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abstract
Article history:
was done by solution casting technique. The ionic conductivity increased with ionic liquid
4 July 2013
mass loadings. The highest ionic conductivity of (5.74 0.01) mS cm1 was achieved upon
electrolytes is enhanced with doping of ionic liquid by showing higher initial decomposition temperature. The most conducting polymer electrolyte is stable up to 250 C. Attenuated total reflectance-Fourier Transform Infrared (ATR-FTIR) confirmed the complexation
Keywords:
PVA
Ionic liquid
Proton conductivity
between PVA, CH3COONH4 and BmImCl. Polymer electrolyte membrane fuel cell (PEMFC)
was fabricated. This electrochemical cell achieved the maximum power density of
18 mW cm2 at room temperature.
Copyright 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Fuel cell
reserved.
Power density
1.
Introduction
Depletion of non-renewable fossil fuel catalyzes the development of environmentally friendly alternative energy sources. Fuel cells are promising candidates as power sources for a
wide range of applications, ranging from portable devices to
electric vehicles [1,2]. Fuel cells are of great interest in the
recent research due to their attractive properties. They offer
many advantages, such as environmentally benign, high energy efficiency and lower emission of pollutants [3,4]. Fuel
cells also do not require the need for rapid recharging process
in the presence of electricity compared to the lithium
rechargeable batteries [5]. Apart from that, fuel cells exhibit
higher energy density than the batteries [6]. The main
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
project is to explore the effect of ionic liquid onto the electrochemical properties of polymer electrolytes and fuel cells.
2.
Experimental
2.1.
Materials
2.2.
Preparation of ionic liquid based-poly(vinyl alcohol)
proton conducting polymer electrolytes
Ionic liquid based-poly(vinyl alcohol) proton conducting
polymer electrolytes were prepared by solution casting technique. PVA was initially dissolved in distilled water. Appropriate amount of CH3COONH4 was subsequently mixed in PVA
solution. The weight ratio of PVA:CH3COONH4 was kept at
70:30. Different mass fraction of BmImCl was thus embedded
into the PVA-CH3COONH4 mixture to prepare ionic liquidbased proton conducting polymer electrolyte. CL 2, CL 5 and
CL 6 were the designations of polymer electrolytes with
respect to addition of 20 wt%, 50 wt% and 60 wt% of BmImCl,
whereas CL 0 was for the polymer electrolyte without incorporation of BmImCl. The resulting solution was stirred thoroughly and heated at 70 C for few hours until a homogenous
colorless solution is obtained. The solution was eventually
casted on glass Petri dish and dried in an oven at 60 C to
obtain a free-standing proton conducting polymer electrolyte
film.
2.3.
Characterization of ionic liquid based-PVA proton
conducting polymer electrolytes
2.3.1.
2.3.2.
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
2.4.
2.4.1.
Cell performances
The performance of PEMFC was done by fuel cell measurement setup which is comprised of Programmable DC power
supply (Model no: 3644A, Array Electronics Co. Ltd. from
Taiwan), rheostat (Model no: ZX97E, Tinsley from United
Kingdom) and Digital Bench Type True RMS multimeter
(UT803, Uni-Trend from Guangdong, Zhina). DC power supply
is employed to provide the current flow through the cell,
whereas the rheostat is used to adjust the current flow. The
measurements of voltage and current flow were probed using
multimeter. The cell potential in every 10 mA of current was
noted down, starting from 10 mA. The current density was
determined by dividing the operational current into surface
area of electrodes (16 cm2). On the other hand, the power
density was calculated using the fundamental equation below:
P IV
(1)
400
350
300
250
200
150
100
Rs
50
Rs+Rb
0
0
3.
3.1.
50
100
150
200
250
300
350
400
l
Rb A
(2)
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
-2.00
-2.50
..
Deprotonation
+H
-3.00
-3.50
-4.00
-4.50
-5.00
-5.50
10
20
30
40
50
60
70
Weight percent of BmImCl (wt %)
80
90
CH
CH2
CH
H
C
CH
H
CH2
CH
CH
OH
OH
H
+
3-butyl-2-chloro-1-methyl-4,5-dihydro-1H-imidazole
Cl
Cl or / and CH3COO
CH
OH
CH2
OH
O
..
CH2
CH
CH2
CH2
CH
:O
..:
CH2
CH
OH
N
or / and
OOCCH3
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
CH
CH2
CH
CH2
:..
