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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8

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Anion exchange membranes based on poly (ether

ether ketone) containing N-spirocyclic quaternary
ammonium cations in phenyl side chain

Lichao Shang a, Dan Yao a, Bohao Pang a, Chengji Zhao a,b,*

a
Key Laboratory of High Performance Plastics, Ministry of Education, College of Chemistry, Jilin University,
Changchun, 130012, PR China
b
Key Laboratory of Advanced Batteries Physics and Technology, Ministry of Education, Jilin University, Changchun,
130012, PR China

highlights

QPEEK-spiro AEMs showed good thermal stability and sufficient mechanical strength.

The bulky N-spirocyclic QA cations was proposed to enhance the alkaline stability.

QPEEK-spiro-pyr showed the highest anion conductivity of 49.6 at 80  C.

The clear phase separation morphology was formed in QPEEK-spiro membranes.

article info abstract

Article history: It was reported that the existence of N-spirocyclic quaternary ammonium (QA) cation
Received 10 January 2021 could improve alkaline stability of anion exchange membrane materials (AEM). Therefore,
Received in revised form the cyclo-quaternization reaction with pyrrolidine (Pyr) and piperidine (Pip) was carried out
26 February 2021 to prepare quaternized poly (ether ether ketone)s bearing five-membered and six-
Accepted 6 March 2021 membered N-spirocyclic quaternary ammonium (QA) groups in the phenyl side chains
Available online 6 April 2021 (QPEEK-spiro-pyr and QPEEK-spiro-pip), respectively. From the transmission electron mi-
croscope, the hydrophilic-hydrophobic phase-separated morphology was formed in
Keywords: QPEEK-spiro membranes after incorporating N-spirocyclic QA cations and bulky spacer
Alkaline fuel cells simultaneously in the phenyl side chain. The effect of N-spirocyclic QA groups on per-
N-spirocyclic QA groups formance of resulted AEMs was then studied in detail. The anion conductivities of QPEEK-
AEMs spiro-pyr and QPEEK-spiro-pip in OH form at 80  C were 49.6 and 30.9 S cm1, respectively.
Poly (ether ether ketone)s The remaining proportions of hydroxide conductivity for QPEEK-spiro-pyr and QPEEK-spiro-
pip membranes after immersing in 1 M NaOH at 60  C were 81.0% and 74.7%, respectively,
which were higher than that of 62.3% for QPEEK-TMA containing conventional QA groups
in the phenyl side chain. Fuel cell assembled with QPEEK-spiro-pyr achieves a peak power
density of 90 mW cm2. These results indicate the strategy of simultaneously introducing
N-spirocyclic QA cations and bulky spacers can improve the performance of AEM to a
certain extent. There are some other factors that influence the alkaline stability of the

