Journal of Membrane Science 425426 (2013) 1122

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Journal of Membrane Science

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

The effect of sulfonated graphene oxide on Sulfonated Poly

(Ether Ether Ketone) membrane for direct methanol fuel cells
Yuseon Heo, Hyungu Im, Jooheon Kim n
School of Chemical Engineering & Materials Science, Chung-Ang University, Heukseok-Dong, Dongjak-Gu, Seoul 156-756, Korea

a r t i c l e i n f o abstract

Article history: A novel composite membrane of sulfonated graphene oxide (s-GO) and SPEEK with various sulfonated
Received 21 June 2012 graphene oxide contents was prepared and investigated. The sulfonation of graphene oxide and PEEK
Received in revised form induces an increase in the number of sulfonic groups (SO3H), which signicantly increases the proton
11 September 2012
conductivity of sulfonated graphene oxide/SPEEK membrane. The introduction of sulfonated graphene
Accepted 12 September 2012
Available online 26 September 2012
oxide in membranes not only improved proton conductivity, but also positively affected the mechanical
properties and the blocking of methanol and water molecules passing through the membrane.
Keywords: Consequently, incorporation of sulfonated graphene oxide into SPEEK membrane has considerably
Poly (ether ether ketone) (PEEK) increased the selectivity of the membrane. Therefore, this sulfonated graphene oxide/SPEEK membrane
Graphene oxide
is a good candidate for usage in direct methanol fuel cells.
Direct methanol fuel cell
& 2012 Elsevier B.V. All rights reserved.

1. Introduction
Direct methanol fuel cells (DMFC) have been recently considered
as promising power sources for portable and transport applications
due to the their high efciency, high power density, compact cell
design and low emissions.[1,2] The proton exchange membrane
(PEM), which transfers protons from the anode to the cathode and
acts as a barrier to the fuel permeable phenomenon, is a vital
component of DMFC. The most common commercially used PEMs
are uorinated ionomers such as Naon because of their high proton
conductivity and chemical stability. However, high cost, methanol
crossover, and loss of conductivity above 80 1C in DMFC still restrict
performance and application.[35] Therefore, numerous studies
have been conducted to develop less expensive materials with low
methanol permeability for DMFC applications. Among the potential
alternatives, sulfonated poly (ether ether ketone) (SPEEK), a proton
conducting polymer formed by electrophilic substitution of the
sulfonic acid groups in the PEEK backbone, is a considerably
attractive material because it has excellent mechanical properties,
resistance to high temperature of up to 300 1C and stability under
acidic conditions. The properties of SPEEK membranes are deter-
mined by their degree of sulfonation (DS). SPEEK membranes show
increasing proton conductivity with increasing DS. However, SPEEK
membranes with high DS levels show gradually deterioration of the
mechanical properties and methanol permeability with increasing
DS.[611] Therefore, to further extend its engineering uses, different
methods are needed to improve the properties of SPEEK membrane
other than controlling DS. Among the various methods, composite
membranes consisting of a polymer backbone and inorganic mate-
rials are potential forms for the materials that could allow control of
the aforementioned properties.
Recently, materials based on graphene oxide as inorganic
llers in polymer composites have been attracting attention as
a result of the potential for applications in electronics and
nanocomposites, due to their extremely high aspect ratio, high
conductivity, high mechanical strength, unique graphitized plane
structure and electrically insulating property.[1220] Ma et al.
reported the improved mechanical strength of epoxy/graphene
nanocomposites.[21] Luo et al. synthesized graphene nanosheet/
polystyrene nanocomposites and showed extraordinary low electrical
percolation thresholds of 0.1 vol%.[22]
This paper reports a novel SPEEK composite membrane that
was prepared using sulfonated graphene oxide and sulfonated
PEEK. The sulfonated graphene oxide was introduced into SPEEK
polymer for improving mechanical properties and methanol
crossover while retaining high proton conductivity. The effect of
sulfonated graphene oxide in the SPEEK membrane is investigated
by membrane properties such as mechanical properties, water
uptake, proton conductivity, and methanol permeability.
2. Experimental methods
2.1. Materials

Graphite with a mean particle size less than 150 mm was obtained
n
Corresponding author. Tel.: 82 2 820 5763; fax: 82 2 824 3495. from Sigma-Aldrich. Poly (ether ether ketone) (PEEK) was obtained
E-mail address: jooheonkim@cau.ac.kr (J. Kim). from Victrex in powder form. Sodium nitrate (NaNO3), potassium

