polymers

Article
Anion Exchange Membrane Based on Sulfonated Poly
(Styrene-Ethylene-Butylene-Styrene) Copolymers
Hye-Seon Park and Chang-Kook Hong *

Polymer Energy Materials Laboratory, School of Chemical Engineering, Chonnam National University,
Gwangju 61186, Korea; [email protected]
* Correspondence: [email protected]

Abstract: Sulfonated poly(styrene-ethylene-butylene-styrene) copolymer (S-SEBS) was prepared as

an anion exchange membrane using the casting method. The prepared S-SEBS was further modified
with sulfonic acid groups and grafted with maleic anhydride (MA) to improve the ionic conducting
properties. The prepared MA-grafted S-SEBS (S-SEBS-g-MA) membranes were characterized by
Fourier transform infrared red (FT-IR) spectroscopy and dynamic modulus analysis (DMA). The
morphology of the S-SEBS and S-SEBS-g-MA was investigated using atomic force microscopy
(AFM) analysis. The modified membranes formed ionic channels by means of association with the
sulfonate group and carboxyl group in the SEBS. The electrochemical properties of the modified
SEBS membranes, such as water uptake capability, impedance spectroscopy, ionic conductivity, and
ionic exchange capacity (IEC), were also measured. The electrochemical analysis revealed that the
S-SEBS-g-MA anion exchange membrane showed ionic conductivity of 0.25 S/cm at 100% relative
humidity, with 72.5% water uptake capacity. Interestingly, we did not observe any changes in their
mechanical and chemical properties, which revealed the robustness of the modified SEBS membrane.





 Keywords: SEBS; membrane; maleic anhydride; water uptake; impedance spectroscopy; ionic con-
Citation: Park, H.-S.; Hong, C.-K. ductivity
Anion Exchange Membrane Based on
Sulfonated Poly (Styrene-Ethylene-
Butylene-Styrene) Copolymers.
Polymers 2021, 13, 1669. https:// 1. Introduction
doi.org/10.3390/polym13101669
The use of renewable energy sources, such as proton exchange membrane fuel cells
(PEMFC), is currently growing significantly owing to their environmental, social and
Academic Editor: Incoronata Tritto
economic benefits [1,2]. The conventional renewable energy sources, such as solar and
wind, are intermittent and often unpredictable due to their dependency on the weather
Received: 10 March 2021
Accepted: 18 May 2021
conditions. These characteristics limit the degree to which utilities can rely upon them, and
Published: 20 May 2021
currently such renewable energy alternatives comprise a small percentage of the primary
power sources on the electrical grid [3]. The need to satisfy the energy demand during
Publisher’s Note: MDPI stays neutral
periods of low energy production has inspired the development of efficient energy storage
with regard to jurisdictional claims in
systems. Recently, the redox flow battery (RFB) has attracted an enormous amount of
published maps and institutional affil- attention as a promising energy storage system for solar power, nuclear power, emergency
iations. uninterruptible power supply (UPS), and for batteries in electric vehicles. In particular,
large-scale storage systems are more beneficial as they offer a guaranteed energy supply
when using renewable energy sources over a long period. RFBs present several advantages
that makes them promising candidates for large-scale energy storage systems; they have
Copyright: © 2021 by the authors.
energy and power density, capacity which can be designed independently and easily
Licensee MDPI, Basel, Switzerland.
modified even after installation, a moderate operational temperature and a long-life, which
This article is an open access article
makes them highly reliable [3,4].
distributed under the terms and An RFB consists of electrolyte tanks from which the oxidant and reductant electrolytes
conditions of the Creative Commons are circulated by pumps, through a cell stack comprising a number of connected cells.
Attribution (CC BY) license (https:// Each cell comprises an anode and a cathode, which are separated by an ion exchange
creativecommons.org/licenses/by/ membrane (IEM). The exchange membrane has been widely used in many fields of life.
4.0/). For example, PEMFC, which includes a membrane, and two electrodes, has grown up with

Polymers 2021, 13, 1669. https://doi.org/10.3390/polym13101669 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 1669 2 of 13

