Journal of Power Sources 294 (2015) 347e353

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Journal of Power Sources

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

Inuence of variously functionalized SBA-15 llers on conductivity

and electrochemical properties of PBI composite membranes for high
temperature polymer fuel cells
S. Angioni, D.C. Villa, A.S. Cattaneo, P. Mustarelli, E. Quartarone*
Dept. of Chemistry and INSTM, University of Pavia, Via Taramelli 16, 27100 Pavia, Italy

h i g h l i g h t s

The effectiveness of SBA-15 functionalization in optimising PBI composites was studied.

The hybrid llers do not improve the PBI properties with respect to pure SBA-15.

Encouraging MEA results (>320 mW cm2) were obtained for membranes with pure SBA-15.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 9 March 2015
Received in revised form
29 May 2015
Accepted 16 June 2015
Available online xxx

The use of inorganic llers is an interesting strategy to improve the electrochemical performances of PBI
membranes for application as electrolytes in HT-PEMFCs. Here, we prepared several mesoporous silica
(SBA-15) based hybrids, functionalised with different moieties, namely acidic (SO3H-), basic (NH2-), and
amphoteric (SO3H-NH2) units. The electrochemical properties of the resulting electrolytes were investigated in terms of proton transport and functional tests by varying the silica functionalization degree in
the range 10e70 mol%, as well as the particles loading in the polymer (0e30 wt%). The actual effectiveness of the SBA-15 functionalization process in improving the electrolyte properties was compared
with both the unlled membrane and the one lled with pristine SBA-15. The best conductivity (~90 mS
cm1 at 120  C, 30%RH) was obtained with PBI composites loaded with 30 wt% of non-functionalized
SBA-15. The use of llers functionalized with acidic, basic of amphoteric groups did not lead to improvements with respect to pure SBA-15. This could be related to the set up of signicant interactions
between the functionalised llers and H3PO4, which negatively inuence the proton mobility. Encouraging MEA results (power peak >320 mW cm2) were obtained in case of membranes based on pure
SBA-15. These performances make the SBA-15/PBI composites particularly interesting for application in
HT-PEMFCs.
2015 Elsevier B.V. All rights reserved.

Keywords:
HT-PEMFC
Polybenzimidazole
Composite membranes
SBA-15
Organiceinorganic hybrids

1. Introduction
The current PEMFC technology deals with two types of devices,
low-temperature (LT, 80e120  C) and high temperature (HT, higher
than 120  C) ones, which differ for operating temperatures, type of
electrolyte and electro-catalyst loadings [1,2]. HT-polymer fuel cells
exhibit several advantages in terms of higher tolerance towards
impurities (e.g. CO) and absence of water management [3,4]. From
this point of view, H3PO4-doped polybenzimidazoles (PBI)

* Corresponding author.
E-mail address: eliana.quartarone@unipv.it (E. Quartarone).
http://dx.doi.org/10.1016/j.jpowsour.2015.06.096
0378-7753/ 2015 Elsevier B.V. All rights reserved.

membranes likely are the best candidates as electrolytes for HTPEMFCs, due to a number of positive aspects including excellent
thermal stability, low gas permeability and good proton transport
above 150  C [5e7].
In spite of the interesting benets shown by PBI-based membranes in terms of proton transport, some important questions are
still open and further improvements are desirable, mainly from the
durability point of view (e.g. cracks and pinhole formation, chemical degradation in highly oxidative environment, worsening of
mechanical properties, loss of dopant). In fact, conductivity comparable to that one generally observed for Naon-based systems
(about 0.1 S cm1 at RH>80% and T~80e90  C) is possible only at
high doping levels and in particular in presence of free acid.

