Invited ReviewAppl. Chem. Eng., Vol. 26, No. 1, February 2015, 1-16
http://dx.doi.org/10.14478/ace.2015.1008
1
이온교환막 공정 및 응용 연구동향
김득주⋅정문기⋅남상용†
경상대학교(2015년 1월 19일 접수)
Research Trends in Ion Exchange Membrane Processes and Practical Applications
Deuk Ju Kim, Moon Ki Jeong, and Sang Yong Nam†
Department of Materials Engineering and Convergence Technology, Engineering Research Institute, Gyeongsang National University, Jinju 660-701 Korea
(Received January 19, 2015)
록
본 리뷰에서는 에너지분야 응용을 위해 사용된 이온교환막을 이용한 분리막 공정에 대하여 정리하였다. 이온교환막은 기능, 균일상, 불균일상과 같은 형태, 사용된 고분자의 종류에 따라 구분되었으며, 양이온 및 음이온 교환막을 제조하기 위한 다양한 방법에 대하여 논문을 참조하여 정리하였다. 이온교환막을 제조하기 위한 최신 연구결과 동향이 보고되었으며, 본 리뷰에서는 분리막의 제조 및 발전되어온 내용과, 분리막을 미래지향적 기술에 사용하기 위한 잠재적 응용분야에 대하여 논의하였다.
AbstractIn this review, we summarized some of membrane processes using the ion exchange membrane typically used in energy applications. Ion exchange membranes are classified according to their functions, formations (e.g. heterogeneous, homoge-neous), and polymer type. Furthermore, various methods to prepare cation exchange membranes and anion exchange mem-branes were discussed in detail and also illustrated through a thorough review of the literature works. There are numerous reports highlighting recent research trends in the ion exchange membrane fabrication, however, in this review we will focus more on discussing the development made in ion exchange membranes and their potential usages in future technologies.
Keywords: Heterogeneous, homogeneous, cation exchange, anion exchange
1. Introduction1)
In the field of the separation and purification science, membrane
technology garners significant interest and is considered as a future
technology due to their numerous advantages such as high energy effi-
ciency, eco-friendliness, and low cost for maintenance expenditure[1].
Nowadays, various types of ion exchange membranes have been devel-
oped and investigated for use in electrodialysis for desalting brackish
waters, reconcentrating brine from seawater reverse osmosis, pervapo-
ration, solid polymer electrolyte, fuel cell applications, and different
ion exchange membrane based electro-membrane processes[2,3]. Ion
exchange membranes differentiate cation and anions; thus, they should
have a high transport number for counter ions. That is, charged groups
† Corresponding Author: Gyeongsang National University, Department of Materials Engineering and Convergence Technology, Jinju 660-701 KoreaTel: +82-55-772-1657 e-mail: [email protected]
pISSN: 1225-0112 eISSN: 2288-4505 @ 2014 The Korean Society of Industrial and Engineering Chemistry. All rights reserved.
are attached to polymer backbones, and the density of the ionic site
in the backbone determines various properties including the ion con-
ductivity, mechanical stability, and chemical stability. For example, a
membrane with a high degree of ionic groups causes high ionic con-
ductivity combined with low mechanical strength. However, a high de-
gree of ionic transport sites improves the electrochemical properties of
the membrane but decreases the mechanical properties and chemical
durability. Thus, these properties must be compromised in order to de-
velop ion exchange membranes with high properties. In this review, we
summarize the different types of ion exchange membranes, preparation
procedures, characterizations, and applications for membrane processes.
2. Material Development
2.1. Commercialized membranes
Since the first paper on ion exchange membranes was published in
