Journal of the Indian Chemical Society 99 (2022) 100410

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Journal of the Indian Chemical Society

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Performance assessment of hybrid multiblock copolymers included with

ionic liquid for fuel cell applications
Swati Awasthi a, Bharti Gaur b, *
a
Department of Chemistry, Kanya Maha Vidyalaya, Jalandhar, 144004, India
b
Department of Chemistry, National Institute of Technology, Hamirpur, 177005, India

A R T I C L E I N F O A B S T R A C T

Keywords: To improve the proton conductivity and thermal stability of proton exchange membrane, hybrid poly (arylene
Multiblock copolymers ether) multiblock copolymers were synthesized by using 6F-bisphenol A monomer. The hydrophobic oligomers
Ionic liquid poly (arylene ether sulfone) containing 6F-bisphenol A with varying molecular weight were copolymerised with
Morphology
hydrophilic oligomer disulfonated poly (arylene ether ketone) containing pendant carboxylic acid group to
Fuel cell performance
prepare multiblock copolymers. For further enhancing the proton conductivity, ionic liquid is embedded into the
synthesized multiblock copolymers to fabricate the hybrid multiblock membranes. The 1H NMR studies
confirmed the synthesis of oligomers and multiblock copolymers whereas the FT-IR spectra revealed the inter­
action of ionic liquid with the multiblock copolymers. The proton conductivity of the membranes has also been
examined at different temperatures and the activation energy required for the proton transport was calculated by
using Arrhenius equation. At 30 ◦ C, the maximum proton conductivity of 0.14 S/cm were shown by hybrid
membrane (with 50% ionic liquid, 6FB1/I.L-50%), which is of 3.5 times greater than that of pristine 6FB1
membrane. Compared with pristine membranes, the hybrid membranes exhibit improved oxidative, thermal and
mechanical stability. Moreover, the scanning electron microscopy (SEM) investigation depicts better phase
separation in hybrid membranes than pristine membranes by forming ionic clusters. The membranes have been
tested in H2/O2 fuel cell and their performance is compared with the state-of-art Nafion 117 membrane.

1. Introduction stability along with high proton conductivity at higher operating tem­
perature conditions [11–14].
The need for green alternative power sources is one of the major The recent years have seen the impetus of the research mainly on
concerns in today’s era. Since the past two decades, proton exchange multiblock copolymers because of the remarkable feature of nano-phase
membrane fuel cells (PEMFCs) have been remarkably playing an separation depicted by the membranes based on such copolymers. The
important role as a green alternative power source for stationary and hydrophobic-hydrophilic domains in multiblock copolymers provide
portable applications [1–3]. The proton exchange membrane (PEMs), better pathway for proton transportation [15–17]. By choosing different
being a cardinal component of PEMFCs facilitates the transportation of monomer structure or varying the block length of multiblock copolymer,
protons from anode to the cathode and act as a barrier for fuel the fuel cell related properties of PEMs such as proton conductivity,
cross-over. The state-of-the-art PEMs based on perfluorosulfonic acid mechanical, thermal and morphological properties can be explored [18,
such as Nafion is the commercially available PEMs possessing excellent 19].
proton conductivity, chemical stability and high fuel cell efficiency. But However, a major issue concerning the commercialization of these
the high production costs, environmental incompatibility and decrease PEMs is that for acquiring maximum proton conductivity of multiblock
in proton conductivity at higher temperature, limits its use for industrial PEMs, the hydrophilic content should be high and this adversely causes
applications [4,5]. In order to overcome these drawbacks, several other reduction in dimensional, mechanical and thermal stability of the PEMs
PEMs like poly (arylene ether), polybenzimidazole, polyimides, etc. [20–22]. The incorporation of the ionic liquids in the main structure of
have been explored in the last two decades [6–10]. But to all of these, the membrane can provide a solution to this apprehension. It can result
poly (arylene ether) PEMs is evidencing more oxidative and mechanical into improved proton conductivity while retaining the dimensional

* Corresponding author.
E-mail address: bhartigaur@gmail.com (B. Gaur).

https://doi.org/10.1016/j.jics.2022.100410
Received 7 January 2022; Received in revised form 17 February 2022; Accepted 1 March 2022
Available online 4 March 2022
0019-4522/© 2022 Indian Chemical Society. Published by Elsevier B.V. All rights reserved.
S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

