P1001/1

J Mater Sci (2013) 48:3665–3671

DOI 10.1007/s10853-013-7162-7

SiO2/sulfonated poly ether ether ketone (SPEEK) composite

nanofiber mat supported proton exchange membranes
for fuel cells
Chanmin Lee • Seong Mu Jo • Jonghyun Choi •

Kyung-Youl Baek • Yen Bach Truong •

Ilias Louis Kyratzis • Yong-Gun Shul

Received: 1 January 2013 / Accepted: 12 January 2013 / Published online: 26 January 2013
Ó Springer Science+Business Media New York 2013

Abstract A composite membrane of silica (SiO2)/sulfo- condition (120 °C and 40 % RH), the maximum power
nated poly (ether ether ketone) (SPEEK) nanofiber mat density was 170 mW/cm2 for the Nafion-impregnated
impregnated with Nafion was fabricated and evaluated for SiO2/SPEEK (40/60 w/w) composite nanofiber membrane
its potential use as a proton conductor for high temperature that was 2.4 times higher than recast Nafion (71 mW/cm2)
polymer electrolyte membrane fuel cells. The supporting while SPEEK film failed.
SiO2/SPEEK composite nanofibrous skeleton was prepared
via electrospinning of a mixture of SPEEK solution and
silica sol prepared from tetraethyl orthosilicate (TEOS). Introduction
The control of hydrolysis and condensation of TEOS
enabled to form entangled SiO2 networks miscible to Proton exchange membrane fuel cell (PEMFC) is one of
SPEEK solution. The prepared SiO2/SPEEK nanofiber mat the most promising energy conversion systems as an
was impregnated with NafionÒ to completely fill the inter- alternative to the internal combustion engine for three
fiber voids to prepare a dense membrane. The morphology reasons: (i) it is a relatively simple system, (ii) it is envi-
of the nanofiber mat and the composite membrane were ronmentally friendly with a high energy conversion effi-
observed by scanning electron microscopy and the pres- ciency, and (iii) its output power is adjustable by a simple
ence of SiO2 and SPEEK in the prepared nanofibers was cell stacking for various applications requiring different
confirmed by FTIR spectroscopy. Proton conductivity and power outputs, just like batteries [1]. Although there have
swelling of the membrane were measured. The H2/O2 been intensive research activities over several decades on
single cell test using the composite membrane as a PEM polymer electrolyte membranes, perfluorosulfonic acid
was performed. At a high temperature and low humidity ionomer (e.g., NafionÒ developed by DuPont) is still con-
sidered as the standard and most reliable membrane
material for PEMFCs [2]. Despite its reliability on proton
conduction and chemical and mechanical stability when
C. Lee  Y.-G. Shul (&) operated below 80 °C and under humidified conditions, the
Graduate Program in Clean Technology, Yonsei University,
performance of perfluorosulfonic acid ionomer membrane
50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, South Korea
e-mail: [email protected] is still not satisfactory at higher temperature ([80 °C) and
partially humidified conditions due to rapid dehydration
S. M. Jo  K.-Y. Baek [3]. Although there are performance issues relating to the
Center for Materials Architecturing, Korea Institute of Science
use of these membranes at higher temperatures and lower
and Technology, 39-1, Hwarangno 14-gil 5, Seongbuk-gu, Seoul
136-791, South Korea humidity fuel cell operating conditions, it is advantageous
to use them at these conditions because both carbon
J. Choi (&)  Y. B. Truong  I. L. Kyratzis monoxide (CO) poisoning and flooding problems can be
Materials Science and Engineering, Commonwealth Scientific
mitigated [4]. To overcome these limitations, hybrid mem-
and Industrial Research Organisation, Bayview Ave, Clayton,
VIC 3168, Australia branes (organic–inorganic composite) with hygroscopic
e-mail: [email protected] particular additives (e.g., SiO2 [5, 6] and TiO2 [6–8]) have

