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PROCESS SYSTEMS ENGINEERING GROUP

SCHOOL OF ENGINEERING

PROCESS SYSTEMS ENGINEERING M.Sc.

(ENERGY SYSTEMS AND THERMAL PROCESSES)

Academic Year 2010-2011

PSE 16: POWER GENERATION

OLUMIDE OLUMAYEGUN

ESSAY ON FUEL CELLS

18 November 2010

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ABSTRACT

This report seeks to give an overview of fuel cells as means of generating


electricity. The aim is to have a better understanding of fuel cells and it various
application. Fuel cell is a developing technology and this report will also enumerate
the future prospect of this mode of generating electricity. Fuel cell can be
considered as an electrochemical device which takes fuel and generate electricity
as it output. It coverts chemical energy directly to electrical energy in a more
efficient manner when compared to heat engines.

Fuel cells can be categorised based on the electrolyte used. The major types of
fuel cells based on the electrolytes are Polymer electrolyte membrane fuel cell
(PEMFC), Alkaline fuel cell (AFC), Phosphoric acid fuel cell (PAFC), Molten
carbonate fuel cell (MCFC), Solid oxide fuel cell (SOFC). The last three belong to a
class of fuel cell regarded as medium or high temperature fuel cells. Direct
methanol fuel cell is also a type of fuel but it considered separately because it is
classified not on the basis of the electrolyte used but on the basis of the fuel,
methanol.

Direct methanol fuel cell has a lot of advantages which include high net energy
density, the fuel is readily available and cheap, small weight of the fuel, and ease
of transportation. But the fuel cell has not witnessed full commercialisation because
of the high cost of producing it, the technical expertise regarding its production is
also not fully developed, and there is lack of common standard among the
organisations producing the fuel cell.

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LIST OF CONTENTS

Title page

Abstract ii

List of Contents iii

1. PRINCIPLE OF FUEL CELL 1

1.1 Introduction 2

1.2 Fuel Cell Operation 3

1.3 Gibbs Free Energy, Electrical Work, and Voltage of Fuel Cell 3

2. TYPES OF FUEL CELLS 4

2.1 Polymer Electrolyte Membrane Fuel Cell (PEMFC) 4

2.2 Alkaline Electrolyte Fuel Cell (AFC) 5

2.3 Phosphoric Acid Fuel Cell (PAFC) 6

2.4 Molten Carbonate Fuel Cell (MCFC) 6

2.5 Solid Oxide Fuel Cell (SOFC) 7

3. DIRECT METHANOL FUEL CELLS (DMFC) 7

3.1 Advantages of Direct Methanol Fuel Cells 8

3.2 Disadvantages of Direct Methanol Fuel Cells 8

3.3 Obstacles to Commercialisation of Direct Methanol Fuel Cells 9

REFERENCES 10

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1. PRINCIPLE OF FUEL CELL

1.1 Introduction

Fuel cells can be considered as an electrochemical device which takes fuel and
generate electricity as it output. In as much as there is supply of fuel it keeps
producing electricity without using up its component parts in the process. This
differentiate a fuel cell from a battery, another electrochemical devices. In a battery
the electrodes are consumed in the process of producing electricity. Fuel cells also
differ from combustion or heat engines in that the chemical energy of the fuel is
converted directly into electricity. In combustion engines the energy of the fuel is
first converted into heat energy which can then be converted to mechanical energy
to generate electricity. This is a very complex process that involves a lot of energy
losses, thus the fuel cell is a better converter chemical energy to useful work than
the heat engines.

The available energy that can be realized from a fuel cell comes from the
difference between the bonding energy of the products and the reactants in the
electrochemical reaction. Take the reaction of hydrogen with oxygen for example,
this can be regarded as a combustion process with hydrogen as the fuel:

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H2 + O2 H2O (1.1)
2

On molecular scale hydrogen gas bonds and oxygen gas bonds are broken and
hydrogen-oxygen bonds are formed by transferring electrons between the
molecules. The bonding energy of the water molecule is lower than the bonding
energies of the hydrogen and oxygen gases. In fuel cells the excess energy is
turned to useful work by causing the electrons to be transferred across a
conducting wire thereby converting chemical energy to electrical energy.
Conversion efficiency can be as high as 60-80% compared to steam engines which
can only be as high as 50% (Winterbone, D.E., 1997).

The electrochemical half reaction for hydrogen combustion is as shown below:

H2 2H+ + 2e- (1.2)

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1
O2 + 2H+ + 2e- H2O (1.3)
2

By spatially separating the reaction sites for the oxidation and reduction half
reaction the electrons released by the first half reaction is made to flow across an
external circuit and hence do useful work before completing the reaction. The
separation of the reaction sites is achieved by means of an electrolyte. Electrolyte
allows the passage of ions but will not allow the electrons to flow through. A fuel
cell will contain at least two electrodes, providing the centres for the half reaction,
separated by the electrolyte. The diagram below is a schematic representation of a
simple fuel cell. The electrodes are made of platinum immersed in aqueous acid
electrolyte.