stability of the PEMs. Ionic liquids are being considered advantageous solvents, dimethyl sulfoxide (DMSO,99.9%, Sigma Aldrich, Germany),
not only because of their chemical and thermal stability, N-methyl-2-pyrrolidone (NMP, 99%, Loba Chemie, India), isopropyl
non-flammability, low volatility, high ionic conductivity at high tem­ alcohol (99.2%, Merck), toluene (99%, Alfa Aesar, England), acetone
peratures, but also for their "green" credentials [23,24]. (99%, Alfa Aesar, England) and hydrochloric acid (36.5–38.0%, Alfa
An experimental study was conducted for synthesis of multiblock Aesar, England) were purchased commercially and used as such.
copolymer embedded with the ionic liquid, wherein phenolphthalein
monomer was used and resulted in better mechanical stability of the 2.2. Synthesis of F-terminated hydrophobic oligomers (6FBPAS-F)
hybrid multiblock PEMs [25]. Now, an attempt has been made to syn­
thesize thermally stable hybrid multiblock membranes with improved To tune the proton conductivity and thermal stability of the mem­
proton conductivity and overall fuel cell performance by using brane, the series of hydrophobic oligomers 6FBPAS-F1, 6FBPAS-F2 and
6F-bisphenol A monomer. The incorporation of bulky –CF3 groups of 6FBPAS-F3 were synthesized via aromatic nucleophilic substitution re­
6F-bisphenol A in the polymer chain can enhance the glass transition action with targeted molecular weight of 5, 8 and 10 kDa, respectively.
temperature and free volume of the polymer, thereby improve other The typical procedure for the synthesis of 6FBPAS-F2 was as follows:
PEMs related properties such as water uptake, ion exchange capacity, 6FBPA (40 mmol, 13.44 gm), FPS (46 mmol, 11.69 gm), K2CO3 (40.6
oxidative, and mechanical stability [26,27]. The impregnation of mmol, 5.61 gm), NMP (40 ml) and toluene (20 ml) were added into a
1-butyl-3-methyl imidazolium tetrafluoroborate (I.L) ionic liquid to the 250 ml three necked round bottom flask equipped with mechanical
multiblock PEMs is being considered to impart high conductivity and stirrer and Dean-Stark trap. The reaction mixture was firstly refluxed at
thermally stability to the hybrid multiblock PEMs and consequently 120 ◦ C for 4h in order to remove the water azeotropically. The reaction
good fuel cell performance even at higher temperatures. temperature was slowly raised to 150 ◦ C and the heating was continued
In the present article the influence of hydrophobic chain length and for the next 22h. Further, a small amount of FPS (0.5 gm) was also added
the content of I.L on PEMs related properties have been studied and to ensure the end-capping of 6FBPAS-F2 and the reaction was further
discussed in detail. Moreover to investigate the better proton conduc­ continued for another 3h. The resulting viscous mixture was cooled to
tivity and thermal stability, the fuel cell performance of 6F-Bisphenol A room temperature and then precipitated out in distilled water. The
based hybrid PEMs has been compared with the phenolphthalein based oligomer precipitated was obtained after washing the crude product for
hybrid PEMs. 3–4 times and dried at 70 ◦ C in a hot air oven for 48h. Fig. 1(a) displays
the reaction scheme for the synthesis of 6FBPAS-F2 oligomer.
2. Experimental
2.3. Synthesis of OH- terminated hydrophilic oligomer (DPA-OH)
2.1. Materials
The DPA-OH hydrophilic oligomer with target molecular weight 8
4,4’-difluorodiphenylsulfone (FPS, 99.9%, Sigma Aldrich, Ger­
kDa was synthesized according to the method reported in our previous
many), 4,4’-difluorodiphenylketone (DFDPK, 99.9%, Sigma Aldrich,
research article [25]. However, the reaction scheme is given in Fig. 1(b).
Germany), 4,4’ – bis (4-hydroxyphenyl) valeric acid (DPA, 97%, Alfa
Aesar, England), 6F-bisphenol A (6FBPA, 97%, Alfa Aesar, England),
potassium carbonate (K2CO3, 99.9%, Loba Chemie, India), fuming sul­ 2.4. Synthesis of hydrophilic-hydrophobic multiblock copolymers 6FB1,
furic acid (30% SO3, Spectrochem, India), ionic liquid 1-butyl-3-methyl 6FB2 and 6FB3
imidazolium tetrafluoroborate (I.L, 99%, SRL, India) were used. All the
The multiblock copolymers 6FB1, 6FB2 and 6FB3 were synthesized

Fig. 1. Synthesis of 6FB2 multiblock copolymer.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

via coupling reaction between F- terminated 6FBPAS-F hydrophobic 2.7.1. Thermal stability
oligomers and OH- terminated DPA-OH hydrophilic oligomer. A typical The thermal stability of the membranes was examined with the help
reaction procedure was given as follows: 6FBPAS-F2 (50 mmol), DPA- of Thermogravimetric\Differential Thermal Analyzer EXSTAR TG/DTA
OH (50 mmol), K2CO3 (55 mmol), NMP (40 ml) and toluene (20 ml) 6300.
were added into a 250 ml three necked round bottom flask equipped For TGA, the sample (10 mg) was heated from 25 to 900 ◦ C in ni­
with a mechanical stirrer and Fig. 1 Synthesis of 6FB2 Multiblock trogen atmosphere at a heating rate of 10 ◦ C min-1. The glass transition
Copolymer. temperature of the membrane was measured by preheating the sample
Dean-Stark trap. After refluxing the reaction mixture for 4h at from room temperature to 110 ◦ C to remove the moisture and then
120 ◦ C, the temperature was slowly raised to 150 ◦ C and maintained for cooled to 50 ◦ C and reheated from 50 ◦ C to 400 ◦ C at a scanning rate of
next 50h until it became highly viscous. The reaction mixture was cooled 10 ◦ C min-1 in nitrogen atmosphere.
down to room temperature and poured into 400 ml of isopropyl alcohol.
The obtained precipitates were filtered and dried in a hot air oven at 2.7.2. Mechanical properties
80 ◦ C for 48h. The reaction scheme is shown in Fig. 1. The other two For testing the mechanical properties of the membrane, the Universal
multiblock copolymers were synthesized by the same procedure and are Testing Machine Zdwick/Roell was used. The membrane samples of 5
listed in Table 1. mm × 25 mm dimension were tested at room temperature with a
stretching speed of 5 mm min-1. Each of the membrane was tested three
2.5. Preparation of pristine and hybrid membranes times and the average value was considered.

For pristine membrane, 1.0 gm of the multiblock copolymer was 2.7.3. Scanning Slectron Microscopy (SEM)
dissolved in 10 ml of DMSO and stirred for 4h at 50 ◦ C to obtain a ho­ SEM analysis of the membranes was performed by using Icon Quanta
mogenous mixture. For hybrid membranes, the I.L was added in 30%, FEG 450 field emission scanning electron microscope (FE-SEM). The
40% and 50% to the homogenous copolymer solution and the mixture sample membranes were sputter coated with gold and the applied
was stirred for 12h. Further, the solution was casted onto a Petri dish and accelerating voltage during scanning was 20 kV.
allowed to dry at 80 ◦ C for 48h. The dried membrane was peeled off and
further acidified with 1 M HCl solution for 12h. The hybrid multiblock 2.7.4. X-ray Diffraction (XRD) study
membranes were denoted as 6FB1/I.L-XX, 6FB2/I.L-XX and 6FB3/I.L- The XRD diffraction patterns of the membrane samples were ob­
XX, where XX refers to the percentage of ionic liquid added to the tained using Bruker D8-Avance diffractometer with Cu- Kα radiations
polymer mixture. Fig. 2(a) and (b) displays the photograph and sche­ source having wavelength of 0.154 nm. The data was collected at a
matic representation of the hybrid multiblock membrane 6FB2/I.L-40%. scanning rate of 2 ◦ min-1 with 2Ɵ varied from 10◦ to 50◦ .

