Electrochimica Acta 187 (2016) 525–534

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Broad temperature adaptability of vanadium redox flow battery—Part

1: Electrolyte research
Shuibo Xiaoa , Lihong Yub , Lantao Wua , Le Liua , Xinping Qiua,c, Jingyu Xia,*
a
Institute of Green Chemistry and Energy, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China
b
School of Applied Chemistry and Biological Technology, Shenzhen Polytechnic, Shenzhen 518055, China
c
Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Article history: The broad temperature adaptability of vanadium redox flow battery (VRFB) is one of the key issues which
Received 27 August 2015 affects the large-scale and safety application of VRFB. Typically, five types of vanadium electrolytes,
Received in revised form 5 November 2015 namely V2+, V3+, V3.5+ (V3+:VO2+ = 1:1), V4+ (VO2+) and V5+ (VO2+), are the most common electrolytes'
Accepted 11 November 2015
status existing in VRFB system. In this work, the physicochemical and electrochemical properties of these
Available online xxx
vanadium electrolytes are studied in detail at a broad temperature range (-35
C–50
C). The results show
that all types of vanadium electrolytes are stable between -25
C–30
C. The temperature fluctuation will
Keywords:
largely influence the conductivity and viscosity of the electrolytes. Besides, the electrochemical
Vanadium redox flow battery
Temperature adaptability
properties of the positive (VO2+) and negative (V3+) electrolytes are greatly affected by the temperature;
Electrolyte and the charge transfer process fluctuates more greatly with the temperature variation than the charge
Static stability diffusion process does. These results enable us to better and more comprehensively evaluate the
Electrochemical properties performance of the electrolyte changing with the temperature, which will be beneficial for the rational
choice of electrolyte for VRFB operation under various conditions.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction its high energy efficiency, elimination of electrolyte cross-

contamination, and low capital cost for large-scale energy storage
As the environment continuously deteriorates, it's more urgent [7–10]. The standard open circuit potential of VRFB is 1.26 V, and it
to develop renewable energy to replace traditional energy uses V(IV)/V(V) and V(II)/V(III) dissolved in sulphuric acid as the
resources. However, the random and intermittent nature of positive and negative electrolytes respectively, carbon fabric
renewable energy resources like solar energy and wind energy materials as the electrodes, and ion exchange membranes (IEMs)
induces instability to the grid, which vastly limits their develop- as the separators [11–13]. Until now, much effort has been devoted
ment [1–3]. In order to smooth out the intermittency of renewable to fully study and promotes the technique of the VRFB, such as low
energy production, electrical energy storage (EES) has become an cost and high ion selectivity membranes [14–18], high activity and
indispensable part to integrate the grid and renewable energy [4]. power density electrodes [19–21], and high concentration and
Among different kind of energy storage technologies, redox flow stability electrolytes [22,23].
batteries (RFB) have been proposed as a promising large-scale EES, The current VRFB technology is still not ready for broad market
owing to its low cost, flexible design, high safety and long cycle-life penetration due to the low energy density (< 25 Wh kg1), which is
[5,6]. mostly caused by the low solubility and stability of the electrolyte
A redox flow battery is an electrochemical system which stores solutions [24]. There are many factors affecting the VRFB
electric energy in two separated electrolyte tanks containing performance such as the concentration of vanadium ions and
different redox couples. Among various RFBs, the all-vanadium sulfuric acid, the operating temperature, the state of charge (SOC)
redox flow battery (VRFB) is one of the most developed RFBs due to and the electrochemical activity of electrodes [25], among which
the operating temperature influence should be especially noticed.
Usually, V(II), V(III), and V(IV) are inclined to form precipitation under
* Corresponding author.
a relatively low temperature, while the V(V) solution presents poor
E-mail address: [email protected] (J. Xi). stability at high temperatures and high vanadium concentrations

http://dx.doi.org/10.1016/j.electacta.2015.11.062
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
526 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534

