Results in Materials 17 (2023) 100366

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Results in Materials
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A mini-review on alkaline stability of imidazolium cations and

imidazolium-based anion exchange membranes
Umme Salma *, Nazmus Shalahin
Department of Chemistry, Mawlana Bhashani Science and Technology University, Santosh, Tangail, 1902, Bangladesh

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

Keywords: An important component of anion-exchange membrane fuel cells (AEMFCs) is an anion exchange membrane
Anion exchange membrane (AEM). AEMFCs have substantial potential to use nonprecious electrocatalysts at high pH and recently attracted
Bulky imidazolium cation much attention. Sufficient long-term stability in highly alkaline conditions and at elevated temperatures is one of
Imidazolium based AEM degradation
the requirements of ideal AEMs. Due to high alkaline stability, imidazolium with various substitutes is an
Chemical stability
auspicious candidate as a stable cation for AEMs. Here, the current improvement of the chemical durability of
imidazolium cations and corresponding AEMs is reviewed. And included the investigations which were done by
both theoretical calculations and experimental studies. The strategy for enhancing the chemical durability of
imidazolium groups and the mechanical properties of equivalent AEMs have been summarized. This study will
offer an outline of some significant features for designing highly alkaline stable imidazolium cationic groups and
their analogous AEMs in the future.

1. Introduction OH− ion conductivity, excellent thermal stability, good mechanical

Fuel cells are efficient energy conversion devices offering electrical
energy by the direct conversion of chemical energy from fuel (for
example CH3OH or H2) [1,2]. Amongst the investigated different cate­
gories of fuel cells, the proton exchange membrane fuel cell (PEMFC) has
received a lot of consideration due to its high efficiencies for energy
conversion, low operating temperature, and high power density [3–9].
However, due to some flaws and technological limitations, such as
complex water management, dependence on platinum catalyst, and high
fuel crossover the significant commercialization of PEMFCs is hindered
[10]. Therefore, AEMFCs have aroused growing interest over PEMFCs in
which instead of protons hydroxide ions are the charge carriers, able to
use nonprecious electrocatalysts, higher volumetric energy density, in
gaseous feeds enhanced tolerance to CO2, reversible efficiencies of fuel
and higher oxygen reduction kinetics [11–26]. AEM, the key component
of AEMFCs, not only transports anion and water between the cathode
and anode but also separates fuels. Low fuel permeability and facilities
of many low-cost polymer backbones are the potential superiorities of
AEM over the proton exchange membrane (PEM) [27,28].
Generally, AEMs are composed of a polymer backbone having
covalently bound cations either onto the backbones or as side chains
[29,30]. For the applications in AEMFCs, an AEM must have enhanced
properties, and adequate long-lasting stability at high temperatures and
in high basic conditions [31,32]. As OH− ion conductivity is naturally
lower than the conductivity of H+ ion, these targets have been shown
challenging for AEMs. Consequently, to enhance OH− ion conductivity,
AEMs are often designed to have a microphase separated structure and
high ion-exchange capacity (IEC). Through these effective ways, the
hopping conduction (Grotthuss mechanism) of OH− anion can be
improved in polymer membranes. Therefore, for AEMFC applications a
highly conductive AEM can be fabricated [17,31,33].
The alkaline stability of an AEM depends on the chemical structure of
both cationic groups and the backbone of the polymer [34–36]. The
highly basic and nucleophilic OH− anion triggered the degradation of
covalently bound cations and the polymer backbone [37]. Recently,
researchers have synthesized a variety of AEMs based on polysulfone,
poly (phenylene oxide) (PPO), poly (phenylene), poly (arylene ether),
poly (ether imide), and poly (olefin) for AEMFCs [34,38–54]. These
polymeric AEMs exhibit potential applications in AEMFCs due to their
relatively high OH− ion conductivity. However, the chemical resistance
of AEMs is affected due to the steric hindrance and electron effect of
some substituents on the polymer backbone [23,55–57]. Conversely, we
should focus on the polymer backbone degradation as a few in­
vestigations are available based on the degradation mechanisms of

* Corresponding author.
E-mail address: ummesalma@mbstu.ac.bd (U. Salma).