1925, various types of membranes have been developed and used in
various fields. In order to develop industrially usable ion exchange
membranes and establish their application technologies, much research
Membrane Type Thickness IEC(mol/g(meq/g)) Area resistance (Ωcm2)
Asahi Chemical Industry Co. Japan
Aciplex K-192 CEM 0.13-0.17 - 1.6-1.9
Aciplex-501SB CEM 0.16-0.20 - 1.5-3.0
Aciplex A-192 AEM >0.15 - 1.8-2.1
Aciplex-501SB AEM 0.14-0.18 - 2.0-3.0
Aciplex A201 AEM 0.22-024 - 3.6-4.2
Aciplex A221 AEM 0.17-0.19 - 1.4-1.7
Asahi Glass Co. Ltd., Japan
CMV CEM 0.15 2.4 2.9
AMV AEM 0.14 1.9 2.0-4.5
ASV AEM - 0.11-0.15 2.3-3.5
HJC CEM 0.83 1.8 -
DSV AEM 0.13-0.17 - -
CSMCRI, Bhavangar India
IPC CEM 0.14-0.16 1.4 1.5-2.0
IPA AEM 0.16-0.18 0.8-0.9 2.0-4.0
HGG CEM 0.22-0.25 0.7-0.8 0.22-0.25
HGA AEM 0.22-0.25 0.4-0.5 5.0-7.0
Dupont Co., USA
Nafion NF-112 CEM 0.051 - -
Nafion NF-1135 CEM 0.089 - -
Nafion NF-115 CEM 0.127 - -
Nafion NF-117 CEM 0.183 0.9 1.5
Nafion 901 CEM 0.4 1.1 3.8
FuMA-Tech GmbH, Germany
FKS CEM 0.090-0.110 0.9 2.0-4.0
FKB CEM 0.100-0.115 0.8 5.0-10.0
FK-40 CEM 0.035-0.045 1.2 1
FKD CEM 0.040-0.060 1 1
FKE CEM 0.050-0.070 > 1 < 3
FTCM-A CEM 0.050-0.060 > 2.2 < 10
FTCM-E CEM 0.500-0.600 > 2.2 < 10
FAS AEM 0.100-0.120 1.1 2.0-4.0
FAB AEM 0.090-0.110 0.8 2.0-4.0
FAN AEM 0.090-0.110 0.8 2.0-4.0
FAA AEM 0.080-0.100 1.1 2.4
FAD AEM 0.080-0.100 1.3 1.2
FTAM-A AEM 0.500-0.600 > 1.7 < 8
FTAM-E AEM 0.500-0.600 > 1.7 < 8
Institute of Plastic Materials, Moscow
MA-40 AEM 0.15 0.6 5
Ionics Inc., USA
CR61-CMP CEM 0.58-0.70 2.2-2.5 11
CR67-HMR CEM 0.53-0.65 2.1-2.45 7.0-11.0
Table 1. Main Properties of Commercially Available Ion Exchange Membranes
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Membrane Type Thickness IEC(mol/g(meq/g)) Area resistance (Ωcm2)
CR67-HMP - - - -
61CZL386 CEM 0.63 2.6 9
AR103QDP AEM 0.56-0.69 1.95-2.20 14.5
AR204SZRA AEM 0.48-0.66 2.3-2.7 6.2-9.3
AR112-B AEM 0.48-0.66 1.3-1.8 20-28
103PZL183 AEM 0.6 1.2 4.9
MEGA a.s., Czeeh Republic
Ralex CM-PES CEM 0.45 (Dry) 2.2 < 9
Ralex CMH-5E CEM 0.6 (Dry) 2.2 < 12
Ralex MH-PES AEM 0.55 (Dry) 1.8 < 8
Ralex AMH-5E AEM 0.7 (Dry) 1.8 < 13
PCA polymerchemie Altmeier GmbH, Germany
PC-SK CEM - - -
PC-SA AEM - - -
PC 100 D AEM 0.08-0.10 1.2 Quat. 5
PC 200 D AEM 0.08-0.10 1.3 Quat. 2
PC Acid 35 AEM 0.08-0.10 1.0 Quat. -
PC Acid 70 AEM 0.08-0.10 1.1 Quat. -
PC Acid 100 AEM 0.08-0.1 0.57 Quat. -
RAI Rescarch Corp., USA
R-5010-H CEM 0.24 0.9 8.0-12.0
R-5030-L AEM 0.24 1 4.0-7.0
R-1010 CEM 0.1 1.2 0.2-0.4
R-1030 AEM 0.1 1 0.7-1.5
Shanghai Chemical Plant of China, China
PE3362 AEM 0.45 1.8-2.0 13.1
Solvay S.A., Belgium
Morgane CDS CEM 0.130-0.170 1.7-2.2 0.7-2.1
Morgane CRA CEM 0.130-0.170 1.4-1.8 1.8-3.0
Morgane ADP AEM 0.130-0.170 1.3-1.7 1.8-2.9
Morgane AW AEM 0.130-0.170 1.0-2.0 0.9-2.5 (HCl 1 M)
1.3-4.4 (HNO3 1 M)
Tokuyama Co., Japan
Neosepta CM-1 CEM 0.13-0.16 2.0-2.5 0.8-2.0
Neosepta CM-2 CEM 0.12-0.16 1.6-2.2 2.0-4.5
Neosepta CMX CEM 0.14-0.20 1.5-1.8 2.0-3.5
Neosepta CMS CEM 0.14-0.17 2.0-2.5 1.5-3.5
Neosepta CMB CEM 0.22-0.26 - 3.0-5.0
Neosepta AM-1 AEM 0.12-0.16 1.8-2.2 1.3-2.0
Neosepta AM-3 AEM 0.11-0.16 1.3-2.0 2.8-5.0
Neosepta AMX AEM 0.12-0.18 1.4-1.7 2.0-3.5
Neosepta AHA AEM 0.18-0.24 1.15-1.25 3.0-5.0
Neosepta ACM AEM 0.10-0.13 1.4-1.7 3.5-5.5
Neosepta ACS AEM 0.12-0.20 1.4-2.0 3.0-6.0
Table 1. To be Continued
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Figure 1. Reaction scheme of the preparation of N/S membrane[5].