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S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

Unfortunately, too large acid amounts lead to issues severely

limiting the cell long-term stability. The leaching out of phosphoric
acid (PA), for instance, leads to dramatic drops in conductivity and
membrane degradation [8], whereas its redistribution in the whole
system (MEA and bipolar plates, BPP) causes acid adsorption of Pt
catalytic active sites in the CL as well as corrosion phenomena of
BPPs and the other components, as GDL, MPL and CL [9].
In order to improve the membrane functional stability, several
strategies were deeply discussed in literature in the recent years.
One interesting approach is to ensure an efcient proton transport,
also in presence of lower amount of PA, by dispersing into the PBI
matrices properly designed llers, which include nanoscale and/or
mesoporous inorganic particles, eventually functionalised [5,10,11].
PBI composite membranes show increased proton conductivity, at
the same time maintaining good mechanical resistance and
chemical stability [12]. From the point of view of the proton
transport, the llers may be passive, i.e. inert towards the ions
motion, or active when containing chemical moieties involved in
the transport mechanisms. In case of PBI composites, the llers can
improve: i) ionic conductivity by increasing the amount of the
doping acid in the PBI membrane, and ii) long-term durability by
reducing the acid leaching. Several materials were checked to this
aim, including micrometric TiO2 [13,14], BPO4 [15], titano-silicates
[16], and silicas with various microstructure and morphology
[10,11,17]. Concerning the long-term stability, hybrid silica, properly
functionalised, for instance with imidazole units, or coated by
zwitterion moieties, showed benecial effects as far as concerns
acid retention capacity of the composite, as well as the permanent
conductivity [18e20]. Due to the large availability of precursors,
silica-based organic-inorganic llers can be easily obtained by
solegel methods with well-tailored physical and chemical properties [21].
Here, we systematically compare the proton conductivity, the
H3PO4 doping level and the functional performances of various PBI
composite membranes, obtained by dispersing different hybrid
silica llers functionalised with acidic, basic and amphoteric units.
The target of the work is to investigate the inuence of the ller
functional groups on the membrane electrochemical properties. To
this aim, various SBA-15 based systems were derivatized with the
following functional moieties: i) R-SO3H; ii) R-NH2; iii) R-SO3H-NH2
amphoteric units, and dispersed in PBI matrices in a compositional
range between 0 and 30 wt%. The membranes were characterised
in terms of proton conductivity, MEA performances and H2
permeability. Similar PBI composites based on pristine SBA-15 were
also discussed for the sake of comparison.

discussed as a comparison. The chosen polymer matrix was poly2,20 -(2,6-pyridine)-5,50 -bibenzimidazole, sketched in Scheme 1
and labelled in the following as PBI_5N (MWav 93000 gmol1
I.V. 1.7 dlg1). Both polymer synthesis and characterization were
previously reported by our group [22].
Concerning the llers, SBA-15-based silica with 3 different types
of functionalization moieties were obtained: i) sulfonic groups; ii)
amino groups; iii) SO3H-NH2 amphoteric ones, as reported in
Scheme 2.
2.1. Synthesis of SBA-15 based llers
Mesoporous SBA-15 silica was synthesized by means of a
template-based solegel procedure, as described by Zhao in 1998
(see Scheme 3) [23]. A proper amount of the template agent,
Pluronic 123, was dissolved in HCl and heated at 40  C. Tetraethylorthosilicate (TEOS) was added, and the mixture was rst
maintained at 40  C for 20 h under stirring, then was aged at 100  C
for 24 h under static conditions in a sealed vessel. The obtained
solid product was ltered, washed with distilled water and nally
with ethanol. In order to remove the template, a calcination step
was performed at 550  C for 6 h in air.
The hybrid SBA-15 type silicas were synthesized by a one-step
process involving the co-condensation of TEOS and the proper
organic precursor (SO3H: 3-mercapto-propyltriethoxysilane; NH2:
3-amino-propyltrimethoxysilane) in presence of the Pluronic 123
template. In the particular case of sulfonic-based SBA-15, a suitable
oxidizing agent (H2O2), was also used, as already reported in the
literature [24]. Functionalization degrees (X) ranging between 10
and 70 SO3H mol% were obtained in the case of SBA-15:SO3H systems, whereas only the composition with X 10 mol% was chosen
for the other llers.
2.2. Preparation of the composite membranes
PBI-composite homogeneous lms were produced by means of
a spraying technique, as recently reported [25]. A proper amount of
polymer powder was dissolved in a sealed ask at 120  C in a DMA/

2. Experimental details
Different PBI-based composite membranes were prepared by
dispersing SBA-15 particles, functionalized with different organic
groups, in a compositional range between 0 and 30 wt%. Composites obtained by adding similar amounts of pristine SBA-15 are also

Scheme 1. Chemical structure of poly-2,20 -(2,6-pyridine)-5,50 -bibenzimidazole.