Electric load
-
e
Platinum electrode

Electrolyte
+
H

H2 O2

Figure 1: Simple fuel cell

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1.2 Fuel Cell Operation

The production of electricity in a fuel cell can be simplified into four basic steps
(O'Hayre, R. P. et al, 2006):

a. Reactant delivery into the fuel cell.


b. Electrochemical reaction – the rate of the chemical reactions at the
electrodes will determine the amount of current that will be produced by the
fuel cell. Catalyst are employed at the electrodes to increase the reaction
rate.
c. Ionic conduction through the electrolyte and electron conduction through the
external circuit .
d. Product removal from the fuel cell – the product of the reaction need to be
remove from the system else they will build up and stop further reaction
from taking place.

The real voltage delivered by a fuel cell is usually less than the thermodynamically
predicted voltage due to losses associated with above steps. For a fuel cell with an
ideal voltage, Eth the real voltage, V can be expressed as:

V = Eth + ρact - ρohmic - ρconc (1.4)

where,
ρact - losses due to activation energy of the electrochemical reaction.
ρohmic- ohmic losses due to ionic conduction through the electrolyte and electron
conduction through external circuit.
ρconc- Concentration losses due to delivery and removal of material.

1.3 Gibbs Free Energy, Electrical Work, and Voltage of Fuel Cell

Gibbs free energy represent the work potential of a system. Hence the maximum
electrical work that can be performed by a fuel cell is given by the change in Gibbs
free energy of the system:

W elect = -Δg (1.5)

Electrical work can be defined as:


W elect = EQ (1.6)

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If n moles of electrons were transferred then the total charge transferred would be:

Q = nF (1.7)

where F is the Faraday constant. Combining the above three equation yields

Δg = -n FE (1.8)

Hence the reversible voltage obtainable from a fuel cell is

g
E= (1.9)
nF

2. TYPES OF FUEL CELLS

Fuel cells can be classified based on their electrolyte. The main types of fuel cell
are:

1. Polymer electrolyte membrane fuel cell (PEMFC).


2. Alkaline fuel cell (AFC).
3. Phosphoric acid fuel cell (PAFC).
4. Molten carbonate fuel cell (MCFC).
5. Solid oxide fuel cell (SOFC).

Direct methanol fuel cell is another type of fuel cell but most researcher consider it
as belonging to a different class as its classification is based on the fuel and not on
the electrolyte used. Phosphoric acid, molten carbonate and solid oxide fuel cells
belong to a class of fuel cell regarded as medium or high temperature fuel cells.

2.1 Polymer Electrolyte Membrane Fuel Cell (PEMFC)

PEMFC uses a proton conducting polymer, perflourinated proton-exchange


membranes, as the electrolyte. The polymer membrane is coated on both side with
a thin layer of platinum-based catalyst and porous carbon electrode. This kind of
sandwich arrangement of electrode-catalyst-membrane-catalyst-electrode is often
referred to as membrane electrode assembly (MEA). The whole structure is less
than 1mm in thickness.

The polymer membrane must contain some amount of water in order to keep its
conductivity hence it operating temperature is limited to 90 0C and below. Also

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because of the low operating temperature the only practical catalyst are platinum-
based catalysts. Direct methanol (liquid fuel) can be used as fuel for PEMFC apart
from the conventional hydrogen fuel. Research into the suitability of liquid fuel for
this type fuel cell is still ongoing. One of the major advantage of PEMFC over other
type of fuel cell is its high power density (300-1000 mW/cm2). It also possess a
good start-stop capability. The PEMFC is suitable for portable application because
of its low-temperature operating condition.

The many advantages of PEMFC are overshadowed by its many limitations which
include stringent thermal control requirement, moisture control, expensive
materials, and susceptibility to CO poisoning (Bocarsly, A. B. and Niangar, E. V. ,
2009). Most of these limitation can be minimised if the PEMFC can be designed to
operate at elevated temperature of about 120-150 0C. Hence recent research has
been in the development high temperature PEMFC, obtaining better catalytic
action with less expensive materials and mitigation of poisoning of polymer
electrolyte membrane by impurity gases.

2.2 Alkaline Electrolyte Fuel Cell (AFC)

The electrolyte employed in AFC is potassium hydroxide and unlike the acid
electrolyte fuel cell where H+ is conducted from the anode to the cathode in the
AFC OH- is conducted from the cathode to the anode. The reaction at the anode
and cathode is shown below:

Anode: H2 + 2OH- 2H2O + 2e- (1.10)

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Cathode: O2 + 2e- + H2O 2OH- (1.11)
2

Water is produced twice as fast as is been consumed hence the need to remove
excess water to avoid dilution of the electrolyte. The main limitation of AFC for
terrestrial application is the degradation the KOH electrolyte by CO2 poisoning as
shown below, therefore pure H2-O2 must be used.