Membrane Type Thickness IEC(mol/g(meq/g)) Area resistance (Ωcm2)
Neosepta AFN AEM 0.15-0.18 2.0-3.5 0.2-1.0
Neosepta AFX AEM 0.14-0.17 1.3-2.0 0.7-1.5
Neosepta ACH-45T AEM - 1.3-2.0 -
A 201 (developing code A-006) 28 1.7 -
A 901 10 1.7 -
Tianwei Membrane Co. Ltd., China
TWEDG AEM 0.16-0.21 1.6-1.9 3.0-5.0
TWDDG AEM 0.18-0.23 1.9-2.1 < 3
TWAPB AEM 0.16-0.21 1.4-1.6 5.0-8.0
TWANS AEM 0.17-0.20 1.2-1.4 6.0-10.0
TWAHP AEM 0.20-0.21 1.2-1.4 < 2
TWAEDI AEM 0.18-0.21 1.6-1.8 6.0-8.0
TWCED CEM 0.16-0.18 1.4-1.6 2.0-4.0
TWCDD CEM 0.16-0.18 1.6-2.0 2.0-4.0
TWCEDI CEM 0.16-0.18 1.2-1.4 5.0-8.0
Table 1. To be Continued
in education institutions, research centers, and companies has focused
on developing novel ion exchange membranes. The various types of
commercialized ion exchange membranes that have been developed are
summarized in Table 1.
2.2. Manufacturing technique for cation exchange membranes
2.2.1. Fluorinated ionomer membranes
Perfluorosulfonic polymers, such as the Nafion® series (Dupont,
USA), are the most widely used membranes in various systems due to
their excellent proton conductivity and chemical stability; these consist
of perfluorinated copolymers in the pendant sulfonic acid group.
However, there are disadvantages that limit the commercialization of
the system[4]. Therefore, in order to overcome this challenge, mod-
ifications of the pristine polymer or composite membrane system are
considered as viable alternatives for other applications. Luo developed
Nafion/sulfonated poly(ether ether ketone) (SPEEK) layered composite
membranes (Figure 1) (N/S membranes) that included a thin layer of
recast Nafion membrane using the chemical crosslinking process[5].
The Nafion layers in the composite membrane functioned as a shield
to prevent oxidation degradation of the membrane, which affects the
performance improvements for the vanadium redox flow battery.
Compan reported the effect of polyaniline intercalations in a composite
membrane polymerized with perfluorinated sulfonic acid polymer on
the electrochemical properties[6]. Furthermore, Kannan developed a
composite membrane based on Nafion® and phospho-silicate materials
(2-(methacryloyloxy)ethyl phosphate (EGMP) and 3-[(meth-
acryloyloxy)propyl]trimethoxysilane (MEMO)). In that study, the ef-
fects of the silica networks (Scheme 1) were investigated[7]. In gen-
eral, the ionic conducting membrane used in the fuel cell exhibited de-
creased ionic conductivity at high temperatures and low humidity.
However, in case of the composite membrane, the proton conductivity
was higher than that of the pristine Nafion® as a result of the silica
networks with hydrogen bonding.
2.2.2. Polysulfone-based ion exchange membranes
Polysulfone-based polymers have been used extensively in various
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Scheme 1. In situ modification of Nafion® membrane using phospho-silicate by infiltration method[7].
Scheme 2. Synthetic pathway : (a) functionalized poly(ether ether ketone) with carboxylic groups; (b) cross-linkable poly(ether ether ketone) with pendent sulfonation groups[12].
Figure 2. Schematic diagram of preparation of SPEEK/PTFE[13].
fields of membrane separation processes including fuel cells, water
treatments system, and gas separation processes, due to their excellent
mechanical, thermal, and chemical stabilities as well as their low
cost[8,9]. A key advantage of polysulfide-based polymers is the easy
control of the synthesis and modification process. The ion exchange-
able property of the polysulfone-based polymers is created through the
introduction of charged groups, particularly from sulfonic acid.
Furthermore, the properties of the modified membranes have been
investigated by numerous researchers. Piluharto investigated the effect
of fixed charges in the sulfonated polysulfone membranes and its cor-
relation with the electrochemical properties[10]. Klaysom developed
sulfonated polyethersulfone membranes and their performance was in-
vestigated for the sulfonation degree for cation exchange membranes.
The sulfonation degree can be easily controlled through varying the ra-
tios of the reaction reagents, temperature, and reaction time. In this
study, the membranes with 40% sulfonation were found to have the
optimal properties compared with other membranes[11].
2.2.3. Poly(ether ether ketone) (PEEK) based membranes
Sulfonated aromatic polymers such as sulfonated poly(arylene ether
ketone) and poly(arylene ether sulfone) have received considerable at-
tention due to their low cost and high chemical stability. However, the
chemical stability and lifetime of hydrocarbon-based polymer mem-
branes still need to be improved. Therefore, many researchers have
been developed various types of hydrocarbon-based polymer mem-
branes with higher proton conductivity as well as mechanical and
chemical durability. As depicted in Scheme 2, Zhou synthesized a ser-
ies of cross-linkable poly(ether ether ketone)s (PEEKs) with pendant
carboxylic acid groups, and their performances ere measured for use
in proton exchange membrane fuel cells (PEMFC). The cross-linked
polymer membranes exhibited excellent thermal and mechanical stabil-
ities, and all PEEKs with pendant sulfionic acid group membranes ex-
hibited lower water uptake and methanol permeability than the com-
mercialized Nafion® membrane[12]. Wei discussed the effect of the re-
inforced composite membranes composed of poly(tetrafluoroethylene)
and sulfonated poly(ether ether ketone) (SPEEK/PTFE) for vanadium
redox flow battery (VRB) applications (Figure 2)[13]. The composite
membranes exhibited higher mechanical stability and much better dura-
bility under the VRB system operation than the SPEEK membranes.