https://doi.org/10.1016/j.rinma.2023.100366
Received 3 October 2022; Received in revised form 21 December 2022; Accepted 6 January 2023
Available online 9 January 2023
2590-048X/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
U. Salma and N. Shalahin
polymer-backbone [34,37,58]. Generally, the AEMs stability limitation
can be solved by choosing an appropriate cationic group [58–60].
Consequently, a variety of cationic groups have been synthesized and
studied by experimental and computational investigations such as
quaternary ammonium (QA) [61–76], imidazolium [36,40,77–85],
benzimidazolium [86–88], phosphazenium [89,90], and pyrrolidinium
[91], phosphatranium [92], phosphonium [93], spirocyclic QA [94,95],
tertiary sulfonium [96], pyridinium [97], guanidinium [98–101], pyr­
azolium [102], and metal cation [103–105]. Recently, it has been
expansively studied to develop alkaline stable AEMs and extensive
progress has been achieved [13,15,22,23]. Nevertheless, the extensive
application of AEMFCs is hindered due to the major obstacle of chemical
stability. Here, we aim to discuss and summarize the chemical durability
of AEMs containing imidazolium cationic groups and review the recent
improvement in approaches for enhancing chemical stability.
Fig. 1. Numerous mechanisms of chemical degradation of QA salt [109].
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Results in Materials 17 (2023) 100366
2. Degradation of imidazolium cationic group
Due to low-cost starting materials and easy synthetic procedures,
among the different cationic groups, the most commonly used cationic
group is tetraalkyl quaternary ammonium (QA) salt. By adding the
chloromethyl groups to the polymer backbone most AEMs are synthe­
sized followed by the synthesis of QA salts through a quaternization
reaction. However, chloromethyl methyl ether is carcinogenic to the
human body [106]. The effective decomposition of QA salts via
numerous paths including Hofmann (β-hydrogen) or E2 elimination
[107], nucleophilic substitution [108], rearrangement reactions, and
N-ylide formation [108,109] as shown in Fig. 1 Is another important
difficulty. Because of QA group degradation, the ionic conductivity and
IEC of AEMs decrease rapidly. Therefore, recently other cationic groups
have been investigated as an alternative to QA cations.
Throughout earlier few years, much attention has been attracted by
U. Salma and N. Shalahin
AEMs containing imidazolium cations. Scientists assumed that in
heterocyclic imidazolium cation a π-conjugated structure is formed
[85,110]. In the π-conjugated system, the positive charges are delocal­
izing (Fig. 2) that hinder the nucleophilic attack of hydroxyl ions. AEMs
having imidazolium salts were reported as higher chemically stable in a
highly basic environment with comparable ionic conductivity. Fang
et al. [79] and Yan et al. [85] stated that their synthesized AEMs based
on imidazolium showed high OH− ion conductivity which was greater
than 10− 2 S cm at room temperature and in 1 M KOH moderate chemical
stability was exhibited at 60 ◦ C for 400 h. Afterward, a series of studies
were reported on AEMs containing imidazolium as cationic groups
[32,36,45,49,53,54,76,80,82,83,99,110–120].
The conductivity, IEC values, and thermal stability of polysulfone
AEMs having imidazolium salts synthesized by the Zhang research group
were comparable to those of AEMs with QA salts [83]. Kim and
co-workers prepared pendant imidazolium containing poly (arylene
ether sulfone)s based crosslinked AEMs by a chlor­
omethylation–Menshutkin reaction [115]. Here, the cationic groups
were not only used as ion conductors but also as cross-linkers. The
synthesized membranes showed high dimensional stability, comparable
OH− ion conductivity, and moderate chemical stability in 2 M NaOH at
60 ◦ C. As the existence of the π-conjugated imidazolium ring attenuated
Hofmann elimination and SN2 substitution reactions all synthesized
AEMs with imidazolium cations exhibited adequate chemical stability.
However, analogous to AEMs having QA cations, the alkaline durability
of AEMs with imidazolium cationic groups is a big challenge.
Recently, several research groups have extensively studied the
chemical stability of imidazolium salts. Researchers observed sufficient
OH− ion conductivity of N-methyl [32,76,79,80,83,85,118,121,122] or
N-alkyl [123–126] benzyl imidazolium based AEMs, whereas for fuel
cell applications the alkaline stabilities exhibited by the unsubstituted
imidazolium was too low [32,53,119,127]. The group of Elabd reported
from 1H NMR spectra analysis that, over a wide range of basic conditions
the AEMs with imidazolium cations were chemically stable, however
under highly basic conditions and/or in a dry condition the AEMs were
unstable [119]. It was indicated from the 1H NMR results that the C2
position of the imidazolium ring was mostly attacked by nucleophilic
OH− ion and hence the degradation occurred by a ring-opening reaction
(Scheme 1) [24,36,113,128]. Hence, to use imidazolium salts in
considerably more vigorous concentrations the chemical stability still
needed to improve.
The group of Pivovar estimated the mechanism of degradation of
benzimidazolium and imidazolium cations by developing theoretical
calculations [129]. They proposed that in imidazolium cations the C2
site of the imidazolium ring was degraded dominantly by a nucleophilic
addition–elimination reaction. By DFT calculations Xie et al. investi­
gated the mechanism of degradation of imidazolium salts [130]. It was
revealed from their study that the imidazolium cations were degraded
via a nucleophilic, ring-opening, and rearrangement reaction mecha­
nism. They also suggested that the alkaline stability of imidazolium
cations cannot be significantly enhanced by tethering the imidazolium
Fig. 2. Positive charge delocalization in imidazolium salts.
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Results in Materials 17 (2023) 100366
ring through methyl, butyl, or benzyl groups to the polymer backbone.
Under basic mediums, imidazolium degrades through four discrete
mechanisms and the degradation paths are directed by the substituent’s
identities (Scheme 2) [49,60,131–135].
3. How to stabilize imidazolium group?
The alkaline durability of imidazolium salts can be boosted by
substituting or functionalization of various substituents. According to
Coats and co-workers, the different degradation pathways of Scheme 2
can be inhibited by using appropriate substituents, which may hinder
the reaction between reactive counter anions and organic cations [60].
3.1. Substitution at the C2 position of the imidazolium ring
Yan et al. proposed that the C2 substitution was an efficient approach
to enhance the chemical stability of imidazolium salts [110]. This group
observed that C2-unsubstituted imidazolium salt was less stable than
substituted imidazolium salts by methyl, isopropyl, or phenyl groups at
the C2 position. The NMR spectroscopy was used to investigate the effect
on chemical durability by C2 substitution. Because of the steric hin­
drance effect and σ– π hyperconjugation effects the chemical stability of
C2-substituted imidazolium salts was remarkably increased at a higher
temperature. They simulated the LUMO energy which determined the
chemical stability by density functional theory (DFT/B3LYP) calcula­
tions. High chemical stability is indicated by high LUMO energy (Fig. 3).
The chemical stability was investigated by using small molecule model
compounds which were consistent with the analogous polymers, this
proposed a strong base for estimation of performance analogous to that
in AEMs. From theoretical calculations, Pivovar and Long also suggested
that both the OH− attack and the ring-opening mechanism can be made
more difficult by steric interference of C2 substitutions [129]. Like other
researchers, Coats et al. also proposed that the reactivity of ring-opening
of the heterocycle and nucleophilic addition can be attenuated through
increasing steric hindrance by adding a methyl group at the C2 position
(Scheme 2a) [60]. The effect of C2 Substitution on chemical stability has
been investigated by numerous research groups [36,84,110,136]. By the
bromination of PPO, Xu et al. prepared C2-methylimidazolium-based
AEMs; which were higher chemically stable than that monomethyl
imidazolium functionalized AEMs [113]. Precisely, based on the studies
of benzimidazolium cations Holdcroft [88], Beyer and co-workers [137]
focus on the importance of C2 substitution by bulky groups.
3.2. Effect of C4,5 substitution on imidazolium ring
Wang et al. assumed that the alkaline durability of imidazolium
cations was also influenced by substitutions at the C-4/5 positions of the
imidazolium ring. This group observed that the α-C-methyl-substituted
imidazolium was considerably more stable compared to the α-C-
unsubstituted cations due to the hyperconjugation between the imid­
azole ring and α-C-substituted methyl group, and the steric effects [130].
According to Coats, the deprotonation reactions (Scheme 2b) might be
prevented by C4,5 substitution which improves the stability of imida­
zolium cations. They predicted the degradation reactions with the
exterior substituents (Scheme 2c and d) as well as the reactions at the
ring sites (Scheme 2a and b). It was proved from hydrogen/deuterium
interchange that the α-hydrogens of the peripheral substituents are
deprotonated in alkaline solutions of protic deuterated solvents. By
substituent alternation, the reactivity of imidazolium can be easily
controlled and the degradation can be prevented by eradicating the
positions of vulnerability. By DFT calculations Ramani [130], Pivovar
[129], and other groups [138,139] predicted that the alkaline stability
can be improved by the C4 and C5 substitutions. Wang et al. [136],
supported this assertion through experimental investigation of C4,5
methyl substituted imidazolium.
U. Salma and N. Shalahin Results in Materials 17 (2023) 100366

