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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5

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Development of crosslinked SEBS-based anion

exchange membranes for water electrolysis:
Investigation of the crosslinker effect

Junghwa Lee a,b, Kyungwhan Min a,b, Soomin Jeon a,b, Sanggil Park b,c,
Hyungjun Kim b,c, Tae-Hyun Kim a,b,*
a
Organic Material Synthesis Laboratory, Department of Chemistry, Incheon National University, 22012, Republic of
Korea
b
Research Institute of Basic Sciences, Core Research Institute, Incheon National University, 119 Academy-ro,
Yeonsu-gu, Incheon, 22012, Republic of Korea
c
Quantum Chemistry Laboratory, Department of Chemistry, Incheon National University, Incheon, 22012, Republic
of Korea

highlights graphical abstract

Crosslinked AEMs were prepared

using three different crosslinkers.

Tris (dimethyl aminomethyl)
phenol (TDMAP) were used as a
new conducting head group.

OH groups on the TDMAP
enhanced the conductivity, stabil-
ity and cell performance of AEM.

article info abstract

Article history: SEBS (styrene-b-(ethylene-co-butylene)-b-styrene)) is a non-aryl-ether-type tri-block

Received 30 November 2022 copolymer widely used as an anion exchange membrane (AEM) material due to its excel-
Received in revised form lent alkaline stability and phase separation properties. However, low tensile strength due
9 February 2023 to the aliphatic chains and the poor physical properties of the SEBS-based membranes limit
Accepted 11 March 2023 their practical application for AEM water electrolysis (AEMWE) or AEM fuel cell (AEMFC). In
Available online 5 April 2023 this study, three types of crosslinked AEMs were prepared using bromohexyl penta-
fluorobenzyl SEBS as a polymer backbone, and three different crosslinkers, dimethyl amine
Keywords: (DMA), tetramethyl diaminohexane (TMHA), and tris(dimethyl aminomethyl) phenol
Anion exchange membranes (TDMAP). Once introduced, these crosslinking agents were converted into the corre-
Water electrolysis sponding conducting head groups. The thermal, chemical, physical, and electrical prop-
Poly(styrene-b-(ethylene-co- erties of the obtained crosslinked membranes were then investigated for use in AEMWE. In
butylene)-b-styrene)) particular, the TDMAP-50x-SEBS membrane with 50% degree of crosslinking experienced
Crosslinker effect hydrogen bonding with water and OH due to the presence of OH groups in the structure of
Hydrogen bonding the crosslinking agent (TDMAP). Because of this, the membrane showed an improved

* Corresponding author. Organic Material Synthesis Laboratory, Department of Chemistry, Incheon National University, 22012, Republic
of Korea.
E-mail address: tkim@inu.ac.kr (T.-H. Kim).
https://doi.org/10.1016/j.ijhydene.2023.03.143
0360-3199/© 2023 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5 24181

morphology and high conductivity (20  C: 31.8 mS cm1, 80  C: 109.9 mS cm1). In addition,
TDMAP induced physical crosslinking by hydrogen bonding between molecules so that the
corresponding membrane (TDMAP-50x-SEBS) exhibited high alkaline and oxidative sta-
bility and good mechanical properties. This SEBS-based membrane has a tensile strength of
18.0 MPa and Young's modulus of 165.14 MPa. The WE single-cell test (1 M KOH solution at
70  C) using TDMAP-50x-SEBS also showed a cell performance of 1190 mA cm2 at 2.0 V.
This is 126% higher than the cell performance measured for FAA-3-50, a commercialized
AEM material, under the same conditions.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