0376-7388/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2012.09.019
12 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122

Fig. 1. Preparation of sulfonated graphene oxide(s-GO).

permanganate (KMnO4), nitric acid (HNO3), sodium hydride (NaH),

propane sultone, tetrahydrofuran, sulfuric acid (H2SO4), N,N-dimethy-
lacetamide (DMAc), methanol (MeOH), deionized water (DI water),
sodium chloride (NaCl) and phenolpthalein (PH indicator) were
purchased from Sigma Chemicals. Hydrochloric acid (HCl) and
hydrogen peroxide (H2O2) were purchased from Samchun Chemicals.

2.2. Synthesis of sulfonated poly (ether ether ketone) (SPEEK)

PEEK powder (12.5 g) was dried overnight in a vacuum oven at

90 1C and dissolved in 200 mL of H2SO4. The mixture was reacted
under mechanical stirring at 55 1C for 3 h. After the reaction, the
mixture solution was dropped into an ice water under continuous
stirring to terminate sulfonation reaction. The precipitated SPEEK
was washed with deionized water until the PH of 67 was
reached to remove the residual sulfuric acid. And then, the SPEEK
was dried in a vacuum oven at 80 1C for 24 h.

2.3. Synthesis of funtionalized graphene oxide (s-GO)

Graphene oxide (GO) was synthesized by using the modied

Hummers method [23]. The manufactured GO (0.2 g) was added to
250 mL of anhydrous THF under vigorous mechanical stirring.
To replace the terminated Na with H in GO, sodium hydride (NaH)
(1.5 g) was added slowly to the GO/THF mixture at 60 1C for 6 h.
Propane sultone (1.5 g) was then added drop wise to the mixture,
and this mixture was reacted at 80 1C for 24 h with constant stirring.
After the reaction, ltered reactant was immersed into an HCl/water
solution for 12 h and then washed with ethanol several times to
remove the residuals. The product was dried in vacuum at 80 1C for
24 h. Fig. 1 gives a schematic diagram of the sulfonation process of
the sulfonated graphene oxide (s-GO).
2.4. Preparation of s-GO/SPEEK membrane
The s-GO/SPEEK membrane was prepared using the solution
casting method. The s-GO was dispersed in DMAc and the weight
ratios of the blends varied from 0% to 10%. The SPEEK (10 wt%)
solution (based on DMAc) was blended with a suspended s-GO
solution. The mixture of s-GO/SPEEK solutions was stirred for
12 h to obtain a homogeneous solution and cast onto Petri dishes
at 60 1C for 56 h. The fabricated s-GO/SPEEK membranes were
peeled off the dishes. The thickness of the membrane was
measured with a digital micrometer.
Fig. 2. FT-IR spectra of PEEK and SPEEK.
2.5. Characterization
2.5.1. Membrane characterization
\The Fourier transform infrared (FT-IR) spectra of the sulfonated
PEEK were obtained using a Bio-rad FTS-1465 (USA). The IR spectra
were collected after 32 scans in the 4000500 cm  1 region in ATR
mode at a resolution of 4 cm  1. The microstructural transformation
of the s-GO/SPEEK composite membranes was analyzed by high
resolution scanning electron microscopy (SEM, S-4300SE. Hitachi).
The EDX measurements were performed with a Thermo NORAN
System 7 EDX analyzer to measure the dispersion of sulfuric acid
groups in the polymer. Thermal degradation and stability of the
membranes were investigated using a thermal gravimetric analyzer
(TGA, SCINCO TGA N-1000) at a heating rate of 10 1C/min from 30 to
800 1C. Differential scanning calorimetry (DSC, SETARAM instrument
DSC 131evo) measurement was employed to study the thermal
transition behavior of membranes. The samples were preheated in
air from 30 1C to 150 1C at 10 1C/min to remove moisture, cooled to
90 1C, then reheated from that temperature to 800 1C at 10 1C/min in
 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122
air. Dynamic mechanical analysis (DMA) was performed with a
Triton instrument. The samples were scanned from 30 to 145 1C at
a heating rate of 5 1C/min.
2.5.2. Water uptake
The s-GO/SPEEK membranes were dried at 80 1C under
vacuum for 12 h, and the weight of the dried membranes was
measured. The membranes were immersed in deionized water at
different temperatures (25 1C, 80 1C). After 24 h, the surface
solution of the wetted membranes was removed with tissue
paper. The wetted membranes were then reweighed. The uptake