Scheme 1. Degradation of imidazolium cationic salt by the ring opening mechanism [24].

Scheme 2. Different routes of degradation of imidazolium cations in basic mediums [60].

3.3. N3 substitution of the imidazolium ring
In addition to the C2 substitution of the imidazole ring, the alkaline
durability of imidazolium cations also might be affected by N3 substi­
tution [120]. The alkaline durability of QA and several N3 substituted
imidazolium cations with methyl, ethyl, isopropyl, butyl, heptyl, octyl,
phenyl, and diphenylmethyl was also compared by the Yan research
group. They simulated the LUMO energy via DFT (GGA-BLYP) calcula­
tions. The imidazolium cations substituted at the N3 position exhibited
enhanced chemical stability to the traditional QA cations. Among the
investigated imidazolium cations, the isopropyl substituted imidazolium
salt was the most stable one which showed the highest LUMO energy
(Fig. 4). The nucleophilic attack of OH− was reduced due to the increase
of electron density of alkyl-substituted imidazolium salts by hyper­
conjugation and electron donating effect among the CH bonds of
substituents and π-conjugated imidazolium ring. The steric hindrance of
the substituents also increased the alkaline durability of imidazolium
cations. They experimentally confirmed the chemical stability by using
model compounds of the imidazolium salts [120]. The outcome of this
study offers an upgraded performance by influencing the molecular
design of highly stable imidazolium functionalized AEMs.
3.4. Electron effect of substituents at C2 and N3 position
Yan and co-workers also investigated the effect of electron donating
and withdrawing groups on LUMO energy by substituting C2 of the
imidazolium salt. In their investigation, the highest alkaline stability
and LUMO energy were observed by the amino substituted imidazolium
salt. The LUMO energy also could significantly increase by substitution
of the cycloalkyl group at the N3 position. They experienced the

