Electrochemistry Communications 6 (2004) 10691074

www.elsevier.com/locate/elecom

Nano-silica layered composite membranes prepared by PECVD

for direct methanol fuel cells
Daejin Kim, M. Aulice Scibioh, Soonjong Kwak, In-Hwan Oh, Heung Yong Ha *
Fuel Cell Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, South Korea
Received 16 June 2004; received in revised form 6 July 2004; accepted 7 July 2004

Abstract
Plasma enhanced chemical vapor deposition (PECVD) technique has been employed to deposit nano-scale lms of silica (10, 32,
68 nm) on Naon membrane. Ion conductivity, methanol permeability and single cell performance of the resultant nano-silica/Nafion composite membranes were measured to ascertain its suitability as a candidate membrane for direct methanol fuel cell (DMFC)
applications. Experimental results revealed that ion conductivity of the composite membrane containing silica lm with 10 nm thickness was similar to the unmodied Naon membrane, but its methanol permeability was reduced to an extent of 40%. Cell performance of the composite membrane with 10 nm silica was higher than that of the bare Naon
membrane by about 20%. The open
circuit voltage (OCV) was increased and the cell temperature at OCV was decreased with an increase in the thickness of the silica
lm. Physical and electrochemical analyses were conducted to investigate the properties of silica-layered membrane and the DMFC
employing the membrane.
 2004 Elsevier B.V. All rights reserved.
Keywords: Composite membrane; DMFC; Ion conductivity; Methanol permeability; Silica/Naon; PECVD

1. Introduction
A direct methanol fuel cell (DMFC) is one of the
most attractive power sources for wide applications
from portable power sources to vehicular applications,
due to the simplicity of the system and the adaptability
of liquid fuel, methanol. One of the main impediments
to practical realization of the DMFC as a power source
is crossover of methanol through the polymer electrolyte
membrane (PEM). This results in poor cell performance.
It is widely accepted that commercially available Nafion
membrane is an advanced material in the present
days as solid electrolyte for low temperature fuel cells.
Naon membrane has attractive properties like good
proton conductivity and chemical stability, in spite of
*

Corresponding author. Tel.: +82-2-958-5275; fax: +82-2-9585199.

E-mail address: hyha@kist.re.kr (H.Y. Ha).
1388-2481/$ - see front matter  2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2004.07.006

its limitation including high cost and methanol permeation. Thus, requirements for a good polymer electrolyte
membrane include high proton conductivity, low permeability for methanol, stability against radical attack and
low cost.
Intensive research eorts are focused mainly on
decreasing the crossover of methanol through the polymer electrolyte membrane while maintaining good ion
conductivity [13]. These attempts on the polymer electrolyte membrane in DMFCs can be broadly classied
into three categories. First one is to manufacture new
membrane that can be synthesized from polyhydrocarbon materials or peruorinated materials [412]. Second
one is to employ inorganicorganic polymer composite
membranes [1318]. The third approach is to employ
surface modied Naon membranes exposed to low
dose electron beam (EB) irradiation, radiation-modied
Naon membranes with vinylphosphonic acid (VPA),
plasma polymerized barrier lms on Naon membranes,

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D. Kim et al. / Electrochemistry Communications 6 (2004) 10691074

the surface-modied Naon membranes using plasma

etching and palladium-sputtering and Pd-layered Naon
membranes, and so on [1923].
Among these new membranes for DMFCs, the
Naon/silica hybrid membrane exhibited advantageous
properties like higher water uptake, lower methanol uptake, higher ion conductivity and greater mechanical
strength than the bare Naon membrane though the
improvements are somewhat controversial depending
on the reports. Miyake et al. [24] reported that the hybrid membranes with higher silica content (10 and 21
wt%) decreased methanol uptake from the liquid phase.
Dimitrova et al. [25,26] noted a rise in conductivity with
the addition of silicon dioxide particles (Aerosil 380) to
Naon compared to the unmodied Naon 117. In
particular, the silica nano-particles retain water even at
high temperatures and this property may prevent drying of the membrane during the fuel cell operation.
Walker [27] added untreated fumed silica in a protonconducting polymer membrane to increase water
absorption and water retention capacity, since fumed silica is hydrophilic with an ability to adsorb moisture.
Jung et al. [18] reported that the proton conductivity
in the silica hybrid membranes was lower than, or equal
to, that in unmodied Naon membranes.
Plasma enhanced chemical vapor deposition
(PECVD) is a lucrative technique for layer fabrications
since one can have easy control over factors like lm
thickness, refractive index and roughness of the layers,
in addition to low deposition temperatures and high
deposition rates associated with this system [28,29].
Hence, PECVD technique was advantageously employed for the low-temperature deposition of silica lms
[3035].
Grounded on these properties of silica and PECVD
technique, we have prepared nano-silica layered Naon
membrane by PECVD technique. The morphology of
Naon/silica composite material was studied using scanning electron microscopy (SEM) and their properties as
a candidate membrane for DMFC were investigated in
terms of ionic conductivity, methanol permeability and
single cell performance measurements.

