Electrochimica Acta 78 (2012) 475–482

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

Influence of organic additives on electrochemical properties of the positive

electrolyte for all-vanadium redox flow battery
Xiaojuan Wu a , Suqin Liu a,∗ , Nanfang Wang a,b , Sui Peng a , Zhangxin He a
a
Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083,
China
b
School of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, China

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

Article history: Inositol and phytic acid have been employed as organic additives of the positive electrolyte for all-
Received 5 January 2012 vanadium redox flow battery (VRFB) to improve its stability and electrochemical reversibility. Thermal
Received in revised form 12 June 2012 stability of the V(V) electrolyte could be improved by both inositol and phytic acid additives. The
Accepted 12 June 2012
results of cyclic voltammetry (CV), steady polarization curve and electrochemical impedance spec-
Available online 30 June 2012
troscopy (EIS) show that the electrochemical activity of the electrolyte with additives is improved
compared to the blank one. The diffusion coefficient of V(IV) species with inositol has been increased
Keywords:
from 0.71–1.16 × 10−6 to 3.11–5.15 × 10−6 cm2 s−1 and the exchange current density was raised from
Organic additives
Electrolyte
2.8 × 10−3 to 11.7 × 10−3 A cm−2 . Moreover, electrochemical results suggest that the positive electrolytes
All-vanadium redox flow battery with organic additives have better cycling stability. The VRFB employing positive electrolyte with inos-
Inositol itol as additive exhibits excellent charge–discharge behavior with an average energy efficiency of 81.5%
Phytic acid at a current density of 30 mA cm−2 . The UV–visible spectroscopy confirms that new substances in V(V)
electrolyte are not formed with both inositol and phytic acid additives.
© 2012 Elsevier Ltd. All rights reserved.

1. Introduction ions [7]. Adding precipitation inhibitors is an effective method

Recently, the vanadium flow battery (VRFB), pioneered at the
University of New South Wales (UNSW) [1–3], has been consid-
ered as an efficient storage unit for a wide range of applications. By
employing V(II)/V(III) and V(IV)/V(V) redox couples in H2 SO4 as the
negative and positive half-cell electrolytes respectively, the capac-
ity and power output of VRFB are dependent on the volume and
concentration of the electrolytes. However, the high energy den-
sity of VRFB (>25 W h kg−1 [4]) is still a challenge, owning to the
poor solubility and stability of the vanadium species, especially the
V(V) electrolyte at elevated temperature which has limited their
further application.
In the sulfuric acid solution, V(V) species exist as hydrated penta
co-ordinated vanadate ion, i.e. [VO2 (H2 O)3 ]+ . This hydrated struc-
ture would be converted to V2 O5 precipitation by de-protonation
process and condensation reaction at elevated temperature [5].
Thermal stability of V(V) solutions can be enhanced by increas-
ing the concentration of supporting electrolyte (H2 SO4 ), which
prevents the process of de-protonation or dimerization of VO2+
ions to V2 O4 2+ and V2 O3 4+ species [6]. However, higher sulfuric
acid concentration favors the precipitation of V(II), V(III) and V(IV)
∗ Corresponding author. Tel.: +86 731 88879850; fax: +86 731 88879850.
E-mail address: sqliu2003@126.com (S. Liu).
for stabilizing vanadium electrolytes. Sodium hexametaphosphate
and alkali metal sulfate were reported as good precipitation
inhibitors for supersaturated vanadyl sulfate solutions [4]. More-
over, several organic additives, which contain one or more OH,
O, NH2 or SH groups, or combinations of these groups so
that they can encapsulate the hydrated penta co-ordinated vana-
date ion and inhibit the precipitation formation, are screened
as potential additives [8]. The stabilizing agent with secondary
or tertiary OH, NH2 and SH groups may resist to oxida-
tion at low concentrations [9]. And the addition alcohols which
have ring or chain structures can stabilize the electrolyte and
increase the solubility of V(II)–V(V) ions in the solution [10].
Thus, we have focused on selecting suitable cyclic organic addi-
tives with OH groups which would not be oxidized to CO2 for
not containing straight chain of carbon atoms. The addition of
such organic agents is expected to improve the performance of
the electrolyte solutions, in terms of stability and electrochemical
reversibility.
In this paper, cyclic organic additives, inositol and phytic acid,
were used as additives to improve the performance of positive
electrolyte for VRFB. To our knowledge, there are no literature
reports on the effect of cyclic organic additives containing OH
on vanadium electrolyte. The kinetic parameters of V(IV) and
V(V) electrolyte solutions with and without additives were com-
pared by means of CV, steady polarization and EIS measurements.

