 (10 mmol L1) + LiI
(2 mmol L1) + LiClO4 (0.2 mol l1) in propylene carbonate solution (c) or
DMFc (10 mmol L1) in 3-methoxypropylnitrile (b).

was approximately 0.7 V more positive than that of the

DMFc + /DMFc couple, but only 0.15 V lower than that of dye
Z709, which implied that the I3/I couple could be considered
as a cathode material if matched with the DMFc + /DMFc
couple in the RFB. Upon solar illumination, the soluble I3 and
DMFc + solutions were injected into the DSSC where photoelectrochemical reactions occurred to oxidize I into I3 in the
presence of a photoexcited dye molecule (dye* + ) at the TiO2
photoanode. In addition, the redox potential of the
DMFc + /DMFc couple was slightly lower than the Fermi potential of the TiO2 photoanode, suggesting that DMFc + was simultaneously reduced to DMFc at the counter electrode by receiving photogenerated electrons from the TiO2 photoanode
during the photocharge process in the DSSC.
dye TiO2 hv ! dye* e TiO2

2 dye* 3 I ! 2 dye I3  at photoanode

DMFc e TiO2 ! DMFc at cathode

After photocharging, the photoelectrochemically generated

I3 and DMFc species could either be stored in two separate
storage reservoirs as cathode- and anode-active materials, or
be directly injected into the RFB to release their chemical
energy as electricity. The discharge reactions in the RFB can be
represented as:
I3  2 e ! 3 I at cathode

DMFc ! DMFc e at anode

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 2. a) Typical photocharge and electrochemical discharge curves of

the rechargeable RFB system in the first two cycles. The photocharge reaction is performed by recirculating the redox species for 2400 s in the DSSC
at 0.025 V and a flow rate of 2 mL s1. b) Photocharge and discharge capacity
versus cycle number over 10 cycles. The discharge process is controlled at
a constant flow rate of 5 mL s1 and at 30 mA. The discharge capacity is calculated based on the anode-active species.

the DSSC rapidly increased to > 0.4 V and then climbed steadily to 0.58 V at a moderate illumination of 40 mW cm2, indicating photoelectrochemical conversion of the redox couples
from their initial discharged states (I and DMFc) to their
charged states (I3 and DMFc + ). In the initial discharge process,
the discharge curve of the RFB contained a sloped voltage plateau of approximately 0.33 V, which was different to the continually decreasing voltage curve that was obtained for the rechargeable solar battery with solid active materials.[9] In the
second cycle, the observed photocharge and discharge curves
were almost identical, demonstrating good stability of the rechargeable solar RFB system. The photocharge capacity and
electrochemical discharge capacity in the third cycle for the
redox couples were 33.1 and 20.4 mAh g1 (108.0 mAh L1 and
66.6 mAh L1), respectively, which demonstrated that 24.9 % of
the redox couples and 61.6 % of the photocharge capacity had
been utilized. Although there was a slow decrease in the disChemSusChem 2013, 6, 802 806

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charge capacity over ten cycles (Figure 2 b), the RFB system operated with considerable cycling stability and demonstrated
achievable photoregeneration of the discharged redox
couples. The slight decrease in discharge capacity during cycling could predominately have originated from incomplete
sealing of the volatile redox species in the recirculating loops
of the microfluidic system. This problem could be overcome
through optimization of the structural design and fabrication
of the fluidic system. Nevertheless, the performances (capacity,
voltage, and stability) revealed that the conversion of solar
energy to chemical or electrical energy, as well as storage in
the battery system, is achievable.
The photocharge performance of this system was further
evaluated by recirculating the two discharged redox couples in
the DSSC, and then discharging the photoregenerated redox
couples in the RFB, thus estimating the photochemical conversion efficiency. Figure 3 a clearly shows that the discharge capacity of the redox couples in the RFB initially increased with
increasing photocharge time, it then decreased with prolonged
photocharge times; this represented a direct dependence of
the photoregeneration efficiency of the redox couples on the
time that they remained under solar illumination. Figure 3 b
shows the time-dependent photocharge efficiencies of this
system, which were calculated from the ratio of the photocharge capacity consumed in the DSSC to the discharge capacity of the redox couples in the RFB. The maximum discharge capacity obtained from the RFB was 53.3 mAh L1, corresponding to a 47.9 % utilization of the photocharge capacity