Scheme 2. Functionalized SBA-15 silica llers.

S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

Scheme 3. Synthesis of hexagonal mesoporous SBA-15 silica.

sec-butylamine (8:2) solution (2 wpol/wsol %). Various amounts of

ller were added, in the range 0e30 % w/w with respect to the
pristine polymer, and the mixture was sonicated for 1/2 h. The
suspension was nally sprayed under N2 ux onto a hot plate (150
 C) in a ventilated home-made chamber. The obtained lm was
peeled out from the cooled plate and washed in deionized water
overnight. Film thickness of about 50 mm was obtained, with
thickness homogeneity of about 98%.
The composite membranes were then doped in a phosphoric
acid (PA) solution (70% w/w) for 24 h and dried at 110  C for 2 h. The
doping level (DL) was calculated as in the following equation (1):

DL%

Wp  Wd
 100
Wd

(1)

where Wp and Wd are the weights of the doped and undoped

membranes, respectively. The resulting values were compared with
those measured by titrating the doped membranes with a NaOH
solution. Differences in DL of about 10% were found, which are
likely related to water adsorption.
2.3. Characterization
N2 adsorption/desorption isotherms were obtained by means of
a Thermo Electron Sorptomatic 1990 instrument on mesoporous
llers previously treated at 150  C under vacuum (103/104 atm)
for 8 h. Adsorption data were analysed by the conventional Brunauer, Emmett and Teller (BET) method [26], whereas desorption
data were treated by means of Barrett, Joyner and Halenda (BJH)
approach, in order to analyse the pore size distributions and specic pore volume even in case of larger pores (up to 300 nm).
Transmission electron microscopy (TEM) experiments were
carried out with an FEI G2 20 HR-TEM instrument equipped with a
LaB6 electron beam source and two 2D at cameras (low resolution
and high resolution) at 200 kV e-beam acceleration. Samples were
suspended in hexane in ultrasonic bath (5 cycles of 15 min of ultrasonic treatment followed by 45 min of rest to cool down the
sample and thus avoid thermal heating), and dispersed on copper
holey carbon lm grids for observation. Image analyses were carried out by using the ImageJ software.
The proton conductivity was measured by means of the
impedance spectroscopy technique, using a frequency response
analyser (FRA Solartron 1255), connected to an electrochemical
interface (Solartron 1287), over the frequency range 1 Hze1 MHz at
a voltage of 100 mV. The membrane was xed to a four-points
BekkTech conductivity cell, connected to the test stand BekkTech
411 for the humidity and temperature control. The impedance
scans were performed at 120  C ranging from 0 to 70% R.H. with a
cell back-pressure of 2.5 bar. The lms were allowed to equilibrate 1
h at each moisture level before of the measurements. The impedance spectra were tted with the ZView 3.0 software (Scribner

349

Associates, Inc.).
The membrane electrode assemblies (MEAs) were prepared by
hot pressing two gas diffusion electrodes (GDE HT-ELAT, ETek) at
130  C and 1 ton for 10 min. The Pt loading was 0.5 mg cm2 at both
the electrodes. The cell active area was 5 cm2. The electrochemical
measurements were performed at 150  C with a BT-552 Membrane
Conductivity & Single Cell Fuel Cell Test System (BekkTech LLC). The
cell was operated at ambient pressure without external humidication of the feed gas steams. In some cases an overpressure was
imposed to the cell. The H2 and air ow rates were 70 sccm and 300
sccm, respectively.
Linear Sweep voltammetry between 0 and 0.7 V (scan rate: 1 mV
s1) was employed to monitor the Hydrogen crossover rate across
the membrane. During the measurement, the cathode gas ow was
switched from air to nitrogen, with a ow rate of 400 sccm at 1 bar,
whereas the anode hydrogen ow was set at 200 sccm at the same
pressure. The anode was taken as both counter and reference
electrode, whereas the cathode served as the working one. The
steady-state current, related to the H2 oxidation, was measured as
an indication of the hydrogen crossover rate by carrying out
potentiostatic assessments at the voltage plateau (0.3 V) for 15 min
at each temperature.

