Materials Science for Energy Technologies 2 (2019) 194–202

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Materials Science for Energy Technologies

CHINESE ROOTS
GLOBAL IMPACT
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Development of polyvinyl alcohol/chitosan blend anion exchange

membrane with mono and di quaternizing agents for application in
alkaline polymer electrolyte fuel cells
K. Hari Gopi, Vishal M. Dhavale, Santoshkumar D. Bhat ⇑
CSIR-Central Electrochemical Research Institute-Madras Unit, CSIR Madras Complex, Chennai 600 113, Tamilnadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Anion exchange membranes (AEM) functionalized by quaternary ammonium moiety are fabricated from
Received 30 November 2018 polyvinyl alcohol/chitosan blend. Polymers namely polyvinyl alcohol (PVA) & chitosan (CS) are quater-
Revised 28 January 2019 nized individually and mixed together to form blend solution, further cross-linked chemically and cast
Accepted 29 January 2019
to form QPVA/QCS membrane followed by thermal treatment. Two types of membranes were prepared
Available online 23 February 2019
via, Quaternization of PVA and CS using alkyl spacers (mono quaternizing agent) and Quaternization of
PVA and CS using dual reagents, of varying wt %. Further, these membranes are cross-linked by chemical
Keywords:
and thermal methods prior to ionic conductivity and ion exchange capacity evaluation. The reaction of
Anion exchange membrane
Polyvinyl alcohol
quaternizing groups with PVA/CS backbone is interpreted using FTIR spectroscopy. The QPVA/QCS mem-
Chitosan brane with 20 wt% of alkyl spacer exhibits enhanced conductivity of 0.0047 S cm
1 at 40 °C in comparison
Blend membrane with all other ratios. Also, the alkaline stability of the optimized QPVA/QCS membrane evaluated till
Morphology 300 h shows an enhanced stability with lesser conductivity loss.
Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction
Currently alkaline polymer electrolyte fuel cells (APEFC) have
gained resurgence with potential interest, because of the use of
solid polymer electrolyte membranes unlike conventional liquid
aqueous KOH solution. Various advantages of APEFC include, sub-
jecting cost effective non-noble metals as electrocatalyst, efficient
water management and reduced fuel crossover with improved effi-
ciency due to less oxidant reduction over-potential in alkaline pH
environment [1]. However the performance of APEFC is largely
dependent on anion exchange membrane (AEMs), which should
have high OH
conductivity with significant long term stability
under alkaline condition [2]. As a consequence, the thirst for new
improved AEM materials has been progressing at a steady pace
in recent years. Because of the high basic and strong nucleophilic
nature, the OH
ions tend to attack the aromatic backbone thereby
cleaves the quaternary cation and thus inducing degradation. Thus,
at present the ultimate challenge is the development of new poly-
mer electrolytes (i.e., AEM) which combines enhanced OH
con-
ductivity with excellent alkaline stability.
An extensive range of various aromatic polymers including poly
(sulfone)s, poly(arylene ether ketone), poly(phenylene oxide), poly
⇑ Corresponding author.
E-mail address: sdbhat@cecri.res.in (S.D. Bhat).
(arylene ether)s and poly(ether ether ketone) have been function-
alized by different routes and have been investigated as anion
exchange membranes (AEMs) [3–10]. These membranes contain
fixed cationic head groups such as quaternary ammonium, pyri-
dinium, imidazolium, guanidinium, sulfonium, phosphonium and
1,4-diazabicyclo-[2,2,2]-octane as charge carriers grafted to the
polymer backbone [11]. The chemical stability of these aromatic
polymers at longer period of operation is limited, because of many
degradation pathways such as SN2 nucleophilic substitution, Hoff-
mann elimination and Ylide intermediate formation [12]. As an
alternative and to prepare stable membranes AEMs are prepared
from aliphatic polymer chains, which do not require any special-
ized reaction conditions unlike chloromethylation and bromina-
tion of aromatic polymers.
Polyvinyl alcohol (PVA) a synthetic polymer has been chosen as
parent polymer due to its properties like ease of preparation, excel-
lent film-formation, and reactive chemical nature favourable for
cross-linking through chemical and thermal methods. In the litera-
ture, many reports are available for the preparation of AEM from
polyvinyl alcohol for several applications. Emmanuel et al. [13]
reported the preparation of AEM through sol–gel reaction of anion
exchange silica precursor (AESP) with PVA in the presence of
tetraethoxysilane (TEOS). These anion-exchange membranes not
only showed high ion-exchange capacities with excellent
mechanical stability, also exhibited excellent acid flux recovery dur-