* Corresponding author. Key Laboratory of High Performance Plastics, Ministry of Education, College of Chemistry, Jilin University,
Changchun, 130012, PR China.
E-mail address: zhaochengji@jlu.edu.cn (C. Zhao).
https://doi.org/10.1016/j.ijhydene.2021.03.059
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8
prepared AEMs, such as the existence of ether bonds in the main chain. However, this work
still provides a valuable reference towards the molecular design of AEMs with improved
performance.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
As a clean energy conversion technology [1e3], anion ex-
change membrane fuel cell (AEMFC) is attracting increasing
attention from scientists in recent years as the alternative to
the mature proton exchange membrane fuel cell (PEMFC).
Meanwhile, one of the most significant advantages of AEMFC
is the fast-electro-kinetics of electrode reaction under alkaline
medium, ensuring it to use non-precious transition metals
and metal oxides as the catalysts [4e9]. Therefore, the whole
fabrication cost of AEMFC could be greatly reduced compared
to PEMFC. As an important core component in AEMFC, anion
exchange membranes (AEMs) not only serve as the separator
between the anode and the cathode, but also as the transport
medium for anions [10,11]. Generally, the ideal AEMs should
have high hydroxide conductivity, robust alkaline stability as
well as good mechanical properties to meet requirement of
AEMFCs with high performance and long-term stability
[12,13]. However, Due to the lack of satisfactory AEMs with
high hydroxide conductivity and sufficient alkali resistance
stability so far, the commercialization and application of
AEMFC have been limited [14e17].
Since the diffusion coefficient of OH- is only a quarter of
that of Hþ, it is difficult for AEMs to reach the conductivity
level of proton exchange membranes [18,19]. Many re-
searchers have proposed many approaches to increase the
conductivity of AEMs. At present, the methods for improving
the ion conductivity include increasing the ionic exchange
capacity (IEC) value and forming ion-aggregated structures
[20]. Among them, the method of increasing the conductivity
by enhancing IEC value is relatively simple. However, under
high IEC conditions, AEMs will suffer from a large water
swelling at high temperatures, which affects the dimensional
stability of AEMs. Thus, cross-linking was used to properly
adjust the AEM’s dimensional stability with lower swelling
ratios at higher temperatures [21]. Liu’s group [22] developed
an AEM by thermal crosslinking without the addition of any
cross-linking agent. The mechanical, thermal and dimen-
sional stabilities of membranes were enhanced remarkably
due to the crosslinking treatment. In addition, many reports
have proposed to construct ion-aggregated structures within
AEMs, which are beneficial to forming a clear hydrophilic/
hydrophobic phase separated morphology and effective ionic
transport channels, thus increasing the ionic conductivity of
AEMs. Therefore, block polymers [23], graft polymers [24] and
comb polymers [25] with special architectures have been
widely investigated in order to increase the size of ionic
clusters and the connectivity of ionic transport channels
within AEMs [26].
19117
Alkaline stability is another challenge for practical usage of
AEMs. Especially, the conventional quaternary ammonium
(QA) cationic groups tethered on the polymer backbone suffer
from severe degradation under alkaline condition. The
degradation is usually caused by nucleophilic substitution,
Hofmann elimination, and other rearrangement reactions
[7,27]. There are many studies on seeking alternatives to QA
functional groups, such as imidazolium [28], phosphonium
[29], guanidinium [30], morpholinium [31], pyrrolidinium [32]
and piperidinium [6]. For instance, Yan [33] prepared several
imidazolium-based AEMs, which show robust alkaline sta-
bility in 1 M NaOH solution at 60  C for 20 days. However, later
studies found that imidazolium-based AEMs are unstable
under some harsh conditions [34]. Marino et al. [35] system-
atically investigated the alkaline stability of 26 cationic model
compounds with different QA types under extremely accel-
erated experimental conditions at high pH and high temper-
ature. The half-time of these compounds was determined
using NMR spectroscopy to compare their alkaline stability.
Among them, N-spirocyclic QA cations, such as 6-azonia-spiro
[5.5] undecane (ASU), exhibit excellent alkaline stability with a
long half-time up to 110 h, which is much higher than that of
conventional tetramethylammonium (61.9 h). They believed
that the conformational restriction and steric hindrance ef-
fects of N-spirocyclic QA cations could stabilize them against
the attack of OH [35e37]. Hence, the incorporation of alkaline
stable N-spirocyclic QA cations into polymers have been
proposed to develop novel AEMs with enhanced alkaline sta-
bility. Zhu et al. [38] tethered ASU groups onto poly(phenyl
ether) (PPO) backbone and prepared AEMs for alkaline fuel
cell. ASU-PPO membranes possess the OH- conductivity of
96 mS cm-1 at 80  C and the peak power density of 178 mW
cm-1. It was also observed that ASU-PPO membranes were
stable in 1 M NaOH at elevated temperatures for 1500 h.
Nevertheless, ASU-PPO membranes exhibited some brittle-
ness, which was mainly attributed to the rigidness of ASU
cation. Yin and Guiver et al. [39] prepared AEMs with PPO
backbone carrying N-spirocyclic 3,6-diazaspiro[5.5]undecane
(DSU) groups. The increased steric hindrance of DSU provided
these AEMs with high retention of IEC and ionic conductivity.
However, due to the existence of the tertiary N atom in DSU
group, the degradation through Hofmann elimination caused
DSU with inferior alkaline resistance compared with ASU
group. Jannasch et al. [40] incorporated bis-N-spirocyclic QA
cations into poly(arylene ether sulfone) backbone. The resul-
