Electrochemistry Communications 6 (2004) 562–565

www.elsevier.com/locate/elecom

MEMS-based design and fabrication of a new concept micro

direct methanol fuel cell (l-DMFC)
Shinji Motokawa a, Mohamed Mohamedi a,*, Toshiyuki Momma a,b
,
Shuichi Shoji c, Tetsuya Osaka a
a
Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
b
CREST, Japan Science and Technology Agency, Japan
c
Department of Electronics, Information and Communication Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-Ku, Tokyo 169-8555, Japan
Received 25 March 2004; received in revised form 13 April 2004; accepted 13 April 2004
Available online 30 April 2004

Abstract

A design for a novel micro direct methanol fuel cell (l-DMFC) of 0.018 cm2 active area is described. The l-DMFC was prepared
using a series of fabrication steps from micro-machined silicon wafer including photolithography, deep reactive ion etching, and
electron beam deposition. The novelty of this structure is that we have fabricated the anodic and cathodic micro-channels arranged
in plane, dissimilar to the conventional bipolar structure. The first objective of the experimental trials was to verify the feasibility of
this novel structure on basis of MEMS technology. Preliminary testing results show that this new concept l-DMFC generates
electricity.

2004 Elsevier B.V. All rights reserved.

Keywords: Micro-fuel cell; Micro-power; Methanol; Micro-DMFC; Electroplating

1. Introduction system design characteristics, operation parameters, as

Several groups are actively engaged in the develop-
ment of low power DMFCs for cellular phone, laptop
computer, portable camera, or powering various micro-
systems. Small fuel cells with various degrees of micro-
fabrication have been reported in the literature [1–8].
Medicine is also a demanding field for this kind of
miniature fuel cells as an implantable micro-power
source for medical devices, such as cerebrospinal fluid
shunt pump and a micro-insulin pump [9]. The research
cited shows that the adaptation of micro-electronic
techniques to micro-electrochemical systems such as
DMFC can be successful. We have to emphasize that
while related work exists, the design and testing of a
micro-fabricated silicon-base miniature methanol/oxy-
gen polymer electrolyte fuel cell remains a novel con-
cept. Since always, different applications imply different
well as materials employed in the device.
Towards that aim, we embarked in an effort to de-
velop a l-DMFC with good compatibility with wafer-
level MEMS process for 1–100 mW class application,
such as distributed micro-sensors and wireless MEMS.
This communication will focus on the design, fabrica-
tion, and preliminary performance evaluation of a novel
concept of l-DMFC. The novelty of the structure pro-
posed in this work is that we have fabricated and ar-
ranged the anodic and cathodic micro-channels in plane
fabricated onto a single silicon substrate. This concept is
different from the conventional bipolar structure where
the anode and cathode channels are made on two sep-
arate substrates.
2. Experimental
2.1. l-DMFC electrode fabrication

*
Corresponding author. Tel./fax: +81-3-5286-2745. The l-DMFC was prepared using a series of fabri-
E-mail address: mohamed@waseda.jp (M. Mohamedi). cation steps tailored from MEMS techniques. This