in which PEMWE typically operates. All of these factors in-

Introduction
Hydrogen has garnered significant attention as a promising
new and renewable energy source to replace fossil fuels [1,2].
Compared to other eco-friendly energy sources, such as
photovoltaic and wind power, hydrogen provides improved
energy density and is highly suitable for large-scale energy
storage systems [3].
Water electrolysis (WE) is increasingly important among
the different available hydrogen production technologies
because of its high efficiency and environmental friendliness
[4]. WE systems are largely categorized according to the type
of electrolyte used. The common systems are alkaline liquid
electrolyte water electrolysis (AWE) [5e7] and proton ex-
change membrane water electrolysis (PEMWE) [8e10].
AWE uses alkaline solutions, such as KOH or NaOH solu-
tions, as electrolytes. In high pH conditions, that is, basic
conditions, oxygen evolution reactions proceed faster than in
acidic conditions, and metallic materials used as catalysts are
unlikely to corrode [11]. Thus, in AWE, inexpensive non-noble
metals can be used as catalysts, unlike in PEMWE [5e7]. With
these advantages, AWE has been recognized as one of the
most cost-effective water electrolysis methods and has been
widely used for decades in various applications for large-scale
hydrogen production [6,7]. However, AWE is based on high-
concentration alkaline electrolyte solutions (30e40 wt%
KOH), which tend to adsorb carbon dioxide (CO2) from the
ambient atmosphere, forming insoluble carbonates. Further-
more, AWE exhibits lower ionic conductivity and chemical
stability than PEMWE, leading to reduced cell performance
and lower hydrogen purity [12].
Meanwhile, PEMWE achieves high ionic conductivity and
durability, leading to improved cell performance. Thus,
PEMWE allows for higher-efficiency production of higher-
purity hydrogen compared to AWE. It is also possible to
replace liquid electrolytes with solid electrolytes, such as
polymer electrolyte membranes, preventing the corrosion of
equipment that liquid electrolytes would otherwise cause.
Moreover, the overall system can be designed with an high
operating pressure [8,9]. With these advantages, for the past
two decades, extensive research and development efforts
have been directed toward PEMWE applications [8e10]. How-
ever, the proton exchange membranes (PEMs) used as elec-
trolytes are expensive, and only a few noble metals, such as
platinum (Pt), iridium (Ir), and ruthenium (Ru), can be used as
catalysts because they can endure the severe acidic conditions
crease the cost of hydrogen production [8].
To overcome the limitations of AWE and PEMWE, anion
exchange membrane water electrolysis (AEMWE) has been
increasingly studied [11,13e15]. In AEMWE, an anion ex-
change membrane (AEM) is used as an electrolyte instead of a
liquid electrolyte, and thus hydrogen production efficiency
and purity are improved compared to AWE. Furthermore,
low-cost non-noble-metal catalysts can be used, reducing
hydrogen production costs compared to PEMWE.
An AEM is an integral part of AEMWE and requires high
ionic conductivity, mechanical properties, and stability under
alkaline conditions [13,14]. Materials typically used in anion
exchange membrane-based alkaline fuel cells (AEMFCs) have
thus far mainly been used in AEMWE applications. As a result,
the performance and durability of most AEMs currently in use
are inferior to those of the PEMs used in PEMWE [11]. There-
fore, developing AEMs with high ionic conductivity, durability,
and cell performance is essential.
Meanwhile, Nafion, a type of PEM composed of a
perfluoroalkyl-based polymer backbone and side chains con-
taining sulfonic acid, has already been commercialized and is
widely used. However, AEM materials with exceptionally high
performance have yet to be developed. At present, materials
composed of a hydrocarbon-based polymer backbone conju-
gated with quaternary ammonium (QA) as ion-conducting
head groups are mainly used as AEMs in AEMFCs [13,16,17].
Aromatic polymers, such as PES (poly (arylene ether sulfone))
[16,17] and PEK (poly (etherketone)) [18,19], and PPO (poly (2,6-
dimethyl-1,4-phenyleneoxide)) [20e22] are mainly used as
polymer backbones. However, these polymer backbones
contain aryl-ether segments and thus are subject to nucleo-
philic attacks by hydroxide ions (OH). This attack is known to
degrade the polymer backbone, leading to reduced chemical
stability [13,21,23]. Therefore, in many recent studies, non-
aryl-ether-type aromatic polymers, such as polyterphenyl
[24e26], polycarbazole [27,28], polydibenzyl [25,29,30], poly-
fluorene [25,30e32], poly (fluorenyl-co-terphenyl) [31,32], poly
(dibenzyl-co-terphenyl) [25,29e31], polybiphenyl [14,26], and
poly (benzimidazole) [33,34], have been employed as the
polymer backbone of AEMs. In addition, non-aryl-ether-type
aliphatic polymers, including polystyrene [35], poly-
norbornene [36,37], poly (styrene-b-(ethylene-co-butylene)-b-
styrene) [38e48], polyethylene [49], and poly (vinyl alcohol)
[50,51], have also been used as the polymer backbone of AEMs.
As ion-conducting head groups, QA [13,16,17], piper-
idinium [29e32,34], triazole quaternary ammonium [22,52], 6-
24182 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
azonia-spiro [5.5]undecane [53,54], imidazolium [34,50,55,56],
morpholinium [55], carbazolium [57], pyrrolidinium [56], pyr-
roline [56], isoindolinium-based cations [58] have been
investigated. The ion conductivity and chemical stability of
AEMs are determined not only by the polymer backbones but
also by the type and structure of the ion-conducting head
groups. Nevertheless, QA and piperidium (Pip) groups have
been most widely used as hydroxide-conducting groups.
In particular, poly (styrene-b-(ethylene-co-butylene)-b-sty-
rene), SEBS, a commercialized rubbery polymer, has drawn
interest as an AEM material due to its phase separation prop-
erty, attributed to its triblock structure, as well as its excellent
alkaline stability. However, its polymer backbone is composed
of aliphatic chains; thus, SEBS exhibits relatively low tensile
strength and sticky behavior. These properties make it difficult
to form a self-standing membrane from this material.
Furthermore, QA-functionalized SEBS membranes exhibit very
high water uptake (WU), causing excessive swelling (SR), which
leads to a degradation in mechanical properties [39,52]. Various
strategies have been developed and implemented to address
these problems, including hydrophilicehydrophobic comb-
type SEBS [42] and crosslinking [43,45,46].
Crosslinking refers to a process in which polymer chains
are linked with each other either physically [37] or chemically
[20,38,43]. Crosslinked AEMs exhibit not only higher physical
properties but also significantly improved thermal, mechani-
cal, and chemical stability (alkaline stability). Because AEMWE
is performed in alkaline conditions at high temperatures
(60e80  C), AEMs used in the process must be sufficiently
thermomechanically stable under such conditions. Most
importantly, these AEMs require sufficient alkaline stability.
Because of their properties, AEMs based on crosslinked SEBS
have received significant attention as promising candidates.
Fig. 1 e Structure of the crosslinked Br-Hex-F5-SEBS 2 polymer membranes (50x-SEBS) 1.
However, crosslinking typically reduces the mobility of poly-
mers by forming a network of polymer chains, which di-
minishes ionic conductivity. The ionic conductivity of an AEM
directly affects the performance of the AEMWE. Therefore,
crosslinking-induced reduction in the ionic conductivity
makes crosslinking-based approaches less favorable for use,
despite their many advantages.
We have recently developed a new AEM by introducing
pentafluorobenzyl groups into SEBS [44]. This AEM with
enhanced hydrophobicity, based on SEBS with penta-
fluorobenzyl group, exhibited excellent phase separation
behavior and improved physical and chemical stability, with
increased ionic conductivity and cell performance.
The present study aimed at developing novel crosslinked
AEMs by introducing dimethyl amine (DMA), tetramethyl-1,6-
hexanediamine (TMHA), and tris(dimethyl aminomethyl)
phenol (TDMAP) as crosslinking groups into SEBS conjugated
with pentafluorobenzyl groups (Fig. 1). Each crosslinker was
expected to react with the SEBS polymer to be converted into
the corresponding QA groups. In other words, DMA, TMHA,
and TDMAP served not only as crosslinkers but also as ion-
conducting head groups. It was expected that the potential
crosslinking-induced reduction in the ionic conductivity of
the crosslinked AEMs would be compensated for by the for-
mation of new ion-conducting head groups, which would
