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Methanol Fuel Cells

Electrochemical Engineering Project


Faris Al-Saadoon

METHANOL FUEL CELLS


Abstract
In this paper, a discussion about direct methanol fuel cells
(DMFC) is provided. The paper starts by presenting some introductory
information about the subject. This information includes historical
background along with the important electrochemical equations and
trends. A review of several research articles on the topic of methanol
fuel cells is then provided. This discussion includes information
regarding the importance of the considered articles, positive and
negative aspects and suggestions for future work. Finally, a general
trend and future outlook section is provided.
Introduction
Direct methanol fuel cells (DMFC) are one type of protonexchange fuel cells that utilize methanol in generating energy. The
main advantage of the DMFCs is the easiness in transporting methanol.
In addition, another advantage of using DMFCs is the use of methanol
as an energy generating liquid. Methanol is generally an energy-dense
chemical that is reasonable stable at all environmental conditions.
Despite these advantages; however, DMFCs have low efficiency

making them a viable option for applications were energy and power
are more important than efficiency.

Cell Operation
In general, DMFCs use a methanol solution (around 1M or about
3% in mass) to carry the reactant into the cell. This type of
electrochemical cells typically operates at temperatures that range
between 50oC and 120oC. On high temperatures, these cells have to be
operated in a pressurized environment. Although their operation is
more efficient at high temperature in pressurized environment, DMFCs
operated under these conditions end up causing so many losses in the
complete system. Therefore, operating these cells in atmosphericpressure conditions is preferred.
When operating DMFCs, a phenomenon by which methanol
diffuses through the membrane without reaction, occurs due to the
methanol cross over. This phenomenon causes a significant decrease in
efficiency because crossed-over methanol, after reaching the airside
(the cathode), immediately reacts with air. This is debated to result in a
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reduction in the cell's voltage. Other problems that might arise when
operating DMFCs include the management of carbon dioxide that is
created at the anode. The ability to maintain the solution water is
another problem that is expected when operating DMFCs. Finally, it is
noted that the only waste products with these types of fuel cells are
carbon dioxide and water. Figure 1 presents a typical schematic of a
methanol fuel cell.

Figure 1: A Schematic of a Methanol Fuel Cell


Chemical Reactions
The chemical reactions involved in DMFCs are heavily dependent
on the oxidation of methanol on a catalyst layer, which results in the
formation of carbon dioxide. In addition, the chemical reaction in
DMFCs involve water consumption at the anode and produced at the
cathode. In this process, Protons (H+) are transported across the proton
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exchange membrane to the cathode where they react with oxygen to


result in the production of water. Electrons, on the other hand, are
transported through an external circuit from the anode to the cathode;
thus, providing power to the devices connected to the cell. The halfreactions involved in this process include:

Table1: Half-Reactions Involved in DMFCs.

Equation

Reaction

Anode

+ C O2
++ 6 e
CH 3 OH + H 2 O 6 H
Oxidation
3 H 2 O
++6 e
3
O +6 H
2 2

Cathode

Overall reaction

Reduction
3
CH 3 OH + O2 2 H 2 O+C O2
2
redox reaction

In the half-reactions of the DMFCs, Platinum is typically used as a


catalyst. This generally results in the loss of cell voltage potential due
to the oxidation of the methanol, which might be present in the
cathode chamber. The replacement of the platinum catalyst, if found,
might result in the reduction of oxygen which in turns results in
alleviating the problem of cross-over. Using platinum, in addition, is
expensive; thus resulting in high costs per kilowatt produced using
DMFCs.
As the methanol oxidation reaction takes place carbon monoxide
(CO) starts to form. This generated CO is heavily adsorbed by the
platinum catalyst; thus, reducing its surface area which in turn results
in reducing the overall performance of the cell. To improve this
problem, another components, such as ruthenium or gold, are added to
the catalyst because these catalysts oxidize water which yields OH
radicals. These OH radicals, generated from the oxidized water
molecules, oxidize carbon monoxide (CO) producing CO2 which is then
released as gas. Using these OH groups in the half reactions, they are
also expressed as:
Table 2: Half-Reactions Expressed Using OH Groups.