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(a) Protic ionic liquid
(b) Matrix plolymers
Figure 3. Chemical structures of [dema][TfO] and SPIs[15].
Figure 4. Chemical structure of SPI and SO2-crosslinked SPI membranes[16].
2.2.4. Polyimide-based ion exchange membrane
Polyimide-based polymeric ion exchange membranes have been de-
veloped for fuel cell applications because high mechanical and chem-
ical durability is required in these systems. Currently, the most com-
monly used proton conductive membranes for VRBs are per-
fluorosulfonic, such as Nafion® membranes, which assure high chem-
ical stability and excellent proton conductivity[8]; however, these mate-
rials have some disadvantages such as high costs and vanadium perme-
ability, which decreases the efficiency of the system. Therefore, poly-
imide-based polymeric membranes have been considered as an
alternative. Zhang et al. synthesized a series of vanadium ion blocking
sulfonated polyimide (SPI) membranes with various non-sulfonated di-
amines that could be used for vanadium redox batteries (VRBs). The
prepared SPI membranes exhibited lower permeability of vanadium ion
compared with that of Nafion® 117, and the IEC and proton con-
ductivity of the SPI membranes were the highest compared with other
polyimide-based membranes and Nafion®. Therefore, they concluded
that the SPI is the most promising candidate for VRB systems[14].
Yasuda et al. developed a polymer structure of the properties of the
composite membranes including a protic ionic liquid, i.e. dieth-
ylmethylammonium trifluoromethanesulfonate ([dema][TfO]), for
non-humidified fuel cell applications and they investigated the effect of
the different structures on the sulfonated polyimides (SPIs) as a matrix.
The multiblocks and random copolymers with sulfonate groups in the
side chain exhibited higher ionic conductivity due to the sequence dis-
tribution of the ionic groups, which depend on the sequence dis-
tribution and connectivity of the ionic channel (Figure 3)[15]. Yaguchi
et al. reported the performance of side chain-type sulfonated polyimide
(SPI) (Figure 4) membranes and cross-linked membranes[16]. The
cross-linked membrane exhibited excellent cell performance at both
high temperatures and low temperatures. This indicates that the hybrid
membranes doped with hydrophilic inorganic porous fillers such as
silica might be useful as high temperature proton exchange membranes
(HTPEMs).
2.3. Manufacturing techniques for anion exchange membranes
Polymers with positively charged quaternary ammonium have numerous
successful applications in fuel cells, flow batteries, water electrolyzers,
electrodialysis (ED), biomaterials, and reverse electrodialysis[17-20]. To
date, commercially available anion exchange membranes (AEMs) have
typically been based on cross-linked polystyrene and are not stable in al-
kaline or electrochemical environments. In other to resolve these prob-
lems, several AEMs based on different polymers, such as poly(phenylene
oxide) (PPO)[21], polysulfone based polymer, poly(vinylalcohol)[22-24],
divinylbenzene[25], and copolymers[26] have been reported in the
literature. These polymers must have well-controlled ionic groups for each
repeating unit group due to the membrane stability. For example, a higher
ionic group density results in excessive swelling and lower dimensional
stability. Therefore, many researchers have developed modified polymeric
materials and investigated the effect of the ionic site on the membrane.
In this section, we summarize the various types of polymeric materials
used to fabricate anion exchange membranes.
2.3.1. Polysulfone-based ion exchange membranes
A commercial polymer material, polysulfone (PSf), has excellent
chemical and thermal stability and mechanical strength[27].
Furthermore, polysulfone can be easily modified using sulfonation, al-
kylation, bromination, and chloromethylation. The polysulfone mem-
brane with functional groups has been widely used in various
applications. Herein, we summarize the research on polysulfone-based
materials and their modification method[28]. Yan et al. reported the
properties of anion exchange membranes synthesized using hal-
omethylation and quaternization of benzylmethyl-containing bisphenol
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Scheme 3. Synthesis of quaternary ammonium-containing polymers from bromination of tetramethyl bisphenol a-based poly(sulfone)s[29].
(a)
(b)
Scheme 4. (a) Synthesis of bis(phenyltrimethylammonium) (PTMA) functionalized copolymers 4 by lithiation chemistry; (b) chemical structures of PAES-QA and PPO-QA for the control experiments[31].
A-based poly(sulfone) (Scheme 3)[29]. In the anion exchange mem-
branes developed in their study, increases in the water content ap-
peared to promote high conductivity even with a low volumetric poly-
mer-bound cation concentration. Furthermore, the relationship between
the volumetric density of the fixed charged sites and the anion con-
ductivity were confirmed. Zhao et al. developed a quaternary ammonia
polysulfone (QAPS) membrane for alkaline anion exchange membrane
fuel cells. Their study focused on improving the mechanical properties
of the QAPS membrane because this membrane exhibited poor me-
chanical strength and a high swelling ratio. The membrane mechanical
strength and dimensional stability using the PTFE support also
increased. Furthermore, this membrane exhibited a high power output
and power density[30]. Li et al. developed commercial polysulfone
functionalized with tertiary amines using lithiation chemistry. The
bis(phenyltrimethylammonium) (PTMA) site was introduced into the
polymer backbone via an ion exchange reaction. The prepared mem-
brane exhibited a significantly lower water uptake and dimensional
swelling compared with the previously reported AEMs. The hydroxide
conductivities of the membranes also exhibited higher values, which
were related to the side chain-type structures of the pendent functional
groups (Scheme 4)[31].