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been suggested. Such composite membranes have shown Experimental

improved thermal stability and hygroscopic properties [9].
However, during the membrane fabrication process via film Materials
casting and solvent evaporation, homogeneous and repro-
ducible dispersion of the additive particles is often chal- Poly ether ether ketone (PEEK; VICTREX 450PF) was
lenging due to the agglomeration of inorganic particles. obtained from VICTREX. Tetraethyl orthosilicate (TEOS),
The agglomeration of inorganic additive particles is N,N-dimethylformamide (DMF), sulfuric acid (H2SO4),
reduced by using smaller particles (i.e., nanoparticles) 37 % hydrochloric acid (HCl), absolute ethanol, and 5 wt%
which disperse more homogeneously in the membrane NafionÒ (1100 EW) solution were purchased from Sigma-
matrix [10]. Aldrich.
Electrospinning is known as a simple and versatile
method to produce nanofiber mats with high surface area, Sulfonation of PEEK
high porosity, controllable pore structures, and mechani-
cal strength [11–13]. The electrospun fibers are used in a PEEK powder was pre-dried in a convection oven at
wide range of research areas, such as high performance 100 °C for 12 h to remove any pre-adsorbed water.
filters, chemical and biomedical materials, protective Approximately 20 g of the dried PEEK powder was added
clothing, and lithium batteries [14, 15]. Although elec- to 200 mL of concentrated H2SO4 (95 wt%). The mixture
trospinning has mainly utilized polymeric materials, was stirred vigorously at room temperature for 120 h under
recently both inorganic and polymeric components have N2 atmosphere. After the reaction, the sulfonated polymer
been electrospun together to produce composite nanofi- solution was slowly dropped into ice-cold deionized water
bres [16–18]. with stirring. The precipitated polymer was filtered and
Electrospun nanofibers incorporated composite mem- washed thoroughly with deionized water until the filtrate
branes for PEMFCs were first introduced by Pintauro et al. liquid became neutral in pH to completely remove any
[19]. The electrospun sulfonated poly(arylene ether sul- residual acid. The washed polymer was then dried under
fone) nanofiber mat provided proton conduction pathway vacuum at 100 °C overnight. The ion exchange capacity
and the inter-fiber pores were filled with inert polyurethane. (IEC) of the prepared SPEEK was determined to be
It was reported that the proton conducting and mechanical 1.97 mmol/g.
properties of the composite membranes were decoupled by
mixing proton conducting polymer nanofibers with an inert Preparation of SiO2 sol
polymer matrix. In subsequent studies on nanofiber com-
posite PEMs, other polymer nanofibers have been used as The silica sol was prepared from TEOS, a silica precursor.
proton conducting channels in the composite membranes TEOS, ethanol, deionized water, and HCl were mixed in a
(e.g., perfluorosulfonic acids) [20, 21]. A reverse version of molar ratio of 1:2:2:0.01 (TEOS:ethanol:water:HCl). First,
the nanofiber composite PEMs, non-conducting nanofiber- 112.8 g TEOS was dissolved in 49.8 g absolute ethanol
reinforced PEMs have also been reported: composite sys- and 19.1 g water in a beaker. Then, 0.564 g HCl was
tems such as polyvinylidene fluoride nanofibers in Nafion slowly added to TEOS/ethanol/water solution under vig-
matrix [22] and polyvinyl alcohol nanofibers in Nafion orous stirring. This solution was constantly stirred and
matrix [23, 24]. heated at 75 °C until the weight of mixture decreases by
In this contribution, we prepared SiO2/SPEEK inor- 65.4 % which took approximately 3 h. After reaction, 10 g
ganic–organic composite nanofiber mats via electros- DMF was added and cooled down to room temperature to
pinning. During nanofiber formation, adapting sol–gel obtain an electrospinnable silica sol. The measured vis-
synthesis, silica was formed in situ and distributed in cosity (using DV-E VISCOMETER, BROOKFIELD) of
the proton conducting polymer nanofiber. The prepared the silica sol was between 170 and 200 cP.
SiO2/SPEEK composite nanofiber mat was then used as
a supporting skeleton. Impregnating with Nafion turned Membrane preparation
the membrane from a nanofiber mat into a dense film.
To examine actual membrane performance in a fuel SiO2/SPEEK composite nanofiber mats were prepared via
cell, we also prepared a membrane electrode assembly electrospinning. 20 wt% SPEEK solution in DMF and pre-
(MEA) with the nanofiber composite membrane. The formed SiO2 sol were mixed in a weight ratio of 40/60
cell performance of the Nafion-impregnated SiO2/SPEEK (SiO2/SPEEK). The mixture precursor solution was elec-
(40/60 w/w) composite membrane was evaluated and trospun by applying a voltage of 15 kV at a distance of
compared with the recast Nafion and SPEEK film 10 cm between the stainless steel needle tip (30G,
membranes. 0.15 mm I.D.) and a fiber collector. Humidity was kept

