i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

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Synthesis and characterization of anion exchange

membranes for alkaline direct methanol fuel cells
Guoshun Liu, Yuming Shang, Xiaofeng Xie*, Shubo Wang, Jinhai Wang, Yaowu Wang,
Zongqiang Mao
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

article info

abstract

Article history:

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics

Received 27 January 2011

and methanol crossover, which are limiting the development of direct methanol fuel cells.

Received in revised form

In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole),

5 April 2011

was prepared through polycondensation, grafting and quaternization. The ionic conduc-

Accepted 7 April 2011

tivity of as-synthesized anion exchange membrane can reach up to 2.79
102 S/cm at

Available online 19 October 2011

70  C. The physical and chemical stability of the anion exchange membranes could also
meet the requirement for alkaline direct methanol fuel cells.

Keywords:

Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd.

Direct methanol fuel cells

All rights reserved.

Alkaline fuel cell

Anion exchange membrane
Quaternary ammonium groups

1.

Introduction

Alkaline Direct Methanol Fuel Cell (ADMFC) in alkaline

working medium has been brought out as a new research
area. A significant advantage of ADMFC is that the cathode
reduction overpotential can be markedly reduced, leading to
high fuel cell efficiencies. Moreover, catalysts in basic medium
are more durable [1], and the inherently faster kinetics of
oxygen reduction reactions in an alkaline fuel cell renders it
possible to employ non-precious metals as catalysts [2],
greatly reducing the cost of the ADMFC.
Anion exchange membrane with alkaline active base is the
core part of ADMFC. Only some specific anions can cross the
membranes, and ion conductivity is related to the progress of
crossing [3]. Practical ion exchange membranes are usually
homogeneous polymers what are added with anti-aging
agent, plasticizer or antioxidant, etc. Anion exchange

membrane used in ADMFC is required to transfer OH, and

alkaline bases must be contained in its chemical structure.
The polymer framework and the molecular weight should
separate fuels to oxidant so that the anion exchange
membrane will maintain stability under working temperature
and certain methanol concentration while its mechanic
capability are supposed to afford the pressure difference
among the membranes. Recently, many kinds of anion
exchange membranes have been developed, such as quaternized poly (ether sulfone) [3e7], quaternized poly (2,6dimethyl-1,4-phenylene oxide) [8], quaternized poly (phthalazinone ether sulfone ketone) [9], quaternized poly (phenylene) [10], and radiation-grafted PVDF, ETFT, and FEP
[11e13],etc.
In this work, quaternized poly(aryl ether oxadiazole), was
prepared through polycondensation, grafting and quaternization. Monomers with fluorine atoms were selected to

* Corresponding author.
E-mail address: xiexf@tsinghua.edu.cn (X. Xie).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.04.047

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

prepared poly(aryl ether) polymers. Quaternary ammonium

structure was introduced to the side chain of the polymers.
The membranes obtained the capacity of transferring ions
with available chemical stability. Ion conductivity reached to
2.79
102 S/cm with the best performance. The physical and
chemical stability of the anion exchange membranes could
meet the requirement for the ADMFC.

2.

Experimental

2.1.

Materials & testing method

2,5-bis(perfluorophenyl)-1,3,4-oxadiazole(AR), hexafluorobisphenol A(AR,)., and the other reagents were bought from
Sinopharm Chemical Reagent Beijing Co.,Ltd.
Infrared absorption spectrometry (Perkin elmer instruments), Nuclear magnetic resonance spectrometry (Oxford
600M instruments), Ion conductivity (Zahner IM6 electrochemical work station). thermal analysis (TA Instruments
2500), under the protection of N2 atmosphere, temperature to
900  C, the heating rate 10  C/min.
A trough made in our lab is used to test the methanol
permeability (P). This trough has two ventricles with the same
volume. Methanol solution of different concentration is
poured into one ventricle when water into another. The
membranes to be tested separated them out. Samples were
taken out at every certain time point. Gas Chromatography
instrument (Shimadzu GC14B) is used to describe the change
of methanol concentration with time and figure out the
methanol permeability.
P

SVB L
ACA

S: the slope of methanol concentration change with time in

room B, VB: the volume of room B, L represents the thickness of
membrane while A represents the area of membranes, CA: the
initial concentration of methanol in room A.

2.2.

