Journal of Membrane Science 510 (2016) 18–26

Contents lists available at ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

A comparative study of Nafion series membranes for vanadium redox

flow batteries
Bo Jiang a,1, Lantao Wu a,1, Lihong Yu b, Xinping Qiu a,c, Jingyu Xi a,n
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

art ic l e i nf o a b s t r a c t

Article history: In this study, a series of the commercial Nafion membranes (equivalent weight of 1100 g mol
1) with
Received 7 January 2016 thickness of 50 μm (Nafion 112), 88 μm (Nafion 1135), 125 μm (Nafion 115), and 175 μm (Nafion 117) are
Received in revised form selected to investigate the thickness impact of Nafion on the performance of vanadium redox flow
1 March 2016
battery (VRFB). VRFBs are evaluated at a broad current density range from 40 to 320 mA cm
2. The self-
Accepted 2 March 2016
discharge process, cell efficiencies, electrolyte utilization, and long-term cycling stability of VRFBs based
Available online 5 March 2016
on various Nafion membranes are compared comprehensively. Owing to the good balance between
Keywords: vanadium ions permeability and membrane resistance, Nafion 115 membrane presents the highest en-
Vanadium redox flow battery ergy efficiency and electrolytes utilization at current density from 120 to 240 mA cm
2. A simple and
Nafion
powerful online monitoring system is developed to monitor the electrolyte imbalance process during the
Membrane thickness
cycle-life test of VRFB. The capacity fading mechanism of VRFBs with different Nafion membranes is also
Cycling performance
Capacity fading discussed.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction VRFB [10,11]. Recently, the research attention has ever been shif-
ted to seeking the alternative non-perfluorinated membranes,
With the increasing requirement of medium- and large-scale such as sulfonated poly(ether ether ketone) (SPEEK), sulfonated
energy storage for the efficient utilization of renewable energy poly(ether sulfone) (SPES), sulfonated poly(imide) (SPI) and poly-
such as wind and solar energy [1–3], all-vanadium redox flow benzimidazole (PBI) [10–14]. Interestingly, inspiration usually
battery (VRFB) has received tremendous attention because of its comes from previous studies in proton exchange membrane fuel
fast response to energy demand change, low environmental im- cells (PEMFC) and direct methanol fuel cells (DMFC) [21]. Other
pact, long life cycle and flexible operation [4–6]. Compared to than cation exchange membranes (CEM), anion exchange mem-
other flow batteries, VRFB utilizes VO2 þ /VO2 þ and V3 þ /V2 þ redox branes (AEM) [15,16] and porous nanofiltration membranes [22]
couples as positive and negative electrolytes respectively, which have also been investigated towards VRFB application. Although
lower cost and probably better cell performance than Nafion, the
avoids the elements' cross-contamination of electrolytes [7–9].
non-perfluorinated membranes are easy to degrade under the
The membrane (separator), which is used to separate the po-
harsh acid and oxidation environment of vanadium electrolytes,
sitive and negative half-cell and to provide ion conduction, is a key
resulting in poor cycling life [23–26]. Therefore, Nafion mem-
component of VRFB since it decides the efficiency, lifespan and
branes are by now still the best choice for most large scale VRFB
cost of VRFB system [10–16]. An ideal membrane for VRFB should
energy storage systems due to its extremely chemical stability [17–
possess high proton conductivity, low vanadium ion permeability,
19,27]. Currently, much effort has been contributed to decrease the
excellent stability, and outstanding mechanical strength. Cur- cost (by using recast ultrathin membrane) and improve the ionic
rently, perfluorinated sulfonic acid membranes such as Nafion selectivity (by the strategy of surface modification or organic–in-
have been commonly used in VRFB for its high proton conductivity organic hybrid) of Nafion based membrane for VRFB application
and superior chemical stability [17–20]. However, high cost and [28–30].
fast crossover of vanadium ions limit its practical application in After thorough literature browsing in the field of VRFB, we
found that Nafion membranes with thickness ranging from 25 μm
n
Corresponding author.
(recast Nafion) [28] to 220 μm (wet Nafion 117) [31] have been
E-mail address: xijy@tsinghua.edu.cn (J. Xi). reported. The performance of VRFBs is highly related to the
1
These authors contributed equally to this paper. properties of membrane, since it governs the coulombic efficiency

http://dx.doi.org/10.1016/j.memsci.2016.03.007
0376-7388/& 2016 Elsevier B.V. All rights reserved.
 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26 19

