Electrochimica Acta 106 (2013) 556–562

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

Effects of organic additives containing NH2 and SO3 H on

electrochemical properties of vanadium redox flow battery
Zhangxing He, Jianlei Liu, Huiguo Han, Yong Chen, Zhi Zhou, Shijie Zheng,
Wei Lu, Suqin Liu ∗ , Zhen He ∗
Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, School of Chemistry and Chemical Engineering, Central South
University, Changsha 410083, China

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

Article history: Effects of methanesulfonic acid (MSA) and aminomethylsulfonic acid (AMSA) as additives for positive
Received 3 February 2013 electrolyte on thermal stability and electrochemical performance are investigated. Both additives can
Received in revised form 10 May 2013 improve the thermal stability of V(V) electrolyte, and AMSA has better effect, especially. The electrochemi-
Accepted 18 May 2013
cal results show that V(IV)/V(V) exhibits superior electrochemical activity and reversibility with additives,
Available online 31 May 2013
and the diffusion coefficient of V(IV) species, exchange current density and reaction rate constant become
larger with additives in positive electrolyte. Among the two additives, AMSA has better effect for improve-
Keywords:
ment of electrochemical activity and kinetics. The cell using positive electrolyte with additive of AMSA
Vanadium redox flow battery
Additives
was assembled and the charge–discharge performance was evaluated. The assembled cell using AMSA
Aminomethyl sulfonic acid as positive electrolyte additive shows good cycling performance, with higher energy efficiency (81.5%)
Thermal stability and larger discharge capacity retention (40 cycles: 82.7%). The improved electrochemical performance
Electrochemical activity may be ascribed to more active sites provided by NH2 group and the enhanced hydrophilicity of the
electrode provided by NH2 and SO3 H groups.
© 2013 Published by Elsevier Ltd.

1. Introduction concentration of sulfuric acid can enhance the thermal stability

With the development of new energy, the redox flow bat-
tery systems have attracted much attention, such as Br2 /Br− vs.
S/S2− [1,2], Br− /Br2 vs. Zn2+ /Zn [3], Fe3+ /Fe2+ vs. Cr2+ /Cr3+ [4,5],
V5+ /V4+ vs. V2+ /V3+ [6,7], etc. [8–11]. Among these technolo-
gies, vanadium redox flow battery (VRFB), originally proposed
by Skyllas-Kazacos et al., has been considered as one of the
most promising energy storage systems for intermittently renew-
able energy because of its long cycle life, high energy efficiency
and environmental friendship [12–16]. The commercial applica-
tion of VRFB significantly promotes the development of VRFB
technology and it shows great prospect for use in station-
ary energy storage, photovoltaic and wind turbine generators
[11,17,18].
Low solubility of V(V) and low electrochemical activity of active
species on the electrode are two major disadvantages of VRFB.
In sulfuric acid solution, hydrated penta co-ordinated vanadate
ion of V(V) would convert to V2 O5 precipitation at high tempera-
ture, which limits the energy density of VRFB [19,20]. Increasing
∗ Corresponding authors. Tel.: +86 731 88879850; fax: +86 731 88879850.
E-mail addresses: sqliu2003@126.com (S. Liu), zhenhe@csu.edu.cn (Z. He).
of V(V), however, it also aggravates the thermal stability of V(II),
V(III) and V(IV) [18,21]. Adding stabilizing agent is one of the
most effective methods to improve the thermal stability of V(V)
[22,23]. Some inorganic and organic additives have been chosen
and achieved good effects. Inorganic additives, such as sodium
hexametaphosphate and alkali metal sulfate, were reported as
good stabilizing agent for supersaturated vanadyl sulfate solutions
[24]. Moreover, organic additives, such as surfactants, dispersants,
or other organic chemicals containing OH and SH groups, can
also enhance the thermal stability of V(V) [22,25,26]. Graphite felt
weaved with carbon fiber is the most widely used electrode for
VRFB because of its wide operation potential range, good stability,
and high specific surface area at reasonable cost, however, graphite
felt electrode shows poor hydrophilicity, electrochemical activity
and kinetics. Up to now, a variety of modifications of graphite felt
have been reported to improve its electrochemical activity, such
as heat treatment [13], acid treatment [27], electrochemical oxi-
dation [28] and introducing functional groups onto the graphite
felt [29]. Recently, Wu [29] reported hydrothermal treatment by
ammonia for graphite felt, by which the polar nitrogenous groups
can be introduced on the surface of graphite felt, leading to faster
charge transfer between electrode and vanadium ions. However,
strict conditions are needed in this case. Can we introduce the

