international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Enhanced power generation, faster transient

response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte
membrane with optimum rGO loading

Priyanka Ghosh a, Sayantanu Mandal a, Sayani Majumdar a,1,

Arundhati Sarkar a, Saibal Ganguly b, Kajari Kargupta a,*
a
Chemical Engineering Department, Jadavpur University, Kolkata, 700032, India
b
Chemical Engineering Department, BITS PILANI, Goa Campus, 403726, India

highlights graphical abstract

Low cost easy synthesis of rGO-PBI

composite electrolyte using MSA
as solvent.

Optimum (1%) and critical (4%)
rGO loading from property-
performance mapping.

2 times power generation at 170  C
using optimum rGO loading.

Enhancement of proton conduc-
tivity from Insitu Impedance
analysis.

Faster transient step response of
fuel cell using 1% rGO.

article info abstract

Article history: Here we report enhanced power generation, faster transient response and longer durability
Received 16 November 2019 of HT-PEMFC by employing a composite membrane of PBI with reduced graphene oxide
Received in revised form (rGO) at an optimum loading of 1%. Easy and low cost synthesis of the composite mem-
11 April 2020 branes at different loading of rGO is achieved using methane sulfonic acid (MSA) as solvent
Accepted 15 April 2020 that resolves the long-standing issue of poor solubility of PBI in the conventional solvents.
Available online xxx Property and performance mapping with respect to rGO loading not only leads to attain the
optimum but also identifies the window of feasible operating zone. It is observed that with
Keywords: very low (1%) rGO content, composite PBI membrane (rGO-PBI-1) offers the maximum
Polybenzimidazole enhancement of all properties viz water uptake, acid uptake, proton conductivity, ion
Reduced graphene oxide exchange capacity, acid retention capacity, chemical stability, yield strength, while beyond
Proton conductivity a threshold/critical loading (~4%) deterioration of electrochemical and mechanical prop-
erties occur. Steady state performance analysis reveals almost two times peak power

* Corresponding author.
E-mail address: karguptakajari2011@gmail.com (K. Kargupta).
1
presently Graduate Research Assistant at University of Illinois at Urbana-Champaign, USA
https://doi.org/10.1016/j.ijhydene.2020.04.124
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
2 international journal of hydrogen energy xxx (xxxx) xxx

Transient response analysis enhancement of HT-PEMFC using rGO-PBI-1 electrolyte membrane at an operating tem-
Fuel cell perature of 170  C; insitu impedance analysis during fuel cell operation reveals sharp decay
in charge transfer resistance. Multiple step response analysis confirms (~2 times) faster
transient response of fuel cell using rGO-PBI-1 while compared to that with pristine PBI
membrane. Fuel cell stability analysis ensures longer durability of operation with negligible
decay in voltage.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

membranes decreased and membrane itself gets sticky and its

Introduction
Proton exchange membranes (PEM) are of great importance in
recent days due to their immense potential in the field of
polymer electrolyte membrane fuel cell (PEMFC) [1,2]. On the
verge of declining fossils fuels, PEMFCs are one of the cleanest
energy sources to deal with the increasing demands of alter-
native energy resources [3]. Wide numbers of proton exchange
membranes have been studied recently for PEMFCs applica-
tion. Most of these commercialized membranes such as
Nafion [4], sulfonated poly(ether ether ketone) (SPEEK) [5],
sulfonated poly(arylene ether sulfone) (SPAES) [6,7], sulfo-
nated polyphenylenes (SPP) [8] etc. suffer lots of limitations
including low thermal stability, poor solubility in solvents, low
glass transition and operational temperature, adverse me-
chanical strength, leaching out of the acids and poor proton
conductivity. Polybenzimidazole (PBI), due to its unique
properties like high thermal stability, excellent mechanical
stability, high glass transition temperature etc., is extensively
studied for the application in high temperature (>100  C)
polymer electrolyte membrane fuel cell (HT-PEMFC) [9e11].
Despite all these excellent properties, PBI has very poor solu-
bility in some selective solvents like N,N-dimethylacetamide
(DMAc), N-methyl-2-pyrrolidone (NMP) etc., [12,13]. In most of
the cases, PBI has been partially dissolved in DMAc by
applying pressure in autoclave and at high temperature. Par-
tial dissolution also causes wastage of valuable PBI polymers.
For uniform membrane thickness and fabrication, use of film
applicator is also necessary in those cases. Higher concen-
tration of PBI in DMAc type polar aprotic solvents cause
agglomeration also [14]. Evaporation of DMAc solvent some-
times makes the membranes brittle or crack may occur [15]. In
spite of having excellent properties, PBI cannot attain
commercialization level due to its very low solubility in
various solvents and poor fabrication processes. An easy,
convenient and low cost method of membrane fabrication is
required for commercialized application of PBI.
Furthermore, recent extensive review of HT-PEMFC based
on PBI [10,11], considered it as the best suitable polymer
electrolyte for large scale HT-PEMFC for automobiles and
mentioned that such commercial applications demand proton
conductivity higher than 101 S/cm at 120  C (25% RH) and
chemical stability in presence of oxidant, fuel and water. In
context of improved proton conductivity, phosphoric acid
doped PBIs are well used and show high proton conductivity in
the temperature range from 100  C to maximum 200  C [16],
but at that high temperature, mechanical properties of the
property deteriorates. To eliminate these drawbacks and to
enhance the membrane properties, inorganic nano sized
fillers have been composited into the polymer matrices.
Several inorganic nano fillers like, Silica [17,18], TiO2 [19,20],
multi walled carbon nano tube (MWCNT) [21], functionalized
MWCNT [22e24], graphene [25e27], zeolites [28] etc. have been
composited with PBI till now. The presence of these inorganic
nano-fillers not only enhances the mechanical properties of
the hybrid electrolyte membrane but also influences the dis-
tribution of water domains in polar cages and in the inter-
connection channels, which are responsible for both water
uptake and proton conductivity [29].
Active carbon materials like CNT, functionalized CNT,
multiwalled CNT and graphene are excellent filler materials
for proton exchange membranes. Zang et al. [21] have re-
ported fabrication of multi walled carbon nanotube (MWNT)
buckypapers and their silver nanoparticle (AgNP) hybrids with
the assistance of a high-performance polymer, poly-
benzimidazole (PBI). Suryani et al. [22] have prepared func-
tionalized multiwall carbon nanotubes composited
polybenzimidazole (MWCNTePBI) through an ozone mediated
process. In order to get improved proton conductive and me-
chanically stable composites of PBI, R. Kannan have
composited phosphonated CNT and multiwall CNTs
(MWCNT) with PBI. They demonstrated a novel dual func-
tionalization strategy to get phosphonate groups on the
sidewalls of CNTs [23]. Phosphonate MWCNT (P-MWCNT)
enhances the performance of the PBI membranes due the
formation of proton conducting networks that formed along
the sidewalls of P-MWCNTs [24].
Several studies are there with graphene oxide or func-
tionalized graphene oxide composited membranes mainly for
proton transportation in PEMFCs. Graphene oxide (GO) a
chemical derivative of graphite, comprises of carbon sheets
decorated with oxygen containing functionalities on the edges
(hydroxyl, carbonyl and carboxyl groups) and on the surface
(hydroxyl and epoxide groups) [30]. These oxygenated hydro-
philic functional groups (e.g., epoxy eOe and hydroxy eOH)
forms one-dimensional hydrogen bonded channels for proton
transport, whereas, Graphene is a two dimensional sp2 hy-
bridized network of carbon. It has gained huge attention
worldwide and most frequently used as fillers in recent years.
Some unique properties like good thermal stability,
outstanding mechanical properties, high surface area, abun-
dant resources, unique two dimensional geometry and light
weight features make graphene an excellent material as fillers

