Electrochimica Acta 130 (2014) 90–96

Contents lists available at ScienceDirect

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

Novel sulfonated poly (ether ether keton)/polyetherimide acid-base

blend membranes for vanadium redox flow battery applications
Shuai Liu a,b , Lihua Wang a,∗ , Yue Ding c , Biqian Liu a , Xutong Han c , Yanlin Song a
a
Key laboratory of Green Printing, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China
b
University of Chinese Academy of Sciences, 100049, P.R. China
c
School of materials science and engineering, Tianjin Polytechnic University, Tianjin, 300387, P. R. China

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

Article history: Novel acid-base blend membranes composed of sulfonated poly (ether ether ketone) (SPEEK) and
Received 18 February 2014 polyetherimide (PEI) were prepared for vanadium redox flow battery (VRB). The blend membranes were
Received in revised form 25 February 2014 characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electronic microscopy
Accepted 25 February 2014
(SEM). The ion exchange capacity (IEC), proton conductivity, water uptake, vanadium ion permeability
Available online 11 March 2014
and mechanical properties were measured. As a result, the acid-base blend membranes exhibit higher
water uptake, IEC and lower vanadium ion permeability compared to Nafion117 membranes and all
Keywords:
these properties decrease with the increase of PEI. In VRB single cell test, the VRB with blend mem-
SPEEK/PEI
Acid-base
branes shows lower charge capacity loss, higher coulombic efficiency (CE) and energy efficiency (EE) than
Proton conductivity Nafion117 membrane. Furthermore, the acid-base blend membranes present stable performance up to
Vanadium ion permeability 50 cycles with no significant decline in CE and EE. All experimental results indicate that the SPEEK/PEI
(S/P) acid-base blend membranes show promising prospects for VRB.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction these membranes are still higher as a result of the complexity of

modification process.
The vanadium redox flow battery (VRB) was pioneered by Recently, several sulfonated aromatic polymers, such as sul-
Skyllas-kazacos in 1985 [1–3] and has attracted considerable atten- fonated poly(ether ether keton)(SPEEK), sulfonated polyimide(SPI),
tion as a large-scale energy storage system due to its high energy and sulfonated polysulfone(SPSF) have been widely investigated
efficiency, long cycle life, fast response time and flexible design. In as candidates in direct methanol fuel cells (DMFC) or vanadium
a VRB system, the ion exchange membrane is one of the key materi- redox flow batteries due to their lower costs, outstanding mechan-
als, which effectively separates the anode and cathode electrolytes ical and chemical stabilities [10–15]. Among them, SPEEK has been
while allowing the transport of protons to complete the circuit. widely studied as proton exchange membrane materials for its good
The ideal membranes used for VRB should exhibit high proton con- mechanical property, low methanol and vanadium ions crossover,
ductivity, low permeability for vanadium ions, and possess high and thermal stability. In order to maximize the proton conductiv-
chemical and mechanical stability [4]. The membranes traditionally ity, the high degree of sulfonation is desired, which often causes
used in VRB are perflurosulfonic acid membranes such as DuPont high swelling and poor mechanical stability.
Nafion membranes. Even though the Nafion membranes show high Blending is a facile way to improve the comprehensive proper-
chemical stability and proton conductivity, the high vanadium ion ties of a matrix [16–18]. Among many types of blend membranes,
permeability and cost have limited their further application [5,6]. the acid-base blend membranes show many attractive properties.
In addition, modification Nafion, modification polyvinylidene flu- Acid-base blend membranes described as organic-organic blend
oride, and non-fluorinated membranes were also investigated and membranes are new class of interesting materials that exhibit
used in VRB [7–9]. These membranes exhibited lower vanadium ion improved proton conductivity and reduced methanol permeability
permeability and good mechanical stability. However, the costs of when applied in DMFC [19–22]. Kerres and co-workers reported
several acid-base blends based on SPEEK and some N-base poly-
mers [23–28]. In this kind of acid-base blend membranes, the
polymer chains cross-linked by the ionic interactions between sul-
∗ Corresponding author. Tel.: +86 10 6265 0812; fax: +86 10 6255 9373. fonic acid groups and N-containing groups, which reduced swelling
E-mail address: [email protected] (L. Wang). and improved stability of the membranes. Besides, polymer

http://dx.doi.org/10.1016/j.electacta.2014.02.144
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96 91

peeled off from the substrates and kept in deionized water before
using.