huge attraction because of its simple operation and fuel availability. The PEMFCs have
attracted attention from energy devices such as portable, mobile and stationary devices,
since it helps in the effective reduction in energy shortage and environmental pollution.
The IEM will play an important role in the future of electrical energy generation, which is
considered as renewable and clean energy. In addition, the IEM facilitates an improved
conductive path between the electrolytes. Therefore, it acts as a membrane separator
by preventing cross-mixing and direct chemical reaction of the oxidant and reductant
electrolytes from the two reservoir tanks [5,6]. Notably, the ion exchange membrane is a
major determinant of redox flow batteries’ performance, highlighting the importance of an
ideal membrane [7].
Perhaps the most commercially advanced RFB industry that uses a proton-exchange
membrane is the vanadium redox-flow battery (VRFB) system [8]. An ion exchange film
is an ionic membrane that can selectively separate cations and anions and is an optional
transmission film with a functional group that can attract or repel the ions. The IEM has
selective permeability to counter-ions due to fixed ions in the actuator. This means that
the charged agonist is fixed to the membrane and selectively transmits only the counter-
ion with different charges than the agonist, and not the co-ion with the same charge as
the agonist. This is called the Donnan exclusion effect—that is, the cation exchange film
selectively permeates the cation, and the anion exchange film selectively permeates the
anion. The Donnan exclusion effect also causes an unbalanced electrochemical potential
difference between the electrolyte and ion exchange membranes, resulting in potential
differences in the boundary of the IEMs. This potential difference causes the ions to
move until both electrochemical potentials reach equilibrium, which is called the Donnan
equilibrium [9]. The most widely used polymer electrolyte membrane is the Nafion 117,
a perfluorinated cation exchange film developed by Dupont in 1968. Perfluorometer ion
exchange membranes have excellent ion conductivity, chemical stability, and dimensional
stability, but crossover occurs due to low ion selection, and above all, they are expensive.
To overcome these shortcomings, many studies are being conducted on the development
of low-cost hydrocarbon ion exchange membranes [10]. Another important reason for the
IEM study is that ion exchange capacity (IEC) will play an important role in the future of
electrical energy generation, which is considered as renewable and clean energy [8].
Earlier studies clearly demonstrated that the block copolymers provide excellent sepa-
ration properties [11–15]. The poly(styrene-ethylene-butylene-styrene) copolymer (SEBS) is
one of the promising materials for membrane separators due to its high thermal, chemical,
and tunable mechanical properties, and cost effectiveness. The SEBS tri-block polymer
has further attracted considerable interest because of its promising proton conducting
properties [16,17]. Moreover, due to its simple structure over well-known Nafion 117,
the SEBS is considered as a promising anion exchange membrane. It is well known that
the key mechanical and electrochemical properties can be tuned via composition of the
backbone, hydrocarbon versus fluorocarbons [17,18]. Generally, sulfonated copolymers are
synthesized either by a direct copolymerization method or post sulfonated technique [19].
Recently, Mohanty et al. functionalized SEBS membranes through borylation using Suzuki
coupling reactions and demonstrated IECs of ca. 2.2 mmol/g [20]. However, the maleic
anhydride (MA)-grafted SEBS membrane not yet studied. The MA has ability to enhance
the electrochemical properties of SEBS membrane due to its promising solubility properties.
Moreover, while many studies have been conducted on IEM with sulfonation of SESB,
the ionic conductivity behavior between sulfonyl and carboxyl functional group in the
ionic exchange membrane has not been carried out in previous studies. In this study,
we investigated the ionic conductivity behavior of the SEBS membrane with the help
of different sulfonyl and carboxylic groups. We synthesized a high-quality sulfonated
SEBS-grafted-MA membrane (S-SEBS-g-MA), which permits higher conductivity than
conventional Nafion 117, and exhibits a good mechanochemical property with the help
of sulfosuccinic acid by cross-linking mechanism. Our electrochemical analysis revealed
that the modified membrane shows improved proton conductivity, IEC and water uptake
Polymers 2021, 13, 1669 3 of 13

properties. In addition, the dynamic modulus analysis (DMA) result confirms the improved
modulus properties.

2. Materials and Methods

2.1. Materials
The polymeric material used in this experiment was poly(styrene-ethylene-butylene-
styrene) copolymer (SEBS, ~118,000 g/mol, 28 wt% polystyrene, Sigma Aldrich, Seoul,
Korea). Maleic anhydride (MA, 98.96 g/mol, Daejung, Siheung, Korea) was used as the
grafting agent. Chloroform (99.8%, Aldrich, Seoul, Korea) and ρ-xylene (99%, Sigma
Aldrich, Seoul, Korea) were used as a solvent, while dicumyl peroxide (DCP, 98%, Sigma
Aldrich, Seoul, Korea), sulfosuccinic acid (SSA, 70 wt%, Sigma Aldrich, Seoul, Korea)
and chlorosulfonic acid (99%, Sigma Aldrich, Seoul, Korea) were used as an initiator, the
crosslinking agent and sulfonation inhibitor, respectively.

2.2. Synthesis of S-SEBS and S-SEBS-g-MA Membrane

2.2.1. Sulfonated SEBS (S-SEBS)
The S-SEBS were prepared by following procedures reported in the previous litera-
ture [21,22]. In this process, 10 wt% SEBS was dissolved completely in chloroform by being
vigorous stirred for 3 h. The 30 mL of above solution was casted in a circular glass Petri-dish
which results in ~150 µm thickness after drying at room temperature for 12 h. The dried
film was removed from the glass substrate and cut into a 1 cm × 1 cm square shape. The
sulfonation agent was prepared by diluting chlorosulfonic acid in 1,2-dichloroethane and
the prepared SEBS membrane was soaking into sulfonation agent for 5 min. Then, the
modified membrane sample washed several times with deionized water. The membrane
was immersed in deionized water over 24 h, before the tests were carried out.

