Materials Science for Energy Technologies 1 (2018) 146–154

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Materials Science for Energy Technologies

CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/materials-science-for-energy-technologies

Investigation of physicochemical and electrochemical properties of

recast Nafion nanocomposite membranes using different loading of
zirconia nanoparticles for proton exchange membrane fuel cell
applications
Mohammad Javad Parnian a,b, Soosan Rowshanzamir a,b,⇑, Jafar Alipour Moghaddam a
a
School of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran 16846-13114, Iran
b
Fuel Cell Laboratory, Green Research Center, Iran University of Science and Technology, Narmak, Tehran, Iran

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

Article history: In this work, Nafion ionomer was prepared by a dissolution method in high pressure-temperature auto-
Received 9 May 2018 clave reactor using Nafion membrane sources. Zirconia nanoparticles were synthesized by the microwave
Revised 24 June 2018 assisted gel combustion method. The synthesized nanoparticles were characterized by XRD and FESEM,
Accepted 25 June 2018
and then added to the Nafion solution to prepare recast Nafion nanocomposite membranes (R-Nafion/
Available online 7 July 2018
ZrO2) with different loading of ZrO2 nanoparticles. Membranes were prepared by recasting method
and characterized in terms of water uptake, dimensional stability, ionic conductivity, chemical stability
Keywords:
(Fenton test), tensile strength, and scanning electron microscope (SEM) techniques. The obtained results
Proton exchange membrane fuel cell
Recast Nafion membrane
for nanocomposite membranes were compared to the filler-free recast Nafion and commercial Nafion
Zirconia nanoparticles membranes. The nanocomposite membranes showed higher water uptake, mechanical and oxidative sta-
Chemical stability bilities and the hygroscopic zirconia nanoparticles resulted higher proton conductivity of nanocomposite
membranes at different temperatures in comparison with pure recast Nafion membrane. The prepared
membranes showed defect free, dense microstructure, and good dispersion of nanoparticles in the mem-
branes’ matrix. The results illustrated the prepared nanocomposite membranes have good physicochem-
ical and electrochemical properties for PEMFC applications.
Ó 2018 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 mal and hydrolytic stability, high proton conduction properties,

compatible with electrodes, and high durability and low cost [5].
Fuel cell is a promising technology for energy shortcoming and Nafion membranes have been used as a standard proton
environmental contamination concerns and it directly converts exchange membrane for PEMFCs because they showed high proton
chemical energy into electrical energy [1,2]. Proton exchange conductivity, thermal properties and chemical stability. The
membrane fuel cells (PEMFCs) are the promising candidate for PEMFCs typically work at lower temperatures (<80 °C) and in this
the stationary power generation and automotive systems because temperature range, they will experience some problems such as
of their lower operating temperature and smaller size in compar- CO poisoning of catalyst [2]. Despite the numerous benefits of
ison with other fuel cell types. An electrolyte, an anode, and a cath- Nafion membranes, they have also some drawbacks such as reduc-
ode are the main parts of a unit cell of the fuel cells [3]. The key tion in the proton conductivity, mechanical and chemical stabili-
component of low-temperature fuel cells is the proton exchange ties at higher temperatures [6]. Therefore, researchers are looking
membranes (PEM), therefore, many of the researches have been for different ideas to ameliorate the performance and properties
focused on the development of these electrolytes [4]. The desired of the PEMFCs [6].
properties for a PEM are consist of good electrochemical stability, In addition, Nafion membranes have high prices and one of the
appropriate chemical and mechanical properties, appropriate ther- PEMFC limitations is this issue. With the commercialization of
PEMFCs and growing use of Nafion membrane, reprocessing or dis-
posal of a large number of used or failed Nafion membranes will
⇑ Corresponding author at: Iran University of Science and Technology, Tehran
16846-13114, Iran.
become an important issue. Therefore, both economic and environ-
E-mail address: Rowshanzamir@iust.ac.ir (S. Rowshanzamir). mental factors encourage researchers to recycle the Nafion mem-