2.3. Characterization of S/P blend membranes

FT-IR spectra of the membranes were measured by

BRUKERTENSOR-27 in the range of 4000-600 cm−1 . The samples
were dried at 80 ◦ C for 1 h before measurement.
The cross-section morphology of the blend membranes were
Fig. 1. Schematic of the interactions between SPEEK and PEI.
examined with a Hitachi S4800 field emission scanning electron
microscope. All the samples for cross-sectional view were fracture
blending is an effective method to improve the mechanical and in liquid nitrogen.
chemical stability via addition of another more stable component. The mechanical properties of the blend membranes were mea-
Commercially available polyetherimide (PEI) has several important sured using a tensile machine (Instron 5567, TA Instruments Co.)
advantages, such as good chemical, thermal stability and low resis- at room temperature. The samples were tested at elongation rate
tance [29–31]. The introduction of PEI (as a base polymer) in the of 5.0 mm min−1 . All membranes were tested five times to obtain
SPEEK (as an acid polymer) membrane is an effective way to prepare an average value.
a new kind of acid-base blend membranes applied in VRB. As seen
in Fig. 1, the interactions between acid and base polymers, such as 2.4. Water uptake and swelling ratio
ionic cross-linking and hydrogen bond, contributed to control the
swelling of membranes. Therefore, the acid-base blend membranes The membranes were dried at 80 ◦ C under vacuum for 24 h and
may have many advantages in VRB application, such as high proton the dry weights of the samples were weighed. Subsequently, the
conductivity, reduced vanadium ions crossover, good mechanical membranes were immersed in deionized water for 24 h at room
flexibility and chemical stability [32,33]. temperature. After quickly wiping off the water adhered to the
In this paper, S/P acid-base blend membranes were fabricated surface of the membranes, the weights and dimensions of wet
with different mass ratios. The microstructure and mechanical membranes were measured. The water uptake and swelling ratio
properties of the membranes were observed. Water uptake, ion could be determined according to the following equations:
exchange capacity, swelling ratio, proton conductivity and vana-
Wwet − Wdry
dium ion permeability were investigated. Compared to Nafion117 water uptake = × 100% (1)
membranes, the acid-base blend membranes exhibited higher Wdry
water uptake, IEC and lower vanadium ion permeability. In the Where Wwet and Wdry are the weights of membranes in wet and
VRB single cell performance, 50 charge-discharge cycles were also dry state, respectively.
discussed and the corresponding coulombic, energy and voltage
efficiencies were obtained. Lwet − Ldry
swelling ratio = × 100% (2)
Ldry
2. Experimental Where Lwet and Ldry are the lengths of membranes in wet and
dry state, respectively.
2.1. Materials
2.5. Ion exchange capacity (IEC)
Nafion117 membrane was purchased from DuPont Co. PEEK
was obtained from Changchun JIDA plastic engineering co. Ltd.
The IEC of membranes was obtained by titration method. The
PEI (Ultem® 1000) was provided from Dongguan BAIFU plastic
dry membranes were immersed in the 1 mol L−1 NaCl solution for
technology co. Ltd. PEI and PEEK were used as received without
24 h. This solution was titrated by 0.01 mol L−1 NaOH with phenol-
further purification. Carbon felt and graphite felt were purchased
phthalein as the indicator. The IEC of the samples was calculated
from Beijing Jixing sheng’an Industry&Trade Co. Ltd., 99.999%; 1-
by following equation:
methyl-2-pyrrolidone (NMP), NaCl, NaOH, MgSO4 and H2 SO4 were
obtained from Beijing chemical reagent co. Ltd. All of them were VNaOH CNaOH
IEC = (3)
used as received without further purification. All water was deion- Wd
ized.
Where VNaOH is the volume of consumed NaOH solution, CNaOH is
the concentration of NaOH solution and Wd is the weight of the dry
2.2. Preparation of blend membranes membrane.Proton conductivity (ı) and Vanadium ion permeability
(P)
SPEEK were prepared as the following procedure: 12 g PEEK The area resistance of the membranes was measured by the
were added into H2 SO4 (98%, 200 mL) at 25 ◦ C with stirring under method as described in literature [9,34]. The measurement was per-
200 rpm for 25 h. Subsequently, the solution was poured into ice- formed with a bi-compartmental device which consists of two cells
cold water under mechanical agitation for 3 h. The solution was separated by the membrane. Both compartments were filled with
stored overnight, followed by thorough washing with deionized 1 mol L−1 H2 SO4 . The effective area of the membrane was 0.785
water. Finally, the SPEEK was dried at 80 ◦ C for 10 h. cm2 . The electric resistance was measured by electrochemical
S/P blend membranes were prepared with six different mass impedance spectroscopy (EIS) (Zahner Zennium) over a frequency
ratios: 100:0(S/P-0), 95:5 (S/P-1), 90:10(S/P-2), 85:15(S/P-3), range from 100 kHz to 100 MHz [35]. The resistance value asso-
80:20(S/P-4) and 75:25(S/P-5). SPEEK and PEI were simultaneously ciated with the membrane conductance was determined from a
dissolved in NMP to form 10wt% solutions with stirring at 60 ◦ C high-frequency intercept of the impedance with the real axis. The
for 12 h. After cooled to room temperature, the resulting polymer area resistance R can be calculated by the following expressions:
solutions were cast on glass plates and dried in a vacuum oven at
80 ◦ C for 6 h, and then at 100 ◦ C for 12 h. The dried membranes were R = (r1 − r2 )S (4)
92 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96

