i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

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Sulfonic acid functionalized graphene oxide paper

sandwiched in sulfonated poly(ether ether ketone):
A proton exchange membrane with high
performance for semi-passive direct methanol fuel
cells

Chenxu Li a,b, Lingling Xiao b, Zhongqing Jiang b,*, Xiaoning Tian b,

Lijuan Luo b, Wangcai Liu b, Zhen-Liang Xu a, Hu Yang a,**,
Zhong-Jie Jiang c,***
a
State Key Laboratory of Chemical Engineering, Membrane Science and Engineering R&D Lab, Chemical Engineering
Research Center, East China University of Science and Technology, Shanghai 200237, China
b
School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, Zhejiang, China
c
New Energy Research Institute, College of Environment and Energy, South China University of Technology,
Guangzhou 510006, China

article info abstract

Article history: Sulfonated poly(ether ether ketone) (SPEEK) membranes have been deposited on the both
Received 10 March 2017 sides of a sulfonic acid functionalized graphene oxide (SGO) paper to form a proton ex-
Received in revised form change membrane (PEM) with a sandwiched structure. The obtained SPEEK/SGO/SPEEK
29 April 2017 membrane could exhibit proton conductivity close to Nafion® 112 and lower methanol
Accepted 17 May 2017 permeability. The use of this SPEEK/SGO/SPEEK membrane greatly improves the perfor-
Available online xxx mance of the semi-passive direct methanol fuel cell (DMFC). The semi-passive DMFC with
the SPEEK/SGO/SPEEK membrane is found to be capable of delivering the peak power
Keywords: density 60% higher than that with the commercial Nafion® 112. This, along with its com-
Sulfonic acid functionalized parable durability to Nafion® 112, strongly suggests the great promise of using the SPEEK/
graphene oxide SGO/SPEEK membrane as the PEM.
Proton exchange membrane © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Semi-passive direct methanol fuel
cell
Sandwiched membrane