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
 international journal of hydrogen energy xxx (xxxx) xxx
with polymer electrolytes. Although graphene and rGO are
mainly regarded as electrical conductors, protons can also
pass across the monolayer of graphene [31e33], and even
water molecules can pass across the rGO sheet [34]. This can
only be possible through atomic-scale defects created on
those nanosheets. Due to the dense, delocalized electron
cloud formed by the p orbitals of graphene [35,36] protons get
hindered to pass through. If defects can be generated by any
ways mainly functionalizing it, development of intercalation
composites, usage of geometrical modification strategies,
heteroatom doping, incorporating hydrophilic functional
groups, creating pores, making composite with metal defects
etc. [37], rGO can be an excellent proton conductor under
ambient conditions [29].
Recent experimental [31] as well as theoretical studies
[29,38] report on in-plane proton conduction in reduced gra-
phene oxide (rGO) films. Under humid condition enhanced on-
plane proton conduction in single layer and bilayer rGO sheets
by water adhesion supports the proton conducting channel/
network formation. Reports are there on either the use of
hydrophilic function groups [27] or allowing water molecules
to be adsorbed on the monolayer rGO sheet or intercalated
into the interlayer space in the bilayer rGO sheets [29]. Re-
ported DFT calculations [29] indicate that water-mediated
hopping is more likely to occur due to its much lower activa-
tion energy than epoxy-mediated hopping and reveal new
prospects for developing efficient solid proton conductors
using rGO. Recently rGO nano composited Nafion has been
proven to possess enhanced proton as well as electron con-
ductivity due to the strong coupling effect exerted by the
functional groups of rGO and the electron withdrawing groups
of Nafion [39]. Very recently it is reported [40] that proton
transmission through single-layer graphene in graphene/
proton-exchange-membrane (PEM) sandwich structures is
more than 100 times faster than for any other cation. Thus
unlike other nano-fillers, rGO, under humid condition is a
good ionic and electronic conductor; proton conduction would
be enhanced at an optimum loading of it and beyond a
threshold value of the loading it may decay.
PBI decorated reduced graphene oxide as supporting ma-
terials in combination with Pd nanowires electro catalyst have
been used in anion exchange membrane fuel cell by Zeng et al.
[41] A very relevant work on graphene PBI composite fabri-
cated by exfoliation of graphite directly into methanesulfonic
acid (MSA) and subsequent in situ polymerization procedures
has been reported by Wang et al. [25] However dimethyl
sulfoxide (DMSO) was further used as solvent to dissolve GP-
OPBI nanocomposites. Composition with GO and SGO en-
hances the conductivity as well as performance of the fuel
cell. Wang et al. [26] have fabricated PBI composites with a
high graphene content (up to 40 wt%) by combination of
solvent-exchange and solution-casting methods. Composite
membranes based on graphene oxide-PBI and sulfonated
graphene oxide-PBI has also been reported by C. Xu et al. [27]
Work on the improvement of durability of the carbon black
electrocatalyst by the coating with PBI has also been reported
by T. Fujigaya et al. [42] Ionic liquid functionalized graphene
oxide (IL-GO) composited PBI membrane was synthesized and
applied to the alkaline anion exchange membrane fuel cells by
C. Wang et al. [43] Recently, PBI grafted graphene have been
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
3
used as a catalyst support for PEMFC to facilitate mass transfer
[44].
Although several works reported on active carbon mate-
rials composited PBI membranes, the major part of the liter-
ature reports are focused only on the property measurement
of the composite membrane and few are on fuel cell polari-
zation data [22e24,27]. As far as the commercialization of PBI
based HT-PEMFC is concerned the performance and opera-
tional aspects viz steady and transient response analysis of
fuel cell as well as durability analysis are imperative. Several
reports on durability analysis of PBI based HT-PEMFC are
available in literature [19,20,27,45]; Lobato et al. [45] have
extensively compared the delayed and non-delayed degrada-
tion of membrane electrode assembly (MEA) having PBI
membrane with/without fillers, respectively. However, tran-
sient response analysis of PBI based HT-PEMFC especially the
role of loading of filler on dynamic response of fuel cell is still
scant. There exists a few reports on general transient
response of PEMFC [46e49].
In this present work we report an easy, low cost, affordable
and convenient route of composite rGO-PBI membrane fabri-
cation. The drawbacks of dissolving PBI polymer, mentioned
above have been overcome by using MSA as the solvent.
Synthesis, characterization and property mapping of rGO-PBI
membrane with different rGO content have been performed.
In particular, the role of rGO loading on different properties of
the composite membrane viz. proton conductivity, water up-
take, acid doping level, ion exchange capacity and mechanical
stress strain behavior are studied; attempt has been made to
predict the window of rGO loading for which proton transport
and properties of the membrane are enhanced beyond that of
pristine PBI. Optimum rGO loading at which properties are
maximized as well as the threshold rGO loading beyond which
properties deteriorate are determined. Steady state polariza-
tion data analysis, durability analysis and transient response
analysis of the PEMFC with optimum rGO-PBI electrolyte
membrane have been performed. For the first time effect of
incorporation of rGO content on the power generation, dura-
bility and transient response of the fuel cell are quantified.
The results are of significance for real life steady and dynamic
operation of the fuel cell.
Experimental
Materials Graphite powder, Potassium permanganate
(KMnO4), Sulfuric acid (H2SO4), Orthophosphoric acid (H3PO4),
Hydrochloric acid (HCl), Hydrogen peroxide (H2O2), Hydrazine
hydrate (NH2NH2) all purchased from E MERCK, Mumbai,
India. 3,3-Diaminobenzidine (DAB) was purchased from
HiMedia, Mumbai, India. Isophthalic acid (IPA), Methane sul-
fonic acid (MSA) was obtained from E MERCK, Mumbai, India.
Polyphosphoric acid was purchased from Spectrochem,
Mumbai, India.
Synthesis of rGO
Graphene oxide (GO) was synthesized by Improved Method
[50]. In this method, concentrated H2SO4 and H3PO4 were
mixed maintaining 9:1 (360 ml:40 ml) ratio and added to
4 international journal of hydrogen energy xxx (xxxx) xxx
graphite flakes (3.0 g, 1 wt equiv.). KMnO4 (18.0 g. 6 wt equiv.)
was added slowly to the mixture under continuous stirring as
the reaction is exothermic in nature. The mixture was kept
stirring for 6 h maintaining 50  C temperature. It was then
cooled at room temperature, diluted with deionised water
(400 ml) and treated with 30% H2O2 to reduce residual per-
manganate and manganese dioxide. The resultant solution
was centrifuged several times and treated with HCl and
further by ethanol. After centrifugation and washing with
deionised water a chocolate brown colour residue was ob-
tained. It was dried, stored and used as per requirement. The
obtained graphene oxide (GO) was dispersed in a mixture of
deionised water and N,N-Dimethylformamide. 1.5 ml of hy-
drazine hydrate was used to reduce it. The mixture was kept
at 100  C overnight. Reduce graphene oxide (rGO) was
observed floating in the liquid. It was then filtered and dried.
The specific surface area of rGO prepared by this method is
320 m2 g-1.
Synthesis of PBI
Polybenzimidazole was synthesized by taking 3,3-
Diaminobenzidine (DAB) and isophthalic acid (IPA) as the
precursor compound and polyphosphoric acid (PPA) as both
the solvent as well as polymeric agent. Initially, in a three
mouth flask attached with condenser, 5 g of DAB was dis-
solved in required amount of PPA with rigorous mechanical
stirring at 140  C. As PPA is highly viscous liquid, rigorous
stirring is required. The solution was stirred until it is not well
mixed and homogeneous. N2 gas was purged to the chamber
of the three mouth flask maintaining inert atmosphere to
avoid moisture which may cause transformation of the poly-
phosphoric acid to orthophosphoric acid. Equimolar amount
of IPA was added to the solution and the temperature was
raised to 200  C. The reaction was allowed to run for 17 h. The
viscous brown coloured mass was then poured into cold
distilled water and washed several times to neutralize it. The
rope like polymer was then cut into pieces and washed again
for neutralization, then dried in oven at 100  C overnight. The
dried polymer was ground in mortar pastle, stored and used
when required.
Fabrication of rGO-PBI nanocomposite membrane
Membrane fabrication was performed by solvent evaporation
method. Required amount of reduced graphene oxide (rGO)
was dispersed in methane sulfonic acid (MSA) by ultra-
sonication for 1 h for well dispersion. PBI was added to it,
the solution was then stirred in a closed chamber at 150  C for
30 min. After complete dissolution of PBI, the slurry was then
cast on a flat bottomed Petri dish and allowed to evaporate the
solvent at 200  C under a ventilated hood until volatility
ceased. It was then cooled down and hot distilled water was
added to peel off the membrane. The excess MSA was then
neutralized by washing the membrane in boiling distilled
water for several times. The membranes were then dried at
100  C to evaporate adsorbed water. Four different composite
membranes were fabricated with 1%, 3%, 6% and 9% weight
percentage of rGO (<10 nm) as filler in PBI. The thickness of all
these membranes are found to be 30 ± 5 mm.
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
The beauty of the work lies not only on the nano-
composition of the valuable nano filler rGO, but also on a very
easy, simple and low cost sol gel fabrication of PBI membranes
as well as rGO-PBI membranes using MSA as solvent. Here use
of MSA allows easy dissolution of PBI in less than 30 min at
150  C without applying high pressure; it results in fabrication
of smooth and homogeneous membrane without using thin
film applicator which leads to low operating/processing cost.
The estimated material cost for preparation of 4 cm2 mem-
brane exclusive of operating costs is more than 100 fold lower
than the cost of commercial PBI membrane.
The membrane fabrication in this process generally fol-
lows two stage; gelation and solidification. The time required
for gelation and solidification decays as the temperature in-
creases. The gelation and solidification kinetics of the mem-
brane fabrication is depicted in Fig. 1(a). Linear form of semi-
log plot of inverse of time of gelation/solidification versus in-
verse absolute temperature reveals that gelation and solidifi-
cation kinetics follows Arrhenius relationship. The image of
pristine PBI and rGO composite PBI membranes with different
rGO loading are shown in Fig. 1(b). From this photographic
image it is visually observable that with increase in the rGO
filler content, the opaqueness and agglomeration increases.
The proposed structure and mechanism of proton conduction
of the rGO-PBI membrane is shown in Fig. 1(c).
Characterization
The characterization of graphene oxide, reduced graphene
oxide, pristine PBI and rGO-PBI nanocomposite membranes
were performed by X-Ray Diffraction (XRD), Fourier-transform
infrared spectroscopy (FTIR), Raman Spectroscopy, Ther-
mogravimetric analysis (TGA) and Field Emission Scanning
Electron Microscopy (FESEM). The XRD analysis was per-
formed using Ultima III, (Rigaku, Japan) applying 40 kV volt-
ages, 30 mA current, 1.2 kW power from 10 to 90 2Ө ranges.
FTIR spectra were measured in PerkinElmer FTIR spectrom-
eter (FT-IR-8400S). The Raman analysis was performed by a JY
Horiba LabRAM HR (lexc 532 nm) within the wave number
range of 100e1400 cm1. The thermal stability of the mem-
branes were measured by TGA using PerkinElmer Pyris Dia-
mond model with 150 ml/min rate of nitrogen flow with a
heating rate 15  C/min. The FESEM images of the membranes
were captured in FEI INSPECT F50 instrument. The mechanical
properties were measured at room temperature on a micro-
tensile meter (LLOYD instrument LR10K plus model) 10 KN
made in England. The samples were cut by strip cutter and
kept between the holders of the instrument, tightened up to
40 N cm and were subsequently pulled at a speed of
100 mm s1.
Property measurements
Several membrane properties such as Water uptake, Acid
doping level, Ion Exchange Capacity, Swelling Ratio, Leaching
test, Chemical stability by Fenton’s test are performed. The
detailed procedure of all these property analysis with formula
and units are described in the S2 section of the supporting
document.
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 1 e (a) Gelation Kinetics (b) Image of pristine PBI and rGO-PBI composite membranes (c) Schematic interlinked layered
structure of rGO-PBI and facile mechanism of proton transport through it.