2.6. Characterization 2.7.5. PEMFC performance

Gas diffusion electrode (GDE) method was used to fabricate the
The structural characterization of the synthesized copolymers was membrane electrode assembly (MEAs). The commercial GDE (Vinpro
done using FT-IR spectroscopy (PerkinElmer Spectrum 65 FT-IR spec­ Technologies, India) coated with Pt (0.8 mg cm-2) and Pt (7%)/Ru(3%)
trophotometer) in the range of 4000–400 cm-1. (0.5 mg cm-2) were used as cathode and anode, respectively. The
The JEOL JNM-ECX500 (500 MHz) spectrometer was used to record membrane sample was coated with 40% Pt/C catalyst using Nafion
1
H NMR spectra of the samples with tetramethylsilane as an internal ionomer (5 wt%, Merck) as binder. The MEA with active surface area of
standard and CDCl3 or DMSO-d6 as the solvent. The number average 6.25 cm2 sandwiched by two electrodes was prepared by hot pressing
molecular weight of the oligomers was calculated from their respective the membrane sample at 130 ◦ C for 3 min at a pressure of 8 MPa. The
1
H NMR spectra. single fuel cell testing was done by supplying H2 (84 mL/min) and O2
The molecular weights of the copolymer samples were also deter­ (400 mL/min) into the anode and cathode, respectively at a temperature
mined by gel permeation chromatography (GPC). The instrument used of 80 ◦ C at 100% relative humidity under ambient pressure.
was PerkinElmer Turbo matrix – 40-gel permeation chromatograph with
THF as a mobile phase. 3. Results and discussion

2.7. Fuel cell related properties 3.1. Synthesis of F-terminated (6FBPAS-F) hydrophobic oligomers

The fundamental properties of PEMs like Water Uptake (WU), A series of hydrophobic oligomers 6FBPAS-F1, 6FBPAS-F2 and
swelling ratio, ion exchange capacity, proton conductivity, methanol 6FBPAS-F3 with targeted molecular weight 5, 8 and 10 kDa, respectively
permeability and oxidative stability were determined by following the were synthesized via step growth condensation reactions. The 1H NMR
same procedure as reported in our previous work [25–27]. spectrum of 6FBPAS-F2 is shown in Fig. 3(i). The most deshielded proton
The activation energy (Ea) of the membrane samples was calculated Hd signal appeared at 7.84 ppm, whereas the peak at 7.03 ppm can be
using Arrhenius equation as follows: assigned to proton Hc. The proton (Hb) adjacent to 6F-isopropylidene
group showed a signal at 7.34 ppm. The peaks of end-group protons
σ = σ0 exp(
− Ea
) (1) Hd′ and Hc′ at 7.88 ppm and 7.08 ppm, respectively, confirmed the end
RT capping of the 6FBPAS-F2 oligomer. The molecular weight of the olig­
omer from the 1H NMR spectrum was determined by taking the integral
where σ is the proton conductivity, σ0 is the pre-exponential factor, R is
ratio of proton Hd in the repeating unit to the corresponding proton Hd′
universal gas constant and T is the absolute temperature.
in the end group. The calculated molecular weight was also compared
with that obtained from GPC analysis and are listed in Table 2. All the
Table 1
three hydrophobic oligomers showed a polydispersity index (PDI) from
List of Multiblock copolymers.
1.21 to 1.41.
Hydrophobic (kDa):Hydrophilic (kDa) 6FBPAS-F based multiblock copolymer

5:8 6FB1
8:8 6FB2
10:8 6FB3

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Fig. 2. (a) Photograph and (b) Schematic representation of the hybrid membrane.

Fig. 3. 1H NMR spectrum of (i) 6FBPAS-F2 and (ii) 6FB2 multiblock copolymer.

