Journal of Membrane Science 467 (2014) 3640

High performance direct methanol fuel cells with

micro/nano-patterned polymer electrolyte membrane
Yoon-Hwan Cho
a,b
, Jin Woo Bae
b
, Ok-Hee Kim
a,b
, Jae Young Jho
b
, Namgee Jung
a,b
,
Kyusoon Shin
b
, Hyelim Choi
c
, Heeman Choe
c
, Yong-Hun Cho
c,n
, Yung-Eun Sung
a,b,1

a
Centre for Nanoparticle Research, Institute for Basic Science (IBS), Seoul National University, Seoul 151-744, South Korea
b
School of Chemical and Biological Engineering, Seoul National University (SNU), Seoul 151-744, South Korea
c
School of Advanced Materials Engineering, Kookmin University, 861-1 Jeongneung-dong, Seoul 136-702, Seongbuk-gu, South Korea



a r t i c l e i n f o

Article history:
Received 14 November 2013
Received in revised form
17 March 2014
Accepted 30 March 2014
Available online 12 April 2014

Keywords:
Direct methanol fuel cell (DMFC)
Thermal imprint lithography (TIL)
Naon 115 membrane
Patterning
Three-phase boundary
a b s t r a c t


The effect of an enlarged specic surface area of the membrane with well-dened line patterns on the
performance of a direct methanol fuel cell (DMFC) is investigated and compared with the baseline
pristine Naon 115 membrane. Line patterns with dimensions ranging from several tens of nanometers
to several micrometers were fabricated on Naon 115 membranes with high reliability using thermal
imprint lithography to ensure an uncollapsible structure. In the case of quasi-nano-patterned membrane
the cell performance increased about 35% compared with that of the pristine Naon 115 membrane
owing to an increased effective three-phase boundary caused by an enlarged specic surface area. Thus
the performance of DMFCs can be improved further by controlling the shape and size of the line patterns
for sufcient formation of the three-phase boundary.
& 2014 Elsevier B.V. All rights reserved.




1. Introduction

The direct methanol fuel cell (DMFC) is an eco-friendly energy
conversion system, generating electricity directly through the
electrochemical reaction of methanol and oxygen [1,2]. Moreover,
the DMFC is one of the best alternative portable power sources
owing to its high energy density as well as the ease with which it
can be applied to small electronic devices [3,4]. On the other hand,
resolving its cost issue, which stems primarily from the use of a Pt
catalyst in the membraneelectrode assembly (MEA), remains the
largest obstacle to the widespread application of DMFCs to mobile
and stationary platforms [5,6]. Accordingly, many attempts have
been made to reduce the amount of Pt in the catalyst layer without
deteriorating the DMFC performance [711].
Several methods of creating as large a three-phase boundary
area as possible, where the reactants, catalysts and electrolyte
coexist in the MEA, have attracted considerable interest because
they might improve the electrochemical performance of DMFCs
and reduce the amount of Pt catalyst needed. For example,
roughening the surface of the electrolyte membrane comprising
the three-phase boundary in the MEA has been attempted


n
Corresponding author. Tel.: 82 2 910 5672; fax: 82 2 910 5674.
E-mail addresses: yhun00@kookmin.ac.kr (Y.-H. Cho),
ysung@snu.ac.kr (Y.-E. Sung).
1
Tel.: 82 2 880 1889; fax: 82 2 888 1604.

recently. Since Sheppard et al. rst reported that the electrolyte
membrane could be roughened by SiC paper [12,13], additional
investigations into modifying the surface structure of the electro-
lyte membrane have been performed by plasma etching or ion
beam bombardment [1417]. Yildirim and coworkers reported the
increased MEA performance with micro-patterned Naon 117
membrane using a hot embossing process [18]. DMFC performance
of electron beam patterned membrane was further investigated by
Omosebi and Besser [19]. Nevertheless, previously modied elec-
trolyte membranes with large specic surface areas had some
limitations regarding the electrochemical fuel cell performance.
The whisker-like structure of the surface-modied electrolyte
membranes collapsed readily during MEA preparation, which
disrupted the three-phase boundary where the electrochemical
reaction occurred. Therefore, it is essential to design an electrolyte
membrane with both an enlarged surface area and robust surface
structure so that an effective three-phase boundary with the
loaded catalysts and reactants can be formed in the MEA, which
thus improves the conversion efciency of electrochemical energy
in DMFCs.
This communication reports the improved single-cell performance
of electrolyte membranes containing well-dened micro-sized, quasi-
nano-sized and nano-sized line patterns. The line patterns were
introduced to the electrolyte membrane to ensure an uncollapsible
structure with a high-specic surface area. Uniform line patterns,
ranging in size from several tens of nanometers to several tens of