4
U. Salma and N. Shalahin
Fig. 3. LUMO energy of C2 substituted and unsubstituted imidazolium cat­
ions [110].
imidazolium salts substituted by cycloheptyl and cyclooctyl group
showed higher LUMO energy than that of the isopropyl group [139].
Accordingly, they expected that for the imidazolium cation the most
suitable C2 and N3 substituents are amino and cyclooctyl groups.
3.5. Effect of the chemical stability of polymer backbone
The backbone of the polymer and cations determine the alkaline
stability of AEMs. During the last years, AEMs have been prepared by
employing poly (phenylene oxide)s or poly (sulfone)s or poly (arylene
ether)s aromatic skeletons with various types of ionomers [140–142].
Nevertheless, many researchers reported that the polar groups con­
taining polymeric backbone are weakened and susceptible to OH− ions
attack due to the intense inductive effect of neighboring cations [46,95,
143]. Particularly, at high temperatures and in high pH conditions, the
degradation of polymeric materials cannot be completely prevented by
having aryl ether bonds [144]. Thus, the chemical stability of polymeric
backbones should be enhanced. Ether bond free aromatic polymers, for
example, poly (benzimidazolium)s [145–148], poly (styrene)s [149],
spiro-ionenes [29], poly (phenylene)s [150], poly (olefin)s [151] show
comparatively better alkaline stability in highly basic condition. By
applying a Ni-catalyzed coupling reaction, poly (phenylene)s-based
AEMs were synthesized by Miyatake et al., which showed outstanding
conductivity in 1 M KOH at 80 ◦ C even after 1000 h [152]. On the other
hand, according to Ramani et al., polymer backbone degradation
probably accelerated due to poly (sulfone)s and results in the deterio­
ration of the chemical stability of AEMs [153]. Holdcroft and Coates
reported main-chain type AEMs by applying Grubbs 2nd catalysts
[154–157].
Fig. 4. Relationship between alkaline stability and LUMO energies [120].
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Results in Materials 17 (2023) 100366
3.6. Linkage mode of cations
The performance of AEMs can be improved by cation position and
the structure of the polymer backbone. Many researchers have reported
that the ionic conductivity and alkaline durability of AEMs might be
influenced by the alkyl spacer length [145,158]. According to the
Hickner research group, AEMs performance is influenced by the alkyl
spacers length of the polymeric backbone and cationic groups. They
observed 5 or 6 carbon atoms between two cationic groups showed the
greatest base stability [52,159]. To accelerate the ionic conductivity and
boost the overall alkaline resistance of the AEMs, a useful and feasible
technique is to build side-chains type polymer architecture having
multi-cations [160,161]. Wu et al. studied the consequence of the
different structures of imidazolium on OH− transport and alkali resis­
tance of AEMs [142]. The research group used molecular dynamics
simulation to study PPO based AEMs with substituted imidazolium
and/or alkyl pendent/side chains. Due to the introduction of alkyl side
chains, the hydration of imidazolium is enhanced which raises OH−
transport, however, the steric effect of PPO on imidazolium is weakened
hence decreasing the alkaline stability. They revealed that the AEMs
based on PPO containing 1,2,4,5- methyl substituted imidazolium cat­
ions and six or eight aliphatic carbon side chains balance out among
OH− transport and alkali resistance of AEMs. In Table 1 we also have
summarized some state of art imidazolium cationic groups and their
alkaline stability. Although it is very difficult to compare as the polymer
backbones and testing conditions are different.
4. Recent developments of imidazolium cations and
imidazolium based AEMs
Nowadays, several research groups paid much attention to
improving the alkaline stability of imidazolium cations by substituting
N1, C2, C4, or, C5 positions with various alkyl or aryl groups.
Fluorene-based AEM having 1-isopropyl-2-methylimidazolium with
long alkyl chains was synthesized by Salma et al. [82]. The alkaline
stability of OH− form membranes was assessed after soaking in 1 M
NaOH solution for 168 h and 360 h at 80 ◦ C. FT-IR spectra were used to
investigate the degradation of the cationic groups of the membrane as
OH− form AEM were not soluble in 1H NMR solvents for example CHCl3,
CH3OH, H2O, and DMSO. With time the absorption peak for conjugated
C–– N bond at 1518 and 1576 cm− 1 was considerably decreased, which
indicates the degradation of imidazolium groups by the nucleophilic
attack of OH− at the C2 site of the imidazolium ring.
Hugar et al. [60] and Yan et al. [136] stated that the degradation of
imidazolium salt in basic conditions can dramatically be suppressed not
only by C2 substitution by bulky groups but also by C4 and C5 substi­
tution by methyl or phenyl groups. In basic conditions, the imidazolium
cationic groups can not sufficiently stabilize by only steric hindrance.
The substituents electron donating effect plays a significant role as well.
1,4,5-trimethyl-2-(2,4,6-trimethoxyphenyl)imidazolium salt containing
U. Salma and N. Shalahin Results in Materials 17 (2023) 100366

Table 1
Alkaline durability of some state-of-art imidazolium cations and AEMs studied with various imidazolium cations.
Cationic group Backbone type Base concentration Test time T Test method Alkaline stability Ref.
[M] [h] [◦ C] [%]

poly (fluorenyl ether ketone sulfone)s 1 48 80 IEC 43 [32]

poly (vinyl 4 1320 60 conductivity 74.6 [186]

benzyl chloride)s

1
poly-(arylene ether sulfone)s 1 400 60 H NMR 68.2 [187]

poly (vinylbenzyl chloride)s 1 480 60 conductivity 92.6 [176]

– 1
5 720 80 H NMR >99 [60]

poly (phenylene oxide)s 1 1000 80 conductivity 90.4 [178]