2.3.2. Poly(ether ether ketone) (PEEK)-based membranes
Poly(ether ether ketone) (PEEK) possesses good mechanical proper-
ties, thermal stability, toughness, and some conductivity depending on
the degree of modification. PEEK is a thermostable polymer with an
aromatic, non-fluorinated backbone in which phenyl groups are sepa-
rated by ether (–O–) and carbonyl (–CO–) linkages. PEEK can be func-
tionalized via sulfonation and quaterinization, which can be controlled
using the reaction time and temperature. Recently, many studies have
developed membranes with high performance through controlling the
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Scheme 5. Synthetic routes of CPAES-Qsand PAES-Qs[32].
Figure 5. The resonance stabilisation of the positive charge should increase from methylated meta-PBI over PBI-OO to PBI-OPO when the two neighboring conjugated systems (indicated by the dotted lines)are separated from each other)[38].
chemical structure and through complexing the membranes with other
polymers or support materials.
Nie et al. reported the effect of the cross-linking of the PEEK-based
polymeric membrane. In their study, a series of CPAES-Qs AEMs con-
taining aromatic side-chain pendant quaternary ammonium groups were
synthesized using a multi-step process, e.g. bromination, quaternization,
alkalization, and cross-linking reaction. The side chain quaternary am-
monium groups and cross-linked structures modified the membrane
structures and this membrane exhibited improved performance (Scheme
5)[32].
Xiong synthesized quaternized cardo polyetherketone (QPEK-C)
membranes for alkaline fuel cells using viachloromethylation, quaterni-
zation, and alkalization of cardo polyetherketone (PEK-C) (Scheme 6).
This membrane exhibited higher proton conductivity and low methanol
permeability as a result of the methanol resistance of the mem-
brane[37].
Xuehong et al. developed poly(ether ether ketone) (PEEK) with pro-
penyl groups using the aromatic nucleophilic polycondensation
reaction. Then, the anion exchange membranes PEEK-g-DMAEMA
were prepared through grafting PEEK with 2-(dimethylamino)ethyl
methacrylate (DMAEMA) (Figure 8). The grafted polymer membranes
exhibited well dispersed microphase structures that were hydrophilic
and hydrophobic, which affect the ion exchange capacity and dimen
sional stability, e.g. water uptake[33].
2.3.3. Polybenzimidazole-based ion exchange membranes
Polybenzimidazole (PBI) is well known for its excellent stability un-
der oxidative and other effective environments[34]. PBI has a hetero-
cyclic benzimidazole ring with an amphoteric character, which can be
easily modified using strong acids used for ionic conductive mem-
brane[35]. However, it is difficult to control the PBI membranes and
it is synthesized under toxic conditions. Therefore, these membranes
were also modified via functionalization and post-chemical treatment
system. PBIs can be doped with strong alkalines such as potassium hy-
droxide, and alkaline-doped PBI membranes have been reported to
have good fuel cell performance. Lee et al. synthesized four types of
poly(dimethyl benzimidazolium) iodide that were used for anion ex-
change membrane fuel cells and then the ion exchange was conducted
via immersing the poly(dimethyl benzimidazolium) iodide membrane in
three different solutions (1 M KOH, K2CO3, and KHCO3). The prop-
erties such as water uptake, ion exchange capacity, and conductivity,
varied depending on the different ion exchange methods and counter
anions in the membrane. Some samples could be good candidates for
anion exchange membrane fuel cells[36].
Jheng prepared polybenzimidazole-based anion exchange membranes
and investigated the degree of imidazolium functionalization (DIF) of
the quaternized polybenzimidazoles (PBIs) effect on the performance
of the anion exchange membrane[37,38]. It was found that poly-
benzimidazole has steric shielding and this affects the polymer’s hy-
drolytic stability under alkaline conditions. Thus, many researchers
have developed the polybenzimidazole-based membranes for various
applications.
2.3.4. Polyvinylalcohol-based ion exchange membrane
Polyvinylalcohol (PVA) has been widely used in the preparation of
cation exchange and hybrid membranes[39]. PVA contains a large
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Scheme 6. Synthesis route soft hequaternized PBIs (mQPBI-X,sQPBI-X,andmsQPBI-X)[37].
Scheme 7. Schematic reaction route for the preparation of SMPEI/PVAcomposite AEMs[40].
amount of hydroxy groups, which have strong hydrogen bonding and
partial covalent bonding between the hydroxy groups of PVA.
PVA-based polymeric membranes have excellent mechanical properties
and suitable ion conductive properties. However, the excess swelling
behavior of the PVA membranes in aqueous media is a significant
problem. Therefore, many researchers have focused on improving the
mechanical properties using composites or cross-linking of the PVA
method. The PVA composite membrane exhibited excellent mechanical
and thermal stability, as well as proton conductivity in fuel cell
systems. Pandey developed anion exchange membranes using PVA and
silica compounds such as modified poly(ethyleneimine) (SMPEI) with
3-glycidoxypropyl-trimethoxysilan (GPTMS) with sol-gel and
cross-linking reactions (Scheme 7)[40]. The composite AEMs exhibited
high electrical properties.