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.06.065
476 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482

Properties such as stability and viscosity of high concentrated elec-
trolyte solutions were also investigated in detail.
2. Experimental
2.4. Viscosity test
Solution viscosity was measured with an Ubbelohde viscometer
tube and all the tests were carried out at the room temperature.

The V(IV) electrolyte solutions were prepared by electrolytic 2.5. Scanning electron microscopy (SEM)
dissolution of V2 O5 in 3.0 M H2 SO4 supporting electrolyte in a two-
compartment electrolysis cell [11]. A certain amount of additives, The surface morphology of the felt electrode sample was char-
inositol or phytic acid, were added into the anode of electrolysis acterized with a scanning electron microscopy (JEOL, JSM-6360LV,
cell in the process of electrolyzing. The V(V) electrolyte solution Japan) at an acceleration voltage of 25 kV.
was prepared by charging the prepared V(IV) solution in a flow
single cell at 60 mA cm−2 . The resulting solution with and without
3. Results and discussion
additives was analyzed by potentiometric redox titration to deter-
mine the valence and concentration of the vanadium ions using a
3.1. Effect of the additive on the UV–vis spectra of V(IV)/V(V)
standardized potassium permanganate solution. In order to ensure
electrolyte
the above redox titration gives an error less than 3%, preliminary
experiments starting from a V(V) solution of reagent V2 O5 [12]. The
Fig. 1 shows the UV–Vis spectra for V(IV) and V(V) electrolyte
UV–visible spectroscopy of the vanadium electrolyte was measured
with and without additives. All the measured V(IV) electrolytes
on a UV–vis spectrometer (UV-3802) in the range of 200–900 nm
are 0.01 M V(IV) in 3 M H2 SO4 and V(V) electrolytes are 0.001 M
using 2.0 cm quartz cell.
V(V) in 3 M H2 SO4 . As seen in Fig. 1, neither a new absorption peak
nor a wavelength shift in electrolyte samples with the additive is
2.1. Thermal stability experiment of V(V) observed compared with the pristine one. The result implies that
the addition of trace amount of inositol or phytic acid could not
During the stability tests, the electrolyte solutions (1.8 M form a new substance or change the concentration of the positive
V(V) + 3.0 M H2 SO4 ) with different additives were statically stored electrolyte [14].
in a temperature-controlled bath at different temperatures (room
temperature, 40, 50 and 60 ◦ C). The samples were monitored regu-
larly for the formation of precipitation and recorded the time when (a) 0.35
a slight precipitation appeared visually. The samples at 60 ◦ C for
one day were filtered and titrated to determine the change in the 0.30
pristine
vanadium concentration.
with additive of phytic acid
0.25 with additive of inositol
Absorbance ( A.U.)

2.2. Electrochemical measurements

0.20
Cyclic voltammetry (CV) tests and steady polarization study
of V(IV) solutions (2.0 M V(IV) + 3.0 M H2 SO4 ) with and without 0.15
additives were performed using the CHI660 electrochemical work-
station (Shanghai Chenhua Instrument Co., Ltd., China). The curves 0.10
of current versus potential were recorded in a three-electrode
electrochemical cell with Pt as the counter electrode, an aqueous 0.05
saturated calomel electrode (SCE) along with a salt bridge full of
saturated potassium chloride solution as reference electrode and a 0.00
400 500 600 700 800 900
graphite plate (1.0 cm × 1.0 cm) as working electrode. Prior to test,
the working electrode was manually polished with 600 and 1200 Wavelength / nm
grit SiC paper and then washed by ultrasonic cleaning in ethanol
and doubly in distilled water for 8 min, respectively [13].
(b)
1.6
Electrochemical impedance spectroscopy (EIS) was conducted
by a ZAHNER-IM6 electrochemical workstation (Germany). The
pristine
sinusoidal excitation voltage applied to the cells was 5 mV with
1.2 with additive of phytic acid
Absorbance ( A.U.)

a frequency range between 0.001 Hz and 100 kHz.