https://doi.org/10.1016/j.mset.2018.06.008
2589-2991/Ó 2018 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/).
 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154 147

branes [7,8]. Recycling of membrane electrode assembly (MEA) corroborated the hydrophilic nature of the selected additives.
that generally contains a Nafion membrane and the platinum- When the nanocomposite membranes were evaluated at very
carbon electrodes, can contribute to solving the economic issues low humidity in fuel cell, significant improvements were observed
in manufacture and use of the PEMFCs. It has been found that in [69]. Giffin et al. [70] reported that Nafion/sulfated-zirconia com-
one MEA, both metal catalysts and the fluorocarbon membrane posite membranes exhibit a high conductivity even at low humid-
can be recycled using a lower alkyl alcohol solution [9]. In the recy- ity conditions [70].
cling procedure, firstly the Nafion membrane must be detached In the present work, nanocomposite membranes based on pre-
from the used MEA and chemical extraction of Nafion membrane pared Nafion solution and different loading of synthesized zirconia
is a perfect solution. So that, the membrane must be dissolved in nanoparticles are prepared by recasting method. The prepared
a suitable solvent and after the dissolution, Nafion membrane nanocomposite membranes (R-Nafion/(2.5–7.5) wt%ZrO2) are
returns to its ionomer form which can be recast to prepare the characterized by water uptake, dimensional stability, ionic conduc-
desired form of film membranes [7,9]. The perfluorosulfonic mem- tivity, chemical stability, and tensile strength and compared with
brane is normally insoluble at room temperature in alcohol and the filler-free recast Nafion and commercial Nafion membranes.
water. But the dissolution can be done at high temperature and Cross section and surface structure of prepared membranes are
high pressure in an ethanol/water mixture [8,10–17]. also studied by SEM.
On the other hand, the lifetime of PEMFC is an important prob-
lem in its use. Durability is one of the main factors hampering the 2. Experimental
PEMFCs commercialization [18]. PEM acts both as a proton con-
ducting medium and a separator of the gases and its degradation 2.1. Materials
has significant effect on the overall durability of PEMFCs. Failure
of the membrane results in high hydrogen and oxygen crossover Concentrated sulfuric acid (H2SO4, 95–97%), hydrogen peroxide
through the PEM and reduced performance of the fuel cell [19]. (H2O2, 30 wt%), sorbitol (C6H14O6), iron sulfate heptahydrate
Therefore, PEM durability and cost are the significant obstacles to (FeSO4
7H2O), sodium hydroxide (NaOH), N,N-Dimethylacetamide
the commercialization of PEMFCs [1,2]. Free-radical scavengers (DMAc), sodium chloride (NaCl) from Merck and zirconyl nitrate
can be used as additives into the membranes to eliminate the rad- hydrate (ZrO(NO3)2
6H2O from Sigma–Aldrich were used. Nafion
ical attacks to the membrane and minimize the membrane degra- 117 membrane was purchased from ElectroChem, Inc.
dation [19–25]. Use of inorganic nanoparticles as additives to
prepare polymeric composite membranes can be a appropriate 2.2. Synthesize of ZrO2 nanoparticles
approach for the improvement of membranes in PEMFC applica-
tions. These composites are able to provide a combination of The microwave assisted gel combustion method was used for
organic and inorganic properties which result in high proton con- the preparation of zirconia nanoparticles base on the following
ductivity and improved mechanical stability and chemical proper- reaction (Eq. (1))
ties [6,26–28]. For this purpose, various additives (metal-oxides,
functionalized metal-oxides, heteropolyacids, and carbon com- 13ZrOðNO3 Þ2
6H2 OðaqÞ þ 5C 6 H14 O6 ðaqÞ