2.2.2. Synthesis MA Grafted S-SEBS (S-SEBS-g-MA)

We used the backbone-functionalization method for the preparation of S-SEBS-g-MA
membrane. The typical scheme used for the preparation is shown in Figure 1. In typical
synthesis, 10 wt% SEBS was dissolved in ρ-xylene for 3 h with continuous stirring. Then,
maleic anhydride (MA) of 10 wt% was added into the SEBS solution under nitrogen gas
at 135 ◦ C and stirred for 1 h. Next, dicumyl peroxide (DCP) as an initiator in ρ-xylene
was added and then stirred for another 1 h. After cooling at room temperature, 0.5 g
sulfosuccinic acid (SSA) is then added in the above solution. The prepared SEBS-g-MA
solution was casted on a glass substrate with a thickness of approximately 150 µm and
then dried for 12 h at room temperature. The completely dried film was carefully removed
from the glass substrate and cut into a square shape (size 1 cm × 1 cm). The SEBS-g-MA
membrane was soaked in sulfonation agent for 5 min, and then washing with deionized
Polymers 2021, 13, x FOR PEER REVIEW 4 of 14
water several times. The membrane was immersed in deionized water over 24 h before the
test was carried out.

Figure 1. Scheme used for the preparation of MA-grafted SEBS based anion exchange
exchange membrane.
membrane.

2.3. Characterizations
2.3.1. Fourier Transform Infrared (FT-IR) Spectroscopy
The FT-IR spectrometer (Spectrum 400, Perkin Elmer, Gwangju, Korea) was used to
investigate the grafting and the functional groups in the synthesized membrane qualita-
tively.
 Polymers 2021, 13, 1669 4 of 13

2.3. Characterizations
2.3.1. Fourier Transform Infrared (FT-IR) Spectroscopy
The FT-IR spectrometer (Spectrum 400, Perkin Elmer, Gwangju, Korea) was used to in-
vestigate the grafting and the functional groups in the synthesized membrane qualitatively.

2.3.2. Gel Permeation Chromatography (GPC)

The measurements were conducted using Shodex KF-804, Shodex KF-802, and Shodex
KF-801 column (HLC-8320 GPC, Tosoh, Gwangju, Korea) at 40 ◦ C with the eluent flow rate
of 1 mL/min and injection of 100 µL. All samples were dissolved in tetrahydrofuran (THF)
before measurements. Polystyrene standard was used as a reference.

2.3.3. Topographical Analysis

The surface topography of the membranes was investigated using atomic force mi-
croscopy (AFM, XE-100, Park system, Gwangju, Korea) operated in tapping mode. For
AFM images, the SEBS-based anion exchange membrane films were prepared on the Si
wafer at 2000 rpm for 30 s and dried overnight in ambient conditions.

2.3.4. Ionic Conductivity

The ionic conductivity of the membrane was obtained by impedance spectroscopy
measurement using a conductivity analyzer (Ivuimstat, HS Technologies, Gwangju, Korea)
with the frequency range of 1 Hz to 1 MHz at room temperature. Before measurements, the
prepared membrane was immersed in deionized water for over 24 h. During measurements,
the contact area of the membrane between electrodes was maximized to reduce errors in
ionic conductivity measurements. The experimental arrangement for ionic conductivity
is shown in Figure 2. For impedance reproducibility and cross-check verification, we
successively repeated samples from each set at least five times. The ionic conductivity of
the membrane was calculated by using the following equation.

L
σ(S/cm) = (1)
RA
Polymers 2021, 13, x FOR PEER REVIEW 5 of 14
where R is the real impedance taken at zero imaginary impedance in the impedance
spectroscopy, and L and A are the thickness and area of the membrane, respectively.

Figure 2. Experimental set-up for the ionic conductivity measurements of the different membranes.
Figure 2. Experimental set-up for the ionic conductivity measurements of the different mem-
2.3.5. Ion Exchange Capacity (IEC)
branes.
For the ion exchange capacity (IEC) measurement, the dried sample with a certain
weight
2.3.5. was immersed
Ion Exchange into(IEC)
Capacity 1 M HCl solution overnight and stirred. The ion exchange
For the ion exchange capacity (IEC) measurement, the dried sample with a certain
weight was immersed into 1 M HCl solution overnight and stirred. The ion exchange ca-
pacity was determined by titrating the solution with 1 M NaOH solution. The IEC of each
sample was measured at least 5 times. The IEC of the membranes was calculated by the
Polymers 2021, 13, 1669 5 of 13

capacity was determined by titrating the solution with 1 M NaOH solution. The IEC of
each sample was measured at least 5 times. The IEC of the membranes was calculated by
the following equation.

MO(HCl) − Me (HCl)
IEC(meq/g) = (2)
Wdry

where Mo(HCl) and Me(HCl) are the milliequivalent (meq) of HCl acquired before and after
the equilibrium, respectively, and Wdry is the mass (g) of the dried membrane.