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: zhongqingjiang@hotmail.com (Z. Jiang), hyang@ecust.edu.cn (H. Yang), eszjiang@scut.edu.cn (Z.-J. Jiang).
http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
Introduction
Fuel cells have drawn tremendous interest due to increased
energy demand [1e3]. Direct methanol fuel cell (DMFCs), as an
important subcategory of fuel cells, have in particular received
a great deal of attention due to their advantages of low
pollutant emission, high efficiency, high power density, easy
re-fueling, wide operating temperature (25e120
C), and
compact cell design, etc. [4,5]. DMFCs use the regenerable
methanol as the fuel. Methanol crossover has been recognized
as one of main obstacles hampering the widespread applica-
tion of the DMFCs in the real-world devices, since the meth-
anol permeated from the anode to the cathode could greatly
deteriorate the activity of the cathodic catalyst, which inevi-
tably reduces the performance of the DMFCs [6e8]. Great ef-
forts have therefore been devoted to developing proton
exchange membranes (PEMs) that could minimize the meth-
anol crossover [9,10].
The traditional DMFCs use perfluorosulfonic ionomers,
such as Nafion, as the PEMs due to their high conductivity and
excellent chemical stability [11,12]. These perfluorosulfonic
Nafion membranes, however, suffer from the inherent draw-
backs of extensive swelling, high cost, and sever methanol
permeability, which have limited the practical applications of
DMFCs [13,14]. Recent progress has demonstrated the poten-
tial use of sulfonated poly(ether ether ketone) (SPEEK) as al-
ternatives to the traditional Nafion-based membranes, since it
possesses a structure comprising ionizable sulfonic acid
groups connecting to a hydrophobic backbone, similar to that
of Nafion [15e19]. As reported previously [20], SPEEK could be
highly sulfonated, which makes it possible to fabricate PEMs
with high proton exchange capacity. The high degree of sul-
fonation, however, renders the SPEEK membrane highly
swollable and even soluble in the methanol solution, which
strongly hinders its direct uses as the PEMs [20]. For the
practical uses, therefore, the modifications used to increase
the dimensional stability of the SPEEKs in the aqueous
methanol solution have been required to improve their us-
ability as the PEM for the DMFCs [17,19,21e23]. Blending with
inorganic or organic fillers [3,24e26], such as zirconia [27],
clays [26], zeolites [28], and heteropolyacids [24], Nafion [15],
polyvinylalcohol (PVA) [29], and sulfonated fullerene [9], to
form composite membranes is a frequently used strategy to
improve the usability of the SPEEK membranes. As demon-
strated previously, the blended SPEEK membranes could
exhibit reduced methanol crossover, improved dimensional
and chemical stability, and enhanced mechanical strength
[17,30,31]. However, these blended membranes usually show
reduced proton conductivity, greatly tampering their practical
uses in fuel cells [6,15].
Compared with inorganic and other organic fillers, gra-
phene oxide (GO) is a most commonly used fillers for the
SPEEK membranes [7,32e36]. GO is the oxidized derivative of
graphene, possessing a highly flexible layered structure. The
specific amphiphilic structure consisting of the graphitic
plane with oxygenous groups, such as hydroxyl, carboxyl, and
epoxide groups, makes GO highly compatible with the SPEEK
matrix. The strong interfacial interaction between the mem-
brane matrix and the graphitic plane of the GO could
Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
strengthen the mechanical stability of the SPEEK membranes.
The large aspect ratio of the graphitic plane could also sup-
press the methanol diffusion through the membrane,
reducing the methanol permeability of the membranes. A
significant amount of work has demonstrated the perfor-
mance improvement of the ionomer membranes when they
are blended with the GO or its derivatives [7,19,32e36]. As
reported by Kim et al. [12], sulfonated graphene oxide (SGO)/
SPEEK composite membranes possessed lower methanol
permeability and higher proton conductivity than the plain
SPEEK membrane. It was pointed out that the SGO incorpo-
ration not only improved proton conductivity and mechanical
properties of the membranes, but blocked the pass of meth-
anol and water molecules through the membrane. Corre-
spondingly, SGO incorporated SPEEK membrane exhibited
high electrochemical selectivity. This is well consistent with
our work [35,36], which shows that the composite membranes
consisting of SPEEK and SGO exhibited increased ion-
exchange capacity (IEC), water uptake, and proton conduc-
tivity, but reduced methanol permeability. The work by He
et al. [37] has also suggested that nanocomposite membranes
comprising sulfonated poly(ether ether ketone) (SPEEK) with
polydopamine-modified graphene oxide (DGO) incorporated
could exhibit much higher thermal and mechanical stabilities
and proton conductivity than the pristine SPEEK. These re-
sults have clearly suggested the great versatility of using the
GO or its derivatives to improve the performance of the SPEEK
membranes. In most of these membranes reported to date,
however, the GO or its derivatives are usually homogeneously
distributed in the SPEEK matrix. Indeed, the blended mem-
branes could be fabricated with more captivating structures,
in which the GO or its derivatives are not uniformly distrib-
uted. With such structures, the GO or its derivatives incorpo-
rated SPEEK membranes may exhibit more fascinating
properties through unique interactions between the GO/de-
rivatives and SPEEK.
In this work, we adopted a new strategy to improve the
performance of the SPEEK membrane as the PEM using the
sulfonated derivative of the GO, i.e. sulfonic acid functional-
ized graphene oxide (SGO) (the synthetic procedure of SGO is
briefly described in Scheme 1). Specifically, a SGO paper was
first prepared by the filtration of the SGO solution through the
membrane filter. The obtained SGO paper was then used as
the substrate for the deposition of the SPEEK membranes on
its both sides, which led to the formation of a SPEEK/SGO/
SPEEK membrane with a sandwiched structure. Due to the
specific structure of the SGO which consists of sulfonic acid
functionalized graphitic plane, the SPEEK/SGO/SPEEK mem-
brane exhibits superior performance as the PEMs and could
even deliver higher proton conductivity and lower methanol
permeability than the blend SPEEK/SGO membrane and
Nafion® 112. Additionally, the semi-passive DMFC with the
SPEEK/SGO/SPEEK membrane is found to deliver a peak power
density higher than that with the blend SPEEK/SGO mem-
brane (in which the SGO is uniformly distributed in the SPEEK
matrix) and the commercial Nafion® 112. This well demon-
strates the superiority of using a sandwiched structure to
obtain the blended membranes with high performance and
the great promise of using the SPEEK/SGO/SPEEK membrane
in fuel cells. Scheme 2 briefly illustrates the sandwiched
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 3

Scheme 1 e Procedure illustration of the SGO synthesis.

