i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0

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Bis-pyridinium crosslinked poly(ether ether

ketone) anion exchange membranes with
enhancement of hydroxide conductivity and
alkaline stability

Yaojie Xu b, Chunhui Zhao a,b,*, Shengmei Huang b, Yonglian Gan b,

Lei Xiong b, Jianping Zhou b,**, Hongbo Liang b
a
Key Laboratory for Microstructural Control of Metallic Materials of Jiangxi Province, Nanchang Hangkong
University, Nanchang, 330063, China
b
School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang, 330063, China

highlights graphical abstract

A series of tunable bis-pyridinium

crosslinked PEEK-BiPy-x AEMs are
synthesized.

Various crosslinking density of
bis-pyridinium is optimized to
promote microphase separation
and guarantee the free volume.

All PEEK-BiPy-x membranes have
distinct microphase separation
structures.

PEEK-BiPy-0.5 AEM shows high
hydroxide conductivity and excel-
lent alkaline stability.

article info abstract

Article history: A series of tunable bis-pyridinium crosslinked PEEK-BiPy-x anion exchange membranes
Received 12 August 2021 (AEMs) are prepared successfully to improve the “trade-off” between ionic conductivity and
Received in revised form alkaline stability. The crosslinking density of bis-pyridinium is optimized to promote
9 November 2021 microphase separation and guarantee the free volume. All the PEEK-BiPy-x membranes have
Accepted 27 November 2021 a distinct microphase separation pattern observed by atomic force microscopy (AFM) and the
Available online 23 December 2021 PEEK-BiPy-x membranes also display adequate thermal, mechanical and dimensional sta-
bility. Impressively, the PEEK-BiPy-0.5 membrane exhibits maximum tensile strength
Keywords: (58.53 MPa) and highest IEC of 1.316 mmol$g1. Meanwhile, its hydroxide conductivity rea-
Bis-pyridinium ches up to 70.86 mS$cm1 at 80  C. Besides, great alkaline stability of PEEK-BiPy-0.5 mem-
Crosslinked brane is obtained with conductivity retention of 91.74% after 1440 h in 1 M NaOH solution,