2.3.6. Sulfonation Degree (SD)

The sulfonation degree (SD) is related to the actual content of sulfonated poly-styrene
group of S-SEBS. The SD was calculated using the following equation.

MP × IEC
SD = (3)
{1000 − (Mf × IEC)}

where Mp is the molecular weight of the non-functional polymer repeat unit (SEBS) and
Mf is the molecular weight of the functional group (SO3 H). The values for Mp and Mf are
18,000 and 81, respectively.

2.3.7. Water Uptake

To evaluate the water uptake of the membrane, the sample with a certain weight was
immersed in deionized water for 24 h at room temperature. After 24 h, the membrane
was taken out and the water on the surface was quickly wiped using filter paper, and
then the membrane was weighed again. The water uptake was calculated according to the
following equation. The water uptake of each sample was measured at least 5 times and
we used the average value.

Wwet − Wdry
Water uptake(%) = × 100 (4)
Wdry

where Wwet and Wdry are the weight of the membrane in the wet and dry state, respectively.

2.3.8. Mechanical Properties

Dynamic mechanical properties of the membranes were measured using dynamic
mechanical analysis (DMA, universal V3.5B, TA instruments, Seoul, Korea) in tension
mode. Samples were heated to 200 ◦ C at frequency of 1 Hz, with a programmed heating
rate of 5 ◦ C/min.

3. Results and Discussion

3.1. Vibrational and GPC Analysis
Figure 3, containing the FT-IR spectra, shows SEBS peaks at 2916 and 2850 cm−1 ,
which represents the CH3 and CH2 stretching. There is another peak at 1454 cm−1 that
correspond to –CH2 , and C=C. S-SEBS has two characteristic peaks at 1226 and 1041 cm−1
because of the S=O symmetric stretching vibration and the S=O asymmetric stretching
vibration of the SO3 H groups, respectively.
 3.1. Vibrational and GPC Analysis
Figure 3, containing the FT-IR spectra, shows SEBS peaks at 2916 and 2850 cm−1,
which represents the CH3 and CH2 stretching. There is another peak at 1454 cm−1 that cor-
respond to –CH2, and C=C. S-SEBS has two characteristic peaks at 1226 and 1041 cm−1
Polymers 2021, 13, 1669 because of the S=O symmetric stretching vibration and the S=O asymmetric stretching vi-6 of 13
bration of the SO3H groups, respectively.

Figure 3. The
Figure FT-IR
3. The spectra
FT-IR of the
spectra of SBES, S-SEBS,
the SBES, andand
S-SEBS, S-SEBS-g-MA membranes.
S-SEBS-g-MA membranes.

However, after grafting − 1 because

However, after grafting by by
MA, MA, S-SEBS-g-MA
S-SEBS-g-MA hashas a new
a new peakpeak
a ata 3306
at 3306
cmcm−1 because

of the
of the hydroxyl
hydroxyl group
group togetherwith
together withsome
some unassociated
unassociated hydroxyl
hydroxylspecies
speciesininthetheregion
region3500–
3200 cmcm − 1−1. There are also several other new peaks at 1942 and 1751 cm − 1 (asymmetric
3500–3200 . There are also several other new peaks at 1942 and 1751 cm−1 (asymmetric
− 1 (C=O stretching of carboxyl group
andand symmetric
symmetric carbonyl
carbonyl vibration
vibration of MA),
of MA), 16001600
cmcm −1 (C=O stretching of carboxyl group
from anhydride), 1379 − 1 − 1
from anhydride), 1379 cmcm (aldehyde),
−1 (aldehyde), 10281028
cm−1cm (the (the deformation
deformation vibration
vibration of theof the
C-HC-H
bond) [23,24]. The FT-IR results suggest that the functional groups
bond) [23,24]. The FT-IR results suggest that the functional groups are responsible for are responsible for ionic
transfer channel of hydroxide ions are successfully
ionic transfer channel of hydroxide ions are successfully grafted on SEBS. grafted on SEBS.
Changes
Changes average
average molecular
molecular weight
weight (Mw(M w ) distribution
) distribution for SEBS,
for SEBS, S-SEBS,
S-SEBS, SEBS-g-MA,
SEBS-g-MA,
S-SEBS-g-MA, and cross-linked S-SEBS-g-MA are presented in Table 1. The Mw ofin
S-SEBS-g-MA, and cross-linked S-SEBS-g-MA (CS-SEBS-g-MA) are presented Table 1.
SEBS-
The M w of SEBS-g-MA, where MA is grafted onto SEBS, is
g-MA, where MA is grafted onto SEBS, is slightly increased compared to SEBS. However, slightly increased compared
afterto sulfonization
SEBS. However, after sulfonization
(S-SEBS, S-SEBS-g-MA), (S-SEBS, S-SEBS-g-MA),
Mw decreased despite Mwthedecreased
additiondespite
of sul- the
addition of sulfonization compared to the pre-sulfonizaiton
fonization compared to the pre-sulfonizaiton samples (SEBS, SEBS-g-MA). From this re- samples (SEBS, SEBS-g-MA).
sult,From this result, occurred
decomposition decomposition
in the occurred in the during
polymer chain polymer chain
the during theCS-SEBS-g-
sulfonization. sulfonization.
CS-SEBS-g-MA has the highest molecular weight because the higher molecular weight
MA has the highest molecular weight because the higher molecular weight content of the
content of the test specimen increases, which is attributable to the crosslinking of the
test specimen increases, which is attributable to the crosslinking of the polymer chain.
polymer chain.
Table 1. Average of Mw S-SEBS, SEBS-g-MA, S-SEBS-g-MA, and cross-linked S-SEBS-g-MA mem-
Table 1. Average of Mw S-SEBS, SEBS-g-MA, S-SEBS-g-MA, and CS-SEBS-g-MA membranes.
branes.
Samples
Samples SEBS S-SEBS
SEBS S-SEBS SEBS-g-MA
SEBS-g-MA S-SEEB-g-MA
S-SEEB-g-MA CS-SSEBS-g-MA
CS-SEBS-g-MA
MwM w (g/mol) 108,589
(g/mol) 108,589 108,493
108,493 110,179
110,179 109,986
109,986 114,241
114,241

