Direct Energy Conversion: Fuel Cells

Sustainable Energy Science and Engineering Center
Direct Energy Conversion: Fuel Cells
References:
Direct Energy Conversion by Stanley W. Angrist, Allyn and Beacon,
1982.
Fuel Cell Systems, Explained by James Larminie and Andrew Dicks,
Wiley, 2003.
Fuel Cell Technology Hand Book, Edited by Gregor Hoogers, CRC
Press, 2002
Fuel Cells
Introduction:
Hydrocarbon Fuels 5
6
Energy stored in Useful power
Combustion
3
chemical bonds
Bypass the conversion-to-heat and mechanical-to-electrical processes

A fuel cell is an electrochemical device in which the chemical energy
of a conventional fuel is converted directly and efficiently into low
voltage, direct current electrical energy. Since the conversion can be
carried out isothermally (at least in theory), the Carnot limitation on
efficiency does not apply.
Fuel Cell Efficiency
10
1
Fuel Cells
William Grove 1839
10
Grove noted with interest that this device, which used platinum
electrodes in contact with dilute sulfuric acid would cause
permanent deflection of a galvanometer connected to the cell. He
also noted the difficulty of producing high current densities in a
fuel cell that uses gases.
Fuel Cells
Mond & Langer (1889) - Gas battery
10
1
Daniell Cell
1 We10 will use the term anode to

mean the electrode at which
5 oxidation takes place - losing of
2 6 9
electrons
1
3
7 4
Cathode is the electrode at which
11
reduction takes place - electrons
are gained from the external circuit
Fuel Cell
The Fuel Cell is a device which converts hydrogen
or other fuel and oxygen into electricity. It
achieves this using a process which is the reverse
of electrolysis of water first identified by William
10
Grove in 1863.
The common types of fuel cells are phosphoric acid (PAFC), molten carbonate
(MCFC), proton exchange membrane (PEMFC), and solid oxide (SOFC), all named
after their electrolytes. Because of their different materials and operating
temperatures, they have varying benefits, applications and challenges, but all share
the potential for high electrical efficiency and low emissions. Because they operate at
sufficiently low temperatures they produce essentially no NOx, and because they
cannot tolerate sulfur and use desulfurized fuel they produce no SOx.
Historical Development
10
1
Fuel Cell Types
1 10
5
2 6 9 1
3
7 4
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Hydrogen - Oxygen Fuel Cell
At the anode the

hydrogen gas ionizes
1 10 releasing electrons and
creating H+ ions (or
5 protons). This reaction
6 9 releases energy.
2 1
3 2H 2 ® 4H + + 4e-
7 4
O2 + 4e- + 4H + ® 2H 2O
11 At the cathode, oxygen
reacts with electrons
taken from the electrode,
a n d H + ions from the
electrolyte, to form water
2H 2 ® 4H + + 4e-
O2 + 4e- + 4H + ® 2H 2O
An acid with free H+ ions. Certain

polymers can also be made to
contain mobile H+ ions - proton
exchange membranes (PEM)
Membrane Electrode Assembly
10
The MEA consists of two electrodes, the anode and the cathode, which are each coated on one side with a thin
catalyst layer and separated by a proton exchange membrane (PEM). The flow-field plates direct hydrogen to the
anode and oxygen (from air) to the cathode.
When hydrogen reaches the catalyst layer, it separates into protons (hydrogen ions) and electrons.
The free electrons, produced at the anode, are conducted in the form of a usable electric current through the
external circuit. At the cathode, oxygen from the air, electrons from the external circuit and protons combine to
form water and heat.
Fuel Cell Stack

Hydrogen
Hydrogen flows through channels in flow field plates to the anode where the
platinum catalyst promotes its separation into protons and electrons.
Hydrogen can be supplied to a fuel cell directly or may be obtained from
natural gas, methanol or petroleum using a fuel processor, which converts
the hydrocarbons into hydrogen and carbon dioxide through a catalytic
chemical reaction.
Membrane Electrode Assembly
Each membrane electrode assembly consists of two electrodes (the anode
and the cathode) with a very thin layer of catalyst, bonded to either side of a
proton exchange membrane.
Air
Air flows through the channels in flow field plates to the cathode. The
hydrogen protons that migrate through the proton exchange membrane
combine with oxygen in air and electrons returning from the external circuit
to form pure water and heat. The air stream also removes the water created
as a by-product of the electrochemical process.
Flow Field Plates
Gases (hydrogen and air) are supplied to the electrodes of the membrane
electrode assembly through channels formed in flow field plates.
Fuel Cell Stack
To obtain the desired amount of electrical power, individual fuel cells are
combined to form a fuel cell stack. Increasing the number of cells in a stack
increases the voltage, while increasing the surface area of the cells increases
the current.
Micro Fuel Cell