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and a 24 % utilization of the redox couples after an illumination time of 2400 s. The highest material utilization of the
redox couples attained was 62.5 %, when the two redox species remained static in the DSSC for photocharging to occur.
The photocharge efficiency of the DSSC also depended on
the flow (recirculation) rates of the redox couples at a given
illumination time (Figure S1). The highest photocharge
efficiency (72.2 %) was observed when the redox couples were
recirculated at a flow rate of 2 mL s1 in the DSSC. Higher or
lower flow rates resulted in decreased photocharge
efficiencies, which implies that an appropriate match between
the interfacial photoelectrochemical kinetics and the mass
transfer dynamics of the redox couples is a critical factor in determining the conversion efficiency from solar energy to chemical energy.
The discharge efficiency in the RFB was greatly affected by
the flow rate of the redox couples and the output current rate,
which were similar to the effects reported for conventional
RFB systems.[1114] As shown in Figure S2, at low current
(10 mA), the discharge capacity (16.48 mAh) from the RFB was
almost equal to the photocharge capacity (16.5 mAh) contribution from the DSSC; therefore, 100 % capacity utilization was
achieved. As the current rate was increased from 30 to 50 mA,
the photocharge/discharge efficiency rapidly decreased from
56.3 to 8 %; this could be attributed to the low redox species
concentration and low flow rates. The discharge capacities
were increased from 3.86 mAh at a flow rate of 1 mL s1 to
13.3 mAh at 20 mL s1, which suggested that the high-rate discharge performance of the RFB could be achieved through
control of the hydrodynamic conditions of the redox species.
A vast amount of research has already been performed to enhance the high-rate performance of RFB systems by using
three-dimensional porous electrodes, highly catalytic electrodes, high linear velocities, and good turbulence promoters,[13]
which will benefit the future improvement of our RFB system.
The total photo-to-chemical-to-electrical energy conversion
efficiency (h0) of this system can be expressed as:
ho hpe hec hce
R
R
R
Jt  DEtdt
DE 0 Jtdt
I  Vdt
R
R



 100%
P i  ti
Jt  DEtdt DE 0 Jtdt

Figure 3. Photocharge and electrochemical discharge profiles of the I3/I

and DMFc + /DMFc redox couples in the DSSC and RFB, respectively. a) The
redox couples (0.6 mL) illuminated at different times and recirculated at
1 mL s1 through the DSSC, and b) photocharge efficiencies of the redox
couples at different illumination times, calculated from the ratio of the integrated photocurrent consumed in the DSSC to the discharge capacity of the
redox couples at a flow rate of 1 mL s1 and a current of 20 mA in the RFB
cell.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Herein, hpe and hec represent the photo-to-electrical and the

photocurrent-to-chemical energy conversion efficiencies of the
DSSC, respectively, at certain times and illuminations, and hce
denotes the chemical-to-electrical energy conversion (discharge) efficiency of the redox couples in the RFB. Pi is the incident power, ti is the illumination time, J(t) is the photocharge
current, and DE is the potential difference of the two redox
couples, which is monitored by using two reference electrodes
in the photoanode and counter electrode chambers of the
DSSC. I and V(t) stand for the discharge current and voltage of
the RFB cell, respectively. DE0 is the potential difference of the
two redox couples at an equilibrium state.
Although hpe in DSSCs can usually exceed 7 %,[15] the photocharging efficiency for the DSSC in this work was only 0.15 %,
that is, several times lower than that of the conventional
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DSSCs. The low hpe value can be attributed to the large illumination area, thick inorganic separator, and the size of our
DSSC, which led to a large internal resistance, thus decreasing
the photo-to-electrical energy conversion efficiency. Further
work is required to enhance the photovoltaic performance
through structural design and optimization of our DSSCs.
Both the hec and hce values in our experiments were determined to be approximately 58 % at moderate flow and discharge rates. The electrical-to-chemical and chemical-to-electrical energy conversion reactions in our DSSC and RFB were similar to the charge/discharge reactions in most common batteries; however, their conversion efficiencies (hec and hce) reach
> 80 %. The lower hec and hce values in our cells were mainly
caused by the potential polarization of the two redox couples,
as evidenced from the large voltage gaps between the photocharge and discharge voltage plateaus (Figure 2), which could
be attributed to insufficient electrocatalysis and mass transport
of the redox couples in our DSSC and RFB. We believe that further development of highly catalytic, three-dimensional electrodes and intelligent control of high linear flow velocities
would greatly improve the photocharge and electrochemical
discharge efficiencies.
In summary, we propose a RFB that can store solar energy in
combination with a DSSC. It is demonstrated that the asfabricated battery with a dye sensitized TiO2 photoanode and
two soluble redox couples (I3/I and DMFc + /DMFc) is able to
achieve photo-to-chemical-to-electrical energy conversion and
photo-to-chemical energy storage. This work provides insight
into new solar battery systems for solar energy conversion and
storage.

pentadienyl)iron (DMFc, 10 mmol L1) + LiClO4 (0.2 mol l1) was

used as the liquid anode for the RFB.

