Results in Physics 14 (2019) 102373

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Preparation and properties of amphoteric ion exchange membrane for all T

vanadium redox flow batteries
⁎
Jianjun Zhanga,b, Xiaohua Chena, Rui Longc, Jianlong Sic, Chun Liua, Sude Maa,
a
Key Laboratory of Fluid and Power Machinery, Ministry of Education, School of Materials Science and Engineering, Xihua University, Chengdu, Sichuan Province
610039, PR China
b
Materials Research and Education Center, Auburn University, Auburn, AL 36849, USA
c
Global Opto-Electro Energy-Saving Technology Co., Ltd., Yibin 644000, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The amphoteric ion exchange membrane basing on cheap polyetheretherketone (PEEK) engineering plastics was
All vanadium redox flow battery prepared by modification reactions and casting method in this investigation. The membrane was characterized
Ion exchange membrane by Fourier transformer infrared and thermogravimetric analysis. The IEC and sheet resistance of the membrane
Ion exchange capacity were also measured. The energy efficiency was tested by an experimental application device. Results show that
Sheet resistance
the sulfonic acid and quaternary ammonium groups are introduced into the molecule chain successfully. The
Energy efficiency
membrane has good thermal stability and IEC as high as 2.58 mol/kg, and the sheet resistance of which is
0.11 Ω/cm2. The energy efficiency of the membrane is 74.87%. The good properties and low price of the product
in this investigation imply the large scale potential applications in VRFBs.

Introduction membrane, and a redox-active species, which is stored in external

Energy is of great importance in light of its strategy and economic
values for all countries in the 21st century. Recent increasing interest in
the integration of renewable energy sources (i.e. wind and solar) has
accelerated efforts to develop efficient, cost-effective, safe and reliable
electric energy storage (EES) [1–3]. Several EES devices are available
for the aforementioned applications, such as secondary batteries (eg.,
Lead-acid, Li-ion, Ni-Cd and redox flow batteries), flywheels and elec-
trochemical supercapacitors [4–6]. There are several redox flow bat-
teries under development [1,7–10]. A commonly investigated redox
flow battery chemistry is the all-vanadium system, for which sulfuric
acid solutions of theV2+/V3+and V4+/V5+ (present as VO2+/VO3+)
redox couples serve as the anolyte and catholyte, respectively. Amongst
these, all vanadium redox flow batteries (VRFBs) are receiving con-
siderable attention at present as one of the most attractive energy-sto-
rage technologies with the unique advantages [11–15] (i.e. tolerance to
deep discharge, long life cycle, active thermal management, advanced
efficiency and independence of energy and power ratings) for both grid-
connected and off-grid energy storage applications. Many kW to MW
energy storage systems have been demonstrated in Japan, USA and
China.
Two half-cells in a VRFBs are separated by a ion exchange
tanks, is pumped into the half-cells of the VRFBs when power is re-
quired, so the membrane is the key unit [16–19]. This membrane is
electrical insulated and is highly ionic conductive [20–23]. The H+ ion
is the major charge carrier inside the membrane. However, due to the
electrical field and concentration gradient across the membrane, va-
nadium ions (VO2+,VO3+, V2+, V3+) are also migrated/diffused
through the membrane. The crossover of vanadium ions not only re-
duces the discharge cell voltage but also reduces the Faraday efficiency.
Therefore, the most important characteristic of the membrane is high
ion conductivity through the membrane to complete the redox circuit
and high selectivity to prevent from the crossover of the redox-active
species, and the performances are reflected by the sheet resistance and
ion exchange content (IEC) of the membrane.
Most of the VRFBs use Nafion as a ion exchange membrane because
it has high H+ conductivity and chemical stability [3]. However, the
price of Nafion remains high, and the crossover of vanadium redox-
active species decreases the energy efficiency of the VRFBs, which are
both drawbacks for the commercialization of VRFBs. Many researches
about the membrane applied on VRFBs were done in recent years to
improve the properties [24–28].
Polyetheretherketone (PEEK) is a novel special engineering plastics
[29–31] with many benzene rings in its molecule chain, so PEEK is acid