0013-4686/$ – see front matter © 2013 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.electacta.2013.05.086
 Z. He et al. / Electrochimica Acta 106 (2013) 556–562
nitrogenous groups to the electrode through electrolyte? Sulfonic
acid exhibits good electrochemical performance in other redox flow
batteries [30–32]. Both of NH2 and SO3 H are hydrophilic groups.
Thus, it is interesting to know if NH2 and SO3 H groups would be
able to improve the thermal stability and electrochemical perfor-
mance of positive electrolyte.
In this paper, methanesulfonic acid (MSA: CH3 SO3 H) and
aminomethylsulfonic acid (AMSA: (NH2 CH2 SO3 H) were used as
additives to improve the thermal stability and electrochemical per-
formance of positive electrolyte for VRFB. It is found that both
additives (MSA, AMSA) can improve the thermal stability and elec-
trochemical performance, of which AMSA shows the best effect.
2. Experimental
2.1. Thermal stability experiment of V(V)
The V(V) electrolyte was prepared by oxidizing VOSO4 in
the positive side of a two-compartment electrolysis cell which
employed H2 SO4 with the same concentration as the catholyte in
the negative side. The termination of electrolysis was determined
by the UV–Vis measurement. Electrolyte of 2.0 M V(V) in 3.0 M
H2 SO4 with additives MSA or AMSA was stored in a temperature-
controlled bath at 50 ◦ C for different immersion time (3 h, 6 h,
9 h, 12 h), respectively. The molar ratio of different additives to
V(V) in all measurements is 1%. At the end of immersion, the
V(V) electrolyte was centrifuged and analyzed by redox titra-
tion to determine the change of the vanadium concentration.
The concentration of V(V) ions was titrated by NaNO2 with N-
phenylanthranilic acid as indicator. The titration was ended when
the color was changed to bright green.
2.2. UV–Vis spectrometry of V(IV) electrolyte
UV–Vis spectrometry of vanadium electrolyte was measured
on UNIC 3802 UV/Vis spectrophotometer (Shanghai, China) in the
range of 400–900 nm using 1.0 cm quartz cell. The measured solu-
tions are 0.04 M V(IV) and 3.0 M H2 SO4 without and with additives.
The molar ratio of additives to V(IV) is 1%. 3.0 M H2 SO4 solution
with 4 × 10−4 M additives was used as the reference solution for
the electrolyte with additives, and 3.0 M H2 SO4 solution was used
as the reference solution for the pristine electrolyte.
2.3. Viscosity measurement
Ubbelohde viscometer was used to measure the viscosity of
vanadium electrolytes with different additives. Viscosity can be
figured out by timing solution with a specified volume flowing
through a capillary tube. The viscosity of electrolytes was calculated
according to the following equation.
gd4 t
=
128V
where  is the viscosity;  solution density; d diameter of capillary;
t average time of the solution flowing through a capillary tube; V
solution volume.
2.4. Electrochemical measurements
Cyclic voltammetry was carried out in the three-electrode sys-
tem between +0.3 V and +1.4 V vs. SCE at a scan rate range of
5–200 mV s−1 . Tafel polarization curve test was carried out in the
three-electrode system at a scan rate of 0.5 mV s−1 . A 1 cm2 graphite
plate and 4 cm2 platinum sheet were used as working electrode and
counter electrode, respectively. Saturated calomel electrode along
with a salt bridge full of saturated potassium chloride solution was
557
used as reference electrode. Prior to each measurement, the work-
ing electrode was polished with 600 and 1200 grit SiC paper and
then washed with distilled water as described in literature [33].
The reference electrode was washed with distilled water, and the
solution in salt bridge was replaced before use. The tests were per-