2.2. Measurement of ion conductivity and methanol

permeability
Ion conductivity of the Naon/silica composite membranes was measured by using a complex impedance
analyzer (ZAHNER IM-6) with a four-point probe
AC electrochemical impedance spectroscopy [36,37]. A
conductivity cell was made up of two platinum foils carrying the current and two platinum wires sensing the
potential drop. The membrane was held in between
two platinum electrodes and the IM-6 impedance analyzer was functioning in galvanostatic mode with AC
current amplitude of 0.01 mA at frequency range from
8 MHz to 10 mHz.
Methanol permeability was measured using an inhouse built permeation cell which consisted of two
compartments that were separated by the membrane
[4]. A 5% methanol solution was fed into one compartment of the cell and deionized water was circulated through the other compartment. Each
compartment was stirred continuously during permeability measurement. A dierential refractive index
detector was employed to monitor the methanol
permeability.
2.3. Single cell performance measurement in DMFC
Electrocatalysts used in the anode and cathode
were unsupported PtRu (50:50 at.%) black and Pt

2. Experimental
2.1. Preparation of Naon/silica composite membranes
Thin layer of silica was deposited on the surface of
Naon 115 membranes by using a PECVD system as
follows. Silicon ethoxide gas was pumped into the chamber where electric eld from RF power source of 10500
W was applied at pressures ranging from 1 to 500 mTorr
at ambient temperature. The thickness of silica layer
coated on Naon membrane has been controlled by varying the deposition time.

Fig. 1. Schematic of a passive DMFC.

D. Kim et al. / Electrochemistry Communications 6 (2004) 10691074

black (Johnson Matthey), respectively. The catalyst

slurry containing Naon solution (DuPont) was directly scattered on the Naon/silica composite membranes using a spray gun and 8 mg/cm2 of catalyst
was coated. Teonized carbon paper (Toray) was set
on the both side of the membrane electrode assembly
(MEA) that could function as diusion layers. The cell
was held together between plastic plates by means of a
set of eight retaining bolts. Single cell performance
was measured by using a passive DMFC where 4.5
M methanol solution was put into the built-in reservoir and methanol was diused into the anode and
air was supplied to the cathode from environment
by a kind of air-breathing action (Fig. 1) [38]. The cell
performance experiments were carried out at room
temperature (273K) and at atmospheric pressure.
Polarization curves were obtained by using an electronic load (DAE GIL 200P).

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3. Results and discussion

Thin silica lms were formed on the Naon membrane by PECVD technique. Thickness of silica lm
was controlled by changing the deposition time. At rst,
the morphology and microstructure of composite membranes were examined using SEM. The SEM images of
surface and cross sectional view of the Naon/silica
composite membranes are shown in Fig. 2. A smooth silica lm was formed on the membrane. Some cracks were
found in the surface of the coated silica layer and it has
been observed that the gaps in the cracks were increased
in proportion to an increase in the thickness of silica
layer. It is assumed that the cracks might be caused by
an increase of cohesive energy according to an increase
in the thickness of silica layer and also by a dierence
in the degree of swelling between two materials. Further,
it can be seen that the silica layer with thickness of 32

Fig. 2. SEM images of Naon/silica composite membranes for various thickness of silica lm: (a) 10 nm; (b) 32 nm; (c) 68 nm.

