Nafion?⁄?

TiO2 Proton Conductive Composite Membranes for

PEMFCs Operating at Elevated Temperature and Reduced Relative
Humidity
Elena Chalkova, Michael B. Pague, Mark V. Fedkin, David J. Wesolowski and Serguei N. Lvov

J. Electrochem. Soc. 2005, Volume 152, Issue 6, Pages A1035-A1040.

doi: 10.1149/1.1895225

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 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲 A1035
0013-4651/2005/152共6兲/A1035/6/$7.00 © The Electrochemical Society, Inc.

Nafion/TiO2 Proton Conductive Composite Membranes

for PEMFCs Operating at Elevated Temperature
and Reduced Relative Humidity
Elena Chalkova,a Michael B. Pague,a,b Mark V. Fedkin,a David J. Wesolowski,c
and Serguei N. Lvova,b,*,z
a
The Energy Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
b
Department of Energy and Geo-Environmental Engineering, The Pennsylvania State University,
University Park, Pennsylvania 16802, USA
c
Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

Nafion/TiO2 composite membranes with different TiO2 contents were studied in an H2 /O2 proton exchange membrane fuel cell
共PEMFC兲 over a wide range of relative humidity 共RH兲 values from 26 to 100% at temperatures of 80 and 120°C. The composite
membranes, which were prepared using a recast procedure, showed a pronounced improvement over unmodified Nafion mem-
branes when operated at 120°C and reduced RH. For instance, at 50% RH, the Nafion/20% TiO2 membrane demonstrated a
performance identical to that of an unmodified Nafion membrane operated at 100% RH. This performance level was comparable
to that of a bare Nafion membrane at 80°C. The high performance of the Nafion/TiO2 composite membranes at low RH was
attributed to improved water retention due to the presence of absorbed water species in the electrical double layer on the TiO2
surface. The zeta potential and thickness of the hydrodynamically immobile water layer at the TiO2 /water interface were discussed
as parameters influencing the water balance in the membranes. The obtained experimental PEMFC performance data were fitted
using an analytical equation, and calculated parameters were analyzed as functions of RH and TiO2 content in the composite
membranes.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.1895225兴 All rights reserved.

Manuscript submitted May 6, 2004; revised manuscript received September 11, 2004. Available electronically April 21, 2005.