pounds) have been added to the Nafion to modify its properties ! 13ZrO2 ðsÞ þ 113H2 OðgÞ þ 30CO2 ðgÞ þ 13N2 ðgÞ ð1Þ
in recent years [29–35]. Hygroscopic oxides such as silica (SiO2),
titania (TiO2), and zirconia (ZrO2) can improve water retention of The precursor and fuel using for the combustion synthesis were
Nafion membrane and act as tuning agents of humidity. High zirconium (IV) oxynitrate hexahydrate and sorbitol, respectively.
retention of water molecules in the membrane facilitates ionic For zirconia synthesis, proper amounts of ZrO(NO3)2
6H2O and
conductivity of Nafion membranes [36]. Studies in this field, con- C6H14O6 were dissolved in a minimum volume of deionized water.
firm the improvement of conductivity through adding hygroscopic Then the prepared gel is exposed to microwave irradiation to syn-
inorganic additives such as SiO2, TiO2, and ZrO2 nanoparticles [37]. thesis the final powder. Finally, the obtained powders were cal-
Some researchers used silica ([38–44]) and functionalized silica cined under air atmosphere at 500 °C for 3 h.
([45–49]) to modify Nafion membranes. For example, Devrim et al.
[39] studied the role of silica filler in properties of Nafion mem- 2.3. Membranes preparation
branes and their results showed inclusion of silica in the Nafion
membrane has a positive effect on the membrane properties For the preparation of the Nafion nanocomposite membranes,
[39]. Titanium oxide [50–57] and functionalized TiO2 [58–60] have the dissolution method at high pressure and temperature auto-
been also used to modify Nafion membranes properties. Matos clave reactor was used to convert commercial Nafion 117 mem-
et al. [54] added titania-based fillers to Nafion matrix and perfor- brane to Nafion solution and then the nanocomposite
mance of composite membranes was higher than filler-free Nafion membranes were prepared by recasting method. Firstly, 1.2 g of
membrane at 130 °C [54]. Nafion 117 membrane was chopped and dissolved in water/etha-
Zirconia [24,37,61–64] and its functionalized types (such as zir- nol (50/50) solution using a high-pressure reactor (Berghof – BR-
conium phosphate [65–68] and sulfated zirconia [69–74]) have 100) at 240 °C for 6 h under nitrogen atmosphere. After dissolution
been incorporated in the Nafion membrane to improve the mem- process, Nafion solution filtered through filter paper to remove any
brane properties. It is worth to mention, different zirconia undesired particle. Then, the solution evaporated at 80 °C and con-
nanoparticles that prepared by different synthesis methods centrated solution mixed with 10 mL of DMAc and the tempera-
showed different effects on the membrane properties. Nafion/ ture of the solution was gradually increased to 90 °C. In order to
ZrO2 composite membranes are usually prepared by recasting or ensure removal of water and ethanol, 5 mL of DMAc was added
in situ sol–gel reaction methods. For instance, Sacca et al. [64] pre- again. Then, an appropriate amount of ZrO2 nanoparticles were
pared Nafion-zirconia composite membranes using commercial added to the solution under stirring at 90 °C for 30 min. After ultra-
ZrO2 for direct methanol fuel cell application. Water retention sonication (Bandelin, SONOPULS HD2200) for 60 min in an ice-
and cell performance were improved by the addition of ZrO2 water bath and degassing for 60 min in a vacuum oven at room
[64]. D’Epifanio et al. [69] prepared Nafion nanocomposite mem- temperature, this solution was cast onto a glass plate and dried
brane using sulfated zirconia nanoparticles as an additive. For this at 100 °C for 2 h. The prepared composite membranes detached
purpose, they used two types of sulfated zirconia and their results from glass by immersing in DI water and placed in a vacuum oven
148 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154