ted AEMs showed good alkaline stability in 1 M alkaline so-
lution at 20  C with almost no change from 1H NMR spectra.
However, they were found to degrade through ring-opening
reaction at the benzylic positions and backbone scission by
19118 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8
the cleavage of CeOeC bonds after immersing in 1 M NaOH at
elevated temperatures.
In addition, some researchers have improved the alkaline
resistance of AEM by introducing long alkyl chains in polymer
backbone to keep the cationic group away from the polymer
backbone [41]. Lin et al. [42] reported an AEM material con-
taining different lengths of alkyl side chains between the
polymer backbone and the cationic groups. The results
showed that the alkaline stability was enhanced by increasing
the length of flexible spacer (n  4). The IEC and anion con-
ductivity of membranes only decreased no more than 10%
after treatment by 1 M KOH solution at 60  C for 720 h.
Therefore, it is proposed that tethering cationic groups onto a
polymer backbone by connecting a bulky spacer in polymer
side chain could also improve the alkaline stability of AEMs
due to the increase of steric hindrance of cationic groups.
In the present work, we proposed a new strategy to prepare
poly (arylene ether)-based AEMs with improved alkaline sta-
bility and ion-aggregated structure by incorporating N-spi-
rocyclic QA cations and bulky benzene spacer simultaneously
in the side chain for the first time. For this purpose, 3, 4-
dimethylphenylhydroquinone (DMPH) was selected as the
comonomer to synthesize a poly (ether ether ketone) con-
taining a pair of adjacent benzylic methyl groups on the
phenyl side chain (PEEK-diMe), which acted as the precursor
for the bromomethylation and cyclo-quaternization to pre-
pare AEMs. According to our previous work [43], the bromi-
nated precursor BrPEEK-diMe-X with two adjacent
bromomethyl groups was synthesized by employing N-bro-
mosuccinimide (NBS) and benzoyl peroxide (BPO) as the
bromination agent and the initiator, respectively. Then, pyr-
rolidine (Pyr) and piperidine (Pip) were reacted with BrPEEK-
diMe-X by cyclo-quaternization to prepare functionalized
poly (ether ether ketone) AEMs with five-membered and six-
membered N-spirocyclic QA groups, respectively. As shown
in Fig. 1, these N-spirocyclic QA groups were linked to the
polymer backbones via a bulky benzene spacer in the side
chains. On one hand, N-spirocyclic QA cations in the phenyl
side chain favored to form a phase-separated morphology,
which could improve the hydroxide conductivity of AEMs
without sacrificing their dimensional stabilities. It could avoid
the excessively swelling of membranes due to the location of
cationic group away from the polymer backbone. On the other
hand, the bulky spacer between polymer backbone and N-
spirocyclic QA cations was proposed to enhance alkaline
stability of the AEMs. In this work, the effect of incorporating
N-spirocyclic QA cations into the phenyl side chain on the
performance of AEMs was deeply studied in terms of micro-
scopic morphology, ionic conductivity, mechanical properties,
alkaline and dimensional stability.
Experimental
Materials
Hexafluorobisphenol A (>98.0%), NBS (99.0%), pyrrolidine
(99.0%) and ethyldiisopropylamine (99.5%) were supplied by
Aladdin Reagent, Shanghai, China. Piperidine (99.5%) and 4.40 -
difluorobenzophenone (99.0%) were obtained from Sigma-
Aldrich Ltd. Potassium carbonate (K2CO3, AR), sulfolane (AR),
1, 1, 2, 2-tetrachloroethane (98.0%) and BPO (AR) were supplied
by Sinopharm Chemical Reagent Co. Ltd, China.
Characterization
NMR
BrPEEK-diMe and QPEEK-spiro copolymers were dissolved in
deuterochloroform (CDCl3) and deuterated dimethylsulfoxide
(DMSO-d6), respectively. Their 1H NMR spectra were then ob-
tained using a 500 MHz spectrometer (Bruker Avance 510,
Germany).
FT-IR
FT-IR measurements of membranes were performed by a
Bruker Vector 22 infrared spectrometer. The measurement
was performed with a wavenumber range of 4000-500 cm1.
Differential scanning calorimetry (DSC)
The Tg values of polymers were obtained according to the
continuity analysis of their DSC curves, which were recorded
on a TA Q20 instrument in the temperature range from 100 to
300  C at a heating and cooling rate of 10  C min1 under the
protection of nitrogen.
Gel permeation chromatography (GPC)
A Shimadzu GPC instrument fitted with GPC-802D gel column
and SPD-M10AVP detector was used to determine the molec-
ular weight of polymer samples. THF was used as the solvent
of samples and the eluent at a flow rate of 1 mL min1 for the
measurement.
Thermogravimetric analysis (TGA)
The thermal stability of membranes was evaluated on a Per-
kinElmer Pyris 1 thermogravimetric analyzer. The samples
were heated from 100 to 750  C at a heating rate of 10  C min1
under N2 atmosphere.
Mechanical properties
The mechanical properties were measured on a Shimadzu
AG-1 1 kN universal testing instrument with a stretching rate
of 2 mm min1 at room temperature. The membrane was cut
into 4 mm  3 cm samples before test, and the thickness was
tested and recorded. The measurement was repeated 10 times
and the average values were adapted from the analysis of
their stress-strain curves.
Transmission electron microscope (TEM)
TEM was used to observe the hydrophilic/hydrophobic phase
separation structure of different AEM materials. The TEM
samples were prepared by epoxy resin embedding and ultra-
thin sectioning. The specific procedure is described as fol-
lows: a certain size of membrane was placed in 2 mol KI so-
lution for 48 h to stain QA cations using I. Then, it was rinsed
repeatedly with deionized water for 8e10 times to remove
excess KI, dried with filter paper, and stored in dry environ-
ment. Finally, the sample was subjected to ultrathin
sectioning on an RMCMTX Ultra ultrathin microtome to
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8 19119