Scheme 2 e The sandwiched structure of the SPEEK/SGO/SPEEK membrane and the operation principle of semi-passive
direct methanol fuel cells.

structure of the SPEEK/SGO/SPEEK membrane and the opera- membrane. The dried membrane was immersed in a 3 M
tion principle of semi-passive direct methanol fuel cells. H2SO4 solution for 24 h at room temperature and thoroughly
washed by water to remove the residual sulfuric acid.

Experimental section Preparation of SGO and the sandwiched SPEEK/SGO/SPEEK

Material synthesis
Sulfonation of PEEK and preparation of the plain SPEEK
membrane
The preparation of the SPEEK was accomplished by the
vigorous stirring of the 5.0 g of the PEEK in 100 mL of
concentrated H2SO4 (95%) at 30
C for 7 h. The obtained SPEEK
was then precipitated in ice-cold water under agitation and
washed with water several times until the pH value of the
solution was close to 7. The resulting polymer was dried under
vacuum at 60
C for 24 h.
For the preparation of the SPEEK membrane, a homoge-
nous DMF solution of the SPEEK was prepared by dissolving 1 g
of the SPEEK into 20 mL of DMF under ultrasonication. The
obtained solution was then cast onto a glass plate and vacuum
dried, which led to the formation of the plain SPEEK
membrane
The synthesis of SGO was carried out with a procedure con-
sisting of the synthesis of the arenediazonium salt and its
subsequent reaction with the GO (synthesized by a modified
Hummer method as described in the Supporting information).
Typically, 1 g of sulfanilic acid (SA), 12 mL of the HCl solution
(the volume of ice water:concentrated HCl ¼ 5:1), and 0.4 g
NaNO2 were successively added into 20 mL of a NaOH solution
(2 wt.%) under mechanical agitation. The reaction was kept at
0
C for 15 min, which led to the formation of the arenedia-
zonium salt. The obtained arenediazonium salts was then
added into 200 mL of the GO suspension with a concentration
of 1 mg mL1. After 4 h of stirring in an ice bath, the product
was washed with water and centrifuged until the pH value of
the solution reached to ~7. After a freeze-drying process, the
sponge like SGO was obtained. Scheme 1 briefly illustrates the
procedure for the preparation of the SGO.