3.2. Topographical Analysis

The triblock copolymer SEBS, consisting of hard and soft blocks that usually exhibit a
phase-separated morphology, which has been widely studied by AFM techniques [25–29].
It is well known that, for high ionic conductivity of the membrane, a continuous network
of a proton conducting phase within the material is essential. To check the surface mor-
phology of membranes, the AFM images of the bare SEBS and modified SEBS membranes
were recorded (Figure 4). In Figure 4a, SEBS membrane has a well-defined micro-phase
separated morphology, where the dark regions represent the soft polyethylene (PE) block
phase. On the other hand, the bright regions represent the stiff polystyrene (PS) phase.
Ion exchange membranes of block copolymers consisting of hydrophilic and hydrophobic
blocks associate uniformly on microscopic scales and their morphologies are aspherical,
cylindrical, or lamellar in shape depending on the relative volume fractions of the con-
stituent components [27,29]. Partially sulfonated SEBS block copolymers are known to
demonstrate self-assembling phenomena, which lead to the separation of microphase
domains [17,29].
 block phase. On the other hand, the bright regions represent the stiff polystyrene (PS)
phase. Ion exchange membranes of block copolymers consisting of hydrophilic and hy-
drophobic blocks associate uniformly on microscopic scales and their morphologies are
aspherical, cylindrical, or lamellar in shape depending on the relative volume fractions of
Polymers 2021, 13, 1669 the constituent components [27,29]. Partially sulfonated SEBS block copolymers7 ofare 13
known to demonstrate self-assembling phenomena, which lead to the separation of mi-
crophase domains [17,29].

Figure
Figure 4.
4. The
The AFM
AFM phase
phase images
images of
of the
the modified membranes. (a)
modified membranes. (a) SEBS, (b) SEBS-g-MA,
SEBS, (b) SEBS-g-MA, (c)
(c) S-SEBS,
S-
SEBS, (d) S-SEBS-g-MA.
(d) S-SEBS-g-MA.

Such microphase
Such microphase separation
separationcan
canresult
resultininthe
theformation
formationof of
continuous
continuous ionic channels
ionic chan-
that enable proton ions transportation through ionic channels. Flexible side
nels that enable proton ions transportation through ionic channels. Flexible side chains chains were
also considered to form microphase separation morphology [26]. As a result,
were also considered to form microphase separation morphology [26]. As a result, we we observed
well-ordered and more
observed well-ordered and continuously
more continuouslyconnected
connected nano-channels.
nano-channels.Proton
Proton transports
through these nano-channels
nano-channels with hydrophilic domains lead to good water uptake and
ion conductivity. The formation of continuous ionic channels led to proton ion transports
through ionic channels. Formation
Formation ofof the continuous ionic channel is dependent on the
hydrophilic functional groups such as SO33H and –COOH. By comparing the SEBS-g-MA
membrane
membrane with
with–COOH
–COOHininFigure
Figure4b4bandandS-SEBS
S-SEBS membrane
membrane with SO3SO
with H in
3 HFigure 4c, dif-
in Figure 4c,
different
ferent morphologies
morphologies areare observed
observed ininthe
theAFM
AFMimages.
images.These
Theseresults
resultsshow
show that
that different
surface chemical composition characteristics occur depending on the functional groups.
Due to this different morphological behavior, ion clusters have different ion transportation
speed. As a result, the ionic conductivity of membranes with a –COOH functional group
is shown to be different from membranes with a SO3 H functional group. A membrane
with two kinds of hydrophobic functional group (SO3 H, –COOH) has well-ordered and
more continuously connected nano-channels than S-SEBS and SEBS-g-MA, which have
single hydrophobic functional groups of SO3 H or COOH, respectively (Figure 4d). These
results show that S-SEBS-g-MA is superior to S-SEBS and SEBS-g-MA as an ionic exchange
membrane.