3. Results and discussions

3.1. The llers
As already stated in the previous section, samples of SBA-15
type silica modied with different groups were prepared by
means of a one-step synthesis by varying the nominal molar fraction, X, between 10 and 70 mol% in the case of SO3H moieties, and
by xing it at 10 mol% for what concerns the other chemical moieties (-NH2 and -SO3H-NH2). The molar ratio, X, is dened as the
molar fraction of the silane precursor with respect to the total
amount of condensation co-reagents, as in the following equation
(Eq. (2)):

X%

nsilane
nsilane nTEOS

(2)

The content of the functionalizing groups effectively incorporated into the silica network was determined through the analysis
of the 29Si NMR spectra, thermogravimetry data, surface charge
measurements and FTIR/Raman spectra, as previously discussed
[27]. A fair agreement with the nominal ones (average discrepancy
~16%) was found, which conrmed that the synthetic process was
successful even for high functionalization degrees.
Table 1 compares the mesostructural properties of the SBA-15
based materials, investigated by collecting their physisorption
data by means of the nitrogen adsorption isotherms. The pores
distribution of pure SBA-15 ller is mono-modal with a maximum
Table 1
Microstructural parameters of the functionalized samples: BET surface area (S), pore
volume (Vp) and pore size (dp,BJH) of the distribution maxima obtained from nitrogen
adsorption measurements.
Sample

-SO3H mol%

S (m2/g)

Vp (cm3/g)

dp,BJH ()

SBA-15
SO3H10%
SO3H20%
SO3H50%

e
10
20
50

744
736
707
600

1.4
1.0
0.95
0.79

SO3H70%
NH210%
NH2-SO3H10%

70
10
10

199
740
721

0.39
0.99
0.97

65
50
40
40, n
120, w
40, n
50
50

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S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

at about 65 . In the case of sulphonic-based llers, pores size

decreases down to 40 with the increase of functionalization degree. For SO3H50% ller a bimodal distribution is observed, which is
characterized by a narrow (n) peak centred between 3 and 5 nm
and by a wide (w) peak between 9.5 and 13.5 nm. The shrinking of
the silica pore dimensions also results in a gradual reduction of
both BET specic surface area and total pore volume, as reported in
Table 1, which denitively indicates an important reduction of the
mesoporous signature of samples with a functionalization degree
higher than 20 mol%. The SBA-15 llers functionalized with 10% of
basic and amphoteric groups displayed values similar to that of the
acidic one.
The mesoporous nature of the SBA-based llers was also
checked by means of TEM analysis. Fig. 1 shows as an example the
transmission electron micrographs of the both SBA-15 and functionalized with 10 mol% of SO3H. As expected, the pristine SBA-15
material shows a well dened and ordered mesoporosity with
highly parallel channels, as shown in Fig. 1a. The estimated wall
thickness and pore diameter are 31 10 and 55 5 , respectively.
Low magnication TEM images (not shown here), suggest irregular
round-like primary particles of approximately 300e500 nm in
diameter with regular linear channels extended along the entire
particle. The SO3H10% sample still shows an ordered mesoporosity
in the core of the primary particles, whereas their surfaces result to
be more defective. Similar morphological images and results were
obtained in case of NH210% and amphoteric units.
3.2. The PBI-based composites: effect of the ller functionalization
degree
In order to investigate the effect of increasing the molar content
of the organic moieties on the functional properties of the PBI_5N
electrolytes, composite membranes were prepared by dispersing
proper amounts of SBA-15:SO3H X% in the polymer, with X ranging
between 10 and 70 mol%. The results obtained for the electrolytes
lled with pristine SBA-15 (X 0) are also reported for the sake of
comparison. Fig. 2 shows the behaviour of the PA doping level,
determined as described above, as a function of X for three composite membranes at different ller concentrations (10e50 wt%).
As a general consideration, the addition of the pure SBA-15 ller
allows increasing the acid uptake of the PBI membranes. The unlled system, in fact, shows DL values of about 100 wt% [25],
whereas acid concentrations in the range 125e150 wt% were obtained for composites prepared with different amounts of pure
SBA-15. Independently on the ller concentration in the composite,
the acid uptake also increases with the number of SO3H in the
mesoporous backbone. Such an effect is particularly evident in case
of membranes lled with 10 wt% of silica, where DL values increase

Fig. 1. TEM images of SBA-15 (a) and SO3H10% (b) llers.