was calculated using the following equation:
W wet W dry
Water uptake%  100 1 were prehydrated for at least 24 h. Each reservoir was separated
W dry
2.5.3. Ion-exchange capacity (IEC)
The IEC of the s-GO/SPEEK membranes was measured using
the titration method. Dry SPEI membranes were immersed in
1 mol of NaCl solution for 24 h to replace all the H with Na .
The amount of H protons released from the membranes was
determined by titration, using a 0.01 M NaOH solution with
phenolphthalein as the PH indicator. The IEC value was obtained
using the following equation:
consumed NaOHml  molality of NaOH
IBC mequiv g 1 2
weight of dried membrane
2.5.4. Proton conductivity
The proton conductivity of the s-GO/SPEEK membranes was
measured by AC impedance spectroscopy (IM-6ex, Zahner) between
0.1 kHz and 1 MHz. Before the conductivity experiments, all samples
were immersed in deionized water for at least 24 h at room
temperature. These samples were sandwiched rapidly between the
two Pt electrodes. The conductivity of all samples was measured
using a two-point method at different temperatures (25 1C, 80 1C).
Fig. 3. 1H NMR spectrum of SPEEK.
13
The proton conductivity (s) was calculated using the following
equation:
h
s 3
RS
where h is the thickness of the conducting membranes, R (O) is the
electro-resistance and S(m2) is the surface dimension of the
membranes.
2.5.5. Methanol permeability
The methanol permeability of the s-GO/SPEEK membranes was
measured using a glass diffusion cell composed of two reservoirs,
each with a capacity of 100 ml. Before each test, the membranes
by a prehydrated membrane. One reservoir was lled with a 10 M
MeOH solution, and deionized water was placed in the other
reservoir. Both compartments were stirred continuously with a
magnetic stirrer during the permeability experiment. The methanol
permeability was found using the equation:
A DK
C B t C A tt 0 4
VB L
where CA and CB are the concentrations of MeOH in the donor and
receptor reservoirs. A and L are the diffusion area and thickness of
the membrane, respectively. The product of D and K is the methanol
permeability (cm2 s  1).
2.5.6. Selectivity (determination of overall membrane
characteristics)
The required membrane characteristics for high performance of a
DMFC are high proton conductivity and low methanol permeability.
An evaluation of the membrane performance can be obtained using
the following expression:
s
F 5
P
where F is a parameter that evaluates the overall membrane
performance in terms of the ratio of the ionic conductivity(s) to
the methanol permeability (P).
14 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122
3. Results and discussion
3.1. Sulfonation of SPEEK
The successful introduction of the sulfonic acid groups was
conrmed by comparing the FT-IR spectra of PEEK and
SPEEK. Fig. 2 shows both spectra of PEEK and SPEEK. In the
SPEEK spectrum, the band at 1488.7 cm  1 corresponding to the
aromatic CC band in PEEK was observed to split into two new
absorption bands at 1474 and 1494 cm  1. These divided bands
Fig. 4. FT-IR spectra of GO and sulfonated GO (s-GO).
Fig. 5. SEM images and EDX spectrum of (a) GO and (b) sulfonated GO (s-GO).
were attributed to the substitution upon sulfonation. The sulfonic
acid group is only attached to the 1.2.4-substitution aromatic ring
between two ether linkages.[24] The new spectra at 1024 and
1080 cm  1 were assigned to the sulfonic acid group in SPEEK, and
are attributed to the SO symmetrical and asymmetric stretching
vibration (OQSQO), respectively. [1,25]
The degree of sulfonation (DS) was determined quantitatively
by using 1H NMR. The 1H NMR spectra of SPEEK are given in Fig. 3.
The presence of sulfonic acid group causes a signicant singlet
signal (HM) at 7.5 ppm. The presence of sulfonic acid group was
assigned to the distinct signal for protons at the M position. The
estimated HM content from the intensity of the HM signal is
equivalent to the SO3H group content. The degree of sulfonation
is given by:
N AHM
P 0 r n r1 6
122N AHA,B,C,D,E,F,G,H,I,J,K,L,N,O
where N is dened as the number of HE per repeat unit, AHM is the
area of the HE signal and AHA,B,C,D,E,F,G,H,I,J,K,L,N,O is the sum of the area
under the signals corresponding to all the other aromatic protons.