at 145 °C for 12 h. The prepared membranes were treated prior to branes. The membrane was placed between two polished copper
characterization as boiling in the 3 wt% H2O2 solution, in DI water, block electrodes quickly hosted in a temperature/humidity con-
in 0.5 M H2SO4, and DI water (each for 1 h and at 80 °C), respec- trollable chamber. Nyquist diagrams were recorded between 1
tively. The nanocomposite membranes with 2.5, 5, and 7.5 wt% Hz and 700 kHz. The Nyquist diagrams were used to obtain the
ZrO2 were prepared. Also, a filler-free Nafion membrane was pre- resistance of membranes. The proton conductivity of the mem-
pared according to the procedure described above. The thickness branes (r) was calculated by the Eq. (6):
of all membranes was about 120 mm.
L
r¼ ð6Þ
R:A
2.4. Characterization
where L, A, and R are the thickness, area, and the resistance of mem-
2.4.1. Characterization of ZrO2 nanoparticles brane, respectively. All experiments were performed for three
X-ray diffraction (XRD) pattern of ZrO2 nanoparticles was samples.
recorded with a PHILIPS PW-1800 diffractometer with Cu-Ka radi-
ation source (k = 0.15418 nm) operating in the 2h range of 10–90°. 2.4.6. Mechanical properties of membranes
The X’Pert High Score software was used for phase identification The tensile strength of membranes (70 mm  10 mm) were
and XRD pattern analysis. The most intense peak was used for crys- obtained by an INSTRON (model 5566) machine under an ambient
tallite size (d) calculation using Scherrer formula (Eq. (2)): condition. A strain rate of 10 mm min1 was used and the test was
continued until failure and stress-strain curves of prepared mem-
0:9k branes were recorded. The tests were repeated three times for each
d¼ ð2Þ
bcosðhÞ membrane.
where h is the Bragg angle of the corresponding peak and b is the
full width at half maximum (FWHM). 2.4.7. Oxidative stability of membranes
In addition, the morphology of prepared zirconia nanoparticles The oxidative stability of the membranes was evaluated by cal-
was observed by the field emission scanning electron microscopy culating the weight loss of membranes in the Fenton test. A piece
(ZEISS) with an accelerating voltage of 15 kV and under high of membrane was dried in a vacuum oven for 10 h and then be
vacuum. weighed. Next, the membranes were placed in 100 mL of Fenton
solution (30 wt% H2O2, 20 ppm Fe2+) for 18 h and the temperature
2.4.2. Scanning electron microscopy (SEM) of membranes was 80 °C. Fenton solution was replaced every 6 h with a fresh
The SEM micrographs (VEGA-TESCAN) under high vacuum and solution. Finally, the membrane was removed from Fenton solution
an accelerating voltage of 30 kV was used to study the morphology and rinsed several times with deionized water. Degraded mem-
of the surface and cross-section of prepared membranes. Each branes were dried for 10 h in a vacuum oven and then weighed.
membrane was frozen in liquid nitrogen and fractured then a thin The weight loss of membrane was calculated from the Eq. (7):
layer of gold was sputtered on the cross section before the test. W final  W initial
Weight lossð%Þ ¼ ð7Þ
W initial
2.4.3. Fourier transform infrared (FTIR)
To study the chemical bond changes in Nafion membrane which where Wfinal is the weight of membranes after immersion in the
occurred during high-temperature dissolution process, FTIR analy- Fenton solution and Wintial is the initial weight of membranes. All
sis of membranes was performed using PerkinElmer FTIR in the experiments were performed for three samples.
range of 400–2000 cm1.
3. Result and discussion
2.4.4. Water uptake (WU) and dimensional stability of membranes
The water uptake and dimensional stability of each membrane 3.1. XRD and FESEM of ZrO2 nanoparticles
were measured by means of the difference between the wet and
dry weight and size of the membranes. Dry weight (Wdry) of mem- X-ray diffraction (XRD) patterns of zirconia nanoparticles is
branes was measured after drying the membrane at 100 °C for 24 h shown in Fig. 1a. Different peaks were specified by Miller indices
in a vacuum oven. Then, the wet weight (Wwet) was measured after ((1 0 1), (1 1 0), (1 1 2), (2 1 1), (2 0 2), (2 2 0), and (2 1 3)). The
immersing the dried membranes in deionized water for 24 h. The obtained XRD pattern is consistent with the JCPDS No. 01-079-
water uptake was calculated using the Eq. (3): 1764 to 01-079-1771. In order to calculate the crystallite size of
W wet  W dry ZrO2 using Scherrer’s formula based on the most intense peak
WU ð%Þ ¼  100 ð3Þ (2h = 30.27°), the full width at half the maximum of the X-ray
W dry
diffraction peak was used. The size of ZrO2 nanoparticles is about
Dimensional stability of samples was calculated using swelling 13 nm. The XRD pattern did not show any characteristic peak of
membranes in DI water. For this purpose, surface area and thick- another crystalline material that confirmed the high purity synthe-
ness of membranes in the wet and dry conditions were measured. sized zirconia nanoparticles.
The swelling ratio (SR%) of thickness and area were calculated The FESEM micrograph of synthesized ZrO2 nanoparticles
using the Eqs. (4) and (5): (Fig. 1b) showed spherical particles and a good separation of
T wet  T dry nanoparticles.
Swelling ratioðThicknessÞð%Þ ¼  100 ð4Þ
T dry
3.2. SEM of membranes
Awet  Adry
Swelling ratioðArealÞð%Þ ¼  100 ð5Þ Preparation of defect free proton exchange membrane is very
Adry
important characteristic of the membrane for reaching high perfor-
mance and stability in fuel cell applications. Fig. 2(a–d) shows SEM
2.4.5. Ionic conductivity of membranes images of recast Nafion membrane and its nanocomposite with dif-
A two probe AC impedance potentiostat/galvanostat (BioLogic ferent content of zirconia nanoparticles. As shown in Fig. 2(a–d),
sp-150) was used to measure the proton conductivity of mem- the thickness of different membranes is in the 115–125 lm range.
 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154 149