Synthesis of monomer(FPOx)

2,5-bis(perfluorophenyl)-1,3,4-oxadiazole
and
hydrazine
sulfate were added into polyphosphoric acid in a roundbottom flask. The reaction was filled with argon three times
for removing air and moisture, was heated 100e150  C with
stirring and maintained until no more gas release was
observed. The reaction solution was poured into mass of
distilled water with stirring until it was cooled down below
80  C. The white precipitate, monomer was acts FPOx, was
collected by filtration and washed with hot water until the
filtrate was neutral.
Element analysis:C14F10N2O(FPOx), theoretical: C,41.81;
F,47.24; N,6.97; O,3.98. practical: C,41.75; N,6.92. MP: theoretical: 156.2e157.4  C; practical: 156.5e157.1  C. 19F
NMR(d,CDCl3): C14F10N2O(FPOx), theoretical: 134.33 (m, 4F
ortho to Ox), 145.10 (m,2F, para to Ox), 158.39 (m, 4F, meta to
Ox), practical:135.19(m,4F, ortho to Ox); 146.00(m,2F, para to
Ox); 159.29(m,4F, meta to Ox).The data from FT-IR and mass
spectrum was nearly the same as the data from the reference [14].

2.3.

849

Preparation of linear polymers(FPAEOx)

FPOx and hexafluorobisphenol A(6F-BPA) were added to N,Ndimethylacetamide (DMAc) with stirring in a flask. KF grinded was added to the mixture at the temperature about 0  C.
After 5 h, The final reaction solution was filtered and dropped
into methanol to precipitate the polymer, which was further
washed with methanol three times prior to being dried to
produce the final product, FPAEOx. A flow sheet of synthesis
processes is shown as Fig. 1.
Comparing with the 19F NMR spectrum of the monomer,
the 19F NMR spectrum of the polymer represents that the
reaction position is actually at the point of p-F atom. 19F NMR
(d,CDCl3): monomer (FPOx), 135.19 (m, 4F, ortho to Ox); 146.00
(m, 2F, para to Ox); 159.29 (m, 4F, meta to Ox). 19F-NMR (d,
CDCl3): polymer(FPAEOx),135.80 (m, 4F, ortho to Ox); 159.61(m,
4F, meta to Ox). The signal peak at 146.00 had disappeared and
the 1H NMR spectrum also presented that the linear structure
of polymer. 1H NMR(d,CDCl3): FPAEOx, 7.05 (m,4H,ortho to Ar);
7.40 (m,4H,meta to Ar).

3.

Results and discussion

3.1.

Linear polymers(FPAEOx)

During the condensation polymerization between aryl halides

and phenol to generate poly(aryl ether), K2CO3 is often used to
absorb inborn hydrogen halides, which moves the equilibrium
to promote the reaction [15]. Because of depression of electron
density in multi-fluorinated aromatic rings, SNAr substitution
is more easily carried on in case of that KF will be used to
absorb the inborn HF as weak alkali. Fig. 2 shows polymerization of FPOx and 6F-BPA.
The molar rate of monomers will affect the molecular
weight of polymers in the polycondensation reaction. To
avoid the error in experiments due to the low rate of molecular weight increase, the accurate molar rate of 1:1 is adopted
in the polycondensation reaction. Considering that the end
group of polymers arent supposed to be phenolic hydroxyl,
which may react with alkaline base producing phenoxy
structure and leading to crosslinking, less than 1% of the
initial quantum of FPOx is added to the reaction system on the
chance of the end group of polymers to be fluorine atom
before the reaction finished.
Table 1 gives out the data of molecular weight of FPAEOx
from different polymerization time by gel permeation chromatography(GPC). Obvious crosslinking would occur when
the reaction time is over 7 h so that the samples couldnt be
tested with GPC. Considering convenience of experimental
operation and physical properties of the membranes, the
polymerization time was fixed on 5 h.

3.2.

Synthesis of anion exchange membrane(QFPAEOx)

FPAEOx
was
dissolved
with
stirring
in
N,NDimethylacetamide (DMAc). p-cresol and KOH was poured to
a flask with the solution. Then cyclohexane was added. water
knockout vessel and condenser pipe were connected to the
flask. The reagents were heated to about 80  C with stirring.

850

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

CF3

HO

OH

N N
F

CF3

FPOx

F
F

CF3

F
F

N N

CF3

F
O

N N
F

6F-BPA

b
F

CF3
O

N N
F

O
F

F
F

CF3
O

N N
F

O
F

F
F

CHN(CH3)3
OH

O
CF3

N N

CF3
O

N N

e
F

F
F

O
CF3

CHN(CH3)3
Br

CF3

N N

N N

d
F

O
CF3

CH2Br

c
F

N N

CF3

N N
F

Fig. 1 e A flow sheet of synthesis processes: (a) polymerization; (b) grafting; (c) bromization; (d) quaternization; and
(e) alkalization.