with additive of inositol

2.3. Cell test 0.8

The testing VRFB consisted of two pieces of graphite felt (the

thickness was 8 cm, Shenhe Carbon Fiber Materials Co., Ltd.), two 0.4
current collectors and a PE-01membrane (Zhejiang Qianqiu Group
Co., Ltd., China). The active area of the electrode was about 30 cm2 .
350 ml of 1.8 M V(IV)/3.0 M H2 SO4 solutions with 3.0% mole/mole 0.0
different additives and 350 ml of 1.8 M V(IV)/3.0 M H2 SO4 solutions
were used as the initial anolyte and catholyte respectively, and 200 300 400 500 600 700 800 900
cyclically pumped into the corresponding half-cell. The galvano- Wavelength / nm
static charge and discharge of the test cell were carried out using
Fig. 1. UV–vis absorption spectra of electrolyte solution. (a) Spectra of the
CT2001C-10V/2A (Wuhan Land Co., China) between 0.7 and 1.7 V
V(IV)–H2 SO4 solution with and without additives. (b) Spectra of the V(V)–H2 SO4
at a current density of 30 mA cm−2 . solution with and without additives.
 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482 477

Table 1
Effect of inorganic additives on the stability of 1.8 M V(V)/3 M H2 SO4 solution.

Time to precipitation Vanadium concentration of the

solution after 1 days at 60 ◦ C
(mol L−1 )

Measured values Error (%) Measured values Error (%)

◦ ◦ ◦ ◦ ◦ ◦ ◦ ◦
25 C 40 C 50 C 60 C 25 C 40 C 50 C 60 C

Pristine >20days 98 h 17 h 3h 0 0.4 3 6 1.29 4

Phytic acid >20days 116 h 25 h 4.5 h 0 0.5 2 4 1.51 4
Inositol > 20days 109 h 23 h 4h 0 0.5 2 5 1.43 3

3.2. Thermal stability 0.06

b
a
To investigate the effects of additives on the stability of V(V) 0.04
at elevated temperatures, sealed samples of each solution were
placed in water baths at 25 ◦ C, 40 ◦ C, 50 ◦ C and 60 ◦ C. The induc- 0.02 c
tion time for the formation of precipitation was recorded and the

Current/A
average data for three repeated operations are presented in Table 1. 0.00
As observed, the formation of precipitation is delayed under all the
studied temperatures by adding selected additives. The concentra- -0.02
tion of the V(V) electrolyte with phytic acid remains 1.51 M after a pristine
1 day at 60 ◦ C, much higher than the pristine one (1.29 M). Despite -0.04 b with additive of inositol
some slight scatter in the data of repeated experiments is observed, c with additive of phytic acid
definite trends in time to precipitation and the change of V(V) -0.06
concentration are seen with different electrolytes. The improved
stability of V(V) electrolyte may be interpreted that the additives -0.08
could facilitate dispersion of the hydrated form of V(V) ions for -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
the synergy of coulombic repulsion and steric hindrance [5,10,15]. Potential vs. SCE/V
Actually, because the additives contain OH and O groups, they
are able to absorb on the surface of the nuclei, which helps to the Fig. 2. Cyclic voltammograms for 2.0 M V(III) solution with different additives.
dispersion of V(V) ions by electrostatically repulsing and inhibits
precipitation by retarding crystal growth [8].

3.3. Electrochemical measurements 0.08

a pristine c
3.3.1. Cyclic voltammetry b with additive of phytic acid
0.06
3.3.1.1. Effect of the additive on the electrode reaction of the negative c with additive of inositol
electrolyte. The effects of additives on the positive electrolyte and b
0.04
negative electrolyte must be considered together for the inevitable
Current/A

transport of the additives across the membrane. The CV of 2.0 M

V(III) in 3.0 M H2 SO4 solution with and without additives obtained 0.02
a
at 10 mV s−1 is shown in Fig. 2. As seen, there is no significant change
caused by the selected additives, which indicates that neither inos- 0.00
itol nor phytic acid would largely change the reversibility of the
V(II)/V(III) redox couple in the negative half-cell. -0.02

3.3.1.2. Effect of the additive on the electrode reaction of the posi- -0.04
tive electrolyte. Fig. 3 displays the CV curves of 2.0 M V(IV) in 3.0 M
H2 SO4 solution with different additives at a scan rate of 10 mV s−1 . 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
The related data based on Fig. 3 are summarized in Table 2. As can Potential vs. SCE/V
be seen, two aspects could be involved for the influence of phytic
acid and inositol on V(IV)/V(V) redox couple. Firstly, the ratios of Fig. 3. Cyclic voltammograms of the electrolyte (2.0 M VOSO4 + 3.0 M H2 SO4 ) with
anodic peak current to cathodic peak current (Ipa /Ipc ) and the peak various additives on graphite electrode: (a) pristine; (b) inositol; (c) phytic acid at a
potential separation for V(IV)/V(V) redox reaction are decreased scan rate of 10 mV s−1 .
obviously, implying both phytic acid and inositol could improve

Table 2
Cyclic voltammograms data for 2.0 M V(IV) solution with different additives on graphite electrode.