The degree of sulfonation in this experiment was calculated to be
56%. [5]
3.2. Characterization of sulfonated graphene oxide
The results of FT-IR analysis indicated differences between GO
and sulfonated GO (s-GO) spectra. Fig. 4 shows both (a) GO and
(b) s-GO. In the spectrum of s-GO, a new band appeared at
1271 cm  1, which have shown typical absorbance for the sulfonic
acid groups (SO3H). Morphological features of the (a) graphene
oxide (GO) and (b) sulfonated graphene oxide (s-GO) were
observed in SEM as shown in Fig. 5. A comparison of the
morphology of GO with that of functionalized GO (s-GO) showed
that the surface of the s-GO was rougher than that of the GO due
to the sulfonation. EDX data conrmed the existence of sulfonic
acid groups on the GO. The EDX spectrum of s-GO (Fig. 5(b))
shows a new additional sulfur peak, which corresponds to the
sulfonic acid groups on the surface of s-GO. The other new peak
 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122
Fig. 6. XPS survey spectra of (a) GO and s-GO, O1s spectra of (b) GO, (c) s-GO, S2p spectrum of (d) s-GO.
(Na) indicated the remaining -SO3Na groups. The XPS survey
spectra of GO and s-GO are presented in Fig. 6, which shows wide
scan spectra in the range of 0800 eV used to identify the surface
elements present with quantitative analysis. In both the GO and
s-GO spectra, Cls and O1s signals appear at 286 and 531 eV,
respectively. After functionalizing the sulfonic acid groups onto
the GO, s-GO shows a new S2p peak at 168 eV.[26] The other new
peak (Na1s at 1068 eV) indicated the remaining -SO3Na groups.
The O1s spectra of s-GO slightly increased compared to that of GO
because of sulfonic groups in s-GO. A detailed analysis of the XPS
spectra presented clear evidence that the GO was chemically
modied, which was conrmed by high resolution spectra of C1s
based on a Gaussian spectral deconvolution. The O1s and S2p
spectra for GO and functionalized GO are presented in Fig. 6(b)
and (d). The O1s peaks of GO (Fig. 6(b)) appearing at 530.7, 531.9,
532.5 and 533.7 eV, originate from the CO, OH, CO and COH,
respectively (The 535.4e V peak is attributed to H2O atoms). This
result indicates that the GO was successfully manufactured using
the hummers method. The O1s spectra of the s-GO (Fig. 6(c)) were
different compared to GO. The OH peak at 531.9 is decreased,
whereas CO peak at 532.5 eV is increased after the sulfonated
reaction of GO. (The 530.1, 533.5, and 534.9eV peaks are attrib-
uted to CQO, COH, and H2O). The S2p peak at 168 eV is
attributed to the binding energy of sulfonic groups, as shown in
Fig. 5(d). These peaks conrmed the existence of sulfonic acid
groups on the surfaces of the GO nanosheet. These results conrmed
15
the successful introduction of the sulfonic acid groups on the
surface of GO.
3.3. Characterization of the s-GO/SPEEK membrane
The 1H NMR analysis of SPEEK and s-GO/SPEEK membrane was
investigated. Fig. 7 shows the 1H NMR spectra range from 1.5 to
2.9 ppm of SPEEK and s-GO 5 wt%/SPEEK membrane. The 1H NMR
spectra of s-GO 5 wt%/SPEEK membrane were found to contain an
additional new signal at 2.525 ppm compared to that of SPEEK
membrane. This is attributed to adding the s-GO into the SPEEK
membrane and this new signal is assigned to the proton in s-GO.
Morphological features of the membranes were observed on
FE-SEM. Fig. 8(a) and (b) show the microscale images of the
cross-sectional area of SPEEK membrane and Fig. 8(c) and
(d) show the those of the cross-sectional area of s-GO 7 wt%/
SPEEK membrane. The various sizes of s-GO particles (0.5 mm
3 mm) are visible in the s-GO/SPEEK membrane at low (Fig. 8(c))
and high (Fig. 8(d)) magnication (s-GO particles are indicated by
arrows), though they are uniformly distributed throughout the
matrix due to the interfacial interaction, which is attributed to
hydrogen bonding between the sulfonated acid groups in s-GO
and polar groups (O-, CQO) in SPEEK (Scheme 1). The FT-IR
analysis of SPEEK and s-GO/SPEEK membrane is conducted to
conrm the hydrogen bonding interaction between s-GO and
SPEEK matrix. Fig. 9 shows the FT-IR spectra of SPEEK and
16 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122