Proton exchange membrane fuel cells 共PEMFCs兲 are a promising
clean energy source for transportation and small-scale stationary
power generation. The current PEMFC technology is based on using
perfluorosulfonic acid polymer membranes 共Nafion兲 operating at
80°C. The operation of PEMFCs at elevated temperatures can sig-
nificantly reduce CO poisoning of the electrode catalysts and the
need for noble metal catalysts. Increasing the operating temperature
would also enhance the electrode reaction kinetics and, conse-
quently, boost the fuel cell efficiency. It would also make the cooling
system for the stack significantly simpler. At the same time, opera-
tion of a PEMFC at elevated temperature presents a challenge for
membrane development, as the membrane material should be ca-
pable of maintaining proper hydration when the water evaporation
rate is high. Nafion membranes experience severe dehydration at
temperatures above 100°C, resulting in a decrease of conductivity
and overall fuel cell efficiency. Significant efforts have been made to
modify Nafion to achieve suitable operation at elevated tempera-
tures. One of the approaches is the incorporation of bifunctional
inorganic particles, which are both hydroscopic and proton conduc-
tive, into the membrane. Good examples of such hydrophilic mate-
rials are framework hydrates, such as zirconium phosphate, and ox-
ides, such as zirconium dioxide, titanium dioxide, and silicon
dioxide.1-3 All these compounds display a high water retention abil-
ity and, when they absorb water, become proton conductive. The
low solubility of these compounds in aqueous media prevents them
from leaching. In recent studies, different types of recast Nafion
membranes containing inorganic additives were fabricated, tested
with respect to their water uptake and conductivity, and then inves-
tigated in high-temperature direct methanol fuel cells.2-7 The experi-
mental data showed that addition of inorganic hydrophilic materials
to Nafion substantially extends the working temperature range and
reduces the methanol crossover rate.3 A few Nafion-based composite
membranes were evaluated in an H2 /O2 共or H2 /air兲 PEMFC at el-
evated temperatures. Composite Nafion/zirconium phosphate mem-
branes8 and Nafion/silicon oxide membranes9,10 were tested at tem-
peratures up 140°C. At the same voltage, almost four times higher
* Electrochemical Society Active Member.
z
E-mail: lvov@psu.edu
current density values were obtained at 130°C and 100% relative
humidity 共RH兲 using a fuel cell employing either a composite
Nafion/23% zirconium phosphate membrane8 or Nafion/10% SiO2
membrane,9 and a six times higher current density was obtained
using a fuel cell employing Aciplex1004/10% SiO2 membrane,
compared to the fuel cell with a commercial unmodified Nafion 115
membrane. A new type of composite membrane, Nafion-Teflon-
Zr共HPO4兲2, for high-temperature PEMFC operation was reported in
Ref. 11. These membranes were prepared by impregnating a porous
Teflon matrix with Nafion and zirconium phosphate and tested in an
H2 /O2 PEMFC at 120°C, ambient pressure, and low RH 共about
35%兲. The maximum power density achieved was about
340 mW cm−2.
Another class of inorganic/organic composite membranes, called
self-humidifying polymer electrolyte membranes, was developed by
Uchida and coauthors.12-15 These membranes contain highly dis-
persed nanosized Pt, which stimulates catalytic recombination of H2
and O2 inside the membrane. This process results in a decrease of
gas crossover and maintains the water content of the composite
membrane. These membranes also contain a hygroscopic metal ox-
ide, which adsorbs the water produced at the Pt particles and at the
cathode. Self-humidifying membranes, in particular Nafion-Pt-TiO2
membranes, exhibited significantly higher water uptake and lower
fuel crossover than did unmodified Nafion membranes.14 The PEM-
FCs employing such membranes demonstrated lower ohmic resis-
tance, when operated with dry H2 and O2 at 80°C and ambient
pressure.14 The methanol crossover of these membranes also
decreased.15
In this study, we attempt to develop a composite proton exchange
membrane that can function at 120°C under reduced RH conditions
at a performance level comparable to that of regular Nafion at 80°C.
Our approach involves incorporation of TiO2 particles into Nafion.
TiO2 was selected as an inorganic additive for the composite mem-
branes based on our previous surface chemistry studies of different
solid oxides.16-18 Our high-temperature microelectrophoresis mea-
surements showed that the rutile polymorph of TiO2 has an isoelec-
tric point 共IEP兲 in the acid part of the pH scale 共5.0-6.5兲 at ambient
conditions, which decreases to around 4.2 as the temperature in-
creases to 200°C. A similar tendency was also established for the pH
of point of zero proton charge of the same TiO2 powder using a
high-temperature potentiometric titration technique.19 Thus, in aque-