formed using the CHI660 C electrochemical workstation (Shanghai
Chenhua Instrument Co., Ltd., China).
2.5. Charge–discharge test
The VRFB charge–discharge tests were performed in
single dynamic cells, which consisted of two pieces of
polyacrylonitrile(PAN)-based graphite felt with the size of
5 cm × 6 cm (Shenhe Carbon Fiber Materials Co., Ltd.), two current
collectors and a perfluorinated ion-exchange membrane (Best
Industrial & Trade Co., Ltd., China). The graphite felt was encircled
and fixed with polyurethane with thickness of 5 cm, and the
plyurethane and current collector was sealed with silicon rubber.
Original electrolyte used in the tests include 160 mL 1.2 M V(IV)
in 3.0 M H2 SO4 as positive electrolyte and 160 mL 1.2 M V(III) in
3.0 M H2 SO4 as negative electrolyte. The state of charge (SOC) is
0% at the start of cycling. During the operation, the electrolyte was
cyclically pumped into the corresponding half-cell with centrifugal
pump (MP-10RN, Shanghai Xinxishan Co., Ltd., China) at a flow
rate of 50 mL min−1 . The charge–discharge tests were carried out
by using CT2001C-10V/2A (Wuhan Land Co., China). The battery
was galvanostatically charged and discharged between 0.7 V and
1.7 V at a current density of 40 mA cm−2 .
2.6. X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) was conducted to
investigate the change of elements on the surface of graphite felt
after charge–discharge test with additive of AMSA on a K-Alpha
1063 (Thermo Fisher Scientific, UK) with Al K␣ X-ray source gener-
ated at 12 kV and 6 mA in an ultra-high vacuum of about 10−9 mBar.
Before testing the XPS, the graphite felt after charge discharge test
with additive of AMSA was treated simply as follow: washed with
deionized water, then dried for 5 h at 60 ◦ C.
3. Results and discussion
3.1. Thermal stability of V(V)
To investigate the thermal stability of V(V) at elevated temper-
ature, sealed V(V) electrolyte with MSA and AMSA was placed in
a water bath at 50 ◦ C, respectively. The effect of additives on the
solubility of V(V) ion at 50 ◦ C is displayed in Fig. 1. The original
concentration of V(V) ion is 2.02 M. It can be found that the concen-
tration of V(V) decreases with the increase of immersion time for all
electrolyte, and the concentration of the electrolyte with additives
of MSA and AMSA is higher than that of the pristine electrolyte for
the same immersion time. The reduction of the V(V) concentration
in the electrolyte with AMSA is less significant than the pristine one
and electrolyte with MSA. Moreover, the concentration of V(V) with
AMSA remains 1.14 M, 0.22 M higher than that of the pristine elec-
trolyte at 50 ◦ C after 12 h. It indicates that the V(V) electrolyte with
additive of AMSA exhibits the best thermal stability. The improved
thermal stability of V(V) electrolyte may be due to that AMSA can
enhance the dispersibility of V(V) ions which is easy to hydrate
and precipitate for synergy of coulombic repulsion and steric hin-
drance [19,23]. AMSA containing NH2 and SO3 H groups can be
adsorbed on the surface of nuclei of V(V) ions, which enhances the
dispersibility of V(V) ions to hinder crystal growth [23].
558 Z. He et al. / Electrochimica Acta 106 (2013) 556–562
Fig. 1. Effect of additives on thermal stability of V(V) electrolyte at the temperature
of 50 ◦ C.
3.2. UV–Vis spectra of V(IV) electrolyte
The UV–Vis spectra for V(IV) electrolyte without and with addi-
tives are shown in Fig. 2. The measured V(IV) electrolyte with
additives is 0.04 M V(IV) in 3 M H2 SO4 with MSA and AMSA, respec-
tively. The characteristic absorption peak of UV–Vis for V(IV)
appears at about 770 nm [34]. It can be observed from Fig. 2, the