Fig. 7. 1H NMR spectrum of SPEEK and s-GO5 wt%/SPEEK membrane.

s-GO/SPEEK membrane. The FT-IR spectra of the hydrogen bond-
ing site are slightly shifted due to the interaction of hydrogen
bond. The remaining OH group bands at 1413 cm  1 and
3440 cm  1 in SPEEK membrane are shifted due to the hydrogen
bonding interaction between OH groups in SPEEK and polar
groups in s-GO, so, in the s-GO/SPEEK membrane, the bands of
0O-H group appeared at 1406 cm  1 and 3404 cm  1. The spectra
of CQO groups in SPEEK membrane is shifted from 1082 cm  1 to
1046 cm  1. The sulfonic groups (SO3H) band in SPEEK mem-
brane is also shifted from 1284 cm  1 to 1277 cm  1. These results
clearly indicate the formation of hydrogen bond between s-GO
and SPEEK. Embedded s-GO particles may impart mechanical
stability to the matrix because of the interaction between parti-
cles and matrix. The uniform distribution of s-GO particles in the
entire matrix is the ideal situation to formulate continuous
conduction pathways in all directions of the membrane. There-
fore, based on SEM morphology and FT-IR, we could expect
improved properties of s-GO/SPEEK membranes compared with
pristine SPEEK membranes.
3.4. Water uptake
It is well known that water in proton exchange membranes
plays an important role in proton conducting because the
adsorbed water can facilitate the transport of protons. That is,
the available acid groups in the membrane and their capacity to
dissociate in water determines the proton conductivity.[24,27]
However, too much water absorption can cause the deterioration
 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122 17

Fig. 8. Cross-sectional images of (a), (b) SPEEK membrane and (c), (d) s-GO/SPEEK membrane.

Scheme 1. Scheme diagram of interaction between SPEEK and s-GO.

of mechanical stability, as well as swelling problems, which will

lead to a fall in membrane performance. Hence, it was very
signicant to determine the water uptake of membranes. The
water uptake of GO/SPEEK and s-GO/SPEEK membranes with
increasing graphene oxide materials is shown in Fig. 10. The
water uptake of SPEEK membrane is higher than that of
Naon117 (33%), but the GO/SPEEK and s-GO/SPEEK membranes
show a decreased trend in water uptake with increasing graphene
oxide content, for uptake values below that of Naon117. However,
the GO and s-GO 1 wt%/SPEEK membranes exhibited slightly
increased values of water uptake compared with SPEEK membrane.
For water uptake of 1 wt% loading GO and s-GO membranes, the
effect of functional groups is greatly inuenced by the blocking
effect due to the very small amount of llers. The functional groups
in introduced llers (hydroxyl groups in GO and sulfonic acid groups
in s-GO) temporarily increased the water adsorption in membranes,
Fig. 9. FT-IR spectra of SPEEK and s-GO/SPEEK membrane.
whereas above 3 wt% loadings of GO and s-GO, the blocking effect
of graphene oxide materials started to dominate, thus reducing the
water uptake of the membranes. That is, the large aspect ratio acts
as barriers to water absorption in SPEEK matrix. The increased
interfacial adhesion due to hydrogen bonds between llers and
polymer also decreased the water uptake of GO/SPEEK and s-GO/
SPEEK membranes. This was because the gap between the ller and
polymer, through which water molecules could pass, was decreased
18 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122