Where r1 and r2 represent the electric resistances of the cell with

and without the membrane respectively.
The proton conductivity was calculated using the equation:

ı = L/R (5)

Where L and R were the thickness and area resistance of the

membrane, respectively.
To measure the permeability of vanadium ions, the membranes
were exposed into a solution of 1.5 mol L−1 VOSO4 and 3 mol L−1
H2 SO4 (the left reservoir) and a solution of 1.5 mol L−1 MgSO4 and
3 mol L−1 H2 SO4 (the right reservoir). MgSO4 was used to equalize
the ionic strengths and to reduce the osmotic pressure effect. The
effective area of the membrane was 0.785 cm2 . Samples from the
right reservoir were taken at a regular time interval and analyzed
for vanadium ions concentration by using an UV-vis spectrome-
ter (UV-2550, SHIMADZU). The vanadium ion permeability was
calculated by the following equation:
dcR (t) P
VR = A [cL − cR (t)] (6)
dt l Fig. 2. FT-IR spectra of S/P acid-base blend membranes.
Where P was the vanadium ion permeability, cL was the vana-
dium ion concentration in the left reservoir, and cR (t) was the
clusters formed by the sulfonic acid groups could broaden the pro-
vanadium ion concentration in the right reservoir as a function
ton transfer channels. The bands for the stretching vibration of the
of time. A and l were the area and thickness of the membrane,
C-N groups of PEI can be observed at 1467 cm−1 , and the stretch-
respectively. VR was the volume of right reservoir. It is supposed
ing vibration of the C = O groups of PEI and SPEEK can be seen at
the change of vanadium ion concentration in the left reservoir can
1650 cm−1 .
always be negligible.