spectra of electrolyte with additives are similar to that of the pris-
tine electrolyte, without new absorption peak and wavelength
shift. The results show that the additives of MSA and AMSA could
not change the bonding style of V and the effective concentration
of V(IV).
3.3. Cyclic voltammetry
Fig. 3 shows the cyclic voltammograms of 2.0 M V(IV) in 3.0 M
H2 SO4 solution without and with additives at a scan rate of
20 mV s−1 . The relevant data of peak current and peak potential
interval are listed in Table 1. It can be known from Fig. 3 that
the additives do not influence the oxygen evolution on charge,
not increasing oxygen evolution or decreasing oxygen evolution,
because there is no increase of current at high potential. It can
be seen from Table 1 that the peak current increases after the
Fig. 2. UV-Vis absorption spectra of V(IV)-H2 SO4 electrolyte with additves.
Fig. 3. Cyclic voltammograms of the electrolyte (2.0 M V(IV) + 3.0 M H2 SO4 ) with
additives on graphite electrode at a scan rate of 20 mV s−1 .
introduction of additives to electrolyte, which indicates that the
electrochemical activity of V(IV)/V(V) is improved. The decrease
of peak potential interval and increased symmetry of peak shapes
prove that the additives cause the enhancement of electrochemi-
cal reversibility of V(IV)/V(V). The results show that V(IV)/V(V) with
additive of AMSA exhibits the highest electrochemical activity and
reversibility. The anodic and cathodic peak current of V(IV)/V(V)
couple are 0.075 and 0.070 A at a scan rate of 20 mV s−1 , respec-
tively, which are much higher than that of pristine electrolyte.
The peak potential interval with additive of AMSA decreases from
191 mV to 113 mV and the ratio of Ipa /Ipc is more close to 1 at a
scan rate of 20 mV s−1 . As all the samples were prepared and tested
on the same conditions, the electrochemical performance of elec-
trolyte was affected by the functional groups of additives. For one
thing, both additives containing hydrophilic groups such as SO3 H
and NH2 can be adsorbed on the surface of graphite plate, which
can enhance the hydrophilicity of graphite plate and increase the
effective concentration of vanadium ions on the surface of graphite
plate. A simple experiment about adsorption character to vanadium
ion was performed to investigated the influence of additives on the
wetting property as described in the literature [29]. The electrolyte
uptake with additives (MSA: 230%, AMSA: 237%) is larger than that
of pristine electrolyte (210%), which indicates that both additives
can enhance the wetting property of electrolyte on the surface of
electrode. For another, according to density functional theory cal-
culations, carbon atoms adjacent to nitrogen atoms possess a high
positive charge density to counterbalance the strong electronic
affinity of the nitrogen atom [29]. The “positive charged” carbon
atoms activated by nitrogen atoms can be employed as the active
sites. Moreover, the viscosity measurement was performed and the
results were listed in Table 2. The viscosity can influence the mass
transfer polarization of the electrolyte. It can be known that the
additives do not influence the viscosity of electrolyte obviously.
Actually, there is slightly increase of viscosity of electrolyte by addi-
tion of additives, and the electrolyte with additive of AMSA exhibits
Table 1
Relevant data obtained from cyclic voltammetry for 2.0 M V(IV) solution with
additives.
Sample Anodic peak, Cathodic Peak potential Ipa /Ipc
Ipc (A) peak, Ipc (A) interval, Ep (V)
Pristine 0.062 0.055 0.191 1.123
MSA 0.066 0.059 0.135 1.118
AMSA 0.075 0.070 0.113 1.076
 Z. He et al. / Electrochimica Acta 106 (2013) 556–562 559