(CE) of cell and is also responsible for a large percentage of the 2.2. Membrane pretreatment
ohmic loss which directly affects the overall voltage efficiency (VE)
and energy efficiency (EE) of the systems [10–12]. For instance, The as-received Nafion membranes were treated by standard
thick membrane has high cell resistance, which straightforwardly procedures which include: first, being boiled in 3 wt% H2O2 solu-
reduce the VE of cell and then further leads to the drop of EE, tion for 1 h and then in deionized water for 1 h; afterwards, being
while thin membrane yields fast crossover of vanadium ions, boiled in 1 M H2SO4 solution for 1 h and then in deionized water
which diminish the CE of cell and contribute to lower EE, and si- for 1 h; finally, being stored in deionized water before use [20].
multaneously increases the imbalance of electrolytes [32–34]. In
addition, the thickness of membrane will also affect the life and 2.3. Membrane characterization
cost of the total VRFB system [35]. In order to find a balance be-
tween price and performance (efficiency and cycling stability), an 2.3.1. Water uptake and swelling ratio
optimized thickness of membrane should be chosen. Before the measurement of water uptake and swelling ratio,
Recently, a few preliminary studies in terms of membrane membranes were immersed in deionized water at room tem-
thickness-related performance of VRFB have been reported perature for 24 h. First, clean the membrane with absorbent paper
[18,32–34]. Researchers from Pacific Northwest National Labora- to remove the surface water of the membrane and measure the
tory have compared the use of Nafion 115 (125 μm), Nafion 212 weight, thickness, length and width instantly. Second, dry the
(50 μm) and Nafion 211 (25 μm) membranes in a 3-cell 1 kW class membranes in vacuum oven at 100 °C for 24 h and then conduct
VRFB stack based on sulfate-chloride mixed acid electrolytes at the corresponding measurements. The water uptake was defined
current density of 80, 160 and 240 mA cm
2. They found that as the ratio of the weight changes before and after drying to the
Nafion 212 could be used as a direct replacement for Nafion 115 weight of dried membrane. The swelling ratio, defined in this
with improved performance and lower costs [18]. On the contrary, work, was the volume expansion rate of wet membrane. They
Jeong et al. revealed that vanadium ions crossover would play were calculated by following equations:
more dominant role than electrochemical reaction resistance in
deciding performance of VRFB; as a result, VRFB using thick Nafion Ww − Wd
Water uptake = × 100%
117 (175 μm) membrane was more stable than that using thin Wd (1)
Nafion 212 (50 μm) under the current density of 6.0–8.4 mA cm
2
[32]. Apart from Nafion membranes, the thickness impact of other
ion exchange membrane (IEM) has also been studied. Jung et al. X w × Yw × Z w − Xd × Yd × Zd
Swelling ratio = × 100%
investigated the different thickness (30, 50, 100 and 150 μm) of Xd × Yd × Zd (2)
SPEEK membranes on performance of VRFB and found that 50 μm
where Ww and Wd represent the weight of membranes before and
thick SPEEK exhibited low over potential, high energy efficiency,
after drying, respectively; Xw and Xd, Yw and Yd, Zw and Zd are the
high maximum power density and small capacity loss rate during
charge–discharge cycles at current density of 40 mA cm
2 [33]. length, width and thickness of wet and dry membranes,
Hickner et al. studied three different thicknesses (28, 45 and respectively.
80 μm) of sulfonated fluorinated poly(arylene ether) (SFPAE)
membranes for VRFB application and concluded that 45 μm was 2.3.2. Ion exchange capacity
the optimized membrane thickness under the current density of The ion exchange capacity (IEC) of membrane was measured by
20–80 mA cm
2 [34]. It can be seen that relatively narrow current traditional titration [37]. Ordinarily, the membranes were dried in
density ranges and only short-term cycle life test (up to 60 cycles) vacuum oven at 100 °C for 24 h and then were weighed. Before the
have been applied to study the effect of membrane thickness on titration, the membrane was soaked in the saturation NaCl solu-
VRFB performance in previous works. The systematic evaluation of tion for another 24 h. Subsequently, the solution was titrated by
Nafion membrane thickness impact on VRFB performance such as 0.1 M NaOH solution. The IEC was calculated according to the
electrolyte utilization, imbalance of electrolyte, and capacity fad- following equation:
ing mechanism have not been revealed yet. CNaOH × VNaOH
In this study, we chose the commercial Nafion series of mem- IEC =
Wd (3)
branes (equivalent weight of 1100 g mol
1) with thickness of
50 μm (Nafion 112), 88 μm (Nafion 1135), 125 μm (Nafion 115), where the VNaOH is the volume of NaOH that consumed during the
and 175 μm (Nafion 117) [36] to investigate the thickness impact titration, the CNaOH is the concentration of NaOH solution and Wd is
of Nafion on VRFB performances under current density of 40– the weight of the dried membrane.
320 mA cm
2. The self-discharge process, cell efficiencies, elec-
trolyte utilization, and long-term cycling stability of VRFBs with 2.3.3. Proton conductivity and area resistance
different Nafion membranes are presented comprehensively. A Proton conductivity (s) of the membrane was measured by the
powerful online monitoring system (OMS) is developed for the device shown in Fig. 2(a). The resistance (R) was determined by
first time to monitor the electrolyte imbalance during the cycle- electrochemical impedance spectroscopy (EIS) using PARSTAT
life test of VRFB. The capacity fading mechanism of VRFBs with 2273 electrochemical station. s was calculated according to the
different Nafion membranes is also discussed in details. following equation:
d
σ=
RS (4)
2. Experimental section
where S and d are the area and effective length of the membrane.
2.1. Materials Area resistance (AR) of the membrane was measured by the
method mentioned elsewhere [38]. A conductivity cell (effective
Nafion 112, 1135, 115 and 117 membranes, denoted as N112, area S of 0.785 cm2) was separated into two chambers by the
N1135, N115 and N117 respectively, were purchased from DuPont membrane and then stuffed with 0.5 M H2SO4, as shown in Fig. 2
Company. Other chemicals were of analytical grade and used (b). The resistance of the cell with membrane (R1) and without
without further purification. membrane (R2) was determined by EIS. AR was obtained by the
20 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26

following equation: ∫ Iddt

CE = × 100%
AR=(R1 − R2)×S (5) ∫ Icdt (6)

2.3.4. VO2 þ permeability

The method of measuring the VO2 þ permeability through the
∫ VdIddt
EE = × 100%
membrane was described in the Ref. [39]. The membrane (effective ∫ VcIcdt (7)
area of 7 cm2) was sandwiched between two diffusion half cells, as
shown in the inset of Fig. 3. The left reservoir was filled with
40 mL of 1.5 M VOSO4 in 3 M H2SO4 solution and the right one was EE
VE = × 100%
CE (8)
filled with 40 mL of 1.5 M MgSO4 in 3 M H2SO4 solution. The two
solutions were continuously stirred to avoid the concentration where Ic and Id represent the charge current and discharge current
polarization. The concentration of VO2 þ in the right reservoir was respectively, Vc and Vd are the charge voltage and discharge vol-
monitored by a UV–vis spectrophotometer (LengGuang 752 S). tage separately.