1
poly (aryl)s 10 240 80 H NMR 97.7 [154]

norbornene copolymers 2 240 60 conductivity 75 [170]

poly (ether sulfone)s 1 168 60 conductivity, IEC, No significant [188]

mechanical strength degradation

poly (bis-arylimidazolium)s 1 600 80 IEC 78 [177]

poly norbornenes 1 240 60 conductivity 88.17 [173]

norbornene copolymers 1 250 60 conductivity 90 [189]

poly (arylene ether 2 240 60 Conductivity, IEC >80 [190]

ketone)s

(continued on next page)

6
U. Salma and N. Shalahin Results in Materials 17 (2023) 100366

Table 1 (continued )
Cationic group Backbone type Base concentration Test time T Test method Alkaline stability Ref.
[M] [h] [◦ C] [%]

long side-chains triblock 1 500 60 conductivity 69 [160]

benzonorbornadiene copolymers

poly (arylene ether sulfone)s 1 144 60 conductivity 80 [49]

poly (arylene ether sulfone)s 1 468 60 conductivity 68.2 [78]

poly (aryl ether ketone)s 2 400 80 conductivity 76 [191]

poly (arylimidazolium)s 10 168 80 conductivity 87 [192]

poly (arylene ether nitrile sulfone)s 1 480 80 conductivity 75 [193]

1
poly (arylene− 10 >2400 80 H NMR No evident of [166]
imidazolium)s degradat ion

vinylbenzyl chloride copolymers 1 360 80 conductivity >70 [194]

poly (2,6-dimethyl-1,4-phenylene oxide) 1 192 80 conductivity, 1H NMR 86.7 [162]

s

1
poly (fluorene alkylene)s 2 360 80 H NMR No degradation [167]

poly (arylene ether ketone)s 4 720 80 IEC No loss [195]

(continued on next page)

