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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

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Synthesis and characterization of a novel poly

(vinyl alcohol)-based zinc oxide (PVA-ZnO)
composite proton exchange membrane for DMFC

Diyan Ul Imaan a, Fasil Qayoom Mir b,*, Babar Ahmad a

a
Mechanical Engineering Department, National Institute of Technology Srinagar, 190006, India
b
Chemical Engineering Department, National Institute of Technology Srinagar, 190006, India

highlights

PVA based composite PEM was fabricated using nano-size ZnO ion-exchanger.

PEM showed good thermal stability upto 280  C.

Good chemical & mechanical stability of PEM was obtained.

Good electrochemical properties (Transport no 0.88 & IEC 0.78 meq.g1) were obtained.

Water uptake and methanol uptake results are better than Nafion 117.

article info abstract

Article history: Electrolyte polymeric membranes were synthesized by impregnating zinc oxide (ZnO)
Received 27 November 2019 nanoparticles (NPs) in a cross-linked PVA matrix for Direct Methanol Fuel Cell (DMFC)
Received in revised form applications. The novel membranes consist of PVA as the support while zinc oxide
2 April 2020 nanoparticles serve as inorganic ion exchangers. The fabricated composite proton ex-
Accepted 1 May 2020 change membranes exhibit a wide variety of advantages which include good thermal and
Available online 29 May 2020 chemical stability. The synthesized membranes demonstrate a high percentage of water
uptake (85%e105%) and a low percentage of methanol uptake (17%e21%). Other important
Keywords: properties such as transport number (0.88) and ion exchange capacity (0.78 meq.g1) were
Ion-exchange membrane also determined, and they were found comparable to Nafion®117. Ionic conductivity
Composite membranes (3.9 mS/cm) of the composite membranes was determined and found comparable to other
ZnO nanoparticles (NPs) PVA based composite membranes reported in literature. Characterization of the mem-
PVA branes was carried out using Fourier-Transform Infrared Spectroscopy (FT-IR), X-ray
DMFC diffraction (XRD), Scanning Electron Microscope (SEM), Energy-dispersive X-ray Spectros-
copy (EDX) and Thermogravimetric analysis (TGA). These characterizations revealed the
structural interaction between the support and the ion exchanger, crystalline nature,
surface morphology, elemental analysis and the thermal stability (upto 280  C) of the
membranes, respectively. The mechanical characterization of the membranes was also
carried out on a Universal Testing Machine (UTM), revealing satisfactory mechanical sta-
bility. The results demonstrate the possibility of synthesis of a low-cost proton exchange
membrane for DMFC applications.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: [email protected] (F.Q. Mir).
https://doi.org/10.1016/j.ijhydene.2020.05.008
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1 12231