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
The sandwiched SPEEK/SGO/SPEEK membranes was pre-
pared by the deposition of the SPEEK membrane on the both
sides of the SGO paper. The preparation process of SPEEK/
SGO/SPEEK sandwiched membrane is briefly illustrated in
Scheme 3. The SGO paper was obtained by filtrating the 40 mL
of the pure aqueous solution of the SGO through the mem-
brane filter. The obtained SGO paper was then placed in the
center of the SPEEK membrane prepared by casting 10 mL of
the DMF solution of 0.25 g SPEEK on a glass plate. This led to
the formation of a SPEEK/SGO membrane with the SPEEK
deposited on one side of the SGO paper after 12 h of drying at
80
C under vacuum. For the formation of the sandwiched
SPEEK/SGO/SPEEK membrane, another DMF solution con-
taining of SPEEK was directly casted on the other side of the
SGO paper. The thickness of this membrane could be
controlled by the concentration and volume of the DMF so-
lution of SPEEK. The obtained sandwiched SPEEK/SGO/SPEEK
membrane was dried at 80
C for another 12 h under vacuum.
The preparation of the sandwiched SPEEK/GO/SPEEK
membrane was carried out by the same procedure used for the
preparation of the sandwiched SPEEK/SGO/SPEEK membrane,
in which the GO paper, instead of the SGO paper, was used for
the deposition of the SPEEK membrane.
Materials characterization
SEM characterization was carried out on a Hitachi S-4500
microscope to investigate the morphology of the membranes.
Before investigation, the membranes were frozen and broken
in liquid nitrogen after drying, then fixed on the sample holder
and gilded by an ion sputtering equipment (Eiko IB-3 ION
COATER). A JEM-2100F transmission electron microscope with
a 200 kV accelerating voltage was employed to collect the TEM
image of the samples. X-ray photoelectron spectra (XPS) of the
samples (XPS, Kratos AXIS Ultra DLD) were collected with an
X-ray photoelectron spectrometer using Al Ka as the excita-
tion source. X-ray diffraction (XRD) patterns of the samples
were recorded using Rigaku D/MAX-2000 with a Cu Ka radia-
tion (l ¼ 0.154056 nm). A Renishaw in Vita Raman spectrom-
eter was used for the collection of the Raman spectra of the
samples. An excitation wavelength of 514.5 nm was used.
Electrochemical measurements
Ion exchange capacity (IEC)
To obtain the IECs, the dried membranes were first soaked in a
saturated NaCl solution for 2 days, which led to the release of
the protons from the membranes through ion exchange. A
Scheme 3 e Brief illustration of the preparation of the sandwiched SPEEK/SGO/SPEEK membrane.
Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
NaOH solution was used for titration. The IECs (meq g1) of the
membranes could be obtained using Eq. (1).
CNaOH  VNaOH
IEC ¼ (1)
mdry
where CNaOH is the concentration of the NaOH solution (mol/
L), VNaOH (mL) is its volume used for the titration, and mdry (g)
represents the mass of the dried membrane.
Methanol permeability
The methanol permeability of the sandwich membrane was
tested by an open circuit potential technique with an Autolab
(IM6e, Zahner, Germany) using a three-electrode system, in
which the Pt foil, the KCl saturated Ag/AgCl, and the Pt/C gas
diffusion electrode were used as the counter electrode, the
reference electrode, and the working electrode, respectively.
The potential values shown in this work were against the
counter electrode. The membrane was placed between the
donor and receptor compartments of the testing cell. The
active area of the membrane exposed to the solution was
~2.06 cm2. A solution consisting of 10% methanol and 0.5 M
H2SO4 was loaded in the donor compartment and 0.5 M H2SO4
with a same volume was in the acceptor compartment. During
the testing, the solutions in these two compartments were
continuously stirred and the pure O2 was steadily flowing in
the vicinity of the working electrode continuously. The
permeation of methanol through the membrane occurred due
to the difference in the concentrations of methanol between
the two compartments. This would lead to a potential drop in
the work electrode. The concentration of methanol in the
acceptor compartment could be then determined by a cali-
bration curve established as described elsewhere [38e40].
For the case of methanol diffusion through a membrane of
a thickness L, the relation between the methanol concentra-
tion in the receptor compartment (CR,t) and the diffusion time
(t) could be displayed as Eq. (2):
 
VR L L2
CR;t ¼ P t  (2)
CD S 6D
where S is the active area of the membrane for permeation
(m2), VR the volume of the solution in the receptor compart-
ment (m3), CD the initial methanol concentration in the donor
compartment (mol/L), and D the diffusion coefficient, and P
the methanol permeability.
Electrochemical selectivity (b, S s/cm3) for the membranes
was measured by considering proton conductivity (s, S/cm)
and methanol permeability (P, cm2/s) into the following rela-
tion [9,25].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 5