Sample Anodic peak, Ipa (mA) Cathodic peak, Ipc (mA) Ep (mVa ) Ipa /Ipc Increased rate

Anodic peak current Cathodic peak current

Pristine 49.10 35.73 237 1.374 – –

Phytic acid 58.63 54.19 141 1.082 16% 34%
Inositol 74.02 57.09 177 1.296 34% 37%
a
Potential vs. SCE.
478 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482

Fig. 4. CV curves of the electrolyte (2.0 M VOSO4 + 3.0 M H2 SO4 ) with various additives on graphite electrode: (a) pristine; (b) inositol; (c) phytic acid at a range of potential
scan rates.

Table 3
Viscosities of 2.0 M V(IV) solution with different additives. 0.36

Sample Pristine Phytic acid Inositol

Pristine
3 0.30 with additive of phytic acid
Viscosity (×10 Pa s) 4.96 4.58 4.33
with additive of inositol
0.24
the redox reversibility of V(IV)/V(V). Secondly, the increasing of
the anodic and cathodic peak currents is observed when the two
I/A

0.18
additives are added into the vanadium electrolyte, which indicates
the improvement of electrode reaction kinetics. This is probably
attributed to the decrease in mass transportation polarization of the 0.12
electrolyte with the additives, which is confirmed by the viscosity
data given in Table 3. Viscosity, as an important property of vana-
0.06
dium solutions, would affect the conductivity and electrochemical
behavior of electrolyte. Increase in viscosity leads to a decrease in
diffusion coefficient of the vanadium ions, which finally results in a 0.00
0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
decrease in the electrode reaction kinetics [16]. As shown in Table 3,
both the additives could effectively reduce the viscosity of the elec- 1/2 1/2 -1/2
v /V s
trolyte in comparison with the pristine one, and the electrolyte with
inositol possesses the lowest viscosity. Fig. 5. Plots of the anodic peak current vs. the square root of scan rates (1/2 ) for the
In order to further investigate the effect of additives on the electrolytes with different additives.
kinetics of electrode reaction, a series of CV curves for solutions
containing different additives on the graphite electrode at various
Moreover, the corresponding diffusion coefficients of the solu-
scan rates are shown in Fig. 4. It presents the typical characteris-
tions with different additives, obtained from Eqs. (1) and (2), are
tics of a quasi-reversible one-electron process for the anodic and
presented in Table 4. It clearly shows that the diffusion coef-
cathodic peak potentials change gradually with the scanning rates.
ficient of V(IV) species is increased from 0.71–1.16 × 10−6 to
For a reversible redox couple, the peak current ip is given in Eq. (1)
1.97–3.26 × 10−6 and 3.11–5.15 × 10−6 cm2 s−1 , with the addition
[17]:
of inositol and phytic acid, respectively, indicating an improvement
ip = 2.69 × 105 n3/2 ACD0 1/2
1/2
(1) in the diffusion of V(IV) and its oxidation. Except the electron trans-
fer step, redox reactions between VO2+ and VO2 + should contain
And for an irreversible redox couple, the peak current ip is given the breaking/formation of the V O chemical bond which seems to
in Eq. (2) [17]: be the most probable chemical step. The chemical step probably
1/2
plays the dominant roles during V(IV)/V(V) reaction [18]. The addi-
ip = 2.99 × 105 n3/2 ˛1/2 ACD0 1/2 (2) tives, with multi hydroxyl groups in the opposite orientation, may
where n is the number of electrons transferred in the reaction, promote the chemical step by coordinating with redox reaction of
A is the work electrode area (1 cm2 ), C is the bulk concentra- V(IV)/V(V) couple [19].
tion of primary reactant, D0 is the diffusion coefficient, and  is
the scanning rate. A plot of the anodic peak current as a func- 3.3.1.3. Effect of the additive on the electrolyte cyclic stability. Fig. 6
tion of the square root of scan rates (1/2 ) is shown in Fig. 5. shows the cyclic stability of V(IV)/V(V) solutions with inositol and

Table 4
The diffusion coefficient of V(IV) species in solution with different additives.