[26]. Detailed studies have been conducted on the solubility of composition of 1.5 M vanadium in 3.875 M total sulphate was
vanadyl sulfate in concentrated sulfuric acid solutions based on the selected in this series of study. The static stability, viscosity,
solubility [27,28]. Great efforts have been directed to prevent or conductivity, cyclic voltammetry and electrochemical impedance
delay the precipitation in the electrolyte of the VRFB. It is found spectroscopy of the electrolytes were investigated and compared.
that high sulfuric acid concentration can dramatically enhance the These features are used to evaluate and predict battery perfor-
stability of V(V) solution. But it also takes negative impact on the mance varying with the temperature, and then can further be used
solubility of the V(II), V(III), and V(IV) ions [22]. Some organic or to determine the electrolyte composition referring to the
inorganic chemicals can be used as additives to stabilize the environment.
vanadium ions [29–34]. These additives could improve the stability
of the electrolyte in a relatively wide range of temperatures (-5
C– 2. Experimental
40
C). Yang et al. proposed another strategy employing chloride
[35] or a sulfate-chloride mixed acid system [24] as the supporting 2.1. Preparation of electrolyte
electrolytes instead of the pure sulfuric acid solutions, which
shows better thermal stability and solubility. The initial V3.5+ electrolyte (V(III)/V(IV) = 1:1) was prepared by
As an energy storage device, VRFB is usually used in different electrolytic dissolution of the suitable weight of V2O5 in the H2SO4
climates areas. The environmental temperature can affect the supporting electrolyte. Then, the V3.5+ electrolyte was injected into
properties of electrolyte and electrode kinetics pronouncedly, a vanadium redox flow battery (VRFB) and charged at a constant
which thereby influences the battery performance. Unfortunately, current density of 80 mA cm2. The detail parameters of the VRFB
there have been few specific reports dealing with the temperature single-cell was described previously [36,37]. By precisely control-
influences on the electrolyte properties. In this paper, we focused ling the charged electric quantity, four kinds of pure vanadium
on temperature effect on the physicochemical and electrochemical electrolyte with single valence could be obtained, namely the
properties of the different vanadium ion solutions (V(II), V(III), V3.5+, violet electrolyte of V(II), the green electrolyte of V(III), the blue
V(IV) and V(V)) from -35
C to 50
C. In order to establish a scientific electrolyte of V(IV) and the yellow electrolyte of V(V). In this paper,
and reasonable research method, the electrolyte with a moderate V(II), V(III), V3.5+, V(IV) and V(V) are used to denote V2+, V3+, V3.5+, V4+

Fig. 1. (a) Photographs of five types of vanadium electrolytes. The corresponding vanadium species changes during precharge and charge-discharge process is also shown in
the figure; (b) Reaction equations of the vanadium electrolytes in positive and negative half-cell during different status of the VRFB; (c) Ionic compositions of the five types of
vanadium electrolytes.
 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534 527

and V5+, respectively. Fig. 1(a) shows the preparation process and viscosity tests, three parallel tests were conducted and the average
the digital photos of five kinds of vanadium electrolytes (in 1 mm values were presented.
cuvette). The required solutions were then placed in sealed glass
jars to be used. 2.4. Electrochemical measurements

2.2. Static stability measurements Cyclic voltammetry (CV) and electrochemical impedance
spectroscopy (EIS, frequency range from 105–102 Hz with
The static stability of all five kinds of vanadium electrolytes amplitude of 10 mV) measurements were performed on PARSTAT
was tested in a thermostat (Guangdong HongZhan Technology Co. 2273 electrochemical workstation (Princeton Applied Research). A
Ltd, PU-80) under various temperatures range from -35
C to classic three-electrode system was used in the measurement,
50
C. The temperature deviation of the thermostat was  0.5
C. which consisted of a glass carbon electrode with 3 mm diameter
The electrolytes were put in sealed volumetric flasks and (used in CV test) or a graphite stick with 6 mm diameter (used in
examined every day. When the electrolyte appeared precipitation EIS test) as working electrode, a graphite plate as counter electrode
at low temperature, then, it was warmed to room temperature or and a saturated calomel electrode (SCE) as reference electrode. The
higher temperature to see if the precipitation could dissolve glassy carbon electrode was firstly polished on chamois with
again. Similarly, if any electrolyte appeared deposition at high 0.3 mm alumina, then cleaned in 1 M H2SO4 through CV from 0 to
temperature, it was cooled to room temperature or lower 1.0 V (vs. SCE) for 5 cycles, and finally cleaned by ultrasonic in
temperature to see if the process is reversible. Three groups of deionized H2O for 10 min. The CV test was carried out from 0 to
samples were tested for the stability study, the results were 1.6 V vs. SCE at different scan rates in 1.5 M V(IV) (positive
repeated and the photos were taken by a digital camera outside electrolyte), while from -1.4 to 0.2 V vs. SCE at different scan rates
the thermostat. in 1.5 M V(III) (negative electrolyte) at various temperatures. All the
CV measurements were taken three times on each temperature
2.3. Conductivity and viscosity measurements and the deviations were less than 0.5%. Therefore, the CV data was
reproducible. The EIS test was implemented in the same positive
Conductivity and viscosity of each electrolyte was measured and negative solutions. In addition, all the potentials are referred to
respectively on a conductivity meter (Mettler Toledo AG, SCE unless otherwise stated. Similarly, the electrolyte had been
SevenEasy S30, Switzerland) and Ubbelohde viscometer at various kept in the thermostat for enough time at each test temperature.
temperatures. Electrolyte was put in the thermostat for enough
time to make sure the temperature reached the set value and then 3. Results and discussion
measured by the conductivity meter as quickly as possible. The
Ubbelohde viscometer with the electrolyte was put in the 3.1. Charge-discharge process analysis
thermostat and the connected pipes were extended outside the
thermostat for operation. The kinematic viscosity was tested when The four kinds of pure vanadium electrolyte used in the
the thermostat was kept at a set temperature for an hour. Viscosity experiment were achieved by charging the initial V3.5+ electrolyte
of the deionized water was used as the reference at each (0.75 M V(III) + 0.75 M V(IV) + 2 M H2SO4) in a VRFB single-cell
temperature. The viscosity of V(II) electrolyte was measured in [36,37]. The dissociation constants of H2SO4 at 25
C are 1.0103
N2 gas atmosphere to avoid oxidation. For the conductivity and (K1) and 1.02102 (K2). The actual value of the proton