Equation

Reaction

+C O2
5 H 2 O+6 e
CH 3 OH +6 OH

Anode

oxidation

6 OH
3
O + 3 H 2 O+6 e
2 2

Cathode

Overall reaction

reduction
3
CH 3 OH + O2 2 H 2 O+C O2
2
redox reaction

Literature Review
Several studies have been conducted to examine the efficiency
of direct methanol fuel cells. Antonucci et al. (1999) investigated direct
methanol fuel cell based on a composite Nafion-silica electrolyte for
high temperature operation. In their study, operation of a liquid-fed
DMFC working at 145C was demonstrated by using a composite
membrane made of Nafion ionomer and silica. Several advantages
have been attained through using the enhanced humidification
conditions of the membrane-electrode (M&E) assembly. For instance,
this enhanced humidification assembly allowed for taking advantage of
the high operation temperature with consequent speeding up of the
methanol oxidation kinetics. It is reported by Antonucci et al. (1999)
that a peak power density of 240 mW/cm 2 for an oxygen-fed cell was
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reached; the measured methanol cross-over rate was 410 6 moles


min1 cm2. A physico-chemical characterization of the cell components
was also reported.
After conducting their study, Antonucci et al. (1999) came up
with the following conclusions:
-

Increase in working temperature, besides favoring the slow


methanol oxidation kinetics with state-of-the-art PtRu bimetallic
catalysts, is thought to contribute to more stable activity levels
of the cell through reduction of poisoning phenomena of the
anode catalyst due to formation of strongly adsorbed reaction

intermediates.
Peak power densities of 250 and 150 mW cm2 in oxygen and
air, respectively, were obtained.
Hamnett (1997) investigated the mechanism and electrocatalysis

in the direct methanol fuel cell. In his study, a unified treatment of the
mechanism of electrocatalysis of methanol oxidation on platinum and
platinum-containing alloys was studied. Several alloys were examined
to evaluate their effect. As reported by Hamnett (1997) the effect of
various alloys is shown to be interpretable within this overall model,
and methods for the systematic improvement of the rate of electrooxidation of methanol are described. According to Hamnett (1997),

some recent results for model direct methanol fuel cells showed that
critical performance parameters for commercial exploitation are now
achievable with modern catalytic formulations and cell designs.
Xiao et al. (2013) examined the performance of a direct
methanol

fuel

cell

using

flexible

proton-conducting

glass-based

composite membrane. In their study, a direct methanol fuel cell


(DMFC) with a proton-conducting composite membrane, which is
synthesized from Nafion/phosphosilicate (NPS) glass and sulfonated
poly(ether ether ketone) (SPEEK) polymer, was prepared, and its
performance was evaluated at different cell temperatures, methanol
flow rates, and oxygen backpressures. The NPS/SPEEK composite
membrane used in this study had a methanol permeability of 7.5
107 cm2 s1. Xiao et al. (2013) reported that the developed DMFC
releases a peak power density of 73.1 mW cm2 at a cell temperature
of 85 C.
Based on the results of their study, Xiao et al. (2013) reported
the following conclusions:
-

A 6NPS/4SPEEK composite membrane with an NPS glass powder


content of 60 wt.% was found to be flexible due to the
incorporation of the SPEEK polymer component, and showed a
low methanol permeability of 7.5 107 cm2 s1.
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The developed DMFC released a peak power density of 73.1 mW


cm2 at a cell temperature of 85 C. Based on the promising
output power, such a low-cost, flexible composite membrane
may possibly be used as an electrolyte in DMFCs.

Future Trends
The focus of recent research is on investigating the performance
of direct methanol fuel cells while varying the various components
composing the cells. To achieve this objective, the underlying
processes of the entire system must be well understood and
established.

Research

efforts

shall

be

distributed

between

understanding underlying process in direct methanol fuel cells and the


synthesis and design of new electrocatlysts or membrane; thus,
leading to faster implementation of technological applications.
Summary and Conclusions
This paper summarized a brief review of literature on direct
methanol fuel cells. Three different articles related to different aspect
of direct methanol fuel cells were presented in this paper. The
conclusions made by the respective authors of the considered articles
were also presented in this paper.

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References
-

Direct Methanol Fuel Cells, Wikipedia, the free encyclopedia.


P.L Antonuccia, A.S Aricb, P Cret b, E Ramunnic, V Antonuccib.,
(1999). Investigation of a direct methanol fuel cell based on a
composite

Nafion-silica

electrolyte

for

high

temperature

operation, Solid State Ionics.


A. Hamnett (1997). Mechanism and electrocatalysis in the direct

methanol fuel cell, Catalysis Today.


A. Hamnett (1997). Mechanism and electrocatalysis in the direct

methanol fuel cell, Catalysis Today.


Ming Xiao, Haibin Li, Zhigang Di, Xiaojing Chen, Huifeng Wang.
(2013). Performance of a direct methanol fuel cell using flexible
proton-conducting glass-based composite membrane, Journal of
Power Sources.

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