in size due to the strengthened interfacial adhesion. Thus, the
decreased gap size effectively prevented the absorption of water
molecules.
The water uptake of s-GO/SPEEK membrane shows a highly
decreased ratio compared to GO/SPEEK membrane, which is
attributed to the difference of interfacial adhesion. In the
GO/SPEEK membranes, the hydrogen bonds are formed by OH
groups in GO, and the O- and CQO groups on PEEK chains,
whereas in the s-GO/SPEEK membranes, the additional functional
groups (SO3H) also participated in these hydrogen bonding
(Scheme 1). Therefore, the s-GO has more hydrogen bonding sites
than GO, thus, the interfacial interaction of s-GO/SPEEK membrane
is stronger than that of GO/SPEEK membrane, which leads to the
water absorption of the s-GO/SPEEK membrane blocking more
effectively than the GO/SPEEK membrane.
Based on the above experiment, it is clear that the introduction
of graphene-oxide-based materials can effectively reduce the
water uptake of SPEEK membranes, and subsequently, mechanical
stability as well.
3.5. Ion exchange capacity (IEC)
The ionic exchange capacity (IEC) is considered to correspond
to the moles of xed SO3 1 sites per gram of polymer. Therefore,
the IEC of the membrane plays a crucial role for the proton
conductivity in DMFCs. Table 1 shows the IEC of GO/SPEEK and
s-GO/SPEEK membranes. The IEC values of s-GO/SPEEK mem-
brane are increased with increased amount of s-GO particles,
whereas the IEC values of GO/SPEEK membranes exhibit little
uctuation. This result is attributed to the s-GO particles, which
have sulfonic acid groups (SO3 ) as xed charge sites, signicantly
affecting the IEC of s-GO/SPEEK membranes. On the other hand,
the IEC of GO/SPEEK membranes are scarcely affected by the ller
(GO) because the GO particles do not possess the sulfonic acid
group. Consequently, the increased s-GO content increases the
amount of suitable sulfonating sites in s-GO/SPEEK membranes,
which corresponds to the increase in charge carriers in the
membranes.
3.6. Proton conductivity and electrical conductivity
The proton conductivity is the most essential property in
DMFC applications. Fig. 11 shows the proton conductivities of
GO/SPEEK and s-GO/SPEEK membranes. In the proton conductiv-
ities of the GO/SPEEK membranes, with the GO particles intro-
duced into the SPEEK matrix, the proton conductivity of the GO/
SPEEK membranes was slightly increased regardless of the
amounts of GO particles. On the other hand, the proton con-
ductivity of s-GO/SPEEK membranes showed increasing trends
with the increase of s-GO loading (up to 8.41  10  3 S cm  1).

Fig. 10. Water uptake of GO/SPEEK and s-GO/SPEEK membranes. Fig. 11. Proton conductivity of GO/SPEEK and s-GO/SPEEK membranes at 80 1C.

Table 1
Water uptake, IEC, proton conductivity and methanol permeability at 80 1C.

GO contents IEC Proton conductivity Methanol permeability s-GO IEC Proton conductivity Methanol permeability
(wt%) (mequiv (mS cm  1) (  10  8cm2 s  1) contents (mequiv (mS cm  1) (  10  7 cm2 s  1)
q  1) (wt%) q  1)