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A1036 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲
ous solutions with pH lower than the IEP, rutile particle surfaces
become positively charged due to surface protonation equilibria, as
illustrated by the following reactions resulting from the Multisite
Complexation 共MUSIC兲 model for TiO2 共rutile兲
⬅Ti-OH−0.31 + H+
⬅Ti-OH2+0.69 关1兴 recast procedure similar to that described by Arico and coauthors2
⬅Ti2-O−0.62 + H+
⬅Ti2-OH+0.38 关2兴
As the temperature increases, the equilibrium constants, KH1 and
KH2, shift toward lower values, which should result in even lower
pH at the TiO2 /water interface. The thermodynamic equilibrium
constants for these reactions are represented as a function of tem-
perature by the following equations19
log KH1 = 2699.5/T − 25.28 + 9.27 log T 关3兴
log KH2 = 1917.3/T − 17.94 + 6.58 log T 关4兴
If the amount of liquid phase is relatively small compared to the
solid phase 共like in a dense slurry or in a membrane兲, Reactions 1
and 2 act as pH buffers, producing mildly acidic solution, as was
confirmed previously.7,16 However, the buffering capacity of the
electrical double layer 共EDL兲 on the TiO2 surface is low at low
content of TiO2 in the membrane and likely would be exceeded by
the intrinsic acidity of the membrane solution, which is due to the
dissociation of sulfonic acid groups20
-SO3H
-SO3− + H+ 共log Ka = 6 at 25°C兲 关5兴 voltage and current of the fuel cell were measured simultaneously
Under fuel cell operation, protons are continuously generated at
the anode side and driven through the membrane pore fluid, but the
sulfonate groups remain largely unprotonated, even at pH values of
0-1. In the absence of essentially immobile counter cations in the
pore fluid, this would tend to retard the free migration of protons
through the membrane, although the hydrophilic nature of the sul-
fonate groups would tend to attract water dipoles. If positively
charged surfaces 共such as that of rutile particles at low pH兲 were
able to counterbalance the negative charge of the sulfonate groups,
the hydrophilic nature of the membrane would be further enhanced
by the presence of both positively and negatively charged species
fixed within the membrane. This might also permit the unhindered
migration of protons through the membrane, as at least some sul-
fonate group charges would be counterbalanced by positively
charged particle surfaces, rather than protons within the pore fluid.
In other words, in the absence of fixed countercharges, the long-
range coulombic attractive force of negatively charged sulfonate
groups would tend to retain protons within the membrane, even as
they are “pushed” through as a result of the external anode/cathode
reactions. If the long-range coulombic attractive force for protons
were disrupted by the presence of fixed positively charged surfaces
within the membrane, the protons might more readily pass through
the membrane pore fluids unhindered.
At the acidic conditions in Nafion-based membranes, TiO2 is
characterized by a relatively high positive surface charge density
and zeta potential due to proton adsorption.17 The high concentra-
tion of protons in the EDL is beneficial from the standpoint of the
hydrophilicity of TiO2-doped composite membranes, because the
water species forming the EDL are retained at the TiO2 surface by
the electric field. Although the water retention properties of the TiO2
powder are also related to the particle morphology, particle size,
aggregation, and porosity, the intrinsic acid-base surface properties
of the TiO2 共zeta potential and surface charge density兲 may play the
primary part in the membrane conductivity and water balance.
Experimental
The TiO2 powder used in this study was pure crystalline rutile
共␣-TiO2兲 obtained from Kronos, Inc. 共Kronos 4020兲. The powder
was sorted, cleaned, and characterized at the Oak Ridge National
Laboratory as described in detail elsewhere.17 The resulting TiO2
material contained no detectable crystalline contaminants and
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mainly consisted of 3-50 ␮m aggregates of anhedral or subhedral
0.1-1.0 ␮m rutile grains. The specific surface area of the powder