7
U. Salma and N. Shalahin
Table 1 (continued )
Cationic group Backbone type Base concentration
[M]
poly (phenylene oxide)s 1 1248
polyethersulfones 10
PPO-based AEM was reported by Yan and coworkers [136]. The imi­
dazolium group was stabilized due to steric hindrance and the high
electron density of 2,4,6-trimethoxyphenyl at the C2 position. The C4
and C5 methyl groups donated the additional electron density. They
observed, in 1 M KOH solution only 5% conductivity was lost at 80 ◦ C for
48 h. Furthermore, in 1 M KOH solution at 60 ◦ C for the 600 h, the
conductivity lost was 17%.
According to Coats and co-workers, the stability of benzyl imidazo­
lium containing C2-aryls can be improved by substituting methyl with
butyl at the N3 position (Scheme 3) [60]. Gu et al. [120], also reported
that the stability of imidazolium is enhanced by N-butyl substituents
compared to N-methyl substituents. Longer alkyl chains enhance cation
stability by decreasing the attack of the nucleophile at α-carbon of the
N3-substituent. Among a series of investigated imidazolium, the most
stable one was when the benzyl group in the N1 position was replaced by
the butyl group and retained the butyl group at the N3 position. From
the 1H NMR, unchanged signal integrations were observed after 30 days
at 2 M KOH and at 5 M KOH, a slight decomposition was detected. It
reveals that the butyl group is more efficient than the benzyl group at the
N1 position of the imidazolium ring to block the nucleophilic addition at
the C2 site. On the other hand, due to the aliphatic substituents, a more
solvable imidazolium cation may remain better solvated and can
decrease the reactive strength of the alkali, protecting the interaction of
the cation with the neighboring nucleophile. As considered, imidazo­
lium having C2 aryl with C4,5 methyl/phenyl substituents are
completely stable at 2 M KOH solutions. Even at 80 ◦ C and 5 M KOH, the
1
H NMR signal integrations exhibited no significant changes over 30
days, when both N1 and N3 positions are substituted by butyl groups.
In 10 M KOH at 80 ◦ C, the alkaline stability of poly (bis-arylimida­
zolium)s was investigated by Fan and co-workers by counting the re­
sidual imidazolium percentage in AEMs with time [154]. They also
Scheme 3. The stability of imidazolium salts with substituents at several po­
sitions in alkaline conditions [60].
8
Results in Materials 17 (2023) 100366
Test time T Test method Alkaline stability Ref.
[h] [◦ C] [%]
80 Conductivity 40 [168]
336 80 Conductiviy 43 [196]
observed when the N-alkyl length increases from methyl to butyl the
stability of imidazolium increases and the remaining percentage of
imidazolium is 66.0% and 97.7% respectively after 240 h. Though, the
1
H NMR spectra revealed that the membranes mainly degraded via the
dealkylation process and a minor ring-opening reaction takes place.
Sheng and coworkers prepared PPO-based AEMs to investigate the
effect of different substituents of imidazolium cations on the properties
of corresponding membranes [162]. The membranes containing imida­
zolium cation with (2,4,6-trimethyl)phenyl at C2 and C4,5 diphenyl and
1-methyl substituents exhibited superior chemical resistance in 1 M
NaOH at 80 ◦ C. After 192 h retained 86.7% of conductivity and 1H NMR
spectra showed no sign of chemical degradation. However, AEMs with
2-(2,6-dimethyl)phenyl-1-methyl-benzimidazolium and 1,2,4,5-tetra­
methylimidazolium retained only 19.8% and 16.9% of conductivity
after alkaline stability test.
Pan et al. [163], Fan et al. [154] and Hugar et al. [60] consecutively
stated that imidazolium cations with N1 and N3 butyl substituents
showed outstanding chemical durability. So, the benzyl group was re­
ported as an unstable part in strongly alkaline conditions at higher
temperatures as in previous reports [61,164]. And they expected that in
future work if α, α′ -dibromo-p-xylene can use instead of dihalogenated
alkanes may improve the chemical stability of poly (bis-ar­
ylimidazolium)s. Meanwhile, the chemical stability of the imidazolium
group can be further improved by introducing bulky mesitylene sub­
stituents [60,165]. Xue et al. synthesized poly (arylene− imidazolium)
AEMs by effectively attaching a novel chemically durable imidazolium
with propylbenzene substituents at N1/N3 position to the backbone of
the polymer through an easy polymerization reaction with
superacid-catalyst where no additional post functionalization was
needed [166]. 1H NMR spectra revealed that in 10 M NaOH alkaline
solution poly (arylene− imidazolium) AEMs were highly stable for 2400
h at 80 ◦ C, and there was no evidence of degradation. Although the
chemical resistance is higher than most of the AEMs reported earlier the
mechanical properties of these polymers need to improve in the future.
Yang et al. also observed the same mechanical problems when they
synthesized aryl ether-free polymers based on bulky imidazolium groups
[167].
The substituted imidazolium cations by bulky groups are chemically
stable in alkaline conditions at elevated temperatures but in most cases,
the film forming capability or mechanical properties of these AEMs are a
big challenge. The film forming capability or the mechanical strength
can be enhanced by the following strategies.
4.1. Flexible and hydrophilic side chains
To enhance the film-forming ability of imidazolium-type AEMs
Zhang and co-workers embedded flexible and hydrophilic polyethylene
glycol chains on the imidazolium cations [168]. Outstanding
film-forming capability with realistic tensile strengths and high
U. Salma and N. Shalahin
elongation at break was exhibited by the synthesized AEMs. The con­
ductivity was preserved by 37.1%–47.9% after soaking for 1248 h in 1 M
NaOH at 80 ◦ C. The effect of side-chain polarity and position on the
performance of AEM was systematically investigated by He and
co-workers [169]. This group synthesized a series of AEMs with an alkyl
extender, alkyl extra side-chain, alkoxy extender, alkoxy extra
side-chain, and membrane without side-chain. The results revealed that
MImPSf-AO-150% AEM having an extra alkoxy chain, showed the
highest water uptake i.e. 77.6%, and OH− ion conductivity of 23.7 mS
cm− 1 at 30 ◦ C. Due to the high stability of the alkoxyl chain and good
hydrogen bond network, the AEM containing alkoxy chain showed
H2/O2 fuel cell peak power density of 404 mW cm− 2 for MImPSf-AO and