through the membrane, which is the product of methanol

Introduction diffusivity (D) times its sorption coefficient (S) ðP ¼ D SÞ [19].
Higher diffusivity ð4:26 106 cm2 =sÞ and sorption coefficient
The main advantage of a fuel cell is the conversion of chem- (0.70) of methanol in Nafion 117 will lead to higher perme-
ical energy directly into electrical energy without the neces- ability or crossover ð2:98  106 cm2 =sÞ, while lower diffusivity
sity of fuel combustion [1e9]. A Direct Methanol Fuel Cell ð1:94 106 cm2 =sÞ and sorption (0.147) of methanol in PVA will
(DMFC) uses methanol as the fuel and its core component is a lead to lower permeability or crossover ð0:28 106 cm2 =sÞ
proton exchange membrane (PEM), which is placed between [19]. Although methanol is soluble in water but due to its
the two electrodes and serves as a thin and solid electrolyte lower diffusivity and solubility in PVA results in lower
barrier for strict permeation of protons [2]. crossover.
The desired requirements for a good PEM include satis- PVA also demonstrates good film forming properties and
factory operation at high temperature and low humidity [1e3]. excellent thermal and mechanical strength [20e22]. Despite
The membrane should have a high water uptake, low meth- these advantages, the pure PVA membranes suffer from a
anol uptake and low methanol crossover (MCO) [2e4]. The lower proton conductivity and low ion exchange capacity
ionic conductivity should be reasonably high along with high (IEC). In order to overcome these problems, researchers are
chemical and mechanical durability (especially at tempera- exploring the possibility of blending PVA with various inor-
tures greater than 80  C for increased CO tolerance). The ganic materials. Current research suggests that PVA is the
production cost should be as low as possible to make the material of choice on account of its good physiochemical
operation economically viable. Nafion® (from DuPont) is, by properties [20e22]. Salarizadeh et al. (2013), Yang & Chiu
far, the most successful membrane in the market, primarily [21,22] have reported that the properties of PVA-based mem-
due to its high proton conductivity, high chemical and me- branes can be enhanced with the addition of some inorganic
chanical stability [1e5]. The main disadvantages include a materials. The inorganic material is selected based on many
significant drop in performance at high temperatures (above criteria including high ion exchange capacity, good physical
80  C) and low humidity (below 30%). A high methanol and chemical properties [23,24]. Polymer electrolytes doped
crossover and higher production cost ($ 600e1200 per m2) are with ion exchangers/fillers that have high specific surface
the main motivating factors for synthesis of a cheaper alter- area, like metal oxides, can improve the intrinsic conductivity
native [10e16]. The improvements in performance can be and mechanical properties of polymeric electrolytes. These
achieved through the synthesis of a polymer composite ion exchangers have capability to increase the proton con-
membrane [16]. ductivity at low temperatures and can increase the stability of
The performance of a DMFC mainly depends on high pro- electrodes [25,26]. Incorporating nanosized inorganic metal
ton conductivity and low methanol crossover. Both the pa- oxides in a polymer matrix has many advantages including
rameters in turn depend on PEM thickness and material water retention, sustaining adequate hydration for proton
properties [17]. There are several studies available in the mobility at high temperatures and lower methanol perme-
literature to understand the mechanism of methanol cross- ability leading to high power density [27].
over [9e16]. The methanol crossover from anode to cathode In a recent investigation, Ana-Maria et al. [25] synthesized
through the membrane takes place by diffusion, convection a novel PVA-based PEM doped with polyaniline and the study
and electro-osmotic drag [9,10]. High tendency of methanol revealed the interaction between the PVA and polyaniline.
crossover across the PEM drastically hinders the overall DMFC Doping of polyaniline in the PVA matrix leads to a drastic in-
performance mainly due to CO cathode catalyst poisoning, crease in proton conductivity up to 80%. The maximum
fuel efficiency reduction and electrode potential reduction due recorded proton conductivity of the synthesized membrane
to methanol oxidation at cathode [11,15]. There are numerous was 2.92 mS/cm which is same as that of Nafion®112. M.M.A.
studies reported in literature which reveals that the mem- Khan et al. [28] used PVC-based zinc oxide membranes to
brane thickness, material and fabrication technique plays an remove heavy toxic metals from water waste. These mem-
important role in mitigating the methanol crossover [9e14]. branes have demonstrated enhanced ion exchange capacity
Blending Nafion with some other materials and by introducing as well as good chemical, mechanical and thermal stability. B.
barrier layers does help in reducing the methanol crossover of Simitha et al. [29] studied blends of PVA with sodium alginate
the membrane. However, these measures have certain and chitosan. It was observed that there is a strong possibility
drawback such as usage of Nafion which is an expensive of synthesizing low cost PVA-based membranes as an alter-
material and by introducing the barrier layer will increase the native to Nafion®117, albeit with a lower proton conductivity.
cost of the membrane. In order to overcome these drawbacks, Mohammad Javad Parnian et al. [30] investigated the
different materials are being employed to either completely physiochemical and electrochemical properties of Nafion
replace Nafion or decrease the methanol crossover without doped with different concentration of zirconia (ZrO2) nano-
any requirement of barrier layer. particles. The results indicated that the composite synthe-
Poly (vinyl alcohol) (PVA) is an inexpensive organic poly- sized membranes had better mechanical stability, chemical
mer which is known for its hydrophilic nature (high affinity properties and conductivity than pure recast Nafion mem-
towards water), low methanol crossover and low methanol brane at different temperatures. D.A Quintana et al. [31]
uptake (low affinity towards methanol). Due to its high water attempted to disperse Nb2O5 into a membrane with fixed PVA:
selectivity, PVA is also used as alcohol dehydrating agent Chitosan ratio of 80:20 doped with fixed amount of H3PO4. The
especially for the alcohol-water azeotrope [18]. Methanol study shows that doping PVA/Chitosan membrane at 6%
crossover could be defined in terms of its permeability (P) Nb2O5 highly enhances the electric, thermal, structural and
12232 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