2.5. Online monitoring system

2.4. VRFB single cell test
An online monitoring system (OMS) was developed for the first
The configuration of VRFB single cell was the same as reported
time to study the volume change of positive and negative elec-
formerly [31,40]. A Nafion membrane (70  70 mm) and two gra-
trolytes during the cycle-life test of VRFB. The OMS consists of a
phite felts (Gansu Haoshi, 50  50  5 mm, thermal activated at
VRFB and a camera, as shown in Fig. 1(a). The camera is connected
420 °C for 10 h) were used as separator and electrodes, respec- to a computer and controlled by a specialize software to auto-
tively. The positive and negative electrolytes were 50 mL of 1.5 M matically record photos of the electrolyte tanks at the end of each
VO2 þ /V3 þ (mol/mol ¼ 1:1) in 2 M free H2SO4 [41]. The electrolytes discharge process of the VRFB. Then the volume of both positive
cycle was driven by peristaltic pumps (BT00-300T) with a flow and negative electrolytes can be analyzed and worked out by
rate of 60 mL min
1. The charge and discharge of the cell was Matlab according to the height of electrolyte in the tanks. Fig. 1
controlled by a battery testing system (BTS, CT-3008W-5V6A, (b) shows the BTS control interface and camera control interface
Neware) with the cut-off voltage of 1.65 V and 0.8 V, respectively. which is real-time monitoring the electrolyte tanks. For example, a
Coulombic efficiency (CE), voltage efficiency (VE) and energy effi- group of monitor images of the VRFB with N115 membrane cycling
ciency (EE) of VRFB were calculated by following equations: at 80 mA cm
2 from 0 to 100 cycles are illustrated in Fig. 1(c),

Fig. 1. Prototype of the OMS: (a) photograph of 4 sets of VRFB single cell and monitor camera, (b) control interface of BTS and OMS, and (c) monitor images record at
different cycle numbers for the VRFB with N115 membrane operated at 80 mA cm
2.
 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26 21

Fig. 2. (a) Proton conductivity measurement device; (b) area resistance measurement device; (c) proton conductivity and area resistance of various Nafion membranes.

which directly revels the electrolyte imbalance process. Detailed microstructure inside the membranes of various thickness [36]. It
results about the online monitor will be discussed later in is worth noting that N112 membrane shows much higher water
Figs. 8 and 9. uptake (44.1%) and swelling ratio (73.9%) compared with other
membranes, suggesting that thinner membrane is easier to absorb
water [42]. The extremely high water uptake and swelling ratio of
3. Results and discussion N112 membrane is disadvantageous for VRFB application [10],
which will be demonstrated by the subsequent discussion. The IEC
3.1. Membrane characterization of all Nafion membranes are around 0.86 mmol g
1 due to the
same chemical structure, which is consistent with their theoretical
The physicochemical properties of various Nafion membranes value (0.91 mmol g
1) [36]. The little deviation of actual values is
including thickness (dry state and wet state), water uptake, possibly caused by experimental errors.
swelling ratio and IEC are listed in Table 1. It should be noted that Fig. 2(a) and (b) illustrate the photographs of measurement
the swelling ratio defined in this work is the volume expansion device for proton conductivity and area resistance, respectively.
rate of wet membrane. The thickness of wet N112, N1135, N115 The testing results with standard error are shown in Fig. 2(c).
and N117 membranes are 71 μm, 112 μm, 161 μm and 220 μm, According to previous reports, proton conductivity of IEM is
respectively. N1135, N115 and N117 membranes have close water mainly affected by IEC [14,43]. Therefore, N112, N1135, N115 and
uptake (32.1–34.1%) and swelling ratio (63.0–69.0%) values and the N117 membranes present approximately the same proton con-
tiny differences are probably caused by the slight distinction of ductivity of about 100 mS cm
1, as shown in Fig. 2(c). These re-
sults are also in agreement with those reported in literatures [36].
Table 1 Area resistance is an important parameter of IEM which de-
Physicochemical properties of Nafion series membranes. termines the voltage efficiency (VE) of a VRFB [44]. For a series of
membranes with the same ionomer chemical structure, area re-
Sample Thickness Thickness Water up- Swelling IEC (mmol g
1)
sistance of membrane will increase with the thickness. It can be
(dry, μm) (wet, μm) take (%) ratio (%)
seen from Fig. 2(c) that the area resistance of Nafion membranes
N112 50 72 717 1 44.17 1.8 73.9 7 1.6 0.84 70.02 raises from 0.30 to 0.87 Ω cm2 with the thickness increasing from
N1135 88 71 1127 2 32.5 72.0 67.6 7 1.4 0.86 70.01 71 to 220 μm.
N115 125 72 1617 2 32.17 2.2 69.0 7 1.5 0.87 70.02
VO2 þ permeability of Nafion membranes was tested by a home-
N117 175 72 220 7 2 34.17 1.1 63.0 7 3.0 0.88 70.01
made device and the concentration of VO2 þ in MgSO4 solution
22 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26