⁎
Corresponding author at: Key Laboratory of Fluid and Power Machinery of Ministry of Education, School of Materials Science and Engineering, Xihua University,
Chengdu 610039, PR China.
E-mail address: masude2007@163.com (S. Ma).

https://doi.org/10.1016/j.rinp.2019.102373
Received 8 April 2019; Received in revised form 18 May 2019; Accepted 18 May 2019
Available online 23 May 2019
2211-3797/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
J. Zhang, et al. Results in Physics 14 (2019) 102373

and corrosion resistant. The polymer is very proper to be applied in the O

VRFBs as ion exchange membrane if it has high IEC and low sheet re-
sistance. O O C PEEK
n
It is the object of this study to develop a cheap membrane with low
sheet resistance, high IEC and energy efficiency, and the research +H2SO4
progresses are reported here.
O

Experimental O O C SPEEK
n
Materials
HSO3 +H2SO4

PEEK powder (VESTAKEEP ® 4000G) was purchased from Evonik +ClCH2OCH3

(Germany) Co. Ltd. Concentrated sulfuric acid (98 wt%), acetone, me- O
thanol, ethanol, dimethyl formamide (DMF), dimethyl acetamide
(DMAC), dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidone (NMP), O O C SCMPEEK
trimethylamine aqueous solution (33%) and chloromethyl methyl ether n
(CME) were purchased from Chengdu Kelong Chemical Co. Ltd HSO3 ClCH2 +H2O
(Chengdu, China). Distilled water was homemade in the laboratory. All
+N(CH3)3
the materials were analytical grades and were used as received without
O
further treatment.
O O C SQAPEEK
Preparation of the amphoteric ion exchange membrane n
+
HSO3 CH2
Preparation of the sulfonated PEEK Cl
Concentrated sulfuric acid (98 wt%) was applied to synthesize sul- N(CH3)3
fonated PEEK (SPEEK) where it was both the reactant and catalyst of
Scheme 1. Preparation principals of SQAPEEK.
the sulfonation reaction [32].
Typically, 4 g PEEK and 240 ml 98% concentrated sulfuric acid were
added into a 500-mL four-necked round-bottom flask equipped with a Thermogravimetric analysis
thermometer, a stirrer, an inlet of dry nitrogen, a condenser, and water Thermogravimetric analysis (TGA) of the membrane sample was
bath. Then the reactant was stirred at 400 rpm for 10 to 15 h while carried out by a thermal analyzer(449F3, NETZSCH). The TGA instru-
maintaining the temperature at 25 °C until the PEEK was dissolved ment was calibrated using calcium oxalate from 40 to 800 °C at a
completely to prepare the SPEEK. heating rate of 10 °C·min−1in a static air atmosphere.