3.3. Ionic Conductivity and Ion Exchange Capacity (IEC)

The ion exchange membranes contain a high concentration of the fixed ionic groups.
On the other hand, the backbone of the membrane is extremely hydrophobic, whereas
the charged acid groups are strongly hydrophilic and polar. The hydrophilic domains
absorb water and form small clusters distributed throughout the backbone. Proton ions
easily permeate the cationic membranes containing fixed negative groups [11]. The ion
 The ion exchange membranes contain a high concentration of the fixed ionic g
On the other hand, the backbone of the membrane is extremely hydrophobic, wher
charged acid groups are strongly hydrophilic and polar. The hydrophilic domains
water and form small clusters distributed throughout the backbone. Proton ions
Polymers 2021, 13, 1669 permeate the cationic membranes containing fixed negative groups8[11]. of 13 The ion

forms with negative functional groups and the membrane with well-formed ion c
have high ionic conductivity. Ideal membranes for an RFB should possess good ch
stability
cluster forms with and high
negative ionic conductivity.
functional groups and theFrom the impedance
membrane results, we ion
with well-formed observed m
drophilic functional groups increased, which generates continuous
clusters have high ionic conductivity. Ideal membranes for an RFB should possess good ionic channels r
sible for increased ionic conductivity, and decreased resistance, Figure
chemical stability and high ionic conductivity. From the impedance results, we observed 5.
more hydrophilic functional groups increased, which generates continuous ionic channels
responsible for increased ionic conductivity, and decreased resistance, Figure 5.

Figure 5. Impedance spectra of spectra

Figure 5. Impedance the Nafion 117,
of the S-SEBS,
Nafion SEBS-g-MA,
117, S-SEBS-g-MA,
S-SEBS, SEBS-g-MA, and cross-linked
S-SEBS-g-MA, S-SEBS-g-MA me
and CS-SEBS-g-
branes. (Impedance data recorded at least for five sample from each set.).
MA membranes. (Impedance data recorded at least for five sample from each set.).

The resulting
The resulting values of ionic values of ionic
conductivity andconductivity
impedanceand are impedance
given in Tableare 2.
given
As in Tabl
expected, the ionic conductivity is enhanced by increasing the concentration
expected, the ionic conductivity is enhanced by increasing the concentration of hydrophilic of
philic
functional groups. Thefunctional
S-SEBS and groups. The S-SEBS
S-SEBS-g-MA andimprovement
exhibit S-SEBS-g-MA inexhibit improvement in ion
ionic conductivity.
ductivity.
The ionic conductivity of The ionic conductivity
the S-SEBS-g-MA of thewith
increases S-SEBS-g-MA
sulfonatedincreases
time and with sulfonated
reaches a tim
maximum value 0.18 S/cm at room temperature. As sulfonated time increases, the ionic
channels also increase, resulting in an increase in the ionic conductivity. Compared with
the ionic conductivity of the S-SEBS membrane (0.1 S/cm), S-SEBS-g-MA shows much
higher ionic conductivity.

Table 2. Degree of sulfonation, ionic conductivity and IEC values obtained for the bare and modified
membranes at room temperature.

Sulfonation Ionic
Resistance IEC
Samples Name Degree Conductivity
(Ω/cm2 ) (meq)
(%) (S/cm)
Nafion 117 0.145 ± 0.002 38.8 ± 0.4 0.06 ± 0.001 0.9 ± 0.002
S-SEBS 0.085 ± 0.0001 45.6 ± 0.1 0.1 ± 0.004 2.1 ± 0.004
SEBS-g-MA 0.06 ± 0.008 65.2 ± 0.1 0.12 ± 0.004 2.8 ± 0.004
S-SEBS-g-MA 0.047 ± 0.003 83.1 ± 0.2 0.18 ± 0.004 3.36 ± 0.06
CS-SEBS-g-MA 0.037 ± 0.002 102.6 ± 0.2 0.25 ± 0.004 3.9 ± 0.06

This is because S-SEBS has only SO3 H, but S-SEBS-g-MA has both SO3 H and COOH,
so S-SEBS-g-MA has many more hydrophilic functional groups than S-SEBS. We also used a
 Polymers 2021, 13, 1669 9 of 13

crosslinking agent containing hydrophilic group to improve both mechanical properties and
ion conductivity. As a result, the CS-SEBS-g-MA, which contains more hydrophilic ionic
channels than the S-SEBS-g-MA, has an ionic conductivity of 0.25 S/cm. This also indicates
that the hydrophilic groups increased the ionic conductivity. Similar to ionic conductivity
IEC, the membranes are strongly dependent on the amount of the hydrophilic functional
groups. The presence of water plays a vital role in ionic conductivity characteristics; its
presence inside the ion exchange membranes offers transport channels for ions. Hence,
higher water content will shorten the ion movement pathway and result in higher ionic
conductivity. In Table 2 and Figure 6, the IEC value of the S-SEBS membrane is 2.1 meq/g
Polymers 2021, 13, x FOR PEER REVIEW
which is much higher than the commercial Nafion 117 membrane, whose IEC is only 10 of 14
0.9
meq/g (Table 2). This means that the IEC also increases as the hydrophilic functional
groups increases.