Fig. 1 e The synthesis of PEEK-diMe, BrPEEK-diMe and QPEEK-spiro copolymers.

prepare TEM sample with a copper mesh grid, and a JEM-2100F Finally, the residual Hþ in HCl solution was titrated with the
electron microscope was used at a voltage of 200 kW to record calibrated NaOH solution by using phenolphthalein as the
the TEM images. indictor. The IEC values were then calculated by follows.

CHCl  VHCl  CNaOH  VNaOH

Ionic exchange capacity IEC mmol g1 ¼  1000 (2.1)
Wd
The measured IEC values were determined by a typical titra-
tion method. First, the hydroxide type AEM was dried in a where Wd is the mass (g) of OH type membrane after thor-
vacuum oven and weighed. Then the dried membrane was oughly drying, CHCl and CNaOH represent the concentration of
immersed into 40 mL of 0.1 M HCl standard solution for 2 days. HCl and NaOH standard solutions (mole L1), and VHCl and
19120 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8
VNaOH represent the volume of consumed HCl and NaOH so-
lutions, respectively.
Water uptake (WU) and swelling ratio (SR)
WU and SR were defined as the percentage change of mass
and size of membranes after water absorption at different
temperatures, respectively. The membrane with a size of
3 cm  3 cm was dried under oven at 60  C for 2 days, and its
weight and the average thickness were measured and recor-
ded. The dried membrane was soaked in deionized water at
fixed temperatures for 24 h. Then the hydrated membrane
was taken out, wiped with the surface water, and measured to
record its weight and thickness. The WU and SR values of
AEMs were calculated by the following equations:
Wwet  Wdry
Water uptake ðWU; %Þ ¼  100
Wdry
Dwet  Ddry
Swelling ratio ðSR; %Þ ¼  100
Ddry
where Wwet and Dwet are mass and thickness of wet AEMs,
respectively; Ddry and Wdry are thickness and mass of dry
AEMs, respectively.
Ionic conductivity
The ionic conductivity measurement was done on a Princeton
Applied Research 2273 Potentiostat electrochemical worksta-
tion using a four-electrode AC impedance method. Prior to
test, the membrane was cut into 1 cm  4.5 cm samples and
fully equilibrated in deionized water for 24 h. During the test,
the temperature is in the range from 30 to 80  C. The ionic
conductivity was calculated by follows.
L was designated as QPEEK-spiro-pip.
s¼
RA
where L is the working electrode spacing (cm), A represents
the cross-sectional area (cm2) of sample and R is sample sur-
face resistance (U).
Alkaline stability
The membrane with a size of 1 cm  4.5 cm was placed in
alkaline solution at 60  C, and taken out at intervals. The
remained ionic conductivity of AEM was measured at 80  C
periodically for estimating its alkaline stability.
Synthesis of poly (ether ether ketone) containing
dimethylphenyl side chains
The bisphenol monomer DMPH was synthesized according to
our previous work [44]. DMPH (6.42 g), hexafluorobisphenol A
(6.72 g), 4,40 -difluorobenzophenone (10.89 g), K2CO3 (8.81 g),
toluene (25 mL) and sulfolane (57 mL) were placed into a
250 mL three-necked flask and stirred in N2 atmosphere. The
mixture was heated to 140  C for 4 h to remove the produced
water in the reaction. After distilling off the toluene, the re-
action temperature was raised to 200e220  C and maintained
until the viscosity of the mixture was basically unchanged.
Then reaction product was poured into deionized water to
precipitate raw product. After washing with deionized water
and then dried in oven, the precursor poly (ether ether ketone)
containing dimethylphenyl side chains was obtained and
named as PEEK-diMe.
Synthesis of poly (ether ether ketone) containing benzyl
bromide side chains
A typical synthesis procedure of bromomethylated PEEK-diMe
is described as follows. PEEK-diMe (5.00 g) and 1, 1, 2, 2-
tetrachloroethane (50 mL) were put into a 100 mL three-
necked flask and mixed to form a uniform orange solution,
and then NBS (5.70 g) and BPO (0.77 g) were put into the flask.
The reaction was kept at 70  C for 10 h. Then the bromome-
thylated PEEK-diMe was precipitated from absolute ethanol,
filtered, pulverized, and dried under an oven at 60  C. The
product is called as BrPEEK-diMe-X (X refers to the molar ratio
(2.2) of NBS/PEEK-diMe).
Synthesis of poly (ether ether ketone) containing N-
spirocyclic QA groups in phenyl side chain
(2.3)
Poly (ether ether ketone)s with N-spirocyclic QA salts were
obtained by a homogeneous cyclo-quaternization method
using pyrrolidine and piperidine, respectively. Here, the syn-
thesis of pyr-functionalized BrPEEK-diMe-2.5 is described as
an example: BrPEEK-diMe-2.5 (2.50 g) and DMF (250 mL) were
added into a 500 mL three-necked flask under N2 protection.
Then N, N-diisopropylethylamine (473 mL) and Pyr (236 mL)
dissolved in DMF (3 mL) were added to a drop funnel, and
dropwise to the above system. After stirring uniformly, the
system was maintained at 60  C for 12 h. Then the product was
precipitated from absolute ethanol, filtered, pulverized, and
dried under an oven at 80  C. According to the similar syn-
thetic procedure, pip-functionalized poly (ether ether ketone)
(2.4)
Preparation of anion exchange membranes
QPEEK-spiro-pyr (1.00 g) was dissolved into 30 mL of DMF to
form a homogeneous solution, which was then poured on a