s image in Fig. 1a shows that it possesses a sheet-like structure,

b¼
P resembling to the morphology of its parent GO (Fig. 1b). This
Proton conductivity
An AC impedance technique was employed to measure the
proton conductivity of the sandwiched membrane. The AC
impedance spectra were collected on an IM6e potentiostat/
galvanostat over the frequency range of 1 MHz to 100 mHz.
Prior to the measurements, the membrane was soaked in DI
water for 24 h and then rapidly placed between two PTFE
plates. The proton conductivity (s) of the membranes could be
extracted from the membrane resistance, Rm, using Eq. (4):
L
sHþ ¼
Rm A
where L and A are the thickness and cross-sectional area of
the membranes, respectively.
Fuel cell evaluation
PtRu/C (40 wt.% Pt and 20 wt.% Ru, Johnson Matthey) was
utilized as the anode catalyst. The Pt/C (40% Pt, Johnson
Matthey) was utilized as the cathode catalyst. The mass
loading of the catalysts on both the electrodes was controlled
to 2.5 mg cm2. The membrane electrode assembly (MEA) was
obtained through hot-pressing the catalyst loaded cathode
and the anode onto the respective sides of the membrane. The
obtained MEA was then assembled into a single semi-passive
DMFC with an active area of 5 cm2. A preheated methanol
solution was supplied into the anode with a rate of
1.0 mL min1. The temperature of the cell was controlled by
heating rods. Polarization curves were recorded with Fideris
(America) to evaluate the performance of the single fuel cell.
Each cell was tested for three times. For comparison, the
performance of the fuel cell with Nafion® 112 was also
investigated. In this work, the semi-passive referred to a
system in which a pump was used for the methanol supply for
the anode while the cathode was free of the oxygen-supplying
component.
Results and discussion
The SGO was fabricated through the sulfonation of the GO
synthesized using the modified Hummers method. The TEM
(3)
suggests that the sulfonation would not alter the morphology
of the GO. Fig. 2a displays the XPS survey spectrum of the SGO,
which shows the peaks corresponding to C, O, and S. This is
different from the XPS survey spectrum of the GO, where only
the peaks assignable to C and O, suggesting that the sulfur
containing groups has been introduced into the GO through
the sulfonation. The presence of sulfur in the SGO could be
further demonstrated by the deconvoluted spectrum of C 1s in
Fig. 2b, where the peak corresponding to CeS could be clearly
identified. The high-resolution S 2p spectrum in Fig. 2c shows
a single peak at 168.3 eV, indicating that sulfur is in the form of
(4) sulfonic acid [11,41]. These results clearly demonstrate the
functionalization of the GO with the sulfonic acid containing
groups through the sulfonation. Additionally, the deconvo-
luted C 1s spectrum of the SGO also shows the peaks corre-
sponding to CeOH, CeOeC, C]O, and OeC]O, suggesting the
presence of oxygenous groups [7,11,42], such as ]CeO, eOH,
eCOOH, and phenol groups, in the SGO, which is similar to
that of the GO. Table 1 shows that the atomic percentage of S
in the SGO is 1.66%, corresponding to 10.1 wt.% of the sulfonic
acid group in the SGO. The sulfonation increases the disorder
of carbon in the graphitic plane. As shown in Fig. 3, the SGO
exhibits a relatively higher value of ID/IG than the GO (ID and IG
are the intensities of the Raman signals arising from the
disordered carbon and the sp2 carbon domains in the graphitic
structure, respectively [19]).
Due to the presence of the sulfonic acid and oxygenous
groups in the graphitic plane, the SGO has a hydrophilic
property, making it readily dispersible in water to form a ho-
mogenous solution. The filtration of the SGO solution through
the membrane filter would lead to the formation of the SGO
paper through layer-by-layered stacking the graphitic plane of
the SGO. Fig. 1c displays a top-view SEM image of the SGO
paper fabricated from the filtration of the SGO solution, where
the rippled and crumpled structure of the graphitic plane on
its surface could be observed. The cross-section SEM image in
the inset of Fig. 1c clearly demonstrates the layered structure
of the SGO paper. Fig. 4 shows that the SGO paper exhibits a
diffraction peak at 2q ¼ 10.04
, which could be attributed to the
(002) reflection of the layer-by-layer stacked graphitic planes.
The interlayer spacing between the SGO nano-sheets calcu-
lated using the DebyeeScherrer is 0.88 nm, which is slightly
larger than the interlayer spacing between the GO nano-

Fig. 1 e TEM images of (a) SGO and (b) GO. Top-view SEM images of (c) SGO papers and (d) GO papers. The insets in (c) and (d)
show the cross sections of the SGO papers and GO papers, respectively.

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

Fig. 2 e XPS survey spectra of (a) GO and SGO; (b) deconvoluted C 1s spectra of GO and SGO; (c) S 2p spectra of GO and SGO.

