A MICRO DIRECT METHANOL FUEL CELL WITH SELF-PUMPING OF LIQUID FUEL

Dennis Desheng Meng* and Chang-Jin CJ Kim

Mechanical and Aerospace Engineering Department, University of California, Los Angeles (UCLA)
Los Angeles, CA, U.S.A.

ABSTRACT In the fuel stack of a DMFC, the electrochemical reactions are:

This paper introduces a micro direct methanol fuel cell CH3OH + H2O 6e- + 6H+ + CO2 , (anode side)
(DMFC) with an imbedded self-pumping mechanism to deliver 1.5O2 + 6e- + 6H+ 3H2O , (cathode side)
liquid fuel. The fuel is propelled without any power consuming CH3OH +1.5O2 2H2O + CO . (overall reaction)
component (e.g., a pump), while removing the CO2 bubbles
generated by the fuel-cell electrochemical reaction of the system. According to this reaction, DMFCs intrinsically generate CO2 gas
Furthermore, the pumping rate is self-regulated by the reaction, i.e., bubbles. If not promptly removed, these bubbles will clog the
by the load. By eliminating the need for a pump and gas/liquid anodic microchannels and aggravate the deleterious methanol
separator, our design allows much simpler systems, which is crossover. The current common practice is to use an external pump
especially beneficial for miniaturization. Although we test with to deliver the fuel and push the gas bubbles to downstream at the
DMFC in this paper, the mechanism applies to other hydrocarbon same time. Then an open tank (gas/liquid separator) can be used to
liquid fuels as well. release CO2 gas [5]. This approach is impractical in a portable
device because of the danger of fuel leakage. Meanwhile, using an
INTRODUCTION external pump to deliver fuel not only takes up a space and
complicates the microsystem, but also claims a significant portion
Due to its much higher energy density than traditional of the power output of DMFC. Since most reported micropumps
batteries, micro direct methanol fuel cell (DMFC) has been require 100 mW or higher of power input, about 10% of the fuel
widely considered as the next generation power source for portable cell total power output (usually ~1 W) has to be consumed by
electronic devices. DMFC has been anticipated to be one of the pumping. This percentage can be even higher if the fuel cell is not
first fuel cells to fully enter the consumer market in the near future working at the maximum power capability.
[1], with a few products already announced [2-4]. However,
several technical hurdles still need to be cleared to make the We have previously proved that nanoporous membrane can
DMFC mature and finally accepted by the consumer market, remove gas bubbles while holding liquid with satisfactory pressure
including the cost, the performance of membrane electrode tolerance [6]. Combined with virtual check valves, the venting
assembly (MEA), and the complexity compared with traditional mechanism has also enabled a new bubble-driven pumping
batteries. mechanism. The gas bubbles generated by electrolysis were
employed to circulate Na2SO4 aqueous solution in a microfluidic
The working principle of DMFC is illustrated in Fig. 1. The loop [7].
aqueous methanol solution is fed into the anodic channel while air
flows through the cathodal channel. A series of electrochemical In this paper, a similar pumping mechanism is applied to a
reactions are enabled by the proton exchange membrane (PEM) DMFC, with the intrinsically generated CO2 gas bubbles as the
and the catalyst layers. Protons migrate from anode to cathode gas source. Therefore, the fuel delivery requires no power input at
through the PEM, while electrons are collected by the anodic all. The design solves the bubble clogging and fuel delivery
electrode and consumed in the cathodal electrode. The problems at the same time. Both the gas/liquid separator and
accumulated electrons provide the continuous current for the external pump are eliminated from the system, allowing an
external circuit. An external pump is usually used to provide a integrated, simply and economic design of DMFC system.
continuous flow of methanol fuel to the anode and maintain the
fuel concentration there. HYDROPHOBIC VENTING

The gas removal approach is implemented by microscopic

CO2 bubbles methanol hydrophobic (or lyophobic for methanol) venting holes, which
anodic
solution allow the gas to pass through relatively undeterred while the liquid
chamber
e- e- e- e- e- e-
menisci blocks the liquid from flowing out. Fig. 2 represents an
proton exchange idealized model to illustrate how liquid can be restricted from
H+ H +
e-
membrane H+ H+
H+
current leaking by its own meniscus. On the sharp corner of the venting
H+ H +
(PEM) H+ H+ H+ holes entrance, this meniscus can assume a range of curvatures, so
e- e- e-
cathodal water
as to balance with the varying pressure across the meniscus
air electrode (transmeniscus pressure) according to the Laplace-Young equation:
chamber droplets
catalyst Pl Po = 2 l cos( ) / r , (1)
where Pl is the pressure of the liquid fuel, Po is the ambient
Figure 1. Working principle of direct methanol fuel cell pressure, l is the surface tension of the liquid fuel, is the angle