across various Nafion membranes as a function of time is shown in

Fig. 3. With the increasing of membrane thickness, the con-
centrations of VO2 þ are decreasing gradually. This phenomenon is
probably due to that the thicker membrane has longer and more
complicated water channels where the water and protons diffuse
through [45], which is adverse to the diffusion of VO2 þ . As a result,
the thicker membrane exhibits lower permeability. Accordingly,
the order of VO2 þ permeability is N112 4N11354N115 4N117.
Generally, thin Nafion membrane is beneficial for improving the
VE of VRFB by decreasing the Ohmic resistance. On the contrary,
thick Nafion membrane could increase the coulombic efficiency
(CE) of VRFB by suppressing the vanadium ions crossover, as
shown in Fig. 3. Therefore, the optimized membrane thickness
with the good balance of area resistance (VE) and vanadium ions
crossover (EE) would lead to better and more stable VRFB
performance.

3.2. VRFB performance evaluation

Fig. 4. Self-discharge curve of VRFBs assembled with different Nafion membranes.
To confirm the property trend of the four Nafion membranes,
the self-discharge test was conducted. Fig. 4 illustrates the self-
discharge curves of VRFBs assembled with various Nafion mem- permeability and side reactions [48]. In this work, the charge
branes starting from 50% state of charge (SOC). The initial open voltage was controlled below 1.65 V to avoid the electrode corro-
circuit voltage (OCV) of VRFBs decreases gradually with the re- sion [40] and the electrolytes were sealed in a N2 protected tank to
duction of membrane thickness, as shown in the inset of Fig. 4. eliminate side reaction of V2 þ in negative half-cell. Therefore, the
This phenomenon can be explained by that the thinner the CE is dominantly affected by the cross-mixing of vanadium ions.
membrane, the faster the vanadium ions crossover during the As shown in Fig. 5(a), thicker membrane exhibits higher CE than
charge process, as confirmed by the VO2 þ permeability test in thinner membrane at different current densities according to
Fig. 3. The OCV of all the four single cells gradually decreases firstly VO2 þ permeation and self-discharge results. The order of CE is
and then sharply drops to 0.8 V, owing to the disappearance of N117 4N1154 N11354N112 membrane. The increasing of CE
VO+2 in positive half-cell [46,47]. The self-discharge time to reach with current density could be attributed to the shorter charge–
0.8 V is 7 h, 15 h, 22 h and 30 h for N112, N1135, N115 and N117 discharge time at higher current density, resulting in lower cross-
membranes, respectively. The OCV decay rate for the thicker mixing of vanadium ions and capacity loss [11,49]. It can be seen
membrane is much lower than the thinner membrane, which from Fig. 5(b) that the VE follows the order of
agrees well with the VO2 þ permeability results (Fig. 3). N112 4 N11354 N115 4N117, which is consistent with the area
To further investigate the performance of the four Nafion resistance results in Fig. 2(c). The highest VE of N112 membrane
membranes in VRFB, the VRFBs assembled with all the afore- could be attributed to the lowest area resistance and IR drop. The
mentioned membranes were run charge–discharge test at current gradual decreasing of VE with the increasing of current density
densities from 40 to 320 mA cm
2. The only exception was that could be assigned to the increasing of internal loss, such as ohmic
the cell with N117 membrane can not be charged and discharged loss, activation loss and mass transfer loss [50]. The EE of VRFB,
at 320 mA cm
2. The profiles of coulombic efficiency (CE), voltage decided by CE and VE, is an important parameter to evaluate the
efficiency, energy efficiency (EE) and discharge capacity as func- energy loss in a charge–discharge process. The data of EE has the
tions of current density are illustrated in Fig. 5. Due to the iden- same order with that of CE at current density of 40 mA cm
2,
tical configuration of VRFB single cell except membrane (see which means that the crossover of vanadium ions plays a decisive
Fig. 1), CE is determined by electrode corrosion, vanadium ions role at lower current densities due to the longer charge–discharge
time. However, it can be seen in Fig. 5(c) that VRFB with N112
shows the highest EE at higher current densities (280 and
320 mA cm
2), which indicates that comparing to CE, VE is the
decisive factors of EE. At the moderate current density from 80 to
240 mA cm
2, VRFB with N115 exhibits the superior EE among all
membranes, owing to the good balance between ohmic resistance
and vanadium ions permeability.
Discharge capacities of VRFBs at various current densities are
shown in Fig. 5(d). The capacities of all VRFBs decrease with the
increasing current density, attributed to the increasing ohmic loss
[51]. Notably, the discharge capacity of VRFB with N112 membrane
drops faster than others at current density from 40 to
200 mA cm
2, owing to the highest vanadium ions permeability.
Compared to other thinner membranes, discharge capacity of
VRFB with the thickest N117 membrane sharply falls with current
density rising from 200 to 280 mA cm
2, suggesting that the low
VE of N117 leads to the harsh discharge capacity loss at high cur-
rent density. When the current density returns to 120 mA cm
2,
the discharge capacities of all VRFBs are lower than that of the
Fig. 3. Concentration change of VO2 þ in MgSO4 solution across different Nafion former cycles, especially for VRFBs with N112 and N1135 mem-
membranes. Inset shows the photograph of diffusion cell. branes, owing to their high vanadium ions permeability. Overall, it
 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26 23

Fig. 5. Cell performance of VRFBs with different Nafion membranes at different current density: (a) CE, (b) VE, (c) EE and (d) discharge capacity.