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below 15 % RH while electrospinning. The collected The wet weight (Mwet) was determined after the mem-
nanofiber mats were dried in air for 12 h to complete branes were soaked in water at 25 °C for 12 h and the
hydrolysis and condensation of SiO2 sol and further dried surface water was removed by consistent force. The wet
in a vacuum oven at 100 °C for 12 h to remove any length (Lwet) was measured after the membranes were
residual solvent. The prepared nanofiber mat (SiO2/ soaked in water at 70 °C for 0.5 h. Both gravimetric and
SPEEK = 40/60) was impregnated with 5 wt% Nafion linear membrane swelling of membranes was determined
solution. 0.006 g of Nafion (solid mass) was added to a unit using the following equation:
area (1 cm2) of the nanofiber mat. Note that the thickness Mwet  Mdry
of the nanofiber mat before the impregnation was 45 lm Gravimetric swelling ð%Þ ¼  100
Mdry
and the thickness was unchanged after the impregnation. Lwet  Ldry
To compare, Nafion film and SPEEK film were cast from Linear swelling ð%Þ ¼  100
Ldry
5 wt% Nafion solution and 20 wt% SPEEK in DMSO at
60 °C. The cast films were further dried in a vacuum at Membrane electrode assembly preparation and single
60 °C overnight. The thickness of cast films was *50 lm. cell performance test

Membrane characterization The catalyst ink was made by mixing 40 wt% Pt/C
(Johnson Matthey) with 5 wt% Nafion (EW 1100) and
The electrospun SiO2/SPEEK composite nanofiber mat and isopropyl alcohol. The catalysts and binder mixture
Nafion-impregnated SiO2/SPEEK composite nanofiber was spray-coated onto both sides of the membrane using
membrane were observed by scanning electron microscope catalyst-coated membrane (CCM) method [25]. The Pt
(JSM-6701F, JEOL). FTIR analysis was performed on a loading on each side of the membrane was controlled at
Spectrum 100 FTIR spectrometer (Perkin-Elmer). Proton 0.4 mg/cm2. The active electrode area was 1 cm2. Carbon
conductivity was measured by AC impedance spectroscopy papers (SGL 10BC) were used as gas diffusion layers
(VSP, BioLogic) in the frequency range of 0.1–10,000 Hz (GDLs) for both electrodes. To evaluate the performance,
at varied temperatures and relative humidity. A four-probe an assembled single cell was fed with humidified gases,
electrode conductivity cell was used. To measure the water H2(g) for anode and O2(g) for cathode. The flow of the gases
uptake (gravimetric and linear), membranes were heated in were controlled in a stoichiometric ratio of 1.5:2.0 (H2:O2),
vacuum oven at 60 °C for 12 h and then the dry weight at atmospheric pressure and then polarization (potential vs.
(Mdry) and length (Ldry) in both x- and y-axis measured. current) curves were recorded using DC electrode load

Fig. 1 SEM images (surface

view) of electrospun a SPEEK
nanofiber mat (at 16 kV, 8 cm,
0.080 mL/h), b SiO2 nanofiber
mat (at 23 kV, 14 cm,
0.025 mL/min), c SiO2/SPEEK
(40/60 w/w) nanofiber mat, and
d fiber diameter distribution of
the SiO2/SPEEK nanofiber mat

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Fig. 2 SEM images (cross-sectional view) of Nafion-impregnated electrospun SiO2/SPEEK (40/60 w/w) nanofiber composite membranes: at
a lower magnification (910,000) and b higher magnification (950,000)