morphological properties of the membrane and can be used in

proton exchange membrane fuel cell (PEMFC). From the brief Characterization
literature mentioned above it is evident that there are possi-
bilities of enhancing the properties of PVA by doping it with Structural characterization
different ionomers or ion exchangers to make it suitable for
DMFC applications. FT-IR spectroscopy of the synthesized PVA-ZnO mem-
In this work, we have synthesized a novel composite branes was performed on Thermo Scientific (Model: Nicolet
membrane by blending PVA, which is an organic polymer iS50 NIR) to identify the functional groups present in the
matrix, with inorganic zinc oxide (ZnO) nanoparticles (NPs) membranes and to analyze the interaction between cross-
which act as the ion exchange for proton transport. ZnO NPs linked PVA and ZnO nanoparticles. SEM-EDS was per-
was chosen as an inorganic ion exchanger due to its good formed with the help of Thermo Fisher (Model: FEI Quanta
properties including wide band gap, good chemical and 200 F) and Oxford Instruments (Model: X-Max), respectively,
thermal stability. Besides these properties ZnO NPs is to analyze the surface morphology and element analysis of
nontoxic in nature, low priced and readily available. The the synthesized membranes. Thermal stability of the
novelty of this work lies in the use of zinc oxide NPs as the membranes was determined by using TGA, Mettler Toledo
ion exchanger with PVA as base. Currently there have been (Model: CH-8603) in the temperature range of 25  Ce650  C
no reports of incorporating ZnO NPs with crosslinked PVA in nitrogen environment and mechanical stability was
for the synthesis of proton exchange membrane in DMFC. measured with Instron xlo (Model: 3365). XRD of the syn-
Physiochemical properties (FTIR, SEM-EDS, EDX, TGA and thesized membranes was done on an X-ray diffractometer
UTM), electrochemical properties (transport number, IEC Make: Rigaku (Model MiniFlex 600 and Smart Lab) at 20  C
and proton conductivity), water uptake, methanol uptake and 60% RH.
and oxidative stability of the synthesized membranes were
also determined. The results show conclusively that the
Chemical stability
synthesized membranes can serve as a low-cost alternative
In order to determine the chemical stability of the synthe-
to PEM.
sized composite membrane, hot Fenton’s reagent (3 wt%
H2O2 and 2 ppm of Fe3þ) was used. First the synthesized
Experimental composite membrane was dried in an oven at 60  C for an
hour and then 4 different (2  2 cm) samples were cut and
Materials and chemicals for membrane preparation labelled as S1, S2, S3 and S4. All the samples where then
weighed with the help of a weighing machine. Each sample
PVA (molecular weight: 125,000), Glutaraldehyde (GA) (25 vol was immersed in Fenton’s reagent for different periods of
%) were purchased from Sigma Aldrich, India. Zinc oxide time. S1 was removed after 6 h, S2 was removed after 12 h,
NPs were purchased from Rankem Avantor, India. Sodium S3 was removed after 18 h and S4 was removed after 24 h.
chloride (NaCl) was also procured from Rankem. Other After removing the samples from the reagent, they were
chemicals like hydrochloric acid (HCl) (assay 35%), meth- quickly dried and weighed to obtain the percentage weight
anol were supplied by Merck Ltd. All the chemicals used in loss [1e3].
the membrane synthesis were of AR grade and double
Water uptake and methanol uptake
deionized water was used for the synthesis and cleaning
purposes.
Dry samples of the synthesized membranes were weighed
Membrane synthesis and afterwards immersed in a Petri dish filled with double
deionized water for 12 h. Then the samples were removed
Simple solution casting method (Fig. 1) was used for the from the dish and the excess water was wiped off with a filter
synthesis of the membranes. Three beakers with 100 ml paper by slightly tapping on the samples. Weighing followed
PVA (5 wt %) solution were prepared at 70  C by constantly immediately. The water uptake value was obtained by using
stirring for 6 h. In one beaker 0.3 g of zinc oxide NPs, in the equation given below [1e3]:
another beaker 0.5 g of zinc oxide NPs and in third beaker

Wwet  Wdry
0.7 g zinc oxide were slowly added while using a magnetic Wuptakeð%Þ ¼  100 (1)
Wdry
stirrer at 60  C for 4 h till a milky white solution was formed.
After that, 1 mL of glutaraldehyde and 0.1 mL of HCl as where Wwet and Wdry represent the weight of the samples in
catalyst were added to all the beakers under continuous wet and dry state, respectively.
stirring at 70  C for 1 h for proper crosslinking of PVA. The Same procedure was used to determine the methanol up-
three solutions were casted on an acrylic sheet and were left take. However, instead of double deionized water, the samples
to dry for 4 h in an oven at 60  C to form a film. Eventually were immersed in methanol.
the films/membranes were carefully peeled off from the
acrylic sheets. Thickness of the membranes was measured Swelling
to be between 102 and 105 mm. Thereafter, the membranes
were kept secured in an airtight container at room Area of the membrane samples was measured before and
temperature. after immersing the samples in the deionized water for 12 h.
 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1 12233

Fig. 1 e Diagram showing the fabrication procedure of synthesized membranes.