10 cm  10 cm glass plate and removed the excess solvent in
an oven at 60  C. Then the AEM was taken out from vacuum
oven together with the glass plate, cooled and placed in an
appropriate amount of deionized water to peel off the mem-
brane, which was designated as QPEEK-spiro-pyr-Br-. After
soaking into 1 M NaHCO3, 1 M NaOH and 1 M Na2CO3 solution
for 48 h, QPEEK-spiro-pyr-Br- was converted into QPEEK-spiro-
pyr-HCO-3, QPEEK-spiro-pyr-CO2- 3 and QPEEK-spiro-pyr-OH-,
respectively. They were immersed into deionized water to
remove excess alkaline solution before use. The thickness of
these prepared AEMs is about 50e60 mm.
Different types of QPEEK-spiro-pip AEMs were prepared by
a similar procedure. They were recorded as QPEEK-spiro-pip-
Br-, QPEEK-spiro-pip-HCO3-, QPEEK-spiro-pip-CO32- and QPEEK-
spiro-pip-OH-, respectively.
Membrane electrode assembly (MEA) and single cell test
MEA was prepared via a catalyst-coated membrane method as
previously reported [45]. The Pt/C catalyst is mixed with iso-
propanol and deionized water in an ionomer solution, and
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8
then ultrasonically dispersed to prepare a catalyst ink. The
catalyst ink is sprayed onto the AEM with the Pt/C loading of
0.5 mg cm2 and 0.3 mg cm2 ionomer. The H2/O2 single cell
test is performed at a humidity of 100% of H2 and O2 at 60  C.
Results and discussion
Synthesis and characterization of AEMs
In Fig. 1, the precursor polymer PEEK-diMe was prepared by
using a nucleophilic substitution polycondensation of 4,40 -
difluorobenzophenone, hexafluorobisphenol A and DMPH
using K2CO3 as the catalyst. DMPH was selected as the
comonomer for the purpose to incorporate a pair of adjacent
benzylic methyl groups on the benzene ring in the phenyl side
chain. Then, the bromomethylated derivatives BrPEEK-diMe-
X for cyclo-quaternization were prepared by using NBS and
BPO as the bromomethylated reagent and the free radical
initiator, respectively. By enhancing the quantity of bromo-
methylation reagent NBS in the reaction, more and more
benzylic methyl groups could be converted to brominated
groups. The molar ratio of NBS/PEEK-diMe, as denoted as X,
was adjusted to control the degree of bromomethylation.
Figure 2 shows the 1H NMR spectra of PEEK-diMe and
BrPEEK-diMe-2.5. It was obviously observed that the charac-
teristic proton peak corresponding to the benzylic methyl
groups (-CH3) of PEEK-diMe at 2.24 ppm almost disappeared
after the bromomethylation reaction in Fig. 2(b). Simulta-
neously, a new characteristic peak attributing to protons of
the newly formed eCH2Br groups emerged at 4.6 ppm.
Furthermore, the characteristic peaks belonging to other
groups in PEEK-diMe and BrPEEK-diMe were basically consis-
tent, indicating that BrPEEK-diMe was successfully synthe-
sized via a bromomethylation reaction. Calculated from 1H
NMR spectrum, the degree of bromomethylation (content of
benzyl bromide groups per repeating unit) is 1.46. Through
GPC test, the Mn of PEEK-diMe and BrPEEK-diMe were deter-
mined to be 1.52  104 and 1.30  104 g mol1, respectively; and
Fig. 2 e The 1H NMR spectra of (a) PEEK-diMe and (b) BrPEEK-diMe-2.5.
19121
the weight average molecular weight (Mw) was 3.64  104 and
3.38  104 g mol1, respectively. The results demonstrate that
both the polymers have a high molecular weight before and
after bromomethylation, which meets the requirement to
form tough and ductile membranes by a solution-casting
method.
QPEEK-spiro-pyr and QPEEK-spiro-pip were prepared by the
cyclo-quaternization reactions of BrPEEK-diMe-2.5 with Pyr
and Pip, respectively, as shown in Fig. 1. The non-nucleophilic
base ethyldiisopropylamine was employed to provide the
basic medium for the reaction. One of the adjacent bromo-
methyl groups in the phenyl side chain was reacted with cy-
clic amine (Pyr or Pip) to form a tertiary amine by a
nucleophilic reaction. Then the tertiary amine could undergo
an intramolecular Menshutkin reaction with the neighboring
bromomethyl group to obtain the desired QPEEK-spiro poly-
mers with N-spirocyclic QA cations in the phenyl side chain.
Figure 3 shows the 1H NMR spectra of QPEEK-spiro-pyr and
QPEEK-spiro-pyr. Compared with Fig. 2 (b), the characteristic
peak at 4.6 ppm assigning to the protons of eCH2Br group
almost disappeared after cyclo-quaternization. Only very
weak signals remained. On the contrary, new signals emerged
at 3.7 ppm (H12) and 4.8 ppm (H11) due to the a-H of spiro N in
the ring. Additionally, the characteristic peaks attributing to
the protons in the methylene on the aliphatic ring were found
at 1.5 ppm and 2.1 ppm, respectively. Moreover, there is no
characteristic peak assigning to the tertiary cyclic amine in-
termediate in Fig. 3. Importantly, the integral area ratio of the
characteristic peak of a-H to the protons on the benzene ring
in main chain proves the successful synthesis of QPEEK-spiro-
pyr and QPEEK-spiro-pip.
Thermal stability
The Tg values of QPEEK-spiro AEMs were determined by DSC.
As listed in Table 2, QPEEK-spiro AEMs have high Tg values in
the range of 239e242  C. This is due to the aromatic rigid
molecular chain of QPEEK-spiro polymers, which hinders the
molecular segment movement. Furthermore, QPEEK-spiro-pip
19122 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8