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2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2004.04.007
 S. Motokawa et al. / Electrochemistry Communications 6 (2004) 562–565
procedure is shown in schematic form in Fig. 1. Begin-
ning with 20 mm
25 mm h1 0 0i oriented silicon (p-
type, 1–10 X cm, 200  20 lm thick) polished on both
front and backsides, a 500 nm layer of silicon dioxide
was grown thermally (wet oxidation at 1100 C for 1 h
and 30 min). To make feedholes and channels, the sili-
con dioxide on the front and backside of the wafer were
patterned by photolithography. Windows were then
opened using buffered hydrogen fluorides etch. To
complete the fabrication process, the channels and
feedholes were then etched using Deep Reactive Ion
Etching (D-RIE) process. D-RIE was performed with a
STS Multiplex ICP Deep Reactive Ion Etcher. Etch rate
was typically 2.5–3.0 lm/min. The feedholes are circu-
lars, 1 mm diameter, and with a hole spacing of 8 and 10
mm horizontally and vertically, respectively. The width
and the depth of the micro-channel are both equal of
100 lm, while the clearance between channels is 100 lm.
In this single cell design and fabrication, only two micro-
channels were fabricated, one for the anode and one for
the cathode.
Subsequently, a 50 nm layer of silicon dioxide was
grown thermally (dry oxidation at 1100 C for 12 min)
on the entire surface of the silicon wafer again. Finally, a
photosensitive dry film for printed wiring boards was
applied to prepare for selective deposition of metal film.
Ti/Au for current collectors were formed by electron-
beam deposition and lift-off method. A 100 nm gold
layer was deposited in an ULVAC CRTM-6000 electron
beam evaporation chamber, preceded by 20 nm titanium
layer just beneath the gold to promote adhesion.
2.2. Cathode and anode catalyst deposition
The methanol anode and oxidant cathode were pre-
pared by electroplating either Pt–Ru or Pt and Pt, re-
spectively, onto the Ti/Au electrodes. The electroplating
solution for Pt was 20 mM H2 PtCl6  6H2 O and 0.5 mM
(CH3 COO)Pb  3H2 O. The deposition was carried by
applying a current density of 30 mA/cm2 during 10 min.
Fig. 1. Schematic of the l-DMFC chip fabrication process.
563
The actual mass loading of Pt was 2.4 mg/cm2 . The Pt–
Ru for methanol oxidation was obtained from a solu-
tion containing 20 mM H2 PtCl6  xH2 O + 20 mM
RuCl3  xH2 O. The deposition was performed at )0.15 V
vs. Ag/AgCl for 5 min. The actual mass loading of Pt–
Ru was 2.85 mg/cm2 . The electroplating process was
carried out at 25 C for both electrodes. Energy dis-
persive X-ray (EDX) analysis showed a platinum/ru-
thenium of 90/10 atomic ratio.
2.3. l-DMFC assembly
DuPontTM Nafion 112 (thickness: 50 lm, equivalent
weight 1100 g/ml, ionic conductivity 0.083 X1 cm1 )
has been used as the proton exchange membrane of the
l-DMFC. The membrane is pretreated as follows. It
was boiled in 1 M H2 O2 solution for 1 h and then rinsed
in boiling in ultra pure water for 1 h to remove any
organic compounds, and finally treated with boiling 1 M
H2 SO4 for 1 h.
Finally, the l-DMFC was assembled by placing the
pretreated Nafion 112 membrane between the patterned
silicon and a glass substrate and the whole was clamped
mechanically for testing. Performance testing was con-
ducted with an electrochemical workstation HZ-3000
HAG-1512l (Hokuto Denko, Japan).
3. Results and discussion
The design of the l-DMFC and its working principle
are depicted in Fig. 2. The fuel solution (CH3 OH/
Fig. 2. Schematic diagrams of our proposed silicon-based methanol/
oxygen micro-fuel cell: (a) top-view of design; (b) cross-sectional
schematic with working principle. Drawings not to scale. CC: current
collector.
564 S. Motokawa et al. / Electrochemistry Communications 6 (2004) 562–565

H2 SO4 /H2 O) is fed to the anode side of the unit cell
where the catalyst promotes the CH3 OH to release
electrons, carbon dioxide, and protons. The electrons
travel in the form of an electric current that can be
utilized before it returns to the cathode side of the fuel
cell where the oxidant solution (O2 -sat./H2 SO4 /H2 O)
has been fed. On the other hand, molecular oxygen re-
acts at the cathode with proton being transported
through the membrane from the anode and produces
water, thereby completing the oxidation–reduction
process. The anode to cathode contact is the thickness of
the Nafion (50 lm) as illustrated in Fig. 2. Here, the
path length from anode to cathode is the clearance be-
tween the two micro-channels, which is 100 lm. Con-
necting both the anode and the cathode to an external
load makes it possible to produce electric power.
The approach shown in Fig. 2 has several advantages
and differs in many ways from previous designs:
• It is of planar structure and essentially an unfolded
fuel cell as shown in Fig. 2, which integrates the an-
ode and cathode onto a single Si surface. Whereas,
the bilayer design uses separate Si wafers with chan-
nels for the anode and cathode.
• The fuel and oxidant are supplied to the cell in iso-
lated, separate micro-channels. Both the fuel and oxi-
dant are distributed in micro-channels throughout
the wafer, and they both possess an exhaust. The iso-
lation of fuel and oxidant precludes one from cross-
ing the fuel and oxidants streams.
• The characteristic length of the system that is the dis-
tance that the protons must travel from anode to
cathode is very short. This makes the system less sen-
sitive to ohmic impedance effect.
• The efficiency of the current collectors is high, because
the catalyst layers are supported on the metal directly.
In addition, the current collectors are directly depos-
ited in the micro-channels. The current does not need
to be pulled out by relatively large metal lines.
• Catalyst electrodes are directly fabricated in the bot-
tom and sidewalls of the micro-channels.
Therefore, this design offers simplicity in the stepwise
integration of substrate, electrodes, and membranes.