Fig. 2. Acid uptake vs. the functionalization degree, X, of PBI-based composite membranes lled with different amounts of SBA-15:Xmol% SO3H.

of about 13% in the range of functionalization degree, X. However,

this behaviour is not monotonous and a decrease is always
observed at 70 wt% of functionalization. As already observed in case
of sulphonated oxy-PBI, too large amounts of SO3H- moieties,
deriving: i) from the increase of the functionalization degree, X,
and/or ii) X being equal, from an enhancement of the ller concentration in the composite, bring to lower acid uptakes [28,29].
This phenomenon was interpreted in terms of intra/interchain interactions between the acid sites coming from the sulphonic groups
and the basic ones, namely the imidazole units in the polymer
framework, which make the nitrogen moieties less available for the
acid dissociation.
The interplay between sulphonation degree and acid uptake is
expected to inuence in the proton transport behaviour of the PBIbased composites. Fig. 3 reports the proton conductivity of the

Fig. 3. Proton Conductivity at 120  C vs. the functionalization degree, X, of PBI-based

composite membranes lled with different concentration of the hybrid systems SBA15:Xmol% SO3H.

S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

membranes reported in Fig. 2 vs. the SO3H concentration in SBA-15,

measured at 120  C and at 30 and 50 RH%, which is an interesting
humidity range for automotive applications [30]. As expected from
the DL results, the proton conductivity generally decreases as X
increases. In case of the composite membranes with 30wt% of ller,
in particular, a sort of threshold may be observed above X 10 mol
% SO3H. Higher amounts of the acid moiety then result in reduced
conductivity and this phenomenon, again, may recall a bridging
arrangement of the SO3H groups between the polymer and H3PO4
molecules inhibiting to some extent the PA-PBI interactions, which
are expected to trigger the proton mobility [29].
However, an interesting result here is that high conductivity
values are observed for membranes lled with SBA-15, both pure
and functionalised up to 10 mol% of SO3H- units. In particular,
values exceeding 70 mS cm1 and 120 mS cm1 were found at 120
 C and RH 30% and 50% for the two composites, respectively. The
PBI_5N:30wt% SBA-15:10 mol%SO3H electrolyte represents a
maximum in the curve obtained by plotting the proton conductivity of the system PBI_5N:SBA-15:10 mol% SO3H against the ller
content, as reported in Fig. 4.
The observed maxima of these non-monotonous behaviours are
typical of (nano)composite electrolytes [10,11] and are interpreted
in terms of optimal composition with the best polymer/ller
interface providing favourable pathways for the proton hopping. At
higher contents, dilution effects occur and the ller acts as a
physical barrier for the H migration. Here, the maxima do correspond to an enhancement of the composite conductivity of about
40% and 29% with respect those found for the unlled PBI_5N
membrane at RH 30% and 50%, respectively. Quite lower proton
conductivity values are generally reported in literature at 120  C for
PBI-based membranes, both unlled as well as composites [5],
which make the present materials particularly appealing as electrolytes for PEMFCs working at temperature lower than those
typically reported for the acid-doped polybenzimidazoles (above
160  C).

Fig. 4. Proton conductivity at 120

based composite membranes.