2.4. Classification of membranes with formations
2.4.1. Homogeneous ion exchange membranes
Homogeneous ion exchange membranes have been synthesized via
direct polymerization or cross-linking processes. Homogeneous mem-
branes consist exclusively of the anion-exchanging material, which
forms a one-phase system. Various approaches are available to prepare
homogeneous membranes. These approaches can be classified into
three categories based on the starting materials.
1. Synthesizing a novel polymer material using a monomer contain-
ing anionic or cationic exchange moiety;
2. Modifying the polymer film through grafting a functional mono-
mer; and,
3. Polymer blending with other functional polymeric materials in-
cluding anionic or cationic moieties.
Recently, a variety of polymeric materials have been developed.
However, the developed novel polymeric membranes have good elec-
trical properties but lower chemical and mechanical stabilities[41,42].
The stability of the polymer electrolyte affects the system performance.
In order to solve these problems, heterogeneous types of membrane
have been investigated widely.
2.4.2. Heterogeneous ion exchange membranes
Heterogeneous ion exchange membranes have been used in various
applications such as electrodialysis, electrophoresis, and
electrodeionization. In general, homogeneous membranes with good elec-
trochemical properties exhibit lower mechanical strengths and chemical
durability. These types membranes exhibit swelling in the water, which
this affects the dimensional stability and results in poor permselectivity.
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공업화학, 제 26 권 제 1 호, 2015
Figure 6. Schematic illustration of (A) semi-IPN structure and (B) chemical structure of SPAES, VPA and DEGDMA[45].
Scheme 8. Synthesis of the quaternized PEK-C membranes[33].
However, heterogeneous membranes exhibit good mechanical strength
because heterogeneous ion exchange membranes have an ion exchange
resin, which is a polymer binder, as chemically resistant fabric or re-
inforcing support[43]. However, this type of membrane has com-
paratively poor electrochemical properties because this support does not
have ion exchange sites. In order to solve these problems, ion exchange
membranes with both good electrochemical can be fabricated using a
combination of suitable ion transfer reinforcing fabrics and polymer
binders. Heterogeneous-type membranes have already been developed
and commercialized in various international companies (Table 1)[44].
2.4.3. Interpenetrating network (IPN) polymer ion exchange
membranes
IPN polymer ion exchange membranes are a method for fabricating
ion exchange membrane that combines the electrochemical and me-
chanical properties using two or more polymers. IPN polymer ion ex-
change membranes exhibit the combined chemical properties of the
component polymers with improved physical properties and high
conductivities. The IPN is composed of one linear polymer (e.g. poly-
ethylene) trapped within the network of another polymer (Figure
6)[45]. Monomer polymerizations under a free radical mechanism yield
a cross-linkable structure of two interpenetrating networks of linear and
polymer molecules. The microphase-separated structure with differently
shaped and sized domains containing ionic groups can be obtained us-
ing chemical treatment or synthesis steps[46,47].
3. Characterizations of ion exchange membranes
3.1. Mechanical and chemical properties
3.1.1. Ion exchange capacity
The ion exchange capacity is determined through equilibrating the
membrane in a 1 M HCl or 1M NaOH solution in order to convert
the membrane into a H+ or OH- form, respectively. Then, the excess
HCl or NaOH is washed from the membrane using distilled water for
24 h; the membrane is equilibrated in distilled water in order to re-
move the last traces of acid or base. Then, the membrane is equilibrat-
ed in NaCl for 24 h and the ion exchange capacity is determined from
the increases in acidity or basicity, which are obtained via the titration
and back titration method.
3.1.2. Mechanical and chemical stability
The mechanical properties related to thickness, swelling, dimensional
stability, and tensile strength of the membrane are important factors for
the system application. In particular, the thickness affects the electrical
properties, such as membrane resistance, as well as the mechanical
properties. Therefore, various types of membrane are used in various
applications according to their performance. Furthermore, the elec-
tro-membrane processes should result in higher chemical durability and
increased lifetimes of the ion exchange membranes under the applied
conditions. The ion exchange membranes were used in various types
of solutions with acids and bases. The samples were exposed to vari-
ous test solutions in order to measure their chemical durability over
time. Then, the membrane was evaluated using visual comparisons and
performance changes before and after treatment.
3.1.3. Electrical resistance
The electrical resistance of ion exchange membranes is an important
factor that determines the performance of the systems. In general, the
resistance value is measured using an AC or electrochemical im-
pedance analyzer. For the electrodialysis process, the membrane resist-
ance was measured in dilute solutions because the ion concentration in
the membrane is relatively high. In contrast, for the membrane resist-
ance of membranes used in fuel cell systems, it is measured in humid
and non-humid conditions. The resistance of the ion exchange mem-
brane is determined from slope of the I-V curve[48].
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Appl. Chem. Eng., Vol. 26, No. 1, 2015
Figure 7. Schematic diagram illustration on the principle of electrodialysis in a stack.
Figure 8. Schematic of EDI process and ion transfer in EDI.
4. Applications
Ion exchange membrane processes can be divided into three types.