The fuel cells are 5 mm3 and generate up to 100 mWatts.
CWRU (Case Western Reserve University)

researchers have miniaturized this process
through the use of micro fabrication
technology, which is used to print multiple
layers of fuel cell components onto a
substrate. Inks were created to replicate
the components of the fuel cell, which
means that the anode, cathode, catalyst
and electrolyte are all made of ink, rather
than traditional fuel cell materials.
Researchers screen printed those inks
onto a ceramic or silicon structure to form
a functioning fuel cell.
Proton Exchange Membrane Fuel Cells

(PEMFC)
PEM fuel cells use a solid polymer membrane (a
thin plastic film) as the electrolyte. This polymer
is permeable to protons when it is saturated with
water, but it does not conduct electrons.
The reactions at the electrodes are as follows:
Anode Reactions: 2H2 => 4H+ + 4e-

Cathode Reactions: O2 + 4H+ + 4e- => 2 H2 O
Overall Cell Reactions: 2H2 + O2 => 2 H2O
Compared to other types of fuel cells, PEMFCs

generate more power for a given volume or weight of
fuel cell. This high-power density characteristic
makes them compact and lightweight. In addition,
the operating temperature is less than 100ºC, which
allows rapid start-up. These traits and the ability to
rapidly change power output are some of the
characteristics that make the PEMFC the top
candidate for automotive power applications.
Alkaline Fuel Cell

Alkaline fuel cells (AFC) are one of the most developed technologies and have
been used since the mid-1960s by NASA in the Apollo and Space Shuttle
programs. The fuel cells on board these spacecraft provide electrical power for
on-board systems, as well as drinking water. AFCs are among the most
efficient in generating electricity at nearly 70%.
Alkaline fuel cells use an electrolyte that is an aqueous (water-based) solution
of potassium hydroxide (KOH) retained in a porous stabilized matrix. The
concentration of KOH can be varied with the fuel cell operating temperature,
which ranges from 65°C to 220°C. The charge carrier for an AFC is the
hydroxyl ion (OH-) that migrates from the cathode to the anode where they
react with hydrogen to produce water and electrons. Water formed at the anode
migrates back to the cathode to regenerate hydroxyl ions. Therefore, the
chemical reactions at the anode and cathode in an AFC are shown below. This
set of reactions in the fuel cell produces electricity and by-product heat.
Anode Reaction: 2 H2 + 4 OH- => 4 H2O + 4 e-
Cathode Reaction: O2 + 2 H2O + 4 e- => 4 OH-
Overall Net Reaction: 2 H2 + O2 => 2 H2O
One characteristic of AFCs is that they are very sensitive to CO2 that may be present in the fuel or air.
The CO 2 reacts with the electrolyte, poisoning it rapidly, and severely degrading the fuel cell
performance. Therefore, AFCs are limited to closed environments, such as space and undersea vehicles,
and must be run on pure hydrogen and oxygen. Furthermore, molecules such as CO, H2O and CH4,
which are harmless or even work as fuels to other fuel cells, are poisons to an AFC.
Alkaline Fuel Cell System
1
Solid Oxide Fuel Cell
Solid oxide fuel cells (SOFC) can also utilize carbon monoxide (CO). This makes them more fuel flexible
and also generally more efficient with available fuels, such as natural gas or propane. Hydrogen and CO can
be produced from natural gas and other fuels by steam reforming, for example. Fuel cells like SOFCs that
can reform natural gas internally have significant advantages in efficiency and simplicity when using
natural gas because they do not need an external reformer. When the ions reach the fuel at the anode they
oxidize the hydrogen to H2O and the CO to CO2. In doing so they release electrons, and if the anode and
cathode are connected to an external circuit this flow of electrons is seen as a dc current. This process
continues as long as fuel and air are supplied to the cell.
Solid Oxide Fuel Cell
10
1
Molten-carbonate Fuel Cell
The diaphragm between the anode and the

cathode consists of a matrix filled with a
carbonate electrolyte. Carbonate ions (CO32-) pass
through the diaphragm and reach the anode. Here
they discharge an oxygen atom, which combines
with the hydrogen flowing past to form water
(H2O). This sets carbon dioxide (CO2) and two
electrons free. The electrons flow over an
electronic conductor to the cathode: current
flows. Similarly, the remaining carbon dioxide
(CO2) is fed to the cathode side, where it absorbs
the electrons and an oxygen atom from the air
that is flowing past. It then re-enters the process
as a carbonate ion.
Carbon Conversion Fuel Cell

