i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 0 8 8 e8 0 9 3

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Development of a planar mDMFC operating at room

temperature

C. D’Urso a,*, V. Baglio a, V. Antonucci a, A.S. Aricò a, S. Specchia b, U.A. Icardi b,c,
G. Saracco b, C. Spinella d, G. D’Arrigo d
a
CNR-ITAE, Via Salita Santa Lucia Sopra Contesse 5, 98126 Messina, Italy
b
Politecnico di Torino, Dept. of Materials Science and Chemical Engineering, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
c
HYSYLAB e Environmental Park S.A., Via Livorno 60, 10144 Torino, Italy
d
CNR-IMM, Stradale Primosole 50, 95121 Catania, Italy

article info abstract

Article history: A co-planar micro Direct Methanol Fuel Cell (mDMFC) configuration was designed, devel-
Received 26 April 2010 oped and tested. The system geometry consisted of anodic and cathodic micro-channels
Received in revised form arranged in the same plane. Firstly, micro-channels for a uniform distribution of oxygen
22 October 2010 and methanol were designed and realized on a polymeric substrate of polycarbonate.
Accepted 19 January 2011 Then, the deposition of the catalytic elements inside the micro-channels by a spray-
Available online 18 February 2011 coating technique was carried out. Micro-channels were then covered by a catalyzed
membrane containing separate anode and cathode layers. Different cell configurations
Keywords: were built, tested and evaluated. It was observed that the open circuit voltage varied
Direct methanol fuel cells significantly as a function of the membrane humidification degree and distance between
Planar design anode and cathode channels in this planar design. In the presence of a large distance
Flow field between the anode and cathode channel, the OCV reached 0.97 V. This high OCV reflected
Methanol cross-over the absence of methanol cross-over due to the specific planar configuration. Regrettably,
the overall cell impedance (ohmic and polarization resistance) limited the performance.
A maximum power density of 1.3 mW cm
2 (active area) was achieved at room tempera-
ture with the smallest distance between anode and cathode (0.25 mm).
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction present unique technological attributes as efficiency, absence

Direct Methanol Fuel Cells (DMFCs) are increasingly being
developed to replace or support batteries, mainly for the high
energy density of methanol [1e6]. DMFCs are promising
candidates as portable power sources because they do not
require any fuel processing and operate at low temperatures
(30e60  C) [7e15]. Market demand for portable, power-hungry
wireless devices (cell phones, laptops, etc.) drives R&D efforts
to mDMFCs, which usually provide less than 50 W of power and
of moving parts and low emissions [16,17]. Moreover, mDMFCs
offer high energy-conversion efficiency, easy storage of liquid
fuel, ambient temperature operation, and simple manufac-
ture. Miniaturized electrocatalytic membranes integrated on
a silicon or polymeric matrix by using micromachining
processes have emerged recently as a possible way to
fabricate miniaturized Polymer Electrolyte Membrane Fuel
Cells (mPEMFCs) for mobile applications [18,19]. Thanks to
the integrated-circuit (IC) fabrication technology [20e22],