Fig. 3 e The 1H NMR spectra of (a) QPEEK-spiro-pyr and (b) QPEEK-spiro-pip.

shows a slightly higher Tg than QPEEK-spiro-pyr. Since the
main chain structure of polymers is consistent, the main
factor affecting the Tg of polymers is the structure of side
chain. The N-hexagonal QA salt as the side chain is much
rigid, so the steric hindrance of intramolecular rotation of
QPEEK-spiro-pip is larger than QPEEK-spiro-pyr.
Figure 4 shows the TGA curves of QPEEK-spiro under N2
atmosphere. The TGA curves of QPEEK-spiro in both Br and
OH forms are similar in thermal weight loss with two ther-
mogravimetric platforms. The first thermogravimetric plat-
form is about 230e370  C, corresponding to the decomposition
of N-spirocyclic QA groups of QPEEK-spiro. The second ther-
mogravimetric platform is above 480  C, which is attributed to
the decomposition of the backbone of QPEEK-spiro. Further-
more, the counterions (Br and OH) have little effect on the
thermal weight loss of QPEEK-spiro membranes. The thermal
decomposition temperature of 5% weight loss was recorded as
Td5%. The Td5% values of QPEEK-spiro-pyr-Br- and QPEEK-spiro-
pyr-OH- are similar, which are 311.5  C and 317.5  C, respec-
tively. Meanwhile, QPEEK-spiro-pip-Br- and QPEEK-spiro-pip-
OH- have a relatively low Td5% of 281.9  C and 301.1  C,
respectively. Additionally, the residual percentage of QPEEK-
spiro at 750  C is in the range of 43.3e54.5%. Therefore, QPEEK-
spiro membranes have good thermal stability, which could
meet the requirements for application in AEMFCs.
Mechanical property
Table 1 exhibits the mechanical properties of AEMs in Br
form. Due to the same polymer backbone and similar side
chain structure, QPEEK-spiro-pyr has comparable mechanical
properties to QPEEK-spiro-pip. Both of them show good me-
chanical properties with the tensile strengths of 66.4 MPa and
68.0 MPa, elongation at break of 13.8% and 13.0%, as well as
Young’s modulus of 906.0 MPa and 883.5 MPa, respectively.
The results show that the mechanical stability of QPEEK-spiro
can fully meet the requirements of MEA fabrication for fuel
cells.
IEC, water uptake and swelling ratio

The IEC values of QPEEK-spiro membranes determined from

1
H NMR spectra and titration are listed in the Table 2. The IEC
of QPEEK-spiro-pip and QPEEK-spiro-pyr calculated from 1H
NMR spectra are 1.35 and 1.57 mmol g1, respectively. How-
ever, the IEC measured from titration are 1.22 and
1.46 mmol g1, respectively. Because of the incomplete ion
exchange and experimental errors in titration, the titrated IEC
values of QPEEK-spiro membranes are lower than their IEC
values obtained from 1H NMR spectra. Furthermore, QPEEK-
spiro-pyr has a higher IEC than that of QPEEK-spiro-pip, due to

Table 1 e The Mechanical Properties of QPEEK-spiro-pyr

and QPEEK-spiro-pip in the Br¡ form.
Sample Tg (oC) Tensile Elongation Young’s
strength at modulus
(MPa) break (%) (MPa)

Fig. 4 e The TGA curves of QPEEK-spiro-pyr and QPEEK- QPEEK-spiro-pyr 239 66.4 ± 3.7 13.8 ± 1.6 906.0 ± 26.9
QPEEK-spiro-pip 242 68.0 ± 3.8 13.0 ± 1.5 883.5 ± 36.4
spiro-pip in the Br¡ and OH¡ form.
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8 19123