Figure 6. Degree of sulfonation, ionic conductivity and IEC of the different membranes studied in
Figure 6. Degree of sulfonation, ionic conductivity and IEC of the different membranes studied in
this work.
this work.
3.4. Water Uptake
Next, we investigated the water uptake behavior of all of the above membranes.
Figure 7 shows the water uptake of the Nafion 117, S-SEBS, SEBS-g-MA, S-SEBS-g-MA and
CS-SEBS-g-MA membrane. Water uptake by the membrane depicts the hydrophobicity of
the membrane. The COOH activity in the membrane increases affinity for water more than
SO3 H, which affected the SEBS-g-MA membrane, causing it to swell more than S-SEBS
membrane. The water uptake value for the S-SEBS membrane containing SO3 H functional
group is 33% and of the SEBS-g-MA membrane containing COOH functional group is 42%
(Figure 7). Thus, S-SEBS exhibits higher ionic conductivity than the SEBS-g-MA membrane,
because of ionic conductivity depending on the hydrophilic functional group and the
main structure material. Although membranes have identical functional groups, they have
differential water uptake values. This is because the water uptake of the membrane is
related to the number of hydrophilic groups in the membrane. In other words, the water
uptake increases with the increase in the hydrophilic portion of the functional groups in
the membrane.
 Figure 6. Degree of sulfonation, ionic conductivity and IEC of the different membranes studied in
this work.
Polymers 2021, 13, 1669 10 of 13

Figure
Figure 7. Water uptake of
Water uptake of the
theNafion
Nafion117,
117,S-SEBS,
S-SEBS,SEBS-g-MA,
SEBS-g-MA,S-SEBS-g-MA,
S-SEBS-g-MA, andand
thethe crosslinked
CS-SEBS-g-MA
S-SEBS-g-MA
membranes asmembranes
a function ofastime.
a function of time.data
Water uptake Water uptake
were datafor
recorded were recorded
at least for at least
five sample fromfive
each
sample from
sample set. each sample set.

In comparison with SEBS-g-MA and S-SEBS-g-MA, the S-SEBS-g-MA shows a much

higher water uptake than the SEBS-g-MA. The SEBS-g-MA contains only a hydrophilic
COOH functional group, while S-SEBS-g-MA comprises two hydrophilic functional groups
of SO3 H and COOH. Thus, the higher water uptake of the S-SEBS-g-MA is due to it having
more hydrophilic groups. To increase the ionic conductivity of membrane, we used the
SSA as a crosslinking agent. SSA has sulfonic acid and carboxylic groups, so SSA play dual
roles in the membranes; ion clustering of the hydrophilic group and crosslinking agent. By
using the SSA, we increased the level of hydrophilic functionality and the water uptake
of CS-SEBS-g-MA to higher than that of S-SEBS-g-MA. Following the results between
ionic conductivity and water uptake, we can expect that investigating the functional
groups such as sulfonyl and carboxylic acid of the membrane leads to increased ion
conductivity. The modified membrane CS-SEBS-g-MA with sulfonyl and carboxylic acid
functional groups leads to improved charge density of the modified membrane. From
conductivity analysis, we observed significant improvement in the ionic conductivity
from 0.1 to 0.18 S/cm, respectively, for the bare S-SEBS to S-SEBS-g-MA membrane with
increasing functional groups. Interestingly, this conductivity reached up to 0.25 S/cm for
CS-SEBS-g-MA membrane. This clearly indicates that water uptake and ionic conductivity
are completely dependent upon the functional groups and cross-linking. This gives rise to
the question of how ion conductivity affects the water uptake behavior of the membrane.
Increasing the number of functional groups is directly proportional to increasing the
ability of H+ transport in the membrane, which leads to improved ionic conductivity and
water uptake.

3.5. Dynamic Mechanical Analysis (DMA)

A general problem of homogeneous sulfonated styrene main-chain polymers is that
these ionomers begin to swell to strong and thus lose their mechanical stability when
reaching a certain sulfonated degree. Therefore, reducing the swelling degree of the
membranes without lowering their proton conductivity too much is required. These
Polymers 2021, 13, 1669 11 of 13