* Corresponding author. Tel.: þ39 090 624210; fax: þ39 090 624247.
E-mail address: durso@itae.cnr.it (C. D’Urso).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.01.109
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 0 8 8 e8 0 9 3
micro-channel patterns of mDMFCs bipolar plates, into which
reactants are fed, can be featured on Si or polymeric matrix
with high resolution and good repeatability. Basically, the
mDMFC has a conventional single cell structure, where a
membrane electrode assembly (MEA) is sandwiched between
two current collectors, made of gold, with fuel/air channels
[23e26].
The aim of the present work, carried out within the Italian
project MICROCELL, was to introduce an innovative micro-
machining process to fabricate mDMFCs presenting good
compatibility with wafer-level MEMS processes, fully
compatible with the standard ULSI (ultra large scale integra-
tion) silicon technology. The realized system geometry pre-
sented a single cell configuration, consisting of polymeric
substrate (in the present case polycarbonate), with anodic and
cathodic micro-channels for the uniform distribution of fuel
and oxygen, respectively, arranged in the same plane,
Pt-based catalysts directly deposited on the walls of the
micro-channels, gas-liquid feed holes, and a proton exchange
membrane as electrolyte on the top of the channels. The
starting point was the manufacturing of micro-channels, fol-
lowed by the deposition of the catalytic materials on the walls
of the micro-channels by spray-coating technique and the
realization (for some experiments) of a catalyst-coated
membrane (CCM) to be placed above the micro-channels. The
realized mDMFC configuration is different from the conven-
tional bipolar structure where the anode and cathode chan-
nels are present on two separate substrates.
After careful and deep modeling carried out by CNR-IMM
and Politecnico di Torino [27], the mDMFC was manufactured at
CNR-IMM laboratories and tested in the CNR-ITAE facilities.
The use of standard technology to deposit catalysts via spray-
coating forced to build up a prototype with geometric
dimensions slightly larger than the initial forecasted micro-
metric sizes.
2. Experimental
The prototypes were manufactured by means of mechanical
erosion of the micro-channels on the polymeric substrate
with a numerical control mechanical device [28]. Thanks to its
Fig. 1 e Pictures of the realized mDMFC system (left side: basic polycarbonate cell; center: basic polycarbonate cell covered by
gold to assure electric contacts; right side: overall mDMFC closed, with holes for the anodic and cathodic inlet/outlet flows).
8089
low weight, low cost and excellent insulating characteristics,
polycarbonate was employed to manufacture the cell. Dif-
ferent channel configurations were machined: the channels
had dimensions of 1 mm in thickness, 1 mm in height and
22.5 mm in length. The separation between the two channels
was fixed at 0.25 mm in one case, and 0.50 mm in the other
case. A thin gold layer was deposited by sputtering, using
a mask to prevent the deposition in the middle part of the cell,
between the anodic and the cathodic channels (to avoid
passage of electric current, and favor only the ions crossing
between the anode and cathode through the membrane).
In Fig. 1, pictures of the produced mDMFC system are shown
(left side: basic polymeric cell; centre: basic polymeric cell
covered by gold to assure electric contacts, where it is possible
to notice the thin space without gold to separate the anodic
and cathodic compartments; right side: closure plate, with
holes for the anodic and cathodic inlet/outlet flows). With
such a configuration, the anode and the cathode were on the
same side of the cell, but electrically separated, and the
membrane covered the whole area: the two channels can be
crossed contemporarily one from the anodic feed and the
other from the cathodic feed.
The deposition of a composite catalytic layer made of 85%
PtRu/C (produced at CNR-ITAE labs [29]) and Nafion ionomer
onto the fuel channels to promote the electro-oxidation of
methanol was carried out by using a spray-coating technique
in the presence of appropriate masks. A similar procedure was
used to deposit the cathode catalytic layer composed of 60%
Pt/C (produced at CNR-ITAE labs [29]) and Nafion ionomer on
the air channels. Finally, the mDMFC was completed by
covering both fuel and air channels with a bare polymeric
proton exchange membrane (Nafion 117) or a catalyst-coated
membrane (CCM) containing separate anode and cathode
layers on the same side. The CCM was coated with specific
PtRu/C and Pt/C catalytic layers in correspondence to fuel and
oxygen channels, respectively, to maximize the active area.
A spray-coating technique was also employed to realize the
catalyzed membrane. A Pt loading of 1 mg cm
2 and
0.25 mg cm
2 was used in the anodic and cathodic channel,
respectively; whereas, the Pt loading in the membrane was
1 mg cm
2 and 0.25 mg cm
2 for the anode and cathode area,
respectively. The complete device was assembled and tested
8090 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 0 8 8 e8 0 9 3

at room temperature. For single cell polarization experiments, 30

aqueous methanol solutions (2e10 M) were fed to the anode 1st test
channel of the mDMFC through a peristaltic pump; dry oxygen
was fed to the cathode channel. For all the carried out
20
experiments, the anode and cathode compartments were at