Fig. 1. (a) XRD pattern and (b) FESEM image of synthesized zirconia powder.

As can be seen, the SEM images of cross section and surface of dif-
ferent prepared membranes showed dense microstructures,
imperfection-free, and an appropriate dispersion of zirconia
nanoparticles in the nanocomposite membranes.

3.3. FTIR analysis of membrane

Fig. 2. Cross-sectional and surface SEM images of recast Nafion and nanocomposite
Fourier transform infrared (FTIR) spectra of the commercial membranes, (a) R-Nafion, (b) R-Nafion/2.5%ZrO2, (c) R-Nafion/5%ZrO2, and (d) R-
Nafion 117 membrane and recast Nafion membrane is shown in Nafion/7.5%ZrO2.
Fig. 3. It shows that the recast Nafion membrane contain molecular
segments similar to Nafion 117. As can be seen, it has the similar
absorptions at 1100–1200 cm1 attributed to the vibrations of of ZrO2 nanoparticles into the Nafion matrix increased water
the CFx. The peaks observed at 1055 cm1 and 1228 cm1 can be uptake of prepared PEMs, especially at the higher temperatures.
assigned to the symmetry and asymmetry stretching vibrations The increased water uptake can be attributed to the hydrophilic
of SO 3 , respectively, while the peak at 975 cm
1
corresponds to nature, the enhanced acidity and surface areas of the ZrO2
C-O-C symmetry stretch [75,76]. nanoparticles that incorporated into the Nafion matrix and
increase in the free volume due to the presence of high concentra-
tion of polymer-filler interfaces [37,62–64,79]. In addition, the
3.4. Water uptake and dimensional stability
results showed for each membrane, water uptake increased in
the higher temperatures.
The water retention in the PEMs is an important parameter
Fig. 4b shows the degree of hydration that was calculated from
because water acts as proton transporting medium for PEMs
water uptake data (Eq. (8))
[63,77,78]. Amount and behavior of absorbed water in the mem-
brane have significant effects on the proton conductivity. There-
10  WU
fore, enhancing the water uptake of membrane especially at the k¼ ð8Þ
IEC  18:02
higher temperature can keep proton conductivity at the appropri-
ate level [44]. In Fig. 4a, the water uptake of R-Nafion/ZrO2 that k is the adsorbed water molecules per sulfonic acid groups
nanocomposite membranes containing various ZrO2 loadings are  
nH2 OðmolÞ
SO ðmolÞ
, WU is the water uptake, and IEC is the ion exchange
compared to filler-free recast Nafion membrane. The incorporation 3
150 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154