* Corresponding author. Key Laboratory for Microstructural Control of Metallic Materials of Jiangxi Province, Nanchang Hangkong
University, Nanchang, 330063, China.
** Corresponding author.
E-mail addresses: zhao.chunhui@nchu.edu.cn (C. Zhao), zf161162@163.com (J. Zhou).
https://doi.org/10.1016/j.ijhydene.2021.11.209
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
6098 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Alkaline stability owing to the crosslinked structure of the AEMs and steric effect of bis-pyridinium cations.
Anion exchange membranes Overall, the PEEK-BiPy-x membranes possess potential applications in AEMs.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Fuel cells are a promising technology that provides sustain-
able energy, which has attracted wide attention from the
world [1e5]. The advantages of fuel cells over the current
technologies are numerous, for example, low pollution, high
electrical efficiency and high energy density. Therefore, this
kind of advanced energy transfer technology is considered
one of the most prospective candidates for an energy crisis
[6,7]. Among a division of fuel cells, polymer electrolyte fuel
cells with the feature of high power density, lightweight and
wide range in applications, including proton exchange mem-
brane fuel cells (PEMFCs) and anion exchange membrane fuel
cells (AEMFCs). Due to the long service life and high stability,
PEMFCs have become the commercialized devices [8e10].
However, a few drawbacks hinder the further development of
PEMFCs, such as low electrode reaction kinetics, expensive
catalysts and high fuel permeability [11e16]. To overcome
those obstacles, developing AEMFCs is a preferable approach
alternatively [17], because of the excellent power density and
low cost [18e20]. One of the most important components of
AEMFCs is the AEMs. The AEMs not only transport ions but
also segregate the fuel [21]. Accordingly, the membrane per-
formance determines the efficiency and lifetime of the cell
system [22,23]. An ideal AEM requires high ion conductivity,
long-term alkaline stability, excellent mechanical and ther-
mal stability. Nevertheless, the current AEMs still suffer from
low hydroxide conductivity and poor alkaline stability, greatly
affecting their practical applications in AEMFCs [24,25].
Therefore, much research has been devoted to improving the
performance of AEMs.
The AEMs are constructed by polymer skeletons and
cationic functional groups. The former supports the AEMs
by suppling the essential mechanical strength. The cationic
functional groups could selectively permit the transfer of
OH [26]. Currently, the polymer skeletons for AEMs are
polyether sulfone (PSF) [27e30], polyphenylene ether (PPO)
[31e33], polyvinyl alcohol (PVA) [34], polybenzimidazole
(PBI) [35] and polyether ether ketone (PEEK) [36e40]. Main-
chain constructed by PEEK were found to possess appro-
priate chemical stability and excellent thermo-mechanical
stability, which has potential applications in AEMs [41].
The cationic groups commonly used in AEMs are quaternary
ammonium groups [42], imidazole groups [43,44], guanidine
groups [45], metal cationic groups [46] and pyridine groups
[47,48]. Notably, ascribing to the pyridine group's delocalized
p-bond-conjugated structure which would restraint the OH
attack effectively, it has been reported to show outstanding
alkaline stability. Besides, the alkaline stability of AEMs can
be available increased via introducing space steric protec-
tion, covalent crosslinking, conjugation effect and electron-
donating groups. High hydroxide conductivity is another
prerequisite for an ideal AEM [49]. A direct way to improve
the hydroxide conductivity is by increasing the number of
cation groups [50]. However, it may cause undue swelling of
the AEMs to weaken the interaction between molecular
chains, decreasing the alkaline stability of AEMs, which