can be concluded that the thinner membrane is more suitable for

VRFB operation at high current densities, while the thicker
membrane is a right choice for VRFB working at low current
densities.
The charge–discharge curves of VRFBs assembled with various
membranes obtained at the current density of 80 and
160 mA cm
2 are compared in Fig. 6(a) and (b), respectively. The
theoretical capacity is 2010 mAh for all VRFBs according to the
50 mL of 1.5 M vanadium active species. It can be seen from Fig. 6
(a) that all VRFBs present close charge curves while the discharge
process is obviously different and thicker membranes provide
higher discharge capacity. This is ascribed to the lower vanadium
ion permeability of the thicker membranes (N117 and N115)
compared to thinner membranes (N1135 and N112). Due to the
higher IR drop and electrochemical reaction resistance at higher
current density, higher charge voltage and lower discharge voltage
are observed in Fig. 6(b), leading to the decreasing of capacities of
all VRFBs. N117 membrane possesses the highest charge voltage
and lowest discharge voltage at 160 mA cm
2 which can be at-
tributed to the maximum thickness and area resistance. N115
membrane possesses the best cell performance owing to the op-
timal balance between vanadium ions permeability and proton Fig. 6. Charge–discharge curves of VRFBs with different Nafion membranes at
conductivity. current density: (a) 80 mA cm
2; (b) 160 mA cm
2.
In addition to EE, electrolyte utilization (EU) is another im-
portant evaluation index of VRFB. High EU is beneficial to improve
the energy density and reduce the electrolyte volume of VRFB shows relatively lower decline rate than others. On the contrary,
system. EU is defined as the ratio of actual discharge capacity to EU of the thickest N117 declines very fast with increasing current
theory discharge capacity (2010 mAh) in this work. As shown in density comparing to other thinner membranes. This phenomenon
Fig. 7, EUs of all VRFBs decrease with the increasing current den- is mainly caused by the fact that the increasing of current density
sity. The cell assembled with N112, the thinnest membrane with leads to higher ohmic polarization for thicker membranes but
highest vanadium ions permeability and lowest area resistance, lower vanadium ions permeability for thinner membranes owing
24 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26

Fig. 7. Electrolyte utilization of VRFBs assembled with different Nafion membranes

at current density from 40 to 320 mA cm
2.

to shorter charge–discharge time. The variation of EU resulted

from the compromise between ohmic polarization and vanadium
ions permeability is in accordance with the EE results in Fig. 5(c).

3.3. Cycling stability of VRFB

To further investigate the cycling stability of all Nafion mem-

branes, four VRFB single cells assembled with various Nafion
membranes were run continuously at a moderate current density
of 80 mA cm
2 until the discharge capacity retention decayed to
50%. The online monitoring system (OMS) was used to record the
volume change of positive and negative electrolytes during the
charge–discharge cycling test, as shown in Fig. 1(a). All batteries
were started at the same time in order to eliminate the system
error. The cycling performances include CE, EE, discharge capacity
retention and electrolyte volume change are illustrated in Fig. 8. It
can be seen that the CE and EE of all Nafion membranes remain
nearly stable during the whole cycle life test, suggesting that there
is no obvious degradation happening under the severe VRFB op-
eration. Moreover, the CE and EE values of N112 (80% and 70%), Fig. 8. Cycle performance of VRFBs with various Nafion membranes at
80 mA cm
2: (a) CE, (b) EE, (c) discharge capacity retention and (d) electrolyte
N1135 (89% and 78%), N115 (92% and 80%) and N117 (93% and 79%)
volume change rate.
are consistent with the results of charge–discharge test in Fig. 5,
demonstrating the good reproducibility of our experiments.
Fast capacity decay is one of the critical issues for VRFB prac- volume change rate of VRFB decreases with the increasing of Na-
tical application. According to previously research, it is believed fion thickness, consistent with the capacity fading tendency in
that the capacity fading over charge–discharge cycling is mainly Fig. 8(c). By carefully comparing Fig. 8(c) and (d), we can find that
caused by the crossover of vanadium ions which leads to the im- the capacity fading rate of VRFBs with thicker membranes (N115
balance of vanadium electrolytes (both volume and concentration) and N117) are basically the same with their electrolyte volume
between positive and negative half-cells [51,52]. As discussed in change rate. Thus, the volume of negative electrolyte decreases to
Figs. 3 and 4, thicker Nafion membrane is beneficial for preventing about 50% when the discharge capacity decays to 50%. However,
vanadium ions permeation. Consequently, the capacity fading rate VRFBs with thinner membranes (N112 and N1135) present faster
decreases with the increasing of membrane thickness, as shown in capacity fading rate compared with their electrolyte volume
Fig. 8(c). When the capacity retention decays to 50%, the VRFBs change rate. When the capacity retention decays to 50%, the vo-
with N112, N1135, N115 and N117 membranes are run for 41, 81, lume reduction rate of negative electrolyte are 30% and 35% for
152 and 200 cycles, respectively. The corresponding electrolyte N112 and N1135, respectively. Unlike other redox flow batteries,
volume change of various VRFB obtained from OMS are displayed capacity fading and electrolyte imbalance of VRFB can be partly
in Fig. 8(d). During the charge–discharge cycling, the transfer rate solved by remixing and redistributing the positive and negative
of V2 þ and V3 þ are higher than those of VO2 þ and VO2 þ , thus bring electrolytes periodically [4,9]. From the aspect of extending
about the net transfer of vanadium species from negative to po- maintenance time, thicker Nafion membrane such as N115 and
sitive half-cell [53,54]. The negative-to-positive transfer of vana- N117 will be better choice for practical VRFB application due to the
dium ions and water during the cycling would result in the volume relatively slow electrolyte imbalance process.
increasing in positive half-cell and decreasing in negative half-cell The broad charge–discharge current density adaptability of
[51]. It can be seen from Fig. 8(d) that along with the cycle pro- VRFB is one of the key issues which affect the large-scale and
ceeding, all VRFBs exhibit the electrolyte imbalance phenomenon. safety application of VRFB. To further evaluate the cycling stability
For example, Fig. 1(c) clearly shows the gradually electrolyte im- of VRFBs with various Nafion membranes at high current density,
balance process of VRFB with N115 membrane. The electrolyte the charge–discharge cycling tests were performed at
 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26 25