was determined by Brunduer, Emmett, and Teller method multipoint
N2 surface area analysis as 2.914 ± 0.004 m2 g−1.17
The composite Nafion/TiO2 membranes were prepared using a
for the preparation of composite Nafion/SiO2 membranes. Appropri-
ate amounts of commercial 5% Nafion solution 共Aldrich兲 and TiO2
powder were mixed and sonicated in an ultrasonic bath. The suspen-
sion was cast and heated at 80°C until dry. The recast composite
films were then hot-pressed at a low pressure 共less than 2 bar兲 at
150°C for 10 min. The thickness of the membranes was about
80 ␮m. The membranes were purified using a standard procedure
described elsewhere.21 Three types of Nafion-based composite
membranes, containing 0, 10, and 20 mass % TiO2, were prepared.
The membrane electrode assemblies 共MEAs兲 were prepared us-
ing a commercial gas diffusion solid polymer electrolyte electrode
of Los Alamos type 共ELAT兲 with double-sided coatings. The elec-
trode specifications were as follows: Pt loading 0.5 mg cm−2 with
20% Pt on Vulcan XC-72 as a catalyst, Nafion loading 0.8 mg cm−2,
and standard poly共tetrafluoroethylene兲 loading. MEAs were pre-
pared by pressing the electrodes on the membrane in a Carver hot
press at 130°C and 50 bar for 40 s.
The fabricated MEAs were coupled with Teflon gas-sealing gas-
kets and placed in a 5 cm2 ElectroChem fuel cell, which can operate
at temperatures up to 130°C and at pressures up to 3.5 bar. The
using an electronic load 共Hewlett-Packard Co.兲 and electrometer
共Keithley Instruments, Inc.兲. The high-temperature fuel cell operat-
ing system was equipped for monitoring the temperature, gas flow
rate, and pressure. Water traps were installed in front of backpres-
sure regulators in the oxygen and hydrogen lines to prevent valve
clogging at a high RH. To ensure data consistency, each fuel cell
arrangement 共compaction force兲 and the operating conditions 共hy-
drogen and oxygen pressures, temperature, and RH兲 were the same
for the tests of membranes with different compositions.
Prior to the high-temperature performance tests, the membranes
were hydrated at ambient temperature using the water produced in
the fuel cell under an external load of 0.01 ⍀. This procedure was
necessary to rehydrate the membranes after hot-pressing. During the
high-temperature PEMFC performance tests, the cell was fed with
humidified reactant gases of high purity. Humidification of both H2
and O2 was temperature controlled. The fuel cell tests were per-
formed at 80 and 120°C, at 26, 50, 80, and 100% RH with a total
pressure 共reactant gas and water vapor兲 of 3 bar. Membranes with
different TiO2 contents 共0, 10, and 20 mass %兲 were tested using an
identical procedure. All the experimental results were obtained un-
der steady-state conditions 共i.e., the current density remained con-
stant in time at a fixed cell voltage兲.
Results and Discussion
The performance of the H2 /O2 PEMFCs employing Nafion/TiO2
composite membranes was evaluated based on cell voltage vs. cur-
rent density 共polarization兲 curves. The current density was calcu-
lated considering the surface area of the gas flow channels. The
effects of the TiO2 content and RH on the PEMFCs performance
were then investigated.
When the membranes were tested at 80°C, an increase in the
TiO2 content had no significant effect on the PEMFC performance
over the entire range of RH used 共from 26 to 100%兲 共Fig. 1兲. The
effect of RH on the PEMFC performance was minor but more pro-
nounced for the Nafion/TiO2 composite membranes than for the
unmodified Nafion membrane. However, at 120°C, the fuel cell per-
formance was affected by both the TiO2 content in membranes and
RH 共Fig. 2兲. The effect of the TiO2 content on PEMFC performance
was greater at reduced RH. When the TiO2 content increased from 0
to 20%, the current density delivered at a cell voltage of 0.6 V
increased, respectively, by 3, 5.8, 1.6, and 1.1 times at 26, 50, 80
共data at 80% RH not shown in Fig. 2兲, and 100% RH. The effect of
 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲
Figure 1. Performance of H2 /O2 PEMFC based on Nafion and Nafion/TiO2
composite membranes at 80°C, 3 bar, 26 and 100% RH. -䉱- 0% TiO2, 26%
RH; -䉭- 0% TiO2, 100% RH; -䊏- 10% TiO2, 26% RH; -䊐- 10% TiO2,