the membranes swell and shrink repeatedly. It should be men-

tion that, insufficient water uptake can lead to reduce proton
conduction, whereas high water uptake leads to high dimen-
sional changes in membranes and membrane failure. Although
higher water uptake is a prerequisite for improving the proton
conduction, the mechanical and dimensional stability is also very
important and should be balanced at appropriate levels. The
thickness and areal swelling ratios of recast Nafion and
nanocomposite membranes are illustrated in Fig. 4(c and d). As
can be seen in Fig. 3c and d, the swelling ratio for nanocompos-
ite membranes were a little higher than filler-free recast Nafion
membrane at different temperatures and these values were
almost near to recast Nafion value. The results showed, for each
membrane in the higher temperature due to increasing the
water uptake, the swelling ratio (thickness and area) increased.
In addition, as can be seen, with increasing the zirconia loading
the swelling ratio (thickness and area) slightly increased. With
increasing the zirconia loading (2.5% to 7.5%), at 80 °C the water
uptake increased by about 6%, 10%, and 13% (in absolute term),
Fig. 3. FTIR spectra of recast Nafion and commercial Nafion 117 membranes. the membrane swelling (thickness) increased by about 1%, 2%,
and 3% (in absolute term), and the membrane swelling (area)
increased by about 1%, 1%, and 2% (in absolute term) rather than
capacity (meq g1). The degree of hydration increases with increas-
pure recast Nafion membrane. These results showed the differ-
ing in zirconia loading and temperature.
ent nanocomposite membranes have higher water uptake and
The proton exchange membranes experienced cycling
appropriate dimensional stability.
between dry and hydrated states during fuel cell operation, thus

Fig. 4. (a) Water uptake, (b) degree of hydration, (c, d) swelling ratio of Nafion/ZrO2 nanocomposite membranes containing various ZrO2 loadings and R-Nafion membrane as
a function of temperature.
 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154 151

3.5. Proton conductivity ent parameters, such as the dispersion of the inorganic filler in the
membrane, the water uptake of the membrane, the composition of
Proton conductivity is one of the most important properties of the material in the membranes, and interaction degree between
proton exchange membranes. Two main mechanisms have been the host polymer and the inorganic particles [39]. As shown in
proposed for proton conduction that are vehicular and Grotthuss Fig. 5a, the proton conductivity enhances by increasing the zirconia
mechanisms, that vehicular is related to bulk transfer and Grotthus loading in the measured range of temperature. This effect is partic-
is related to surface transfer and in both the water molecules have ularly evident at high temperature and can be attributed to the
a very important role. The essential parameters in PEM conduction increased water retention property of ZrO2 doped membranes
are the water molecules existence and appropriate amount of pro- [63]. The improvement of the conductivity of Nafion/ZrO2 mem-
ton exchange sites. branes at 100 °C shows their potentials for application in high tem-
The proton conductivity results of filler-free recast Nafion perature PEMFCs. The incremental effect of adding the ZrO2 on the
membrane and Nafion/ZrO2 nanocomposite membranes at the dif- conductivity of polymeric membrane is also reported by some
ferent temperatures and 100% RH are shown in Fig. 5. For better researchers [62,63,80,81].
comparison, the conductivity results of commercial Nafion 117 As can be seen, the conductivities of all the prepared mem-
are also plotted in this figure (Fig. 5). The proton conductivity of branes raised with increasing the temperature. The results showed
recast Nafion membranes is lower than commercial Nafion mem- the protons get more energy to skip the fixed charges in the mem-
brane that is reasonable because the recast membrane was pro- brane by the temperature increasing, therefore, the proton conduc-
duced from a dissolution process in high pressure and tivity enhanced at the higher temperatures. As the membrane is
temperature autoclave reactor and some sulfonic acid groups and exposed to water, the hydrophilic parts of the membrane swell
the main chain of polymer might change during the process. and provide more channels for protons conduction through the
As can be seen in Fig. 5, by incorporation of ZrO2 nanoparticles membrane and higher water level adds the size and number of
into the membrane matrix, the proton conductivity enhanced. In a these channels and improves the proton transportation. Jalani
nanocomposite membrane, proton conductivity depends on differ- et al. [62] have attributed high conductivity of Nafion-ZrO2 mem-
brane at high temperature and low humidity to the higher water
uptake and increased acidity compared to filler-free Nafion mem-
brane [62].
Fig. 5b shows the results of the proton conduction activation
energy for different membranes that were obtained based on the
proton conductivity results up to 80 °C and Arrhenius equation
(Eq. (9)).