2OH- +CO2 CO32- +H2O (1.12)

Advantages offered by AFC include improved cathode performance, non-precious


metal such as nickel can be used as catalyst and extremely inexpensive
electrolyte.

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2.3 Phosphoric Acid Fuel Cell (PAFC)

Phosphorous acid fuel cell uses liquid H3PO4 as electrolyte. The electrolyte is
embedded in SiC matrix between two porous graphite electrodes coated with a
platinum catalyst (O'Hayre, R. P. et al, 2006) . The half reaction is as follows:

Anode: H2 2H+ + 2e- (1.13)


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Cathode: O2 + 2H+ + 2e- H2O (1.14)
2

PAFC will operate optimally in the temperature range of about 180- 210 0C with
electrical efficiency of about 40% but could be as high as 70% when used in a
combined heat and power application. The technology of PAFC is relatively
matured but current research interest is how to make it cost competitive with
conventional power technologies.

2.4 Molten Carbonate Fuel Cell (MCFC)

In MCFC the electrolyte is a molten mixture of Li2CO3 and K2CO3 sustained by


LiOAlO2 matrix. The mobile charge carrier is carbonate ion, CO 32- and the reaction
at the anode and cathode is as follows:

Anode : H2 + CO32- CO2 +H2O + 2e- (1.15)


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Cathode: O2 + CO2 + 2e- CO32- (1.16)
2
There is the need for recirculation of CO2 because the CO2 is produced at the
anode to be consumed at the cathode. It does not suffer from CO poisoning like
most other fuel cell, the CO is actually a fuel. The anode electrode is usually
nickel/chromium alloy while the cathode is made of lithiated nickel oxide hence the
advantages of using non-precious catalyst. It enjoys fuel flexibility as hydrogen,
methane and simple alcohol could be used as fuel. One of its advantage is the
corrosive nature of the molten electrolyte. MCFC is most suitable for stationary,
continuous power application.

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2.5 Solid Oxide Fuel Cell (SOFC)

SOFC is made of solid oxide ceramic electrolyte sandwiched between two porous
electrodes (Sammes, N.M. and SpringerLink, 2006). The common electrolyte
material is yttria-stabilised Zirconia (YSZ). The anode is usually made of Ni/8YSZ
material while typical cathode material is strontium doped LaMnO 3 (LSM). In SOFC
O2- is the mobile ion conductor and the reactions at the anode and cathode are

Anode: H2 + O2- →H2O +2e- (1.17)


Cathode: O2 + 2e- → O2- (1.18)

Water is produced at the anode unlike PEMFC, AFC and PAFC in which water is
produced at the cathode. The operating temperature is between 600 and 1000 0C.
Although the high operating temperature could lead to low open circuit voltage but
at the same time it increases its performance with the possibility of inwardly
processing hydrocarbon.

3. DIRECT METHANOL FUEL CELLS (DMFC)

Direct methanol fuel cells use methanol, a liquid fuel, in place of pure hydrogen. It
require water at the anode as an additional reactant. Even though in principle
methanol could be used with any of the electrolytes its use is only practicable with
the PEMFC. If used in the high temperature electrolyte fuel cells methanol will lose
the simplicity of its being a liquid fuel. Also it produce CO2 which makes it
inapplicable in AFC. The reaction at the electrodes are

Anode: CH3OH +6OH- → CO2 +5H2O +6e- (1.19)


Cathode: 1 O2 + 6H+ 6e- → 3H2O (1.20)
The overall reaction is
CH3OH + 1 O2 → 2H2O +CO2 (1.21)

One major characteristics of DMFC is that there is a considerable voltage loss at


the anode in addition to the loss at the cathode common to all other fuel cell
(Larminie, J., Dicks, A. and Knovel, 2003).

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3.1 Advantages of Direct Methanol Fuel Cells

High net energy density – energy density of methanol is close to those of


hydrocarbon fuels. The net energy density of methanol is about 18.9 MJ/kg
compared to hydrogen which is about 0.72 MJ/kg (Larminie, J., Dicks, A.
and Knovel, 2003).
Readily available and cheap fuel – Methanol can be produced from
various sources such as wood, natural gas and coal. This makes the fuel
readily available and cheap.
Reduce weight of the fuel cell – DMFC does not need a fuel vaporiser
which is a complex, heavy and space consuming component of other fuel
cells running on pure hydrogen. This makes DMFC light weight compared to
other fuel cells.
Simpler to use and could be refill easily – Methanol being a liquid is
easier to use and could be refill easily. It does not require reformer like
hydrogen fuel and could be used at room temperature and pressure.
Ease of transportation - the technology for transporting liquid material is
well developed hence methanol could be delivered to the public using
existing infrastructure.