4. Conclusions

A series of commercialized Nafion membranes (N112, N1135,

N115 and N117) with different thickness have been investigated
towards VRFB application. Our work demonstrates that: (1) The
thicker membrane exhibits lower vanadium ions permeability. As
a result, the order of self-discharge time and CE is
N112o N1135o N115 oN117, while the discharge capacity fading
rate and electrolyte volume change rate show a completely op-
posite trend; (2) The thinner membrane with lower area resistance
is more suitable for VRFB operation at high current densities,
while thicker membrane with higher area resistance is a right
choice for VRFB working at low current densities. Owing to the
good balance between vanadium ions permeability and membrane
resistance, N115 membrane presents the highest energy efficiency
and electrolyte utilization at current density from 120 to
240 mA cm
2; (3) The inconsistent decreasing speed between
discharge capacity and negative electrolyte volume could be at-
tributed to the combining impact of vanadium ions crossover and
undesirable side reaction occurring at high current density. In
conclusion, from overall comparison, such as energy efficiency,
electrolyte utilization, capacity decay and electrolyte imbalance as
well as the material cost, N115 is by now the most suitable
membrane for VRFB application.

Acknowledgments

This work was supported by the National Natural Science

Foundation of China (21576154), Natural Science Foundation of
Guangdong Province (2015A030313894) and Basic Research Pro-
ject of Shenzhen City (JCYJ20150331151358143,
JCYJ20150630114140630 and JCYJ20140417115840235).

References

[1] C. Menictas, M. Skyllas-Kazacos, T.M. Lim (Eds.), Advances in Batteries for

Fig. 9. Cycle performance of VRFBs with various Nafion membranes at Medium- and Large-scale Energy Storage, Woodhead Publishing, Cambridge,
160 mA cm
2: (a) CE, (b) EE, (c) discharge capacity retention and (d) electrolyte UK, 2015.
[2] B. Dunn, H. Kamath, J.M. Tarascon, Electrical energy storage for the grid: a
volume change rate.
battery of choices, Science 334 (2011) 928–935.
[3] Z. Yang, J. Zhang, M.C.W. Kintner-Meyer, X. Lu, D. Choi, J.P. Lemmon, J. Liu,
Electrochemical energy storage for green grid, Chem. Rev. 111 (2011)
160 mA cm
2 for 200 cycles unless the discharge capacity decayed 3577–3613.
[4] M. Skyllas-Kazacos, M.H. Chakrabarti, S.A. Hajimolana, F.S. Mjalli, M. Saleem,
to 50%. As shown in Fig. 9(a) and (b), the CEs are basically stable Progress in flow battery research and development, J. Electrochem. Soc. 158
during the entire test cycles while the EEs express a slightly de- (2011) R55–R79.
cline with the increasing of cycle number. This probably arises [5] W. Wang, Q. Luo, B. Li, X. Wei, L. Li, Z. Yang, Recent progress in redox flow
battery research and development, Adv. Funct. Mater. 23 (2013) 970–986.
from the accumulation of side reaction at high current density. [6] G.L. Soloveichik, Flow batteries: current status and trends, Chem. Rev. 115
Besides, the CE and EE values of all VRFBs are consistent with the (2015) 11533–11558.
results of charge–discharge test in Fig. 5. The capacity decay in [7] A. Parasuraman, T.M. Lim, C. Menictas, M. Skyllas-Kazacos, Review of materials
research and development for vanadium redox flow battery applications,
Fig. 9(c) and electrolyte volume change in Fig. 9(d) of four VRFBs
Electrochim. Acta 101 (2013) 27–40.
present the same tendency with that at 80 mA cm
2. However, [8] C. Ding, H. Zhang, X. Li, T. Liu, F. Xing, Vanadium flow battery for energy
owing to the short charge–discharge time at high current density storage: prospects and challenges, J. Phys. Chem. Lett. 4 (2013) 1281–1294.
accordance with low vanadium ions permeability, the capacity [9] W. Zhang, J. Xi, Z. Li, H. Zhou, L. Liu, Z. Wu, X. Qiu, Electrochemical activation of
graphite felt electrode for VO2 þ /VO2 þ redox couple application, Electrochim.
fading rate and electrolyte volume change rate at 160 mA cm
2 Acta 89 (2013) 429–435.
are slower than that at 80 mA cm
2. When the capacity retention [10] X. Li, H. Zhang, Z. Mai, H. Zhang, I. Vankelecom, Ion exchange membranes for
decays to 50%, the VRFBs with N112 and N1135 membranes are vanadium redox battery (VRB) applications, Energy Environ. Sci. 4 (2011)
1147–1160.
run for 70 and 123 cycles combined with 33.6% and 34.2% of vo- [11] B. Schwenzer, J. Zhang, S. Kim, L. Li, J. Liu, Z. Yang, Membrane development for
lume reduction rate of negative electrolyte, respectively. After 200 vanadium redox flow batteries, ChemSusChem 4 (2011) 1388–1406.
cycles, the capacity retention of VRFBs with N115 and N117 [12] Z. Li, J. Xi, H. Zhou, L. Liu, Z. Wu, X. Qiu, L. Chen, Preparation and character-
ization of sulfonated poly(ether ether ketone)/polyvinylidene fluoride blend
membranes are 54.2% and 59.2% combined with 38.9% and 27.6%
membrane for vanadium redox flow battery application, J. Power Sources 237
of volume reduction rate of negative electrolyte, respectively. The (2013) 132–140.
inconsistent decreasing rate between discharge capacity and ne- [13] N.L. Doan, T.K.A. Hoang, P. Chen, Recent development of polymer membranes
gative electrolyte volume could be attributed to the combining as separators for all-vanadium redox flow batteries, RSC Adv. 5 (2015)
72805–72815.
impact of vanadium ions crossover and undesirable side reaction [14] K.D. Kreuer, Ion conducting membranes for fuel cells and other electro-
occurring at high current density. chemical devices, Chem. Mater. 26 (2014) 361–380.
26 B. Jiang et al. / Journal of Membrane Science 510 (2016) 18–26