O:
CH
CH2
CH2
CH
:O
..:
Cl or / and CH3COO
and ion aggregates as the ion pairs can block the transport
pathway within the polymer chains.
3.2.
CH2
CH
:O
..:
N
CH2
CH
O
CH2
CH
CH2
O H
N
CH
:O
..:
N
Cl or / and CH3COO
Beyond adulteration of 50 wt% of BmImCl, the ionic conductivity is found to be lower in value. This is ascribed to the
agglomeration of ions. Excessive ions in the polymer electrolyte could form ion pairs and ion aggregates. These ion pairs
and ion aggregates might block the conducting pathway and
hinder the proton from transportation, leading to lower ionic
conductivity. The amount of proton for conduction is also
decreased in the presence of ion pairs and ion aggregates. At
high concentration of ionic liquid, NH
4 cations could rather
form ion pairs with other anions than provide proton for
transportation. Similar observation goes to BmIm cations.
These cations help in providing the conducting site as aforementioned above. However, at high mass loadings, the cations
could form ion neutral pairs with anions and thus turn the
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
Upon addition of salt and ionic liquid, the mass loss in this
stage is significantly decreased. Besides, the starting decomposition temperature in this stage is improved. These observations deduct the contribution from the complexation
120
100
Weight (%)
80
60
40
20
0
0
100
200
Pure PVA
300
CL 0
400
CL 2
CL 5
500
600
CL 6
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
3.3.
Attenuated total reflectance-Fourier Transform
Infrared (ATR-FTIR)
The PVAeCH3COONH4 polymer electrolyte systems have been
prepared and investigated. The FTIR results and the
complexation between PVA and CH3COONH4 have been
elucidated in the literature [15,20,26e32]. Therefore, the
interaction between PVA and CH3COONH4 is not discussed in
this present work. The interactions between ionic liquid and
ammonium acetate-doped polymer electrolyte are also
analyzed and discussed in details. Fig. 4 depicts the ATR-FTIR
spectra of CL 0, BmImCl, CL 2, CL 5 and CL 6. On the other
hand, the band assignment of the spectra is summarized in
Table 1. The ATR-FTIR spectrum of CL 5 is investigated as it
achieves the maximum ionic conducting as aforementioned
in section 3.1. Upon adulteration of BmImCl, sixteen new
peaks have been formed by comparing Fig. 4(a) with Fig. 3(d).
These peaks are CeH vibrational mode for cyclic BmIm at
655 cm1, 693 cm1, 3109 cm1 and 3159 cm1 [33], CeH
bending mode for cyclic BmIm at 752 cm1 [33], in-plane CeH
bending mode of imidazolium ring at 890 cm1 [34], in-plane
CeNeC bending mode at 951 cm1 [35], out-of-plane CeH
wagging mode in alkyl chain at 1019 cm1 [34], CH3eN
stretching mode at 1168 cm1 [36], CH2 symmetric bending
mode at 1335 cm1 [33], CH3 asymmetric stretching mode at
1378 cm1 [33], CH3 asymmetric bending mode at 1428 cm1
and 1456 cm1 [36], C]N stretching mode at 1540 cm1 [37]
and CeC and CeN bending modes of imidazolium ring at
1696 cm1 [33]. Some characteristic peaks of CL 0 are disappeared with doping of BmImCl. Examples of these characteristic peaks are the combinations of CHOH bending mode,
CH3 in-plane deformation and CeH wagging mode at
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
CL 0
CL 2
CL 5
CL 6
655
655, 693,
3109, 3159
e
657
657, 703,
e, e
e
e
662, 698,
3113, 3152
730
655
655, 698,
3103, 3159
e
746
791
e
900
e
e
844
e
753
e
846
885
752
e
846
890
751
e
848
e
e
940
1018
918
e
e
918
951
1019
918
951
1021
918
e
1019
e
1132
e
1089
e
1140
1092
e
1143
1092
e
1140
1089
e
1142
1163
e
1289
e
e
1236
e
1329
1169
1236
e
e
1168
1236
e
e
e
1236
e
e
1337
1388
1413
1434
1465
1517
1560
e
e
e
1675
e
e
1414
e
e
e
e
1561
1648
1669
e
1335
1378
1409
e
1453
1504
e
1567
1648
e
1696
1335
1378
e
1428
1456
e
1540
1571
1647
e
1696
1332
1375
1410
e
e
1504
e
1559
1652
e
1699
e
2872, 2950,
2966
e
3091
1701
2850, 2906,
2937
3259
e
e
2876, 2911,
2940
3332
e
e
2870, 2939
e
2850, 2911,
2938
3260
e
the CeO coordination bond when the ionic liquid is complexed with polymer backbone.