D. Kim et al. / Electrochemistry Communications 6 (2004) 10691074

Table 1
Ion conductivity and methanol permeability of Naon/silica composite
membranes
Membrane material

Ion conductivity
(S/cm)

Methanol permeability
(cm2/s)

Naon 115
Naon10 nm silica lm
Naon32 nm silica lm
Naon68 nm silica lm

0.098
0.091
0.076
0.077

2.77 10
1.68 10
0.91 10
0.92 10

(100%)
(93%)
(78%)
(79%)

6
6
6
6

(100%)
(61%)
(33%)
(33%)

. 10-3 ( -1 cm-3 s)

80

60

40

20

0
Nafion

10 nm silica

32 nm silica

68 nm silica

Fig. 3. Ratio (U) of ion conductivity to methanol permeability of

Naon/silica composite membranes.

700

40

Nafion 115
silica 10 nm
silica 32 nm
silica 68 nm

600

35
30

500

25
20

400
15
300

10
5

200

Power Density (mW/cm2)

and 68 nm in composite membrane were found to be detached from Naon lm. Consequently, the contact
resistance between electrode and membrane would increase, causing a reduction in cell performance when
used as solid electrolyte membrane material in fuel cell
[39,40].
The ion conductivity and methanol permeability of
Naon/silica composite membranes are given in Table
1. The relative ion conductivity and methanol permeability in the Naon/silica composite membranes compared with those in untreated Naon membrane are
given in parenthesis. The ion conductivity of the Nafion/silica composite membrane with 10 nm thickness
was similar to the unmodied Naon membrane
(0.091 S/cm), however, its methanol permeability
(1.68 10 6 cm2/s) was reduced to an extent of 40%.
Naon/silica composite membranes with thicker silica
layers such as 32 and 68 nm showed lower ion conductivity by about 20% and their methanol permeability
were reduced up about 70% than those of bare Naon
membrane. Fig. 3 shows the ratio between ion conductivity and methanol permeability, a characteristic factor
(U), in each Naon/silica composite membrane under
this study. It can be seen that the ratios (U) of all the
composite membranes coated with silica are higher than
that of bare Naon. It indicates that the Naon/silica
composite membranes exhibit superior characteristics

Voltage (mV)

1072

0
100
-20

20

40

60

80

100

120

140

160

-5
180

Current Density (mA/cm2)

Fig. 4. DMFC single cell performance with Naon/silica composite

membranes.

than Naon membrane in their properties for DMFC

applications [41].
The single cell performance of DMFC with Naon/
silica composite membranes as solid electrolytes is
shown in Fig. 4. The performance with 10-nm
Naon/silica composite membrane (36 mW/cm2) was
higher than that of the Naon membrane (30 mW/
cm2) by about 20%. However, the other thicker Nafion/silica membranes (32, 68 nm thick silica) showed
lower power density compared with bare Naon 115.
The decrease of cell performance in the presence of
32- and 68-nm Naon/silica composite membranes
might be caused by increased contact resistance as
can be seen from SEM image of Naon/silica composite membranes in Fig. 2.
The cell temperature and voltage of Naon/silica
composite membranes at OCV are shown in Fig. 5.
The cell temperature decreased and OCV increased with
increasing the thickness of silica lm, indicating that the
Naon/silica composite membranes reduced methanol
crossover to the cathode side and thereby the extent of
methanol oxidation reaction and the mixed potential
generated in the cathode are decreased. That is, the
amount of permeated methanol through the polymer
electrolyte membrane was lowered according to increase
in thickness of silica layer.
Fig. 6 shows the resistance of the cells with Naon/silica composite membranes that was measured by AC milliohm tester (HIOKI) at OCV. The resistance of Naon/
silica composite membrane with 10 nm silica thickness
was same as that of bare Naon, while the other Nafion/silica composite membranes with higher silica thickness (32, 68 nm) showed cell resistance two or three
times larger than that of the Naon membrane. This result further conrmed the poor cell performance of
DMFC when Naon/silica composite membranes with
thickness of 32 and 68 nm silica were employed.

D. Kim et al. / Electrochemistry Communications 6 (2004) 10691074

ion lm, the PECVD approach is found to be a promising one in coating very thin lm of silica on Naon
membrane.

0.66
Temperature
OCV

48

0.64
0.62

46
0.60
44
0.58
42

Voltage (V)

Temperature (oC) at OCV

50

0.56
40

0.54

38

0.52
Nafion 115

10 nm silica

32 nm silica

68 nm silica

Fig. 5. Cell temperature and voltage of Naon/silica composite

membranes at OCV.

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4. Conclusions
The performance of passive DMFC with nano-silica
layered Naon composite membranes prepared by
PECVD technique was investigated. The thickness of silica layer coated on the Naon membrane was 10, 32 and
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