3.2. Hydrophilic-hydrophobic multiblock copolymers 6FB1, 6FB2 and Fig. 4 represents the FT-IR spectra of pristine 6FB2 and hybrid 6FB2/I.L
6FB3 multiblock membranes. The presence of characteristic peaks at 3161 cm-
1
and 3096 cm-1 confirmed the.
Fig. 3(ii) displayed the 1H NMR spectrum of 6FB2 multiblock -CH stretching vibrations of imidazole ring of cation in the hybrid
copolymer. The methyl protons (H1) of DPA appeared at 1.5 ppm and membranes. The pristine membrane 6FB2 showed a broad absorption
methylene protons (H2 and H3) of pentanoic group of DPA showed band at 3396 cm-1 indicating the –OH stretching vibrations due to car­
resonating signals at 1.8 ppm and 2.1 ppm, respectively. The most boxylic and sulfonic acid groups. However, in case of hybrid mem­
deshielded proton Ha present at the ortho position of the electron branes, the broadening and intensity of these bands get decreased,
withdrawing sodium sulfonate group appeared downfield at 8.1 ppm. which was ascribed to the electrostatic interactions between imidazo­
However, the aromatic protons (Hd, He, Hf and Hg) of 6FBPA-F2 hy­ lium cation of I.L with the sulfonic/carboxylic acid groups of the
drophobic oligomer showed resonating signals from 7.2 to 7.9 ppm. copolymer.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Table 2 channels and cationic mixtures such as H3O+, H5O2+, H9O4+, etc. in
Characteristics of oligomers. water medium. Therefore, the level of water absorption in the PEMs
Oligomer Target M.Wt. Mn, NMR Mn, GPC Mw, GPC PDIc depends upon the presence of hydrophilic moieties in the membrane. It
(kDa)a (kDa)b (kDa)c (kDa)c can be observed from Fig. 5(a) that pristine 6FB3 exhibited lower water
6FBPAS-F1 5 4.9 4.8 6.8 1.41 uptake (12%) than 6FB1 membrane (9.8%) due to smaller hydrophilic
6FBPAS-F2 8 7.6 7.8 10.3 1.32 block length. Therefore, 6FB3 with more hydrophobic character resists
6FBPAS-F3 10 9.5 11.6 14.1 1.21 the change in dimensional stability and showed minimum swelling ratio
DPA-OH 8 7.8 8.6 12.2 1.41 Fig. 5(b). In case of hybrid membranes, for example 6FB3/I.L, the water
[28]
uptake increases from (10.4 - 11.38) % with the addition of I.L as 30%,
a
Calculated by using Carothers equation. 40% and 50%. This can be attributed to the presence of hydrophilic
b
Determined from 1H NMR spectra and. imidazolium cation and [BF4]- of I.L. The anion of I.L [BF4]- might forms
c
Obtained from GPC. hydrogen bond with the absorbed water molecules or stimulate this type
of bonding within the hydrated membrane structure [29]. In the similar
The C–O bending peak of –COOH group in the pristine membrane pattern, all hybrid membranes exhibited slightly higher swelling ratio as
appeared at 1400 cm-1 which depicted decrease in intensity for I.L compared to corresponding pristine membranes Fig. 5(b). Although the
embedded hybrid membranes. Moreover, the broadening of the asym­ relative increase in water uptake and swelling ratio of hybrid mem­
metric and symmetric peaks of sulfonated groups at 1105 cm-1 and 1014 branes are not so high, therefore they can be promising candidate as
cm-1, respectively, corroborate the complexation of I.L with the multi­ proton exchange membrane for fuel cells.
block copolymer.
3.4. Ion exchange capacity (IEC) and proton conductivity
3.3. Water uptake and swelling ratio
The IEC values and proton conductivity of the membranes are listed
Water uptake of the PEMs plays an important role in the proton in Table 3. The pristine 6FB1 membrane showed higher IEC than 6FB2
transport mechanism. Generally, protons are transported either via and 6FB3 membrane. The reason for this can be attributed to the fact
Grotthus or Vehicular mechanisms through the hydrogen-bonded ionic that the pristine membrane 6FB1 contains greater hydrophilic content

Fig. 4. FT-IR spectra of 6FB2 pristine and 6FB2/I.L hybrid multiblock membranes.

Fig. 5. (a) Water uptake and (b) swelling ratio of pristine and hybrid membranes with various content of I.L.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Table 3
Properties of membranes.
Samples IEC σ (Scm- Ea (kJ mol- Methanol Selectivity
1 1
(meq ) ) permeability ( ratio ( × 106
gm-1) (30 ◦ C) × 10-7 cm2 s-1) Sscm-3)

6FB1 1.25 0.04 4.98 5.1 0.07

6FB1/I.L 1.29 0.07 4.57 4.6 0.15
-30%
6FB1/I.L 1.32 0.11 4.23 4.4 0.25
-40%
6FB1/I.L 1.34 0.14 3.92 4.3 0.32
-50%
6FB2 1.19 0.02 5.34 4.9 0.04
6FB2/I.L 1.24 0.05 4.98 4.5 0.11
- 30%
6FB2/I.L 1.26 0.08 4.64 4.3 0.18
- 40%
6FB2/I.L 1.29 0.11 4.41 4.1 0.26
– 50%
6FB3 1.16 0.01 5.48 4.5 0.02
6FB3/I.L 1.18 0.03 5.05 4.0 0.07
– 30%
6FB3/I.L 1.21 0.06 4.84 3.8 0.15
– 40%
6FB3/I.L 1.25 0.08 4.55 3.6 0.22
– 50%
Nafion® 0.90 0.076 ————— 10.1 0.07
117a
a
31.

than the other two pristine membranes and having larger numbers of
sulfonic/carboxylic acid groups which accordingly act as proton
exchangeable sites in the membrane. Thus, the membrane 6FB1 shows
higher capacity to exchange protons and hence show higher IEC [30].
The incorporation of I.L as 30%, 40% and 50% resulted into the
enhanced proton conductivity of the hybrid membranes. This may be
due to the electrostatic interaction between the ionic (sulfonic/carbox­
ylic) groups of the multiblock copolymer and imidazolium cation of I.L.
This ionic synergism between the I.L and the acidic groups provides a
free pathway for the protons to travel.
The proton conductivity of the sample membranes was also
measured at different temperatures 40 ◦ C, 60 ◦ C and 80 ◦ C and the re­
sults are shown in Fig. 6(a). However, the observed increase in the
proton conductivity at higher temperatures might be due to the decrease
in the viscosity of I.L which expedites the polymer chain mobility and
makes proton transport easy. The activation energy of all the mem­
branes was calculated by plotting a graph between ln (proton conduc­
tivity) v/s T-1 by using Arrhenius equation (Fig. 6(b)). All the
Fig. 6. (a) Proton conductivity as a function of temperature and (b) Arrhenius
membranes showed very low activation energy in the range of 3.9 - 5.48
plot of membranes.
kJ mol-1 as compare to Nafion 117 (9 kJ mol-1).
The interaction of polar and bulky –CF3 groups in the 6FB2 with the
[BF4]- anion of the I.L creates repulsive environment which easily influences the fuel cell performance of the membranes. With the addi­
displace the protons from their acidic sites and hence causes faster tion of I.L, the proton conductivity increases and methanol permeability
proton transportation with low activation energy. According to Hasani- decreases causing higher selectivity ratio of hybrid membranes
Sadrabadi et al. [32], with such lower activation energy, the protons are (Table 3). The hybrid membranes showed selectivity ratio in the range of
assumed to be transported primarily through vehicular mechanism in 0.02 - 0.32 which was higher than state-of-art Nafion 117 membrane
the membranes. [33]. Therefore, these hybrid multiblock membranes could be consid­
ered as promising PEMs for fuel cell applications.