(KFM2030, KIKUSUI) at 4 different testing conditions SiO2/SPEEK composite nanofiber surface and Nafion
(75 °C and 100 % RH, 90 °C and 100 % RH, 110 °C and matrix was observed possibly due to good compatibility
60 % RH, and, 120 °C and 40 % RH). between sulfonated polymers, SPEEK in the nanofiber and
Nafion in the matrix. For the SiO2/SPEEK composite
nanofiber, it was observed that the nanofibers remained
Results and discussion intact during the impregnation process so a uniform distri-
bution was ensured, while for the SPEEK alone the nanof-
Electrospun mat and membrane morphology ibers were immediately dissolved by the Nafion solution
whose solvent was a mixture of water and lower aliphatic
The two electrospinnable solutions were prepared sepa- alcohols (information given by Sigma-Aldrich). The final
rately. Electrospinnable SPEEK solution was easily pre- membrane composition was calculated using the dry
pared simply by dissolution of SPEEK (20 wt%) in DMF. weights of the SiO2/SPEEK nanofiber mat and the Nafion-
On the other hand, to make silica sol electrospinnable, impregnated SiO2/SPEEK nanofiber membrane and was
hydrolysis and condensation of the silica precursor (TEOS) Nafion:SiO2:SPEEK = 88.2:4.7:7.1 by weight. Both the
must be carefully controlled. To prevent further condensa- SiO2/SPEEK composite nanofiber mat and the Nafion-
tion of the silica sol that might cause solidification, a drying impregnated SiO2/SPEEK nanofiber composite membrane
control chemical additive (e.g., DMF) was added [26]. A were flexible and easy to handle.
silica sol solution with viscosity in the range of 170–200 cP
was successfully electrospun (see Fig. 1b). The mixture of
SPEEK solution and silica sol with 40/60 SiO2/SPEEK
weight ratio was also electrospun successfully. Silica load-
ing in the nanofibers was increased to a maximum electro-
spinnable content to increase the hygroscopic property of
the resulting nanofiber mat. It was found empirically that
40 wt% SiO2 content was a limit. The solutions with higher
than 40 % content of silica sol underwent severe phase
separation and electrospinning of such solutions was
unsuccessful due to droplet formation. Figure 1c–d shows
the surface of electrospun SiO2/SPEEK (40/60 w/w) com-
posite nanofiber mat and its fiber diameter distribution. The
nanofiber mat consists of bead- and droplet-free nanofibers
with fiber diameters in the range of between 180 and 367 nm
and an average fiber diameter of 232 nm. Since the elec-
trospun nanofiber mat was highly porous (porosity [
90 %), the inter-fiber pores were successfully filled with
Nafion ionomer to prepare a dense membrane film. Figure 2
shows that the inter-fiber void spaces were completely Fig. 3 FTIR spectra of the PEEK, SPEEK, and SiO2/SPEEK
filled by Nafion ionomer. The good adhesion between the nanofiber mat