* Corresponding author: Dennis Desheng Meng, 37-129 Engr. IV, UCLA, CA 90095, Tel: (310)825-3977, Email: [email protected]

Solid-State Sensors, Actuators, and Microsystems Workshop

0-9640024-6-9/hh2006/$202006TRF 120 Hilton Head Island, South Carolina, June 4-8, 2006
between meniscus and the capillary wall, and r is the radius of the shape, e.g., a diverging hydrophilic shape [10]. By making the
capillary. microchannel hydrophilic (e.g., SiO2), a surface energy difference
gas between its hydrophilic surface and the hydrophobic membrane
P0
can make the latter a bubble trap [11]. Once a bubble reaches the
solid
2r hydrophobic nanoporous membrane, it will be drawn into the
wall
membrane region (Fig. 3-b). Through the venting holes in the
membrane, the bubble is vented out without liquid loss. The liquid
liquid fuel then fills into the section symmetrically to replace the vacancy left
Pl by the gas bubble. A pumping cycle is thus completed and a net
pumping to the right is achieved.

Vgright
Vgleft
Figure 2. Hydrophobic venting by a microscopic venting hole bubble source
a. Directional bubble growth
The maximum transmeniscus pressure that can be withstood
without leakage (leakage onset pressure) is determined by the size Vt
of the venting hole as well as the surface properties associated with
hydrophilic hydrophobic
the hydrophobic material. Due to their intrinsic hydrophobicity and
small pore size, hydrophobic nanoporous membranes can provide b. Built-in bubble transportation
very high leakage onset pressure. Successful venting of gas Vcleft Vcright
bubbles has been achieved for both pure water and methanol fuel net flow
with a concentration as high as 10 M, by employing porous
polypropylene membrane with a nominal pore radius of 0.1 m c. Symmetric bubble collapsing
(from Chemplex). The fuel is proven to be contained without Figure 3. Micropumping by directional growth and
leakage under the over-pressures as high as 200 kPa for both pure hydrophobic venting of bubbles
water and 10 M methanol, fulfilling the requirement of the current-
as well as next-generation DMFC [8]. By using this self-pumping method, liquid circulation in a
sealed closed-loop microchannel has been demonstrated by using
PUMPING BY HYDROPHOBIC VENTING electrolytic gas bubbles (H2 and O2). By applying 2-85 mW power
input, the liquid is circulated at a volumetric flow rate of 4.5-13.5
A new bubble-driven pumping mechanism [9] has been nL/s in the particular pump loop. Compared with the similar
developed utilizing hydrophobic venting, as Fig. 3 illustrates. A thermal-bubble-driven pump, the electrochemical-bubble-driven
group of small hydrophilic capillaries are fabricated on the left side micropump exhibits better controllability and biocompatibility
of the bubble source to serve as a virtual check valve for gas with 10-100 times higher power efficiency.
bubbles. When a bubble grows at a location close to this virtual
check valve (as Fig. 3-a shows), expansion of the left menisci of FABRICATION AND ACTIVATION OF DMFC
the bubble is hindered due to its capability to provide higher
capillary pressure than the right meniscus does. Consequently, the In this paper, a similar pumping mechanism is applied to a
bubble only grows to the right and pushes the liquid rightward. DMFC, with the intrinsically generated CO2 gas bubbles as the
The bubbles generated in the middle of the microchannel can be gas source. Therefore, the fuel delivery requires no power input.
pushed by the leftmost one to the right. This rightward bubble
motion can also be promoted by proper design of the channel

Plexiglas fixture

Pyrex glass virtual check valve porous membrane

fuel reservoir fuel cell anode methanol/water

MEA
refueling
inlet metal cathode
silicone oxygen breather epoxy
layers breather
rubber
Pyrex glass cover
breather
Plexiglas fixture outlet

Figure 4. The cross-section of assembled self-pumping DMFC

The cross-section of the assembled self-pumping DMFC is breather cover are fabricated by DRIE, followed by metal
shown in Fig. 4. Microchannels of the anode, the cathode and the evaporation (0.01 m Cr, 3 m Cu and 0.5 m Au). The anode and