http://dx.doi.org/10.1016/j.memsci.2014.03.069
0376-7388/& 2014 Elsevier B.V. All rights reserved.
Contents lists available at ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci
Y.-H. Cho et al. / Journal of Membrane Science 467 (2014) 3640 37

micrometers, were developed to measure quantitatively the effect of
an enlarged specic membrane surface area on the performance of
DMFCs. The well-dened line patterns were imprinted on both sides
of an electrolyte membrane by thermal imprint lithography (TIL)
[2022]. TIL is expected to increase the reactive surface area of the
three-phase boundary and enhance the performance of DMFCs
considerably because a wide range of well-dened line patterns can
be fabricated on an electrolyte membrane without collapsing the
structure.


2. Experimental methods

2.1. Preparation of micro-patterned master molds [23]

Periodic micro-scaled and quasi-nano-scaled Si line patterns
were fabricated using photolithography at the Korea Advanced
Nano Fab Center (KANC). An n-type Si (100) wafer (MEMC Electro-
nic Materials, Inc.) was etched by piranha solution (3:1 mixture of
concentrated sulfuric acid and 30% hydrogen peroxide) at room
temperature for 1 h and ultrasonicated with acetone to clean the
surface of Si wafer. Photoresist (AZ7210) was spun-cast on the
cleaned Si wafer substrate at 3000 rpm resulting in 1 m thick
layer, followed by baking at 100 1C for 90 s. Exposure was per-
formed with a manual mask aligner (EVD620, EVD) at 40 mJ cm
- 2
and followed by post-exposure bake at 110 1C for 60 s. After
development, the patterned photoresist on the Si wafer was baked
at 120 1C for 90 s and the Si wafer substrate was selectively etched
with inductively coupled plasma (Multiplex ICP, STS). Leftover
photoresist on the etched Si wafer was removed with the Micro-
wave Asher (ALA-0601E, AMS). Height and line intervals of the two
patterns are 1 m and 15 m, and 700 nm and 700 nm for micro-
scaled and quasi-nano-scaled patterns, respectively.
2.2. Preparation of nano-patterned master mold [24]

Periodic nano-scaled Si line pattern was fabricated using e-beam
lithography (JBX9300FS, JEOL) at the Korea Advanced Nano Fab
Center (KANC). Height and line intervals of the periodic nano-scaled
Si master mold were 70 nm and 200 nm, respectively, upon which
several Rigiex master molds were replicated. ZEP 520A was used
as an e-beam resist and the exposure does used was 300 C cm
- 2
.
UV-curable polymer solution (MINS 311, Minuta tech.) was dropped
on the Si master line pattern template. Adhesion promoter-coated
PET lm (Minuta tech.) was then placed on top of the MINS 311 as a
supporting layer. After UV-curing for 20 s, rigiex master mold was
physically detached from the Si master. Prior to use, the rigiex
master molds were aged for several hours.


2.3. Fabrication of MEAs with the patterned Naon membranes and
the pristine Naon 115 membrane

Fabrication of the MEA with the line-patterned Naon membrane
is shown schematically in Fig. 1. Naon 115 membrane (equivalent
weight value 1100 g eq.
- 1
, thickness: 120 m, DuPont) was used as
a polymer electrolyte membrane for the DMFC. First, line-patterned
master molds were in contact with both sides of Naon 115
membrane, and pressed with 200 Pa at 180 1C for 1 h in a vacuum
oven. Following slow cooling to room temperature and release of
mechanical pressure, the resulting Naon membranes were
immersed in distilled water for 24 h at 50 1C so that the patterned
Naon membrane can naturally detach from the master molds. To
remove remaining impurities prior to applying the patterned Naon
membrane to the MEA, the patterned Naon membranes were
treated sequentially in a 3 wt% solution of hydrogen peroxide,
distilled water, 0.5 M sulfuric acid, and distilled water, each at 70 1C