The first type is related to the separation of salt, acid, and bases from
electrolyte solutions. In this process, the driving force is the electrical
potential. The second type is the electrochemical reaction that produces
various chemicals such as chlorine, acid, and bases; the chlorine-alka-
line process is the dominant electrochemical production process. The
third type is the conversion of chemicals into electrical energy. The
polymer electrolyte fuel cell is the most significant application of ion
exchange membranes in energy conversion devices. Among these vari-
ous applications using ion exchange membranes, we summarize the
typical applications from recent research in this section.
4.1. Electrodialysis
4.1.1. Electrodialysis (ED)
The principle of electrodialysis (ED) is illustrated in Figure. 7. The
anion and cation exchange membranes are arranged with alternating
patterns between the anode and cathode. Then, an ionic salt solution
is inserted into these cells, and the electrical potential is established be-
tween the anode and cathode. Next, the positively charged cations
move to the cathode and the negatively charged anions move to the
anode. That is, both the positively charged cations and negatively
charged anions pass through the anion exchange membrane.
Recently, in many applications, electrodialysis is in direct competi-
tion with other separation processes such as the desalination of salt-de-
pleted waters for industrial use or for potable water from brackish wa-
ter and ion exchange. ED has an important function in large-scale in-
dustrial applications. This system requires membranes with high per-
formance related to better selectivity, lower electrical resistance, and
improved thermal, chemical, and mechanical properties in order to im-
prove the energy efficiency and commercialization capabilities.
4.1.2. Electrodeionization (EDI)
Electrically driven electrodeionization (EDI) is a hybrid separation
process that combines electrodialysis and ion exchange. EDI has gar-
nered increasing attention for the removal/recovery of ions from water.
There are different types of applications for EDI in the removal and
concentration of various species from effluent streams.
Cation and anion exchange membranes are placed between the elec-
trode systems. The central compartment is filled with ion exchangeable
materials that enhance the transport of cations or anions under the driv-
ing force of a direct current. A transverse DC electrical field is applied
using an external power source with electrodes at the ends of the mem-
branes and compartments, as depicted in Figure 8. The ion exchange
membranes have a critical function in the EDI processes because they
are responsible for accepting or rejecting ions in the diluted and con-
centrated compartments. In this case, ion exchange membranes with
high performance are achieved through the selective control and trans-
port of ionic species. When the EDI system is operating, a water dis-
sociation reaction occurs with the production of hydrogen (H+) and hy-
droxyl (OH-) ions. The produced H+ and OH- ions continuously re-
generate the ion exchange resins electrochemically without using re-
generating chemicals. Therefore, many researchers have focused on the
development of ion exchange membranes with excellent performance
for application in water purification, ion removal, and ion concentration.
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공업화학, 제 26 권 제 1 호, 2015
Membrane type Materials Application Reference
AEM Poly(sulfone)s-PTFE AEM [30]
AEM Poly(sulfone) AEM [31]
AEM polybenzimidazoles AEM [37]
AEM polybenzimidazoles AEM [36]
AEM polyaryleneethersulfone AEM [32]
AEM poly(phenylene oxide) (PPO), AEM [21]
AEM polybenzimidazole AEM [65]
CEM polyimide VRB [14]
CEM polyimide PEMFC [15]
CEM polyimide PEMFC [16]
CEM Polybenzimidazol PEMFC [65]
CEM 3D-SRGO Water treatment [66]
CEM Polyethyleneimine Water treatment [67]
CEM Sulponated Polyvinylidene fluoride Water treatment [68]
CEM Fe2O3-SO4
2-/sPPO Water treatment [69]
CEM Polyethyleneimine/Poly(acrylic acid) Water treatment [70]
CEM polyethersulfone MFC [71]
CEM Poly(Phenylsulfone)MFC [72]
AEM PVA-co-PE, N,N,N’,N’-tetramethyl-1,6-hexanediamine, PVBC
CEM MF-4SC Ion exchange membrane [73]
CEM sulfonated poly(phenylene oxide) Alkali recovery [74]
CEM Two types of Polyethylene added Carbon fibers Electrodialysis [75]
CEM CMPES (MEGA a.s., Czech Republic)Characteristic Evaluation [76]
AEM AMH-PES (MEGA a.s., Czech Republic)
CEM FQB (Hefei Chemjoy Polymer Materials Co. Ltd)Diffusion dialysis, electrodialysis [77]
AEM FSB (Hefei Chemjoy Polymer Materials Co. Ltd)
AEM AR204-SZRA-412 (Ionics, USA) Electrodialysis [78]
CEM PVC based-co-zeolite nanoparticle desalination [79]
CEM Sulfonated polyether ether ketone microbial electrolysis cell [80]
CEM PtIm2I2/Nafion PEMFC [81]
CEM Nafion-324 (DuPont) Filtration of ecotoxicity [82]
CEM PS/PVC Characteristic Evaluation [83]
CEM S-PVDF Characteristic Evaluation [84]
CEM Polyvinylchloride Characteristic Evaluation [85]
CEM CMI-7000 (Membrane International, USA) MFC [86]
CEMNeosepta® Food industry [87]
AEM
CEM CMX (Neosepta CMX-AMX. Tokuyama Soda, Japan)Electrodialysis [88]
AEM AMX (Neosepta CMX-AMX. Tokuyama Soda, Japan)
CEM CMX (Neosepta®)Neutralization dialysis (ND) [89]
AEM AMX (Neosepta®)
AEMRalex AM(H)-PES (Mega a.s., Czech Republic)
AR 103 QDP (GEIonics)Electrodialysis [90]
AEM FAB(FuMA-Tech GmbH, Germany) bioelectroanalysis [91]
AEM KOH doped PVA–PDDA MFC [92]