Electrochemical characterization graphite grooves. H2 gas is humidified by passing it through

The temperature dependent proton conductivities of the
membranes are determined by using potentiostat/galvanostat
Metrohm Autolab AUT84999 PGSTAT 302 N (Eco Chemie, The
Netherlands) in a two probe method over the frequency range
1 Hz to 1 MHz with the sine wave amplitude of 10 mV. Con-
stant voltage is supplied through Autolab potentiostat. The
membranes are sandwiched between two Platinum disc
electrodes. The complete set up is attached with temperature
controller heater and placed in an insulating chamber as
shown in literature [51]. A sinusoidal voltage signal from the
Autolab potentiostat is applied across this platinum plate and
membrane combination. Conductivity has been calculated
from the following formula [52].
s ¼ (L/A)  (1/R) (Scm1)
Where R ¼ Resistance in U, L ¼ distance between the two
electrodes in cm, A ¼ Area of platinum plates electrodes in
cm2.
Membrane electrode assemblies (MEA) fabrication and fuel
cell performance
The membrane electrode assembly (MEA) is designed by
sandwiching a piece of membrane between two carbon
black Pt loaded (0.5 mg cm2) electrodes (Sainergy Fuel Cell
India Pvt. Ltd., Chennai, India) and hot pressing it for 5 min
with a load of 40 kg cm2 at 130  C. The active area of the
MEA is 4 cm2. The MEA is placed between two channelized
a humidifier chamber set at 70  C and then passed through
anode with a flow rate of 2 L per minute (LPM). O2 gas is
passed through cathode with flow rate of 1 L per minute
(LPM). The total system is bound with a support and one
temperature controlled heater is attached with it to main-
tain the operating temperature. The set up is attached to
load box to measure the current-voltage (IeV) data. The
single cell is operated by varying temperature from 70  C to
180  C at a fixed humidifier temperature at 70  C. At a spe-
cific operating temperature, the fuel cell under a constant
load current (0.3 A cm2), is allowed to attain the steady
state and the corresponding voltage is measured. Polariza-
tion curves were obtained by applying a current staircase
and measuring the voltage. The effect of operating temper-
ature and the role of rGO content of the composite mem-
brane on the voltage versus current and power versus
current plots are studied. The durability of the MEAs were
measured by applying a constant load current at the best
operating cell temperature.
Transient response analysis
Step response analysis of the fuel cell is performed. For a fixed
set of operating variables (cell temperature, humidifier tem-
perature, oxygen and hydrogen flow rates), a constant load
current is applied. Fuel cell is allowed to attain the steady
state. A step change is applied to a single operating variable
(operating temperature) and respective change in output
(deviational voltage) is noted. Considering, the fuel cell as a
first order system, for step input the response is

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
6 international journal of hydrogen energy xxx (xxxx) xxx

increase in 2q value corresponds to the decrease in interplanar

t/t
distance. In case of the rGO-PBI composite membrane, due to
DV(t) ¼ KpDT (1-e )
the effect of crosslinking, a shift in the peak from 25 (for
pristine PBI) is observed. The rGO-PBI nanocomposite mem-
Where DV is the deviational voltage, DT is the step input in
brane shows broad peak at 2q ¼ 24.8 which is the combina-
terms of deviational temperature, Kp is the steady state gain
tion peak of the pristine PBI and the rGO. rGO-PBI-1 has been
and t is the time constant of a first order system that char-
chosen for the analysis as the representative one. It is clearly
acterizes the response of the system towards a step input. The
observed from Fig. 2(a) that the amorphous nature of the rGO-
time constant t is calculated as the time taken to attain 63.2%
PBI-1 plot has been reduced compared to the pristine PBI
of the steady state value. The system attains the steady state
membrane, due to the incorporation of the rGO into the
at a time approximately equals to 4t. Multiple increasing steps
polymer matrices. Pristine PBI and rGO both have peak very
and decreasing steps are also applied and corresponding time
near to each other (2q ¼ 24.7 for rGO and 2q ¼ 25 for pristine
constants are analysed. Effect of rGO loading of the composite
PBI). Thus rGO-PBI composite membrane has a combination
membrane on the response time is quantified.
peak of these two at 2q ¼ 24.8 . A peak near 2q ¼ 44 in case
rGO might be from the short range impurity scattering effect
due to the presence of atomic scale defects [54]. While the
Result & discussion
formation of the composite, cross linkages between the
polymer and the reduced graphene oxide occur and as a result
Structural analysis
the effect of the short range impurity scattering disappears.
Absence of any peak around 10.2 in the rGO-PBI composite
XRD analysis was performed to examine the crystalline or
membrane confirms that rGO was not oxidised and remained
amorphous nature of the membranes and the GO and rGO.
in reduced state during composite membrane formation. It
The X-ray patterns of the pristine PBI, composite PBI and the
also confirms that the MSA is a non-oxidising solvent and
GO, rGO are shown in Fig. 2(a). It can be well observed that GO
chemically does not interact with rGO. The XRD analysis also
gives a peak at 2q ¼ 10.2 which is due to the 001 plane con-
concludes that GO has been successfully reduced to rGO by
firming GO [53]. Reduction of GO with hydrazine hydrate is
hydrazine hydrate.
supported by the formation of reduced graphene oxide (rGO)
The structure of the compounds is further confirmed by
which gives a broad peak at 2q ¼ 24.7 . The pristine PBI
FTIR spectra as shown in Fig. 2(b) and (c). The FTIR spectra of
membranes shows a broad peak at around 2q ¼ 25 which
GO and rGO are shown in Fig. 2(b) and for PBI and composite
represents the spacing between the two parallel benzimid-
PBI it is shown in Fig. 2(c) The FTIR spectra of GO in Fig. 2(b)
azole chains [20]. This pattern confirms the amorphous phase
shows a broad absorption peak at 3396 cm1 due to the
of the PBI polymeric membrane. A shift is observed in the 2q
stretching vibration of the hydroxyl group located on the
for the composite PBI membrane around 25 . In XRD, an
plane of GO [55]. The characteristic peaks of stretching

Fig. 2 e (a) XRD analysis of GO, rGO, Pristine PBI and the composite rGO-PBI membrane (b) FTIR spectra of GO and rGO (c) FTIR
spectra of pristine PBI and the composite rGO-PBI membrane.

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
 international journal of hydrogen energy xxx (xxxx) xxx 7