Preparation of the sulfonated chlorine methyl PEEK membrane
As the PEEK was completely dissolved in the concentrated sulfuric
acid, 80 ml CME was poured into the flask following the temperature of
reactant was reduced to 0 °C. The reactant was kept for a certain time
(i.e. 60 to 120 min) to obtain the sulfonated chlorine methyl PEEK
(SCMPEEK). The solid SCMPEEK was separated from the solution by
precipitation in the mixture of ice and water, and then thoroughly
cleaned with distilled water. The clean SCMPEEK was dried in a va-
cuum oven for 24 h at 60 °C.
The dry SCMPEEK was weighed and dissolved into the NMP to
prepare 10 wt% solution, and then the solution was poured into a
horizontal glass template to prepare a SCMPEEK membrane. After le-
veled and dried at 60 °C for 24 h, the SCMPEEK membrane was peeled
off from the glass template.
Preparation of the sulfonated quaternization amphoteric PEEK membrane
The sulfonated quaternization amphoteric PEEK (SQAPEEK) mem-
brane was obtained by being immersed into trimethylamine aqueous
solution (33%) at 40 °C for 48 h of the SCMPEEK membrane. Then the
membrane was thoroughly cleaned by distilled water.
The chemical structures and preparation principals of SQAPEEK
from the initial raw material (i.e. PEEK) were shown in Scheme 1.
Characterization
Fourier transformer infraredanalysis
Fourier transformer infrared (FTIR) spectra of the membrane
sample was recorded in the range of 4000–400 cm−1 using FTIR spec-
trometer (VERTEX 70, BRUKER, Stuttgart, Germany) on a KBr disk at
the resolution of 4 cm−1 for 32 scans.
Ion exchange capacity
The ion exchange capacity (IEC) of the membranes was measured by
the back titration method. Typically, 0.5 g membrane sample was dried
for 2 h at 60 °C in the drying oven, then was equilibrated by 50 ml
0.01 mol·L−1 HCl standard solution for 48 h, and followed by back ti-
tration of 0.01 mol·L−1 NaOH standard solution with phenolphthalein
to be the indicator. Another 50 ml 0.01 mol·L−1 HCl standard solution
was applied as the blank sample for control experiment. The measured
IEC (mol·Kg−1) of the membrane was calculated by the following Eq.
(1) and was taken the average of three times as the final measurement
value.
CHCl × (Vb − Vs)
IEC= × 1000
Mdry (1)
−1
where CHCl is the concentration (mol·L ) of HCl standard solution, Vb
and Vs is the consumed volumes (ml) of NaOH standard solution for the
blank sample and the SQAPEEK membrane sample respectively, and
Mdry is the mass (g) of the dry membrane sample.
Sheet resistance
The sheet resistance of the SQAPEEK membranes was measured by
the alternating current (AC) impedance method. Resistance of the
electrolyte solution (R) is proportional to the distance between the two
electrodes (L), and is inversely proportional to the cross-sectional area
of the electrode (A) and conductivity (k). The computation formula (2)
is shown as follows.
L L
R= −
K1A K2A (2)
where K1 and K2 are the conductivity of the electrolyte solution
equipped with membrane sample and no membrane sample

2
J. Zhang, et al. Results in Physics 14 (2019) 102373

SQAPEEK

Transmittance
SCMPEEK

SPEEK

Scheme 2. Schematic diagram of homemade conductivity test device. 4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber(cm )
respectively.
Conductivity was tested with homemade conductance slot and Fig. 1. Fourier transform infrared spectra of SPEEK, SCMPEEK and SQAPEEK.
electrode. The conductivity test device was shown in Scheme 2.
sulfonic acid, chloromethylation and quaternary ammonium groups
Electrical performance [32–35]. The sulfonic acid, chloromethylation and quaternary ammo-
The electrical performances of the homemade SQAPEEK membrane nium groups were all typical hydrophilic ionic groups, and which were
and Nafion 117 membrane were conducted by using a experimental introduced successively into PEEK to form SPEEK (i.e. introducing of
VRFBs system (Dongfang elctric Corp. China) at current density of sulfonic acid group), SCMPEEK (i.e. introducing of sulfonic acid and
80 mA cm−2. The key parameters of the charge-discharge experiments chloromethylation groups) and SQAPEEK (i.e. ulfonic acid, chlor-
were shown in Table 1. omethylation and quaternary ammonium groups).

Discharge time (min)

Current efficiency= × 100%
Charge time (min) (3) Thermo gravimetric analysis

Discharge time (min)