Fig. 4. Cyclic voltammograms of the electrolyte (2.0 M V(IV) + 3.0 M H2 SO4 ) with additives on graphite electrode at a range of scan rates. (a) the pristine, (b) MSA, (c) AMSA.

the lowest viscosity, which is favorable to the mass transfer of
vanadium ions.
In order to further investigate the effect of additives on mass
transfer of V(IV)/V(V), a series of cyclic voltammograms of elec-
trolyte samples with additives at a range of scan rates are shown in
Fig. 4. The reduction peak of V(V) shifts to the negative potential and
the oxidation peak of V(IV) shifts to the positive potential with the
scan rate increasing for all electrolyte with and without electrolyte.
The peak potential intervals are much greater than 59 mV, which
suggests that the electrode reaction is not completely reversible.
However, the cyclic voltammograms show that the oxidation and
reduction peak shapes are more symmetrical, and the Ipa /Ipc at low
scan rates is close to 1. Therefore, the redox reaction of V(IV)/V(V)
couple on graphite electrode is quasi-reversible [35]. For a quasi-
reversible redox couple, the peak current ip is given in Eq. (1) [36]:
rate measurement range [11,37]. As the peak shapes of oxidation
peak and reduction peak are symmetrical, we can assume that a is
0.5 and K(, a) equals to 0.8 under a wide range of  [35].
In the V(IV)/V(V) quasi-reversible reaction, single electron
transfer process, under 298 K the Eq. (1) can be simplified to Eq.
(2) [36].
ip = (2.152 × 105 )AD1/2 C0 v1/2 (2)
The graphite electrode area is 1 cm2 , and the initial concentra-
tion of V(IV) is 2.0 mol L−1 . The corresponding diffusion coefficients
of the solutions with additives obtained from Eq. (2) are listed
in Table 3. It can be observed from Table 3 that the diffusion
coefficients of V(IV) species with MSA and AMSA increase from
0.75 × 10−6 to 0.81 × 10−6 and 0.95 × 10−6 cm2 s−1 , respectively.