vibration of the carboxyl group at the edges of the GO sheet
(~1737 cm1), aromatic C]C bonds (~1623 cm1), stretching
vibration of epoxy CeO (~1219 cm1), presence of CeO
(~1050 cm1) [56,57]. Huge decrease in the intensities of the
peaks is observed in the case of rGO. The absence of the
characteristic peak of eCOOH located at 1737 cm1 suggests
that reduction have taken place and maximum of the eCOOH
group have been removed from the eGO surfaces by the
reduction process [58]. In case of rGO, peak at 1635 cm1 and
1396 cm1 is attributed to the in-plane C]C stretching, and
1106 cm1 is attributed to the CeOH stretching which further
confirms the reduction of GO [57e59].
The FTIR spectra of PBI and rGO composite PBI membranes
are illustrated in Fig. 2(c). The huge drop for all the membranes
in the region of 4000e3500 cm1 is attributed to the eOH
stretching of the physiosorbed water molecules. The peaks in
the region 3500 to 2000 corresponds to the NeH stretch and
the hydrogen bond interaction of NeH/H bond. The peak at
1630 cm1 is due to the C]N bond and peak at 1460 cm1 is
attributed to the in-plane deformation peak of the imidazole
ring respectively [60,61]. A small peak at 2360 cm1 is present
in all the composite membranes whereas absent in the pris-
tine one. This is the characteristic peak of carbon compound
which confirms the presence of rGO in the PBI composites.
With increase in the loading of rGO, the intensity of the peaks
decreases indicating hydrogen bonding between the NeH
groups in the PBI repeat unit.
To determine the reduction GO and to analyse the struc-
tural and electronic conjugate states, defects, nature of
layering of rGO, Raman spectroscopic analysis were carried
out. The Raman spectra of GO and rGO is shown in Fig. 3(a).
The Raman spectrum of GO displayed D band and G band at
1342 cm1, 1594 cm1 respectively maintaining the intensity
ratio of the D to G band (ID/IG) 0.84. Whereas the same D band
and G band for rGO shows peak at 1355 cm1, 1585 cm1
respectively providing the intensity ratio of the D to G band
(ID/IG) 0.85. The G band corresponds to the characteristic peak
of sp2 hybrid structure which in turn represents the symmetry
and crystallinity of the carbon materials. The D band is the
characteristic peak of the surface defects and disorder of the
graphite layers [59]. Increase in the intensity ratio indicates
that more structural defects has been incorporated into rGO
after reduction of GO. To check the state of rGO after meth-
anesulfonic acid (MSA) treatment, rGO was treated in MSA at
120  C for 6 h and checked by Raman spectra. The result is
shown in Fig. 3(a) and it is almost exactly the same as rGO. The
ID/IG value obtained for this rGO is also 0.85. This result also
confirms rGO is in reduced state after the treatment with MSA
and in the rGO-PBI composite membrane, it is in reduced state
also. The interlinked proposed structure of the rGO-PBI
membrane as confirmed from the structural characteriza-
tion is shown in Fig. 1(c). The polybenzimidazole backbone is
linked with the reduced graphene oxide by hydrogen bonding
of the eNH site of the PBI.
Mechanical strength measurement
It is well known that rGO possesses very high intrinsic me-
chanical properties and very large specific surface area. These
properties make rGO an excellent filler for the reinforcement

Fig. 3 e (a) Raman spectra of GO and rGO (b) Stress-Strain curves of PBI and rGO-PBI composite membranes
Thermogravimetric analysis of (c) undoped and (d) doped PBI and composite PBI membranes.

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
8 international journal of hydrogen energy xxx (xxxx) xxx
of polymers. Extended sheet like array of rGO allows strong
interaction with surrounding polymers. In this study, poly-
benzimidazole (PBI) polymer with excellent thermal proper-
ties is composited with rGO. The stress-strain curve of pristine
PBI and rGO-PBI composite membranes are depicted in
Fig. 3(b). The strong interaction between the imidazole group
of PBI and the rGO backbone leads to high mechanical prop-
erties. The interactions include hydrogen bonding between
the imidazole group of PBI and end carboxylic group, p-p in-
teractions between the polymer backbone and rGO backbone,
van der Waals interaction between the polymer and rGO
sheets. Large specific surface area of rGO leads to good
dispersion and strong interfacial interactions. Thus compo-
sition shows better result than the pristine one and rGO-PBI-1
shows the best result. The yield strength of pristine PBI is
61.102 whereas for rGO-PBI-1 it is 78.55 MPa suggesting
incorporation of rGO enhances the mechanical strength of the
membrane. Similarly the ultimate strength of rGO-PBI-1 is
much higher (101.657 MPa) than the pristine one (70.471 MPa).
Due to the large specific surface area, strong interfacial in-
teractions and extended backbone, rGO sheet could act as
cross linking agent to the polymer backbone resulting in
enhancement in the mechanical properties. When rGO con-
tent is relatively low, rGO sheets are individually dispersed in
the matrix [26]. It is observed from Fig. 3(b) that with increase
in the rGO contents, beyond a critical/threshold value the ul-
timate strength and strain value decreases with further in-
crease in the rGO content. With low content of rGO, the
mechanical property could be simultaneously improved based
on several toughening mechanisms such as crack deflection
and crack bridging [62]. However, composites with high con-
tent of filler, the ultimate strain and toughness always dete-
riorate [63,64]. In this study it is also observed that when high
content of rGO is added to the polymer matrix, due to the large
surface area of rGO, large amount of polymer chains would be
immobilized onto the filler surface because of the strong in-
teractions between rGO and PBI. As a result the number of free
polymer chains continuously decreases with addition of rGO.
Moreover, the confinement of free polymer chains between
rGO sheets also restricts the mobility of the polymer chains
when subjected to uniaxial tension, which could also
contribute to the decreased ultimate strain [65].
Thermal stability
TGA was performed for both the doped and undoped mem-
branes to check the acid doping level as well as the thermal
stability. TGA analysis of the undoped and doped membranes
is shown in Fig. 3(c) and (d), respectively. From Fig. 3(c), it is
observed that all the undoped membranes have same pattern
of weight loss under thermal analysis and there is no signifi-
cant weight loss for any particular membrane. Two distinct
weight loss patterns are observed for undoped membranes:
one around 100  Ce150  C due to the adsorbed water content,
another around 500  C which is attributable to the polymer
backbone and the organic moieties. From Fig. 3(d), it is clearly
observable that there are significant changes in the weight
loss pattern of the undoped and doped membranes. Among all
the membranes rGO-PBI-1 shows the maximum weight loss
which confirms that maximum acid is adsorbed by this
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
membrane. Three distinct patterns of weight loss are clearly
observed from the TGA analysis of doped membranes: one
around 100  Ce150  C due to the adsorbed water content as
both the PBI polymer and rGO are hygroscopic in nature. The
second loss appearing at around 160 e220  C is attributable to
the thermal degradation of phosphoric acid. Self-dehydration
of phosphoric acid generates pyrophosphoric and triphos-
phoric acid [20,66]. The third loss starts around 550  C and it is
due to the degradation of the organic polymer moieties. The
corresponding derivative of the weight loss of the undoped
and doped pristine PBI and composite membranes are also
shown Fig. 3(c) and (d). Proper position of weight loss can be
better understood from the derivative plot.
Morphological analysis
The FESEM micrographs of the pristine and composite mem-
branes are shown in Fig. S1 in the supporting documents.
Smooth and uniform surface is clearly observed in the FESEM
image of pristine PBI membrane as depicted in Fig. S1(a). The
morphology of rGO is shown in Fig. S1(b). It is evident from the
images that the extent of agglomeration increases with in-
crease in the inorganic loading. A membrane with only 3% of
rGO loading shows much agglomeration with average
agglomerate size 39.8  48.6 nm2 [Fig. S1(d)]. Increase in the
rGO loading to 6% increases agglomeration with average
agglomerate size 270  165.6 nm2 [Fig. S1(e)]. 9% of rGO con-
tent drastically increases the agglomeration resulting big
lumps covering almost maximum area clearly observable
from Fig. S1(f). Whereas in the case of 1% rGO loading, the
formation of agglomerates is not very much evident compared
to the other membranes and the average agglomerate size is
17  22 nm2 approximately. A very smooth and uniform dis-
tribution of rGO nano fillers are observed throughout the
surface of 1% rGO-PBI composite membrane as shown in
Fig. S1(c). Due to local action and agglomeration factor rGO
appeared as globular in the composite membranes.
Property measurement
Several properties like water uptake, swelling ratio, acid
doping level, ion-exchange capacity, and the proton conduc-
tivity of the membranes are measured; Leaching test and
study on chemical stability by Fenton’s test are performed; the
detailed procedure of property measurements are described in
S2 section of the supporting document and the results are
illustrated in Table 1 and in Fig. 4. Water uptake enhances on
rGO incorporation because, both the PBI polymer and the rGO
nano fillers are hydrophilic in nature; these also affect
swelling ratio similarly. Phosphoric acid is used as acid media
due to its non-volatile nature, high temperature sustainability
and more hopping sites for proton transport [67]. With
hydrogen bonding network chain and self-dissociation to
H4POþ 
4 and H2PO4 , proton transportation goes easier with
orthophosphoric acid [68]. PBI being a basic polymer, always
shows good acid doping level after immersion in acid. On rGO
composition, 2.8 times enhancement in acid doping level is
achieved from pristine PBI to rGO-PBI-1 composite mem-
branes. Ion exchange capacity (IEC) is the measure of the ease
of proton release or hopping and 1% rGO-PBI membrane
 international journal of hydrogen energy xxx (xxxx) xxx 9

Table 1 e Comparative property analysis of the pristine PBI membrane and the rGO nano composited membranes: water
uptake, swelling ratio, acid doping level, ion exchange capacity, proton conductivity, chemical stability, leaching test.
Wt% Water Swelling Acid Doping Ion Exchange Proton Conductivity Fenton’s test Acid remaining in
Uptake (%) ratio (%) Level Capacity (meq g-1) (at 170  C) (S cm-1) (after 100 h) (%) Leaching test (%)
0 20.01 13.45 3.17 2.03 0.05 92.14 35.51
0.5 30.87 24.88 6.63 5.41 0.09 94.68 48.33
1 36.39 31.14 8.93 7.58 0.12 95.88 54.89
3 34.43 26.78 6.04 4.60 0.06 93.47 47.36
6 24.95 19.56 5.14 3.92 0.03 90.49 37.06
9 22.74 18.87 5.06 3.23 0.02 88.16 39.59