3.5. Methanol permeability and selectivity ratio

3.6. Oxidative stability
As expected, the hydrophobic –CF3 moieties present in the multi­
block membranes are very less permeable to methanol molecules. To examine the oxidative stability of PEMs, the membrane sample
Therefore, the methanol permeability of 6FB3 membrane having was soaked in Fenton’s reagent (6% H2O2 containing 3 ppm FeSO4) up
maximum number of –CF3 groups was lesser as compare to the other to 12h at 80 ◦ C. The Fig. 7 depicted the mass loss of the membrane
pristine membranes (Table 3). The incorporation of bulky [BF4]- anions sample after 4, 6, 8 and 12 h. The presence of highly withdrawing groups
of I.L in the multiblock copolymers further blocks the passage for i.e. sulfone, ketone and bulky hydrophobic –CF3 groups in the multi­
methanol molecules, resulting into the lower methanol permeability of block membrane resist the electrophilic attack of hydroxy or perhydroxy
the hybrid membranes. radicals and resulted into the higher oxidative stability of synthesized
The selectivity ratio of proton conductivity to methanol permeability multiblock membranes. However, the sulfonic/carboxylic acidic sites

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

present as free entity in the membrane may have leach out.

3.8. Thermal stability

The thermal properties of the membranes were studied by TGA and

DSC. The TGA curves of pristine 6FB1, 6FB2 and 6FB3 membranes are
shown in Fig. 9(a). All the membranes showed similar weight loss pat­
terns i.e. three step weight losses. The first weight loss up to 120 ◦ C was
due to the evaporation of residual solvent and moisture. The second
weight loss in the range of 411–433 ◦ C can be ascribed to the degra­
dation of sulfonic/carboxylic groups present in the membrane. The
weight loss step at temperatures above 588 ◦ C was due to the thermal
decomposition of main polymer chain of multiblock copolymer. The
comparative TGA curves for hydrophobic oligomers (6FBPAS-F1/F2/
F3) and hydrophilic oligomer DPA-OH are also shown in Fig. S1(Sup­
plementary Material). Due to the presence of 6F-moiety in the hydro­
phobic oligomers, they showed high thermal stability as compare to
Fig. 7. Oxidative stability of pristine and hybrid membranes at different
hydrophilic oligomer.
time intervals. Also, 6FBPAS-F3 with highest hydrophobic content is thermally
more stable than 6FBPAS-F2 and 6FBPAS-F1 oligomers. As expected,
6FB3 multiblock PEM owing to its longer hydrophobic block length
are more prone for radical attack and this accelerated the deterioration
exhibited more thermal stability than 6FB2 and 6FB3.
of polymer chains. For comparison, the 6FB1 multiblock membrane
Fig. 9(b) compared the TGA curves of 6FB2 pristine membrane with
possessing longer hydrophilic block length, exhibited more mass loss
their hybrid counterparts. The results indicated that with the addition of
than in case of 6FB1 [34].
I.L, the hybrid membranes possessed enhanced thermal stability, which
Moreover, in hybrid membranes the interactions of sulfonic/car­
may be due to its strong interaction with sulfonic/carboxylic acid groups
boxylic acidic groups with imidazolium cation of I.L have rendered the
present in the pristine membrane. This interaction would also govern the
membranes resistant towards radical attack which is reflected by their
degradation temperature of these acidic groups. Feng et al. have also
higher mass residue in oxidative environment.
reported the ionic liquid to exhibit thermal stability up to 300 ◦ C [35] .
The pristine membrane 6FB2 exhibited single Tg at 282 ◦ C, whereas all
3.7. Leaching of ionic liquid the hybrid membranes showed two Tg’s. For example, 6FB2/I.L-30%
have Tg1 (285 ◦ C) for the hydrophobic segment and higher Tg2 (350 ◦ C)
Leaching test is important to assess the I.L retention ability of hybrid for hydrophilic segment owing to its restricted mobility by strong ionic
membranes. It was done by immersing the sample in distilled water for groups interaction. With 40% I.L, both Tg1 and Tg2 are increased by 4 ◦ C.
48 h at 80 ◦ C. From Fig. 8, it was observed that all the hybrid membranes However with the further increase in the content of the I.L in case of
showed more leaching of I.L with increase in its content as 30%, 40% 6FB2/I.L-50%, notably, the Tg1 appeared at 281 ◦ C and Tg2 at 360 ◦ C.
and 50%. Notably, the increase was most pronounced for 6FB3 multi­ This result indicates that higher ratio of I.L causes plasticization effect,
block copolymer based hybrid membranes as compared to the other two which provides more flexibility to the membranes. Therefore, a decrease
(6FB2 and 6FB3) hybrid multiblock membranes. A possible explanation in Tg1 was observed whereas the strong electrostatic interaction
for this might be the higher hydrophobic character of 6FB3 multiblock increased the Tg2.
copolymer, which is not able to electrostatically hold the I.L in the
hybrid membrane, and thus, showed lower I.L retention. Therefore, in 3.9. Mechanical properties
6FB3/I.L- 50% the extra amount of I.L which did not interact and was
The mechanical properties of all the pristine and hybrid membranes
were measured and are listed in Table 4. All the pristine membranes
impart tensile strength in the range of 38 - 46.7 MPa which is signifi­
cantly greater than Nafion 117.
However, elongation at break of Nafion 117 is much higher because
of the presence of flexible –CF2 linkages in the main chain of its polymer
structure.
All the hybrid membranes displayed very high tensile strength due to
the ionic interactions of I.L with the multiblock copolymer. For 6FB3,
which has higher hydrophobic block length, the tensile strength
increased from 54.6 to 61.2 MPa with the increase in the content of I.L
from 30% to 40%. However at 50% of I.L, the tensile strength decreased
to 59.3 MPa. This is possibly due to the off-stoichiometric ratio of I.L,
which acts as plasticiser and provides more flexibility to the polymer
chains. From these results it can conclude that hybrid membranes with
optimized ratio of 40% I.L show the desired mechanical properties and
are best suited for fuel cell application.