Fig. 1. Schematic illustration of the fabrication of the MEA using the line-patterned Naon membrane. (a) Line patterns on both sides of the Naon 115 membrane were
replicated by the master molds using TIL. And then, (b) the MEA was fabricated by directly spraying the Pt/C catalyst ink onto the both sides of line-patterned Naon
membrane without a hot-pressing process.
38 Y.-H. Cho et al. / Journal of Membrane Science 467 (2014) 3640

for 1 h. After treatment, the patterned Naon membranes were
preserved in distilled water to keep the patterned Naon membrane
fully hydrated. The catalyst ink was prepared by ultrasonication, from
the following elements: 75 wt% carbon-supported PtRu (Johnson
Matthey) for anode and 60 wt% carbon-supported Pt (Johnson
Matthey) for cathode, 5 wt% Naon solution (DuPont), isopropyl
alcohol (Aldrich), and deionized water. The content of Naon solution
was 30 wt%, and the ratio of IPA and water was 3:1. Finally, MEAs
with an active area of 5 cm
2
were fabricated by directly spraying the
catalyst ink on both sides of the patterned Naon membranes
without a hot-pressing process [25]. The amounts of PtRu/C and
Pt/C catalyst used in the spraying technique were 2.0 mg cm
- 2
and
1.5 mg cm
- 2
, respectively. An MEA with a pristine Naon 115
membrane was fabricated by the above-described procedure, except
for the thermal imprinting lithography. After drying the MEAs for 1 h
at room temperature, the single cell was assembled with the MEA,
gas diffusion layer (GDL), and graphite plates. All the single cells were
clamped with torque of 60 kgf cm.


2.4. Characterization

The morphology of the line-patterned master molds, the inversely
line-replicated Naon membranes, and the membraneelectrode
interface were investigated using a FE-SEM (JSM-6700F, JEOL) with
an acceleration voltage of 5 kV. In order to investigate changes in the
chemical properties of the surface of the thermal imprinted mem-
brane, FT-IR ATR spectra (Thermo Scientic, Nicolet 6700) were
obtained from 32 scans at a resolution of 4 cm
- 1
from 4000
- 1
to
400 cm
- 1
, as seen in Fig. S1. Wide Angle X-ray Scattering (WAXS,
Bruker) patterns were recorded in the diffraction angular range of 10
401 2, using a GD 2000 transmission diffractometer produced by Ital
Structures, working in the Seemann-Bohlin geometry, and with a
quartz crystal monochromator of the Johansson type on the primary
X-ray beam using CuK radiation. Small Angle X-ray Scattering (SAXS)
patterns were recorded by an MBraun system, using the CuK radiation
from a Philips PW 1830 X-rays generator in the diffraction angular
range of 191 2. The membrane through-plane proton conductivity
was determined according to the impedance technique by means of
solartron 1260 Impedance/Gain Phase Anayser (IM6, Zahner) in the
frequency range 100 mHz10 kHz at a signal amplitude 100 mV.
Membrane disc, 8 mm in diameter was sandwiched between two
Pt plates. To evaluate DMFC performance, single cells were operated
at a constant temperature of 60 1C and ambient pressure, by feeding
1.0 M methanol solution (0.5 ml min
- 1
) and dry air (200 sccm) for
the anode and cathode, respectively. The voltages of operating single
cells were obtained with increasing current density, by using a fuel
cell test station (CNL Energy) to measure the currentvoltage char-
acteristics [26,27]. The single cell test was performed with three
different cells, of which the mean values were taken with their error
bars based on 7standard deviation values.


3. Results and discussion

Before the electrolyte membranes were patterned by TIL, master
molds of the line patterns with a range of periodicities under
several tens of micrometers had been prepared by photolithography
for micropatterning and quasi-nanopatterning [23] as well as e-
beam lithography and imprinting process for nanopatterning [24].
Electrolyte membranes with enlarged specic surface areas were
fabricated by sandwiching a Naon membrane between the master
molds with well-dened periodic line patterns, followed by thermal
imprinting and removal of the master molds. Fig. 2 shows cross-
sectional images of the line-patterned master molds (top) along
with their corresponding electrolyte membranes (bottom), as
observed by eld-emission scanning electron microscopy (FE-
SEM). As shown in Fig. 2ac (top), the width/spacing/height of the
three master molds were 10/5/1 m, 700/700/700 nm, and 90/110/
70 nm, respectively. The top images show well-dened lines for
each type of line pattern on both the micro and nano-scales
indicating the quality of the master molds.
The inverse structure of each master mold was transferred to the
surface of a thin Naon membrane by TIL. Fig. 2df (bottom) shows
these line-patterned surface morphologies. The imprinted Naon
membranes have well-dened line patterns with width/spacing/
height values of 5/10/1 m, 700/700/700 nm, and 110/90/70 nm,
respectively. Based on the FE-SEM images, the uniform line patterns
from the master molds, which range in size from several tens of
nanometers to several tens of micrometers, were well-replicated on