minimize the reduction of the ionic conductivity.
TDMAP, in particular, contains a hydroxy (OH) group,
which tends to form hydrogen bonds with water or hydroxide
ions (OH). This will not only enhance the hydrophilicity of
TDMAP-functionalized AEMs but also induce further physical
crosslinking within the TDMAP-functionalized SEBS mem-
branes, possibly leading to improved ionic conductivity, cell
performance, and chemophysical stability (Fig. 1).
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Experimental
Materials
Aluminum chloride (AlCl3), 6-bromohexanoyl chloride (6BHC),
2,3,4,5,6-pentafluorobenzoyl chloride (PFBC), DMA, tetra-
methyl-1,6-hexanediamine (TMHA), tris(dimethylamino-
methyl)phenol (TDMAP), and trimethylamine solution (45 wt
% in H2O) were purchased from Sigma-Aldrich (St. Louis, MO,
USA). Triethylsilane was obtained from Alfa Aesar (Haverhill,
MA, USA). Trifluoroacetic acid was obtained from Daejung
Chemicals & Metals (Siheung-si, South Korea). Poly (styrene-b-
ethylene-co-butylene-b-styrene) (SEBS, A1535H) with 57%
styrene content was obtained from Kraton (Houston, TX,
USA). All other chemicals were obtained from other com-
mercial sources.
Fabrication of 50 mol% crosslinked SEBS membranes with
different crosslinkers (50x-SEBS)
Br-Hex-F5-SEBS 2 (0.4 g) and HPLC-grade chloroform (20 mL)
were placed in 25-mL vials, and the mixture was stirred until a
homogenous solution was obtained. The polymers 2 were
used as follows: DMA, TMHA, and TDMAP crosslinkers were
used for Br-Hex-F5-SEBS 2, and all membranes were prepared
at a ratio of 50 mol% relative to the Br-Hex-F5-SEBS 2. The
polymer solution was cooled to room temperature (RT) and
poured into a glass Petri dish through a cotton filter before
being allowed to dry at RT for 24 h. The membranes were
peeled from the Petri dish and immersed in DI water to
remove any residual solvent. Next, the membranes were
soaked in trimethylamine (TMA) solution at 45  C for 24 h.
Then, the membranes were washed with DI water to remove
excess TMA. Finally, the membranes were immersed in 1 M
KOH solution for at least 24 h at RT to exchange Br ions with
OH ions and washed with DI water several times to remove
excess KOH before any measurements were performed.
Synthesis of polymers
Synthesis of 6-bromohexanoyl SEBS (Br-HexeCOeSEBS) 4
SEBS (10.00 g, 54.73 mmol) was poured into a 1000-mL two-neck
round-bottom flask with a magnetic stirrer under a nitrogen
atmosphere and dissolved in dichloromethane (320 mL). After
the polymer was fully dissolved, aluminum chloride (5.47 g,
41.05 mmol) and 6-bromohexanoyl chloride (8.76 g,
41.05 mmol) in dichloromethane (80 mL) were added slowly
with a dropping funnel. After 24 h, the reaction mixture was
poured into a large amount of methanol (1500 mL), and the
precipitated polymer was filtered onto filter paper and washed
with ethanol several times to remove any residual reactants.
The obtained polymer was dried in a desiccator at RT for 24 h,
and this yielded Br-HexeCOeSEBS 4, a white rubbery product
with an 80% molar ratio of bromohexanoyl-functionalized side
chains (16.5 g, 98.3%); dH (400 MHz, CDCl3) 7.92e7.37 (3H, broad
signal, H6,7), 7.26e6.28 (5H, broad signal, H8e10), 3.50e3.38 (2H,
broad signal, H1), 3.03e2.80 (2H, broad signal, H5), 2.69e2.35
(1H, broad signal, H12), 2.01e0.56 (24H, broad signal,
H2e4,11,13e15); ATR-FT-IR (neat) 2920e2850 (CeH stretching),
1680e1600 (C]O stretching), 696 (CeBr stretching) cm1.
24183
Synthesis of Br-Hex-F5-CO-SEBS 3
In a 500-mL two-neck round-bottom flask fitted with a
magnetic stirrer, Br-HexeCOeSEBS 4 (16.5 g, 44.83 mmol) was
dissolved in dichloromethane (250 mL) to make a homoge-
neous solution. A heterogeneous solution of aluminum
chloride (1.49 g, 11.21 mmol) and 2,3,4,5,6-pentafluorobenzoyl
chloride (1.55 mL, 11.21 mmol) was prepared in
dichloromethane(70 mL). After the aluminum chloride and
2,3,4,5,6-pentafluorobenzoyl chloride solution was fully dis-
solved, it was slowly added to the Br-HexeCOeSEBS 4 solution
using a dropping funnel at RT at N2 atmosphere. The mixture
was stirred overnight, then poured into methanol (1500 mL) to
precipitate a polymer which was washed and filtered several
times with methanol, then dried in a vacuum oven for at least
24 h. This yielded Br-Hex-F5-CO-SEBS 3, a white rubbery
product with a 10% molar ratio of pentafluorobenzoyl-
functionalized side chains (18.0 g, 98.9%); dH (400 MHz, CDCl3)
7.92e7.37 (3H, broad signal, H6e7,16e17), 7.26e6.28 (5H, broad
signal, H8e10), 3.50e3.38 (2H, broad signal, H1), 3.03e2.80 (3H,
broad signal, H5,19), 2.69e2.35 (1H, broad signal, H12), 2.01e0.56
(30H, broad signal, H2e4,11,13e15,18); dF (400 MHz, CDCl3) 145 (2H,
s, Hb), 156 (1H, s, Ha), 165 (2H, s, Hc); ATR-FTIR (neat)
2922e2850 (CeH stretching), 1680e1600 (C]O stretching),
1480e1110 (CeF stretching), 694 (CeBr stretching) cm1.
Reduction of Br-Hex-F5-CO-SEBS 3 to Br-Hex-F5-SEBS 2
In a 500-mL two-neck, round-bottom flask connected to a
reflux condenser and fitted with a magnetic stirrer under an
N2 atmosphere, Br-Hex-F5-CO-SEBS 3 (18 g, 52.91 mmol) was
dissolved in chloroform. After the polymer was fully dis-
solved, triethyl silane (84.52 mL, 529.1 mmol) and trifluoro-
acetic acid (80.96 mL, 1058 mmol) were added. The reaction
temperature was slowly heated to 105  C and maintained at
this temperature for 48 h. The reaction mixture was then
cooled to RT, and 1 M KOH (400 mL) was added to neutralize
the remaining trifluoroacetic acid. The organic layer was
poured into methanol (1500 mL), and the precipitated polymer
was filtered and washed with methanol several times to
remove any residual reactants. The resulting polymer was
dried in a vacuum oven at RT for 24 h to produce the desired
product, Br-Hex-F5-SEBS 2. It appeared to be a white rubbery
product (17.2 g, 94.21%); dH (400 MHz, CDCl3) 7.21e6.27 (11H,
broad signal, H6e10,16,17), 4.05e3.85 (1H, broad signal, H19’),
3.48e3.34 (2H, broad signal, H1), 2.66e2.27 (4H, broad signal,
H5,5',12,19), 1.99e0.59 (39H, broad signal, H2e4,11,13e15,18); ATR-
FT-IR (neat) 2922e2850 (CeH stretching), 1480e1110 (CeF
stretching), 694 (CeBr stretching) cm1.
Characterization and measurements
The supporting information describes all the characterization
and measurement methods in detail.
Results and discussion
Synthesis and characterization of bromohexyl-pentafluoro-
SEBS (Br-Hex-F5-SEBS 2)
Crosslinked polymer membranes with enhanced hydropho-
bicity were developed as follows. First, a SEBS polymer
24184 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
containing both bromohexyl and penta-fluorobenzyl groups
(Br-Hex-F5-SEBS 2) was synthesized according to the
following procedure (Scheme S1). More specifically, 6-
bromohexanoyl chloride was introduced into a commercial
SEBS through a FriedeleCrafts acylation reaction using AlCl3
as a catalyst to synthesize Br-HexeCOeSEBS 4, a SEBS poly-
mer conjugated with bromohexanoyl groups. Polymer 4 was
then subjected to a FriedeleCrafts acylation reaction using
pentafluorobenzoyl chloride to introduce hydrophobic side
chains. As a result, Br-Hex-F5-CO-SEBS 3 was obtained. Sub-
sequently, the carbonyl (-C]O) groups contained in bromo-
hexanoyl and pentafluorobenzoyl groups were reduced using
triethylsilane and trifluoroacetic acid to synthesize bromo-
hexyl pentafluoro-SEBS (Br-Hex-F5-SEBS 2).
Here, an attempt was made to reduce bromohexanoyl and
pentafluorobenzoyl groups because carbonyl groups in an
AEM could lead to side reactions, for example, the degradation
of its polymer backbone due to nucleophilic attacks by hy-
droxide ions (OH) in alkaline conditions [13,52].
After each synthesis stage, the structure of the obtained
polymers was examined using 1H NMR spectroscopy (Fig. S1).
After the FriedeleCrafts acylation, bromohexanoyl groups
were introduced into Br-HexeCOeSEBS 4, which was
confirmed by the appearance of new aromatic peaks (H6e7) at
7.89e7.47 ppm and a proton peak (H12) in the benzyl position at
2.48 ppm. In addition, the appearance of a proton peak (H1) on
the carbon next to the bromine at 3.43 ppm and a proton peak
(H5) on the carbon next to the carbonyl groups at 2.96 ppm can
all be attributed to bromohexanoyl groups and further
confirmed the successful synthesis of Br-HexeCOeSEBS 4. Not
only that, the relative integral ratio of the proton peak (H5) of
the carbon next to the carbonyl groups and the proton peak
(H1) of the carbon next to the bromine attributed to bromo-
hexanoyl groups was calculated. This calculation confirmed
that about 80 mol% of the styrene units had been functional-
ized by bromohexanoyl groups. If the functionalization degree
of bromohexanoyl groups in SEBS is not sufficiently high, it is
less likely that the desired ionic conductivity will be achieved