2.6. VRB single cell performance 3.2. Morphology of the membranes

A VRB single cell was manufactured by sandwiching the mem- The microstructure could influence the properties of mem-
brane between two pieces of carbon felt electrodes with effective branes. SEM images for cross-section of acid-base blend mem-
reaction area of 9 cm2 . The felt was carbon felt and the current branes are shown in Fig. 3. Apparently, the blend membranes
collector material was graphite felt. The cell geometry: carbon felt (Fig. 3b-3f) exhibit different morphology compared with SPEEK
was 12 × 12 × 0.4 cm, current collector material was 4 × 4 × 1.5 cm, membranes (Fig. 3a). Pristine SPEEK membrane present planar
cell geometry was 12 × 10 × 10 cm and inter-electrode gap was structure while the blend membranes exhibit phase-separated
7 cm. The solutions of 1.5 mol L−1 V3+ in 3.0 mol L−1 H2 SO4 and microstructure distinctly. In addition, these images display the for-
1.5 mol L−1 VO2+ in 3.0 mol L−1 H2 SO4 were served as initial nega- mation of small (<0.5 ␮m) spherical domains of PEI at a 5% PEI
tive and positive electrolyte, respectively. The volume of electrolyte content and their growth up to ∼0.7 ␮m at 15% PEI and ∼1 ␮m
on each side of the cell was 60 mL. Both the positive electrolyte at 25% PEI. Compared with Fig. 3(a), Fig. 3(f) shows evident micro-
and negative electrolyte were cyclically pumped into the corre- phase separation, which might be attributed to hydrogen bond and
sponding half-cell at 20 mL min−1 . Charge-discharge cycling test ionic interactions between SPEEK and PEI [31,36]. With the increase
was conducted by LAND CT2001A with a constant current density of PEI, there will be more unbounded PEI units, which also facilities
of 50 mA cm−2 at 25 ◦ C. To avoid the corrosion of carbon felt, the the phase separation.
cut-off voltage for charge and discharge was set as 1.65 V and 0.8 V
respectively. 3.3. Mechanical properties
The coulombic efficiency (CE), voltage efficiency (VE), and
energy efficiency (EE) of the cell are calculated as following equa- The mechanical strength of the blend membranes is signifi-
tions cant for VRB application to assure its stability as the electrolyte
Qdis I t t passes across the membrane. The mechanical strength of SPEEK
CE = × 100% = ch dis × 100% = dis × 100% (7) membrane and the blend membranes were measured at room tem-
Qch Ich tch tch
perature.
Vdis As shown in Fig. 4, the blend membranes show higher ten-
VE = × 100% (8)
Vch sile strength with the addition of PEI. The tensile strength rises
EE = CE × VE (9) from 20.8 MPa to 37.1 MPa with the content of PEI increase from
0% to 25%. Such enhancement in tensile strength is due to the
ionic crosslinking and close packed molecules in acid-base blend
3. Results and discussion
membranes. However, the ionic crosslinking also reduces molec-
ular flexibility, hence the blend membranes become more fragile
3.1. FT-IR
and the elongation at break is decreased.
FT-IR spectra of S/P acid-base blend membranes are shown
in Fig. 2. As for the S/P membranes, the bands at 708 cm−1 , 3.4. IEC, Water uptake and Swelling ratio
1071 cm−1 , 1279 cm−1 are assigned to the stretching vibration
of–SO3 H groups. This is confirmed that the sulfonic acid groups are The IEC, water uptake, swelling ratio are important param-
successfully introduced to the resulting polymer. The hydrophilic eters for a membrane to be characterized. These properties of
 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96 93

Fig. 3. SEM images for cross-section of acid-base blend membranes: (a) S/P-0; (b) S/P-1; (c) S/P-2; (d) S/P-3; (e) S/P-4; (f) S/P-5. Scale bar is 3 ␮m.