Fig. 3. Picture of the fabricated l-DMFC prototype. One-cent coin is shown for scaling reference.

Fig. 4. l-DMFC testing using 2 M methanol solution with methanol flow and oxygen flow both equal to 10 lL/min: (a) Voltage–current density
profiles; (b) power density plots. Measurements were made at ambient temperature and under atmospheric pressure.
 S. Motokawa et al. / Electrochemistry Communications 6 (2004) 562–565
The plane view structure of prototype l-DMFC fabri-
cated using MEMS technology is shown in Fig. 3.
The performance of the l-DMFC was assessed at
ambient temperature using 2 M CH3 OH/0.5 M H2 SO4 /
H2 O as the fuel and O2 -sat./0.5 M H2 SO4 /H2 O as the
oxidant. The O2 saturated solution was prepared by
using oxygen bubbling into 0.5 M H2 SO4 /H2 O solution.
The supply test of fuel was made by means of a micro-
syringe pump connected to the fabricated l-DMFC
unit. Fig. 4(a) shows cell polarization curves operated at
Pt and Pt–Ru anode electrodes using 2 M methanol
solution at ambient temperature and atmospheric pres-
sure. When a 2 M methanol solution was supplied, the
voltage of the unit cell increased to OCV in 2 s and
maintained until the fuel was exhausted. The OCV for
Pt cell was 300 mV while for Pt–Ru cell of 400 mV. The
maximum power density is 0.44 mW/cm2 at 3 mA/cm2 at
Pt electrode. While, the maximum power density
reached 0.78 mW/cm2 at 3.6 mA/cm2 for cell with Pt–Ru
anode.
When it is compared with other macro DMFC unit
cell, the output voltage (400 mV) of the fabricated
lDMFC unit cell is 1/1.25. The reasons for the low
output voltage may be described as follows: (1) The
Nafion membrane was just placed between the patterned
silicon and the glass substrate, i.e., we do not use any
high pressure bonding. This brings a decrease in reaction
area relatively. (2) The composition of the Pt–Ru anode
catalyst used in our cell is not optimal. The composition
used in most of the technical works is Pt–Ru: 1:1 atomic
ratio. It is still necessary to optimize the electroplating
conditions to obtain the desired composition of the Pt–
Ru catalyst so as to increase the l-DMFC performance.
4. Conclusions
Aspects of the design, materials and fabrication of a
micro-fabricated methanol fuel cell have been presented.
Our concept of a novel structure lies in that the anodic
and cathodic micro-channels arranged in a plane, unlike
565
the conventional bipolar design. The first objective of
the experimental trials was simply to verify the feasi-
bility of this novel structure on basis of MEMS tech-
nology. Thus a l-DMFC on a silicon wafer has been
successfully fabricated using photolithography, deep
reactive ion etching, and electron beam deposition. Test
results were able to confirm that this new concept of
l-DMFC generates electricity. The performance of the
cell was measured at ambient temperature was of mW/
cm2 class. The laboratory aims further to improve the
performance of this l-DMFC and establish the assem-
bling technique for practical applications.
Acknowledgements
This work was supported by a Grant-in-Aid for Sci-
entific Research on the priority area of DMFC (Grant
no. 13134204), COE Research ‘‘Molecular Nano-Engi-
neering’’, and 21C-COE Programme ‘‘Practical Nano-
Chemistry’’ from The Ministry of Education, Culture,
Sports, Science and Technology (MEXT), Japan. We
would like to thank Dr. Mizuno of Nanotechnology
Laboratory for suggestions on fluid injection system.
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