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the cathode are then anodically bonded to two pieces of Pyrex
glass. A Plexiglas fixture is used to sandwich MEA (E-TEK) VERIFICATION OF FUEL CIRCULATION
between the anode and the cathode. Silicone rubber sheets are
added between the Plexiglas fixture and the DMFC device to After activation, the fuel cell can be brought to operation
ensure uniform clamping pressure. A piece of nanoporous condition with both the refueling inlet and the refueling outlet
polypropylene film (Chemplex) is glued between the anode and closed. They can be used to refuel the fuel cell if the fuel in the
the breather cover by epoxy to remove CO2 gas bubbles during reservoir is used up. The gas bubbles generated by the
operation. The breather outlet is connected to a valve via tubing. electrochemical reaction are used as the gas source in a self-
The venting can be stopped by closing the valve to perform the pumping mechanism to circulate the fuel, as Fig. 5 indicated. This
control experiment. The layout of the anode microchannels, the fuel circulation mechanism does not require any external power
return loop and the reservoir is shown in Fig. 5. input. Similar bubble motion pattern as in [7] has been observed
throughout the flow field. Fig. 7 demonstrates the bubble motion at
the end of an anodic microchannel, as well as the successful
refueling outlet anodic moicrochannels
bubble removal.
area A
t = 0s
reservoir bubble
flow directions
during operation t = 0.07s
refueling
inlet venting membrane
fuel return loop breather t = 0.13s

DRIE etching depth: an enlarged view

50m: of area A t = 0.2s
300m:
550m (through wafer):
t = 0.27s
Figure 5. Layout of anodic microfluidic loop
t = 0.33s
After assembly, the MEA of the fuel cell is activated
according to the procedure provided by the manufacturer. Hot DI
water at 90 oC is first flowed through the anode microchannels t = 0.4s
with a flow rate of 5 mL/min for 1.5 hours to activate the proton
exchange membrane. Then, 2 M methanol at 90 oC is flowed
through the anode microchannels with a flow rate of 5 mL/min for t = 0.47s
3 hours. Meanwhile, oxygen is flown through the cathode channel
at ~100 mL/min. The cell voltage is controlled at ~0.25 V by
t = 0.53s the next bubble
connecting it to a variable resistor. This second step activates the
catalyst. During activation, an external pump is used to deliver the
anodic liquid from the refueling inlet to the refueling outlet in
Figure 7. Bubble removal by the breather
Fig. 5. A pressurized gas tank is used to provide the cathodal gas
flow. The measured polarization and power density curves of the
DMFC after activation are shown in Fig. 6. This test has been In order to further verify the fuel circulation, the self-
performed with 5 ml/min 2 M methanol flow at anode, ~ 100 sustainability of the DMFC is tested by loading the fuel cell with
ml/min oxygen flow at cathode and 80 oC cell temperature. a 1.3 resister and measuring the power output over time, as
shown in Fig.-8. The self-sustainability experiments were
700 100 performed under 80 oC, with 2 M methanol in the anode and ~ 100
ml/min oxygen flow in the cathode. The operation time span (~ 8
600 min) confirmed the sufficient fuel delivery, because the given
voltage (mV)

power density (mW/cm2)

80 reservoir is theoretically supposed to support an operation time of

500 ~ 9 min at the peak power output of this electrical load. As a
60 reference, a control experiment was performed by closing the valve
400 connected to the breather outlet, i.e., blocking CO2 venting and
disabling the self-pumping mechanism. In the control experiment,
300 40 gas bubbles were observed to grow and fill the entire anodic
200
microchannel, and power output dropped rapidly after about 2.5
power mins. Furthermore, fuel leakage was eventually observed, leading
20
100 voltage to the failure of the DMFC device.

0 0
0 100 200 300 400 5002 600 700
current density (mA/cm )

Figure 6. Polarization and power density curves of the

assembled DMFC after MEA activation

122
 80 DMFC with external pump (flow rate: 5ml/min)
REFERENCES
output power (mW) 70
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ACKNOWLEDGEMENT

The authors would like to thank Professor C.-M. Ho, Dr. T.

Cubaud and Dr. T. J. Yen for their discussions and suggestions, as
well as Mr. J. Jenkins and Ms. A. Lee for the help with the
manuscript.

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