3.2 Disadvantages of Direct Methanol Fuel Cells

Slow rate of reaction at the anode – the reaction at the anode progresses
so much slowly when compared to hydrogen reaction. The reaction occurs
by many complex steps which can even produce CO as intermediate
product. The CO can act as a poison. The overall effect is that DMFC has
low exchange current resulting in high activation overvoltage loss at the
anode (O'Hayre, R. P., et al, 2006).
Fuel crossover – DMFC also experience significant crossing over of
methanol from the anode to the cathode through the electrolyte. The
polymer electrolyte membrane commonly use with DMFC is a very good
absorber of methanol. The methanol will mix with water and crosses rapidly
to the cathode. This will result in reduced open circuit voltage as methanol
that could have reacted at the anode to liberate electrons is being lost
through this process.
Loss of fuel through evaporation – for any reasonable increase in the
temperature of the fuel cell methanol will evaporate and escape with the
carbon dioxide gas. This amounts to loss of useful fuel and in some systems

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the methanol have to be condensed out of the carbon dioxide thereby
adding to the complexity of the system.
Poor performance compared to the hydrogen fuel – as a result of the
above limitations of DMFC its performance is very poor when compared to
proton exchange membrane fuel cells running on hydrogen.

3.3 Obstacles to Commercialisation of Direct Methanol Fuel Cells

Despite the many benefit of Direct Methanol fuel cells there are still many hurdles
to be crossed before full commercialisation can be achieved. One of the major
hindrances to commercialisation of the fuel cell is the high cost of production which
translate to high price for the end users. DMFC uses expensive platinum as the
cathode and even the more expensive platinum/ rubidium as the anode. Price has
been a major limitation to full commercialisation of DMFC; electrolyte made of thick
expensive polymer and even with that still waste a lot of fuel.

Another obstacles to commercialization of DMFC has to do with technical expertise


regarding the production of the fuel cells. Currently DMFC have low overall
efficiency and power density and there is also the need for miniaturisation. Further
technological development in electrode and electrolyte manufacturing is necessary
for rapid move toward commercialization. Zhang J. (2008) was of the opinion that
„for early DMFC commercialization the target total catalyst loading for the entire
membrane electrolyte assembly (MEA) (composed of both cathode and anode
catalyst layers as well as membrane) must be reduced from the current 2.0–8.0
mgPt cm-2 to a level < 1.0 mgPt cm-2 without performance compromise‟.

Also lack of common standard among the organisation involved in the production
of DMFC poses an obstacles to the commercialisation. According to Makuch G.
(2004) there is need for “cross-organizational coordination to ensure market
acceptance and commercial success”. There is the need for standardisation of the
packaging especially the methanol cartridge. This will allow the users flexibility in
the purchase and use of the component parts.

Furthermore government regulation/legislation regarding the use of methanol in


some countries needs to be amended in order to hasten the journey toward
commercialisation of DMFC. Methanol is classified as hazardous and inflammable
material and even restricted on some airlines. The regulations need to be amended
to delineate between the use of methanol as fuel in fuel cell in which case it has
been properly packaged in cartridges and other common use.

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REFERENCES

Bocarsly, A. B. and Niangar, E. V. (2009), "FUEL CELLS - PROTON-EXCHANGE


MEMBRANE FUEL CELLS | Membranes: Elevated Temperature", in Jürgen
Garche (ed.) Encyclopedia of Electrochemical Power Sources, Elsevier,
Amsterdam, pp. 724-733.

Larminie, J., Dicks, A. and Knovel, ( 2003), Fuel cell systems explained, 2nd ed., J.
Wiley, Chichester, West Sussex.

Makuch G. (2004), Micro Fuel Cells Strive for Commercialization


http://powerelectronics.com/power_management/battery_portable_power_manage
ment/power_micro_fuel_cells_3/ (Accessed 2010 14/11)

O'Hayre, R. P., Cha S., Colella W., and Prinz F. B., (2006), Fuel cell fundamentals,
John Wiley & Sons, Hoboken, N.J.

Sammes, N.M. and SpringerLink, ( 2006), Fuel cell technology, Springer, London

Winterbone, D.E., ( 1997), Advanced Thermodynamics for Engineers, Elsevier.

Zhang J. (2008), PEM Fuel Cell Electrocatalysis, Institute for Fuel Cell Innovation,
National Research Council Canada.
http://www.scitopics.com/PEM_fuel_cell_electrocatalysis.html (Accessed 2010
14/11)

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