because insufficient functionalization leads to a reduction in
the IEC of the resultant ion-conducting polymers. For that
reason, in the present study, the functionalization degree was
set to about 80 mol% to ensure sufficient ionic conductivity and
cell performance.
Following the synthesis of Br-HexeCOeSEBS 4, penta-
fluorobenzoyl groups were introduced as a hydrophobic unit
into the aromatic unit of SEBS that had not been functional-
ized with bromohexanoyl groups. As a result, fluorinated ar-
omatic proton (H16e17) peaks appeared at 7.89e7.47 ppm, and
these peaks overlapped with the acylated aromatic proton
(H6,7) peaks of Br-HexeCOeSEBS 4. In addition, a benzylic
proton (H19) peak attributed to the newly appeared fluorinated
aromatic unit at 2.96 ppm appeared in the down-field range
compared to the benzylic proton peak (H12) of Br-
HexeCOeSEBS 4 at 2.48 ppm, and this confirmed the suc-
cessful synthesis of Br-Hex-F5-CO-SEBS 3. Here, the fluori-
nated aromatic benzylic proton (H19) peak overlapped with the
H5 peak of the carbon next to the carbonyl groups of Br-
HexeCOeSEBS 4. The functionalization degree of the penta-
fluorobenzoyl groups was determined by calculating the
relative integral ratio of the H1 peak and the H5,19 peak
attributed to both the bromohexanoyl and pentafluorobenzoyl
groups in Br-Hex-F5-CO-SEBS 3 and the relative integral ratio
of the H1 peak and the H5 peak in Br-HexeCOeSEBS 4 and
estimating the difference between the two ratios. Based on
this result, it was confirmed that about 10 mol% of the styrene
units in SEBS had been functionalized by pentafluorobenzoyl
groups. In the 19F NMR spectrum of Br-Hex-F5-CO-SEBS (3),
three aryl-F peaks were observed at 140, 152, and
160 ppm, respectively, confirming the above result (Fig. S1c).
Finally, after the reduction process was completed, the H5
peak shifted in the up-field direction to about 2.5 ppm,
resulting from the reduction of carbonyl groups, and a
benzylic H5’ signal appeared in place of the carbonyl group
peak. Similarly, the benzylic peak (H19) of the fluorinated ar-
omatic unit also shifted up-field to 2.5 ppm due to the
reduction of the aromatic unit conjugated with penta-
fluorobenzoyl groups and the carbonyl groups between the
pentafluorobenzoyl groups, which led to the formation of a
new benzylic proton peak (H19’). In the 1H NMR spectra, the
proton peak (H5) of the carbon next to the carbonyl groups at
2.96 ppm and the fluorinated aromatic benzylic position pro-
ton peak (H19) in Br-Hex-F5-CO-SEBS 3 completely dis-
appeared, confirming the successful synthesis of bromohexyl-
pentafluoro-SEBS (Br-Hex-F5-SEBS 2) (Fig. S1d).
The structure of the obtained polymers at each synthesis
stage was also examined using comparative FT-IR spectro-
scopic methods (Fig. S2). In Br-HexeCOeSEBS 4 and Br-Hex-
F5-CO-SEBS 3, strong absorption peaks attributed to the
carbonyl groups (-C]O) were observed between 1680 and
1600 cm1. However, these peaks completely disappeared in
Br-Hex-F5-SEBS 2, confirming that the reduction process
proceeded in a stoichiometric manner. In Br-Hex-F5-CO-SEBS
3 and Br-Hex-F5-SEBS 2 conjugated with pentafluorobenzoyl
groups, aryl-F peaks were found at 1480, 1320, and 1110 cm1,
respectively, confirming the structure.
Fabrication and characterization of the 50x-SEBS
membranes with differentcrosslinkers
Br-Hex-F5-SEBS 2 was subjected to in situ membrane-casting
and crosslinking in parallel using different crosslinkers,
including DMA, TMHA, and TDMAP, to fabricate three types of
crosslinked membranes (50x-SEBS) (Fig. 1). The molar ratio of
the Br group of Br-Hex-F5-SEBS 2 and each of the three
crosslinkers was set to 50 mol%. That is, the degree of cross-
linking was set to 50% for all three membranes. These three
crosslinkers react with Br-Hex-F5-SEBS 2 and are converted
into their corresponding quaternary ammoniums. Thus, these
three crosslinkers also serve as the ion-conducting head
groups in their respective membranes.
Next, the obtained membranes were treated with a TMA
solution to convert the remaining Br groups in Br-Hex-F5-
SEBS 2 (i.e., those that had not reacted with the crosslinker
to form tetramethyl quaternary ammonium (TQA)). Last, the
membranes were treated with a KOH solution to obtain
membranes in their hydroxide ion form (OH). The three
SEBS membranes crosslinked by different crosslinkers
(DMA, TMHA, and TDMAP) with a crosslinking degree of 50%
were named DMA-50x-SEBS, TMHA-50x-SEBS, and TDMAP-
50x-SEBS, respectively. All three crosslinked membranes
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Fig. 2 e Photographs of crosslinked 50x-SEBS membranes 1 with different crosslinkers.
were in the form of a flexible film with a thickness of
35e40 mm (Fig. 2).
The structural analysis of the three crosslinked mem-
branes (50x-SEBSs) was performed using gel fraction analysis,
FT-IR spectroscopy, and XPS. First, gel fraction analysis was
performed to indirectly evaluate the degree of crosslinking. All
three membranes were found to have a high gel fraction, i.e.,
98.54% for DMA-50x-SEBS, 98.26% for TMHA-50x-SEBS, and
98.08% for TDMAP-50x-SEBS (Table S1).
In the FT-IR spectra of all three membranes, a strong CeH
stretching peak (2920e2850 cm1) attributed to hydrocarbons,
a CeH bending peak (1738 cm1) attributed to the aromatic
unit of SEBS, a peak attributed to the pentafluoro groups
(1480e1460 cm1), and a CeN stretching peak (at 1625 cm1)
appeared due to crosslinking, as shown in Fig. S3.
Finally, the crosslinking degree of the three crosslinked
membranes (50x-SEBSs) was examined using XPS, as shown
in Fig. S4a. The Br atom contained in the bromohexanoyl
group of Br-Hex-F5-SEBS 2 is in a CeBr bond and has a binding
energy of 68.8 eV. However, after the conversion into quater-
nary ammoniums, Br remains in an ionic state (NþBr) and
has a lower binding energy of 66.28 eV. The area ratio of the
two peaks corresponding to these two types of Br was calcu-
lated. The results showed that the peak area ratios of the two
types of Br (CeBr and NþBr) were about 47:53, 51:49, and 52:48
for DMA-50x-SEBS, TMHA-50x-SEBS, and TDMAP-50x-SEBS,
respectively, indicating that the target crosslinking degree of
50 mol% was achieved in all three membranes. To replace the
remaining bromide in the crosslinked 50x-SEBS with quater-
nary ammonium (QA), the 50x-SEBS membranes were further
immersed in a TMA solution. The XPS analyses of the 50x-
SEBS membranes were then analyzed, which confirmed that
the quaternarization was complete by showing that the Br
peak at 68.8 eV, corresponding to the CeBr, completely dis-
appeared after TMA treatment (Fig. S4b).
Analysis of hydrogen bonding
Among the 50x-SEBS membranes, TMHA-50x-SEBS, which
used TMHA as a crosslinker, was unique in that hydroxy (OH)
groups were present, which provides sites for hydrogen bonds
in addition to the crosslinking of the polymer chains. For
verification, the three crosslinked membranes (50x-SEBSs)
24185
were immersed in deionized water and then dried at 50% RH.
Then, FT-IR spectroscopy was performed on the membranes,
as shown in Fig. 3. In DMA-50x-SEBS and TMHA-50x-SEBS, an
OeH stretching peak attributed to the water absorbed by the
membrane was observed near 3404 cm1. In TDMAP-50x-
SEBS, however, the corresponding peak shift to 3346 cm1.
This result confirmed the formation of additional hydrogen
bonds between the crosslinker TDMAP and water in TDMAP-
50x-SEBS [59].
In addition, the density of the 50x-SEBS membranes was
measured under dry and wet conditions, as summarized in
Table S2. The measured density increased in the order DMA-
50x-SEBS < TMHA-50x-SEBS < TDMAP-50x-SEBS for both dry
and wet conditions. TDMAP-50x-SEBS exhibited a higher
density than DMA-50x-SEBS and TMHA-50x-SEBS because the
membrane not only interacted with water but also induced
each polymer component to interact through hydrogen bonds.
Next, the interactions among the water, hydroxide ions,
and each conducting group were confirmed using radial dis-
tribution function (RDF) methods based on molecular dy-
namics (MD) simulations (Fig. 4). The results showed that,
with regard to the interaction between each conducting group
Fig. 3 e FT-IR spectra of DMA-50x-SEBS (black), TMHA-50x-
SEBS (blue) and TDMAP-50x-SEBS (red). (For interpretation
of the references to color in this figure legend, the reader is
referred to the Web version of this article.)
24186 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Fig. 4 e Radial distribution functions (RDFs) of (a) cationic groups with H2O and (b) cationic groups with OH¡ of the 50x-SEBSs
membranes.
and water, only two relevant peaks (4.6
A and 6.0
A) were
observed in TMHA-50x-SEBS and DMA-50x-SEBS, while, in
TDMAP-50x-SEBS, three relevant RDF peaks (1.7
A, 4.6