Sample Pristine Phytic acid Inositol

Calculated values Error (%) Calculated values Error (%) Calculated values Error (%)
−1
D × 10 (cm s
6 2
) 0.71–1.16 2 1.97–3.26 5 3.11–5.15 4
 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482 479

0.08 (a) 70 pristine

with additive of inositol with additive of phytic acid
0.06 60 with additive of inositol

50
0.04

-2
Current/A

j / mA cm
40
0.02
30
0.00
20

-0.02
10

-0.04 0
0.75 0.80 0.85 0.90 0.95 1.00 1.05 1.10 1.15 1.20
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
E vs. SCE/ V
Potential vs. SCE/V
Fig. 7. Steady polarization curves for 2.0 M VOSO4 + 3.0 M H2 SO4 solution with dif-
ferent additives on graphite electrode at a scan rate of 1 mV s−1 .
0.08 (b)
with additive of phytic acid

0.06

0.04
Current/A

0.02

0.00

-0.02

-0.04

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Potential vs. SCE/V

Fig. 6. Cyclic voltammograms (40 scans) of electrolyte solutions with various addi-
tives: (a) inositol and (b) phytic acid.

Fig. 8. Nyquist plots of the electrolytes with and without additives at ambient tem-
perature.
phytic acid at a graphite electrode during the initial 40 cycles at
a scan of 10 mV s−1 . As the scans proceeded, almost no variation
is observed on the peak shape and the peak potential separation,
where Rct is the charge-transfer resistance, R is the univer-
suggesting that the positive electrolyte with selected additives have
sal gas constant, T is the Kelvin temperature, n is the number
good cycling stability.
of electrons transferred in the electrode reaction, F is the
Faraday constant, k0 is rate constant and C0 is the solution
3.3.2. Steady state polarization study concentration [13,20].
The steady state polarization curves of V(IV) solution with The steady state polarization curves for 2.0 M VOSO4 + 3 M
different additives were employed to determine polarization resis- H2 SO4 solution with different additives on graphite electrode are
tance, exchange current density and electrochemical reaction rate shown in Fig. 7 and the corresponding parameter obtained from
constant. At relatively low overvoltage area, current density and Eq. (3) are listed in Table 5. As observed, the polarization resistance
overvoltage yield are approximately straight line [16]. The param- of the electrolyte with inositol is the smallest (2.2 ) with a high-
eters could be calculated as follows: est exchange current density and reaction rate constant, which is
consistent with the results of CV tests. The results reveal that the
 RT i0 anodic oxidation of V(IV) on graphite electrode process becomes
Rct = , i0 = , k0 = (3)
i nFRct nFC0 much faster with adding inositol or phytic acid into electrolyte,

Table 5
Kinetic parameters for 2.0 M VOSO4 + 3 M H2 SO4 solution with different additives on graphite electrode.

Sample Polarization resistance, Rct ( cm2 ) Exchange current density, j0 (mA cm−2 ) Rate constant, K0 (10−5 cm s−1 )

Pristine 10.1 2.8 1.45

Phytic acid 4.1 6.3 3.26
Inositol 2.2 11.7 6.06
480 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482

1.8

a Pristine
1.6
b Phytic acid
Potential vs. SCE/V

c Inositol
1.4
c
b
1.2
a

1.0

0.8

0.6 Fig. 10. The positive pole of disassembled cell: (a) phytic acid; (b) pristine; (c)
0 4 8 12 16 20 24 28
inositol.
Time/h