Fig. 2. (a) Photographs of five types of electrolytes at low temperature; (b) Photographs of re-dissolution of the precipitation that formed at low temperature.
528 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534

concentration in five types of vanadium electrolytes should be temperatures. Fig. 2(a) shows the photographs of the electrolytes,
between the two cases (the first dissociation and fully dissociation) which are taken at 0 h, 5 h, 10 h, 24 h and 48 h at temperatures from
while maintain the same trend. To simplify the process, we -20
C to -35
C, respectively. It is observed that all the electrolytes
assumed that the sulfuric acid was fully dissociated and did not are stable at -20
C and -25
C through 48 hours, with no
consider other ionic effect. The detailed reactions and the transfer precipitation or freezing. The V(III) solution precipitates within
of electron and proton during charge and discharge processes in less than 24 hours at -30
C, while the other electrolytes are stable
the positive and negative half-cells of VRFB are illustrated in for more than 48 hours. When the electrolytes are kept at -35
C,
Fig. 1(b). As observed, in the process of precharge, the V3+ is the V(II) and V(III) solutions precipitate or freeze within less than
oxidized into VO2+ and there have protons and electrons been one hour, and the V3.5+ mixed solution precipitates in less than
produced at the positive half-cell, an inverse reaction happened 10 hours. In the purpose of testing the reversibility of the
simultaneously at the negative half-cell. If careful analysis of this precipitation, the solutions are subsequently warmed to 25
C.
process, 0.75 M electrons transfer from the positive to the negative After 30 minutes, the precipitation dissolves completely and
half-cell through external circuit; and meanwhile, 0.75 M protons recovers to the initial state, as is shown in Fig. 2(b). Accordingly,
transfer from the positive to the negative half-cell through the the precipitation of the V(II), V(III) and V3.5+ solution at low
membrane. The final consequence of this step is equivalent to that temperatures could redissolve when the temperature goes up,
0.75 M protons transfer from negative electrolyte to positive which can be considered as a reversible process.
electrolyte, which leads to that the concentration of proton in Moreover, the stability of the electrolytes at high temperatures
positive electrolyte is higher than that in negative electrolyte. The from 30
C to 50
C is shown in Fig. 3. Obviously, the V(V)
similar situation occurs during the charge process, but in reverse precipitates out at 35
C, 40
C, 45
C and 50
C in 80 hours,
during discharge. Fig. 1(c) illustrates the ionic compositions of the 60 hours, 10 hours and 7 hours respectively, and the precipitations
five types of vanadium electrolytes. These five vanadium electro- can't redissolve at low temperatures. According to previous report
lytes are corresponding to different state of charge of the cell, [7], the precipitation is V2O5 formed via a deprotonation reaction
including different proton concentration. The following test and as following:
analysis are performed to study the performance of these five
[VO2(H2O)3]+ ! H3VO4 + H3O+
vanadium electrolytes at various temperatures.