A, and
6.0

A) were observed, as shown in Fig. 4a. In the RDF analysis
method, peaks corresponding to non-covalent bonding in-
teractions, including hydrogen bonding, appear at 1.6e2.9
A,
while peaks attributed to electrostatic interactions are
observed at 4.0
A or higher [33,59].
The same tendency was also found in the RDF results
regarding the interaction between each conducting group and
hydroxide ions (Fig. 4b). In TDMAP-50x-SEBS, in which OH
groups were present, a total of three RDF peaks corresponding
to hydrogen bonding interactions (1.3e3.2
A), ionic in-
teractions (4.6

A), and electrostatic interactions (5.7
A) were
observed in TDMAP-50x-SEBS. Meanwhile, in TMHA-50x-SEBS
and DMA-50x-SEBS, only one RDF peak corresponding to
electrostatic interactions (at 5.7

A) was observed [33,36]. These
results further confirmed that TDMAP, which contained OH
groups, unlike DMA and TMHA, induced the formation of
stronger hydrogen bonds between water and hydroxide ions.
The interactions ‘between each conducting group and hy-
droxide ions’ and ‘between each conducting group and water’
were expected to induce hydroxide ions to form not only a
hydrogen bonding network but also a hydrophilic area or an
ion-conducting channel through ionic interactions. Therefore,
TDMAP-50x-SEBS was expected to exhibit improved
morphology and ionic conductivity.
IEC, WU, and swelling ratio
The IEC of a polymer is defined as the milliequivalent of the
number of ion-conducting head groups per unit mass of the
polymer. The IEC is one of the major factors that affect the
overall physical, chemical, and electrochemical properties of
AEMs, including the WU and ionic conductivity.
The theoretical IEC of the three crosslinked membranes
(50x-SEBSs) was calculated based on the number of moles of
bromine groups calculated from the relative integral ratio of
the H5 signal and the H12 signal in the 1H NMR spectra of Br-
Hex-F5-SEBS 2 as a precursor polymer, as well as the total
mass of the polymer and crosslinker used (Br-Hex-F5-SEBS 2
and either DMA, TMHA, or TDMAP). The results showed that
the theoretical IECs of DMA-50x-SEBS, TMHA-50x-SEBS, and
TDMAP-50x-SEBS were 2.29, 2.14, and 2.13 meq g1,
respectively.
Next, the IECs of the three 50x-SEBS membranes 1 were
experimentally measured using back titration. The results
showed that the experimental IECs of DMA-50x-SEBS, TMHA-
50x-SEBS, and TDMAP-50x-SEBS were 2.25, 2.12, and 2.11 meq
g1, respectively (Table 1). The theoretical and experimental
IEC values were very close to each other in all 50x-SEBS
membranes 1, and these results indirectly confirm that the
target degree of crosslinking of about 50 mol% was achieved in
all three crosslinked SEBS membranes, in agreement with the
XPS data.
In general, in WE, water serves as a medium to conduct
hydroxide ions; thus, the higher the IEC of an AEM is, the
greater its WU becomes. Therefore, higher ionic conductivity
can be achieved [25,28,32]. An excessively high WU, however,
causes over-swelling, leading to degradation in the mechani-
cal and physical properties of the membrane, as well as a
further reduction in the ionic conductivity due to the dilution
effect [18,24]. Therefore, it is important to appropriately adjust
the IEC of AEMs to maintain their WU at a suitable level,
thereby achieving high ionic conductivity and excellent me-
chanical properties.
Pure SEBS-based AEMs exhibit relatively high WU and SR
compared to AEMs based on aromatic polymer backbones due
to their elastic aliphatic chains. The present study used three
different types of crosslinkers to fabricate SEBS-based cross-
linked polymer membranes. These crosslinkers were ex-
pected to contribute to not only reducing the excessive WU
attributed to the elastic nature of SEBS but also further
improving mechanical properties.
The WU and SR of the three 50x-SEBS membranes 1 were
measured at 20  C and 80  C (Table 1). The WU of DMA-50x-
SEBS, TMHA-50x-SEBS, and TDMAP-50x-SEBS were 133.7%,
36.0%, and 54.3% at 20  C and 186.4%, 61.8%, and 71.3% at 80  C,
respectively. Notably, DMA-50x-SEBS with DMA used as a
crosslinker exhibited a significantly higher WU than TMHA-
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Table 1 e Ion exchange capacity (IEC), water uptake (WU), and swelling ratio (SR) of the 50x-SEBS membranes with different
crosslinkers.
Membrane IEC (meq g1) Water uptake (%)
 
The a
Exp b
20 C 80 C
DMA-50x-SEBS 2.29 2.25 133.7 186.4
±0.02
TMHA-50x-SEBS 2.14 2.12 36.0 61.8
±0.02
TDMAP-50x-SEBS 2.13 2.11 54.3 71.3
±0.02
a
Theoretical values calculated based on 1H NMR spectra.
b
Experimental values obtained by back titration.
50x-SEBS and TDMAP-50x-SEBS. Furthermore, the SR of DMA-
50x-SEBS was over three times higher than those of TMHA-
50x-SEBS and TDMAP-50x-SEBS at both 20  C and 80  C
(Table 1). In contrast, TDMAP-50x-SEBS exhibited relatively
low WU and SR. This was attributed to the combination of the
phenolic crosslinker, which resulted in reduced flexibility
compared to the aliphatic chain-based crosslinkers, with the
hydrogen bonds formed by the OH groups [33,59]. TMHA-50x-
SEBS exhibited the lowest WU among the three 50x-SEBS
membranes. This was attributed to the aliphatic chains
(hexyl, C6) in its crosslinker, which led to significantly
increased hydrophobicity.
Mechanical and thermal properties
The thermal stability of the 50x-SEBS membranes was deter-
mined using TGA and DSC (Fig. S5). In the TGA curves, weight
loss from thermal degradation occurred in three stages
(Fig. S5a). The first weight loss occurred below 100  C, attrib-
uted to the evaporation of the solvents or water remaining in
the membrane. Here, the degree of weight loss was found to
increase as the WU of each membrane measured at 20  C
increased (i.e., in the order TMHA-50x-SEBS < TDMAP-50x-
SEBS < DMA-50x-SEBS). The second weight loss was attributed
to the degradation of the QA, which corresponds to the
portion of the crosslinker that has been converted into con-
ducting head groups. The degradation temperature varied
slightly depending on the crosslinker used. Based on the de-
rivative thermogravimetry (DTG) curves, the degradation
temperature of each conducting head group was analyzed in
more detail. The degradation temperatures of the conducting
head groups of DMA-50x-SEBS, TMHA-50x-SEBS, and TDMAP-
50x-SEBS were 249  C, 260  C, and 257  C, respectively. Finally,
the third weight loss occurred from 450 to 500  C, which was
attributed to the degradation of the polymer backbone of the
50x-SEBS membranes.
DSC was further performed in the temperature range of
0e140  C, and no significant Tg (glass transition temperature)
peaks were observed within this temperature range in any of
the 50x-SEBS membranes (Fig. S5b). In general, SEBS triblock
copolymers exhibit two different thermal transitions: one
with a Tg of 50  C, attributed to the polyethylene-based SEBS
backbone as an amorphous segment, and one with a Tg of
60  C, attributed to the polystyrene unit as a hard segment
[47,60]. In contrast, in 50x-SEBSs, no Tg peaks were observed,
even in the temperature range above the Tg of the polystyrene
24187
Swelling ratio (%)
 