After KOH powder vanished, the reaction system was allowed

to react for another 1 h. The cooled solution was poured into
100 mL of methanol to precipitate the polymer which was to
be filtrated and washed. The dried polymer was obtained.
Grafted FPAEOx was dissolved in 1,2-dichloroethane with
stirring. n-bromosuccinimide(NBS) and Azobisisbutyronitrile(AIBN) were added to the solution to react for about 1h.
The clear solution was poured into methanol. The white
precipitate was collected by filtration and washed with
methanol. The dried polymers were dissolved in 1,2dichloroethane and the solution was casted to prepare

membranes which were of 40e50 mm. The membranes were

marinated into trimethylamine solution (10%) for about 48 h.
Deionized water was used to wash the membranes which was
marinated into KOH solution (10%) for 24 h. the anion
exchange membrane was obtained and stored in deionized
water.
The signal peak of benzyl appeares in the 1H NMR of
Grafted FPAEOx. Its chemical shift is about 2.25 same as the
signal peak of benzyl in p-cresol. Simultaneity, the signal peak
of H on benzene ring turns wild, whose chemical shift is
between 6.6 and 7.2. The signal peak of phenolic hydroxyl has

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

851

Fig. 2 e Polymerization of monomer and hexafluorobisphenol A.

Table 1 e Molecular weight of FPAEOx.

Polymerization time/h
4
5
6

Mn/
104

1.79
2.65
5.02

1.78
1.76
1.6

dipped in trimethylamine solution for about 48h to generate

quaternary ammonium structure, and further dealt with KOH
converting to alkaline structure [5]. Quaternization reaction
creates the new polymer (QFPAEOx) which cant be dissolved
in CDCl3. The signal peak appears at 888 cm1 in FT-IR spectrum which suggests the formation of CeN bond.

3.3.
Ion conductivity of anion exchange
membranes(QFPAEOx)

vanished, so it can be believable that p-cresol has been connected with the main chain of polymers through chemical
bonds.
Halogenation of benzyl is carried on by WohleZiegler
reaction. NBS is used to be brominating agent while AIBN is
used to be initiator. This reaction is good at selectivity so that
the H on benzene ring will not be substituted [16]. The signal
peak appears at the chemical shift of 4.41 in 1H NMR spectrum
of brominated polymers. It is the specific peak of methyl
bromide which represents bromination has taken place
normally.
Fig. 3 shows the schematic diagram of halogenation and
quaternization reaction. After halogenation, the polymers are

The ion conductivity of QFPAEOx under different temperatures is measured. Because of Hoffmann degradation of
quaternary ammonium bases, the word temperature of
ADMFC is actually below 80  C. When the temperature is
above 80  C, the EIS seems to be transpired. Therefore, the
temperature range in the experiment is between 20 and 70  C.
The results suggest that the ion conductivity is about
2
102 S/cm in the range of experimental temperature. The
highest conductivity is up to 2.90
102 S/cm. Ion conductivity rises when the temperature moves up.

Fig. 3 e Schematic diagram of halogenation and

quaternization reaction.

Fig. 4 e Effect of temperature on ion conductivity of

membrane.

852

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

be prepared. Ion conductivity of the membrane reached up to

2.90
102 S/cm, and showed good performance at methanol
resistance. It can be used in the area of Alkaline Direct
Methanol Fuel Cells.

1.0
0.9

Weight/%

0.8
0.7
0.6

Acknowledgments

0.5

grafted FPAEOx
bromized FPAEOx
QFPAEOx

0.4

The work was funded by Natural Science Foundation of China

(50911140287, 50973055, 51003053).

0.3
100

200

300

400

500

600

700

800

references

T/
Fig. 5 e TGA curves of different polymers.

Fig. 4 shows ion conductivity of membrane under different

temperature. The conductivity results are about at the level of
102 S/cm, which is the same as the results reported by the
references [10,13,17] of anion exchange membranes of
quaternary ammonium type (range between 103e1
101 S/
cm). It is proved that QFPAEOx membrane is capable of
transferring anions stably from 20  C to 70  C.

3.4.

Thermal stability of QFPAEOx membrane

Thermal stability is one of the criterions of membrane

stability, which decides the temperature limit of membrane
using. The same TGA tests are carried on to the membranes of
grafted FPAEOx, bromized FPAEOx and QFPAEOx. With the
introduction of functional bases, the stability degree of weight
loss decreases. For the membrane of QFPAEOx, the weight
percentage decreases at 100  C because of water loss of
membranes, and the weight loss at 200  C is as a result of
complete decomposition of quaternary ammonium bases.
Above 600  C, the main chain of polymers begin to break
down. Quaternary ammonium base is the most unstable bases
in anion exchange membranes. With the increased temperature, CeN bond has broken down. So did the quaternary
ammonium structure [18]. Therefore, the thermal stability of
membranes is capable of satisfying the need of alkaline direct
methanol fuel cells. Fig. 5 shows TGA curve of different
polymer.
The result of methanol permeability is 1.19
107 (cm2/s).
It is between the range (106e108 cm2/s) of methanol
permeability of common anion exchange membranes. It is
proved that QFPAEOx membrane will meet the requirement in
methanol resistance for being used in the methanol solution
environment.