acid-base blend membranes and Nafion117 membrane are pre- can improve the proton conductivity. However, it also leads to
sented in Table 1. poor dimensional stability and high vanadium permeability. As
Many significant properties of the membrane, such as proton expected, tertiary nitrogen groups in PEI reduce the amount of free
conductivity and water uptake, are related to IEC. IEC directly sulfonic acid groups by acid-base interactions. High content of PEI
depends on the content of free sulfonic acid groups in the mem- leads water uptake reduced, indicating the increase of hydropho-
brane. It can be seen that the IEC of the blend membranes decreased bicity within the blend membranes. Moreover, the formation of
with increase of the PEI. One reason is due to the content of SPEEK cross-linked network structure reduces free volume in blend mem-
decrease when PEI was added in, the number of sulfonic acid groups branes for water molecules which leads to water uptake decrease.
reduced. Moreover, the measured IEC values of the blend mem- The swelling ratio reflects dimensional stability, and the lower
branes are lower than the theoretical values calculated from the swelling ratio is required for keeping membrane dimensional stable
content of SPEEK. This phenomenon implies the formation of acid- for a long time. Similar to the water uptake, all blend membranes
base pairs between amino groups and the sulfonic acid groups. show decreased swelling ratio with increase of the PEI, which is
Water uptake is another important parameter for ion exchange beneficial for the application as ion exchange membranes [37].
membrane. It has a great influence on the proton conductivity Permeability of vanadium ion is a crucial parameter for VRB,
and dimensional stability of the membrane. High water uptake which represents the ability to prevent the crossover of positive

Table 1
Basic properties of the acid-base blend membranes and Nafion117 membrane.

Membrane IEC(mmol g−1 ) P(10−8 cm2 s−1 ) Water uptake (%) Swelling ratio (%)

S/P-0 1.79 11.2 38.4 20.1

S/P-1 1.55 5.61 36.4 18.7
S/P-2 1.42 5.50 33.5 17.4
S/P-3 1.38 4.78 32.9 16.9
S/P-4 1.25 3.78 27.8 15.7
S/P-5 1.19 2.39 21.9 14.2
Nafion117 0.91 65.1 19.3 16.4
94 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96

Fig. 4. The mechanical properties of the acid-base blend membranes.

Fig. 5. Concentration of vanadium ion in the right reservoir of the cell with S/P
and negative electrolytes. Diffusion of vanadium ions across the acid-base blend membranes and Nafion117 membrane.
membrane will lead to self-discharge of the battery. In this study,
the vanadium ion permeability of blend membranes and Nafion
117 membrane was measured. The concentration of vanadium ion
in the right reservoir as a function of time is depicted in Fig. 5, and
the calculated vanadium permeability coefficients are illustrated interactions improve the homogeneity and introduce cross-linked
in Table 1. All the blend membranes have lower permeability than structure. The possible acid-base interactions structure is shown in
that of Nafion117 membrane. The permeability of the S/P-5 mem- Fig. 6. This structure helps to control the vanadium ions crossover.
brane is only 2.39 × 10−8 cm2 s−1 compared to 6.5 × 10−7 cm2 s−1 Therefore, the S/P blend membranes are favorable for application
of Nafion117 membrane, it also can be seen the permeability of in the VRB system for their lower vanadium ion permeability.
blend membranes decrease with the increase of PEI, the perme- Besides, the proton conductivity is the most important perfor-
ability of the S/P-0 membrane is 11.2 × 10−8 cm2 s−1 compared to mance properties for membranes used in battery systems. It is
2.39 × 10−8 cm2 s−1 of the S/P-5 membrane. mainly determined by water uptake, IEC and microstructure of the
The difference in vanadium ion permeability of blend membranes. The transport of protons requires channels formed
membranes and Nafion117 membrane is determined by their by sulfonic acid groups. Proton transportation and vanadium per-
microstructure [38,39]. The microstructure of Nafion117 mem- meation take place through the same hydrophilic channels in the
brane contains two parts: the high hydrophilic sulfonic function membranes.
groups and high hydrophobic fluorocarbon backbones. It would As seen in Fig. 7. It is clear that the higher the PEI content,
give rise to hydrophobic/hydrophilic micro-phase separation. Due the lower the proton conductivity of the blend membranes. Due
to the high flexibility of the fluorocarbon, the hydrophilic sulfonic to cross-linked structure and the decrease of SPEEK content, the
groups’ clusters tended to form hydrophilic domains. Not only pro- reduction of proton conductivity can be explained by the reduced
tons but also vanadium ions could penetrate through the Nafion available sulfonic acid groups for transferring protons. However,
membrane through these domains during using in VRB. Compared the proton conductivities of blend membranes (except S/P-5) are
with Nafion117 membrane, the backbone of SPEEK is rigid and still higher than 0.065 S cm−1 (close to 0.083 S cm−1 of Nafion117
less hydrophobic which prevents dispersed sulfonic groups from membrane), which makes them interesting for using in VRB. It
aggregating to hydrophilic domains. Thus, the water filled chan- could be attributed to acid-base pairs between amino groups and
nels in SPEEK membrane are narrow and branched compared with the sulfonic acid groups which act as proton-conducting structures
those in Nafion membrane. In S/P blend membranes, the acid-base [40,41].