The swelling ratio of the membrane was calculated with the experiments, the synthesized membranes were equilibrated
help of equation below: with 0.01 M NaCl solution for 24 h. In one compartment, lower

 concentration of NaCl (0.01 M) was used, and in other
Awet  Adry compartment higher concentration of NaCl (0.10 M) was uti-
Swelling ð%Þ ¼  100 (2)
Adry lized. A multi meter (make: Fluke, mode: 15Bþ) was connected
where Adry and Awet are the dry and wet area of the mem- to the Ag/AgCl electrodes to measure the potential difference
brane, respectively. between the two compartments of the diffusion cell. Counter
ion transport number of the membrane was calculated with
Ion exchange capacity (IEC) the help of Plank-Henderson equation, Eq. (4) [1,2]:
8 9
>
> >
>
Classical acid-base titration method was used to determine 1 < nFE =
the ion exchange capacity of the membranes. Dry synthesized tþ ¼ 1þ (4)
2>> RTln CC12 >
>
: ;
membrane samples were first weighed and then equilibrated
in 100 ml of 1 M sodium chloride solution (NaCl) separately for
where tþ is the counter ion transport number of Naþ ion, F is
24 h in order to achieve the exchange of Hþ ions with Naþ
the Faraday’s constant 96,485 C mol1, E is the membrane
ions. Eventually the solutions were titrated back with 0.1 M
potential, R is the universal gas constant 8.314 J mol1K1, T is
sodium hydroxide. Phenolphthalein was used as an indicator
the temperature in Kelvin, n is the valency of cation, C1 is the
during the process. Regeneration of the membranes was done
higher concentration of NaCl solution (0.1 M) and C2 is the
by immersing the membrane in 0.1 M HCl solution for 12 h. IEC
lower concentration of NaCl solution (0.01 M).
of the membrane is governed by the equation below [1,2]:

V  M Proton conductivity
IEC ¼ (3)
Wdry
Proton conductivity of the membranes was obtained by
where IEC is ion exchange capacity (meq.g1), V the added
measuring the resistance of the membranes with the help of
titrant volume at equivalent point (ml), M the molar concen-
two compartment cell (exposed area of 9 cm2) and potentiostat/
tration of the titrant and Wdry is the dry mass of the sample (g).
galvanostat (Make: AutoLab). The resistance of the cell was
measured with and without the membrane using two probe
Transport number
impedance method at 30  C. The membranes were first equil-
ibrated at 0.1 M HCl solution for 24 h before the tests were
Two compartment diffusion cell was used to measure the
performed. After equilibrating, the thickness of the mem-
membrane potential. The volume of each compartment was
branes was measured (161 mm, 163 mm and 158 mm for 0.3 g ZnO-
25 cm3. The synthesized membrane was tightly wedged be-
PVA membrane 0.5 g ZnO-PVA membrane and 0.7 g ZnO-PVA
tween two compartments of the diffusion cell with an
membrane respectively). Then the membranes were installed
exposed area of 13 cm2. Two Ag/AgCl wires were used as
in the cell and the compartments of cell were filled with a 0.5 M
electrodes to obtain the membrane potential. Both Ag/AgCl
solution of HCl. The maximum perturbation amplitude was set
electrodes were placed inside each compartment of the cell
to 10 mV and was scanned from 1 MHz to 10 MHz. The
0.5 cm away from membrane. Before performing the
12234 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

resistance of the membranes was obtained by subtracting the between the two. Instead there is an adequate physical mixing
values of resistance of the cell without membrane from the of support and the ion exchanger.
resistance of the cell with membrane. Proton conductivity of
the membranes were calculated with the help of Eq. (5) [33]. XRD