eventually reach a limit leading to membrane rupture [51].
Hence, improving the “trade-off” between ion conductivity
and alkaline stability is still a crucial issue in the develop-
ment of AEMs at present [52e54].
The construction of microphase separation is an efficient
way to keep the balance between hydroxide conductivity and
stability of AEMs [55e57]. And the microphase segregation
results from the polarity difference between the side chains
and the backbones [58]. A distinct hydrophilic/hydrophobic
microphase segregation is beneficial for ionic transport. Thus,
high ionic conductivity is expected for AEMs [59]. Shin et al.
[60] synthesized hydrocarbon-based polymers with an
apparent microphase separation structure, indicating that a
well-defined morphology structure is fundamental to
acquiring dramatic performance for AEMs. Dong et al. [61]
synthesized a series of the multiblock copolymer and
branched cation functional groups compactly to build micro-
phase separation for promoting ion transport. He et al. [41]
utilize an ether-containing flexible, hydrophilic crosslinker to
build microphase separation and form connected ion trans-
port channels within the membrane. Apart from those, the
strategy of crosslinking has been demonstrated to be a valid
approach to adjust the ionic transport channel, improving the
microphase separation [62,63]. However, ordinary alkyl
crosslinkers always make AEMs mechanically brittle and
reduce their alkaline stability as well as intemperate cross-
linking density reduces the free volume and limits molecular
movement, limiting the applications of these crosslinked
AEMs [64e66].
Herein, a series of bis-pyridinium crosslinked AEMs were
designed and synthesized. The PEEK is selected as the poly-
mer backbone, because of its high thermal, mechanical and
chemical stabilities as well as commercial availability [67].
The aromatic ether bond allows more rotational freedom
along the polymer backbone with increased activity and good
film-forming properties. Bis-pyridinium cation functional
group was used to restraint the OH attack effectively to
enhance the alkaline stability and it formed crosslinked AEMs
having the microphase separation structures to improve ionic
conductivity, which contributing to ameliorating the “trade-
off” between hydroxide conductivity and alkaline stability
[68,69]. The regulatory mechanism of the bis-pyridinium
about the performances of PEEK-BiPy-x AEMs (water uptake,
swelling ratio, hydroxide conductivity, chemical and thermal
stabilities) was investigated in detail.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Experiment
Materials
4,40 -difluorobenzophenone (DFBP, 99%), hexafluorobisphenol
A (BPA-6F, 98%), methylhydroquinone (THQ, 98%) and 1,2-
bis(4-pyridyl)ethane were purchased from Sarn Chemical
Technology (Shanghai). Azodiisobutyronitrile (AIBN, AR) was
obtained by further purification and N-bromosuccinimide
(NBS, AR) were purchased from Aladdin. N, N-dimethylace-
tamide (DMAc, AR), and N-methyl pyrrolidone (NMP, AR) were
purchased from Shanghai Maclean Biochemical Technology.
Synthesis of polyether ether ketone backbone (PEEKeCH3ex)
The PEEKeCH3ex was synthesized via polycondensation re-
action, where x (x ¼ 0.3, 0.5, 0.7, and 1.0) represented the mole
percent of THQ. The synthetic route is shown in Fig. 1. Herein,
we choose the synthesis process of PEEKeCH3e0.5 as an
example. DFBP (2.000 g, 9.166 mmol), BPA-6F (1.541 g,
4.583 mmol), THQ (0.993 g, 4.583 mmol), K2CO3 (2.534 g,
18.322 mmol), 40 mL DMAc, and 10 mL toluene were added
into a 100 mL three-neck round bottom flask. Primarily, all the
additions were reacted at 140  C for 4 h and then stirred at
170  C for another 24 h, and whole the process needed to be
carried out under N2 atmosphere. After that, pour the mixture
into deionized water slowly. Finally, the obtained precipitate
was washed with methanol for 3 times and dried at 60  C for
24 h. The PEEKeCH3e0.5 was obtained as light brown solid