100% RH; -⽧- 20% TiO2, 26% RH; -〫- 20% TiO2, 100% RH.
RH 共ranging from 26 to 100%兲 was significant for the unmodified
Nafion membrane. The performance of the Nafion/TiO2 composite
membranes was more RH sensitive at reduced RH values. The effect
of TiO2 content on the power density delivered by the PEMFCs at a
constant voltage of 0.7 V at different RH values is shown in Fig. 3.
The results obtained for fuel cell performance and power density
can be attributed to the enhanced water retention properties of TiO2.
Hydrophilic TiO2 evidently improved the water retention properties
of the membranes and, therefore, their hydration, which in turn fa-
vors the Nafion proton conductivity and fuel cell performance. Im-
provement of membrane humidification due to addition of TiO2 was
more evident at reduced RH because, in this case, the initial water
uptake of the membranes was small, and the fraction of water asso-
ciated with the solid oxide particles was significantly higher than
that in the case of well-hydrated membranes. Water retention by
TiO2 substantially changed the level of membrane hydration and,
consequently, its conductivity and the performance of PEMFCs. At a
high RH, when Nafion contains enough water to effectively conduct
protons, addition of moisture to the membranes did not substantially
change the membrane hydration and conductivity.
Figure 2. Performance of H2 /O2 PEMFC based on Nafion and Nafion/TiO2
composite membranes at 120°C, 3 bar, 26, 50, and 100% RH. -䉱- 0% TiO2,
26% RH; -䊏- 0% TiO2, 50% RH ; -⽧- 0% TiO2, 100% RH; -x- 10% TiO2,
26% RH; -+- 10% TiO2, 50% RH; -ⴱ- 10% TiO2, 100% RH; -䉭- 20% TiO2,
26% RH; -䊐- 20% TiO2, 50% RH; -〫- 20% TiO2, 100% RH.
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A1037
Figure 3. Effect of TiO2 content of membrane on PEMFC power density at
0.7 V, 120°C, and 3 bar for various RH values. -䉱- 26% RH; -䊏- 50% RH;
-⽧- 100% RH.
The performance of the PEMFC was also influenced by the de-
crease in partial pressures of the reactant gases in the feed fuel
stream at operating conditions. When the fuel cell was operated at
120°C and total pressure of 3 bar, the increase of RH from 26 to
100% lowered the partial pressures of the reactant gases by the order
of 2.5, which negatively affected the performance of the fuel cell.
However, according to our data 共Fig. 2兲, this effect was much
smaller than the effect of membrane hydration 共the performance of
the membranes always substantially increased with increasing RH兲.
When the fuel cell was operated at 80°C, the decrease in H2 and
O2 partial pressures due to RH increase was relatively small. De-
hydration of the membranes at this temperature was also insignifi-
cant; thus, the RH and addition of hydrophilic TiO2 powder to the
membrane material was not expected to significantly affect the fuel
cell performance. Our results 共Fig. 1兲 are in agreement with this
assumption.
The PEMFC performance obtained at 80°C was higher than that
at 120°C for all membranes at all RH values studied. When the
temperature was increased from 80 to 120°C, the performance de-
clined much more significantly at reduced RH and for unmodified
Nafion membranes 共Fig. 4 and 5兲. For the fully hydrated mem-
branes, the performance decrease was probably due to the decreased
partial pressures of the reactant gases in the feed 共related to increas-
Figure 4. Performance of H2 /O2 PEMFC based on Nafion and Nafion/TiO2
composite membranes at 80 and 120°C, 3 bar, and 100% RH. -䉱- 0% TiO2,
120°C; -䊏- 10% TiO2, 120°C; -⽧- 20% TiO2, 120°C; -䉭- 0% TiO2, 80°C;
-䊐- 10% TiO2, 80°C; -〫- 20% TiO2, 80°C.
A1038 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲
Figure 5. Performance of H2 /O2 PEMFC based on Nafion and Nafion/TiO2
composite membranes at 80 and 120°C, 3 bar, and 50% RH. -䉱- 0% TiO2,
120°C; -䊏- 10% TiO2, 120°C; ⽧- 20% TiO2, 120°C; -䉭- 0% TiO2, 80°C;
-䊐- 10% TiO2, 80°C; -〫- 20% TiO2, 80°C.
ing the humidifying temperature兲. When the PEMFC was tested at
100% RH and constant hydrogen and oxygen partial pressures, the
performance was higher at 120°C than at 80°C. At 50% RH, the
magnitude of gas partial pressure reduction with increasing tempera-
ture was much smaller and the decrease in fuel cell performance was