s ¼ L=RS (5) XRD study of the synthesized membranes was used to analyze
where, s (mS/cm) is the proton conductivity, L (cm) is the the crystalline nature of the synthesized composite mem-
thickness of membrane, R (U)is the resistance of membrane branes. XRD patterns of the synthesized membranes and
and S (cm2) is the exposed area of the membrane. crosslinked PVA membrane are illustrated in Fig. 3. For
crosslinked PVA, XRD patterns show broad peaks at 11.19 of
2q indicating intermolecular distance of amorphous phase, a
Results and discussion relatively broad peak was obtained at 2q value of 20 which
shows the semi crystalline nature of the film [29,32,33,38].
FT-IR spectroscopy However, it is evident from Fig. 3 that doping crosslinked PVA
with ZnO NPs has increased the crystalline phase in all the
FT-IR spectroscopy was used in order to study the crosslinking synthesized membranes, due to the presence of sharp peaks
of PVA matrix by Glutaraldehyde and the interactions be- in XRD spectrum. The relatively sharp XRD peaks at around 2q
tween the crosslinked PVA matrix and ZnO NPs. FT-IR spec- value of 32.1 , 34.5 , 36.2 , 47 , 58.3 , 68.1 and 70.9 of the
trum of all three synthesized membranes are very similar to synthesized membranes were in accordance with the XRD
each other, as seen in Fig. 2. The broader transmission at 3260 peaks of ZnO NPs [37,39,40]. Comparing XRD patterns of 0.3 g
cm1 and 2920 cm1 represents OeH stretching and eCH2 ZnO-PVA membrane with 0.7 ZnO-PVA membrane, it was
stretching respectively and 1420 cm1 band represents eCH3 evident that the percentage crystallinity has increased with
bending [32,33]. The peak around 1750 cm1 is due to eCHO the increase in ZnO NPs concentration. This crystalline na-
stretching, representing the PVA crosslinking by glutaralde- ture, which was introduced in the membranes by doping them
hyde [2]. The band around 1090 cm1 proves the formation of with the ZnO NPs, is an important reason for enhancing ion
acetal linkage [29]. The bands around 1090 cm1 links to eCeO conducting properties [41] and are in accordance with the
unbounded and it could be related with PVA crystallinity proton conductivity results.
[34,35]. Bands around 1320 cm1 and 1420 cm1 are assigned to
eCeOH bond and CeH stretching, respectively [36]. The SEM-EDX
spectrum showed peaks around 594 cm1 and 475 cm1 which
correspond to ZneO NPs stretching mode [23,37]. There are no The surface morphology of the dry membranes was observed
significant changes in the FT-IR peaks of crosslinked PVA and with the help of a SEM and the images of the synthesized
ZnO NPs which proves that there is no chemical interaction composite membranes are shown in Fig. 4.

Fig. 2 e FT-IR spectrum of the synthesized membranes.

 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1 12235

Fig. 3 e XRD patterns of crosslinked PVA, 0.3 g ZnO-PVA membrane, 0.5 g ZnO-PVA membrane and 0.7 g ZnO-PVA
membrane. Semi crystalline nature of crosslinked PVA membrane is evident. Sharp peaks are observed in all the
synthesized membranes showing presence of crystalline phase.