3.10. SEM analysis

The surface morphology of the membranes were analysed with the

help of SEM. The SEM micrographs of all the sample pristine and hybrid
Fig. 8. Leaching test of hybrid membranes at different ratio of I.L. membranes are shown in Fig. 10.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Fig. 9. Comparison of thermal stabilities of pristine and hybrid multiblock copolymer membranes.

ionic channels get shortened in 6FB3 due to greater hydrophobic char­

Table 4
acter (Fig. 10(c)). As shown in Fig. 10(b), the homogenous phase sep­
Mechanical properties of the membranes.
aration was observed in 6FB2 membrane having equal block length of
Sr. No. Tensile strength Young’s Modulus Elongation at break hydrophobic and hydrophilic blocks.
(MPa) (MPa) (%)
With the addition of I.L, there was aggregation of ionic clusters in the
6FB1 38.1 202.6 71 hybrid membranes. The size of ionic clusters in the hybrid membranes
6FB1/I.L 49.5 242.4 84
were found to increase in 6FB1 hybrid membranes as shown in SEM
-30%
6FB1/I.L 55.6 262.2 92 images of Fig. 10(a1), Fig. 10(a2) and Fig. 10(a3). However, the
-40% homogenously aggregated ionic clusters were observed in 6FB2 hybrid
6FB1/I.L 54.3 246.8 108 membranes, providing better interconnected protonic channels for high
-50% proton conductivity of the membranes as revealed in Fig. 10(b1) 6FB2/I.
6FB2 42.4 225.6 78
6FB2/I.L - 53.6 262.7 92
L-30%, Fig. 10(b2) 6FB2/I.L-40% and Fig. 10(b3) 6FB2/I.L-50%. For
30% 6FB3 hybrid membranes in Fig. 10(c1) 6FB3/I.L-30%, Fig. 10(c2) 6FB3/
6FB2/I.L - 60.2 283.9 107 I.L-40% and Fig. 10(c3) 6FB3/I.L-50%, the ionic clusters were unevenly
40% distributed and the micrographs of the membranes depict very poorly
6FB2/I.L – 61.3 294.7 120
connected ionic channels and hence were responsible for their lesser
50%
6FB3 46.7 248.4 76 proton conductivity than other hybrid membranes.
6FB3/I.L – 54.6 267.6 88
30% 3.11. XRD study
6FB3/I.L – 61.2 288.6 97
40%
6FB3/I.L – 59.3 285.1 109 The amorphous nature of multiblock copolymers was investigated by
50% using XRD analysis.
Nafion® 117a 30.3 — 270 Fig. 11 shows the diffraction patterns of (a) 6FB1, (b) 6FB2 and (c)
a
[30]. 6FB3 pristine and hybrid membranes. The small intensity of the peaks in
case of all the samples suggests the fact that amount of crystalline
It is evident from the Fig. 10 that all the membranes have well- component is very less in the otherwise amorphous part. It can also be
defined phase separated morphology. The pristine membrane 6FB1 in observed from the Fig. 11(a) that the intensity of peaks at 2θ = 28◦ , 38◦ ,
Fig. 10(a) depicted longer hydrophilic/ionic channels whereas these 41◦ and 51◦ for 6FB1 pristine membrane decrease with the addition of I.
L and also, simultaneously a few small intensity peaks appear. The

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Fig. 10. SEM micrographs of (a) 6FB1, (b) 6FB2, (c) 6FB3, (a1) 6FB1/I.L-30%, (b1) 6FB2/I.L-30%, (c1) 6FB3/I.L-30%, (a2) 6FB1/I.L-40%, (b2) 6FB2/I.L-40%, (c2)
6F B3/I.L-40%, (a3) 6FB1/I.L-50%, (b3) 6FB2/I.L-50%, (c3) 6FB3/I.L-50% membranes.

decrease in the intensity of the peaks suggests decrease in the crystal­ It is also apparent from the Fig. 11 that for the three pristine mem­
linity, which may be caused by the incorporation of I.L in between the branes (a) 6FB1, (b) 6FB2 and (c) 6FB3, the increase in the hexafluoro
chains. moiety with the increase in the block length of the hydrophobic block
The appearance of the new small intensity peaks with the addition of gives rise to greater amorphous nature of the membranes. Since, the
I.L confirmed random dispersion of I.L into the multiblock copolymer peaks at 2θ = 30◦ , 31◦ and 38◦ either show decrease in intensity or
membranes. Addition of 50% I.L to the membranes caused plasticization completely disappear. However, the peaks have completely disappeared
effect and hence the membranes show greater amorphous character. The in case of 6FB2/I.L-50% hybrid membrane. These results indicate that
same trend is observed for other membrane samples of 6FB2 and 6FB3 in the crystalline behavior of multiblock copolymers has been decreased
Fig. 11(b) and (c), respectively. This results suggest that the amorphous with the increment in the content of I.L in the hybrid membranes.
nature of multiblock increases with the addition of I.L in the hybrid
membrane.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

Fig. 11. XRD plots of (a) 6FB1, (b) 6FB2 and (c) 6FB3 pristine membranes and their hybrid counterparts.