[15] S. Maurya, S.H. Shin, Y. Kim, S.H. Moon, A review on recent developments of ether ketone) membrane on performance of vanadium redox flow battery, J.
anion exchange membranes for fuel cells and redox flow batteries, RSC Adv. 5 Electrochem. Soc. 163 (2016) A5090–A5096.
(2015) 37206–37230. [34] D. Chen, M.A. Hickner, E. Agar, E.C. Kumbur, Optimizing membrane thickness
[16] J.R. Varcoe, P. Atanassov, D.R. Dekel, A.M. Herring, M.A. Hickner, P.A. Kohl, A. for vanadium redox flow batteries, J. Membr. Sci. 437 (2013) 108–113.
R. Kucernak, W.E. Mustain, K. Nijmeijer, K. Scott, T. Xu, L. Zhuang, Anion-ex- [35] Ion Power, Inc. – Nafions Products. 〈www.ion-power.com〉.
change membranes in electrochemical energy systems, Energy Environ. Sci. 7 [36] K.A. Mauritz, R.B. Moore, State of understanding of Nafion, Chem. Rev. 104
(2014) 3135–3191. (2004) 4535–4585.
[17] P. Zhao, H. Zhang, H. Zhou, J. Chen, S. Gao, B. Yi, Characteristics and perfor- [37] Z. Li, W. Dai, L. Yu, J. Xi, X. Qiu, L. Chen, Sulfonated poly(ether ether ketone)/
mance of 10 kW class all-vanadium redox-flow battery stack, J. Power Sources mesoporous silica hybrid membrane for high performance vanadium redox
162 (2006) 1416–1420. flow battery, J. Power Sources 257 (2014) 221–229.
[18] D. Reed, E. Thomsen, W. Wang, Z. Nie, B. Li, X. Wei, B. Koeppel, V. Sprenkle, [38] W. Dai, L. Yu, Z. Li, J. Yan, Le Liu, J. Xi, X. Qiu, Sulfonated Poly(ether ether
Performance of Nafion N115, Nafion NR-212, and Nafion NR-211 in a 1 kW ketone)/graphene composite membrane for vanadium redox flow battery,
class all vanadium mixed acid redox flow battery, J. Power Sources 285 (2015) Electrochim. Acta 132 (2014) 200–207.
425–430. [39] X. Luo, Z. Lu, J. Xi, Z. Wu, W. Zhu, L. Chen, X. Qiu, Influence of permeation of
[19] D. Reed, E. Thomsen, B. Li, W. Wang, Z. Nie, B. Koeppel, J. Kizewski, V. Sprenkle, vanadium ions through PVDF-g-PSSA membranes on performances of vana-
Stack developments in a kW class all vanadium mixed acid redox flow battery dium redox flow batteries, J. Phys. Chem. B 109 (2005) 20310–20314.
at the pacific northwest national laboratory, J. Electrochem. Soc. 163 (2016) [40] Z. Li, W. Dai, L. Yu, L. Liu, J. Xi, X. Qiu, L. Chen, Properties investigation of
A5211–A5219. sulfonated poly (ether ether ketone)/polyacrylonitrile acid–base blend mem-
[20] J. Xi, Z. Wu, X. Qiu, L. Chen, Nafion/SiO2 hybrid membrane for vanadium redox brane for vanadium redox flow battery application, ACS Appl. Mater. Interfaces
flow battery, J. Power Sources 166 (2007) 531–536. 6 (2014) 18885–18893.
[21] M.A. Hickner, H. Ghassemi, Y.S. Kim, B.R. Einsla, J.E. McGrath, Alternative [41] S. Xiao, L. Yu, L. Wu, L. Liu, X. Qiu, J. Xi, Broad temperature adaptability of
polymer systems for proton exchange membranes (PEMs), Chem. Rev. 104 vanadium redox flow battery – Part 1: electrolyte research, Electrochim. Acta
(2004) 4587–4612. 187 (2016) 525–534.
[22] H. Zhang, H. Zhang, X. Li, Z. Mai, J. Zhang, Nanofiltration (NF) membranes: the [42] W. Xie, R.M. Darling, M.L. Perry, Processing and pretreatment effects on va-
next generation separators for all vanadium redox flow batteries (VRBs), En- nadium transport in Nafion membranes, J. Electrochem. Soc. 163 (2016)
ergy Environ. Sci. 4 (2011) 1676–1679. A5084–A5089.
[23] D. Chen, M.A. Hickner, V5 þ degradation of sulfonated Radel membranes for [43] K.D. Kreuer, On the development of proton conducting polymer membranes
vanadium redox flow batteries, Phys. Chem. Chem. Phys. 15 (2013) for hydrogen and methanol fuel cells, J. Membr. Sci. 185 (2001) 29–39.
11299–11305. [44] X. Wu, J. Hu, J. Liu, Q. Zhou, W. Zhou, H. Li, Y. Wu, Ion exchange membranes for