Fig. 4(aec) represents 0.3 g ZnO-PVA membrane at three The atomic and weight percentage data of EDX is sum-
different magnifications (2500, 5000 and 10,000, respec- marized in Table 1. From the EDX data we can see a difference
tively). Fig. 4(def) represent 0.5 g ZnO-PVA membrane at three in atomic and weight percentage of element zinc in 0.5 g ZnO-
different magnifications (2500, 5000 and 10,000, respec- PVA membrane and 0.3 g ZnO-PVA membrane. There is 66.6
tively). While as Fig. 4(gei) shows 0.7 g ZnO-PVA membrane at wt% difference of ZnO NPs in the two synthesized membranes
three different magnifications (2500, 5000 and 10,000, which is in accordance to the 62.28 wt % difference of element
respectively). zinc as shown in EDX. This proves a relatively even distribu-
It is evident from the images that the dispersion of ZnO tion of ZnO NPs in both the synthesized membranes. A fair
NPs in the PVA matrix of all the membranes is acceptably distribution of ZnO (NPs) in 0.7 g ZnO- PVA membrane was
uniform. The synthesized membranes are without any holes, also observed.
fractures or cracks for all three magnifications used. Even at
the magnification of 10,000 there were no traces of pores Thermal analysis
which confirms the dense structure of the synthesized
composite membranes. White shades in the SEM images Thermal stability with water retention capability at high tem-
show some amount of aggression due to inorganic ion perature is one of most desirable characteristics of a good proton
exchanger. Fair amount of aggression was observed in 0.7 g exchange membrane. Proton conductivity at high temperature
Zno-PVA membrane Fig. 4(gei) and could have been reduced is directly related to the water retention of a membrane. Proton
by using an ultrasonic sonicator during membrane synthe- conductivity will be optimum if the membrane is adequately
sis. Overall, the synthesized composite membranes are hydrated at elevated temperatures. TGA curves of the synthe-
compact, homogeneous, smooth and have defect free sized composite membranes are shown in Fig. 6.
surfaces. There are three major degradation stages. First degrada-
EDX spectrum and SEM image of the synthesized mem- tion stage occurs between 100  C and 150  C, which is asso-
branes are shown in Fig. 5(a and b, c). Same element peaks, ciated with a loss of remnant water molecules retained by the
including carbon, oxygen, zinc and platinum, were found in membrane. This shows that water can be retained by the
the EDX spectrum of all the synthesized membranes. composite membrane up to 150  C. Weight loss percentage for
Platinum peaks were due to the platinum coating of the both synthesized membranes during first degradation stage is
samples before SEM to get the better quality SEM images. The only 5% which is comparable to Nafion® 117. About 1e2%
atomic and weight percentage values of the platinum were weight loss was observed in the temperature range of 150

ignored in the EDX system. The presence of carbon and oxy- Ce280  C for both synthesized membranes which is again
gen is mainly due to the organic PVA while the presence of comparable to Nafion® 117. Second degradation stage occurs
element zinc confirms the presence of inorganic ion in the temperature range of 280  Ce380  C which is attributed
exchanger. to the decomposition of polymer chain associated with
12236 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

Fig. 4 e Top view SEM images of the composite membranes (a, b and c) attributes to 0.3 g ZnO-PVA, (d, e and f) attributes to
0.5 g ZnO-PVA membranes and (g,h and i) is attributed to 0.7 g ZnO-PVA membrane at three different magnifications
(2500£, 5000£ and 10,000£).

hydroxyl side group. In second degradation stage, there is Tensile strength

approximately 42% weight loss for both the membranes which
is higher than Nafion® 117 [33]. The final degradation stage for A proper mechanical strength is essential for a good PEM
the membrane is in the temperature range of 380  Ce465  C in because it will face many processes in which it has to suffer
which there is a complete decomposition of main chain of different stresses like high pressure during the preparation of
PVA [42]. The residual weight for the 0.3 g ZnO-PVA membrane MEA and during the installation of MEA in the fuel cell. A
is approximately 25.2% and for the 0.5 g ZnO-PVA membrane universal testing machine Instron (Model: 3365) USA. Inc was
it is approximately 42.1%. The difference in the percentage of used to carry out the tests concerning tensile strength. The
residual weight (67%) complies with the difference in the cross-sectional area of the samples was obtained by
concentration (66.6%) of ZnO NPs present in both membranes. measuring the width and thickness of the samples. The length
This proves that there was a complete decomposition of the of the samples was adjusted to 20 mm so that the sample is
base (PVA). Crosslinking PVA with glutaraldehyde has signif- placed correctly between the grips of universal testing ma-
icantly increased the thermal stability of the synthesized chine. The grip length was 5 mm each and the speed of testing
membranes as compared to pure PVA membranes [42]. The was set to 10 mm/min. The standard considered for the
high concentration of ZnO NPs does not have any significant testing is ASTM D 882.
role in the thermal stability of the synthesized membranes, Fig. 7 shows the stress-strain curve of the synthesized
except contributing to high percentage residual weight. The composite membranes and crosslinked PVA membrane. It
TGA analysis shows that the membranes are fairly stable up to shows tensile strength as a function of ZnO NPs loading in the
280  C. PVA matrix. The results demonstrate the enhancement of
 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1 12237

Fig. 6 e TGA curve for synthesized composite membranes.

concentration of ion exchanger there is an increase in the

brittle nature of the membranes as the strain value of the 0.7 g
ZnO-PVA membrane (23) is less than that of 0.5 g ZnO-PVA
membrane (26). The same can be verified by XRD results.
It is worth noticing that with the increase in the concen-
tration of inorganic exchanger, the tensile strength increases
which is in accordance to that of claims made in the literature
[25,27,30].