https://doi.org/10.1016/j.mset.2019.01.010
2589-2991/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202
ing diffusion dialysis. Das et al. [14] described the cross-linking of
poly(vinyl alcohol) (PVA) with 1,4-cyclohexanedimethanol digly-
cidyl ether (CHDMG) in presence of KOH solution to synthesize an
anion conducting polymer electrolyte membrane which exhibited
ionic conductivities of 2.2–4.7 mS cm
1. Recently, Irfan et al. [15]
reported sol–gel method of preparing novel anion exchange mem-
brane from polyvinyl alcohol (PVA), quaternized 1-hydroxy-N, N-
dimethyl-N-(pyridine-2-ylmethyl) methanaminium (QUDAP) and
tetraethyl orthosilicate (TEOS). The limitation with cross-linked
type of quaternized PVA membrane is that, they have less tensile
strength, which can be improved by methods like blending with
other polymers, insertion of inorganic materials in the polymer
matrix.
Chitosan (CS) a polysaccharide was obtained by the alkaline
deacetylation of chitin. Chitosan with its less toxic and biodegrad-
able nature is the most abundantly used natural polymer. In addi-
tion, its hydrophilicity, film forming property, high mechanical
strength and chemical resistance realize chitosan as a potential
membrane material. Chitosan when quaternized using (2,3-
Epoxypropyl) trimethylammonium chloride (EPTMAC) gives 2-
hydroxypropyl trimethyl ammonium chloride chitosan (HACC) as
product, which finds its application in waste water treatment. In
a similar way, this kind of membrane will also find its application
as solid polymer electrolyte for fuel cells. Wan et al. [16] prepared
a series of quaternized-chitosan polymer using glycidyltrimethyl
ammonium chloride with varying degree of quaternization. These
quaternized-chitosan derivatives are synthesised by reaction with
N-alkyl groups containing quaternary ammonium moiety which
can provide anion-exchange functional groups.
Blends of synthetic polymers like polyvinyl alcohol and poly-
styrene are combined with natural polymers like chitosan, starch
and cellulose and investigated for various applications. Anion
exchange membranes with semi-interpenetrating polymer net-
work (semi-IPN) based on quaternized chitosan (QCS) and polystyr-
ene (PS) was reported by Wang [17]. Liao et al. [18] synthesized
quaternized chitosan nano-particles and incorporated in to quater-
nized polyvinyl alcohol (Q-PVA) matrix to fabricate a composite
polymer membrane, which helps to retain the dimensional stabil-
ity, minimize the interfacial resistance and improve the ion trans-
port. Xiong et al. synthesized cross-linked composite membrane
from quaternized poly(vinyl alcohol) (QPVA) and quaternized chi-
tosan (2-hydroxypropyltrimethyl ammonium chloride chitosan,
HACC) using glutaraldehyde as the cross-linking reagent [19].
The current study focuses on a facile way of developing anion
conducting blend membrane based on PVA and CS under ambient
conditions, avoiding the carcinogenic chemicals for chloromethyla-
tion and bromination. The two polymers polyvinyl alcohol (PVA)
and chitosan (CS) are quaternized individually and mixed together
to form a blend solution, cross-linked and cast to form QPVA/QCS
membrane. Two type of membranes are prepared using dual quat-
ernization agents such as hexadecyltrimethylammonium bromide
(HDT) and 2,3,5-triphenyltetrazolium chloride (TPTZ). A series of
quaternized membranes were developed by incorporating HDT &
TPTZ of varying weight percentage in relation to polymer. The
structural and thermal stability of the membranes were investi-
gated by techniques such as FT-IR, FE-SEM and TGA. These mem-
branes are also characterized for their transport properties like
ion exchange capacity (IEC) and ionic conductivity.