requirements are achieved by cross-linking of the ionomer membrane [30]. Flexible ionomer
networks can be built up via ionic crosslinking which contain ionic crosslinks formed by
proton transfer. By adding elements with relatively strong electrical voice such as SOH3
and -COOH, it is possible to synthesize colorless and transparent polymer materials by
forming an undetermined curved chain structure.
The hydroperoxide sites at the macromolecules can cause radical chain scission [31].
C–H bond of polystyrene is easily attacked by oxygen, forming hydroperoxide radicals [30].
The hydroperoxide sites at the macromolecules can cause radical chain scission. Ionomer
crosslinked membranes show reduced brittleness when dried out, compared to uncross-
linked or covalently cross-linked ionomer membranes, which is possibly caused by the
flexibleness of ionic cross-links [31]. We used the SSA which contains two types of hy-
drophilic groups, i.e., SO3 H and COOH as the crosslink agent. The use of the SSA results
in a higher ionic conductivity and improved physical properties of the ion exchange mem-
brane. We compared the storage modulus before and after crosslinking of the ion exchange
membrane. We observed that the storage modulus of the S-SEBS and S-SEBS-g-MA showed
similar behavior, but the storage modulus of the CS-SEBS-g-MA increased by crosslinking
Polymers 2021, 13, x FOR PEER REVIEW 12 of 14
between the molecular chains of S-SEBS-g-MA and SSA (Figure 8). The CS-SEBS-g-MA
membrane exhibited 50% higher storage modulus than the SEBS-g-MA membrane. These
results show that SSA is a good crosslinking agent for the SEBS-g-MA to enhance the
mechanical properties and ion conductivity.

Figure 8. Storage
Storage modulus
modulus of the S-SEBS, S-SEBS-g-MA and cross-linked
CS-SEBS-g-MA S-SEBS-g-MA.
.

4. Conclusions
4. Conclusions
In conclusion,
In conclusion, wewe successfully
successfully prepared
prepared the
the ionic
ionic exchange
exchange membrane
membrane fromfrom SEBS via
SEBS via
sulfonation, grafting MA and crosslinking. This study showed that the ionic
sulfonation, grafting MA and crosslinking. This study showed that the ionic conductivityconductivity
properties of
properties of the
the SEBS
SEBS membrane
membraneisisimproved
improvedby bychemical
chemicalmodification
modification and
andcross-linked
cross-linkedS-
SEBS-g-MA and
S-SEBS-g-MA may
and be be
may suitable for for
suitable applying RFBRFB
applying as a as
membrane in strong
a membrane acid electrolyte.
in strong acid elec-
Sulfonated SEBS block copolymers have continuous ionic channels, while
trolyte. Sulfonated SEBS block copolymers have continuous ionic channels, while the AFM show
the
direct evidence of well-ordered, nano-sized, and continuous ionic channels.
AFM show direct evidence of well-ordered, nano-sized, and continuous ionic channels. The FT-IR
result
The shows
FT-IR the sulfonic
result shows theacid groups,acid
sulfonic carboxylic
groups,groups, andgroups,
carboxylic grafted and
MA grafted
being successfully
MA being
introduced into SEBS. Our ion conductivity analysis revealed a significant
successfully introduced into SEBS. Our ion conductivity analysis revealed improvement in
a significant
the ionic conductivity from 0.1 to 0.25 S/cm, respectively for bare S-SEBS to CS-SEBS-g-MA
improvement in the ionic conductivity from 0.1 to 0.25 S/cm, respectively for bare S-SEBS
to CS-SEBS-g-MA membrane with increasing functional groups. Additionally, the ionic
conductivity, water uptake and IEC of the S-SEBS, SEBS-g-MA, S-SEBS-g-MA and CS-
SEBS-g-MA membrane are higher than those of the commercial Nafion 117 membrane.
Ionic conductivity of the ionic exchange membrane increases with increasing functional
Polymers 2021, 13, 1669 12 of 13

membrane with increasing functional groups. Additionally, the ionic conductivity, water
uptake and IEC of the S-SEBS, SEBS-g-MA, S-SEBS-g-MA and CS-SEBS-g-MA membrane
are higher than those of the commercial Nafion 117 membrane. Ionic conductivity of
the ionic exchange membrane increases with increasing functional group concentration.
These results indicate the modified membrane is a promising candidate for large-scale
energy storage systems that can further explored in the future. By manufacturing anion
exchange membrane based on non-fluoro polymers such as SEBS, it will be possible to
get price competitiveness compared to Nafion 117. Moreover, SEBS-based copolymers
can be synthesized by different functional groups, which facilitates the improved ionic
conductivity. The lower mechanical properties than conventional Nafion 117 can be
improved by blending with alternative polymers or adding crosslink agents. We believe
that this method could open up alternative strategy and promising approaches for its
further development.

Author Contributions: Conceptualization, H.-S.P. and C.-K.H.; methodology, H.-S.P.; validation,

H.-S.P. and C.-K.H.; formal analysis, H.-S.P.; investigation, H.-S.P.; data curation, H.-S.P. and C.-
K.H.; writing—original draft preparation, H.-S.P.; writing—review and editing, H.-S.P. and C.-K.H.;
visualization, H.-S.P.; supervision, C.-K.H.; project administration, C.-K.H.; funding acquisition,
C.-K.H. All authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by the Jeollanam-do, Korea, under Regional Specialized
Industry Development Program of Next-generation stent innovation processing advance technology
support project (R&D, B0080621000341).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: Authors have no conflicts to declare.

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