mainly due to membrane dehydration at 120°C. In this case, the
composite membranes showed a significant advantage over the un-
modified Nafion membranes, confirming that hydrophilic TiO2 pro-
vides better water retention than bare Nafion polymer at a reduced
RH. Performance of the composite Nafion/20% TiO2 membrane at
120°C and 50% RH was comparable to the performance of the un-
modified Nafion membranes at 80°C and 100% RH. This result
demonstrates that using the new composite membrane that contains
20 mass % of TiO2 allows increasing the operating temperature of
the PEMFC from 80 to 120°C at a reduced 共50%兲 RH without any
significant performance loss.
A membrane stability test was conducted with the Nafion/10%
TiO2 composite membrane at 120°C and 50% RH 共Fig. 6兲. The fuel
cell power level was relatively stable with a total decline of about
7% for 45 h. The performance of the recast Nafion membrane at the
same operating conditions sharply declined after 25 h operation.
Adjemian and coauthors9 tested a recast Nafion and a Nafion/SiO2
composite membranes for 50 h and also found that the composite
membranes had much higher stability at elevated temperatures.
Figure 6. Duration test for recast Nafion/10% TiO2 membrane.
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Figure 7. Model structure of the EDL at the TiO2 /water interface.
Although the basic mechanical properties, such as tensile
strength, were not measured in this study for the composite mem-
branes, it is considered an important future step in predicting the
membrane properties in relation to the TiO2 content. The effect of
the TiO2 content on the mechanical strength of Nafion/TiO2 com-
posite membranes can be different in dry and wet states. According
to Ref. 22, the membrane tensile strength tends to decrease with
increasing TiO2 content in Nafion. As was shown by the study of the
TiO2 profile across the membrane using X-ray energy dispersive
spectroscopy with a scanning microscope, the TiO2 component was
mainly concentrated in the near-surface zone. The presence of such
an oxide-rich layer in Nafion membranes lessened the membrane
tensile strength.
The benefits of having TiO2 particles in the fuel cell membrane
can be related to both water retention and proton conductivity. The
water retention increases due to the adsorption of the aqueous spe-
cies H+ and OH− in the EDL of the solid particles. The adsorbed
species in the EDL are under an electrical field, which provides the
force retaining water at the surface and an admixture of TiO2 to
Nafion is able to increase the potential ability of the membrane to
intake water. When the temperature is increased above 100°C, the
water incorporated into the EDL of solid oxide particles does not
evaporate as easily as does the “free” water in the Nafion polymer.
The ability of a particular solid oxide to retain water depends on the
strength of the electrostatic attraction within the EDL. The primary
indicator of this attractive force is the zeta potential at the solid
oxide/water interface. In most cases, a higher magnitude of the zeta
potential implies a higher proton charge and, therefore, a higher
concentration of water species adsorbed 共retained兲 at the solid oxide
surface. The zeta potential is the surface potential measured at the
shear plane, which is located at a hypothetical distance Ds from the
surface and divides the hydrodynamically immobile and mobile
parts of the EDL 共Fig. 7兲. Therefore, the experimental data on zeta
potential at the solid oxide/water interface can be used to estimate
the Ds parameter and to determine the geometric thickness of the
part of the EDL that is strongly attached to the particle surface.
As a result of zeta potential data fitting using the temperature-
compensated MUSIC model combined with the basic Stern repre-
sentation of the EDL,17,19 the shear plane positions 共Ds兲 of rutile
particles were determined at 3.5 and 6.1 nm from the head of the
diffuse layer at ionic strengths of 0.01 and 0.001 mol kg−1, respec-
tively. The Ds parameter was primarily a function of ionic strength,
while its variation with temperature was within the range of experi-
 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲 A1039