3.12. PEMFC performance 4. Conclusions

The fuel cell performance of the fabricated PEMs was also carried out The nano-phase separated multiblock copolymers 6FB1, 6FB2 and
for its practical application as next generation PEMs. The 6FB2 pristine 6FB3 were successfully synthesized by varying the hydrophobic block
and its hybrid membranes were fabricated into MEAs and tested in fuel length containing 6F-bisphenol A monomer and further the block co­
cells at 80 ◦ C. The polarisation curves and power densities for 6FB2 polymers were treated with ionic liquid to prepare hybrid multiblock
membranes are given in Fig. 12(a). At current density of 0.4 Acm-2, the membranes. All the hybrid membranes exhibit improved fuel cell related
pristine 6FB2 showed voltage 0.49 V and power densities of 0.19 Wcm-2. properties as summarized below:
For hybrid membranes, with the addition of I.L, the voltage and power
densities values increased up to 0.59 V and 0.23 Wcm-2, respectively i. The prepared hybrid membranes showed greater proton con­
[36]. ductivity than their pristine counterparts and the maximum
This improved performance of hybrid membranes with the addition proton conductivity (0.14 Scm-1) was obtained with 50% of I.L in
of I.L is found to be in good agreement with the proton conductivity data the 6FB1/I.L hybrid membrane.
values. For 6FB2/I.L-40%, the maximum power density (0.212 Wcm-2) ii. The complexation of I.L with the sulfonic/carboxylic acidic
was found to be higher than Nafion 117 (0.190 Wcm-2) [36]. Moreover, groups of multiblock copolymer resulted into increased oxidative
the fuel cell testing of previously synthesized phenolphthalein based and mechanical stability of the hybrid membranes.
hybrid membranes [25] was also done and the results are compared with iii. The thermal stability of synthesized multiblock copolymers was
that of 6FB2 hybrid membranes (Fig. 12(b)). The voltage and power very high (>400 ◦ C), and further augmentation was observed on
densities of P2 hybrid membranes at 0.4 Acm-2 were found to be in the the addition of I.L in the hybrid membranes.
range of (0.15 -0.33) V and (0.06 – 0.13) Wcm-2. Therefore, the hybrid iv. SEM and XRD analysis was also found to be useful to reveal the
multiblock copolymers synthesized in the present study are comparably phase separation and amorphous nature of the membranes.
more suitable for use in PEMFC. v. Through comparison with previously synthesized hybrid mem­
branes, the hybrid membranes of the present study i.e. 6FB2/I.L
showed fuel cell performance which was better than P2/I.L.

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S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

[5] P. Sun, Z. Li, F. Dong, et al., High temperature proton exchange membranes based
on cerium sulfophenyl phosphate doped polybenzimidazole by end-group
protection and hot-pressing method, Int. J. Hydrogen Energy 42 (2017) 486–495.
[6] C. Jangu, A.M. Savage, Z. Zhang, et al., Sulfonimide-containing triblock
copolymers for improved conductivity and mechanical performance, Macromol
(Washington, DC, United States) 48 (2015) 4520–4528.
[7] X. Guo, W. Li, J. Fang, et al., Synthesis and properties of novel multiblock
copolyimides consisting of benzimidazole-groups-containing sulfonated polyimide
hydrophilic blocks and non-sulfonated polyimide hydrophobic blocks as proton
exchange membranes, Electrochim. Acta 177 (2015) 151–160.
[8] A.N. Lai, L.S. Wang, C.X. Lin, et al., Phenolphthalein-based poly(arylene ether
sulfone nitrile)s multiblock copolymers as anion exchange membranes for alkaline
fuel cells, ACS Appl. Mater. Interfaces 7 (2015) 8284.
[9] H. Li, J. Wu, C. Zhao, et al., Proton-conducting membranes based on
benzimidazole-containing sulfonated poly(ether ether ketone) compared with their
carboxyl acid form, Int. J. Hydrogen Energy 34 (2009) 8622–8629.
[10] G. Xu, Z. Wu, Z. Xie, et al., Graphene quantum dot reinforced hyperbranched
polyamide proton exchange membrane for direct methanol fuel cell, Int. J.
Hydrogen Energy (2020), https://doi.org/10.1016/j.ijhydene.2020.06.303. Epub
ahead of print.
[11] A. Iulianelli, I. Gatto, F. Trotta, et al., Electrochemical characterization of
sulfonated PEEK-WC membranes for PEM fuel cells, Int. J. Hydrogen Energy 38
(2013) 551–557.
[12] X. Yan, S. Gu, G. He, et al., Imidazolium-functionalized poly(ether ether ketone) as
membrane and electrode ionomer for low-temperature alkaline membrane direct
methanol fuel cell, J. Power Sources 250 (2014) 90–97.
[13] M. Prathap, K. Poonkuzhali, M.M. Berlina, Synthesis and Characterization of
Sulfonated Poly (ether ether ketone)/Zinc Cobalt Oxide Composite Membranes for
Fuel Cell Applications, 2020, https://doi.org/10.1177/0954008320922296. Epub
ahead of print.
[14] A.R. Kim, M. Vinothkannan, D.J. Yoo, Sulfonated (poly ether ether ketone) and
graphene oxide: a ternary hybrid membrane architecture for electrolyte
applications in proton exchange membrane fuel cells, J. Energy Chem. 27 (2018)
1247–1260.
[15] Y.A. Elabd, M.A. Hickner, Block copolymers for fuel cells, Macromolecules 44
(2011) 1–11.
[16] B. Kim, R. Kannan, K.S. Nahm, D.J. Yoo, Development and characterization of
highly conducting nonfluorinated di and triblock copolymers for polymer
electrolyte membranes, J. Dispersion Sci. Technol. 37 (2016) 1315–1323.
[17] C. He, F. Mighri, M.D. Guiver, et al., Tuning surface hydrophilicity/hydrophobicity
of hydrocarbon proton exchange membranes (PEMs), J. Colloid Interface Sci. 466
(2016) 168–177.
[18] J.Y. Chu, A.R. Kim, K.S. Nahm, H.K. Lee, D.J. Yoo, Synthesis and characterization
of partially fluorinated sulfonated poly (arylene biphenylsulfone ketone) block
copolymers containing 6F-BPA and perfluorobiphenylene units, Int. J. Hydrogen
Fig. 12. Comparison of fuel cell performance of (a) 6FB2 and (b) P2 hybrid Energy 38 (2013) 6268–6274.
multiblock membranes. [19] K.H. Lee, J.Y. Chu, V. Mohanraj, A.R. Kim, M.H. Song, D.J. Yoo, Enhanced ion
conductivity of sulfonated poly (arylene ether sulfone) block copolymers linked by
aliphatic chains constructing wide-range ion cluster for proton conducting
From these results, it can be concluded that the hybrid membranes electrolytes, Int. J. Hydrogen Energy 45 (2020) 29297–29307.
reported in this article possess the requisite properties of proton ex­ [20] A.R. Kim, M. Vinothkannan, D.J. Yoo, Sulfonated-fluorinated copolymer blending
change membranes and can serve as cardinal component in the fuel membranes containing SPEEK for use as the electrolyte in polymer electrolyte fuel
cells (PEFC), Int. J. Hydrogen Energy 42 (2017) 4349–4365.
cells. [21] K.H. Lee, J.Y. Chu, A.R. Kim, K.S. Nahm, C.J. Kim, D.J. Yoo, Densely sulfonated
block copolymer composite membranes containing phosphotungstic acid for fuel
Declaration of competing interest cell membranes, J. Membr. Sci. 434 (2013) 35–43.
[22] H. Jang, T. Ryu, S.C. Sutradhar, et al., Studies of sulfonated poly(phenylene)-block-
poly(ethersulfone) for proton exchange membrane fuel cell, Int. J. Hydrogen
The authors declare that they have no known competing financial Energy (2017) 1–9.
interests or personal relationships that could have appeared to influence [23] Y. Yang, H. Gao, L. Zheng, RSC Advances Anhydrous proton exchange membranes
at elevated temperatures : eff ect of protic ionic liquids and crosslinker on proton
the work reported in this paper.
conductivity, RSC Adv. 5 (2015) 17683–17689.
[24] L.G. Trindade, L. Zanchet, J.C. Padilha, F. Celso, S.D. Mikhailenko, M.R. Becker, M.
Appendix A. Supplementary data R. De Souza, In fl uence of ionic liquids on the properties of sulfonated polymer
membranes, Mater. Chem. Phys. 148 (2014) 648–654.
[25] S. Awasthi, B. Gaur, Polymer electrolytes: ionic liquid modified phenolphthalein
Supplementary data to this article can be found online at https://doi. based hybrid multiblock poly(arylene ether) copolymers, J. Electrochem. Soc. 164
org/10.1016/j.jics.2022.100410. (2017) H5057–H5067.
[26] V. Kiran, B. Gaur, Sulfonated poly (arylene ether sulfone) proton exchange
membranes for fuel cell applications, Green Process. Synth. 4 (2015) 283–297.
References [27] S. Awasthi, V. Kiran, B. Gaur, Cross-linked poly (ether ether ketone): cost effective
proton exchange membranes for fuel cell application, Bull. Mater. Sci. 41 (2018)
[1] Y. Hu, X. Li, L. Yan, et al., Improving the overall characteristics of proton exchange 1–10.
membranes via nanophase separation Technologies: a progress review, Fuel Cell. [28] S. Awasthi, V. Kiran, B. Gaur, Influence of hydrophobic block length and ionic
1–15 (2017). liquid on the performance of multiblock poly (arylene ether) proton exchange
[2] Z. Zhang, K. Jetsrisuparb, A. Wokaun, et al., Study of nitrile-containing proton membrane, Int. J. Hydrogen Energy 42 (2017) 11710–11723.
exchange membranes prepared by radiation grafting: performance and degradation [29] C.D. Tran, S.H.D.E.P. Lacerda, D. Oliveira, Absorption of water by room-
in the polymer electrolyte fuel cell, J. Power Sources 243 (2013) 306–316. temperature ionic liquids : effect of anions on concentration and state of water,
[3] G. Çelik, M. Barsbay, O. Güven, Towards new proton exchange membrane Appl. Spectrosc. 57 (2003) 152–157.
materials with enhanced performance via RAFT polymerization, Polym. Chem. 7 [30] S.K. Ryu, A.R. Kim, M. Vinothkannan, K.H. Lee, J.Y. Chu, D.J. Yoo, Enhancing
(2016) 701–714. physicochemical properties and single cell performance of sulfonated poly (arylene
[4] J. Zheng, J. Wang, S. Zhang, et al., Synthesis of novel cardo poly(arylene ether ether)(SPAE) membrane by incorporation of phosphotungstic acid and graphene
sulfone)s with bulky and rigid side chains for direct methanol fuel cells, J. Power oxide: a potential electrolyte for proton exchange membrane fuel cells, Polymers
Sources 245 (2014) 1005–1013. 13 (2021) 2364.