Fig. 2. FE-SEM images of line-patterned master molds (top) and the replicated Naon membranes (bottom). Various line-patterned master molds with well-dened line
patterns (a)(c) were prepared. The structure of the master molds are inversely replicated on the Naon substrates by TIL. The lines on the Naon substrate are (d) 5 m in
width, 10 m in spacing, and 1 m in height; (e) 700 nm, 700 nm, and 700 nm; (f) 110 nm, 90 nm, and 70 nm, respectively.
Y.-H. Cho et al. / Journal of Membrane Science 467 (2014) 3640 39

Table 1
Summary of the performance characteriztion results for the tested membranes. The data were obtained from Supplementary Fig. S4 and Fig. 3.

Membrane Proton conductivity
(S cm
- 1
)
Methanol crossover
(cm
2
s
- 1
)
Current density at 0.4 V
(A cm
- 2
)
Maximum power density
(W cm
- 2
)
Pristine Naon 115 0.100 2.02 x 10
- 6
0.17370.003 0.10470.002
Patterned Naon membrane with 5/10/1 m 0.105 2.00 x 10
- 6
0.17970.001 0.12270.003
Patterned Naon membrane with 700/700/700 nm 0.100 2.01 x 10
- 6
0.19370.001 0.13870.003
Patterned Naon membrane with 110/90/10 nm 0.106 2.02 x 10
- 6
0.14570.002 0.10970.002

the Naon membranes by TIL without collapsing the structure. Based
on estimations of enlarged specic surface areas of the imprinted
Naon membranes, the specic surface areas of the imprinted Naon
membranes were approximately 113%, 200%, and 170%, compared to
that of the pristine Naon 115 membrane, when their width/spacing/
height values were 5/10/1 m, 700/700/700 nm, and 110/90/70 nm,
respectively. These observations suggest that uncollapsed line patterns
can be prepared readily on the Naon membranes by TIL and the
surface area to volume ratio can be controlled straightforwardly. These
results may provide solutions to improving the formation of an
effective three-phase boundary in the MEA, which leads to DMFCs
with better performance. In previous studies, surface roughening of
the electrolyte membrane for extremely enlarged surface area was not
successful in improving the formation of a stable three-phase bound-
ary during the preparation of MEA owing to the instability of
electrolyte membrane surface structure [14,15], which made it difcult
to demonstrate the effect of an enlarged specic surface area of the
membrane on the performance of DMFCs. In this study, Fourier
transform infrared (FT-IR) spectroscopy in ATR mode, wide-angle X-
ray scattering (WAXS), and small-angle X-ray scattering (SAXS) were
performed to examine the changes in the chemical properties of
the surface of the thermal-imprinted membrane. As shown in Figs.
S1S3, no peak shift was observed in the FT-IR spectrum of the
patterned Naon membrane, which was measured by considering all
wave numbers similar to that of the untreated Naon 115 membrane.
This suggests that TIL used to improve the MEA performance did not
cause any major changes in the chemical properties of the Naon
membrane. Furthermore, the proton conductivity and methanol cross-
over rate of the patterned Naon membrane were unaffected by TIL, as
shown in Fig. S4 and Table 1.
The MEAs were fabricated by spraying the well-dispersed 75 wt%
PtRu/C and 60 wt% Pt/C catalysts in the anode and cathode sides,
respectively, on the pristine and line-patterned Naon membranes,
followed by single-cell tests to measure the performance of the
prepared MEAs in a 1 M methanol/air DMFC. Fig. 3 shows the
single-cell performance of the MEAs fabricated using the pristine
and patterned Naon membranes as a polymer electrolyte. The open-
circuit voltages of almost all the single cells were held constant at
0.76 V, regardless of the membrane surface structure, which suggests
that methanol crossover from the anode to cathode across the
patterned Naon membrane did not affect the performance of the
DMFC, despite the patterning introduced to both sides of the Naon
membrane. The current density of the pristine Naon 115 membrane
was measured to be 0.173 A cm
- 2
at a cell voltage of 0.4 V, and its
evaluated maximum power density was 0.104 W cm
- 2
. The current
densities of the MEAs with the micro-patterned and quasi-nano-
patterned membranes were respectively 0.179 and 0.193 A cm
- 2
at
0.4 V, whereas that of the MEA with the nano-patterned membrane
was only 0.145 A cm
- 2
. Furthermore, the similar trend was observed
in the maximum power density measurements; the maximum power
densities were 0.122, 0.138, and 0.109 W cm
- 2
for the line-patterned
membranes with width/spacing/height values of 5/10/1 m, 700/700/
700 nm, and 110/90/70 nm, respectively. The performance results are
summarized in Table 1. Compared with the MEA of the pristine Naon
115 membrane, the MEA of the Naon membrane line-patterned in
quasi nanoscale showed remarkably improved performance ("" 35%