[24] Z. Yuan, X. Li, J. Hu, W. Xu, J. Cao, H. Zhang, Degradation mechanism of sul- redox flow batteries, Pure Appl. Chem. 86 (2014) 633–649.
fonated poly(ether ether ketone) (SPEEK) ion exchange membranes under [45] K. Schmidt-Rohr, Q. Chen, Parallel cylindrical water nanochannels in Nafion
vanadium flow battery medium, Phys. Chem. Chem. Phys. 16 (2014) fuel-cell membranes, Nat. Mater. 7 (2008) 75–83.
19841–19847. [46] J. Sun, D. Shi, H. Zhong, X. Li, H. Zhang, Investigations on the self-discharge
[25] J. Xi, Z. Li, L. Yu, B. Yin, L. Wang, L. Liu, X. Qiu, L. Chen, Effect of degree of process in vanadium flow battery, J. Power Sources 294 (2015) 562–568.
sulfonation and casting solvent on sulfonated poly(ether ether ketone) [47] J. Sun, X. Li, X. Xi, Q. Lai, T. Liu, H. Zhang, The transfer behavior of different ions
membrane for vanadium redox flow battery, J. Power Sources 285 (2015) across anion and cation exchange membranes under vanadium flow battery
195–204. medium, J. Power Sources 271 (2014) 1–7.
[26] Z. Yuan, X. Li, Y. Zhao, H. Zhang, Mechanism of polysulfone-based anion ex- [48] D. Chen, M.A. Hickner, E. Agar, E.C. Kumbur, Selective anion exchange mem-
change membranes degradation in vanadium flow battery, ACS Appl. Mater. branes for high coulombic efficiency vanadium redox flow batteries, Electro-
Interfaces 7 (2015) 19446–19454. chem. Commun. 26 (2013) 37–40.
[27] B.R. Chalamala, T. Soundappan, G.R. Fisher, M.R. Anstey, V.V. Viswanathan, M. [49] D. Chen, M.A. Hickner, E. Agar, E.C. Kumbur, Optimized anion exchange
L. Perry, Redox flow batteries: an engineering perspective, Proc. IEEE 102 membranes for vanadium redox flow batteries, ACS Appl. Mater. Interfaces 5
(2014) 976–999. (2013) 7559–7566.
[28] X. Teng, J. Dai, F. Bi, G. Yin, Ultra-thin polytetrafluoroethene/Nafion/silica [50] R. Yang, Z. Cao, S. Yang, I. Michos, Z. Xu, J. Dong, Colloidal silicalite-nafion
composite membrane with high performance for vanadium redox flow bat- composite ion exchange membrane for vanadium redox-flow battery, J.
tery, J. Power Sources 272 (2014) 113–120. Membr. Sci. 484 (2015) 1–9.
[29] J. Xi, Z. Wu, X. Teng, Y. Zhao, L. Chen, X. Qiu, Self-assembled polyelectrolyte [51] Q. Luo, L. Li, W. Wang, Z. Nie, X. Wei, B. Li, B. Chen, Z. Yang, V. Sprenkle, Ca-
multilayer modified Nafion membrane with suppressed vanadium ion cross- pacity decay and remediation of Nafion-based all-vanadium redox flow bat-
over for vanadium redox flow batteries, J. Mater. Chem. 18 (2008) 1232–1238. teries, ChemSusChem 6 (2013) 268–274.
[30] L. Yu, F. Lin, L. Xu, J. Xi, A recast Nafion/Graphene oxide composite membrane [52] B. Li, Q. Luo, X. Wei, Z. Nie, E. Thomsen, B. Chen, V. Sprenkle, W. Wang, Ca-
for advanced vanadium redox flow battery, RSC Adv. 6 (2016) 3756–3763. pacity decay mechanism of microporous separator-based all-vanadium redox
[31] W. Dai, Y. Shen, Z. Li, L. Yu, J. Xi, X. Qiu, SPEEK/Graphene oxide nanocomposite flow batteries and its recovery, ChemSusChem 7 (2014) 577–584.
membranes with superior cyclability for highly efficient vanadium redox flow [53] Q. Luo, L. Li, Z. Nie, W. Wang, X. Wei, B. Li, B. Chen, Z. Yang, In-situ in-
battery, J. Mater. Chem. A 2 (2014) 12423–12432. vestigation of vanadium ion transport in redox flow battery, J. Power Sources
[32] S. Jeong, L.H. Kim, Y. Kwon, S. Kim, Effect of nafion membrane thickness on 218 (2012) 15–20.
performance of vanadium redox flow battery, Korean J. Chem. Eng. 31 (2014) [54] C. Sun, J. Chen, H. Zhang, X. Han, Q. Luo, Investigations on transfer of water
2081–2087. and vanadium ions across Nafion membrane in an operating vanadium redox
[33] H.Y. Jung, S. Jeong, Y. Kwon, The effect of different thick sulfonated poly (ether flow battery, J. Power Sources 195 (2010) 890–897.