20 C (Dl) 80 C (Dl) 20  C (Dt) 80  C (Dt)
28.9 30.3 18.6 27.9
5.3 12.7 5.8 9.7
9.0 16.7 6.7 13.0
segment, indicating that the introduction of fluorine groups
into SEBS led to increased hydrophobicity, which, combined
with their crosslinked structure, resulted in enhanced thermal
stability. This suggests that the developed membranes would
be thermally stable from 60 to 80  C, the typical operating
temperature range of WE.
In WE, an AEM is supposed to serve not only as an elec-
trolyte to effectively conduct hydroxide ions but also as a
separator between the anode and cathode. Thus, it is also
important for an AEM to suppress hydrogen and oxygen
crossover, in which the hydrogen generated on the cathode
side crosses to the anode side or the oxygen generated on the
anode side crosses to the cathode side during WE [4,11,13].
When a high voltage is applied during AEMWE, hydrogen
crossover may occur, in which H2 generated on the cathode
side crosses to the anode side, which may degrade the overall
cell performance [8,11]. Therefore, when used as a separator,
AEMs should be highly thermally stable and provide excellent
mechanical stability and low hydrogen permeability.
In the present study, the stressestrain curves of the three
50x-SEBS membranes were measured at 50% RH to evaluate
and compare their mechanical properties. The results
confirmed that the tensile stress of TDMAP-50x-SEBS was
relatively high at about 18 MPa, although it is an elastic SEBS-
based polymer membrane (Fig. 5a). This is attributed to the
phenolic structure of the crosslinker, which causes the for-
mation of additional hydrogen bonds, as previously confirmed
by the FT-IR spectra measured at 50% RH. This additional
physical crosslinking effect accounts for the superiority of
TDMAP-50x-SEBS to the other two membranes in terms of
stress. DMA-50x-SEBS exhibited a low tensile stress of
12.3 MPa, which was attributed to its high WU, leading to
plasticization effects. Meanwhile, the strains of the three 50x-
SEBS membranes showed the opposite tendency to their
tensile stresses. The strain was found to increase in the order
TDMAP-50x-SEBS (56%) < TMHA-50x-SEBS (89%) < DMA-50x-
SEBS (115%), and this tendency was attributed to the plasti-
cization effect of water.
The Young's modulus of the 50x-SEBS membranes were
compared with those of SEBS membranes with enhanced
hydrophobicity [40,42,44] and SEBS-based crosslinked mem-
branes [40,43,45] reported in the literature (Fig. 5b). The three
50x-SEBS membranes exhibited significantly higher Young's
modulus than the SEBS membranes with enhanced hydro-
phobicity (squares, Fig. 5b) and SEBS-based crosslinked
membranes (circles, Fig. 5b). TDMAP-50x-SEBS exhibited
24188 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Fig. 5 e (a) Stressestrain curves of the 50x-SEBS membranes measured at 50% RH and (b) Young's modulus of the 50x-SEBS
membranes in comparison with various SEBS AEMs with enhanced hydrophobicity [40,42,44] and SEBS-based crosslinked
AEMs [40,43,45].
excellent mechanical properties; its tensile strength and
Young's modulus were over three times greater than those of
the existing SEBS-based membranes and crosslinked AEMs.
The hydrogen permeability of the three 50x-SEBS mem-
branes was measured. The hydrogen permeability was found
to decrease sharply in the order DMA-50x-SEBS (30.3
barrer) > TMHA-50x-SEBS (21.6 barrer) > TDMAP-50x-SEBS
(10.4 barrer) (Fig. S6). TMHA-50x-SEBS exhibited a hydrogen
permeability about two times lower than that of DMA-50x-
SEBS due to the entanglement of aliphatic chains (hexyl, C6)
of the crosslinker [29]. TDMAP-50x-SEBS exhibited the lowest
permeability due to its well-packed polymer chains, which
result from the hydrogen bonds of the OH groups [37,55,59].
The 50x-SEBS membranes were fabricated by introducing
three different crosslinkers into SEBS with enhanced hydro-
phobicity, and the above results confirmed their superiority in
terms of thermal and mechanical stability and low hydrogen
permeability. Notably, TDMAP-50x-SEBS achieved the best
performance because of its additional hydrogen bonds.
Morphological analysis
The morphology of the three 50x-SEBS membranes was
analyzed and compared using AFM, transmission electron
microscopy (TEM), and X-ray diffraction (XRD) analysis.
First, AFM surface images of the 50x-SEBS membranes
were obtained at 50% RH and compared, especially with
respect to the formation and distribution of ion channels
(Fig. 6aec). In all of the 50x-SEBS membranes, clear phase
separation was observed between dark hydrophilic areas with
a dark contrast and bright hydrophobic areas.
In DMA-50x-SEBS, the hydrophilic area was greater than
the hydrophobic area because of its high WU, but it was
difficult to determine whether ion channels had formed. In
TMHA-50x-SEBS, the ion channels were more connected than
in DMA-50x-SEBS, but no clear phase separation was
observed. In contrast, in TDMAP-50x-SEBS, well-developed
ion channels were observed throughout the matrix, showing
clear phase separation, despite its low WU. These results were
attributed to the structure of the crosslinker (or ion-
conducting head group) used; unlike DMA and TMHA,
TDMAP contains an additional hydroxy group, thereby
enhancing the interaction between water and the membrane
through hydrogen bonds [18,22,50].
Meanwhile, the morphology of an AEM in water is more
relevant to the actual performance of AEMWE than the
morphology at 50% RH. However, the AFM instrument did not
allow measurements in water, and thus, AFM surface images
of the 50x-SEBS membranes were obtained while they were
holding as much water as possible. To this end, the mem-
branes were immersed in water at 20  C and then dried at RT
before their morphology was studied. This way, morphological
analysis was conducted at conditions similar to the actual
operating conditions of WE. The results were compared with
those obtained from the membranes that had not been treated
with water (Fig. 6aec). In all three 50x-SEBS membranes, an
improvement in morphology was observed. More specifically,
in TMHA-50x-SEBS, the connection of the ion channels was
more pronounced after immersion in water (Fig. 6e), but there
was no significant difference in the size of the ion channels
with or without water treatment (Fig. 6b). In DMA-50x-SEBS,
however, the hydrophilic area was more pronounced after
immersion in water (Fig. 6e). This was attributed to its high
WU, which was about 3.7 times greater than that of TMHA-50x-
SEBS, leading to an enhanced interaction with a larger amount
of water. TDMAP-50x-SEBS showed the most significant dif-
ference in morphology due to water treatment. In this mem-
brane, well-developed ion channels were observed, showing a
more pronounced phase separation compared to the other two
membranes with different crosslinkers, i.e., DMA-50x-SEBS
and TMHA-50x-SEBS (Fig. 6f). Based on these results, TDMAP-
50x-SEBS was expected to exhibit the best cell performance
in water, the condition in which WE typically operates.
The morphology of the 50x-SEBS membranes was further
analyzed using TEM surface image analysis. In all of the 50x-
SEBS membranes, a uniform surface was observed with no
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5 24189

Fig. 6 e (aec) AFM surface images of the membranes at 50% RH, (def) AFM surface images at 50% RH and dry conditions after
being treated with water at 20  C for 24 h, and (gei) TEM surface images: (a, d, and g) DMA-50x-SEBS; (b, e, and h) TMHA-50x-
SEBS; and (c, f, and i) TDMAP-50x-SEBS.

defects. The connection of ion clusters became more pro-
nounced in the order DMA-50x-SEBS < TMHA-50x-SEBS <
TDMAP-50x-SEBS. This result was consistent with the ten-
dency observed in the AFM results (Fig. 6gei).
Next, small-angle X-ray scattering (SAXS) of the 50x-SEBS
membranes was measured using XRD to examine and compare
the size and distribution of ion clusters in each membrane
(Fig. 7 and Table S3). DMA-50x-SEBS and TMHA-50x-SEBS
exhibited a single q value at 0.1459