Fig. 4 e (a) Chemical Stability test (b) Arrhenius plot of proton conductivity measurement (c) Property mapping of pristine PBI
and all composite membranes.

shows highest IEC value of 7.582 meq g1. In order to deter-
mine the acid retention capability of the membranes, acid
leaching test is performed. One of the most drawbacks of
proton exchange membranes for PEM fuel cell is acid leaching
which causes degradation of the fuel cell performances.
Excess leaching of acid corrodes the valuable platinum loaded
electrodes and also increases the ohmic resistance of the
system [10,69]. Acid retention increases from pristine PBI to
1% rGO-PBI membrane then it decreases. The radical oxidative
stability of PEMFC is evaluated by Fenton’s Test. While
working on fuel cell, the radicals like HO$ and HOO$ are
formed and attack the proton exchange membrane causing
degradation [70]. Polymer containing hydrogen bond can be
attacked by these radicals. In Fenton’s test, these radicals as
described are obtained from Fe2þ catalysed H2O2 decomposi-
tion [71]. rGO having a 2D network structure are being cross
linked with the PBI polymer network as shown in Fig. 1(c)
resulting enhanced free radical oxidative stability. The results
are shown in Fig. 4(a). Hydrogen bonding of the polymer
chains with rGO, protects terminal bonds of PBI from the
attack by Fenton’s reagent.
The temperature dependent proton conductivity mea-
surements are performed for all the membranes and the re-
sults are plotted in Fig. 4(b). It is observed that with increase in
the temperature, proton conductivity increases for all the
membranes including the pristine PBI membranes: it reaches
the maxima at 170  C and then decreases. Proton transport of
H3PO4 doped PBI membranes generally follows two mode of
transportation; (i) the exchange of proton via hydrogen bonds
between solvent molecules such as phosphate, water, N-het-
erocycles of PBI and (ii) through the self-diffusion of phos-
phate ions and water molecules. The membranes soaked in
orthophosphoric acid follow the following proton transport
pathways as suggested by Ma et al. [72].

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
10 international journal of hydrogen energy xxx (xxxx) xxx

and strong bonding between the polymeric chain and the rGO
network. This actually affects in the result and makes 1% rGO-
H3PO4 to H2O > H3PO4 to H2PO
4
þ
> NeH to H2PO
4
þ
> NeH to
PBI the most stable one. This is due to the fact that lower
H2O > NeHþ to NeH
loading allows better dispersion and large available specific
surface area (per unit volume) and higher loading causes
The proton conductivity directly depends on the number of
agglomeration leading to lower dispersion. More specific sur-
proton carriers and their mobility and both these parameters
face area allows more active site, thus more adsorbing site.
are function of temperature [73]. With increase in the tem-
Thus rGO-PBI-1 with 1% inorganic loading leads to lower
perature, the splitting of the H3PO4 gets easier and number of
agglomeration and higher specific surface area resulting
protons increases. The ion mobility also gets enhanced due to
higher value of proton conductivity. However, to understand
the easy and fast movement of the protons at higher tem-
the properties of the membrane with rGO loading lower than
perature. Thus temperature plays an important role in deter-
1%, another membrane with 0.5% rGO loading has
mining the conductivity. Here, Fig. 4(b) also depicts that
been fabricated and its properties are checked and depicted in
proton conductivity of all the membranes increases with in-
Fig. 4(c) and Table 1. It is observed that the optimal loading at
crease in the temperature from 50  C to 170  C and then de-
1% remains unaltered. Fig. 4(c) and Table 1 summarize the
creases. Beyond 170  C, membranes get sticky and
results of the different property analysis of pristine and rGO
performance starts to deteriorate.
loaded PBI membranes. It is revealed that all the properties as
The heterocyclic polymer Polybenzimidazole contains
well as property enhancement with respect to pristine PBI
both proton donor (eNHe) and proton acceptor (-NH ¼ )
membrane is maximized for the optimum rGO-loading of 1%.
hydrogen bonding sites [14] which on acid doping exhibit
It is also evident that beyond ~4% critical loading, proton
specific interactions with acid and water molecules for proton
conductivity, mechanical strain, chemical stability of the
transportation. rGO being a two-dimensional layered struc-
composite membrane deteriorate even below that of pristine
ture of extended network of carbon, when composited with
PBI membrane. Thus mapping of property-loading expresses a
these heterocyclic PBI polymer, forms parallel or sandwiched
window of rGO-loading (0e ~4%) that leads to enhancement of
conjugative layers of PBI and rGO (refer to Fig. 1(c)). In humid
property over pristine PBI. The experimental data of property
condition, water molecules attach to the rGO sheet creating
versus rGO inorganic loading are interpolated to obtain the
defects in the delocalized electron cloud formed by the p or-
critical loading.
bitals of graphene [35,36]. These defects result proton trans-
port in this 2D network. PBI itself is very hydrophilic and in
Steady state performance of a fuel cell, insitu impedance
addition, the presence of rGO in PBI increases water uptake
analysis
and acid uptake by oxygen containing functional groups. The
conjugative alignment of rGO and PBI in the composite
The steady state polarization data, voltage versus current
membranes, allows an extended pathways of proton trans-
density and power density versus current density of the fuel
port by crosslinking of PBI chain and rGO network by
cell with pristine PBI and with rGO-PBI composite membranes
hydrogen bonding as well as van der Waals interaction. Upon
are shown in Fig. 5. The pristine PBI shows the maximum
acid doping, phosphoric acid takes part in the extended
power density of 0.368 Wcm2 at 170  C operating tempera-
interaction resulting channelized network for proton trans-
ture. It is observed from Fig. 5(a) that only below a critical rGO
port. In this rGO-PBI hybrid material, strong coupling effects,
loading of the composite PBI membrane, fuel cell performance
exerted by the functional groups of rGO and the electron
enhances over that of pristine PBI membrane and the
withdrawing groups of PBI, have played a crucial role in the
maximum enhancement is attained by fuel cell with rGO-PBI-
enhancement of proton conductivities [39]. The strong cross-
1 membrane. Around 2 times enhancement of the maximum
linking and coupling phenomena is confirmed by the peak
power density is achieved from pristine PBI to rGO-PBI-1. The
shifting of PBI in the XRD. The mechanism of proton transport
temperature dependant fuel cell performance of rGO-PBI-1
is shown in Fig. 1(c). rGO-PBI-1 shows the best conductivity
membrane is shown in Fig. 5(b). It is observed from the
value among all the rGO composite membranes. It is clear
figure that with increase in the temperature, the fuel cell
from the Fig. 4(b) that with more inorganic fillers, conductivity
performance enhances and it shows the best result at 170  C,
decreases. It is clearly understandable from the results that
beyond which it decays. At 170  C the maximum power den-
with rGO nano fillers incorporation, all the properties en-
sity of 0.743 Wcm2 is achieved for rGO-PBI-1. The fuel cell
hances and for a lower loading (here 1%) of the rGO nano
performance has good correlation with the proton conduc-
fillers, it gives the best result. This is because incorporation of
tivity of the membranes and follows the same trend. All
rGO into the PBI matrices increases the active adsorption site
membranes show almost similar open circuit potential. The
with eNH of PBI as well as the rGO nanosheet. With increase
rGO-PBI-1 shows better performance for the entire range of
in the rGO loading, extent of coagulation increases leading to
resistive losses viz. activation, ohmic and mass transport
aggregation of the particles; these causes drastic decrease in
losses. The interface between electrolyte and electro catalyst
the active rGO site in the membranes. From the proposed
plays an important role in determining the activation polari-
structure and the mechanistic pathways, this can also be well
zation loss. More the interfacial contact of the electro-catalyst
understood. Agglomeration hinders acid retention by blocking
and the electrolyte, lesser is the activation loss. Electrolyte
active sites resulting decrease in the performance of acid
here in this case is determined by the active sites of the
retention for higher loading. Uniform distribution of rGO
membranes which in turn is highest for rGO-PBI-1 membrane.
throughout the polymeric matrix allows greater cross-linking
In case of rGO-PBI-1, rGO are well dispersed throughout the

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
 international journal of hydrogen energy xxx (xxxx) xxx 11

Fig. 5 e (a) Comparison between the fuel cell performance of pristine PBI and rGO-PBI composite membranes at cell
temperature (TCell) ¼ 170  C, humidifier temperature (TH) ¼ 70  C, H2 flow rate ¼ 2 LPM, O2 flow rate ¼ 1 LPM (b) Temperature
dependent fuel cell performance of rGO-PBI-1 membrane at TH ¼ 70  C, H2 flow rate ¼ 2 LPM, O2 flow rate ¼ 1 LPM, Insitu
impedance Nyquist plots for (c) Pristine PBI and rGO-PBI composite membranes at TCell ¼ 170  C and TH ¼ 70  C (d) rGO-PBI-1
at different cell temperatures and TH ¼ 70  C both by passing hydrogen (flow rate 2 LPM) and oxygen (flow rate 1 LPM) at
anode and cathode respectively with an overpotential of 50 mV (e) Randles circuit at low temperature (f) Randles circuit at
high temperature.