r ¼ r0 eðRT Þ
Ea
ð9Þ
where r (mS cm ) is proton conductivity, r0 is pre-exponential
1

factor, Ea (kJ mol1) is the minimum activation energy of proton

conduction through the membrane, R (8.314 J mol1 K1) is the uni-
versal gas constant, and T (K) is the absolute temperature. As can be
seen in Fig. 5b, an addition in nanoparticle loading caused a slight
reduction trend of Ea for nanocomposite membranes rather than
recast Nafion membrane that is consistent with proton conduction
results. The results showed the activation energy for commercial
Nafion 117 was 1.98 kJ mol1, and Ea of recast Nafion (R-Nafion)
was 2.268 kJ mol1 that decreased to 2.038 kJ mol1 with the incor-
poration of zirconia nanoparticles (R-Nafion/7.5%ZrO2).

3.6. Chemical stability (Fenton test)

Accelerated ex-situ Fenton test was used to evaluate the chem-

ical degradation rate of recast Nafion and nanocomposite mem-
branes. During this test, free radicals are produced by the
reaction of the iron source and hydrogen peroxide in an aqueous
solution as reported by Haber and Weiss [82]. As shown in Eqs.
(10)–(14), the oxidation state of iron during the reaction with
hydrogen peroxide changes between Fe2+ and Fe3+. Different inter-
mediate unstable species (free radicals) are generated which attack
the vulnerable parts of the membrane structure [83,84].
H2 O2 +Fe2þ !HO +OH +Fe3þ ð10Þ

Fe2þ +HO !Fe3þ +OH ð11Þ

H2 O2 +HO !HOO +H2 O ð12Þ

Fe2þ +HOO !Fe3þ +HOO ð13Þ

Fig. 5. (a) Proton conductivity of R-Nafion/ZrO2 composites, recast Nafion and
commercial Nafion 117 membranes and 100%RH, as a function of temperature, (b)
Arrhenius plots of proton conductivity in the temperature range of 30–80 °C. Fe3þ +HOO !Fe2þ +Hþ +O2 ð14Þ
152 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154

Fig. 7. Maximum tensile strength and elongation at break of different prepared

membranes and commercial Nafion membrane.