 1/2
F3
ip = 0.4463 n32 AD1/2 C0 v1/2 K(, ˛) (1)
RT

where ip is the peak current, F is the Faraday constant, T is the Kelvin

temperature, R is the gas constant, n is the electron transfer number,
A is the surface area of electrode, D is the diffusion coefficient, C0 is
the concentration of active species, v is the CV scan rate and K(, a)
is related to the degree of irreversibility [35]. A plot of the oxidation
peak current as a function of the square root of scan rates (1/2 ) is
shown in Fig. 5. Generally, K(, a) is relevant to CV scan rate, and ip
is not proportional to 1/2 for a quasi-reversible reaction. However,
in the present system, ip is obviously proportional to 1/2 as shown
in Fig. 5. Thereby, K(, a) can be treated as a constant in the scan

Table 2
The viscosity of 1.0 M V(IV) electrolyte with different additives.

Sample Pristine MSA AMSA

Viscosity (Pa s) 3.51 × 10−3 3.45 × 10−3 3.43 × 10−3 Fig. 5. Plots of the anodic peak current vs. the square root of scan rates (1/2 ) for the
electrolyte with additives.
560 Z. He et al. / Electrochimica Acta 106 (2013) 556–562
Fig. 6. Tafel polarization curves for 1.0 M V(IV) + 1.0 M V(V) + 3 M H2 SO4 solution with additives on graphite electrode at a scan rate of 1 mV s−1 . (a) The pristine, (b) MSA, (c)
AMSA.
The diffusion coefficient of V(IV) with additive of AMSA increases
26.7% compared to the pristine electrolyte. V(IV) species in
solution with additive of AMSA has the best transfer performance.
Except the electron transfer step, redox reactions between V(IV)
and V(V) should contain the breaking/formation of V O chemi-
cal bond which seems to be the most probable chemical step. The
chemical step probably plays the dominant roles during V(IV)/V(V)
reaction [6,23]. The additives containing NH2 and SO3 H groups
may promote the chemical step by coordinating with redox reac-
tion of V(IV)/V(V) couple [29]. Moreover, the reduced viscosity of
electrolyte and enhanced hydrophilicity of electrode by the intro-
duction of additives can benefit for the transfer of vanadium ions.
3.4. Tafel polarization curve study
The Tafel polarization curves of V(IV)/V(V) solution with addi-
tives were employed to determine exchange current density and
electrochemical reaction rate constant. At relatively high overvolt-
age area, overpotential is partly proportional to the logarithm of
current density, and the electrochemical anodic polarization rule
of the V(IV)/V(V) couple in sulfuric acid at the graphite electrode
could meet Butler–Volmer equation [38], i.e.:
2.3RT 2.3RT
˛ = − logj0 + logja
ˇF ˇF
where ˛ is the anodic overpotential, R is the universal gas constant,
T is the Kelvin temperature, ˇ is the transfer coefficient of the anode
Table 3
The diffusion coefficients of V(IV) species with additives.
Sample Diffusion coefficient (cm2 s−1 )
Pristine 0.75 × 10−6
With additive of MSA 0.81 × 10−6
With additive of AMSA 0.95 × 10−6
reaction, F is the Faraday constant, j0 is the exchange current density
and ja is the anodic current density. ˇ is assumed as 0.5 according
to the results of cyclic voltammetry measurement [35]. This is in
conformance with the Tafel equation. Fig. 6 shows the Tafel polar-
ization curves for 1.0 M V(IV) + 1.0 M V(V) + 3 M H2 SO4 solution
with additives on graphite electrode. It can be observed that there is
a linear relationship between the anodic overpotential and the log-
arithm of current density in the overpotential range of 40–80 mV.
Extrapolating the linear part of the polarization curve to intersect
with the equilibrium potential line, the point of intersection corre-
sponds to the exchange current density. According to the relational
expression, reaction rate constant can be obtained [39], i.e.:
j0
k0 = (4)
ˇ
nFCO CRa
where k0 is the reaction rate constant, j0 is the exchange current
density, n is the number of electrons transferred in the electrode
reaction, F is the Faraday constant, CO is the concentration of
oxidation species, CR is the concentration of reduction species, ˇ
is the transfer coefficient of oxidation reaction and ˛ is transfer
coefficient of reduction reaction. The kinetic parameters of the
V(IV)/V(V) redox reaction in sulfuric acid with additives are listed
in Table 4. The exchange current density and reaction rate constant
(3)
of electrolyte with additives are larger than that of the pristine
one, with the largest exchange current density and reaction
Table 4
Kinetic parameters for 1.0 M V(IV) + 1.0 M V(V) + 3 M H2 SO4 solution with additives
on graphite electrode.
Sample Exchange current Reaction rate
density, j0 (mA cm−2 ) constant, k0 (cm s−1 )
Pristine 2.33 2.41 × 10−6
MSA 2.65 2.74 × 10−6
AMSA 3.05 3.16 × 10−6
 Z. He et al. / Electrochimica Acta 106 (2013) 556–562 561

Fig. 7. Discharge capacity of the cells as a function of cycle number without and Fig. 8. Coulombic and energy efficiency of the cells using electrolyte without and
with AMSA at a current density of 40 mA cm−2 . with AMSA at a current density of 40 mA cm−2 .