A1. Using Bragg's law, the
q value was converted into a d-spacing of about 4.31 nm. In
these two membranes, ion clusters with a d-spacing of 4.31 nm
were formed. In contrast, in TDMAP-50x-SEBS, which had the
most pronounced phase separation, as confirmed in the AFM
and TEM results, two additional peaks were observed at
7.01 nm and 13.17 nm. A total of three ion cluster peaks, cor-
responding to 1q, 1.89q, and 3.07q, were observed, and this
confirmed that TDMAP-50x-SEBS exhibited the most pro-
nounced phase separation. This separation was attributed to
the hydrogen bonding arising from the phenolic structure of its
crosslinker, which led to increased hydrophilicity. This resul-
ted in the formation of well-developed ionic channels, and this
effect, combined with the enhanced interaction with neigh-
boring water, led to significantly enhanced phase separation.
Hydroxide ion conductivity
In WE, hydrogen (H2) is generated in the cathode while the
hydroxide ions (OH) generated in the cathode move to the
24190 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
Fig. 7 e Small-angle X-ray scattering (SAXS) profiles of the 50x-SEBS membranes with different crosslinkers.
anode. Thus, ionic conductivity is one of the most important
factors in determining the overall cell performance of AEMWE
[28,31,61,62]. In the present study, the hydroxide ion conduc-
tivity of the three 50x-SEBS membranes was measured in
water at 20e80  C to examine their ionic conductivity with
respect to the type of crosslinker (or ion-conducting head
group) used (Table 2).
The hydroxide ion conductivity increased in the order
TMHA-50x-SEBS < DMA-50x-SEBS < TDMAP-50x-SEBS.
TDMAP-50x-SEBS exhibited the highest ionic conductivity,
31.8e109.9 mS cm1, while the TMHA-50x-SEBS exhibited the
lowest ionic conductivity, 31.0e92.1 mS cm1 (Table 2). How-
ever, given the difference in the IEC between the three AEMs,
the normalized conductivity was further estimated to exclude
the effect of variation in the IEC (Fig. 8a). The results showed
that TDMAP-50x-SEBS exhibited the highest ionic conductiv-
ity in both absolute and normalized terms. This was attributed
to its well-developed morphology, which arose from its
enhanced interaction with water, as confirmed by the AFM
and TEM results [33,52].
In addition, the conductivities of the 50x-SEBS membranes
normalized to their IEC levels were compared with those of
existing SEBS-based membranes [39e42,44], SEBS-based
Table 2 e Hydroxide ion conductivity in water of the 50x-
SEBS membranes at different temperatures.
Membrane OH Conductivity (mS cm1)
20  C 40  C 60  C
DMA-50x-SEBS 31.0 ± 0.24 49.8 ± 0.13 70.0 ± 0.47 93.6 ± 0.52
TMHA-50x-SEBS 27.1 ± 0.16 49.1 ± 1.08 69.8 ± 0.16 92.1 ± 0.24
TDMAP-50x-SEBS 31.8 ± 0.17 52.0 ± 0.57 70.2 ± 0.57 109.9 ± 0.80
crosslinked membranes [38,40,45e48], and commercial poly-
mer membranes, including Fumatech FAA-3 [15], as shown in
Fig. 8b. All three of the 50x-SEBS membranes exhibited higher
normalized conductivity than the existing SEBS-based mem-
branes (blue dotted box), SEBS-based crosslinked membranes
(red dotted box), and commercial polymer membranes (black
dotted box). TDMAP-50x-SEBS exhibited the highest normal-
ized conductivity even though its IEC was the lowest among
the three 50x-SEBS membranes at 2.11 meq g1.
Next, the ionic conductivity of the 50x-SEBS membranes
measured in the temperature range of 20e80  C was plotted as
a function of the hydration number (l), shown in Fig. S7. As
discussed above, water also serves as a medium for ion con-
duction, and, thus, the larger the l of an AEM, the more water
molecules bound to each conducting head group, and the
more efficient its ionic conduction is [17,54].
In the present study, although the hydration number of
TDMAP-50x-SEBS was smaller than that of DMA-50x-SEBS,
TDMAP-50x-SEBS exhibited the highest conductivity at high
temperatures (80  C). The most efficient ionic conduction
occurred in TDMAP-50x-SEBS. In contrast, DMA-50x-SEBS,
which had the largest l value, showed lower ionic conduc-
tivity than TDMAP-50x-SEBS for all temperature conditions.
This was attributed to the overhydrated state of DMA-50x-
SEBS, which led to dilution effects and reduced its ionic con-
duction efficiency [18,24].
Chemical stability
80  C The alkaline stability of the three 50x-SEBS membranes was
examined as follows. While each membrane was immersed in
a 2 M KOH solution at 80  C for 864 h, its ionic conductivity and
IEC were measured at certain intervals to determine how they
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5 24191

Fig. 8 e (a) Normalized conductivity vs. temperature of the 50x-SEBS membranes in water and (b) comparison of IEC vs.
normalized conductivity of the 50x-SEBS membranes with those of representative membranes from the literature
[15,38e42,44e48].

changed over time (Fig. 9). Furthermore, their structure was
compared before and after the 864-h treatment based on their
FT-IR spectra (Fig. S8).
First, the ionic conductivities of the three membranes after
864 h were 93.3%e96.1% of their respective initial levels.
TMHA-50x-SEBS exhibited the highest conductivity retention
at 96.1% (Fig. 9a). The IEC retention of all the membranes after
864 h was in the range of 94.7%e98.4%. TMHA-50x-SEBS
exhibited the highest IEC retention at 98.4% (Fig. 9b). Overall,
the ionic conductivity and IEC retention tests confirmed that
the alkaline stability decreased in the order TMHA-50x-
SEBS > TDMAP-50x-SEBS > DMA-50x-SEBS. This tendency can
be explained by the morphology analysis discussed above.
More specifically, the degree of morphological development
was determined by the type of crosslinker (or ion-conducting
head group) used; the higher the degree of morphological
development was, the more effectively the AEM could
suppress chemical degradation by OH ions in alkaline con-
ditions [17,63]. Although TDMAP-50x-SEBS contained benzylic
positions, which are known to be the most vulnerable to
degradation by OH ions, the membrane exhibited similar
stability to TMHA-50x-SEBS; the difference was only 0.6%. The
conductivity retentions of TMHA-50x-SEBS and TDMAP-50x-
SEBS after 864 h were 96.1% and 95.5%, respectively. The IEC
retention of TDMAP-50x-SEBS was also very similar to that of
TMHA-50x-SEBS, with a difference of only 0.5%. This was
attributed not only to the improved alkaline stability of
TDMAP-50x-SEBS, which resulted from the introduction of a
crosslinked structure, but also to the additional hydrogen
bonds formed by TDMAP as a crosslinker, which led to the
most pronounced phase separation and hence enhanced
chemical resistance [18,21].
After the alkaline stability test was completed, FT-IR
spectral analysis was performed to examine changes in the
polymer structure (Fig. S8). The FT-IR analysis results showed
no significant structural change after the stability test in
TMHA-50x-SEBS and TDMAP-50x-SEBS. However, in DMA-
50x-SEBS, which had the lowest alkaline stability, the peak

