이온교환막 공정 및 응용 연구동향 · 2015-02-09 · technology due to their numerous advantages such as high energy effi-ciency, eco-friendliness, and low cost for maintenance

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

2 김득주⋅정문기⋅남상용

공업화학, 제 26 권 제 1 호, 2015

3이온교환막 공정 및 응용 연구동향

Appl. Chem. Eng., Vol. 26, No. 1, 2015


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


공업화학, 제 26 권 제 1 호, 2015

Figure 1. Reaction scheme of the preparation of N/S membrane[5].


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



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.


공업화학, 제 26 권 제 1 호, 2015

(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



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


공업화학, 제 26 권 제 1 호, 2015

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



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.


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].



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.


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



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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이온교환막 공정 및 응용 연구동향 · 2015-02-09 · technology due to their numerous advantages such as high energy effi-ciency, eco-friendliness, and low cost for maintenance