0 0.75 1.0823 5.5219 0 0.75 1.0823 5.5219

1 1.04 2.7389 5.1816 1 1.03 4.5006 4.9874
3 1.07 2.8000 4.7649 3 1.35 6.8408 4.3654
5 1.11 2.8662 4.3447 5 1.65 8.4177 3.8194
7 0.98 2.4416 4.0635 7 1.55 7.8408 3.3265
10 0.84 2.0303 3.8692 10 1.49 5.5408 2.6388
 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122
Scheme 2. Mechanism of proton transport in s-GO/SPEEK membrane.
Table 2
Electrical conductivity of s-GO/SPEEK membrane at room temperature.
s-GO contents(wt%) Electrical conductivity (  10  7 S/cm)
SPEEK 6.26
s-GO 1 wt%/SPEEK 6.01
s-GO 5 wt%/SPEEK 5.83
s-GO 10 wt%/SPEEK 5.48
At s-GO loading above 7 wt%, the proton conductivity of s-GO/
SPEEK membrane decreased.
The absorbed water molecules, which can act as vehicles by
carrying along protons that are attached to them in such a form such
as H3O , H5O2 and H9O4 through the aqueous media,[24] slightly
increased the proton conductivity of GO/SPEEK membranes due to
the hydroxyl groups in GO particles. However, the reason that the
proton conductivity of GO/SPEEK does not show increasing trends of
the proton conductivity values is that the GO particles do not
possess the sulfonic acid groups, which can transport the protons
through the formed ionic channel. As shown in Scheme 2, the
mechanism of proton transport of (b) s-GO/SPEEK membrane shows
more dense sulfonic acid groups than (a) GO/SPEEK membranes,
which is attributed to the introduction of sulfonated GO (s-GO).
The proton transport in membranes requires well-connected chan-
nels formed by ion clusters of hydrophilic sulfonated functional
groups. The increased density of sulfonic acid sites due to the
introduction of s-GO in s-GO/SPEEK membranes formed the chan-
nels with good connectivity. Protons could be transported quickly in
these channels, which leads to the increasing of the proton con-
ductivity of the s-GO/SPEEK membrane. However, with further s-GO
loading up to 7 wt%, the blocking effect starts to dominate, thus
decreasing the proton conductivity of the membranes. That is, the
addition of too many planar s-GO particles obstructed the polymer
chain movement in the ionic cluster. Hence, the suitable loading
amounts of s-GO (approximately 5 wt%) were seen to promote
proton transport in the s-GO/SPEEK membranes.
High electrical conductivity is an undesirable property in PEMs
for direct methanol fuel cells.[28] As shown in Table 2, the electrical
conductivities of s-GO/SPEEK membrane are generally low, which is
consistent with the magnitude of the insulator. The electrical
conductivity of s-GO/SPEEK membrane is slightly decreased when
adding the s-GO particles because the electrical conductivity of GO
particles (6.8  10  8 S/cm) is lower than that of SPEEK matrix.
[20,29,30]
3.7. Methanol permeability
Methanol permeability is an important factor in DMFC appli-
cations because it produces excellent effective energy density in
19
DMFC systems. The methanol permeability of GO/SPEEK and s-GO/
SPEEK membranes is shown in Table 1. It can be seen that the
methanol permeability of GO/SPEEK and s-GO/SPEEK membranes
decreased with increment of GO and s-GO loading, and was
generally lower than that of Naon 117 (2.91  10  6 cm2 s  1).
The differences in methanol the permeability of SPEEK and Naon
is explained by their microstructure. The Naon membrane pro-
duces easy hydrophobic/hydrophilic separation, due to the extre-
mely high hydrophobicity of the peruorinated backbone and high
hydrophilicity of the sulfonic acid groups. The sulfonic acid groups
aggregate to form hydrophilic domains. The well-connected hydro-
philic domains function as a substance transport channels. Not only
proton and water but also some smaller polar molecules such as
methanol can get through these channels. This phenomenon leads
to high methanol permeability. On the other hand, the microstruc-
ture of SPEEK membrane has smaller hydrophobicity/hydrophilicity
differences (the backbone is less hydrophobic and the sulfonic acid
group is less acidic) compared with Naon polymer. Therefore, the
separation into the hydrophobic and hydrophilic domain is less
pronounced, which leads to lower methanol permeability than
Naon117.[2,31,32]
Furthermore, the dispersed GO and s-GO particles in SPEEK
polymer act as barriers to connected hydrophilic channels. GO
and s-GO particles obstruct the methanol from migrating through
the membrane. This blocking effect of GO and s-GO particles in
the polymer leads a decreasing trend in methanol permeability.
The interfacial interaction between graphene-oxide-based mate-
rials (GO and s-GO) and SPEEK polymer also decreases methanol
permeability. Because the transport of methanol in membranes
also requires relatively broad hydrophilic channels, the interfacial
interaction between graphene-based materials and SPEEK
restricts the formation of the channels in membranes, which
leads to low methanol permeability (Scheme 1 shows the inter-
action between s-GO and SPEEK). When comparing GO/SPEEK
membranes and s-GO/SPEEK membranes, the s-GO/SPEEK mem-
brane exhibited more reduced methanol permeability than
GO/SPEEK membrane. As mentioned above, this phenomenon is
attributed to the interfacial adhesion of s-GO/SPEEK membrane
being stronger than that of GO/SPEEK membrane. The s-GO/SPEEK
membrane more effectively obstructed the migration of methanol
molecules than the GO/SPEEK membrane, because of the narrower
gap between the ller and polymers due to strong interfacial
adhesion.
3.8. Selectivity
The PEMs in DMFCs are required to possess high proton
conductivity and low methanol permeability.[33] The selectivity,
which is dened as the ratio of proton conductivity to methanol
permeability, is a factor for evaluating membrane performance in
20 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122

Fig. 12. The selectivity (ratio of proton conductivity to methanol permeability)

of Naon, pristine SPEEK and s-GO/SPEEK membranes.

terms of both proton conductivity and methanol permeability.