rate constant of AMSA at 3.05 mA cm−2 and 3.16 × 10−6 cm s−1 , high effective concentration of active species. A simple experiment
respectively. It indicates that the additives can reduce electro- of graphite felt after the charge–discharge test with and without
chemical polarization, and the AMSA has superior effect, which is AMSA as additive about adsorption character to vanadium ion was
attributed to the improved diffusion performance and enhanced performed as described in the literature [29]. The electrolyte uptake
hydrophilicity on the surface of graphite electrode. The results are of graphite felt with AMSA can reach 348%, higher than that of pris-
consistent with the results of cyclic voltammetry measurement. tine sample (300%), which indicates that AMSA can be adsorbed on
the surface of graphite felt and enhance the wetting property of
3.5. Cycling performance of VRFB graphite felt after charge–discharge test. For another thing, adding
of AMSA can reduce charge transfer resistance. The result is consis-
The charge–discharge tests were performed using a single tent with the results of cyclic voltammetry and Tafel polarization
dynamic cell. Fig. 7 shows the discharge capacity of the cells as curve measurement.
a function of cycle number without and with AMSA in the posi-
tive electrolyte at a current density of 40 mA cm−2 . As observed, 3.6. X-ray photoelectron spectroscopy
the initial discharge capacity of the cells without and with AMSA
is 4075 and 4084 mA h, respectively. The theoretical capacity can In order to investigate the content change of elements on the
be calculated as 5146 mA h, thus the utility ratio of active species surface of graphite felt, the XPS measurement of graphite felt before
can reach 79.2% and 79.4%, respectively. With the increase of cycle and after 40 charge–discharge cycles was carried out in the binding
number, the capacity fading of the pristine cell is more serious than energy range of 1–1350 eV. Fig. 9 shows the XPS spectra of graphite
the cell with additive of AMSA. After 40 cycles, the discharge capac- felt before and after charge–discharge tests with additive of AMSA.
ity of the cells without and with AMSA is 3068.6 and 3371.3 mA h, The N1s and S2p signal of graphite felt after charge–discharge tests
respectively. The discharge capacity retention of the cell with AMSA with additive of AMSA are stronger than that of the pristine graphite
in 40 cycles is 82.7%, 7.6% higher than that of the pristine cell. The
improvement of discharge capacity retention with AMSA may be
ascribed to the adsorption of AMSA on the electrode, providing
more active sites and better hydrophilicity. The state of charge after
the charge in the 20th cycle with additive of AMSA is 95.1%, higher
than that of the pristine (93.2%), which indicates that the electro-
chemical polarization of reaction on the electrode in VRFB using
electrolyte with additive of AMSA is lower than that of the pristine.
Fig. 8 shows the coulombic and energy efficiency of the cells
without and with AMSA as a function of cycle number at a cur-
rent density of 40 mA cm−2 . It can be known from Fig. 8 that the
coulombic efficiency of the cells with and without additive slightly
improves with increasing of cycle number, which is due to that
with increasing of cycle number, the capacity of cell decreases
and the charge–discharge time becomes shorter, which can reduce
the crossover of vanadium ions across the membrane, so there is
slightly improvement of coulombic efficiency with increasing of
cycle number. Moreover, with the increase of cycle number, the
energy efficiency of both cells keeps stable, and the average energy
efficiency of the cell with AMSA can reach 81.5%, 1.6% higher than
that of the pristine cell. This phenomenon can be explained as fol-
lows. For one thing, adsorption of AMSA on the surface of electrode Fig. 9. XPS spectra of graphite felt before and after charge–discharge tests with the
can provide more active sites and better hydrophilicity, keeping additive of AMSA.
562 Z. He et al. / Electrochimica Acta 106 (2013) 556–562
Table 5
Content change of elements on the surface of graphite felt from XPS.
Name Peak BE (eV) Pristine (%) AMSA (%)
S2p 169.18 0.61 2.40
C1s 284.78 82.27 76.34
N1s 401.28 1.47 2.85
O1s 532.28 15.65 19.21
felt. The content change of elements on the surface of graphite felt
from XPS is shown in Table 5. As observed, the content of S increases
from 0.61% to 2.40% and the content of N increases from 1.47% to
2.85%. It indicates that AMSA containing SO3 H and NH2 groups
can be adsorbed on the surface of graphite felt.
4. Conclusions
In this research, the effect of two organic additives, MSA and
AMSA, on the thermal stability and electrochemical performance of
positive electrolyte for VRFB are investigated. The thermal stabil-
ity of V(V) electrolyte is improved obviously by adding AMSA. The
electrochemical measurements suggest that better reaction kinet-
ics is achieved by adding AMSA, with larger diffusion coefficient
of V(IV), exchange current density and electrochemical reaction
rate constant improved. Moreover, the assembled cell with AMSA
as additive of positive electrolyte exhibits higher energy efficiency
(81.5%) and larger discharge capacity retention (40 cycles: 82.7%).
The XPS results indicate that NH2 and SO3 H groups can be
introduced on the surface of electrode. The improved electrochem-
ical performance may be ascribed to more active sites provided by
NH2 group and enhanced hydrophilicity of the electrode provided
by NH2 and SO3 H groups.
Acknowledgements
This work was financially supported by the Major State Basic
Research Development Program of China (973 Program) (No.
2010CB227201) and Innovation Project of Graduate of Hunan
Province (No. CX2012B115).
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