Ionic conductivity
Table 2 e IEC water uptake, hydroxide conductivity of
QPEEK-spiro membranes.
Figure 7 shows the anion conductivity of AEMs with different
Membrane IECa IECb WUc sc
counter-ion forms at different temperatures. It should be
(mmol g ) (mmol g ) (%) (mS cm1)
1 1
noted that OH conductivity is the essential parameter for
QPEEK-spiro-pyr 1.57 1.46 33.9 49.6 determining AEMs in practical application. Nevertheless, the
QPEEK-spiro-pip 1.35 1.22 31.6 30.9
OH conductivity is much sensitive to CO2 in ambient air.
a
Calculated from 1H NMR spectra. Therefore, the measured values are usually affected by the
b
Estimated by titration.
conversion from the OH to CO32/HCO3. So, the conductivity
c
WU and s were tested at 80  C in OH form.
measurement of other anions is also of significance, especially
when the ambient air is fed as the oxidant in H2/air AEMFC. As
expected, the anion conductivity gradually increases with
its relatively lower molecular weight of five-membered N-
temperature, which is attributed to accelerated ion migration
spirocyclic side chain.
and enhanced water mobility at elevated temperatures. For
Higher IEC usually accompanies with higher water ab-
example, the hydroxide conductivity of QPEEK-spiro-pyr in-
sorption, including WU and SW. As is well known, increasing
creases by 2 times when the temperature increases from 30  C
water absorption in the AEMs can facilitate the formation of
to 80  C. In comparison with QPEEK-spiro-pip, QPEEK-spiro-pyr
efficient ionic transport channel and improve the ionic con-
with a higher IEC exhibits much higher anion conductivities,
ductivity; however, the WU and SR values should be
although the chemical structure of the two types of mem-
controlled at a rational level to restrict excessively swelling
branes is similar. As displayed in Fig. 8, the anion conductivity
and maintain sufficient dimensional stability. As a compari-
of AEMs follows the order OH> CO2  
3 > HCO3 > Br , which is
son to QPEEK-spiro membranes in the hydroxide (OH) form,
similar in order to other AEMs reported previously [46e48].
the WU and SR values of QPEEK-spiro membranes in the bro-
This is associated with different ion mobility in the mem-
mide (Br), bicarbonate (HCO3) and carbonate (CO32) forms
branes. OH has a smaller ion radius, so it has a higher ion
were also measured, and the results are displayed in Fig. 5. As
mobility, which makes OH-type AEM have higher ion con-
expected, both WU and SR values increased with the tem-
ductivity than other counter-ions.
perature increasing for QPEEK-spiro membranes in any
counter-ion forms. Compared to QPEEK-spiro-pip, QPEEK-
spiro-pyr with a higher IEC exhibited higher WU and SR values. Membrane morphology
It should be noted that the WU values of all AEMs measured at
80  C are below 35%, and the SR values are below 25%. These In Fig. 9, the black region stands for the hydrophilic ionic
results indicate that the bulky spacer between polymer clusters that are formed by the aggregation of N-spirocyclic
backbone and N-spirocyclic QA cations is beneficial to mini- QA groups in the phenyl side chains, and the white region
mizing the undesired effects of water absorption on dimen- represents the hydrophobic aromatic polymer backbone. It
sional stability of hydrated membranes. could be observed from TEM images that the hydrophilic ionic
Figure 6 compares the WU and SR values of QPEEK-spiro clusters are uniformly dispersed in hydrophobic domains,
membranes in different counter-ion forms. The order of WU indicating the existence of distinct micro-phase separation
and SR values of AEMs follows OH>CO2   morphology in QPEEK-spiro membranes. This could be
3 >HCO3 >Br , which
is consistence with the alkalinity order of counter-anions ascribed to the location of N-spirocyclic QA cations in the side
(OH>CO2   chain. Moreover, QPEEK-spiro-pyr with a higher IEC exhibits
3 >HCO3 >Br ). Therefore, it is assumed that the
water absorption is likely associated with the alkalinity and the more distinct and interconnected micro-phase separation
migration ability of counter-anions. morphology than QPEEK-spiro-pip. It is beneficial to the

Fig. 5 e The water uptake (a) and swelling ratio (b) of QPEEK-spiro-pyr and QPEEK-spiro-pip in different ion forms.
19124 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8
Fig. 6 e The water uptake (a) and swelling ratio (b) of QPEEK-spiro-pyr and QPEEK-spiro-pip in different anionic forms at
80  C.
Fig. 7 e The hydroxide conductivity of QPEEK-spiro-pyr and
QPEEK-spiro-pip in different counter-ion forms.
Fig. 8 e The hydroxide conductivity at 80  C of QPEEK-
spiro-pyr and QPEEK-spiro-pip in different counter-ion
forms.
formation of a better interpenetrating “transport channel”,
which facilitates the conduction of anions in QPEEK-spiro-pyr.
Alkaline stability
In this work, the alkaline stability of QPEEK-spiro membranes
was assessed by recording the changes in the anion conduc-
tivity at time intervals after immersing in 1 M NaOH solution
at 60  C. As shown in Fig. 10, the anion conductivity of QPEEK-
spiro membranes decreased within the first 17 days, and then
declined less rapidly. The remaining proportions of hydroxide
conductivity for QPEEK-spiro-pyr and QPEEK-spiro-pip mem-
branes after 20 days test were 81.0% and 74.7%, respectively,
which were much higher than that of 62.3% for QPEEK-TMA
containing conventional QA groups in the phenyl side chain
[43]. The remaining proportion was also higher than that of
QPEEKs with hetero-cycloaliphatic QA groups [43]. Table 3 also
compares the alkaline stability of QPEEK-spiro membrane
with AEMs with similar main-chain structure reported by
other groups. It could be observed that the incorporation of N-
spirocyclic QA cations in the phenyl side chain could increase
the steric hindrance of N-spirocyclic QA cations, and then
improve the alkaline stability to some extent. Fig. 11 shows
the FTIR of QPEEK-spiro-pyr and QPEEK-spiro-pip membranes
before and after immersion in 1 M NaOH solution at 60  C up to
20 days. There is no distinct change observed from their FT-IR
spectra. After alkaline treatment, only the intensity of the
absorption peaks at 1034 and 1299 cm1 corresponding to the
CeN bond of the N-spirocyclic QA groups decreased slightly.
This finding is associated with the decline of the hydroxide
conductivity. The partial degradation of N-spirocyclic QA
groups was possibly caused by a ring-opening SN2 substitution
[40]. Furthermore, under the alkaline system, the OH ions
could attack the ether bond (CeO) in the polymer backbone,
thus causing the main chain scission. Table 4 displays the
mechanical properties of QPEEK-spiro AEMs before and after
immersion in 1 M NaOH at 60  C for 20 days. As shown in Table
4, the tensile strength and the elongation at break of QPEEK-
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8 19125

Fig. 9 e Transmission electron microscopic (TEM) observation of membranes.

spiro-pyr decreased slightly from 66.4 MPa to 58.9 MPa, and

from 13.8% to 11.5%, respectively. However, the Young’s
modulus significantly decreased from 906 MPa to 235.8 MPa.
At the same time, the tensile strength of QPEEK-spiro-pip
decreased slightly from 68.0 MPa to 63.5 MPa; however, the
elongation at break was reduced from 13.0% to 3.5%, and the
Young’s modulus was reduced from 883.5 MPa to 116.6 MPa.
Although the bulky phenyl side chain spacer was proposed to
avoid the electron-withdrawing attract of the QA on the aro-
matic CeO bonds, the backbone scission of QPEEK remain
unaddressed in this work, especially for QPEEK-spiro-pip.
Further research will be focused on the development of aryl
ether bonds free polymer backbone containing N-spirocyclic
QA cations in the side chain.