3.2. Broad temperature stability analysis

2 H3VO4 ! V2O5 + 3H2O
In previous research [38–40], it had been confirmed that high
acid concentration was good to the stability of V(V) ion at high 3.3. Conductivity and viscosity analysis
temperature, but bad to the stability of V(II), V(III), and V(IV) ions at
low temperature. This will limit the operating temperature range Ionic conductivity of the vanadium electrolyte will have great
in 10-40
C for VRFB. In order to extend the operating temperature effect on the performance of VRFB, such as the electrode kinetics
range, especially under extreme temperatures (-35
C - 50
C), and the resistance of the battery. S. Corcuera et al. had studied the
1.5 M vanadium concentration was chosen to test the stability of conductivity of 1.6 M V in 4.2 M sulphate electrolyte corresponding
the electrolyte and the operating performance of VRFB in this to different SOC of the VRFB positive half-cell at 10
C, 22
C and
series of work. The five types of vanadium electrolyte are kept in 43
C and found that the conductivity increases with temperature
the thermostat to test the low temperature stability in various [41]. M. Skyllas-Kazacos et al. had studied the effect of composition

Fig. 3. Photographs of five types of electrolytes at high temperature.

 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534 529

on conductivity at 22
C and found that the conductivity changes concentration of vanadium (V) and sulphate [25]. A. Mousa and M.
with the concentration of vanadium ion and total sulfate [42]. Skyllas-Kazacos had also investigated the possible factors like the
Therefore, the impact of temperature on the conductivity of sulphate concentration and temperature (15
C - 40
C), which will
vanadium electrolyte was also studied in this work. The ionic affect the properties of negative electrolyte [44]. Both temperature
conductivity (s ) of five types of vanadium electrolytes as a function and concentration will affect the viscosity of vanadium electrolyte.
of temperature are shown in Fig. 4(a). Obviously, the s of all Variable temperature solution viscosity (h) data for different types
electrolytes is increasing with temperature. The conductivity of of electrolyte are shown in Fig. 4(b). The viscosity of pure water is
V(V) electrolyte ranks highest, followed by the V(II) electrolyte and shown as benchmark. For each electrolyte, the viscosity is observed
V(IV) electrolyte, the V3.5+ electrolyte and V(III) electrolyte in namely to decrease with temperature increasing, and apparently, the
array. It's worth noting that the V(II) electrolyte and V(IV) electrolyte viscosity in low temperature is much larger than that in high
almost have the same conductivity at all tested temperatures. This temperature. What's more, it increases suddenly below 0
C, and
tendency is in accordance with the proton concentration of the the value at -20
C is almost 10 times larger than that at 50
C.
electrolyte as shown in the inset of Fig. 4(a) (also see Fig. 1(c)). However, the viscosity of V(II), V(IV) and V(V) electrolytes are very
Recently, S. Suarez had found out that the conductivity of the close to each other at a definite temperature, except that of the V(III)
electrolyte is related to the vanadium and proton concentration electrolyte. According to the Stokes-Einstein equation as shown
[43]. However, the vanadium concentrations of these five electro- below [43]:
lytes are the same (1.5 M) and so the s may be decided mainly by
the proton concentration. kB T
D¼
As a significant feature of VRFB, the electrolytes are cyclically h
pumped through the battery (stack) when it is working. Therefore,
where kB and T are the Boltzmann constant and temperature of the
the viscosity of the electrolyte is an important parameter which
solution, respectively. For a established temperature, hwill
affects the uniform distribution of electrolyte in the battery and the
increase with the decrease of the diffusion coefficient. According
energy consumption of the pump. F. Rahman and M. Skyllas-
to previous report [45,46], the V(III) electrolyte was supposed to
Kazacos had taken a specific research on the viscosity of the
have the biggest viscosity for its lowest diffusion coefficient, which
positive electrolyte and found that the viscosity increases with the
is in accordance with the experiment result here.
The differences in s and h for the electrolyte may be due to a
number of factors. The conductivity of electrolyte is mainly decided
by the quantity and electromigration velocity of ions. On one hand,
the velocity of the ions increases with the temperature. On the other
hand, these five electrolytes are different in aspects of the proton
concentration and the vanadium valence. The existence forms of the
vanadium species in acidic conditions are usually regarded as VO2+
(V(V)), VO2+ (V(IV)), V(H2O)63+ (V(III)) and V(H2O)62+ (V(II)) [45]. The
difference in existence form leads to the different diffusion
coefficient and Stokes radius of the vanadium species. These
elements give combined influence to the s and h. Anyhow,
temperature has great influence on the conductivity and viscosity
of the electrolyte, and then temperature could strongly affects the
VRFB cell performance.