Fig. 3. Polarization and power density curves of MEAs fabricated using the pristine
Naon 115 membrane (black square: ), and patterned Naon membranes with
line patterns of 5 m in width, 10 m in spacing, and 1 m in height (green triangle:
); 110 nm, 90 nm, and 70 nm (red circle: ); 700 nm, 700 nm, and 700 nm (blue
triangle ), respectively. (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)



increase in maximum power density) in the DMFC owing to the
enlarged specic surface area of the membrane. This dramatic increase
in performance without the additional use of more Pt electrocatalyst is
substantial. Adequately spaced line patterns, particularly on the quasi
nanoscale, as shown in Fig. 4(ac), appear to increase the interface
contact area of the three phase boundary in the same geometric size,
thereby improving the fuel cell performance signicantly and increas-
ing the Pt utilization effectively. Therefore, a properly patterned
electrolyte membrane with an uncollapsible structure and high-
specic surface area are the key parameters determining the perfor-
mance of DMFCs.
On the other hand, the MEA with the Naon membrane line-
patterned on the nanoscale exhibited the worst single-cell perfor-
mance. The performance at 0.4 V was even poorer than that of the
single cell with the pristine Naon 115 membrane. Indeed, we
expected that single cell performance of the MEA with the Naon
membrane line-patterned on the nanoscale could exhibit better
than those of the MEAs with the pristine membrane and micro-
patterned membrane, in anticipation for the large specic surface
area of the nano-patterned Naon membrane with a stable
structure formation as shown in Fig. 2(f). The Pt/C catalyst
particles often agglomerated to form particles of more than several
hundreds of nanometers when sprayed over the line-patterned
Naon membrane (Fig. S1) [25]. As such, the agglomerated Pt/C
catalyst particles could not penetrate into the narrow intervals of
the nano-patterned membrane despite its good stability, deterior-
ating the formation of an effective three-phase boundary in the
MEA, as shown in Fig. 4(c). On the other hand, the reactive area of
the three-phase boundary could increase when the surface struc-
ture of the Naon membrane was modulated appropriately on the
microscale level as compared with the nanoscale level. Moreover,
the patterning scale was further optimized on the quasi nanoscale
level (several hundreds of nanometers).
38 Y.-H. Cho et al. / Journal of Membrane Science 467 (2014) 3640


Fig. 4. Cross-sectional FE-SEM images of membraneelectrode interface prepared by patterned Naon membranes with line patterns of (a) 5 m in width, 10 m in spacing,
and 1 m in height; (b) 700 nm, 700 nm, and 700 nm; (c) 110 nm, 90 nm, and 70 nm, respectively.

4. Conclusions

In summary, this study demonstrates the effect of an enlarged
specic surface area of the membrane with well-dened line
patterns on the performance of a DMFC, compared with the
baseline pristine Naon 115 membrane. The well-dened line
patterns with high reliability, ranging in size from several tens of
nanometers to several micrometers, are developed on a Naon
membrane by soft lithography without collapsing the structure. In
particular, the current density of the quasi-nano-patterned Naon
membrane is increased by approximately 35% in a DMFC, com-
pared with that of the pristine Naon 115 membrane. This is
attributed to an increase in the effective three-phase boundary
caused by the enlarged specic surface area of the electrolyte
membrane in the MEA. On the other hand, the nano-patterned
Naon membrane exhibits relatively poor performance at 0.4 V
because the agglomerated Pt/C catalyst particles inhibit contact
with the nano-patterned electrolyte membrane, causing insuf-
cient formation of the three-phase boundary. This suggests that
the performance of DMFCs can be improved further by controlling
the shape and size of the line patterns on the electrolyte mem-
brane; more importantly, an appropriate choice of line pattern can
reduce effectively the amount of Pt catalyst used while maintain-
ing the same performance level.


Acknowledgments

This work was supported by the Institute for Basic Science (IBS)
in Korea. Y.-H. C. acknowledges nancial support by the Priority
Research Centre Program (2009-0093814) and Basic Science
Research Program (2013R1A1A2061636) through NRF funded by
the Ministry of Education, Republic of Korea.


Appendix A. Supplementary material

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.memsci.2014.03.
069.

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