sheets in the GO papers synthesized in the similar manner

(the diffraction peak corresponding to the (002) reflection of
Table 1 e Comparison of elemental composition of GO
and SGO and their relative atomic percentages. the graphitic planes in the GO paper is at 2q ¼ 10.57
as shown
in Fig. 4, which is comparable to the reported data [43]). This
Samples O 1s [at.%] C 1s [at.%] S 2p [at.%]
suggests that the sulfonation increases the interlayer spacing
GO 25.18 74.72 0
of the graphitic plane in the SGO paper due to the relative
SGO 24.61 73.74 1.66
larger sulfonic acid containing groups. In the SGO paper, the
interlayer spacing between the SGO nano-sheets would act as
the channels for the proton transport when used as the PEM.
The relatively larger interlay spacing is therefore favorable to
increase the proton conductivity of the SGO paper (corrobo-
rated below), since it increases the dimension of the channels
for the proton transport [34,44].
The deposition of the SPEEK membranes on the both sides
of the SGO paper would lead to the formation of the SPEEK/
SGO/SPEEK membrane with a sandwiched structure (the
detailed preparation process of the SPEEK/SGO/SPEEK mem-
brane is illustrated in Scheme 3). Fig. 5a shows the SEM images
of the upper and lower surfaces of the SPEEK/SGO/SPEEK
membrane, which indicates that the SPEEK/SGO/SPEEK
membrane has a relatively smooth and dense surface without
pinholes observed. This is similar to the surface of the plain
SPEEK membrane shown in Fig. S1(ESI), suggesting that the
deposition onto the SGO paper would not change the micro-
structure of the SPEEK membrane. The cross-section SEM
image in Fig. 5b clearly demonstrates that the SPEEK/SGO/
SPEEK membrane has a sandwiched structure, in which the
SGO paper with a thickness of 52.3 ± 2.6 mm clamped in the
middle of two SPEEK membranes could be clearly identified.
The thicknesses of the SPEEK membranes on the both sides of
the SGO paper are 45.0 ± 2.2 mm, which lead to the formation of
the SPEEK/SGO/SPEEK membrane with a symmetric structure.
The absence of the distinct interface between the SGO paper
and the SPEEK membranes suggests a good compatibility be-
tween SGO and SPEEK due to the good affinity of the sulfo-
nated SGO to SPEEK and the strong interaction between the
graphitic plane of SGO and SPEEK.
To demonstrate the potential use of the SPEEK/SGO/SPEEK
Fig. 3 e Raman spectra of GO and SGO. membrane as the PEM, its IEC and proton conductivity were

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 7

tested. Table 2 indicates that the SPEEK/SGO/SPEEK mem-

brane has a relatively higher IEC when compared with the
plain SPEEK membrane of a comparable thickness. Corre-
spondingly, the SPEEK/SGO/SPEEK membrane exhibits higher
proton conductivity than the plain SPEEK membrane at the
low and high temperatures. This indicates the insertion of the
SGO paper in the SPEEK membrane to form a sandwiched
structure would increase the usability of the SPEEK membrane
as the PEM. The presence of the sulfonated structure in the
SGO could be considered as the main reason leading to the
higher proton conductivity of the SPEEK/SGO/SPEEK mem-
brane. The sulfonated structure does not only provide more
sulfonic acid groups available for the proton transport, but
increases the interlayer spacing between the SGO nano-sheets
in the SGO paper, both of which could promote the improve-
ment of the proton conductivity. This is unlike the SPEEK/GO/
SPEEK membrane, in which the lack of sulfonic acid groups in
the GO paper decreases the IEC of the SPEEK/GO/SPEEK
membrane (Table 2), while the relatively lower interlayer
spacing between the GO nano-sheets in the GO paper retards
the transport of the proton through the membrane. Conse-
quently, although the SPEEK/GO/SPEEK membrane is pre-
pared with a structure similar to the SPEEK/SGO/SPEEK
membrane, it exhibits much lower proton conductivity than
that of the SPEEK/SGO/SPEEK membrane. Most interestingly,
the SPEEK/SGO/SPEEK membrane could even exhibit the pro-
ton conductivity close to Nafion® 112, which strongly suggests
that the SPEEK/SGO/SPEEK membrane could be used as the
PEM.
Fig. 4 e XRD patterns of GO and SGO papers. Fig. 6 displays the plots of CR,tVRL/(CDS) vs. t for the plain
SPEEK, the SPEEK/GO/SPEEK and the SPEEK/SGO/SPEEK

Fig. 5 e (a) Upper and lower surface SEM images of the sandwiched SPEEK/SGO/SPEEK membrane; (b) Cross-section SEM
image of the SPEEK/SGO/SPEEK membrane.