383 mW cm− 2 for MImPSf-EO and extended durability of 137 min for
MImPSf-AO and 133 min for MImPSf-EO at 100 mAcm− 2 which is higher
compared to AEMs of similar IEC.
4.2. Self-cross-linking of epoxy groups of norbornene
He et al. incorporated a flexible side chain terminated with imida­
zolium to norbornene copolymer backbone having an epoxy group
[170]. The epoxy groups enhanced the solubility of the copolymer
backbone in ordinary organic solvent and have the self-cross-linking
ability. 75% of the hydroxide conductivities of AEMs remained after
10 days at 60 ◦ C in 2 M NaOH solutions. This research group also
investigated the alkaline stability of polynorbornene AEMs via replacing
N1-substituents such as methyl, isopropyl, butyl, benzyl, or dodecyl on
2-methylimidazolium. 2-Methylimidazolium AEM having N1-butyl or
isopropyl groups exhibited much more chemical stability than the others
[171]. In 1 M NaOH at 60 ◦ C for 720 h, only 17% and 14% conductivity
were lost respectively and TGA curves and FT-IR spectra were almost
unaltered. Moreover, the stability and base durability arise from the
cross-linking structure of N1-substituted imidazolium cations. This
confirms the previously reported results [172–175]. Seemingly, they
attributed the vulnerability of N1- long chain dodecyl containing cations
due to a micelle or aggregation of the dodecyl substituent. As a result,
the hyperconjugation effects of π-conjugated imidazolium ring and
N1-dodecyl substituents are hindered and the long N1-dodecyl group
may retain the cations away from one another, which may enhance the
instability of C2 group [175]. Whereas, the benzyl substituted imida­
zolium was unstable due to the electron withdrawing effects of the
benzyl group that enhanced the nucleophilic attack of OH− [60,86].
4.3. Homogeneous crosslinking by using PBI
1-butyl-4,5-dimethyl-imidazolium based AEMs with homogeneous
crosslinked poly (vinyl benzyl chloride/polybenzimidazole was syn­
thesized by Hao et al. [176]. Imidazolium with N1 long alkyl groups
and methyl substituents at C4,5 enhanced the chemical stability of
AEMs due to hyper-conjugation and steric hindrance effects. And only
7.4% conductivity was lost at 60 ◦ C in 1 M KOH for 480 h. Yang and
his research group synthesized two bis-imidazole compounds from 2,
4,5-triphenylimidazole or 2-phenylbenzimidazole with 1,4-dibromobu­
tane [177]. Later, they prepared two novel poly (bis-arylimidazolium)
ionenes from their synthesized bis-imidazole compounds and
α,α′ -dibromo-p-xylene by a Menshutkin reaction. They verified the
chemical structure of prepared imidazolium groups and ionenes by 1H
NMR spectroscopy. And excellent thermal stability of ionenes was also
indicated in TGA. However, due to the low intrinsic viscosity of
ionenes, they could not acquire pure membranes. That’s why via a
co-casting method, blend membranes with outstanding dimensional
durability were synthesized by using PBI as an enhanced material.
The AEM based on bulky tri-phenyl group substituted imidazolium
showed higher chemical durability than benzimidazolium containing
AEM as a result of steric hindrance of bulky groups. 1H NMR revealed
that in 1 M KOH solution for 600 h at 80 ◦ C, 69.2% conductivity was
retained by the Ptpim-34%/PBI membrane.
9
Results in Materials 17 (2023) 100366
4.4. Small molecule crosslinker
Zhang and his group synthesized 2-mesityl-4,5-diphenyl-1H-imida­
zolium based PPO AEMs [178]. Due to the poor film-forming capa­
bility of the bulky imidazolium groups, an alkaline stable AEM through
crosslinked networks was synthesized via a hydrophilic dithiol cross­
linker. A conductivity of 11.2 mS cm− 1 at 20 ◦ C was observed for bro­
mide ions and bromine conductivity in 1 M NaOH at 80 ◦ C was retained
90.4% after 1000 h. He et al. used a transition metal catalyst to syn­
thesize post-functionalized vinyl addition-type block copolymer from
5-norbornene-2-methylene-(6-bromohexyl) ether and 5-norbornene-2-­
methylenehexyl ether by controllable addition copolymerization
[179]. A series of AEMs was prepared by using 1,6-Bis(2-methylimidazo­
lium) as a crosslinking agent. The OH− conductivity was maintained as
85.07 mS cm -1 at 80 ◦ C and alkaline stability of more than 500 h at
25 ◦ C. Ding and co-workers designed and synthesized PPO based AEMs
with bis-imidazolium cation cross-linkers containing flexible long-chain
[180]. Amongst these PPO-based AEMs, BMImH-PPO containing the
lengthiest flexible bis-imidazolium cationic cross-linker owns the lowest
IEC but displays the highest conductivity of 24.10 mS cm− 1 at 20 ◦ C and
highest power density of 325.7 mW cm− 2 at 60 ◦ C. Additionally, after
immersing BMImH-PPO membrane in 2 M KOH at 80 ◦ C for 480 h, only
10% and 6% IEC and conductivity respectively were decreased.
4.5. Semi/mutual-interpenetrating network
Crosslinked AEMs with brominated PPO matrix were fabricated by
using imidazole containing polyvinyl alcohol as a macromolecular cross-
linking group [181]. The enhanced ion conductivity and alkaline
durability at higher temperatures are the advantages of macromolecular
crosslinked structures. Furthermore, crosslinked AEM with IEC of 1.54
mmol/g showed ionic conductivity of 78.8 mS cm− 1 at 80 ◦ C. After
treatment in 1 M NaOH at 80 ◦ C for 1000 h, the ionic conductivity re­
tains 75% of the initial value. By introducing flexible polyvinyl alcohol
to the rigid photo-crosslinked PPO network Yang et al. prepared a series
of AEMs having a semi-interpenetrating polymer network [182]. Such
an approach bestows AEM with tunable composition and enhanced
mechanical strength. The utmost OH− ion conductivity, a relatively
lower swelling ratio, and the highest mechanical strength of 30.8 MPa
were exhibited by the AEM with an IEC of 1.46 mmol/g. Most impor­
tantly, a semi-interpenetrating polymer network improves the alkaline
stability of these AEMs. 66.5% of the initial OH− ion conductivity is
retained after immersing in 1 M NaOH at 80 ◦ C for 1000 h.
4.6. Membrane supported composite
Wang et al. manufactured a series of membrane supported compos­
ites by using imidazolium functionalized metal organic frameworks
(ImMOFs) and QPPO [183]. ImMOFs resisted the continuous attack of
polymeric backbone by hydroxyl groups and take part in OH− ion
conduction. Precisely, the membrane QPPO/7%ImMOFs showed OH−
ion conductivities of 0.726 mS cm− 1 at − 25 ◦ C and 42.1 ± 1.9 mS cm− 1