C

vs. SBA-15:Xmol% SO3H loading content of PBI-

351

3.3. The PBI-based composites: effect of the ller chemical nature

As already stated in the Introduction, in order to address the
inuence of the acidity/basicity of silica active llers on the proton
transport of PBI composites, hybrid materials with different organic
side chains were explored. By considering the results obtained for
the system SBA-15:XSO3H, llers containing only 10 mol% of
functional moieties were used in case of basic SBA-15:NH2 and
amphoteric SBA-15:SO3H/NH2 hybrids. Fig. 5 compares the doping
levels and the proton conductivity at 120  C and RH 30% obtained
for the PBI-composite membranes, lled with 30 wt% of pure SBA15 (F) and of the different hybrids, functionalized with 10 mol% of
organic moieties (F-SO3H, F-NH2, F-AMPH). The values measured
for the unlled membrane (UF) are also reported for the sake of
comparison. This experimental set-up (in terms of RH and T) was
chosen in order to directly compare such membranes with Naonbased systems working in similar conditions and also to test the PBI
composites through an operating protocol closer to the automotive
one. Concerning the acid uptake, the presence of the ller slightly
improves the polymer afnity towards the acid, likely due to an
increase of the system hydrophilicity. The best enhancement with
respect to the unlled membrane (about 20%) is obtained by using
the SO3H based ller (F-SO3H).
In contrast, more relevant differences may be observed for what
concerns the proton transport, when the ller composition is
changed. Except for the amphoteric one, the presence of llers
brings to conductivity improvements with respect to the unlled
electrolyte. In particular, by comparing the systems including the
acidic and basic units in the ller, the SO3H-based composite (FSO3H) shows higher conductivity than the NH2-based one (F-NH2).
However, the best performances in terms of transport are showed
by the PBI composite lled with pure SBA-15 (F), which displays a
proton conductivity of about 90 mS cm1 at 120  C and RH 30%.
This suggests that functionalising llers with acid or basic units
may favour interactions among the hybrid material, the polymer
matrix and the phosphoric acid, which reduce to some extent the
proton mobility. In the case of SBA-15:NH2 (F-NH2), for instance,
the protonation due to the doping with PA would likely lead to the
formation of NH3-moieties whose acidity is mild and not enough to
support the proton motion via the typical Grotthuss mechanism.
By taking into account such results, we can conclude that
tailoring of the hybrid ller is a crucial point in the optimization of
the membrane proton transport. The organic modication of the

Fig. 5. Acid uptake (grey bars) and proton conductivity (black bars) at RH 30% and T
120  C of unlled PBI (UF) and PBI composite membranes lled with 30 wt% of SBA15 (F) and with differently functionalised SBA-15 hybrids (functionalization degree, X
10 mol%).

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S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

inorganic materials is not ever a winning strategy to improve the

functional properties of the electrolytes. In case of the mesoporous
systems investigated in the present work, in fact, the best performances are observed by using unmodied SBA-15 ller, which may
be dispersed in the polymer, even with high loadings, to obtain high
conductivity values at temperatures lower than those generally
used for PBI-based fuel cells [25]. Functionalized llers seem to be
successful only if they do not alter the sensitive acid/base equilibrium, which makes the PBI systems suitable as proton conductors,
as recently demonstrated for composite lled with imidazolebased SiO2 [19]. The derivatizing moieties should, in fact, be
properly modulated in order to actually assist the H migration via
Grotthuss mechanism without interfering with the PA dissociation
and without blocking favourable inter-chain interactions with the
protons. Solid-state NMR studies on these composite membranes
are now in progress to address such mechanisms, and will be object
of a forthcoming paper.

3.4. The MEA functional performances

The electrochemical properties of the composite membranes
were also investigated by means of functional tests on cells
assembled with commercial GDEs at 150  C and without any
external humidication, as described in the experimental section.
The composite membrane with the amphoteric ller was not
considered due to its low proton conductivity. Fig. 6 compares the
polarization curves of MEAs based on composite membranes, lled
with pure SBA-15 (F) and acid (F50%SO3H and F10%SO3H) and basic
hybrids (F-10%NH2), with that one obtained by using unlled
PBI_5N as the electrolyte (UF). Open circuit voltages, OCV, higher
than 0.9 V and comparable electrochemical performances of about
550e600 mV were obtained for each tested cell at 200 mA cm2.
Remarkable differences were, in contrast, found in the activation
region (300e600 mA cm2) where the charge transfer through the
interface occurs. In particular, lower voltage were obtained in case
of MEAs based on composite systems including the basic ller (F10%NH2) and the acid ones with the highest functionalization degree (F-50%SO3H). Such different cell behaviour may be likely
related to both nature and amount of grafting chains in the silica
backbone, which could play a disturbing effect at some level on the

Fig. 6. Polarization curves of MEAs based on both unlled PBI (UF) and composite
membranes lled with 30 wt% of SBA-15 (F) and of functionalised SBA-15, collected at
150  C without any external humidication.