Table I. Electrochemical kinetic parameters for PEMFC employing Nafion/TiO2 composite membranes at 120°C.

120°C Relative humidity 共%兲

26 50 100
TiO2 Cont. R io R io R io
共%兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲
0 1.71 1.207 0.145 6.6 ⫻ 10−4 1.19 1.189 0.082 3.4 ⫻ 10−4 0.22 1.160 0.043 6.2 ⫻ 10−5
10 0.48 1.207 0.137 7.0 ⫻ 10−4 0.30 1.189 0.043 2.1 ⫻ 10−5 0.15 1.160 0.042 3.0 ⫻ 10−5
20 0.48 1.207 0.117 6.1 ⫻ 10−4 0.29 1.189 0.036 6.4 ⫻ 10−6 0.25 1.160 0.028 2.1 ⫻ 10−6

mental error. Based on these values, the volume of hydrodynami-
cally immobile water retained by the EDL can be estimated as
EDL
VH 2O
= SA ⫻ Ds 关6兴
where SA is the specific surface area of the TiO2 powder used
共2.914 m2 g−1兲. This estimation involves the assumption that the
compact 共Stern兲 part of the EDL is very thin and its contribution to
the EDL volume is negligible. With Ds = 6.1 nm, Eq. 6 yields the
volume of 0.0018 cm3 of adsorbed water per gram of TiO2 powder.
This value is only 0.8% of the maximum total water uptake deter-
mined for the fully hydrated Nafion/20% TiO2 composite
membrane.16 Therefore, if the membrane is at 100% RH, the pres-
ence of the solid oxide phase would not bring significant benefits to
membrane hydration. This suggestion is confirmed by the experi-
mental data at RH 100% 共Fig. 2兲, when the fuel cell performance
curves for the composite membranes and unmodified Nafion are
almost identical. However, at a reduced RH, the advantage of the
composite membranes is obvious 共Fig. 2兲, which means that the
fraction of water associated with solid oxide particles should be
significantly higher than that for complete hydration. Although the
TiO2 microparticles are able to enhance water retention of the mem-
branes, the maximum water uptake of the fully hydrated composite
membranes was not significantly higher than that of the unmodified
Nafion membranes. Because of this observation and also the large
size of the TiO2 particles 共up to 5-10 micrometers兲, we do not as-
sume any changes in the Nafion nanostructure. The composite is
rather considered to be a physical mixture of Nafion and TiO2.
Although the water in the compact part of the EDL is not be-
lieved to make a significant input to membrane hydration, the
weakly bound water in the membrane can also be affected by the
electric field at the contact between Nafion and TiO2. Under acidic
conditions, the surface of TiO2 has a high positive charge, whereas
the surface of Nafion is negatively charged due to dissociation of
sulfo groups 共uSO3H兲. Thus, water molecules located between
these two surfaces should be influenced by an electric field. Al-
though the charged solid oxide surface acts as a water retainer, this
water can easily diffuse into Nafion and participate in ion transport.
The cell potential 共V兲 vs. current density 共i兲 behavior at different
temperatures, RH values, and TiO2 content in the membranes was
analyzed by fitting this data to the following equation
V = Vr − A ln共i/io兲 − Ri 关7兴
where Vr is the reversible cell potential 共calculated using the Nernst
equation兲, A and io are Tafel parameters, and R is the resistance,
which causes a linear variation of V with i.23
A nonlinear parameter estimation code included in the SigmaPlot
software was used to determine the parameters A,io, and R. Equation
7 was modified and presented as
V = Vo − A ln i − Ri 关8兴
where Vo is defined as
Vo = Vr + A ln io 关9兴
At first, all cell potential 共V兲 vs. current density 共i兲 data were
fitted to Eq. 8, and the parameters Vo, A, and R were derived from
this equation. The calculation yielded the values of these parameters
with correlation coefficients in excess of 0.995 and small standard
deviation. Then, the parameter io was calculated from Eq. 9. The
values of the reversible potential 共Vr兲 at 80 and 120°C and different
RH values were calculated from the Nernst equation, assuming that
the steam behaves as an ideal gas.
The electrochemical kinetic parameters derived from Eq. 8 and 9
are presented in Tables I and II. As seen from the tables, the param-
eter R, which predominantly represents the ohmic resistance of the
membrane, was not affected by TiO2 content in membranes and RH
at the temperature of 80°C, but their effect is clearly pronounced at
120°C 共Fig. 8兲. When RH decreased, the increase in resistance was
significantly higher for unmodified Nafion membranes than for
Nafion/TiO2 composite membranes. This fact is a clear manifesta-
tion of the ability of TiO2 to reduce membrane resistance due to its
good water retention properties. The presence of TiO2 in the mem-
branes and the RH change affect more than just the resistance of the
membranes. The Tafel slope A decreased with the increase of TiO2
content in membranes and RH very slightly at 80°C, and signifi-
cantly at 120°C 共Fig. 9兲. This means that the increase of RH in the
cell and the contact of the electrodes with hydrated TiO2 particles
also improved the hydration of the ion-conducting phase in the elec-
trode 共Nafion兲, which positively affects the electrochemical kinetics
of the electrodes. The obtained parameter io showed an increase with
the temperature and a decrease with the TiO2 content and RH. This

Table II. Electrochemical kinetic parameters for PEMFC employing Nafion/TiO2 composite membranes at 80°C.