membrane leading to more uniform and homogeneous dis-
tribution of the nanoparticles. These homogeneous distribu-
tion leads to better adsorption of the electrolyte leading to
good electrolyte electro-catalyst contact and thus lesser acti-
vation loss. The increased mass transport for rGO-PBI-1 can be
explained by the increased hopping sites for proton transport
which in turn also reflects in the highest current density. The
drop in performance in the case of rGO-PBI-6 and especially
for rGO-PBI-9 is due to the three dimensional constraints
caused by the higher rGO content that would restrict the
swelling of PBI matrix during phosphoric acid uptake and also
due to the agglomeration.
The enhanced performance of the fuel cell with rGO-PBI
membrane is further explained by the insitu impedance
measurements of the pristine and composite membranes.
The Fig. 5(c) shows the fitted and experimental Nyquist plots
of the pristine PBI and the rGO composited PBI membranes at
170  C temperature and 50 mV over potential. The plots
consist of two semicircles. One arises in the high frequency
region at low temperature and with increasing temperature
another arises in the low frequency range. The hydrogen
oxidation reaction (HOR) corresponds to the high frequency
region semicircle and the oxygen reduction reaction (ORR)
relates to the low frequency region semicircle. Both the
semicircle merges smoothly due to the less significant facile
kinetics of the HOR. The ORR kinetics is very slow. Increase in
temperature improves ORR kinetics and it is reflected from
decrease in charge transfer resistance [24]. The corresponding
Randles circuit are shown in Fig. 5(e) and (f) where R1, RC.T, CPE
represents ohmic resistance, charge transfer resistance, and
constant phase element, respectively. The R2 and CPE2
attributed to the additional contribution of the semicircle
arised at high temperature.
It is observed from the Fig. 5(c) and (d) that for rGO-PBI-1,
the charge transfer resistance of the ORR at 170  C at 50 mV
overpotential decreases compared to the pristine one. Lower
charge transfer resistance in turn generates higher conduc-
tivity. Thus in terms of impedance measurements it can also
be said that rGO loading improves the membranes conduc-
tivity as well as performance of the fuel cell. With higher

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
12 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 6 e (a) Fuel cell property mapping at 170  C (b) Stability plot with respect to time for rGO-PBI and pristine PBI at TCell ¼
170  C, TH ¼ 70  C under a fixed load 0.3 Acm¡2.

Fig. 7 e Transient step response of (a) increasing cell temperature in pristine PBI (b) decreasing cell temperature in pristine
PBI (c) increasing cell temperature in rGO-PBI-1 (d) decreasing cell temperature in rGO-PBI-1 (e) step input of increasing
temperature (f) step input of decreasing temperature.

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
 international journal of hydrogen energy xxx (xxxx) xxx 13

Table 2 e Step response analysis data of fuel cell with Pristine PBI and rGO-PBI-1 membrane.
Membrane used Step in Tcell t (time constant of the step Kp (steady-state gain in voltage
response of a fuel cell) (Second) for step change in Tcell)
PBI (increasing step) 90e110 2244 0.00150
110e130 1860 0.00124
130e150 1401 0.00104
150e170 982 0.00090
PBI (decreasing step) 170e150 1207 0.00119
150e130 1249 0.00171
130e110 1351 0.00174
110e90 1665 0.00188
rGO-PBI (increasing step) 90e110 1074 0.00166
110e130 786.7 0.00102
130e150 511 0.00070
150e170 443 0.00059
rGO-PBI (decreasing step) 170e150 632.2 0.00113
150e130 689.2 0.00182
130e110 899 0.00234
110e90 1394 0.00308

loading (more than 1%), the charge transfer resistance in-
creases leading to lower performance. Increased rigidity and
agglomeration affects binding of the electrodes to the mem-
brane; thus the poor electrolyte-electrode interface affects the
MEA resulting increased charge transfer resistance, decreased
conductivity and poor fuel cell performance. The temperature
effect on the insitu impedance measurements of the rGO-PBI-
1 membrane is studied and the fitted and experimental results
at 50 mV over-potential with different temperatures are
shown in Fig. 5(d). The effect is observed from varying tem-
perature 50  Ce180  C. With increase in temperature, the
charge transfer resistance decreases indicating good perfor-
mance. The corresponding charge transfer resistance of the
membranes are measured from the Nyquist plot fitting and
plotted in Fig. 6(a). The threshold load current and the peak
power density of the membranes are also plotted in Fig. 6(a). It
is observed that 1% rGO-PBI membrane gives the best result in
all aspects. Up to 9% rGO was loaded with PBI to check the
extreme agglomeration rate. Beyond 9%, further loading is not
feasible as severe agglomeration hinders the easy and smooth
film formation. The best result obtained at 170  C and then it
starts to decay. At 180  C, the membranes start to melt.
The durability of the membrane electrode assembly was
checked both for PBI and rGO-PBI-1 membrane. As mentioned
in literature [45] the decline in performance responsible for
short lifetime of HT-PEMFC with PBI may be due to oxidative
degradation of the polymer, catalyst agglomeration, corrosion
of the carbon support and loss of ionic conductivity due to
H3PO4 condensation at high temperatures. In order to check
the decay in performance at 170  C operating temperature,
constant load current of 0.3 Acm2 was applied and the vari-
ations of voltage over 48 h were noted. Fig. 6(b) compares the
durability of pristine PBI and rGO-PBI-1. Over 48 h continuous
operation, 31.8% decay in the voltage was observed in case of
PBI membrane whereas only 10.2% (~1687 mV/h) decay was
observed in case of rGO-PBI-1. Incorporation of rGO consid-
erably reduces the percent decay of voltage per hour
compared to that for pristine PBI. Fuel cell with rGO-PBI dis-
plays 0.2125% decay/h compared to 0.66% decay/h with pris-
tine PBI. This is in accordance with the earlier reports by
Lobato et al. [45] that the absence of fillers or modifications in
the membrane in the MEA tested, leads to a non-delayed
degradation of the system. Also, the value of percent decay/
h (of voltage) of HT-PEMFC using PBI-based membranes in this
study is of the same order of magnitudes and close to that of
percent decay/h of current density for fuel cell reported by
Lobato et al. [45]. However, PBI membranes composited with
TiO2, (non carbonaceous material) reported in literature
[19,20] displayed much better durability [0.0086%, 0.068%
decay/h].
Analysis of transient response of fuel cell: faster response of
PEMFC with rGO-PBI-1 composite membrane
Fig. 7(a,b,c,d) illustrates the step response of a PEMFC with
pristine PBI membrane and with rGO-PBI-1 composite

Table 3 e Comparison of the performance of rGO-PBI-1 with the other composite PBI with active carbon materials reported
in literatures.
Sl. No. Matrices Solvent Proton Operating Maximum Voltage Mechanical Ref
Conductivity temperature Peak Power Efficiency Property (MPa)
(S cm-1) Density (W cm-2) (%) (OCP)
1 PBI/MWCNTeNafion(N-0.2) DMAc 0.05 (160  C) 150 0.7 83.3 ~95 22
2 Phosphonated MWCNT-PBI DMAc e 140 0.780 ~66.6 100 23
3 PhosphonatedCNT-PBI DMAc >0.105 140 0.780 ~72.5 80 24
4 SGO - PBI DMAc 0.052 175 0.600 ~78.3 e 27
5 rGO-PBI-1 MSA 0.126 170 0.743 79.7 78.55 This work

Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
14 international journal of hydrogen energy xxx (xxxx) xxx
membrane, in terms of deviational voltage versus time when
multiple step inputs of operating temperature (Fig. 7e and f)
are applied. Both the increasing trend (Fig. 7(e)) and decreasing
(Fig. 7(f)) step inputs of operating temperature are introduced.
Considering 1st order system the time constant t and steady
state gain Kp values are evaluated and tabulated in Table 2.
Increase in time constant with the decreasing operating
temperature implies the sluggish response of fuel cell at lower
temperature. This may be inferred from the Kp values that
over the whole range of operating temperature, the transient
response of fuel cell with rGO-PBI-1 is almost two times faster
than that with pristine PBI membrane. The results are of sig-
nificance in context to real life operation and control of a
PEMFC.
Table 3 summarizes and compares the property and per-
formance of rGO-PBI-1 (the present work), with reported data
on composite PBI with various active carbon materials
[22e24,27]. Literatures particularly on proton exchange
membrane fuel cell performance of active carbon material
composited PBI are very few. Suryani et al. [22] have prepared
Nafion- and polybenzimidazole (PBI)-functionalized multi-
walled carbon nanotubes (MWCNTeNafion and MWCNTePBI)
through an ozone mediated process and used as additives to
fabricate PBI/MWCNT nanocomposite membranes. The filler
MWCNT itself was treated with PBI through ozone mediated
process and then again composited with PBI implying very
complicated and costly way of synthesis. The nanocomposite
membranes containing 0.2 wt% of MWCNTeNafion (N-0.2)
and MWCNTePBI (P-0.2) have proton conductivities of 0.05
and 0.08 S cm1 at 160  C respectively and the maximum
power densities of 700 and 600 mW cm1, at 150  C respec-
tively. R. Kannan et al. have synthesized both phosphonated
multiwall carbon nanotube-polybenzimidazole [23] and
phosphonated carbon nanotube-polybenzimidazole [24]
nanocomposite membranes for the enhancement of fuel cell
performance and achieved 0.780 Wcm2 power densities at
140  C in both case. Sulfonated graphene oxide composited PBI
membranes was fabricated by C. Xu et al. and 0.052 S cm1
proton conductivity and 0.600 Wcm2 power density was
achieved at 175  C [27].
In summary, in the present study, effect of rGO loading in
rGO-PBI composite membrane on its property, steady and
transient performance while used in PEMFC are studied and
mapped. For the first time effect of inorganic loading on
membrane on the transient response of fuel cell is studied.
Conclusions
rGO-PBI composite electrolytes membranes are synthesized
for different rGO loading using MSA as the solvent that re-
solves the long-standing problem of poor solubility of PBI;
characterized and tested for fuel cell power generation.
Property-performance mapping reveals that the optimum
rGO loading is 1% because at this low loading planar rGO with
high specific surface area, crosslinked and sandwiched be-
tween PBI chains, enhances water and acid uptake, provides
extended pathways for proton conduction, enhances charge
transfer, improves the value of proton conductivity up to
0.126 S cm1and produces greater power (0.743 W/cm2), it
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
offers durable operation; faster transient response, higher
mechanical strain and chemical stability. More than 4%
loading is not recommended because of aggregation and
lower dispersion; all properties are degraded below that of
pristine PBI. The results are of significance for steady and
transient operation and commercialization of PBI based HT-
PEMFC.
Acknowledgement
One of the authors P. Ghosh, acknowledges Department of
Science and Technology, Ministry of Science and Technology,
India, (DST WOSA, File No. SR/WOS-A/ET-40/2016), for her
research fellowship. The financial assistance from the Uni-
versity Grants Commission (UGC), India, (File No. 41-369/
2012(SR)) is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2020.04.124.
references
[1] Steele BCH, Heinzel A. Materials for fuel-cell technologies.
Nature 2001;414:345.
[2] Bose S, Kuila T, Nguyen TXH, Kim NH, Lau K-t, Lee JH.
Polymer membranes for high temperature proton exchange
membrane fuel cell: recent advances and challenges. Prog
Polym Sci 2011;36:813e43.
[3] Devanathan R. Recent developments in proton exchange
membranes for fuel cells. Energy Environ Sci
2008;1:101e19.
[4] Sahu AK, Pitchumani S, Sridhar P, Shukla AK. Nafion and
modified-Nafion membranes for polymer electrolyte fuel
cells: an overview. Bull Mater Sci 2009;32:285e94.
[5] Ghosh P, Dhole CK, Ganguly S, Banerjee D, Kargupta K.
Phosphosilicate gel-sulfonated poly(ether ether ketone)
nanocomposite membrane for polymer electrolyte
membrane fuel cell. Mater Today: Proc 2018;5:2186e92.
[6] Lee CH, Min KA, Park HB, Hong YT, Jung BO, Lee YM.
Sulfonated poly(arylene ether sulfone)esilica
nanocomposite membrane for direct methanol fuel cell
(DMFC). J Membr Sci 2007;303:258e66.
[7] Ko T, Kim K, Jung B-K, Cha S-H, Kim S-K, Lee J-C. Cross-
linked sulfonated poly(arylene ether sulfone) membranes
formed by in situ casting and click reaction for applications
in fuel cells. Macromolecules 2015;48:1104e14.
[8] He L, Fujimoto CH, Cornelius CJ, Perahia D. From solutions to
membranes: structure studies of sulfonated polyphenylene
ionomers. Macromolecules 2009;42:7084e90.
[9] Wang Y, Goh SH, Chung T-S. Miscibility study of Torlon®
polyamide-imide with Matrimid® 5218 polyimide and
polybenzimidazole. Polymer 2007;48:2901e9.
[10] Quartarone E, Mustarelli P. Polymer fuel cells based on
polybenzimidazole/H3PO4. Energy Environ Sci
2012;5:6436e44.
[11] Quartarone E, Angioni S. Polymer and composite membranes
for proton-conducting, high-temperature fuel cells: a critical
review. Materials 2017;10:687.
 international journal of hydrogen energy xxx (xxxx) xxx
[12] Chung T-S. A critical review of polybenzimidazoles. J
Macromol Sci, Chem 1997;37:277e301.
[13] Peinemann KV, Nunes SP. Membranes for energy conversion.
2008.
[14] Sannigrahi A, Arunbabu D, Sankar RM, Jana T. Aggregation
behavior of polybenzimidazole in aprotic polar solvent.
Macromolecules 2007;40:2844e51.
[15] Kim E-K, Lee SY, Nam SY, Yoo SJ, Kim JY, Jang JH, et al.
Synthesis of high molecular weight polybenzimidazole using
a highly pure monomer under mild conditions. Polym Int
2017;66:1812e8.
[16] Lobato J, Can ~ izares P, Rodrigo MA, Linares JJ, Manjavacas G.
Synthesis and characterisation of poly[2,2-(m-phenylene)-
5,5-bibenzimidazole] as polymer electrolyte membrane for
high temperature PEMFCs. J Membr Sci 2006;280:351e62.
[17] Pu H, Liu L, Chang Z, Yuan J. Organic/inorganic composite
membranes based on polybenzimidazole and nano-SiO2.
Electrochim Acta 2009;54:7536e41.
[18] Ghosh S, Maity S, Jana T. Polybenzimidazole/silica
nanocomposites: organic-inorganic hybrid membranes for
PEM fuel cell. J Mater Chem 2011;21:14897e906.
[19] Lobato J, Can ~ izares P, Rodrigo MA, Úbeda D, Pinar FJ.
Enhancement of the fuel cell performance of a high
temperature proton exchange membrane fuel cell running
with titanium composite polybenzimidazole-based
membranes. J Power Sources 2011;196:8265e71.
[20] Pinar FJ, Canizares P, Rodrigo MA, Ubeda D, Lobato J.
Titanium composite PBI-based membranes for high
temperature polymer electrolyte membrane fuel cells. Effect
on titanium dioxide amount. RSC Adv 2012;2:1547e56.
[21] Zhang Y, Wang Y, Yu J, Chen L, Zhu J, Hu Z.
Polybenzimidazole assisted fabrication of multiwalled
carbon nanotube buckypapers and their silver nanoparticle
hybrids. RSC Adv 2014;4:35904e13.
[22] Suryani Chang C-M, Liu Y-L, Lee YM. Polybenzimidazole
membranes modified with polyelectrolyte-functionalized
multiwalled carbon nanotubes for proton exchange
membrane fuel cells. J Mater Chem 2011;21:7480e6.
[23] Kannan R, Aher PP, Palaniselvam T, Kurungot S, Kharul UK,
Pillai VK. Artificially designed membranes using
phosphonated multiwall carbon
NanotubePolybenzimidazole composites for polymer
electrolyte fuel cells. J Phys Chem Lett 2010;1:2109e13.
[24] Kannan R, Kagalwala HN, Chaudhari HD, Kharul UK,
Kurungot S, Pillai VK. Improved performance of
phosphonated carbon nanotube-polybenzimidazole
composite membranes in proton exchange membrane fuel
cells. J Mater Chem 2011;21:7223e31.
[25] Wang Y, Shi Z, Fang J, Xu H, Ma X, Yin J. Direct exfoliation of
graphene in methanesulfonic acid and facile synthesis of
graphene/polybenzimidazole nanocomposites. J Mater Chem
2011;21:505e12.
[26] Wang Y, Chen L, Yu J, Zhu J, Shi Z, Hu Z. Strong and
conductive polybenzimidazole composites with high
graphene contents. RSC Adv 2013;3:12255e66.
[27] Xu C, Cao Y, Kumar R, Wu X, Wang X, Scott K. A
polybenzimidazole/sulfonated graphite oxide composite
membrane for high temperature polymer electrolyte
membrane fuel cells. J Mater Chem 2011;21:11359e64.