(3.876 g, 88.7%).
1
H NMR (CDCl3, 500 MHz, TMS, 298 K): d 7.82 ppm (broad,
8H), d 7.41 ppm (broad, 8H), d 7.02 ppm (broad, 9H), d 6.96 ppm
(broad, 2H), d 2.21 ppm (s, 3H).
Synthesis of brominated polyether ether ketone backbone
(PEEK-CH2Br-x)
The PEEK-CH2Br-0.5 was synthesized via bromination reac-
tion, PEEKeCH3e0.5 (1.327 g, 1.626 mmol) and 40 mL chloro-
benzene were put into a three-neck round bottom flask. After
stirring the mixture for 30 min, NBS (0.289 g, 1.626 mmol) and
AIBN (0.016 g, 0.098 mmol) were added. The resulting mixture
was reacted at 75  C for 24 h, and then poured into ethanol
solution which appeared powder precipitation immediately.
The precipitate was washed with methanol 3 times and drying
at 60  C for 24 h. PEEK-CH2Br-0.5 was obtained as white solid
(1.473 g, 91.2%).
1
H NMR (CDCl3, 500 MHz, TMS, 298 K): d 7.82 ppm (broad,
8H), d 7.41 ppm (broad, 8H), d 7.02 ppm (broad, 9H), d 6.96 ppm
(broad, 2H), d 4.50 ppm (s, 2H), d 2.17 ppm (s, 3H).
Preparation of membrane (PEEK-BiPy-x)
The PEEK-BiPy-x was synthesized via the click chemistry re-
action between PEEK-CH2Br-x and 1,2-bis(4-pyridyl)ethane. The
details are as follows: PEEK-CH2Br-0.5 (1.000 g, 2.451 mmol) was
solubilized into NMP to form a 5 wt% mixture solution. After the
6099
addition of 1,2-bis(4-pyridyl)ethane (0.113 g, 0.613 mmol), the
established admixture was stirred for 1 h at room temperature,
and then instill in a clean PTFE mold and dried at 60  C for 12 h
to get the membrane in bromide form. The obtained membrane
was detached from the PTFE mold and then immersed in NaOH
aqueous solution to get the membrane in the hydroxide form.
Finally, the PEEK-BiPy-0.5 membrane was obtained after
washing with deionized water.
Characterization
Chemical structure
The chemical structures of PEEKeCH3ex and PEEK-CH2Br-x
were characterized by AVANCE III 500 M nuclear magnetic
resonance hydrogen spectroscopy (1H NMR) from BRUKER,
Switzerland. The internal standard is tetramethylsilane (TMS)
and deuterated chloroform (CDCl3) as the solvent. The mem-
brane structure is characterized by total reflection using a
VERTEX70 FTIR spectrometer from BRUKER, Germany. The
scan wavenumber is ranged from 600 cm1 to 4000 cm1, and
the resolution is 2 cm1.
Gel permeation chromatography (GPC)
The molecular weight and polydispersity of PEEKeCH3ex
were determined by GPC on a Waters 1515 HPLC pump. And
the GPC equipped with three styrene columns (Waters HT4,
HT5, and HT6) and a Waters 2414 refractive index detector.
The PEEKeCH3ex sample concentration is 1 mg mL1 and the
eluent is tetrahydrofuran (THF) with a flow rate of
1.0 mL min1. All the PEEKeCH3ex molecular weight was
calibrated with a standard polystyrene sample.
Morphology
The morphology of AEMs was conducted by Scanning electron
microscopy (SEM, FEI Nova Nano SEM450) and atomic force
microscope (AFM, Agilent5500). Before the test, the specimens
were treated with spray-gold. The surface and cross-section
are observed; the cross-section of membranes was formed
through fracturing in liquid nitrogen. As for AFM, the mem-
brane samples were measured in a tapping mode to observe
the microstructure.
Gel fraction and crosslinking density
Gel fraction was measured by soaking the membrane in NMP
at 60  C for 24 h, then washed the membrane with distilled
water and dried completely. The gel fraction was obtained by
Eq. (1), where Wa and Wb are the weight of membranes before
and after solubility tests, respectively.
Wb
Gel fraction ¼  100% (1)
Wa
The crosslinking density was determined by differential
scanning calorimetry (DSC 6220). The test temperature rises
from 30  C to 200  C with the heating rate of 10  C$min1. From
the DSC curves can be observed the glass-transition temper-
atures (Tg), which represent free volume. Additionally, the
crosslinking density is proportional to the free volume.
6100 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0