Fig. 9. Charge–discharge curves for vanadium redox flow cell employed electrolyte
with different additives at a current density of 30 mA cm−1 .
probably due to the improved diffusion and oxidation ability of the
V(IV).
3.3.3. Electrochemical impedance spectroscopy
The Nyquist plots of the electrolytes with and without additives
at ambient temperature are presented in Fig. 8. Each plot consists
of a semicircle in the high frequency region and a straight line in
the low frequency region. The semicircle in high frequency region
is related to the charge transfer process and the straight line in the
low frequency region represents the diffusion limited process [19].
Equivalent circuit model is also proposed in Fig. 6, where R1 stands
for the resistance composed of electrolyte resistance (Rs ) and the
electrode resistance (Re ), CPE is the constant phase element of inter-
face between the electrolyte and the electrode, R2 and W represent
the charge transfer resistance in the electrochemical process and
Warburg diffusion impedance, respectively [21,22]. The simulation
results obtained by Zsimpwin software are shown in Table 6. There
are significant differences in R1 and R2 for each sample. Meantime,
the electrolytes with inositol and phytic acid exhibit a lower elec-
trolyte resistance and charge transfer resistance than the pristine
one, indicating that the transfer of vanadium ion and electron is
more feasible.
In order to determine reproducibility, all the electrochemical
measurements were repeated. Some slight fluctuations in the date

Fig. 11. The SEM images of the positive graphite felts of disassembled cell after 20 charge–discharge cycles: (a) phytic acid; (b) pristine; (c) inositol.
 X. Wu et al. / Electrochimica Acta 78 (2012) 475–482 481

100 Table 6
(a) Fitting results of EIS.

Sample R1 ( cm2 ) CPE R2 ( cm2 )

Y0 n
90
Pristine 3.769 8.822 × 10−8 0.9887 27.21
Phytic acid 2.572 1.563 × 10−7 1 10.57
4.119 × 10−7
Efficiency(%)

Inositol 1.099 1 2.846

80

on the positive graphite felt of the sample with phytic acid, which
Coulombic efficiency
should be VOPO4 ·2H2 O(s) [24].
Voltage efficiency
70 Fig. 12a shows the columbic, voltage and the energy efficiency
Energy efficiency
of the cell employing the vanadium electrolyte with inositol as a
function of cycling number. With the increasing of circle times, the
columbic efficiency keeps stable and remains above 98.4%, and the
60 average energy efficiency maintains 81.5% at the current density of
0 2 4 6 8 10 12 14 16 18 20 30 mA cm−2 . The capacity loss for the pristine one and the one with
Cycle Number inositol are presented in Fig. 12b. With the cycle increasing, the
cell with inositol exhibits less discharge capacity fading compared
16 to the pristine one, which is probably ascribed to the higher stability
(b) of vanadium solutions with inositol. Overall, the cell using inositol
14 modified electrolyte exhibits better electrochemical performance
compared with the blank one.
12
4. Conclusions
10
Capacity/Ah

The effects of two cyclic organic additives, phytic acid and

8
inositol, on the stability and electrochemical behavior of posi-
Charge for cell with inositol tive electrolyte for VRFB were studied. Thermal stability of the
Discharge for cell with inosital V(V) electrolyte was improved by both phytic acid and inositol,
6
Charge for pristine as demonstrated by the stability tests. The electrochemical mea-
Discharge for pristine surements indicated that better reaction kinetics was achieved
4
by adding phytic acid and inositol, resulting in the improvement
of V(IV) diffusion coefficient, exchange current density and elec-
2 trochemical reaction rate constant. Besides, the addition of trace
amount of the two additives did not alter the electrochemical prop-
0 2 4 6 8 10 12 14 16 18 20
erties of the negative electrolyte. More importantly, it was found
Cycle Number that the VRFB employing the vanadium electrolyte with inositol as
positive electrolyte exhibited better charge–discharge characteris-
Fig. 12. Cycle performance of VRB. (a) Columbic, voltage and the energy efficiency of
VRFB using the vanadium electrolyte with inositol as a function of cycling number. tic and less discharge capacity fade rate with cycles in comparison
(b) Charge and discharge capacities of VRFB with and without inositol. with the pristine one. Note that the capacity of the VRFB employing
the electrolyte with phytic acid decreased significantly, probably
owning to the formation of sediments on the positive graphite
are observed due to experiment errors, however, the slight discrep- felt. Anyway, inositol could be used as a promising additive for the
ancies are acceptable and trends are defined. positive electrolyte of VRFB.

Acknowledgements
3.4. Electrochemical performance of VRFB
This work was financially supported by the National Key Basic
The charge–discharge experiments were performed using a sin-
Research Program of China (973 Program) (No. 2010CB227201) and
gle VRFB cell. Fig. 9 shows the charge–discharge curves of a 1.8 M
National Natural Science Foundation of China (No. 51072234).
vanadium electrolyte with and without additives. Note that the cell
with addictives in positive electrolytes presents a lower charging
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