2. Experimental
2.1. Materials
Polyvinyl alcohol with 88% degree of hydrolysis was purchased
from Fisher Scientific India Pvt. Ltd. Chitosan and hexade-
195
cyltrimethylammonium bromide (99%) (HDT) was procured from
Acros Organics, India. Glutaraldehyde solution (25% in water) and
2,3,5-triphenyltetrazolium chloride (TPTZ) supplied from Loba
Chemie was used. Sodium sulphate (Na2SO4), Silver nitrate
(AgNO3) and Potassium hydroxide pellets were purchased from
Merck chemicals.
2.2. Membrane fabrication
2.2.1. Preparation of PV/CS-HDT membrane
Firstly, polyvinyl alcohol was dissolved in 10 mL of de-ionised
water at 60 °C to form 5 wt% solution. The solution was cooled
and varying amount of HDT (10, 15, 20 & 25 wt%) was added. This
mixture was ultra-sonicated for 30 min and then stirred for 12 h at
room temperature. Similarly, chitosan was dissolved separately in
10 mL of 2% acetic acid solution to prepare 0.55 wt% solution. To
this solution, different wt% of HDT (10, 15, 20 & 25 wt%) was added
followed by ultra-sonication for 30 min and stirring at room tem-
perature for 12 h. These two resulting solutions are mixed together
and further stirred for 1 h. Then, 0.6 mL of Glutaraldehyde (GA)
was added for chemical cross-linking and further stirred for
30 min. The solution was then poured on flat glass plate and dried
at room temperature. The formed membrane is referred as
PV/CS-HDT.
2.2.2. Preparation of PV-HDT/CS-TPTZ membrane
Polyvinyl alcohol was dissolved in 10 mL of de-ionised water to
prepare 5 wt% solution. To this added different wt% of HDT (10, 15,
20 & 25), followed by ultra-sonication for 30 min and stirred at
room temperature for 12 h. In parallel, chitosan was dissolved in
10 mL of 2% acetic acid solution to form 0.55 wt% solution. To this,
varying amount of TPTZ (10, 15, 20 & 25 wt%) was added, ultra-
sonicated for 30 min and stirred for 12 h at room temperature.
As mentioned above, the two solutions are blended together and
further stirred for 1 h. Then GA (0.6 mL) was added to the mixture
for cross-linking with 30 min stirring. It was cast on a flat glass
plate for drying at room temperature. The formed membrane is
referred as PV-HDT/CS-TPTZ.
Further, above two types of membranes are thermally cross-
linked by placing in vacuum oven at 80 °C for 15 h. Finally, the
cross-linked membranes (Br
or Cl
form) were immersed in 2 M
KOH solution for 12 h to facilitate ion-exchange. Then the mem-
branes were washed with de-ionized water (DI) to remove residual
KOH and stored in DI water prior to use. The presumed interaction
between PVA and CS with HDT and TPTZ is represented in
Scheme 1.
2.3. Structural characterization of membranes
The chemical interaction of cross-linked quaternized PV/CS
membranes were analysed by Fourier transform infrared (FTIR)
spectroscopy using Thermo Scientific Nexus 670 FT-IR spectropho-
tometer in the range of 4000–400 cm
1 under ATR mode. A field
emission scanning electron microscope (FE-SEM) (Model-MIRA3
LMU) was used to capture the surface morphology images of
PV/CS-HDT and PV-HDT/CS-TPTZ membranes with varying wt%.
Prior to imaging, the membrane samples were dried under vacuum
followed by gold (Au) sputtering for 60 sec. Atomic force micro-
scopy (AFM) images of the AEM (optimized wt%) are captured on
PicoSPM- Picoscan 2100 (Molecular Imaging, USA) in tapping mode
with the scan area of 90  90 mm. The thermal decomposition of
membrane samples was examined on TG-DSC analyzer (STA-449F3
NETZSCH, Germany). The thermal stability was recorded starting
from temperature of 30 till 800 °C at a heating rate of 5 °C min
1
under nitrogen atmosphere.
196 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202