electrode components. Impedance spectra, not shown here, performed on the same MEAs reported in Fig. 6, show, in fact, higher
resistance semicircles in case of cells based on F-10NH2 and F-50%
SO3H membranes. A denitive explanation is not easy at this stage
and further investigations are in progress to better address this
point.
Also the cell power peaks seem to be greatly affected by the
membrane. In case of MEAs prepared by both unlled (UF) and pure
SBA-15 (F) based membranes, power densities exceeding 300 mW
cm2 were easily obtained. In the case of electrolytes containing
functionalised silica, the electrochemical performances drastically
worsen giving low power maxima, in particular when SBA-15:NH2
ller (F-10%NH2) was used (<200 mW cm2). Also the use of highly
functionalized SBA-15:SO3H (X 50 mol%) (F-50%SO3H) led to bad
results. Such behaviour well reects what we already observed for
proton conductivity.
The effects of the llers on the membrane selectivity, e.g. the
presence of cracks or pinholes eventually caused by the dispersion
of the particles, was checked by measuring the H2 permeability,
which is a key parameter in the test protocols for the evaluation of
the cell durability [31,32]. Fig. 7 shows the gas permeation coefcients, kH2, of the sprayed composite membranes, based on pure
SBA-15 (F) and SBA-15:XSO3H with X 10 (F-10%SO3H) and 50 mol
% (S-50%SO3H), measured in the temperature range 70 e150  C. As
expected, a linear trend is observed for each electrolyte. Contrary to
the composite lled with silica including the highest SO3H content
(X 50 mol%), whose permeability is remarkably higher (about 4 
1015 mol cm1 s1 Pa1), kH2 values of ~1.5  1015 mol cm1 s1
Pa1 at 150  C are determined for all the composite membranes.
These values are comparable to what found for the unlled systems
(UF) (namely 1.54  1015 mol cm1 s1 Pa1 at 150  C) and they
are also remarkably lower than those ones recently obtained by Li.
et al. in case of PBI lled by organically-modied clays [33]. This
suggests that the presence of well-distributed llers in composite
membranes does preserve the low gas permeability typical of the
PBI-based membranes.
The activation energies, Ea.H2, for hydrogen permeation were
estimated to be 7 kJ mol1 in case of SBA-15 (F), 12.2 and 15.7 kJ
mol1 for SBA-15:XSO3H with X 10 (F-10%SO3H) and 50 mol% (S50%SO3H), respectively, and 10 kJ mol1 for the unlled system
(UF). Higher Ea.H2 of about 21 kJ mol1 were reported for Naon
membranes in the temperature range between 25 and 80  C under

Fig. 7. Arrhenius behaviour of the hydrogen permeability coefcients for both unlled
PBI (UF) and composite membranes lled with 30 wt% of SBA-15 (F) and of SBA15:XSO3H.

S. Angioni et al. / Journal of Power Sources 294 (2015) 347e353

fuel cells conditions [32].

4. Conclusions
Several PBI-based composite membranes were produced as
electrolytes for HT-PEMFCs by properly dispersing dened amounts
of pure and hybrid SBA-15 particles, functionalized with different
organic moieties, acid (SO3H), basic (NH2) and amphoteric (NH2SO3H). The inuence of key factors such as the chemical nature of
the derivatizing units, the SBA-15 functionalization degree, X, and
the ller amount in the polymer on the functional properties of the
composites were investigated by means of conductivity measurements and in situ electrochemical tests. By comparing the unlled
membrane with the composite ones, the following concluding remarks may be outlined: i) with respect to the unlled PBI electrolyte, the composite systems show higher PA doping level and
improved proton transport, in particular at ller loading of about
30wt%; ii) functionalization levels, X, higher than 10 mol% cause the
membrane proton conductivity to decrease; iii) SBA-15 modication by using acid or basic moieties, namely amines and sulfonic
groups, leads to not satisfying results for what concerns the
membrane electrochemical performances, if compared to what
observed for pure SBA-15 based membranes. The highest proton
conductivity was obtained for the composite PBI-30wt%SBA-15,
which showed values exceeding 90 mS cm1 at 120  C and 30 RH
%. MEAs based on such membrane showed electrochemical performances of about 0.6 mV at 200 mA cm2 and power peak of 320
mW cm2.
Acknowledgements
This work was done in the frame of the project nanced by
Italian Ministry of University and Research (MIUR) (PRIN 2010,
2010CYTWAW). The authors are also grateful to Dr. Sergio Brutti
(University of Basilicata, Italy) and Dr. Stefania Grandi (University of
Pavia, Italy) for the TEM analysis and N2 isotherms on the SBA-15
llers, respectively.
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