-Z" / Ohm cm2

the atmospheric pressure. Reactant flow rates were
1 ml min
1 and 40 ml min
1 for methanol/water mixture and
oxygen stream, respectively. The performance and durability 10
of the device were investigated by polarization and chro-
noamperometric measurements by using an AUTOLAB
PGSTAT 302 Potentiostat/Galvanostat (Metrohm) equipped 0
with a Frequency Response Analyzer. The Electrochemical 0 10 20 30 40 50 60
Impedance Spectroscopy (EIS) measurements were performed Z' / Ohm cm2
at open circuit voltage (OCV) in a frequency range between 80
1 MHz and 1 Hz by frequency sweeping in the single sine
70 2nd test
mode. The amplitude of the sinusoidal excitation signal was
0.01 V. The ohmic drop was determined by measuring inter- 60
cept at high frequency on the real axis in the Nyquist plot. 50

-Z" / Ohm cm2

40

3. Results and discussion 30

20
In a first experiment (1st test), the distance between the anodic 10
and cathodic channel was 0.25 mm (similar to the thickness of
0
a Nafion 117 membrane in a wet form). A dry catalyst-coated
0 20 40 60 80 100 120
membrane (CCM) was used, without any additional catalyst Z' / Ohm cm2
layer coated on channels’ walls. The polarization curve for
150
this cell configuration is reported in Fig. 2. A low open circuit
voltage (OCV) was observed (0.47 V): this could indicate a large 3rd test
120
methanol cross-over. Yet, this phenomenon should be dis-
carded in the present configuration due to the architecture,
-Z" / Ohm cm2

90
the large distance between anode and cathode and the use of
a dry CCM. More probably, the low OCV was produced by
60
a mismatching between the CCM and the flow field that
reduced the distance between anode and cathode. The
30
impedance spectroscopy analysis (Fig. 3) allowed the deter-
mination of the ohmic drop for this cell configuration. It was
very high (17 U cm2) compared to a classical cell design. This 0
0 40 80 120 160 200
was probably due to the use of a dry CCM. The small channel Z' / Ohm cm2
width in which the methanol solution flowed did not allow
a good hydration of the dry membrane between the anode and Fig. 3 e Impedance Spectroscopy (Nyquist plots) at OCV for
cathode (as necessary for Hþ ions migration). A maximum the three different tests (different cell configurations).

0.6 0.0016
2 M methanol concentration; oxygen feed
0.5
0.0014 power density of 1.3 mW cm
2 was obtained in these
Power density / W cm-2

0.0012 conditions.
Cell potential / V

0.4 1st test In a second experiment (2nd test, see Fig. 4), in order to
0.001
avoid the possible mismatching between the CCM and the
0.3 0.0008
flow field, a cell with a distance of 0.5 mm between the anode
0.0006 and cathode channel was used. In this case, catalysts were
0.2
0.0004 sprayed only on the channels’ walls and a wet bare Nafion
0.1 117 membrane was employed. In a third experiment (3rd test,
0.0002
see Fig. 4), the anode-cathode distance was maintained
0 0 constant at 0.5 mm, whereas the catalysts were deposited on
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 both the channels’ wall and the membrane (in a dry form):
Current density / A cm-2
practically, a CCM membrane with the same characteristics of
Fig. 2 e Polarization and power density curve for the first the one used in the 1st experiment was employed. The open
test (0.25 mm distance between anode and cathode, CCM, circuit voltage varied significantly as a function of the
no catalyst in the channels). membrane humidification and distance between anode and
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 0 8 8 e8 0 9 3 8091

1.2 0.004

2 M methanol concentration; oxygen feed

1
0.003

Current density / A cm
Cell potential / V

0.8
1st test
0.002
0.6 2nd test
3rd test
0.4
0.001

0.2

0
0 0 200 400 600 800 1000 1200 1400 1600 1800 2000
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 Time / min
Current density / A cm-2
Fig. 6 e Chronoamperometric curve recorded at 0.35 V for
Fig. 4 e Polarization curves: comparison among the three the cell with 0.5 mm distance between anode and cathode
different cell configurations. by feeding 10 M methanol solution at the anode.