2.6. Alkaline stability

The chemical stability of the optimized membrane was evalu-

ated as reported in our previous literature [21]. Briefly, the mem-
brane sample was kept immersed in 4 M KOH solution at 80 °C,
in a closely tight glass container for 300 h. Then, the membrane
was taken out from the container and washed with Millipore water
to remove the residual adsorbed KOH. Further, the membrane was
dipped in 1 M HCl solution to convert it to Cl
form. After neutral-
izing, the membrane was immersed in Millipore water before eval-
uating its ionic conductivity and IEC. Any change in the ionic
conductivity of alkaline treated membrane was measured and
determined.

3. Results and discussion

3.1. Fourier transform infrared (FT-IR) spectroscopy for the

membranes

The existence of chemical functional groups of PV and CS pre-

sent in composite AEM with varying weight percentages of HDT
& TPTZ were investigated by FTIR and are depicted in Fig. 1. The
band at 3600 cm
1 is the characteristic AOH stretching of back-
bone, present in both QPVA and QCS spectra. In QPVA, the CAO
stretching peak of PVA backbone appears at around 1200 cm
1.
The appearance of band at 1670 cm
1 and at 1517 cm
1 corresponds

1.02

Scheme 1. Mechanistic interaction between PVA and CS with HDT and TPTZ. C-N streching
O-H streching

2.4. Determination of ion exchange capacity (IEC)

Transmittance

0.99

The Mohr’s titration procedure was followed to determine the

ion exchange capacity of AEM [20]. Pre-weighed membranes (in
Br
& Cl
form) are immersed in Na2SO4 (0.5 M) solution for 8 h,
for ion exchange to sulfate (SO2
4 ) form. The released bromide
0.96
and chloride ions were back-titrated against AgNO3 solution
PV/CS-HDT(10 wt%)
(0.1 M) using potassium chromate as an indicator. The molar
PV/CS-HDT(15 wt%)
amount of anions present in the membrane which was exchanged C-H streching
PV/CS-HDT(20 wt%)
was evaluated by measuring the amount of AgNO3 consumed in PV/CS-HDT(25 wt%)
the titration through the following relation, 0.93
4000 3500 3000 2500 2000 1500 1000 500

1

Volume of AgNO3  Molarity of AgNO3
IEC mmol g ¼
Dry membrane weight
ð1Þ Wavenumber (cm-1)

2.5. Conductivity measurements 1.00 O-H streching

The anion conductivity of AEM under fully hydrated condition

Transmittance

were carried out in an ESPEC-temperature & humidity chamber 0.96

(SH-242) interfaced with a single channel potentiostat (BioLogic, C-N streching
SP-150), scanned over the frequency of 1 Hz to 1 MHz using a
four-probe AC electrochemical impedance technique. Before the 0.92
measurements, the membranes were equilibrated in de-ionized
PV-HDT/CS-TPTZ(10 wt%)
water for at least 24 h, and then placed in the four-probe setup.
PV-HDT/CS-TPTZ(15 wt%)
The conductivity was determined from Nyquist plot, through the 0.88 PV-HDT/CS-TPTZ(20 wt%)
intersection of high-frequency intercept with real axis. The con- PV-HDT/CS-TPTZ(25 wt%)
ductivity for series of AEM was calculated at different tempera-
tures of 30–80 °C using the equation, 0.84
4000 3500 3000 2500 2000 1500 1000 500
L
r¼ ð2Þ Wavenumber (cm ) -1
RA
where L is the thickness in cm, R is membrane resistance in X and A Fig. 1. FTIR spectra of PV/CS-HDT & PV-HDT/CS-TPTZ composite membranes with
is the contact area of membrane. varying wt%.
 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202 197

to the ANH2 stretching of chitosan [22]. In the FTIR spectra of PV/-
CS-HDT, a sharp and strong peak occurring at 2885 cm
1 and
2985 cm
1 corresponds to CAH stretching of ACH2 groups from
HDT [21], which does not appear in the spectra of PV-HDT/
CS-TPTZ membranes. With increasing HDT content to polymer,
the intensity of these bands increase as it is evident from the
figure. The absorption peaks at 960 and 950 cm
1 in the IR spectra
of PV/CS-HDT and PV-HDT/CS-TPTZ composite membranes
represent the characteristic absorption of quaternary ammonium
groups [19]. These findings elucidate that quaternary ammonium
groups are present in both the polymers.
3.2. Membrane morphology studies
The surface morphologies (FE-SEM) of PV/CS, PV/CS-HDT and
PV-HDT/CS-TPTZ membranes with varying HDT and TPTZ wt %
are depicted in Figs. 2 and 3 respectively. As seen from Fig. 2a, pris-
tine PV/CS membrane displayed smooth and homogeneous surface.