Carbon (C) and oxygen (O2) can react in a high-
temperature fuel cell with the carbon, delivering electrons
(e) to an external circuit that can power a motor. The net
electrochemical reaction— carbon and oxygen forming
carbon dioxide—is the same as the chemical reaction for
carbon combustion, but it allows greater efficiency for
electricity production. The pure carbon dioxide (CO2)
product can be sequestered in an underground reservoir
or used to displace underground deposits of oil and gas.
Instead of using gaseous fuels, as is typically done, the new technology uses aggregates of
extremely fine (10- to 1,000-nanometer-diameter) carbon particles distributed in a mixture of
molten lithium, sodium, or potassium carbonate at a temperature of 750 to 850°C. The overall
cell reaction is carbon and oxygen (from ambient air) forming carbon dioxide and electricity.
The reaction yields 80 percent of the carbon–oxygen combustion energy as electricity. It
provides up to 1 kilowatt of power per square meter of cell surface area—a rate sufficiently
high for practical applications. Yet no burning of the carbon takes place.
Direct Methanol Fuel Cell

Fuel cell that utilizes methanol as fuel. When providing
current, methanol is electrochemically oxidized at the anode
electrocatalyst to produce electrons which travel through the
external circuit to the cathode electrocatalyst where they are
consumed together with oxygen in a reduction reaction. The
circuit is maintained within the cell by the conduction of
protons in the electrolyte.
In modern cells, electrolytes based on proton conducting
polymer electrolyte membranes (e.g., Nafion™) are often
used, since these allow for convenient cell design and for
high temperature and pressure operation. The overall reaction
occurring in the DMFC is the same as that for the direct
combustion of methanol,
CH3OH + 3/2O2 CO2 + 2H2O
Since the fuel cell operates isothermally, all the free energy associated with this reaction
should in principle be converted to electrical energy. However, kinetic constraints within
both electrode reactions together with the net resistive components of the cell means that
this is never achieved. As a result, the working voltage of the cell falls with increasing
current drain. These losses are known as polarization and minimizing the factors that give
rise to them is a major aim in fuel cell research.

1 10
Condenser
5
2 6 9 1
3
7 4
11
Fuel cell stack
Load
Fuel Cell Applications

Stationary power generation ~ 5 - 250 kW
Portable applications ~ 1 kW or lower
Automotive applications ~ 5 - 100 kW
Airplane Applications ~ 10 - 250 kW
1kW = 1.3404826 horsepower

Stationary Power Generation

Important factors:
The hours of operation per year
The electric efficiency of the electricity generation process
The capital investment
Fuel cells are particularly suitable for on-site power generation.
Utilizing the heat generated by the fuel cell improves the overall
efficiency - Combined Heat and Power generation (CHP).
PEMPC Power Plant

Process Flow Diagram for a Ballard 250 kW PEMFC Plant
1 10
5
2 6 9 1
3
7 4
11
GM Fuel Cell Powered Automobile

Electrovan -1967
Zero Emission Vehicle - 2006
PEM FC modules
Alkaline fuel cell modules

supplying 32 kW
Hydrogen Fuel Cell Car

Automotive Applications
1 10
5
2 6 9 1
3
7 4
11
Fuel Cell Performance

Fuel Cell Powered Automobile - Progress
1 10
5
2 6 9 1
3
7 4
11
Daimler-Chrysler NeCar:

Ford Focus Hydrogen -powered fuel cell vehicle

Honda fuel cell car
Methanol Fuel Cell Powered Automobile

Toyota’s Methanol-powered Fuel cell Electric Vehicle
1 10
5
2 6 9 1
3
7 4
11
Fuel Cell Powered Automobile
An x-ray view of Mitsubishi's new

fuel cell Grandis minivan.
Portable Application
Typically well under 100W of power with significantly higher power densities or larger
energy storage capacity than those of advanced batteries.
Power generation on a larger scale , say 1 kw continuous output to replace gasoline or
diesel generators or supply quiet electric power on boats, caravans or trucks.
Solar Powered Airplane