Fig. 6. Schematic of the possible conduction model.

 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96 95

Fig. 8. Charge-discharge curves for VRB with Nafion117 and S/P acid-base blend
Fig. 7. The proton conductivity of the acid-base blend membranes and Nafion117 membranes.
membrane.

3.5. VRB single cell performance

The VRB single cell performance with Nafion117 and S/P blend
membranes is shown in Table 2. The charge–discharge test was
performed under the same current density of 50 mA cm−2 .
The CE of VRB with all blend membranes is much higher than
that of the VRB with Nafion117 membrane. In addition, with the
increase of PEI, the CE rises from 90.2% to 97.7%, and then it reduces
to 93.9%. It is due to the CE of VRB determined by the vanadium ion
permeability and ion conductivity of the membranes. All the blend
membranes have much lower permeability than Nafion117 mem-
brane. Moreover, with the increase of PEI, the proton conductivity
and vanadium ion permeability reduced. So the balance between
ion conductivity and vanadium permeability could be achieved
with S/P blend membranes in VRB system.
The typical charge-discharge curves of VRB single cell with blend
membranes and Nafion117 membrane are presented in Fig. 8. It can
Fig. 9. The self-discharge of the VRB with Nafion117 and S/P-3 acid-base blend
be seen that the EE of single cell with blend membranes are a little membranes.
lower than that of Nafion117 membrane. At the same time, the VE
of VRB with blend membranes cut down with the increase of PEI.
As illustrated, the OCV value gradually decreases with the time
It is attributed to the lower proton conductivity of the blend mem-
at first and rapidly drops to 0.8 V. It can be seen that the time of
branes. As seen in Fig. 8, there is a capacity difference in the different
OCV with S/P-3 acid-base membrane can last for more than 46 h
systems. The cell capacity is controlled by the proton conductivity,
beyond 0.8 V, which is nearly 2.5 times longer than Nafion117
cycle time and vanadium ion permeability. The low conductivity
of blend membrane leads to short cycle time. The capacity of VRB
with blend membranes is lower than that of Nafion117. At the same
time, with the increase of PEI, the proton conductivity and the cell
capacity of the blend membranes decreased.
The value of open circuit voltage (OCV) can be used to investigate
the self-discharge degree of VRB and reveal the transferring of the
vanadium ions across the membranes. Fig. 9 displays the OCV of the
VRB with Nafion117 and S/P-3 acid-base blend membranes charged
to a state of charge at 50%.

Table 2
VRB single cell performance of Nafion117 and acid-base blend membranes.

Membrane CE(%) VE(%) EE(%)

S/P-0 90.2 91.1 82.2

S/P-1 90.9 89.6 81.4
S/P-2 92.8 89.1 82.7
S/P-3 97.7 88.9 86.9
S/P-4 94.5 86.5 81.7
S/P-5 93.9 85.0 79.8
Fig. 10. Cycling performance of VRB with S/P-3 acid-base blend membrane at a
Nafion117 89.9 90.8 81.6
current density of 50 mA cm−2 .
96 S. Liu et al. / Electrochimica Acta 130 (2014) 90–96

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