(a) (b)

(c) (d)

(e)
Fig. 2. FE-SEM images of (a) pristine PV/CS (b) PV/CS-HDT-10 wt% (c) PV/CS-HDT-15 wt% (d) PV/CS-HDT-20 wt% and (e) PV/CS-HDT-25 wt% membranes.
198 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202
(a)
(c)
Fig. 3. FE-SEM images of (a) PV-HDT/CS-TPTZ-10 wt% (b) PV-HDT/CS-TPTZ-15 wt% (c) PV-HDT/CS-TPTZ-20 wt% and (d) PV-HDT/CS-TPTZ-25 wt% membranes.
With the increased addition of HDT to PV/CS polymer (Fig. 2b–e),
one can observe the dispersion of ionic filler particles on to the
blend polymer matrix. The density of distributed ionic particles
on the polymer matrix increases with increased wt % of HDT. At
optimized 20 wt% of HDT, a protective layer is formed over the
polymer surface which could help to improve the polymer stabil-
ity. However at higher wt %, the aggregation of HDT particles
increases, reducing the ionic functional groups. Fig. 3 presents
the effect of dual quaternization agents on the PV/CS polymer sur-
face. With increasing wt %, the distribution of particles over the
polymer matrix increases which can be seen from the Fig. 3a–d.
Since two different quaternizing agents are involved, the dis-
tributed particles could be oriented perpendicular to each other
polymer chain due to the electrostatic repulsion, thus, forming
an inter-linking network as seen in Fig. 3d.
The topological and 3-D AFM images for PV/CS, PV/CS-HDT and
PV-HDT/CS-TPTZ composite membranes containing optimized wt
% of HDT & TPTZ (20 wt%) respectively, are captured and are repre-
sented in Fig. 4 with the scan area of 90  90 mm. Pristine PV/CS
membrane (Fig. 4a) showed plain flat surface with homogeneous
morphology, while addition of HDT to PV & CS as well as addition
of HDT to PV & CS to TPTZ displayed phase separated heteroge-
neous morphology. For PV/CS-HDT (Fig. 4b) membrane, the uni-
form distribution of ionic particles is seen throughout the scan
area. In the 3-D image, the ionic domains of quaternary ammonium
are spread over the polymer matrix, thereby helps to enhance the
ionic conductivity of membrane. For PV-HDT/CS-TPTZ membrane,
because of the inter-linking of different functional groups the
(b)
(d)
quaternary ammonium domains are clustered and distributed ran-
domly (non-uniform) over the polymer matrix as evident from
Fig. 4c. In the 3-D image, the ionic domains have less coverage of
ionic groups on the polymer surface, because of reduced quater-
nary ammonium groups.
3.3. Thermal stabilities of membranes
TGA analysis were carried out for PV/CS, PV/CS-HDT and PV-
HDT/CS-TPTZ membranes of varying weight percentages under
identical experimental condition, to analyse the thermal stability
of composite membrane. The TGA curve of PV/CS membrane in
Fig. 5 shows three prominent weight loss regions. The first region
loss at 80–100 °C corresponds to removal of surface adsorbed
and chemical bound water molecule, with the weight loss of
10 wt%. The second transition starts at 210 till maximum of
310 °C is due to the thermal decomposition of PV and CS polymer.
The third transition region at around 410–460 °C is due to the C–C
cleavage of the polymer backbone [19,23]. With the addition of
HDT and TPTZ, shift in TGA curve was observed. The addition of
HDT and TPTZ fasten the second stage degradation and reduced
the degradation temperature to approximately 180–200 °C due to
the presence of quaternary ammonium group in both additives.
With the increase in wt% of HDT and TPTZ, the weight loss around
200–300 °C also increases. This increase in second region loss spec-
ifies that more quaternary ammonium groups could be attached to
polymer backbone. The third stage degradation trend was
observed almost at same temperature with the addition of HDT
 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202
Fig. 4. AFM topological and 3D images of (a) PV/CS (b) PV/CS-HDT-20 wt% and (c) PV-HDT/CS-TPTZ-20 wt% composite membranes.
and TPTZ, whereas weight loss was minimized due to the formed
cross-linking network present in composite membranes. Thus, it
is inferred that the thermal stability of composite membrane was