Helios
Instead of jet fuel, Helios has about 62,000 solar cells across the wing. The solar cells collect
energy from the Sun and convert it to electricity, which runs the 14 small motors, which turn the
14 propellers. The propellers are specially designed to pull the aircraft aloft even in the very thin
air that's 18 miles high. The next project for the Helios is to use fuel cells to store enough of the
sun's energy during the day to continue flying through the night. When this happens, Helios will be
able to stay up for weeks and months at a time.
The Helios, developed by Paul McCready, CEO of Aerovironment Corp.,
March 11, 2002
DIGITAL PHOTOS FROM SOLAR AIRPLANE TO IMPROVE COFFEE HARVEST
Funded by NASA
Electric Powered Airplane
The new Electric Plane, or E-Plane, is a high-speed, all-

carbon French DynAero Lafayette III, built and donated by
American Ghiles Aircraft. The E-Plane is being converted
from a combustion engine to electric propulsion in three
stages. The first flights, planned for next year, will be on
1
lithium ion batteries. The next flights will be powered by a
combination of lithium ion batteries augmented by a fuel
cell. Finally, the aircraft will be powered totally by a
hydrogen fuel cell, with a range of more than 500 miles.
Supported by Foundation for Advancing Science and

Technology Education (FASTec) showed off the plane it is
developing as the world’s first piloted fuel-cell-powered
aircraft.
Fuel Cell Based Aircraft Propulsion
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5
2 6 9 1
3
7 4
11
Source: NASA TM-2003-212393

Fuel Cell Powered Aircraft
1
Fuel Cell Motorbike to Hit US Streets
Top Speed: 50 mph (80 kmh)

Range: 100 miles (160 km)
Hydrogen Storage tank capacity: 1 kg
QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
Cost: $6,000 - 8000

Manufacturer: Intelligent Energy,
London, UK
ENY: Emission Neutral Vehicle
Intellig ent Energy is currently developing d evices called reformers that extract
hydrogen from biodiesel fuels (typi cally m ade from vegetable oils or animal fats)
and ethanol (generally m ade from grain or corn). The units would sell for around
U.S. $1,500 and could produce enough hydrogen to fill up the ENV for about 25
cents per tank,. Eggl eston said.
National Geographic News, August 2, 2005
PEM Fuel Cell Performance

Fuel Cell System

FC Implementation Requirements
GM Zero Emission Vehicle - 2006
Source: NY Times, September 22, 2006

Direct Energy Conversion: Fuel Cells

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Sustainable Energy Science and Engineering Center

Direct Energy Conversion: Fuel Cells

Bypass the conversion-to-heat and mechanical-to-electrical processes

Fuel Cell Efficiency

1 We10 will use the term anode to

Fuel Cell Types

Hydrogen - Oxygen Fuel Cell

At the anode the

An acid with free H+ ions. Certain

Membrane Electrode Assembly

Fuel Cell Stack

Micro Fuel Cell

CWRU (Case Western Reserve University)

Proton Exchange Membrane Fuel Cells

The reactions at the electrodes are as follows:

Anode Reactions: 2H2 => 4H+ + 4e-

Compared to other types of fuel cells, PEMFCs

Alkaline Fuel Cell

Alkaline Fuel Cell System

Solid Oxide Fuel Cell

Solid Oxide Fuel Cell

Molten-carbonate Fuel Cell

The diaphragm between the anode and the

Carbon Conversion Fuel Cell

Direct Methanol Fuel Cell

Direct Methanol Fuel Cell

Direct Methanol Fuel Cell

Fuel Cell Applications

1kW = 1.3404826 horsepower

Stationary Power Generation

PEMPC Power Plant

GM Fuel Cell Powered Automobile

Zero Emission Vehicle - 2006

Alkaline fuel cell modules

Hydrogen Fuel Cell Car

Fuel Cell Performance

Fuel Cell Powered Automobile - Progress

Fuel Cell Powered Automobile - Progress

Fuel Cell Powered Automobile - Progress

Fuel Cell Powered Automobile - Progress

Methanol Fuel Cell Powered Automobile

Fuel Cell Powered Automobile

An x-ray view of Mitsubishi's new

Solar Powered Airplane

Electric Powered Airplane

The new Electric Plane, or E-Plane, is a high-speed, all-

Supported by Foundation for Advancing Science and

Fuel Cell Based Aircraft Propulsion

Source: NASA TM-2003-212393

Fuel Cell Powered Aircraft

Fuel Cell Motorbike to Hit US Streets

Top Speed: 50 mph (80 kmh)

Cost: $6,000 - 8000

PEM Fuel Cell Performance

Fuel Cell System

GM Zero Emission Vehicle - 2006

Source: NY Times, September 22, 2006

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