Fig. 1 e Synthesis route of crosslinked PEEK-BiPy-x.

Water uptake (WU) and swelling ratio (SR)

Mw  Md
WU ¼  100% (2)
Md
The Water uptake and swelling ratio of the PEEK-BiPy-x
membranes were measured by weight and dimension
Lw  Ld
change before and after drying. At room temperature, the SR ¼ ð Þ  100% (3)
Ld
membrane was immersed in distilled water fully for 24 h, then
disposed of the excess water after taking it out quickly to re- Ion exchange capacity (IEC)
cord the weight and size. The weight and size of the dry
membrane were gotten after drying at 60  C to a constant The back titration method was utilized to conduct the ion
weight. The WU and SR can be calculated by Eq. (2) and Eq. (3). exchange capacity (IEC, mmol$g1). Firstly, a dry sample was
Md and Mw are the weights of dry and wet, Ld and Lw are the soaked in a specific volume of HCl (0.01 M) solution for 24 h to
widths of dry and wet, respectively. exchange the ion. Then the solution completed ion exchange
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
was titrated by NaOH solution at the same concentration with
HCl. Eq. (4) was served for the IEC calculation. V1 and V2
represent the volumes of the HCl and NaOH solution,
respectively. C1 and C2 represent the concentrations of the HCl
and NaOH solution, respectively. The m is the weight of the
dry membrane sample.
C1 V1  C1 V2
IEC ¼
m
Mechanical and thermal stability
The mechanical behavior of the PEEK-BiPy-x membranes was
tested by a universal testing machine (UTM 4203) with the
tensile rate of 10 mm$min1 and 100% RH. The thermogravi-
metric analyzer (NETZSCH-TG209F3) was used to give an
assessment of AEMs thermal stability, which temperature
range from 30  C to 900  C and the sample was heated with a
ramp rate of 10  C$min1 under an N2 flow.
Hydroxide conductivity
The hydroxide conductivity (s, mS$cm1) of PEEK-BiPy-x AEM is
calculated by measuring the AC impedance of the membrane
with a frequency range of 1 MHze1 Hz and a potential ampli-
tude of 10 mA by Shanghai CHI 760 E electrochemical work-
station. The test method was as follows: The membrane was
immersed in distilled water under an N2 atmosphere for 24 h to
equilibrate its water absorption. The membrane is fixed be-
tween two pairs of copper electrodes. The impedance was
recorded at various temperatures and 100% RH. The water bath
heats the vessel to a certain temperature, and the impedance of
the membrane (R, kU) is measured after 2 h of equilibration.
The ionic conductivity of the membrane is calculated from Eq.
(5). L is the length between the two electrodes of the copper
plate; A is the effective cross-sectional area and R is the
alternating-current impedance of the membrane.
L
s¼
AR
Alkaline stability
Characterization of alkaline stability as follows: the PEEK-
BiPy-x membranes were measured in 1 M NaOH solution at
room temperature, and made a renewal of NaOH solution
every 96 h. During the test, the membrane was taken out and
washed with distilled water. The membrane samples re-
tentions of hydroxide conductivity at 80  C for different pe-
riods to evaluate alkaline stability. The whole process was
carried out under N2 protection to remove the interference of
carbonate ions on the results of hydroxide conductivity.
Results and discussion
Structure characterization
The 1H NMR spectrums of PEEKeCH3e0.5 and PEEK-CH2Br-0.5
polymer were shown in Fig. 2. The signal at 7.26 ppm is the
peak of deuterated chloroform. The signals at 6.96 ppm and
7.02 ppm are ascribed to the proton peaks of THQ and BPA-6F,
6101
(4)
Fig. 2 e 1H NMR spectra of the PEEKeCH3e0.5 and PEEK-
CH2Br-0.5.
respectively. The signals at 7.41 ppm and 7.82 ppm were
ascribed to the proton peaks of the DFBP. The signal observed
at 2.27 ppm was ascribed to the proton peak on methyl.
Comparing with the 1H NMR spectra of PEEKeCH3e0.5, a new
signal appeared at 4.5 ppm in the 1H NMR spectra of PEEK-
CH2Br-0.5, which confirmed the signal is the methylene pro-
ton of bromomethyl. This means PEEKeCH3e0.5 and PEEK-
CH2Br-0.5 polymer were successfully synthesized. And other
1
H NMR spectrums of PEEKeCH3ex and PEEK-CH2Br-x were
shown in Fig. S1 and Fig. S2.
Table S1 shows the number average molecular weight (Mn),
weight average molecular weight (Mw) and polydispersity. All
the Mn of PEEKeCH3ex can reach 2  104 Da. Generally, the
(5) higher molecular weight, the better film-forming perfor-
mance. The polymer backbone should be consisted of rigid
repeating units with high enough molecular weight [70],
providing mechanical stability for AEMs. The PEEKeCH3ex
molecular weight is sufficient for membrane formation.
The results about the selectivity of film-forming solvents
and solvent-resistance of films are as shown in Table S2. The
PEEK-CH2Br-x can be completely dissolved in NMP, DMF,
DMAc, THF, and DMSO, which indicates their good process-
ability. However, after crosslinking reaction, the prepared
membranes are insoluble in THF and DMSO. The solubility of
the membrane is significantly decreased. It partly sub-
stantiates the success of crosslinking reaction and indicates
the good solvent resistance of the prepared membrane.
The total reflectance infrared spectrum of the crosslinked
PEEK-BiPy-x membranes is depicted in Fig. 3; the absorption
bands observed around 1247 cm1 are belonged to the
CeOeC group of the PEEKeCH3ex polymer backbone.
Furthermore, the vibration peak at 1159 cm1 related to the
CeN of pyridinium groups. Additionally, the absorption band
at 1600 cm1 and 1485 cm1 are confirmed to the stretching