AEM Vanadyl sulphate, di-vanadium tri-sulfate, sulfuric acid, phosphoric acid VRFB [93]
AEM PAN-co-PDMA-co-PnBA Characteristic Evaluation [94]
CEM polyvinylchloride Electrodialysis [95]
CEM PEEK PEMFC [96]
Table 2. Recent Trends in the Research on Ion Exchange Membrane
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Appl. Chem. Eng., Vol. 26, No. 1, 2015
4.2. Polymer electrolytes
4.2.1. Fuel cells
Fuel cells are electrochemical reactors in which the chemical energy
is converted into electrical energy[23,49-51]. There are different types
of fuel cells that operate at different temperatures between 100 and
1000 [52,53]. Low temperature fuel cells utilize ion exchange mem-
branes as ion-conducting layers between two electrodes. However, in
this field, the membrane degradation is a key obstacle because the ion
exchange membranes used in fuel cells are highly dependent on the
lifetime of the membrane. For these reasons, perfluoro sulfonic acid
(PFSA) membranes are widely used in fuel cell systems due to their
high chemical durability and mechanical strength. However,
PFSA-based membranes have limitations such as degradation by free
radical attacks on reactive end groups, high cost, and complex prepara-
tion steps. Therefore, various aromatic polymers have been investigated
for use as electrolytes in fuel cell systems, e.g. sulfonated aromatic
polymers, particularly poly(arylene ether ketone) and poly(ether sul-
fone), and polyimide-based polymers[54,55]. These types of polymer
have exhibited good performance compared with Nafion® membranes.
However, this polymer must resolve its durability problems in order to
be commercialized in fuel cells[56-58].
4.2.2. Redox flow batteries
Vanadium redox flow batteries (VRBs) were developed by
Skyllas-Kazacos in 1985; these are a new type of fuel cell that can
store energy in a liquid electrolyte[59]. The energy generation step us-
ing the VRB is as follows. First, the acid aqueous solution electrolyte
is supplied to the cell via a liquid pump, and the energy is charged
and discharged through the ion exchange membrane during two differ-
ence reactions (oxidation and reduction). VRBs are being studied ex-
tensively in order to develop a new generation of energy storage sys-
tems because they have many advantages such as long cycle life, flexi-
ble design, fast response time, low pollution emitting in energy storage,
and low production or maintenance cost[60,61]. A key component of
VRBs and fuel cells is the ion exchange membrane[62]. That is, the
ion exchange membrane used in the VRB system should have a high
ionic conductivity and low vanadium permeability for high perform-
ance achievement. Furthermore, VRB systems operate under exposure
to strong vanadium electrolytes, so the ion exchange membrane also
requires excellent chemical durability and mechanical strength[63].
Nowadays, most ion exchange membranes exhibit lower chemical re-
sistance, which affects the membrane durability. For these reasons,
semi-fluorinated-based polymeric membranes, such as the Nafion® ser-
ies (Dupont, USA), are widely used in VRB systems. This type of
membrane exhibits high proton conductivity and excellent stability in
vanadium aqueous solutions, but it has high vanadium perme-
ability[63,64]. Therefore, the current research on anion exchange mem-
branes is focusing on resolving these problems and improving the ion
exchange membrane.
5. Summary
Here, the materials, classifications, and techniques for ion exchange
membranes were reviewed. Membrane separation techniques have be-
come attractive and gained popularity due to their numerous advan-
tages when compared with other separation techniques. In order to ob-
tain better system performance, the ion exchange membrane has been
continually developed by many researchers. Therefore, we summarized
the recent research trends in the development of ion exchange mem-
branes in Table 2.
In this review, it was demonstrated that it is necessary to know and
understand the various properties of membranes and methods to pre-
pare membranes with suitable properties for different applications. It
can be seen that different polymeric membranes are used in different
applications because the polymeric materials have different structures,
stabilities, ionic conductivities, and membrane resistances. The mem-
branes were also classified into different categories with different
formations. Recently, heterogeneous membranes have been widely used
in various fields due to their high mechanical strength; however, they
have poor electrochemical properties. Therefore, the many researchers
have focused on developing novel ion exchange membranes through
the introduction of ion exchangeable materials. However, more im-
provements are required in order for these to be adapted to various ap-
plications, and more research must be conducted in order to optimize
the performance of the ion exchange membranes. In order to achieve
public objectivity and commercialization of the membrane separation
system, academia, industry, and government should make a concerted
effort to cooperate in their development. A membrane separation sys-
tem that uses ion exchange membranes can promote comprehensive
utilization of renewable resources and contribute toward sustainable en-
ergy resources.
Acknowledgements
This work was supported by the Technology Innovation Program
(Industrial Strategic technology development program) funded By the
Ministry of Trade, industry and Energy (MI. Korea).
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