Fuel cell performance

H2/O2 single cell tests were carried out to further evaluate the
comprehensive performance of QPEEK-spiro-pyr and QPEEK-
Fig. 10 e The remaining percent of hydroxide conductivity
spiro-pip membranes. From the Fig. 12. QPEEK-spiro-pyr ex-
by soaking QPEEK-spiro membranes and QPEEK-TMA in
hibits a higher peak power density of 90 mW cm2, which is
OH¡ form in 1 M NaOH.

Table 3 e The alkaline stability comparison of AEMs.

Membrane IECb (mmol g1) Alkaline stability Time ref
h
remaining Condition
QPEEK-spiro-pyr 1.46 81% 1 M NaOH 60  C 480 This work
QPEEK-spiro-pip 1.22 74.7% 1 M NaOH 60  C 480 This work
Di-35% 0.86 60.3% 2 M KOH 60  C 120 [49]
Mono-68% 1.19 49.6% 2 M KOH 60  C 120 [49]
20PDM-20%PEG2000 2.09 68% 1 M KOH 60  C 300 [50]
QAPPO 2.01 35.6% 1 M KOH 80  C 288 [51]
ImPSU-1.0%-QCDs 2.20 61.21% 1 M NaOH 60  C 500 [52]
QPEEK-TMA 1.63 62.3% 1 M NaOH 60  C 576 [43]
19126 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8

Fig. 11 e FT-IR of QPEEK-spiro-pyr (a) and QPEEK-spiro-pip (b) before and after alkali aging in 1 M aqueous NaOH at 60  C for
20 days.

Table 4 e The mechanical properties of QPEEK-spiro membranes before and after OH¡ treatment for 20 days.
Sample Tensile strength Elongation at break (%) Young’s modulus
(MPa) (MPa)
Before After Before After Before After
QPEEK-spiro-pyr 66.4 ± 3.7 58.9 ± 6.2 13.8 ± 1.6 11.5 ± 0.9 906.0 ± 26.9 235.80 ± 25.7
QPEEK-spiro-pip 68.0 ± 3.8 63.5 ± 2.7 13.0 ± 1.5 3.5 ± 0.7 883.5 ± 36.4 116.6 ± 4.3

cyclo-quaternization reaction of BrPEEK-diMe-X with Pyr and

Fig. 12 e Power density and polarization curves of QPEEK-
spiro membranes at 60  C.
higher than that of QPEEK-spiro-pip (55 mW cm2). This is
consistent with the higher ionic conductivity of QPEEK-spiro-
pyr than that of QPEEK-spiro-pip. However, the fuel cell per-
formance is still low and needed to be improved by further
optimizing MEA assembly and operating condition.
Pip, respectively. The results show that QPEEK-spiro AEMs
displayed good thermal stability and sufficient mechanical
strength for MEA fabrication. Among them, QPEEK-spiro-pyr
exhibited higher IEC, WU, SR and anion conductivity than
those of QPEEK-spiro-pip. For the same QPEEK-spiro membrane
in different counter-ion forms, the WU and anion conductivity
follow the order of OH->CO32->HCO3->Br-. TEM images
indicated that the hydrophilic-hydrophobic microphase sep-
aration morphology was formed in QPEEK-spiro membranes.
After 20 days alkaline stability test, the remaining proportions
of hydroxide conductivity of QPEEK-spiro-pyr and QPEEK-
spiro-pip membranes were 81.0% and 74.7%, respectively,
indicating QPEEK-spiro-pyr has better alkaline stability. How-
ever, the decreased mechanical strength and elongation of
QPEEK-spiro membranes after alkaline treatment suggest the
backbone scission of QPEEK remains unaddressed in this
work, especially for QPEEK-spiro-pip. Nevertheless, the strat-
egy of incorporating N-spirocyclic QA cations and bulky
spacer simultaneously in the side chain provides a valuable
reference towards the molecular design of AEMs with
improved performance. Future research will be focused on the
development of aryl ether bonds free polymer backbone
containing N-spirocyclic QA cations in the side chain.

Declaration of competing interest

Conclusions
The authors declare that they have no known competing
QPEEK-spiro-pyr and QPEEK-spiro-pip with N-spirocyclic QA financial interests or personal relationships that could have
cations in phenyl side chain were successfully prepared via a appeared to influence the work reported in this paper.
 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 6 ( 2 0 2 1 ) 1 9 1 1 6 e1 9 1 2 8 19127

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