vibrational of the ammonium group and the absorption band
at 1647 cm1 is ascribed to C]O group, indicating that the
6102 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Fig. 3 e Total reflectance infrared spectrum of PEEK-BiPy-x.
crosslinking reaction works in PEEK-BiPy-x membranes
successfully.
Free volume
Free volume is a critical factor associated with the properties
of AEMs. Differential scanning calorimetry (DSC) is employed
to evaluate the free volume properties [41,71,72]. As expressed
in Fig. 4, the glass-transition temperatures (Tg) increases with
the increase of the bis-pyridinium crosslinking density, which
decreased the free volume. The PEEK-BiPy-0.3 membrane
shows a low Tg at 106  C, originating from the lower packing
density between polymer chains. Higher Tg is observed in
PEEK-BiPy-0.5 and PEEK-BiPy-0.7 membranes at 113  C and
116  C, respectively. The least free volume of the PEEK-BiPy-1.0
membrane may be due to the high effective crosslinking
Fig. 4 e The DSC curves of PEEK-BiPy-x.
density, and the Tg of the PEEK-BiPy-1.0 membrane is obtained
at 124  C. The greater free volume can make the polymer
segments easier to move, promoting the make-up of ion
transport channels, which may be beneficial to the improve-
ment of the ion conductivity [73].
Morphology characterization
The PEEK-BiPy-x membranes are light yellow, flexible and
dense, as the digital photos shown in Fig. 5a. Furthermore, the
surface and cross-section topography of all membranes are
observed through SEM. As presented in Fig. 5b, it is clearly
observed that membrane surfaces are uniform, dense, smooth
and without any defects. Fig. 5c shows the cross-section view
of membranes, there are none pores can be found. Meanwhile,
the thickness of the prepared membranes is estimated to be
around 20~70 mm. Thin AEMs tend to reduce the ohmic loss in
cell voltage and thus promote the power density of the
AEMFCs [74]. Therefore, the PEEK-BiPy-x membranes exhibi-
ted a homogeneous morphology, which is suitable for their
applications in AEMFCs.
It is accepted that a well-developed self-assembled
morphology is significant to accomplish high conductivity for
AEMs [48]. As the AFM images exhibited in Fig. 6, the dark
region represents the hydrophilic region, mainly composed of
hydrophilic ion clusters and water; the light region is associ-
ated with hydrophobic polymer backbone [75]. The results
showed that all PEEK-BiPy-x membranes have distinct
microphase separation structures and the crosslinking den-
sity also affects the degree of microphase separation. Gener-
ally, the microphase separation of the AEMs facilitates the
aggregation ion clusters and enlarges ion transport channels,
increasing the conductivity [55]. Notably, the AFM image of
PEEK-BiPy-0.5 (Fig. 6b) shows better microphase separation in
which the hydrophilic area is larger and well connected.
While, the AFM images of PEEK-BiPy-0.7 (Fig. 6c) and PEEK-
BiPy-1.0 (Fig. 6d) membranes show smaller ion clusters due
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Fig. 5 e Digital photos (a1~a4), surface (b1~b4) and cross-sectional (c1~c4) SEM images of PEEK-BiPy-0.3, PEEK-BiPy-0.5, PEEK-
BiPy-0.7 and PEEK-BiPy-1.0.
to the higher crosslinking density, resulting in the less free
volume to developed the self-assembled difficultly. The
reason is that the hydrophilicity and flexibility are incomplete,
restricting the aggregation of the bis-pyridinium functional
cations [41]. Proper crosslinking density is favorable for self-
assembly of backbones, encouraging for forming larger ionic
clusters in the AEM.
IEC, gel fraction, water uptake (WU) and swelling ratio (SR)
As a key parameter of AEMs, the IEC value of AEMs indicates
the content of its exchangeable ion groups and affects con-
ductivity, water uptake, swelling ratio values and mechanical
properties directly [32]. Table 1 lists the titrated IEC values,
which range from 0.9 mmol$g1 to 1.4 mmol$g1. While the
PEEK-BiPy-0.5 membrane shows the highest IEC of
1.316 mmol$g1, which is higher than that of PEEK-BiPy-0.7
and PEEK-BiPy-1.0 membranes. The cause may lie in the fact
that crosslinking density increased with the augmentation of
the functional site in PEEK-CH2Br-x. Besides, the gel fraction of
PEEK-Bipy-x membranes is higher than 85%, also proved the
successful crosslinked structure.
6103
In addition, the WU and SR can lead an impact on the
dimensional stability and hydroxide conductivity. In a way,
low WU is not contributed to the OH transport within AEMs.
While, extravagant WU may cause swelling severely and lead
to poor dimensional stability and hydroxide conductivity.
Therefore, it is necessary to pay attention to regulating the
WU of AEMs [76]. As expected, WU and SR perform a similar
disciplinary with the IEC, as illustrated in Fig. 7. Reducing the
free volume of crosslinked PEEK-BiPy-x membranes makes
water migrate difficult [42], resulting in the WU and SR of
PEEK-BiPy-0.7 and PEEK-BiPy-1.0 membranes lower than
PEEK-BiPy-0.5 membranes. The WU results can also be sup-
ported by water contact and the details as shown in Fig. S3. To
sum up, the PEEK-BiPy-0.5 membranes have the most appro-
priate IEC and good dimensional stability, favoring ion
transport.
Hydroxide conductivity
Hydroxide conductivity is one of the significant factors in
evaluating the performance of the membrane, which deter-
mined the potential value of AEMs. Fig. 8a portrays the
6104 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0