4.

Conclusions

2,5-bis(perfluorophenyl)-1,3,4- oxadiazole was synthesized. It

was used to react with 6F-BPA to get the polymers (FPAEOx).
Through grafting, brominating and quaternization, the polymer membranes with quaternary ammonium structure had

[1] McLean GF, Niet T, Prince-Richard S, Djilali N. An assessment

of alkaline fuel cell technology. Journal of Hydrogen Energy
2002;27:507e26.
[2] Wang JH, Li SH, Zhang SB. Novel hydroxide-conducting
polyelectrolyte composed of an poly (arylene ether sulfone)
containing pendant quaternary guanidinium groups for
alkaline fuel cell applications. Macromolecules 2010;43:
3890e6.
[3] Hibbs M, Hickner M, Alam T. Transport properties of
hydroxide and proton conducting membranes. Chemistry of
Materials 2008;20:2566e73.
[4] Komkova EN, Stamatialis DF, Strathmann H, Wessling M.
Anion-exchange membranes containing diamines:
preparation and stability in alkaline solution. Journal of
Membrane Science 2004;244:25e34.
[5] Li L, Wang YX. Quaternized polyethersulfone cardo anion
exchange membranes for direct methanol alkaline fuel cells.
Journal of Membrane Science 2005;262:1e4.
[6] Pan J, Lu SF, Li Y, Huang AB, Zhuang L, Lu JT. Highperformance alkaline polymer electrolyte for fuel cell
applications. Advanced Functional Materials 2010;20:312e9.
[7] Wang GG, Weng YM, Chu D, Chen RR, Xie D. Developing
a polysulfone-based alkaline anion exchange membrane for
improved ionic conductivity. Journal of Membrane Science
2009;332:63e8.
[8] Xu TW. Ion exchange membranes: state of their
development and perspective. Journal of Membrane Science
2005;263:1e29.
[9] Fang J, Shen PK. Quaternized poly (phthalazinon ether
sulfone ketone) membrane for anion exchange membrane
fuel cells. Journal of Membrane Science 2006;285:317e22.
[10] Hibbs MR, Fujimoto CH, Cornelius CJ. Synthesis and
characterization of poly(phenylene)-based anion exchange
membranes for alkaline fuel cells. Macromolecules 2009;42:
8316e21.
[11] Varcoe JR, Slade RTC, Yee ELH, Poynton SD, Driscoll DJ,
Apperley DC. Poly (ethylene-co-tetrafluoroethylene) -derived
radiation-grafted anion-exchange membrane with
properties specifically tailored for application in metalcation-free alkaline polymer electrolyte fuel cells. Chemistry
of Materials 2007;19:2686e93.
[12] Herman H, Slade RTC, Varcoe JR. The radiation-grafting of
vinylbenzyl chloride onto poly (hexafluoropropylene-cotetrafluoroethylene) films with subsequent conversion to
alkaline anion-exchange membranes: optimisation of the
experimental conditions and characterization. Journal of
Membrane Science 2003;218:147e63.
[13] Danks TN, Slade RTC, Varcoe JR. Alkaline anion-exchange
radiation-grafted membranes for possible electrochemical
application in fuel cells. Journal of Materials Chemistry 2003;
13:712e21.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 8 4 8 e8 5 3

[14] Ding J, Day M. Novel highly fluorinated poly (arylene ether1,3,4-oxadiazole)s, their preparation, and sensory properties
to fluoride anion. Macromolecules 2006;39:6054e62.
[15] Saegusa Y, Iwasaki T, Nakamura S. Synthesis and
characterization of 1,3,4-oxadiazole containing polyethers
from 2,5-bis(4-fluoropheny1)-1,3,4 oxadiazole and various
aromatic diols. Macromolecular Chemistry and Physics 2007;
198:1799e808.
[16] Miyatake K, Zhou H, Watanabe M. Synthesis and properties
of novel sulfonated poly(phenylene ether). Journal of

853

Polymer Science Part A: Polymer Chemistry 2005;43:

1741e4.
[17] Abuin GC, Nonjola P, Franceschini EA, Izraelevitch FH,
Mathe MK, Corti HR. Characterization of an anionicexchange membranes for direct methanol alkaline fuel cells.
Journal of Hydrogen Energy 2010;35:5849e54.
[18] Macomber C, Boncella J, Pivovar B, Rau JA. Decomposition
pathways of an alkaline fuel cell membrane material
component via evolved gas analysis. Journal of Thermal
Analysis and Calorimetry 2008;93(1):225e9.