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abstract
Article history:
Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics
and methanol crossover, which are limiting the development of direct methanol fuel cells.
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-
tivity of as-synthesized anion exchange membrane can reach up to 2.79 102 S/cm at
70 C. The physical and chemical stability of the anion exchange membranes could also
meet the requirement for alkaline direct methanol fuel cells.
Keywords:
1.
Introduction
* 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
2.
Experimental
2.1.
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
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
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.
3.1.
Linear polymers(FPAEOx)
3.2.
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.
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
Mn/ 104
1.79
2.65
5.02
1.78
1.76
1.6
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.
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
1.0
0.9
Weight/%
0.8
0.7
0.6
Acknowledgments
0.5
grafted FPAEOx
bromized FPAEOx
QFPAEOx
0.4
0.3
100
200
300
400
500
600
700
800
references
T/
Fig. 5 e TGA curves of different polymers.
3.4.
4.
Conclusions
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