Fig. 6 e AFM phase images of (a) PEEK-BiPy-0.3, (b) PEEK-BiPy-0.5, (c) PEEK-BiPy-0.7 and (d) PEEK-BiPy-1.0.

association between the conductivity and temperature of

Table 1 e IEC, gel fraction,WU and SR of PEEK-BiPy-x. PEEK-BiPy-x membranes. The hydroxide conductivity of PEEK-
BiPy-x membranes increased with temperature increasing
Membrane IEC (mmol$g1) gel fraction (%) WU(%) SR(%)
over a range of 30~80  C, attributed to the accelerated mobility
PEEK-Bipy-0.3 0.984 86.6 6.54 2.39 of OH in water. Additionally, the space between polymer
PEEK-Bipy-0.5 1.316 88.4 10.23 2.94
chains may be expanded by the elevating of temperature,
PEEK-Bipy-0.7 1.125 88.1 9.60 2.72
PEEK-Bipy-1.0 1.047 87.3 7.71 2.67
which will broaden the ion transport channels and reduce the
ion diffusion resistance, contributing to the increase of the
conductivity. The PEEK-BiPy-0.5 membrane reached a
maximum conductivity of 70.86 mS cm1 at 80  C, which could
be attributed to the formation of larger ionic cluster, as proved
in AFM. The higher conductivity also originates from higher
water uptake and develops interconnected ion transport
channels. Obviously, the conductivity of PEEK-BiPy-0.7 and
PEEK-BiPy-1.0 membranes are inferior to that of PEEK-BiPy-
0.5, owing to less free volume enables polymer segments to
move hard, obstructing the formation of the ion transport
channel. The hydroxide conductivity of PEEK-BiPy-x mem-
branes compared with those reported in literature as shown in
Table S3, showing that the PEEK-BiPy-x membranes can meet
the requirements of AEMs about hydroxide conduction.
The Arrhenius equation can explain the correlation of
conductivity against temperature, and the activation energy
(Ea) about hydroxide conductivity in membranes can be
resultant from the slopes of the ln(s)-1000/T graph for PEEK-
BiPy-x membranes as shown in Fig. 8b. It displays the corre-
Fig. 7 e Water uptake and swelling ratio of PEEK-BiPy-x. sponding activation energy for OH transport, calculated from
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0 6105

Fig. 8 e (a) Hydroxide conductivity and (b) Arrhenius curves of OH¡ within PEEK-BiPy-x.

the Arrhenius equation. The activation energy of the PEEK- as shown in Table S4, showing that the PEEK-BiPy-x is above
BiPy-0.5 membrane was lower than that of the others. The medium level. Despite this, the prepared membranes are
lower activation energy reduced the ion transport energy tenacious adequately to satisfied the mechanical demands for
barrier and it contributed to the directional transfer of OH, fuel cells.
further demonstrating that the channels constructed with the
appropriate crosslinking density could enhance hydroxide
transport.

Mechanical properties

The assembly of fuel cells has an incline in mechanical

damage of AEMs, resulting in failure of the fuel cell perfor-
mance before chemical degradation in an alkaline environ-
ment [59]. Therefore, the plenty of mechanical ability is the
basis for AEMs in the long-term operation of fuel cells [77].
Table 2 shows the tensile strength, young's modulus, and
elongation break of PEEK-BiPy-x membranes. The tensile
strength of the PEEK-BiPy-x membranes increased firstly and
then decreased. Particularly, the PEEK-BiPy-0.5 membrane
reached a maximum tensile strength of 58.53 MPa, attributed
to the most appropriate crosslinking density. Crosslinking
improves the linkage between the molecular chains, making
them less susceptible to relative slip and increasing the tensile
strength. However, PEEK-BiPy-0.7 and PEEK-BiPy-1.0 mem- Fig. 9 e TGA curves of the PEEK-BiPy-x.
branes lead to a decrease in tensile strength by contrast with
the PEEK-BiPy-0.5 membrane. The crosslinking network will
hinder the directional arrangement of molecular chains and
prevent crystallization when the crosslinking density is
excessive. It will also aggravate the unevenness of cross-
linking bond distribution, resulting in more uneven stress
distribution and decreasing the tensile strength. The elonga-
tion break of PEEK-BiPy-x membranes was gradually
increased with the range of 7.02e16.75%, which suggested the
flexibility of membranes. The mechanical properties of PEEK-
BiPy-x membranes compared with those reported in literature

Table 2 e Mechanical properties of PEEK-BiPy-x.