3.4. Electrochemical performance

3.4.1. Positive electrolyte

As discussed above, the positive electrolyte consists of 1.5 M
V(IV) + 4.75 M H+ + 3.875 SO42, which equals to 1.5 M V(IV) +
2.375 M H2SO4. The CV results of the positive electrolyte in various
temperatures with different scan rates are shown in Fig. 5. It
reveals that, for a given scan rate, firstly, both the anodic peak (ipa)
and the cathodic peak (ipc) current densities of the V(IV)/V(V) couple
decreases apparently with the decrease of temperature. For
example, the ipa decreases from 199.6 mA cm2 to 32.3 mA cm2
when the temperature decreases from 50
C to -10
C at the scan
rate of 200 mV s1. Secondly, the separation between oxidation and
reduction peak potential (DV) increases with the temperature
drops. For instance, the DVincreases from 0.18 V to more than 0.9 V
when temperature decreases from 50
C to -10
C at the scan rate of
20 mV s1, and apparently, the redox peak at -10
C is not clearly
perhaps mainly for the reason that electrode's activity was poor.
The value of –Ipc/Ipa with various scan rates in different
temperature is shown in Fig. 5(h). It can be seen that the value of
–Ipc/Ipa increases with temperature from -10
C to 30
C and then
maintain relatively stable from 30
C to 50
C, suggests a more
complex reaction mechanism that requires further investigation.
Fig. 4. (a) Impact of temperature on the conductivity of five types of electrolytes. These results indicate that the activity and reversibility of the
Inset shows the concentration of proton in different vanadium electrolyte; (b)
electrolyte is greatly affected by temperature, and a higher
Impact of temperature on the viscosity of five types of electrolytes.
530 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534

Fig. 5. (a)-(g) CV curves of V(IV)/V(V) redox couple record at 50
C – -10
C with different scan rates; (h) Values of –Ipc/Ipa with different scan rates at different temperatures; (i)
Plots of peak current density versus the square root of scan rates at different temperatures.

temperature can facilitate the redox reactions of V(IV)/V(V) couple. ip = 0.4958(F3/RT)1/2a1/2ACD21/2n1/2 (irreversible reaction) (2)
Fig. 5(i) illustrates the relationship between the redox peak current
where F is the Faraday constant, T is the Kelvin temperature, R is the
density and the square root of the scan rate. A linear relationship
universal gas constant, C is the bulk concentration of primary
can be seen from the two parameters, and the slope of the line is
reactant,A is the geometric area of the working electrode, D1 and D2
decreasing with the reducing of temperature.
represent the diffusion coefficient for a reversible reaction and an
From the above discussion, the V(IV)/V(V) redox couple here is a
irreversible reaction respectively, n is the scan rate, a stands for the
quasi-reversible reaction. In theory, the value of the diffusion
transfer coefficient for an irreversible reaction. Though the Eqs. (1)
coefficient (D) for a quasi-reversible reaction is between that for a
and (2) were used to calculated diffusion coefficients in dilute
reversible one (D1) and an irreversible one (D2) [47]. For a one-step
solutions, they can be used here to allow indicative estimates and
and one electron reversible and irreversible reaction, the peak
trends of the diffusion coefficients under different temperatures.
current density ip is given in the following equations [48]:
On accounting of Eqs. (1) and (2), when T = 50
C = 323.15 K,
ip = 0.4463(F3/RT)1/2ACD11/2n1/2 (reversible reaction) (1) based on the known experimental factors, D1 and D2 can be finally
deduced to the following equations:

Table 1
Diffusion coefficient D1 (cm2 s1) and D2 (cm2 s1) of positive and negative electrolytes at different temperatures.