80°C Relative humidity 共%兲

26 50 100
TiO2 Cont. R io R io R io
共%兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲 共⍀ cm2兲 Vr 共V兲 A 共V兲 共A cm−2兲
0 0.22 1.225 0.040 6.1 ⫻ 10−6 0.23 1.214 0.037 6.3 ⫻ 10−6 0.24 1.201 0.037 1.1 ⫻ 10−5
10 0.26 1.225 0.046 1.4 ⫻ 10−5 0.23 1.214 0.033 2.5 ⫻ 10−6 0.26 1.201 0.032 3.4 ⫻ 10−6
20 0.26 1.225 0.032 9.8 ⫻ 10−7 0.32 1.214 0.027 3.8 ⫻ 10−7 0.25 1.201 0.026 3.9 ⫻ 10−7

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A1040 Journal of The Electrochemical Society, 152 共6兲 A1035-A1040 共2005兲
Figure 8. Ohmic resistance of fuel cells employing membranes of varying
TiO2 content at different RH and 120°C. -䉱- 0% TiO2; -䊏- 10% TiO2; -⽧-
20% TiO2.
parameter, as calculated from Eq. 7, is not the real exchange current
density, but rather represents a combination of the exchange current
density and the internal current density, which occurs due to mem-
brane gas permeability. We would assume the internal current den-
sity increases with increasing TiO2 content and increasing RH. In
addition, the increase of RH at operating conditions 共total pressure
of 3 bar兲, leads to the reduction of gas partial pressure and, conse-
quently, io.
Conclusions
Composite Nafion/10% TiO2 and Nafion/20% TiO2 membranes
showed a considerable improvement over unmodified Nafion mem-
branes in the PEMFC performance at 120°C, 3 bar, and reduced RH.
Figure 9. Tafel parameter A of Eq. 7, calculated from voltage 共V兲 vs. current
density 共i兲 of fuel cell employing membranes with varying TiO2 content at
different RH, at 120°C. -䉱- 0% TiO2; -䊏- 10% TiO2; ; -⽧- −20% TiO2.
Downloaded on 2012-12-18 to IP 150.108.161.71 address. Redistribution subject to ECS license or copyright; see www.esltbd.org
At 50% RH and a cell voltage of 0.6 V, the Nafion/20% TiO2 mem-
branes delivered a six times higher current density than that obtained
with an unmodified Nafion membrane. The PEMFC operated with a
Nafion/20% TiO2 membrane at 50% RH exhibited a performance
identical to that of the PEMFC operated with an unmodified Nafion
membrane at 100% RH. This demonstrates that the addition of 20%
TiO2 to Nafion makes it possible to operate PEMFCs at 120°C and
50% RH instead of 100% without loss of performance. This perfor-
mance level is comparable to that of bare Nafion at 80°C. This
improvement is mainly attributed to the enhanced water retention
properties of the new composite membranes and the increase in
proton conductivity of the membranes due to TiO2 contribution. The
water content of the membrane is not significantly affected by the
presence of solid oxide at RH 100%, but it becomes strongly con-
trolled by the solid oxide phase in the RH range 26-50%. The high
water retention of composite membranes at reduced RH is due to the
electrostatic attraction within EDL on the surface of TiO2. We
speculate that the water species absorbed in the EDL may provide
significant membrane conductivity at low RH.
Acknowledgments
The authors gratefully acknowledge the financial support of this
work by Department of Energy contracts DE-FC36-01GO11085 and
DE-AC05-00OR22725.
The Energy Institute of The Pennsylvania State University assisted in
meeting the publication costs of this article.
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