Chemical stability
Fig. 5 e EDX spectrum and SEM images of (a) 0.3 g ZnO-PVA
membranes, (b) 0.5 g ZnO-PVA membranes and (c) 0.7 g Fenton’s reagent test is a chemical stability test which is
ZnO-PVA membrane. Peaks of carbon, zinc and oxygen broadly used to measure the resistance of a PEM against the
were observed. attack of radical species (OH
and OOH
) which get generated
at the two electrodes of a direct methanol fuel cell [1e3]. Fig. 8
shows the percentage weight loss of the synthesized mem-
branes under Fenton’s reagent test with different immersion
tensile strength of the composite membranes as compared to times. The total loss in weight of 0.3 g ZnO-PVA membrane is
the pure crosslinked PVA membrane. The reason behind the 5.8%, for 0.5 g ZnO-PVA membrane the loss is 5.1% and for 0.7 g
increase in mechanical stability is mostly attributed to high ZnO-PVA membrane the loss is 4.9% membrane after 24 h. The
reinforcement due to dispersion, large surface area and phys- loss in the weight of the synthesized composite membranes is
ical interaction of ZnO NPs with PVA matrix, limiting the due to the attack of radical species on the PVA matrix. The
movement of chain segments of PVA matrix [43]. It is evident difference in the weight loss percentage between the mem-
from Fig. 7 that the tensile strength of the synthesized com- branes is due to the difference in the concentration of inor-
posite membranes is considerably higher compared to the ganic ion exchange (ZnO NPs). Inorganic ion exchangers are
crosslinked PVA membrane (28 MPa). Tensile strength of 0.3 g resistant to the Fenton’s reagent. The oxidative stability of the
ZnO-PVA membrane is same as Nafion® 117 (34 MPa) while the synthesized membrane showed better results in contrast to
tensile strength of 0.5 g ZnO-PVA membrane is 43 MPa which is Nafion®117 (7%), as the synthesized membranes show less
higher than Nafion® 117 [33]. The maximum tensile strength weight loss compared to Nafion® 117 (7%) [33]. The synthe-
value of 43.5 MPa was shown by 0.7 g ZnO-PVA membrane. sized membranes were able to maintain the structural integ-
From the results it can also be seen that with increase in the rity without punctures or breakage.

Table 1 e Atomic and weight percentage of elements present in the synthesized composite membranes.
Type of synthesized Membrane Carbon Oxygen Zinc Total
At % Wt % At % Wt % At % Wt % At % Wt %
0.3 g ZnO-PVA membrane 57.20 45.11 39.73 41.74 3.06 13.15 100 100
0.5 g ZnO-PVA membrane 57.64 42.39 37.02 36.27 5.33 21.34 100 100
0.7 g ZnO-PVA membrane 55.54 41.77 38.34 32.11 6.12 26.12 100 100
12238 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

Fig. 7 e Stress-strain diagram of the synthesized membranes and crosslinked PVA membrane.

Water uptake, methanol uptake and swelling mobility of ions in the membrane. Table 2 shows the water
uptake, methanol uptake and swelling (%) values of the syn-
Water uptake and methanol uptake greatly influence the thesized composite membranes at two different temperatures
properties of the membrane. Water uptake plays a vital role in (30  C and 60  C).
the ion conductivity. Adequately hydrated membrane will The synthesized membranes demonstrated highest values
have a high ion conductivity since water will increase the of water uptake of 97% for 0.3 g ZnO-PVA membrane, 105%

Fig. 8 e Chemical stability of the synthesized composite membranes under Fenton’s reagent.
 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1 12239

Table 2 e Water uptake, methanol uptake and swelling of the synthesized membranes.
Type of synthesized membrane Water Uptake % Methanol Uptake % Swelling %
30  C 60  C 30  C 60  C 30  C 60  C
0.3 g ZnO-PVA membrane 85 97 17 19 54 58
0.5 g ZnO-PVA membrane 93 105 17.5 21 56 61
0.7 g ZnO-PVA membrane 92 105 18 21 55 60