Experimental Section

Acknowledgements

The DSSC was composed of a dye-sensitized TiO2 photoanode,

a counter cathode, and a Li + glass ceramic separator (LiSICON),
which were clamped together with two plastic spacers inserted
into the two sides of the separator to distance the anode and cathode chambers. The TiO2 photoanode was prepared by coating
a TiO2 paste [0.6 g TiO2 (P25, Degussa), 0.12 g ethyl cellulose, 1 mL
terpineol, and 9 mL ethanol] onto a fluorine-doped tin oxide glass
(FTO, 15 W cm2, Nippon Sheet Glass), followed by sintering the
anode at 500 8C for 30 min to form a mesoporous TiO2 film of approximately 10 mm thickness. The photoanode was sensitized by
immersing it into a 5  104 mol L1 ethanolic solution of
RuLL(NCS)2 (L = 2,2bipyridyl-4,4-dicarboxylic acid L = 4,4-dinonyl2,2bipyridine; Ruthenizer 520-DN or Z907, Solaronix) overnight.
The anode was then rinsed it with anhydrous ethanol and dried.
The counter electrode was prepared through electrochemical deposition of platinum black onto FTO glass in an aqueous solution of
H2PtCl6 (0.5 mmol L1). The LiSICON lithium-ion-based conducting
glass ceramic (LiCGC, 0.15 mm-thick, Li1 + x + yAlxTi2xSiyP3yO12) was
purchased from OHARA Inc., Japan.

Financial Support from the 973 Program (2009CB220100) of

China is gratefully acknowledged.

The RFB was fabricated following the procedure for the DSSC described above, except a pair of platinized electrodes was used as
the anode and cathode. The platinized electrodes were prepared
in the same way as the counter electrode for the DSSC. A propylene carbonate (PC) solution containing I2 (10 mmol L1) + LiI
(2 mmol L1) + iClO4 (0.2 mol L1) was used as the liquid cathode,
and 3-methoxypropylnitrile solution with bis(pentamethylcyclo 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The photocharging process was performed by using a dual-channel microfluidic pump (Longerpump, Baoding, China) to inject the
two redox electrolytes into the individual photoanode and cathode
chambers at a constant illumination intensity of 40 mW cm2 and
a constant voltage of 0.025 V; this pump was also used to collect
the photoregenerated redox electrolytes in two syringes (1 mL).
To evaluate the photo-to-chemical conversion efficiencies, the
photocharge reactions were conducted at controlled illumination
times with various flow rates of the redox electrolytes, or at controlled flow rates with various illumination times. Similarly, the electrochemical discharge process of the redox couples was performed
by recirculating the photoregenerated redox electrolytes in the
anodic and cathodic chambers of the RFB at a constant current
with various flow rates, or at a constant flow rate with changing
discharge currents. The discharged redox electrolytes were separately accumulated in two syringes (1 mL) for subsequent photocharge. The microfluidic pumps used for recirculating the redox
electrolytes in the RFB were the same type as those used for the
DSSC. Both the volumes of the two redox electrolytes for DSSC
and RFB experiments were controlled at 0.3 mL. The change in the
potential difference of the redox couples during photocharging
was monitored by using a pair of platinum reference electrodes inserted into the anodic and cathodic chambers of the DSSC; the
photocurrent was recorded with an IM6e electrochemical workstation (Zahner, Germany). The discharge curves of the RFB were
recorded by using a CHI 600A electrochemical workstation (Shanghai, China). The incident light for the photocharge was produced
from a solar light simulator (Oriel 91160-1000, USA) and adjusted
to give a power density of 40 mW cm2. The intensity of the incident light was characterized with a radiant power/energy meter
(Oriel, 70260) before each experiment.

Keywords: dye-sensitized solar cells energy conversion

recharge redox flow batteries solar storage
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Received: December 15, 2012

Published online on April 4, 2013

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