Voltage efficiency= × 100%
Charge time (min)
Discharge integral (V. min)
Energy efficiency= × 100%
Charge integral (V. min)
Results and discussion
Chemical structure
The FT-IR spectra of SPEEK, SCMPEEK and SQAPEEK were all
shown in Fig. 1. From this Figure, vibration absorption peaks corre-
sponding to the O]S]O bond in the sulfonic acid group at 1125 cm−1
on the SPEEK curve and 1243 cm−1 on the SCMPEEK and SQAPEEK
curve were found, which meant the sulfonic acid group was introduced
in SPEEK, SCMPEEK and SQAPEEK successfully. Some other char-
acteristic peaks (i.e. the strong absorption peaks at 1507 cm−1 proved
the existence of benzenes, and the absorption peaks at 1116 cm−1
verified the eOe bond between two benzene rings) had also been found
in SPEEK, SCMPEEK and SQAPEEK membranes. The weak absorption
peaks near 2875 cm−1 on SCMPEEK and SQAPEEK curves verified the
CeH bond of in eCH2Cl.
The stretching vibration absorption of CeN bond in the quaternary
ammonium group was found at 1394 cm−1 on the SQAPEEK curve. All
the characteristic peaks implied the SQAPEEK membranes possess
TGA thermograms of PEEK, SPEEK, SCMPEEK and SQAPEEK were
(4) given in Fig. 2 and the degradation temperatures of which were given in
Table 2.
As shown in Fig. 2 and Table 2, the PEEK began its decomposition at
(5)
586 °C (corresponding to the sample weight loss of 5%) or so, and ap-
proximately 40% weight lost as the temperature was risen to 634 °C.
The PEEK sample degraded into one step corresponding to the de-
composition of its molecular backbone. The SPEEK sample degraded
into two steps assigning to the release of sulfur-containing ingredients
and decomposition of molecular backbone respectively. SCMPEEK
sample began its decomposition at 189 °C (corresponding to the sample
weight loss of 5%) or so and which degraded into three steps corre-
sponding to the release of chlorine-containing ingredients [36], re-
moval of the methylene groups, and decomposition of molecular
backbone respectively. Similarly, SQAPEEK sample began its decom-
position at about 146 °C (corresponding to the sample weight loss of
5%) and which degraded into three steps attributing to the release of
the decomposed products (typically, CH3OH and NH3) [37] of qua-
ternary ammonium groups, the removal of residual groups (i.e.
eCH2OH and eCH2N (CH3)2) of the degraded quaternary ammonium
groups, and decomposition of molecular backbone respectively. The
decomposition temperature of SQAPEEK sample at 146 °C is high en-
ough so as to the membrane be applied in VRFBs.

Table 1
Parameters of the charge-discharge experiment.
Charge time (min) Discharge time(min) Average charge voltage (V) Average discharge voltage(V) Charge integral (V.min) Discharge integral (V.min)

SQAPEEK 38.333 37.022 1.637 1.253 62.763 46.990

Nafion 32.700 30.787 1.567 1.223 51.233 37.964

The current efficiency, voltage efficiency and energy efficiency were calculated according to formula (3–5).