Table 3 e IEC, transport number and proton conductivity of the synthesized membranes.
Type of synthesized membrane IEC (meq.g1) Transport number at 25  C Proton conductivity (mS/cm) at 25  C
0.3 g ZnO-PVA membrane 0.69 0.80 1.2
0.5 g ZnO-PVA membrane 0.76 0.88 3.3
0.7 g ZnO-PVA membrane 0.78 0.88 3.9

for 0.5 g ZnO-PVA membrane and 105% for 0.7 g ZnO-PVA Proton conductivity
membrane at 60  C. All the synthesized membranes have
better water uptake values as compared to pure PVA (74%) The proton conductivity of the synthesized membranes at
and Nafion® 117 (29.2%) [29,33,44]. The high water uptake room temperature (25  C) is shown in Table 3. The measured
values are attributed to OH groups of PVA which are highly proton conductivity of the 0.3 g ZnO-PVA synthesized mem-
hydrophilic in nature. Increase in the water uptake values of brane is 1.2 mS/cm while as the proton conductivity of 0.5 g
the synthesized membranes from 30  C to 60  C may ZnO-PVA membrane is 3.3 mS/cm. The maximum proton
contribute to high ion conductivity at 60  C. Even though conductivity was found to be 3.9 mS/cm for 0.7 g ZnO-PVA
proper hydration of the membrane plays a vital role in ionic membrane. It is worth noticing that with the increase in the
conductivity, excessive water uptake can adversely affect the concentration of ion exchanger from 0.3 g to 0.5 g in the PVA
mechanical properties of the membrane. Therefore, modu- matrix, there is a drastic increase (175%) in the proton con-
lating water uptake value is crucial in overall membrane ductivity. A limited increase (18.18%) in proton conductivity
performance. was observed when the concentration of ZnO NPs was raised
The lowest methanol uptake for 0.3 g ZnO-PVA membrane from 0.5 g to 0.7 g. The overall increase in proton conductivity
was 17% at 30  C and for 0.7 g ZnO-PVA membrane it was 18% was found to be 225% when the concentration of ZnO NPs was
at 30  C. Temperature did not play any significant role in raised from 0.3 g to 0.7 g. The proton conductivity of a plain
methanol uptake. Low methanol uptake by the synthesized PVA is 106 S/cm2 [29,32] which is less than all the synthesized
membranes is due to methanol resisting properties of PVA membranes. The proton conductivity results revealed in this
[18,19]. All the values of the synthesized membranes show study are competitive among other composite membranes
decent results as compared Nafion® 117 which has methanol [25,32,46,47].
uptake of 16.5% [33].

Ion exchange capacity and transport number Conclusion

The IEC and transport number of the synthesized membranes In this study, three different proton exchange membranes
are shown in Table 3. The IEC (0.69 meq.g1 for 0.3 g ZnO-PVA based on poly (vinyl alcohol) doped with three different
membrane, 0.76 meq.g1 for 0.5 g ZnO-PVA and 0.78 meq.g1 concentrations of ZnO NPs were synthesized using solution
for 0.7 g ZnO-PVA membrane) of the synthesized membranes casting method for DMFC application. With an increase in
are comparable to most of the PVA-based membranes re- the concentration of ZnO NPs, there is an increase in most of
ported in literature and is significantly higher than pure PVA the desired characteristics including IEC, transport number,
membrane (0.499 meq.g1) [29]. proton conductivity, mechanical stability, water uptake and
The counter ion transport number (0.80 for 0.3 g ZnO-PVA chemical stability. Although there was no significant dif-
membrane and 0.88 for both 0.5 g ZnO-PVA and 0.7 g ZnO- ference in the thermal characteristics of the synthesized
PVA membrane) is comparable with Nafion® 117 (0.96). It is membranes, all the membranes demonstrated acceptable
worth noticing that with the increase in the concentration of thermal properties. With an increase of ZnO NPs from 0.3 g
inorganic ion exchanger in the crosslinked PVA, the IEC and to 0.7 g in the PVA matrix, there is 13.04%, 10% and 225% rise
transport number of the membrane increases. This may be in IEC, transport number and proton conductivity,
attributed to zinc oxide NPs providing more active sites for ion respectively.
absorption and a greater number of exchangeable ions due to The study shows that a carefully chosen quantity of inor-
their excellent absorption and exchange characteristics ganic ion exchanger can improve the desired characteristics
[24,44,45]. It is evident from the results that the number of of the membrane. These membranes do offer some significant
exchangeable ions must be more in 0.5 g ZnO-PVA membrane improvements over Nafion®, including better mechanical as
and 0.7 g ZnO-PVA membrane as compared to 0.3 g ZnO-PVA well as chemical stability, superior water uptake and low
membrane, therefore increasing IEC and transport number. synthesis cost. However, their ion conducting properties
12240 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 4 6 ( 2 0 2 1 ) 1 2 2 3 0 e1 2 2 4 1

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