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Table 1 Membrane swelling in water overlapped with the peak associated with the symmetric
Membrane Gravimetric Linear
O=S=O stretching (1077 cm-1) of sulfonyl groups but the
swellinga (%) swellingb (%) peak was much larger than the corresponding peak of the
SPEEK alone sample. The characteristic peaks of both SiO2
Nafion-impregnated SiO2/SPEEK 26.4 ± 1.1 \3.3
and SPEEK proved the presence of both SiO2 and SPEEK in
Recast Nafion 13.9 ± 0.5 13.3 ± 6.7 the electrospun composite nanofiber mat.
SPEEK film 21.7 ± 2.3 160 ± 20
a
Measured at 25 °C Water uptake and proton conductivity
b
Measured at 70 °C
The gravimetric water uptake of the Nafion-impregnated
SiO2/SPEEK nanofiber membrane was 26.4 % in water at
room temperature which was higher than the water uptake
of recast Nafion and SPEEK film at the same condition as
shown in Table 1. This indicated that the dispersed silica
component contributed to attracting more water inside the
Nafion-impregnated SiO2/SPEEK nanofiber membrane
compared to pristine films without additives due to strong
bonding of water to silica. Linear swelling of the mem-
branes behaved differently from the gravimetric swelling.
While negligible length change (\3.3 %) in either x- or
y-axis of the Nafion-impregnated SiO2/SPEEK nanofiber
membrane was observed, the linear swelling of Nafion and
SPEEK was 13.3 and 160 % in x- and y-axes, respectively.
This was expected since the nanofiber skeleton held the
Fig. 4 Proton conductivity of the Nafion-impregnated SiO2/SPEEK structure together and prevent size increases by the swell-
composite nanofiber membrane, recast Nafion and SPEEK film at ing force of the matrix polymer. Although the nanofiber
a 75 °C and 100 % RH, b 90 °C and 100 % RH, c 110 °C and 60 % structure occupied only 11.8 wt% in the entire membrane,
RH, and d 120 °C and 40 % RH
it provided enough strength to repel the swelling force of
the matrix polymer. The proton conductivity of the com-
FTIR posite membrane under different temperatures and relative
humidities is shown in Fig. 4. The composite membrane
The FTIR spectra of PEEK, SPEEK, and SiO2/SPEEK are exhibited a maximum proton conductivity of approxi-
shown in Fig. 3. Differences in IR spectrum of sulfonated mately 0.077 S/cm at 90 °C and 100 % RH. For all
PEEK compared to un-modified PEEK confirmed the membranes, increasing temperature above 90 °C signifi-
presence of sulfonyl groups in SPEEK. The peak of pure cantly decreased their proton conductivity. The proton
PEEK identified at 1492 cm-1 proved the presence of C–C conductivity of the composite membrane was higher than
aromatic ring [27] and the peak intensity was decreased and that of recast Nafion or SPEEK film at all four testing
the peak was observed to split into two absorption bands at conditions: 75 °C/100 % RH, 90 °C/100 % RH, 110 °C/
1490 and 1472 cm-1 for SPEEK [28, 29]. In addition, 60 % RH, 120 °C/40 % RH. It should be noted that
compared to pure PEEK, new absorption peaks for SPEEK SPEEK film was already unstable at higher temperatures
observed at 1024, 1077, and 1251 cm-1 indicated the sul- and lower humidity conditions (at 110 °C/60 % RH and
fonic acid groups in SPEEK. The three characteristic peaks 120 °C/40 % RH) so the proton conductivity was not
of the sulfonyl groups were assigned to asymmetric O=S=O measured.
stretching, symmetric O=S=O stretching, and S=O stretch-
ing, respectively [29, 30]. The characteristic peaks of sul- Single cell performance
fonated PEEK were also observed for the SiO2/SPEEK
composite nanofiber mat that proved the presence of Polarization curves of single cells with the Nafion-
SPEEK. Besides, the peaks at 446 and 950 cm-1 corre- impregnated SiO2/SPEEK composite nanofiber membrane,
sponded to the characteristic peaks of silica. The peaks recast Nafion and SPEEK film were recorded under dif-
observed at 446 and 950 cm-1 were attributed to the ferent testing conditions; (i) 75 °C and 100 % RH, (ii)
bending and linear stretching of Si–O–Si, respectively [31, 90 °C and 100 % RH, (iii) 110 °C and 60 % RH, and (iv)
32]. A peak for asymmetric stretching vibration of Si–O–Si 120 °C and 40 % RH (from the mildest to the most harsh
was also expected to be observed at 1075 cm-1 and the peak conditions). As shown in Fig. 5, at 75 and 90 °C, and fully

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Fig. 5 Polarization curves of

the Nafion-impregnated SiO2/
SPEEK composite nanofiber
membrane, recast Nafion and
SPEEK film at a 75 °C and
100 % RH, b 90 °C and 100 %
RH, c 110 °C and 60 % RH,
and d 120 °C and 40 % RH

Fig. 6 Power density curves of

the Nafion-impregnated SiO2/
SPEEK composite nenofiber
membrane, recast Nafion and
SPEEK film at a 75 °C and
100 % RH, b 90 °C and 100 %
RH, c 110 °C and 60 % RH,
and d 120 °C and 40 % RH

humidified condition (100 % RH), the nanofiber composite recast Nafion was only half that of the Nafion-impregnated
membrane performed slightly better than recast Nafion and SiO2/SPEEK composite nanofiber membrane. The poor
SPEEK film. At 90 °C, all three samples had similar performance of SPEEK film was attributed to the thermal
polarization. At higher temperatures and lower humidity, and hydrolytic instability of the membrane. The maximum
the performance difference was significant. The maximum power density of the nanofiber composite membrane was
current density that SPEEK film drew was only 0.1 A/cm2 170 mW/cm2 compared to 71 mW/cm2 for recast Nafion
at 110 °C and 60 % RH. At 120 °C and 40 % RH, the (see Fig. 6). The performance improvement of SiO2/
SPEEK film failed and the maximum current density of SPEEK nanofiber structured Nafion membrane over recast

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Nafion or SPEEK film was significant at high temperature Government (MEST) (NRF-2009-C1AAA001-2009-0092926) and
and low humidity operating conditions due to better water CSIRO, Advanced Materials Theme, Australia.
retention capability of well-distributed silica and the rein-
forcing effect of nanofiber mat as a structural support.
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