[28] Eguiza  bal A, Lemus J, Pina MP. On the incorporation of protic
ionic liquids imbibed in large pore zeolites to
polybenzimidazole membranes for high temperature proton
exchange membrane fuel cells. J Power Sources
2013;222:483e92.
[29] Ri G-C, Kim J-S, Yu C-J. Role of water molecules in enhancing
the proton conductivity on reduced graphene oxide under
high humidity. Phys Rev Appl 2018;10.
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
15
[30] Fei F, Cseri L, Szekely G, Blanford CF. Robust covalently
cross-linked polybenzimidazole/graphene oxide membranes
for high-flux organic solvent nanofiltration. ACS Appl Mater
Interfaces 2018;10:16140e7.
[31] Hu S, Lozada-Hidalgo M, Wang FC, Mishchenko A, Schedin F,
Nair RR, et al. Proton transport through one-atom-thick
crystals. Nature 2014;516:227e30.
[32] Walker MI, Braeuninger-Weimer P, Weatherup RS,
Hofmann S, Keyser UF. Measuring the proton selectivity of
graphene membranes. Appl Phys Lett 2015;107:213104.
[33] Goh K, Karahan HE, Wei L, Bae T-H, Fane AG, Wang R, et al.
Carbon nanomaterials for advancing separation membranes:
a strategic perspective. Carbon 2016;109:694e710.
[34] Nair RR, Wu HA, Jayaram PN, Grigorieva IV, Geim AK.
Unimpeded permeation of water through helium-
leaketight graphene-based membranes. Science
2012;335:442e4.
[35] Tsetseris L, Pantelides ST. Graphene: an impermeable or
selectively permeable membrane for atomic species? Carbon
2014;67:58e63.
[36] Berry V. Impermeability of graphene and its applications.
Carbon 2013;62:1e10.
[37] Cordeiro G. Defect engineering in reduced graphene oxide
toward advanced energy conversion. Graphene Oxide - Appl
Opportun 2018:93e106.
[38] Kroes JMH, Fasolino A, Katsnelson MI. Density functional
based simulations of proton permeation of graphene and
hexagonal boron nitride. Phys Chem Chem Phys
2017;19:5813e7.
[39] Aragaw BA, Su W-N, Rick J, Hwang B-J. Highly efficient
synthesis of reduced graphene oxideeNafion
nanocomposites with strong coupling for enhanced proton
and electron conduction. RSC Adv 2013;3:23212e21.
[40] Bukola S, Beard K, Korzeniewski C, Harris JM, Creager SE.
Single-layer graphene sandwiched between proton-
exchange membranes for selective proton transmission. ACS
Appl Nano Mater 2019;2:964e74.
[41] Zeng L, Zhao TS, An L, Zhao G, Yan XH. A high-performance
sandwiched-porous polybenzimidazole membrane with
enhanced alkaline retention for anion exchange membrane
fuel cells. Energy Environ Sci 2015;8:2768e74.
[42] Fujigaya T, Hirata S, Berber MR, Nakashima N. Improved
durability of electrocatalyst based on coating of carbon black
with polybenzimidazole and their application in polymer
electrolyte fuel cells. ACS Appl Mater Interfaces
2016;8:14494e502.
[43] Wang C, Lin B, Qiao G, Wang L, Zhu L, Chu F, et al.
Polybenzimidazole/ionic liquid functionalized graphene
oxide nanocomposite membrane for alkaline anion
exchange membrane fuel cells. Mater Lett 2016;173:219e22.
[44] Li C, Liu Y, Yu K, Ferreira PJ, Xie J. Highly stable
polybenzimidazole (PBI) grafted graphene as a catalyst
support for polymer electrolyte membrane fuel cells. ECS
Trans 2019;92:553e8.
[45] Úbeda D, Can ~ izares P, Rodrigo MA, Pinar FJ, Lobato J.
Durability study of HTPEMFC through current distribution
measurements and the application of a model. Int J
Hydrogen Energy 2014;39:21678e87.
[46] Cho J, Ha T, Park J, Kim H-S, Min K, Lee E, et al. Analysis of
transient response of a unit proton-exchange membrane fuel
cell with a degraded gas diffusion layer. Int J Hydrogen
Energy 2011;36:6090e8.
[47] Serincan F, Yesilyurt S. Transient analysis of proton
electrolyte membrane fuel cells (PEMFC) at start-up and
failure. Fuel Cell 2007;7:118e27.
[48] Hu M, Gu A, Wang M, Zhu X, Yu L. Three dimensional, two
phase flow mathematical model for PEM fuel cell: Part I.
16 international journal of hydrogen energy xxx (xxxx) xxx
model development. Energy Convers Manag
2004;45:1861e82.
[49] Edwards RL, Demuren A. Regression analysis of PEM fuel cell
transient response. Int J Energy Environ Eng 2016;7:329e41.
[50] Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z,
Slesarev A, et al. Improved synthesis of graphene oxide. ACS
Nano 2010;4:4806e14.
[51] Ghosh P, Dhole CK, Ganguly S, Banerjee D, Kargupta K.
Portable smart highly proton conductive all inorganic gel
paste electrolyte with optimum phosphorous to silicon ratio
for enhanced durable operation of a fuel cell. Sustainable
Energy Fuels 2018;2:1737e48.
[52] Ngamsantivongsa P, Lin H-L, Yu TL. Crosslinked ethyl
phosphoric acid grafted polybenzimidazole and
polybenzimidazole blend membranes for high-temperature
proton exchange membrane fuel cells. J Polym Res
2016;23:22.
[53] Mishra SK, Tripathi SN, Choudhary V, Gupta BD. SPR based
fibre optic ammonia gas sensor utilizing nanocomposite film
of PMMA/reduced graphene oxide prepared by in situ
polymerization. Sens Actuators, B 2014;199:190e200.
[54] Stobinski L, Lesiak B, Malolepszy A, Mazurkiewicz M,
Mierzwa B, Zemek J, et al. Graphene oxide and reduced
graphene oxide studied by the XRD, TEM and electron
spectroscopy methods. J Electron Spectrosc Relat Phenom
2014;195:145e54.
[55] Muthoosamy K, Bai RG, Abubakar IB, Sudheer SM, Lim HN,
Loh HS, et al. Exceedingly biocompatible and thin-layered
reduced graphene oxide nanosheets using an eco-friendly
mushroom extract strategy. Int J Nanomed 2015;10:1505e19.
[56] Lu J, Li Y, Li S, Jiang SP. Self-assembled platinum
nanoparticles on sulfonic acid-grafted graphene as effective
electrocatalysts for methanol oxidation in direct methanol
fuel cells. Sci Rep 2016;6:21530.
[57] Das AK, Srivastav M, Layek RK, Uddin ME, Jung D, Kim NH,
et al. Iodide-mediated room temperature reduction of
graphene oxide: a rapid chemical route for the synthesis of a
bifunctional electrocatalyst. J Mater Chem 2014;2:1332e40.
[58] Hu N, Yang Z, Wang Y, Zhang L, Wang Y, Huang X, et al.
Ultrafast and sensitive room temperature NH3 gas sensors
based on chemically reduced graphene oxide.
Nanotechnology 2013;25:025502.
[59] Gong Y, Li D, Fu Q, Pan C. Influence of graphene
microstructures on electrochemical performance for
supercapacitors. Prog Nat Sci: Met Mater Int 2015;25:379e85.
[60] Ghosh P, Halder D, Ganguly S, Banerjee D, Kargupta K.
Phosphosilicate gel-polybenzimidazole nanocomposite
Please cite this article as: Ghosh P et al., Enhanced power generation, faster transient response and longer durability of HT-PEMFC using
composite polybenzimidazole electrolyte membrane with optimum rGO loading, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2020.04.124
novel membrane for fuel cell application. Int J Plast Technol
2014;18:403e8.
[61] Jiang F, Pu H, Meyer W, Guan Y, Wan D. A new anhydrous
proton conductor based on polybenzimidazole and tridecyl
phosphate. Electrochim Acta 2008;53:4495e9.
[62] Ozbas B, O’Neill CD, Register RA, Aksay IA, Prud’homme RK,
Adamson DH. Multifunctional elastomer nanocomposites
with functionalized graphene single sheets. J Polym Sci, Part
B: Polym Phys 2012;50:910e6.
[63] Khan U, May P, O’Neill A, Coleman JN. Development of stiff,
strong, yet tough composites by the addition of solvent
exfoliated graphene to polyurethane. Carbon
2010;48:4035e41.
[64] Khan U, May P, O’Neill A, Vilatela JJ, Windle AH, Coleman JN.
Tuning the mechanical properties of composites from
elastomeric to rigid thermoplastic by controlled addition of
carbon nanotubes. Small 2011;7:1579e86.
[65] Tang Z, Lei Y, Guo B, Zhang L, Jia D. The use of rhodamine B-
decorated graphene as a reinforcement in polyvinyl alcohol
composites. Polymer 2012;53:673e80.
[66] Lobato J, Can ~ izares P, Rodrigo MA, Linares JJ. PBI-based
polymer electrolyte membranes fuel cells: temperature
effects on cell performance and catalyst stability.
Electrochim Acta 2007;52:3910e20.
[67] Handlos AE, Nixon AC. Vapor pressure of phosphoric acid at
high temperature and pressure. Ind Eng Chem
1956;48:1960e2.
[68] Munson RA. Self-dissociative equilibria in molten
phosphoric acid. J Phys Chem 1964;68:3374e7.
[69] Lobato J, Can ~ izares P, Rodrigo MA, Úbeda D, Pinar FJ.
Promising TiOSO4 composite polybenzimidazole-based
membranes for high temperature PEMFCs. ChemSusChem
2011;4:1489e97.
[70] Shen C-H, Jheng L-c, Hsu SL-c, Tse-Wei Wang J. Phosphoric
acid-doped cross-linked porous polybenzimidazole
membranes for proton exchange membrane fuel cells. J
Mater Chem 2011;21:15660e5.
[71] Asano N, Aoki M, Suzuki S, Miyatake K, Uchida H,
Watanabe M. Aliphatic/aromatic polyimide ionomers as a
proton conductive membrane for fuel cell applications. J Am
Chem Soc 2006;128:1762e9.
[72] Ma Y-L, Wainright JS, Litt MH, Savinell RF. Conductivity of
PBI membranes for high-temperature polymer electrolyte
fuel cells. J Electrochem Soc 2004;151:A8e16.
[73] Lobato J, Can ~ izares P, Rodrigo MA, Linares JJ, Aguilar JA.
Improved polybenzimidazole films for H3PO4-doped PBI-
based high temperature PEMFC. J Membr Sci 2007;306:47e55.