cathode channels. In the 2nd test the OCV was 0.63 V, similar to
To increase the performance using the cell with a distance
that recorded with a classical sandwiched MEA. This was
of 0.5 mm, an experiment with high methanol concentration
likely due to the use of a wet membrane that allowed the
(10 M) as fuel was carried out. This high methanol concen-
migration of the Hþ ions from the anode to the cathode. In
tration allowed increasing the wettability of the membrane,
fact, the cell resistance in this case was about 5 U cm2 (it was
reducing in this way the overall impedance and consequently
in any case very high due to the large distance between anode
increasing the performance (Fig. 5). In fact, the maximum
and cathode). In the 3rd test, in the presence of a large distance
power density was about 1.2 mW cm
2, approaching the
between the anode and cathode channel and in the presence
performance obtained with the lowest distance between
of an almost dry membrane, the OCV reached 0.97 V. This high
anode and cathode (0.25 mm). The short-circuit current
OCV reflected the absence of methanol cross-over due to the
density was 10 mA cm
2, about one order of magnitude higher
specific planar design. Regrettably, the cell resistance was
than the previous experiment with 2 M methanol solution.
very high (20 U cm2). However, the polarization curves for this
Yet, the OCV was about half compared to the value recorded
device were not controlled by the ohmic drop, as observed in
with 2 M solution, indicating the presence of a larger methanol
Fig. 3: they were controlled by the occurrence of large mass
cross-over, due to the increased wettability of the membrane
transfer limitations as well as charge transfer resistance. In
under these conditions.
fact, the contribution of polarization resistance to the overall
In order to assess the durability of this configuration under
impedance (low frequency) was for the 2nd test one order of
these conditions, i.e., 10 M methanol solution at the anode,
magnitude larger than the ohmic resistance. Moreover, in the
oxygen at the cathode, a catalyst layer both on the channels’
first experiment (1st test in Fig. 3) the overall impedance
walls and on the membrane, distance between anode and
(ohmic þ polarization) was the lowest. For this reason, despite
cathode of 0.5 mm (the same cell configuration of the 3rd test),
the fact that the ohmic resistance was large in the 1st exper-
a chronoamperometric test at 0.35 V was carried out. The cell
iment, the area specific resistance (the slop of polarization
was continuously operated for about 30 h (Fig. 6). During this
curve) was the smallest. Accordingly, the lowest overall
period a small decrease of current density was recorded,
impedance determined the occurrence of the highest current
probably due to the methanol cross-over. Moreover, a small
density in the 1st test.
leakage of the catalyst from the anodic channel during oper-
ation could be the cause of this decrease of performance (even
0.6 0.0014 if the amount of catalyst present in the membrane in addition
0.0012
to that sprayed onto the channel was high enough to assure
0.5 10 M
a suitable methanol conversion). In any case, performance
Power density / W cm

0.001
degradation similar to that recorded with state-of-art mini-
Cell potential / V

0.4
0.0008 stacks was noticed [9,30e36].
0.3
0.0006
0.2
0.0004
4. Conclusions
0.1 0.0002

0 0 A co-planar design of a mDMFC, in which anodic and cathodic

0 0.002 0.004 0.006 0.008 0.01 0.012
micro-channels are located in the same plane, was carried
Current density / A cm
out. Different cell configurations were manufactured, tested
Fig. 5 e Polarization and power density curve recorded for and evaluated. It was observed that the open circuit voltage
the cell with 0.5 mm distance between anode and cathode varied significantly as a function of the membrane humidifi-
by feeding 10 M methanol solution at the anode. cation and distance between anode and cathode channels in
8092 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 0 8 8 e8 0 9 3
this planar design. In the presence of a large distance between
the anode and cathode channel, the OCV reached 0.97 V. This
voltage was obtained by using an almost dry membrane. This
high OCV reflected the absence of methanol cross-over due to
the specific co-planar design. Regrettably, the overall cell
impedance limited the performance. A maximum power
density of 1.3 mW cm
2 (active area) was achieved at room
temperature with the smallest distance between anode and
cathode (0.25 mm). Similar performance with a proper
stability was recorded with the largest distance between
anode and cathode (0.5 mm) by using 10 M methanol
concentration at the anode. Although the performance
recorded for this planar design was lower than the state-of-art
passive DMFCs, this approach may be of interest for electronic
devices requiring small electrical power due to a good
perspective of integration with the power source. However, an
optimization of the system in terms of deposition of the
catalysts onto the micro-channels’ walls is required and it
may allow enhancing significantly the performance.
Acknowledgment
The authors gratefully acknowledge the Regione Piemonte
(Torino, Italy) for funding the MICROCELL project (2005e2008).
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