Fig. 6. Weight loss values of composite membranes during Fenton test as a function
of ZrO2 loading.
ical shocks, and dimensional instability in cycling during wet and
dry conditions in the different temperatures. Mechanical strengths
One of the methods to improve the durability of PEMs is the of the nanocomposite membranes containing different ZrO2 load-
incorporation of a hydrogen peroxide decomposition catalysts ing were measured at ambient condition. Tensile strength and
and free radical scavengers into the membrane matrix, that they elongation at break of prepared R-Nafion/ZrO2 nanocomposite,
reduce the H2O2 concentration and subsequently reduces the filler-free R-Nafion and commercial Nafion 117 membranes are
membrane degradation [24]. Weight loss of membrane was used presented in Fig. 7.
to quantify the membrane’s durability. Amounts of weight loss of As noted in the literature, metal oxide based inorganic additives
tested membranes during Fenton test are shown in Fig. 6. As can modifies the mechanical properties of the membrane [6]. As can be
be seen in the Fig. 6, the ZrO2 nanoparticles embedded in the mem- obviously seen in Fig. 7, the tensile strength of nanocomposite
brane result in the reduction in membrane’s weight loss after Fen- membranes is higher than that of R-Nafion membrane. The tensile
ton test which is in agreement with the results obtained by Xiao strength of nanocomposite membranes was raised by increasing
et al. [24]. The membrane weight loss during the Fenton test for the amount of filler which demonstrates the increased intermolec-
the filler-free R-Nafion and R-Nafion/5%ZrO2 is 10.36% and 2.39%, ular forces (i.e. hydrogen bonding and electrostatic forces) between
respectively. Adding a small amount of ZrO2 nanoparticles signifi- the ZrO2 nanoparticles and Nafion polymer matrix. Improvement
cantly improved chemical stability of Nafion membrane in the of mechanical strength is also attributed to good dispersion of
harsh oxidative medium. Obviously oxidative stability of mem- ZrO2 nanoparticles in the Nafion matrix [40].
branes enhanced with increasing ZrO2 loading due to the role of The polymeric chains in the pure matrix have significant slip-
these nanoparticles in the decomposition of hydrogen peroxide page capability and presence of nanoparticles was decreased the
that resulted lower free radical production and subsequently mobility of molecules. The elongation at break results showed a
higher chemical durability of membrane [24]. reverse trend rather than tensile strength and with zirconia load-
In order to demonstrate the reason why ZrO2 has the ability to ing increasing they reduced and R-Nafion/7.5%ZrO2 showed the
mitigate the membrane degradation, Xiao et al. [24] prepared Pt- lowest elongation data.
ZrO2/C and Pt/C and performed the RRDE measurement to estimate
the H2O2 generation and their results showed ZrO2 reduced the 4. Conclusions
H2O2 production and therefore, the incorporation of ZrO2 nanopar-
ticles in the membrane can decompose H2O2 to water and oxygen. In this work, the effect of different loading of zirconia nanopar-
The produced H2O2 during fuel cell operation or existed H2O2 in ticles on physicochemical and electrochemical properties of recast
the Fenton solution can diffuse into the membrane, and will be Nafion membranes was investigated. Zirconia nanoparticles were
decomposed by the ZrO2 embedded and therefore, zirconia synthesized by gel combustion method. The synthesized nanopar-
nanoparticles reduced the free radicals’ concentration. The R- ticles were characterized by FESEM and XRD. The nanocomposite
Nafion/7.5%ZrO2 membrane (containing 7.5 wt%ZrO2) presents a membranes (R-Nafion/x wt%ZrO2, x = 2.5–7.5) were prepared by
higher weight loss compared to the R-Nafion/5%ZrO2 membrane recast method using prepared Nafion solution and zirconia
(containing 5 wt%ZrO2), probably the presence of excess filler, nanoparticles. The prepared membranes were characterized by
caused the formation of some filler agglomeration in the mem- WU, dimensional stability, proton conductivity, mechanical prop-
brane matrix that caused the reduction of ZrO2 effect on the degra- erties, oxidative stability, and SEM tests. The results showed
dation agents. nanocomposite membranes had higher water uptake rather than
pure recast Nafion membrane and appropriate dimensional stabil-
3.7. Tensile strength ity. The proton conductivity of different membranes experienced
an increase by increasing the temperature and also in each temper-
The appropriate mechanical properties are essential for proton ature it increased by ZrO2 loading. In addition, the results indicated
exchange membranes because during different process these that the nanocomposite membranes had better mechanical proper-
membranes suffered under different stresses such as high applied ties and chemical durability rather than pure recast Nafion and
pressure during membrane electrode assembly, different mechan- these parameters were improved by zirconia content increasing.
 M.J. Parnian et al. / Materials Science for Energy Technologies 1 (2018) 146–154 153

Furthermore, SEM results showed the pure recast Nafion and membrane based on sulfonated poly (ether ether ketone), Energy 94 (2016)
292–303.
nanocomposite membranes had homogeneous structure. The
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