Table 2 e IEC, s, and P of the plain SPEEK, the SPEEK/GO/SPEEK, the SPEEK/SGO/SPEEK membranes, blend SPEEK/SGO
membrane, and Nafion® 112.
Membranes Thickness (mm) IEC (meq g1) s (mS cm1) Pa (106 cm2 s1) bb (104 S s cm3)
45
C 65
C 80
C
SPEEK 137.6 ± 1.4 1.96 ± 0.02 32.7 ± 0.3 64.1 ± 0.6 109.4 ± 1.1 5.57 ± 0.16 1.15
SPEEK/GO/SPEEK 156.5 ± 1.6 1.79 ± 0.02 38.6 ± 0.4 49.6 ± 0.5 78.4 ± 0.8 2.30 ± 0.12 2.16
SPEEK/SGO/SPEEK 142.2 ± 1.4 2.17 ± 0.02 76.1 ± 0.8 92.7 ± 0.9 140.5 ± 1.4 2.60 ± 0.13 3.57
Blend SPEEK/SGO membrane 141.7 ± 1.4 1.93 ± 0.02 60.2 ± 0.6 81.6 ± 0.8 128.9 ± 1.3 3.56 ± 0.18 2.29
Nafion® 112 53.2 ± 0.5 0.94 ± 0.01 88.1 ± 0.9 128.4 ± 1.3 138.6 ± 1.4 4.89 ± 0.15 2.63
a
The data for P was obtained at 25
C.
b
The data s obtained at 65
C was used for b calculation.

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

the plain SPEEK membrane, as shown in Table 2. Worth noting

Fig. 6 e Plots of CR,tVRL/(CDS) vs. t for the plain SPEEK, the
SPEEK/GO/SPEEK, the SPEEK/SGO/SPEEK membranes, and
blend SPEEK/SGO membrane and Nafion® 112. The dots are
the experimental data and the straight lines are their
fitting using Eq. (2).
membranes and Nafion® 112. The fitting of the experimental
data using Eq. (2) shows a lower slope for the SPEEK/SGO/
SPEEK membrane than that for Nafion® 112, indicating that
the SPEEK/SGO/SPEEK membrane has a lower methanol
permeability, as indicated in Table 2. This further demon-
strates that the SPEEK/SGO/SPEEK membrane could be used as
the PEM, since the lower methanol permeability could reduce
the methanol crossover through the PEM, which could effec-
tively protect the cathodic catalysts from poisoning by the
permeated methanol. We would attribute the presence of the
SGO paper consisting of the carbon layers with the graphitic
plane to the main reason resulting in the lower methanol
permeability of the SPEEK/SGO/SPEEK membrane, because the
high aspect ratio of the graphitic plane could largely hinder
the diffusion of methanol through the SPEEK/SGO/SPEEK
membrane. This could be demonstrated by the observation
that the SPEEK/GO/SPEEK and the SPEEK/SGO/SPEEK mem-
branes both exhibit much lower methanol permeability than
is that the methanol permeability of the SPEEK/SGO/SPEEK
membranes is slightly higher than that of the SPEEK/GO/
SPEEK membrane. This is well consistent with the fact that the
SGO paper in the SPEEK/SGO/SPEEK membranes has a higher
interlayer spacing between the graphitic plane, which would
enhance the diffusivity of methanol through the membrane.
Most interestingly, the SPEEK/SGO/SPEEK membrane could
even exhibit much lower methanol permeability, but higher
proton conductivity than that of the blend SPEEK/SGO mem-
brane with a comparable thickness (the detailed fabrication
procedure of the blend SPEEK/SGO membrane is given in the
Supporting information). This result strongly suggests the
superiority of using the SPEEK/SGO/SPEEK membrane with a
sandwiched structure as a PEM for fuel cells.
The results shown above clearly demonstrate that the
sandwiching of SGO enhances the proton conductivity, but
reduces the methanol permeability of the SPEEK/SGO/SPEEK
membrane. This suggests a higher electrochemical selectivity
of the SPEEK/SGO/SPEEK membrane. As shown in Table 2,
among all the membranes, the SPEEK/SGO/SPEEK membrane
shows the highest selectivity of 3.57  104 S s cm3, which are
~3 times and ~2 times higher than that of the plain SPEEK
membrane (1.15  104 S s cm3) and the SPEEK/GO/SPEEK
membrane (2.16  104 S s cm3), respectively. Additionally, the
selectivity of the SPEEK/SGO/SPEEK membrane is also higher
than that of Nafion® 112 and the blend SPEEK/SGO membrane.
The practical application of the SPEEK/SGO/SPEEK mem-
brane was evaluated by its use as the PEM in the semi-passive
DMFC. The polarization curves in Fig. 7a show that the cell
with the SPEEK/SGO/SPEEK membrane has a relatively higher
open circuit voltage (OCV) than Nafion® 112. This is well
consistent with the result in Table 2, which demonstrates a
lower methanol permeability of the SPEEK/SGO/SPEEK mem-
brane than that of Nafion® 112. The most interesting is that
the cell with the SPEEK/SGO/SPEEK membrane can deliver a
peak power density of ~42.5 mW cm2 when operated in 1.0 M
methanol at 65
C, whereas the peak power density of the cell
with Nafion® 112 is only ~26.5 mW cm2. This indicates 60% of
the increase in the peak power density when the SPEEK/SGO/
SPEEK membrane, instead of Nafion® 112, is used as the PEM