increased by the addition of HDT and TPTZ.
3.4. Ion exchange capacity (IEC) of AEM
The ion exchange capacity (IEC) indicates the amount of inter-
changeable hydrophilic functional groups grafted to the polymer
matrix, directly relating to the ionic conductivity of membrane
[15]. The IEC for all prepared quaternized membranes with varying
wt % of HDT & TPTZ were calculated and presented in Table 1. It is
evident that, the IEC of membranes improves with the increase in
the amount of HDT & TPTZ in the polymer matrix. For PV/CS-HDT,
as the wt % of HDT added to the polymer increases, there is corre-
sponding increment in IEC. The membrane with 10 wt% HDT
exhibited an IEC of 0.28 mmol g
1, whereas further addition to
15 wt% increased the IEC to 0.45 mmol g
1. The PV/CS-HDT-20 wt
% membrane showed a higher IEC of 0.70 mmol g
1 when com-
pared with other ratios, due to the increased amount of quaternary
199
(a)
(b)
(c)
ammonium groups incorporated, thereby improving the IEC.
However, membrane with excess of HDT (25 wt%) displayed a
decreased IEC. Similarly for PV-HDT/CS-TPTZ membrane, 10 wt%
HDT to PV& 10 wt% TPTZ to CS exhibits an IEC of 0.23 mmol g
1,
whereas 15 wt% of HDT & TPTZ addition to PV/CS blend showed
an IEC of 0.38 mmol g
1. The PV/CS polymer with further addition
of 20 wt% of HDT & TPTZ, exhibited an IEC of 0.60 mmol g
1. How-
ever, the increase of both HDT & TPTZ beyond 20 wt% lead to decre-
ment in IEC presumably due to the aggregation of particles, thus
reducing their interaction with polymer and their ionic conduction.
This trend of enhanced IEC shows that varying wt % of HDT & TPTZ
into the PV/CS matrix, increased the number of charged quaternary
ammonium (N+(CH3)3) groups, which have direct influence on the
ionic conductivity of quaternized membranes.
3.5. Membrane’s ionic conductivity
The ionic conductivity of an AEM is strongly dependent on the
concentration of quaternary ammonium groups incorporated into
the polymer matrix [18]. The QPVA/QCS membranes with
200 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202
Fig. 5. TG plot of PV/CS-HDT & PV-HDT/CS-TPTZ composite membranes with
varying wt% at a heating rate of 5 °C min
1 in N2 atmosphere.
increasing percentage of HDT & TPTZ (10, 15, 20 & 25 wt%) were
studied for impedance measurements to evaluate conductivity at
different temperatures and are represented in Fig. 6. The conduc-
tivity of all the quaternized membranes shows a linear increase
as a function of temperature. As seen from the figure for PV/CS-
HDT, the ionic conductivity increases with increase in wt % of
HDT incorporated in PV/CS matrix. There is an increment in con-
ductivity at R.T. from 3.08  10
3 S cm
1 to 4.10  10
3 S cm
1,
when the HDT content in the PV/CS increases from 10 to 20 wt%.
However, the same membranes showed enhanced conductivity of
5.05  10
3 S cm
1 to 7.20  10
3 S cm
1 at 70 °C, wherein HDT
increased from 10 to 20 wt%. The similar trend is followed for
the PV-HDT/CS-TPTZ membrane also, while increasing the wt%
Table 1
Membrane compositions and their characteristic properties.
Membranes HDT w.r.t PV
PV/CS-HDT 10 wt%
15 wt%
20 wt%
25 wt%
PV-HDT/CS-TPTZ 10 wt%
15 wt%
20 wt%
25 wt%
Fig. 6. Ionic conductivity of various PV/CS-HDT and PV-HDT/CS-TPTZ composite
membranes as a function of temperature.
from 10 to 20 wt% as seen in Table 1. As it is seen, the increase
of HDT and TPTZ to PV/CS polymer showed conductivity improve-
ment trend similar to IEC results. This could be due to the increase
in the number of charge carrier head groups in composite
membranes, thereby increasing the ionic conductivity. In compar-
ison, PV/CS-HDT membranes displayed better conductivity than
PV-HDT/CS-TPTZ membranes, could be due to the aggregation of
ionic groups in the later than the former.
3.6. Chemical stability
Generally, AEM degradation occurs because of the loss of catio-
nic head group or decomposition of polymer backbone. Thus, AEM
with excellent alkaline stability are desired to be used as solid elec-
trolyte for alkaline fuel cell application. The alkaline stability was
evaluated by treating the optimized PV/CS-HDT-20 wt% membrane