Temperature (
C) Positive electrolyte Negative electrolyte

Oxidation Reduction Oxidation Reduction

D1 D2 D1 D2 D1 D2 D1 D2
-10 1.7810-8 2.8910-8 4.7910-11 7.7710-11 1.3510-8 2.1910-8 3.2810-8 5.3210-8
0 5.4110-8 8.7910-8 4.8110-9 7.7910-9 2.0310-8 3.2910-8 4.5510-8 7.3710-8
10 1.0410-7 1.6910-7 1.0310-8 1.6710-8 2.9710-8 4.8210-8 6.4810-8 1.0510-7
20 1.5410-7 2.4910-7 5.0110-8 8.1310-8 4.6510-8 7.5310-8 8.0910-8 1.3110-7
30 4.0210-7 6.5110-7 2.2310-7 3.6110-7 6.5910-8 1.0710-7 8.7810-8 1.4210-7
40 6.6810-7 1.0810-6 4.0410-7 6.5510-7 9.6110-8 1.5610-7 9.8310-8 1.5910-7
50 9.8710-7 1.6010-6 5.6010-7 9.0710-7 1.2810-7 2.0710-7 1.1810-7 1.9210-7
 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534 531

D1 = 6.68  106k2 (3) kinetic control region. The semicircle is extended by the moving
charge-complexes close to the Helmholtz plane and is represented
by an interfacial contact capacitance (Cc) and charge transfer
D2 = 1.08  105k2 (4) resistance (Rct). In the quiet low frequency range, the charge-
complexes have enough time to get over the activation energy and
where kstands for the slope of the line which the variables are the
reach the region near the Helmholtz plane. These charge-
current density (ip) and the square root of scan rate (n1/2).
complexes finally occupy all surfaces inside the micro-pores of
Consequently, the slope k is fitted and obtained from Fig. 5(i),
the electrodes and consist of the electrical double layer capacitance
and the diffusion coefficient D1 and D2 of the positive electrolyte at
(Cdl). The diffusion control regime is directed by the low frequency
different temperatures are obtained and listed in Table 1. It is
range which is contributed by Cdl. All the circuit elements related to
observed that, no matter what the oxidation process or the
the Nyquist plot can be arranged to form an equivalent circuit as
reduction reaction, the diffusion coefficient D increases with the
shown in the inset of Fig. 6(c). It is used to fit the Nyquist spectra
temperature increasing. Besides, the diffusion coefficient D of the
measured for the electrolyte at different temperatures. In the
oxidation reaction is bigger than that of the reduction reaction for
equivalent circuit where the interfacial contact capacitance Cc and
the positive electrolyte. In other words, a higher temperature can
the electrical double layer Cdl are replaced by a constant phase
elevate the diffusivity of the vanadium ions and intensify the
element (CPE) in order to compensate for the depressed semicircle
processes of mass transfer and charge transfer, and finally improve
in the kinetic control and fully fit the line in the diffusion control
the activity of the positive redox reaction.
[50]. The diffusion resistance that be interpreted using the
The effect of temperature on electrochemical behaviors of
Warburg diffusion element (W) in the diffusion control regime,
positive electrolyte is further investigated through EIS. Fig. 6(a)
is a main element to influence the performance of the circuit.
shows the Nyquist spectrum of 20
C at different polarization
The Nyquist plots of positive electrolyte at different temper-
potentials, and all spectra contain a semi-circle in the high
atures are shown in Fig. 6(b). The plot indicates that the redox
frequency region and a straight line in the low frequency. For the
reaction of V(IV)/V(V) couple is simultaneously controlled by the
polarization potential can bring in influence on the test [49], a
charge transfer process at high frequency and the diffusion process
potential near the start potential of the oxidation reaction in the CV
at low frequency. In other words, the reaction is a mixture of
curve (see Fig. 5) is chosen to take the following temperature
kinetic and diffusion-controlled process. It's obviously seen in
influence test. Usually, a Nyquist spectrum can be explained in the
Fig. 6(c) that, Rb and Rct clearly decrease with the increase of
following way. The electrical double layer in the pores of the
temperature which corresponds well with the former test results.
electrode is composed of the charge-complexes diffusing towards
On the basis of the data which was fitted by ZsimpWin software
the Helmholtz plane inside the pores. The first cross point on the
with the equivalent circuit, the temperature gives slight influence
real axis of the plot in the high-frequency region is represented as
on the W, for the electrolyte is aqueous phase, and the diffusion in
the bulk solution resistance of the electrolyte, electrode resistance
solution can satisfy the reaction need. However, the change of the
and the contact resistance (Rb). It is followed by a semicircle in the
Rct indicates that the temperature could evidently affect the charge
range of high frequency to medium frequencies, a region where
transfer process, which may be caused by the loss of activity of the
only small number of charge-complexes can get over the activation
electrode. The temperature dependence of the charge transfer
energy to shift with the alternating potential, which is called the
resistance Rct can be better understood in the form of the activation