11
S. Awasthi and B. Gaur Journal of the Indian Chemical Society 99 (2022) 100410

[31] Y. Zhang, X. Fei, G. Zhang, et al., Preparation and properties of epoxy-based cross- [34] A.R. Kim, M. Vinothkannan, K.H. Lee, J.Y. Chu, S.K. Ryu, H.G. Kim, D.J. Yoo,
linked sulfonated poly(arylene ether ketone) proton exchange membrane for direct Ameliorated performance of sulfonated poly (arylene ether sulfone) block
methanol fuel cell applications, Int. J. Hydrogen Energy 35 (2010) 6409–6417. copolymers with increased hydrophilic oligomer ratio in proton-exchange
[32] M.M. Hasani-sadrabadi, E. Dashtimoghadam, K. Sarikhani, Electrochemical membrane fuel cells operating at 80% relative humidity, Polymers 12 (2020) 1871.
Investigation of Sulfonated Poly (Ether Ether Ketone)/Clay Nanocomposite [35] W.Q. Feng, Y.H. Lu, Y. Chen, Y.W. Lu, T. Yang, Thermal stability of imidazolium-
Membranes for Moderate Temperature Fuel Cell Applications, vol. 195, 2010, based ionic liquids investigated by TG and FTIR techniques, J. Therm. Anal.
pp. 2450–2456. Calorim. 125 (2016) 143–154.
[33] Y. Zhang, G. Zhang, Y. Wan, et al., Synthesis and characterization of poly(arylene [36] L.G. Trindade, M.R. Becker, C.L.P. Fabrıcio Celso, M. Emilse, R.F. Martini, S.A. de,
ether ketone)s bearing pendant sulfonic acid groups for proton exchange Modification of sulfonated poly (ether ether ketone) membranes by impregnation
membrane materials, J. Polym. Sci. Part A Polym Chem 48 (2010) 5824–5832. with the ionic liquid 1-butyl-3-Methylimidazolium tetrafluoroborate for proton
exchange membrane fuel cell applications, Polym. Eng. Sci. (2016) 3–10.

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