at 80 ◦ C. After immersing for a long-time in 2 M KOH the composite
membranes exhibited high OH− ion conductivity. The OH− ion con­
ductivities of QPPO/7%ImMOFs remained at 0.29 mS cm− 1 and 0.26
mS cm− 1 at − 25 ◦ C, 45.4 mS cm− 1, and 40.5 mS cm− 1 at 60 ◦ C after
soaking in 2 M KOH for 768 h at RT and 433 h at 60 ◦ C. The ImMOFs also
enhanced the mechanical properties of the composite membranes. A
highly OH− ion conducting AEM was fabricated by Tang et al. by
combining imidazolated poly (2,6-dimethyl-1,4-phenylene oxide)
(ImPPO) and poly ionic liquids modified MIL101 (PIL@MIL101) [184].
The hybrid membrane showed OH− ion conductivity of 138 mS cm− 1 at
80 ◦ C which is 176% higher than that of the pure membrane. Moreover,
the mechanical properties and stability of the hybrid membranes were
surprisingly increased. By applying Imidazole functionalized PEEK as an
organic matrix and GO/ZIF-8 as fillers a series of novel AEMs were
U. Salma and N. Shalahin
fabricated by Wang and co-workers [185]. The hybrid AEMs exhibited
the ionic conductivities of 39.38 mS cm− 1 to 43.64 mS cm− 1 at 30 ◦ C,
100% RH and whereas 59.21 mS cm− 1 to 86.87 mS cm− 1 at 80 ◦ C, 100%
RH. The membrane Im-PEEK/GO/ZIF-8-1% showed higher tensile
strength and ionic conductivity (86.87 mS cm− 1 at 80 ◦ C and 38.21 MPa)
than that of the pristine membrane (59.21 mS cm− 1 at 80 ◦ C and 19.47
MPa). After soaking in 2 M NaOH solution at 60 ◦ C for 400 h, 92.01%
ionic conductivity was retained in Im-PEEK/GO/ZIF-8-1% hybrid
membrane. From the above results, it can be said that the hybrid
membranes can manage the trade-off effect amongst the ionic conduc­
tivity and alkali resistance stability.
Throughout the former few years, scientists gave much attention to
imidazolium as a cationic group and imidazolium functionalized AEMs.
On one side, the higher chemical durability of imidazolium salts and
imidazolium containing AEMs ascends from the π-conjugated imidazole
ring [85,197,198]. On the other side, the imidazole ring has a unique
chemical structure and is easy to design, various derivatives can be
obtained by substituting the imidazolium group [36,45,49,53,54,76,80,
82,83,99,110–120]. We have summarized the alkaline durability of
some investigated state-of-art AEMs based on various imidazolium cat­
ions in Table 1. The direct comparison of the reported alkaline durability
results is a relatively hard task as researchers used dissimilar investi­
gational conditions for example base concentrations, times, tempera­
tures, diverse backbones and by using various approaches including IEC,
TGA, 1H NMR, and FTIR.
Due to the easy synthetic procedure, N-substituted imidazolium
cations with various substituents were designed and studied. A nucleo­
philic substitution reaction between a halogenoalkane and the lone-pair
electrons of a nitrogen atom easily synthesizes N-substituted imidazo­
lium cations. Very recently several research groups investigated C2-, C4-
, and C5-substituted imidazolium cations by bulky substituents although
these substitutions were considerably more difficult than N-substitution
[60,154,162,166–168,177,178,192]. In most cases, the imidazolium
cations with bulky substituents were chemically durable in alkaline
conditions at high temperatures but the film forming ability or me­
chanical strength of the AEMs was very poor. To enhance the film
forming capability some groups attached epoxy groups, “thiol-ene”
crosslinkers, hydrophilic flexible alkyl side chains, flexible alkoxy
spacer, or blend with polybenzimidazole (PBI) as an enhanced material.
AEMs with outstanding mechanical performance was synthesized by
crosslinking strategy using self-cross-linking of epoxy groups of nor­
bornene, homogeneous crosslinking by using PBI, small molecule cross
linker, semi/mutual-interpenetrating polymer network, or synthesizing
membrane supported composite. Consequently, for the improvement of
AEMs with high chemical durability, besides N3-substituted imidazo­
lium cations C2-, C4-, and C5-substituted cations have also attracted
much more attention due to the strong electron-donation effect and
large steric hindrance effect of the imidazolium ring.
5. Conclusions
For the practical application of AEMFCs, one of the significant con­
cerns is the long-term alkali resistance of AEMs. To boost the alkaline
durability of AEMs, extensive investigations have been performed.
Imidazolium is an attractive target as a cationic group for AEMs as the
synthetic procedure is convenient, easy to modify, and stabilize by
resonance. Several research groups investigated the alkaline durability
of N1, C2, and C4,5 substituted imidazolium cations and their corre­
sponding AEMs. Nevertheless, bulky imidazolium-based membranes
showed unfavorable performance in fuel cells due to their poor film-
forming capability. To enhance the durability and mechanical proper­
ties of AEMs, one of the effective methods is cross-linking. Here, some
state-of-art imidazolium cations with AEMs in terms of alkaline dura­
bility are summarized. To predict the alkaline durability of imidazolium
cationic groups the improvement of computational designs is vital. The
AEMs having extremely alkaline stable imidazolium cations can be
10
Results in Materials 17 (2023) 100366
designed by combining theoretical calculations and experimental in­
vestigations. Therefore, based on the above discussion further investi­
gation in detail is necessary for AEMs having imidazolium cationic
groups with high longevity to achieve outstanding performance in the
practical AEMFC.
Credit author statement
Umme Salma: Conceptualization, Validation, Investigation, Writing-
Original draft preparation, Reviewing and Editing, Visualization, Naz­
mus Shalahin: Resources, Drawing of Chemical Structures.
Funding source
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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.
Data availability
No data was used for the research described in the article.
Acknowledgment
We gratefully thank Assoc. Prof. Dr. Aysha Ferdoushi (Mawlana
Bhashani Science and Technology University, Bangladesh), Md. Mah­
mudul Hasan (Asst. prof. of NTRC, Waseda University, Japan) and
Rashedul Islam Ripon (PhD student, Fukushima University, Japan) for
their cordial support during manuscript preparation.
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