Fig. 9 e (a) Hydroxide ion conductivity retention measured at 20  C and (b) IEC retention after treatment with 2 M KOH at
80  C of the 50x-SEBS membranes.
24192 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
corresponding to CeN stretching at 1630 cm1 slightly
decreased in intensity after the stability test. This confirmed
that some of the conducting head groups had been degraded
by OH ions [38,44].
Overall, after being treated in a 2 M KOH solution at 80  C
(i.e., alkaline conditions), none of the 50x-SEBS membranes
showed any significant changes in their ionic conductivity and
IEC compared to the initial levels. Such enhanced alkaline
stability was attributed to the introduction of the fluorine unit
into the SEBS with a non-aryl-ether backbone structure, which
led to improved hydrophobicity [44], combined with the effect
of crosslinking [40,46], which increased the alkaline stability
of its main polymer backbone and conducting head groups.
Meanwhile, the phase separation behavior of the 50x-SEBS
membranes also improved their chemical stability [21].
Next, Fenton's tests were conducted at 60  C for 120 h to
evaluate the oxidative stability of the three 50x-SEBS mem-
branes (Fig. S9a). The results showed that the weight retention
of DMA-50x-SEBS, TMHA-50x-SEBS, and TDMAP-50x-SEBS
after 120 h was 83.3%, 92.1%, and 90%, respectively. DMA-
50x-SEBS exhibited a relatively large weight loss compared to
TMHA-50x-SEBS and TDMAP-50x-SEBS. This tendency was
further confirmed by the color change observed in each
membrane after the 120-hr oxidative stability test (Figs. S9beg).
As expected, the most pronounced color change was observed
in DMA-50x-SEBS. Based on these results, DMA-50x-SEBS was
degraded the most by the radicals generated at oxidative sta-
bility test conditions. The other two crosslinked membranes
(i.e., TMHA-50x-SEBS and TDMAP-50x-SEBS) exhibited rela-
tively high oxidative stability in the same conditions.
In general, membranes with a more pronounced phase
separation exhibit higher oxidative stability [29,63]. Therefore,
the low oxidative stability of DMA-50x-SEBS is attributed to its
poor phase separation, previously confirmed by the TEM
surface analysis results. In the case of the TDMAP-50x-SEBS,
even though it has a phenolic group with an easily oxidiz-
able structure [64,65], this membrane showed similar stability
to that of the TMHA-50x-SEBS because of its well-developed
phase separation.
Fig. 10 e AEMWE single-cell performance of FAA-3-50,
TMHA-50x-SEBS, and TDMAP-50x-SEBS measured in a 1 M
KOH solution at a cell temperature of 70  C.
Table 3 e Comparison of AEMWE single-cell performance
at 1.8 and 2.0 V for TMHA-50x-SEBS, TDMAP-50x-SEBS,
and FAA-3-50.
Membrane TMHA-50x-SEBS TDMAP-50x-SEBS FAA-3-50
Current 706 (1.8 V) 740 (1.8 V) 701 (1.8 V)
density 1107 (2.0 V) 1190 (2.0 V) 946 (2.0 V)
[mA cm2]
Single-cell performance test
AEMWE single-cell tests were performed using the developed
AEMs (Fig. 10). The cell performance of the 50x-SEBS mem-
branes was measured in a 1 M KOH solution at 70  C. The
DMA-50x-SEBS membrane exhibited excessive swelling,
which hinders building a stable MEA using the membrane.
Therefore, only TMHA-50x-SEBS and TDMAP-50x-SEBS were
used to fabricate MEAs for AEMWE single-cell tests.
The results showed that, at 1.8 V, TDMAP-50x-SEBS
exhibited the highest performance at 740 mA cm2, slightly
higher than that of TMHA-50x-SEBS at 706 mA cm2 (Fig. 10
and Table 3). This result was consistent with the trend pre-
viously observed in the morphological analysis and ionic
conductivity results; TDMAP-50x-SEBS, with the most pro-
nounced phase separation and ionic conductivity, exhibited
the highest cell performance.
The WE performance of the 50x-SEBS membranes was
then compared with that of a single cell based on FAA-3-50, a
commercial AEM material, measured in the same conditions
as in the present study. The single-cell performance of the
FAA-3-50 membranes showed higher voltages than 50x-SEBS
membranes in the low current density region (below 1.8 V).
However, this was reversed in the high current density region
(above 1.8 V). This result was attributed to the low ion con-
ductivity of the FAA-3-50 membrane (80.4 mS cm1 at 80  C),
that is, the ohmic resistance has a dominant effect on the
single cell performance above 1.7 V [66].
Finally, the WE performance of TMHA-50x-SEBS and
TDMAP-50x-SEBS was compared with those of existing com-
mercial AEMs reported in the literature (Fig. S10) [11,13e15].
Given that the cell performance of AEMWE varies depending
on a range of parameters, including catalyst loading, ionomer
type, temperature, and flow rates, it is difficult to compare the
performance of individual AEMs in an absolute manner.
However, TMHA-50x-SEBS and TDMAP-50x-SEBS exhibited
cell performance equivalent or superior to some commercial
AEMs reported in the literature, although their catalyst
loading was lower. In the present study, TMHA-50x-SEBS and
TDMAP-50x-SEBS were developed by crosslinking SEBS with
enhanced hydrophobicity using TMHA and TDMAP as a
crosslinker, respectively, and the major findings of the present
study demonstrate their applicability as AEMWE materials.
Conclusion
Crosslinked membranes (50x-SEBS) were prepared to be used
as new AEM materials for AEMWE using three types of
crosslinking agents (DMA, TMHA, and TDMAP) on the bro-
mohexyl pentafluorobenzyl SEBS. In particular, using a
 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 8 ( 2 0 2 3 ) 2 4 1 8 0 e2 4 1 9 5
TDMAP crosslinking agent containing an OH group in its
structure induced an additional physical crosslinking through
intermolecular hydrogen bonds. As a result, the TDMAP-
functionalized SEBS membrane, TDMAP-50x-SEBS, showed
very high mechanical properties, with a tensile stress of
18 MPa and Young's modulus of 165 MPa, the highest among
the three 50x-SEBS membranes. In addition, the TDMAP-50x-
SEBS membrane showed the best phase separation due to
the interaction between the OH group of the crosslinker and
water, resulting in the highest normalized conductivity
despite having the lowest IEC value among the three types of
50x-SEBS membranes. That is, the highest ion conduction
efficiency was achieved by the hydrogen bonding induced by
the crosslinking agent, and MD simulation results confirmed
the interaction between the crosslinking agent and water.
All three 50x-SEBS membranes showed good alkaline sta-
bility (retaining more than 93% conductivity in 2 M KOH so-
lution at 80  C) because chemical crosslinking was introduced
to the polymer structure by introducing fluorine groups onto
the non-aryl ether type SEBS. In particular, the TMHA-50x-
SEBS and TDMAP-50x-SEBS membranes also exhibited good
oxidation stability (more than 90% of retained weight at 60  C
for 120 h), which was attributed to the excellent phase sepa-
ration of these membranes.
Among the three developed crosslinked SEBS-based
membranes, TMHA-50x-SEBS and TDMAP-50x-SEBS showed
high AEMWE single-cell performance with current densities of
706 mA cm2 and 740 mA cm2, respectively, at 1.8 V. This is
comparable or superior to the commercially available FAA-3-
50 (701 mA cm2 at 1.8 V) under the same conditions.
Overall, we successfully demonstrated the applicability of
a strategy to induce interaction with water or OH along with
physical crosslinking between molecules by introducing OH
groups in crosslinked SEBS with enhanced hydrophobicity.
This strategy developed a new AEM material for AEMWE with
excellent mechanical properties, physicochemical stability,
high conductivity, and good cell performance.
Notes
The authors declare no competing interests.
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.
Acknowledgment
This work was supported by the Industrial Strategic Tech-
nology Development Program(20015599) funded By the Min-
istry of Trade, Industry and Energy. Part of this work was also
supported by the Core Research Institute(CRI) Program, the
Basic Science Research Program through the National
Research Foundation of Korea funded by the Ministry of Ed-
ucation (NRF-2017R1A6A1A06015181).
24193
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2023.03.143.
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