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DOI: 10.1002/cssc.201200962
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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
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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.
Experimental Section
Acknowledgements
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.
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