The selectivity factor is usually used as an indicator for the
applicability of membranes by comparing its value with those
of commercial materials. A higher selectivity value implies better
applicability in DMFCs. Fig. 12 shows the selectivity of s-GO/
SPEEK membranes and Naon. The selectivity of the SPEEK
membrane was signicantly improved with the introduction of
s-GO, and s-GO/SPEEK membranes showed better performance
compared to Naon. These results were attributed to the addition
of s-GO impacting the reduction of methanol crossover. The
maximum selectivity appears at 7 wt% s-GO loading. This selec-
tivity value of the s-GO 7 wt%/SPEEK membrane is approximately
4 times that of Naon. Therefore, s-GO/SPEEK membranes are
denitely promising materials for DMFC applications.

3.9. Thermal analysis and dynamic mechanical behavior of

s-GO/SPEEK membrane

The dimensional and thermal stability affect the performance

and durability of the membrane during fuel cell operation at high
temperature.[34] The thermal stability was examined by both
TGA and DSC. Fig. 13(a) shows the TGA thermal graph of the
SPEEK and s-GO/SPEEK membrane. The TGA curves showed two
distinct weight loss steps, the rst of which around 300 1C was
attributed to the splitting-off of sulfonic acid groups of SPEEK.
The second thermal degradation at approximately 500 1C was
assigned to the decomposition of the main chain of the polymer.
These results indicated that all the membranes are thermally
stable at about 300 1C, which is satisfactory for usage as proton-
conducting materials. Fig. 13(b) shows the DSC thermograms
(2nd heating) for the SPEEK and s-GO/SPEEK membrane. The DSC
result indicated the glass transition temperature (Tg) of SPEEK and
s-GO/SPEEK membrane occur at approximately 200 1C. There is
nearly no shift in the Tg between SPEEK and s-GO/SPEEK mem-
brane. It can be seen that the thermal stability of s-GO/SPEEK
membranes is maintained.
The addition of functionalized GO as the ller also signicantly
inuenced the mechanical properties of the s-GO/SPEEK membranes.
Fig. 14(a) shows a signicantly improved modulus of s-GO/SPEEK
membranes compared to SPEEK membrane. The mechanical beha-
vior of the s-GO/SPEEK membranes exhibited an enhancing trend
Fig. 13. The thermal analysis of the (a) TGA curve and (b) DSC curve of SPEEK and
s-GO/SPEEK membrane.
with increasing contents of s-GO. The reason is that the graphene-
based materials have an excellent elastic modulus (1100 GPa) and
intrinsic strength (125 GPa).[35] Another factor is the hydrogen
bonds between the s-GO and SPEEK. As mentioned, these effects
increase the interfacial adhesion between the s-GO and SPEEK, which
leads to the enhanced mechanical properties of membranes.
On the other hand, with further increase in s-GO content from
5 wt% to 10 wt%, the modulus increased slightly from 1.52 GPa to
1.6 GPa, which is ascribed to the phenomenon of graphene-based
material restacking that occurs due to the van der Waals forces in
the nanosheets. The slippage of the piled graphene-based
nanosheets will lead to less effective enhancement of the mechan-
ical properties of the composites.[17,36] The tan delta curves of
s-GO/SPEEK membranes as a function of temperature is shown as in
Fig. 14(b). The value of tan delta of the s-GO/SPEEK membranes
slightly decreased with increments of s-GO contents, which is
 Y. Heo et al. / Journal of Membrane Science 425426 (2013) 1122
Fig. 14. (a) Storage modulus and (b) tand of s-GO/SPEEK membranes.
attributed to the s-GO nanosheets hindering the motion of matrix
chains.
4. Conclusion
Composite membranes based on SPEEK with embedded
sulfonated graphene oxide (s-GO) were prepared, and their proper-
ties were investigated. The introduction of s-GO particles into SPEEK
membrane improved the proton conductivity of the s-GO/SPEEK
membranes up to 8.41  10  3 S cm  1, which is attributed to the
amount of sulfonic acid groups being increased by incorporating
s-GO, which formed more dense proton transport networks in the
membrane. The mechanical strength of the s-GO/SPEEK membrane
is also signicantly enhanced because the graphene-oxide-based
materials have better mechanical properties, and the interfacial
21
interaction between s-GO and SPEEK was increased by the hydrogen
bonding. The s-GO particles positively affected the blocking proper-
ties against water and methanol molecules, which led to decreased
water uptake and methanol permeability. Lower methanol perme-
ability (2.6388  10  7 cm2 s  1) and higher selectivity of the s-GO/
SPEEK membranes compared with Naon were shown. Based on
these results, it might be considered that this membrane showed
good potential for use as PEMs in DMFC applications.
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