3
J. Zhang, et al. Results in Physics 14 (2019) 102373

100

90

80
Weight/%

70

60
PEEK
SPEEK
50 SCMPEEK
SQAPEEK

40
100 200 300 400 500 600 700

Fig. 2. TGA of PEEK, SPEEK, SCMPEEK and SQAPEEK. Fig. 4. Charge-discharge curves of Nafion 117, and SQAPEEK membrane
samples at current density of 80 mA cm−2.
Table 2
TGA data for PEEK, SPEEK, SCMPEEK, and SQAPEEK samples. found that the sheet resistance decreased gradually while the IEC in-
Sample T5%/oC T10%/oC T20%/oC T40%/oC T50%/oC creased except the Nafion 117 sample, and the sheet resistance of
SQAPEEK membrane was 0.11 Ω cm−2 (i.e. about 10% higher than
PEEK 586 594 605 634 – which of Nafion 117). Which implies that the factors of increasing IEC
SPEEK 294 347 523 598 –
SCMPEEK 189 229 303 519 637
can also decrease the sheet resistance.
SQAPEEK 146 281 348 567 –
Electrical performance
Note: TX%/oC is the temperature corresponds to the sample weight loss x%.
The charge-discharge curves of the VRFBs system with homemade
Ion exchange capacity SQAPEEK and Nafion 117 membrane respectively operated on the ex-
perimental VRFBs system at current density of 80 mA.cm−2 were
In general, ion exchange capacity (IEC) dominates the properties of shown in Fig. 4.
VRFBs (i.e. voltage efficiency, current efficiency and energy efficiency). From Fig. 4 it was found that the charge-discharge curves of the two
As shown in Fig. 3, IEC of SPEEK, SCMPEEK and SQAPEEK membrane samples showed similar trends as the charge or discharge processes
samples was gradually improved comparing with Nafion 117 mem- were carried out, and which meant the two samples might have similar
brane respectively while the IEC of SQAPEEK was 2.58 mol·Kg−1. The electrical performance.
changes of IEC illustrate the modification reactions (i.e. sulfonation, The efficiencies (i.e. calculated according to formula (3)–(5)) of the
chloromethylation and quaternary ammonium reactions) can enhance VRFBs system with the homemade SQAPEEK and Nafion 117 mem-
the IECs of PEEK [38]. The results might be caused by the introduction brane respectively were shown in Table 3 and Fig. 5.
of different hydrophilic ionic groups and the introduction was proved From this figure it was found that the current and voltage efficiency
by the FTIR (i.e. show in Fig. 1). of the homemade membrane was slightly higher and lower than that of
Nafion 117 sample (i.e. 96.58% VS 94.15%, 76.56% VS 78.04%) re-
spectively, and the energy efficiency of the homemade membrane was
Sheet resistance
almost equal to but slightly higher than that of the Nafion 117 sample
(i.e. 74.87% VS 74.10%).
The sheet resistance of Nafion 117, SPEEK, SCMPEEK and SQAPEEK
membrane samples was also shown in Fig. 3. From this Figure it was
Conclusions

In this investigation, the amphoteric ion exchange membrane of

SQAPEEK for all vanadium redox flow batteries (VRFBs) was success-
fully prepared by a solution-casting method basing on the modification
reactions of PEEK so as to overcome the shortcomings (i.e. very ex-
pensive) of commercial Nafion 117 membrane. In this work, the sul-
fonic acid, chloromethyl and quaternary ammonium groups were in-
troduced into the SQAPEEK molecule chain by sulfonation,
chloromethylation and quaternization reaction respectively.
Although it was known that the quaternary ammonium groups in

Table 3
Efficiencies of the VRFBs system.
Current efficiency Voltage efficiency Energy efficiency
(%) (%) (%)

SQAPEEK 96.58 76.56 74.87

Fig. 3. IEC and sheet resistance of Nafion 117, SPEEK, SCMPEEK and SQAPEEK
Nafion 94.15 78.04 74.10
membrane samples.

4
J. Zhang, et al.
Fig. 5. Electrical performance of homemade SQAPEEK and Nafion 117 mem-
brane samples.
the SQAPEEK molecule chain can improve the resistance of vanadium
ions and increase the energy efficiency of VRFBs, the energy efficiency
(i.e. 74.87%) of the experimental VRFBs with the homemade mem-
brane in this study was not increased obviously, which might imply that
there are no enough quaternary ammonium groups in the molecule
chain. However, the homemade membrane is very cheap, and the IEC
and sheet resistance of the homemade SQAPEEK membrane is
2.58 mol·kg−1 and 0.11 Ω·cm−2 respectively, while it has good thermal
stability (i.e. T5% =146 °C). All the results show that the membrane in
the investigation is one of the promising candidates being applied as the
ion exchange membranes in VRFBs.
Acknowledgments
This work was financially supported by Sichuan Science and
Technology Program (No. 2019JDTD0024 & No. 2019ZHCG0048),
Military and civilian integration project of Sichuan province (No. zyf-
2018-089), Yibin Science and Technology Program (No. 2018YG05 and
No. 2017YG02), Chunhui Project from Education Ministry of China
(No. Z2017066), Scientific Research Fund of Sichuan Education
Department, China (No. 18ZA0445) and “Xihua Scholars” program of
Xihua University.
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