Membrane Tensile Young's Elongation
Strength (MPa) modulus (MPa) break (%)
PEEK-BiPy-0.3 24.10 343.30 7.02
PEEK-BiPy-0.5 58.53 700.12 8.36
PEEK-BiPy-0.7 50.56 397.17 12.73
Fig. 10 e The hydroxide conductivity retention of PEEK-
PEEK-BiPy-1.0 40.86 243.94 16.75
BiPy-x in 1 M NaOH solution at RT.
6106 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Fig. 11 e (a) Total reflectance infrared spectrum and (b) TGA curves of PEEK-BiPy-0.3, PEEK-BiPy-0.5 before and after alkaline
resistance test.
Thermal stability
The membrane material needs to maintain a stable structure
for a long time at a higher temperature. As plotted in Fig. 9,
The TGA curves of PEEK-BiPy-x membranes display three
degradation stages; these stages are correlated to the thermal
degradation of bis-pyridinium groups and PEEK backbone. The
initial weight loss between 100  C and 350  C comes from the
decomposition of the bis-pyridinium groups. There are two
significant degradation peaks around 445  C and 495  C in the
TGA curves due to the degradation of the PEEK backbone. In
summary, the thermal stability of PEEK-BiPy-x membranes is
sufficient to meet industrial requirements.
Alkaline stability
Alkaline stability is another pivotal parameters besides hy-
droxide conductivity in practical applications for AEMs [78].
Great alkaline stability is an indispensable security for long-
term operation in a higher pH environment. At present, the
conventional approach for monitoring the alkaline stability is
to check the degradation degree of membranes at a specific
temperature and pH environment. Herein, the PEEK-BiPy-x
membranes were soaked in 1 M NaOH solution to observe
the loss of conductivity. All the PEEK-BiPy-x membranes
remained intact, unbroken and flexible after 1440 h. The
change in hydroxide conductivity of the AEMs was recorded
during the alkaline test. As illustrated in Fig. 10, the hydroxide
conductivity of all membranes shows only a slight decrease.
The conductivity of PEEK-BiPy-0.3, PEEK-BiPy-0.5, PEEK-BiPy-
0.7, and PEEK-BiPy-1.0 decreased by only 13.73%, 8.26%, and
11.86% and 14.22%, respectively. The good alkaline stability of
the PEEK-BiPy-x membranes can be ascribed to the synergistic
effect of the stable p-bond-conjugated structure of pyridine
and the crosslinked structure between molecular chains [41].
As shown in Table S3, compared with previous literature, the
PEEK-BiPy-x membranes keep a good balance between ionic
conductivity and alkaline stability than other AEMs.
The total reflectance infrared spectrum was used to further
investigate the changes of membrane structure after the
alkaline resistance test. As analyzed from Fig. 11a, the in-
tensity of the band at 1247 cm1 (CeOeC stretch vibration of
the polymer backbone) and the band at 1159 cm1 (CeN
stretch vibration of the pyridinium groups) are almost un-
changed. The stretching vibrational of ammonium group ab-
sorption band at 1647 cm1, 1600 cm1 and 1485 cm1 are also
imperfect, indicating the structure of PEEK-BiPy-x membranes
had no damage. Fig. 11b displays the TGA curves of the PEEK-
BiPy-x membranes before and after alkaline resistance test,
and the membranes can still keep outstanding thermal sta-
bility. In brief, the PEEK-BiPy-x membranes have excellent
alkaline stability which has the capacity in an application for
the fuel cell.
Conclusions
In summary, a series of tunable bis-pyridinium crosslinked
PEEK-BiPy-x membranes were prepared successfully. The
crosslinking architecture of bis-pyridinium was optimized to
facilitate cations aggregation and guarantee the free volume
simultaneously. The PEEK-BiPy-x membranes with low WU
and SR exhibit adequate dimensional stability, thermal and
mechanical stability. Remarkably, the PEEK-BiPy-0.5 mem-
brane performance maximum tensile strength (58.53 MPa)
and highest IEC of 1.316 mmol$g1. The hydroxide conduc-
tivity of the PEEK-BiPy-0.5 membrane attains to
70.86 mS$cm1 at 80  C. Besides, outstanding alkaline stability
of PEEK-BiPy-0.5 was obtained, which keeping a hydroxide
conductivity retention of 91.74% after 1440 h in 1 M NaOH
solution, owing to the crosslinked structure of the AEMs and
steric effect of the bis-pyridinium cation. In short, the bis-
pyridinium crosslinked PEEK-BiPy-x membranes are contrib-
uted to ameliorating the “trade-off” between hydroxide con-
ductivity and alkaline stability, which would have a promising
application in AEMFCs.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 6 0 9 7 e6 1 1 0
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the Graduate Student Innovation
Special Foundation of Jiangxi Province (YC2020-S511), Founda-
tion of Key Laboratory for Microstructural Control of Metallic
Materials of Jiangxi Province (EJ201901456), Doctoral Scientific
Research Foundation of Nanchang Hangkong University
(EA201801237, EA202101189), Scientific Foundation of Jiangxi
Education Department (GJJ180546), Natural Science Foundation
of Jiangxi Province (20202BABL214017, 20202BAB204012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.11.209.
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