The sharp peak at 1163 cm1 is designated as CH3eN
stretching mode, whereas the weak peak at 1388 cm1 is
associated with CH3 asymmetric stretching mode. The first
peak exhibits upward shift to 1168 cm1 with reduced peak
intensity of 31.11%, from 44.11% to 13% in transmittance
mode. On the contrary, the latter peak shifts to lower wavenumber to 1378 where its intensity is gradually reduced from
3.17% to 0.73% in transmittance mode. The peak at 1414 cm1
is designated as CeH deformation mode. However, the inclusion of 50 wt% of ionic liquid induces to the formation
double peaks at 1456 cm1 and 1428 cm1, as shown in Fig. 6.
The change in shape is suggestive of the overlap of CeH
deformation mode at 1413 cm1, CH3 asymmetric bending
mode at 1434 cm1 and CH3 symmetric bending mode at
1465 cm1. This can be proven using the deconvolution
method. The peaks are fitted and deconvoluted as illustrated
662
e
3347
e
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
0.05
0.04
0.03
1465 cm-1
Absorbance
1434 cm-1
0.02
0.01
1413 cm-1
-0.01
1380
1400
1420
Original curve
1460
1440
Wavenumber (cm-1)
Fitted curve
1480
1500
Deconvoluted peaks
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
10
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 x x x ( 2 0 1 3 ) 1 e1 2
3.4.
Cell performances
In order to study the effect of ionic liquid onto the electrochemical performances of fuel cell, four fuel cells are assembled by sandwiching CL0, CL 2, CL 5 or CL 6 between anode and
cathode and further analyzed. Electrolyzer is used to generate
hydrogen and oxygen gases. The hydrogen gas is connected to
anode, whereas the oxygen is channeled to cathode. Below are
the general reactions in both electrodes.
Anode : 2H2 /4H 4e
Cathode : 4H O2 /2H2 O
Complete reaction : 2H2 O2 /2H2 O
Hydrogen gas which acts as fuel will be split into positively
charged hydrogen (or known as proton) and negatively
charged electrons in the presence of catalyst layer at anode.
For next step, the polymer electrolyte membrane allows the
protons to travel from anode to cathode. In contrast, the
electrons are transported along the external circuit to cathode
and hence create electrical current. Eventually, the combinations between proton and oxygen with the help of electrons
will form water as by-product at cathode side. This by-product
will be flowed out from the system.
The open-circuit voltage (Voc) is determined when no current flows into the fuel cell. This is known as the initial voltage
prior to the cell voltage measurement. Figs. 8 and 9 depict the
cell potential and power density of the electrochemical cells
with different current density at room temperature, respectively. The Voc of CL 0, CL 2, CL 5 and CL 6 are 0.27 V, 0.37 V,
0.66 V and 0.56 V, respectively as illustrated in Fig. 8. As can
been seen in current density-potential curves, the cell potential of ionic liquid-based polymer electrolytes are higher
than that of polymer electrolytes without inclusion of ionic
liquid. This is mainly attributed to the strong plasticizing effect of ionic liquid. The plasticizing effect of ionic liquid not
only helps in promoting the proton conduction by weakening
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
20
30
40
50
Current density (mAcm-2)
CL 0
CL 2
CL 5
60
70
CL 6
Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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 x x x ( 2 0 1 3 ) 1 e1 2
4.
Conclusion
11
Acknowledgment
This work was supported by the High Impact Research Grant
(J-21002-73851) from University of Malaya and eScienceFund
(16e02e03e6031) from Ministry of Science, Technology and
Innovation (MOSTI), Malaysia. Gratitude also goes to Peruntukan Penyelidikan Pascasiswazah (PPP), Universiti Malaysia.
One of the authors, ChiameWen Liew gratefully acknowledges the Skim Bright Sparks Universiti Malaya (SBSUM) for
scholarship award.
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polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092
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Please cite this article in press as: Liew C-W, et al., A novel approach on ionic liquid-based poly(vinyl alcohol) proton conductive
polymer electrolytes for fuel cell applications, International Journal of Hydrogen Energy (2013), http://dx.doi.org/10.1016/
j.ijhydene.2013.07.092