Fig. 6. (a) EIS results of V(IV)/V(V) redox couple record under different polarization potentials at 20
C; (b) EIS results of V(IV)/V(V) redox couple record at different temperatures
under 0.800 V; (c) Values of Rb and Rct at different temperatures; (d) An Arrhenius plot of the temperature-dependence of Rct.
532 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534

energy E following an Arrhenius-type equation [50]: between oxidation and reduction peak potential (DV) is increasing
  with the decreasing of temperatures. Thirdly, Fig. 7(h) shows the
1 DE value of –Ipc/Ipa with various scan rates at different temperatures,
¼ Aexp  ð5Þ
R0 RT
from which we could see the value are closer to 1 at high
where A is a constant,DE is the activation energy, R is the gas temperatures, while farther away to 1 at low temperatures. These
constant, and T is the absolute temperature. Replacing R0 by the results also suggest that the activity and reversibility of the
value of Rct and plotting lnRct versus 1/T, we can get the activation negative electrolyte is greatly affected by temperature, and a
energy Ea from the slope of the line shown in Fig. 6(d), which is to higher temperature can facilitate the redox reactions of V(II)/V(III)
overcome the charge transfer resistance Rct in the kinetic control couple. Fig. 7(i) illustrates the relationship between the redox peak
regime. As illustrated in Fig. 6(d), an activation energy of 28.5 kJ current density and the square root of the scan rate, for which a
mol1 can be received, which explains the potential energy linear relationship could be seen from the two parameters, and the
difference resulted from the temperature change. slope of the line is decreasing with the reducing of temperature.
The diffusion coefficient D could be calculated from Eqs. (3) and (4)
3.4.2. Negative electrolyte which is listed in Table 1. Apparently, the diffusion coefficient Dis
The negative electrolyte is composed of 1.5 M V(III) + 3.25 M H+ + going up with the increasing of the temperature, and the D of
3.875 M SO42, which is equal to 1.5 M V(III) + 1.625 M H2SO4. In reduction reaction is bigger than that of the oxidation reaction
order to study the electrochemical influence of temperature to the which is opposite to that of the positive electrolyte. Therefore a
negative electrolyte, CV and EIS test are also conducted to see the higher temperature can elevate the diffusivity of the vanadium
change with temperature. Fig. 7(a)-(g) expresses the CV curves of ions and intensify the processes of mass transfer and charge
the negative electrolyte at various temperatures with different transfer, and as well finally improve the activity of the negative
scan rates. As a matter of fact, the variation tendency is the same as reaction.
the positive electrolyte (see Fig. 5). Firstly, the oxidation and In addition, the Nyquist plot of the negative electrolyte is
reduction peak current density are decreasing with the tempera- shown in Fig. 8. The plot indicates that the redox reaction of
ture going down, e.g. the ipa decreases from 94.5 mA cm2 to V(II)/V(III) couple is also a mixture of kinetic and diffusion-
37.8 mA cm2 when the temperature decreases from 50
C to -10
C controlled process. It's clearly in Fig. 8(c) that, the Rb and Rct are
at the scan rate of 200 mV s1, but the oxidation peak current decreasing with the temperature, the Rct of the negative
density is smaller than the reduction peak current density which is electrolyte is larger than that of the positive electrolyte. The
opposite to that of the positive electrolyte. Secondly, the separation activation energy could also been calculated by Eq. (5) as shown in

Fig. 7. (a)-(g) CV curves of V(II)/V(III) redox couple record at 50
C–-10
C with different scan rates; (h) Values of –Ipc/Ipa with different scan rates at different temperatures; (i)
Plots of peak current density versus the square root of scan rates at different temperatures.
 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534 533

Fig. 8. (a) EIS results of V(II)/V(III) redox couple record under different polarization potentials at 20
C; (b) EIS results of V(IV)/V(V) redox couple record at different temperatures
under -0.600 V; (c) Values of Rb and Rct at different temperatures; (d) An Arrhenius plot of the temperature-dependence of Rct.

Fig. 8(d), a value of 21.9 kJ mol1 that is comparable to the positive JCYJ20150331151358143, JCYJ20140417115840235 and
electrolyte (28.5 kJ mol1), unveiling a similar temperature effect JCYJ20140509172959960).
on both resistances.
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