Fig. 7 e (a) Polarization curves of the semi-passive DMFCs using the SPEEK, SPEEK/GO/SPEEK, SPEEK/SGO/SPEEK
membranes, and blend SPEEK/SGO membrane and Nafion® 112 in 1.0 M methanol at 65
C. (b) Stability of the semi-passive
DMFCs with the SPEEK, the SPEEK/SGO/SPEEK membrane and Nafion® 112 in 1.0 M methanol at the current density of
40 mA cm¡2 (65
C).

Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
for the semi-passive DMFC. These results clearly corroborate
the superiority of the SPEEK/SGO/SPEEK membrane over
Nafion® 112. The high electrochemical performance of the cell
with the SPEEK/SGO/SPEEK membrane could be ascribed to
the comparable proton conductivity and lower methanol
permeability of the SPEEK/SGO/SPEEK membrane in compar-
ison with Nafion® 112. Additionally, Fig. 7a also shows that the
cell with the SPEEK/SGO/SPEEK membrane could exhibit
higher performance than those with the plain SPEEK, the
SPEEK/GO/SPEEK membranes, and the blend SPEEK/SGO
membrane. This is consistent with the observation that the
SPEEK/SGO/SPEEK membrane has much higher proton con-
ductivity than the plain SPEEK, the SPEEK/GO/SPEEK mem-
branes, and the blend SPEEK/SGO membrane.
The semi-passive DMFC with the SPEEK/SGO/SPEEK
membrane was then subjected to the stability measurement
and compared with Nafion® 112. Fig. 7b shows that under the
constant current density of 40 mA cm2 the semi-passive
DMFCs with the SPEEK/SGO/SPEEK membrane only show a
slight drop in the output voltage with a retention of 85.4% after
22.5 h of the continuous operation. This is comparable to the
cell with Nafion® 112 (85.0%) and much higher than the cell
with the pristine SPEEK membrane (56.7%), indicating the
good stability of the cell with the SPEEK/SGO/SPEEK mem-
brane. The most interesting is that the output voltage of the
cell with the SPEEK/SGO/SPEEK membrane is always higher
than that of the cell with Nafion® 112 and the pristine SPEEK
membrane. This further demonstrates the outperformance of
the SPEEK/SGO/SPEEK membrane. These results clearly sug-
gest the promising use of the SPEEK/SGO/SPEEK membrane as
the PEM to replace the commercial Nafion.
Conclusions
In summary, the sandwiched SPEEK/SGO/SPEEK membrane
has been successfully synthesized by depositing the SPEEK
membranes onto the both sides of the SGO paper. Due to its
specific structure, the SPEEK/SGO/SPEEK membrane exhibits
proton conductivity close to Nafion® 112 and lower methanol
permeability, which make it highly promising as the PEM for
fuel cells. When used in the semi-passive DMFCs, the cell with
the SPEEK/SGO/SPEEK membrane could exhibit a peak power
density which is 60% higher than that with Nafion® 112. This,
along with its good stability, clearly demonstrates the poten-
tial use of the sandwiched SPEEK/SGO/SPEEK membrane as
the PEM for the fuel cells. The work shown here is of great
interest since it provides a new strategy to fabricate the high
performance PEM with a novel structure and is also applicable
for the design of the specific membrane for many other
applications.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (Nos. 11474101 and U1532139),
the “Outstanding Talent and Team Plans Program” of South
China University of Technology, the Zhejiang Provincial
Please cite this article in press as: Li C, et al., Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether
ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells, International Journal
of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.126
9
Natural Science Foundation (No. LY14B030001), the Guang-
dong Innovative and Entepreneurial Research Team Program
(No. 2014ZT05N200).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2017.05.126.
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