TPTZw.r.t CS IEC (mmol g
1) Ionic conductivity at 40 °C (mS cm
1)
– 0.28 3.56
– 0.45 4.14
– 0.70 4.67
– 0.58 4.26
10 wt% 0.23 3.06
15 wt% 0.38 3.43
20 wt% 0.60 3.91
25 wt% 0.46 3.55
 K. Hari Gopi et al. / Materials Science for Energy Technologies 2 (2019) 194–202
Fig. 7. Ionic conductivity of PV/CS-HDT-20 wt% membrane before and after alkaline
stability.
in high concentrated KOH solution and at high temperature for
duration of 300 h. Then, the membrane is ion-exchanged to
Cl
form, to measure its conductivity after stability. The change
in conductivity of membrane before and after alkaline testing, as
a function of temperature is displayed in Fig. 7. It is inferred from
figure that the conductivity decreases gradually with time, because
of the loss of quaternary ammonium groups from polymer back-
bone. The PV/CS-HDT- 20 wt% membrane showed a conductivity
of 4.10  10
3 S cm
1 at 30 °C whereas the same membrane
showed a decreased conductivity of 3.51  10
3 S cm
1 after
alkaline stability. The loss of membrane conductivity after 300 h
of alkaline stability was calculated to be only within 15%.
3.7. Fuel cell polarization study
The fabrication of membrane electrode assembly and single cell
performance evaluation was carried out using the procedure
reported in our earlier literature [21]. The nitrogen content intro-
duced into the polymer during quaternization plays a potential
role in improving the ionic conductivity of membrane which in
turn determines the performance in APEFCs. Fig. 8 displays the cell
polarization curve of MEA comprising QPVA/QCS membrane
(PV/CS- HDT-20 wt%) in H2/O2 fuel cell operated at 40 °C. The
QPVA/QCS membrane with 20 wt% HDT was chosen for cell
polarization, due to its increased ion exchange capacity and ionic
1.0
Cell Voltage (V)
0.8
0.6
0.4
0.2
0 5 10 15 20 25 30 35 40
Current Density (mA cm-2)
Fig. 8. I-V polarization curve of PV/CS-HDT-20 wt% membrane operated at 40 °C.
201
conductivity when compared to other ratios. It is to be pointed
that, a peak power density of 15 mW cm
2 at a load current den-
sity of 27.5 mA cm
2 was attained for the optimized QPVA/QCS
based MEA. In order to improve the performance, further work is
in progress to study and optimize the effect of various parameters
like cell temperature, ionomer wt % etc.
4. Conclusions
Two series of AEM were prepared by blending poly(vinyl alco-
hol) and chitosan using mono quaternizing as well as dual quater-
nization reagents. In the first series of membrane, both PV and CS
are quaternized using HDT whereas in the second type PV was
quaternized with HDT & CS quaternized with TPTZ, added in vary-
ing weight percentages. The interaction of quaternizing groups
with the PVA/CS backbone was interpreted using FTIR spec-
troscopy. Further, these membranes were cross-linked by chemical
and thermal methods and evaluated for ionic conductivity and ion
exchange capacity. From the above results it is evident that, PV/CS-
HDT membranes demonstrate better conductivity in comparison
with PV-HDT/CS-TPTZ membranes. The QPVA/QCS membrane with
20 wt% of alkyl spacer (HDT) demonstrated a higher conductivity
of 0.0047 S cm
1 at 40 °C in comparison with all other ratios. The
increasing wt % amount of HDT & TPTZ on the polymer surface
was visualized from FE-SEM images. Also, the alkaline stability
reveals that, the PV/CS-HDT- 20 wt% membrane retains 85% of its
conductivity after 300 h. From the results it can be concluded that
polymer quaternized with HDT is a viable option to be subjected as
electrolyte in APEFC.
Conflict of interest
On behalf of all the authors, I hereby declare that this manu-
script has no conflict of interest.
Acknowledgements
Financial support from Council of Scientific and Industrial
Research (CSIR) Govt. of India, under CSIR Young Scientist Award
Project-DU-MLP-0090 (CSIR-YSA) is gratefully acknowledged.
Authors also thank Director, CSIR-Central Electrochemical
Research Institute and Scientist-In-Charge, CECRI Madras Unit for
their valuable suggestions and support.
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