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The World of Energy

Chapter 17 – Fuel Cells

17.1. Introduction

Fuel Cells

Ch. 17 - 2
The Promise of Fuel Cells

 “A score of nonutility companies are well

advanced toward developing a powerful
chemical fuel cell, which could sit in some
hidden closet of every home silently
ticking off electric power.”

 Theodore Levitt, “Marketing Myopia,” Harvard

Business Review, 1960

Ch. 17 - 3
Theodore Levitt, “Marketing Myopia,” Harvard Business Review, 1960
Ion transport observed by William Grove in 1839…Based on
hydrogen-oxygen, sulfuric acid electrolyte, and platinum

“I cannot but regard the experiment

as an important one…”
William Grove to Michael Faraday
October 22, 1842

Ch. 17 - 4
Energy Landscape – Near Future

 Power generation (and/or storage and conditioning)

equipment located at or near the point of use - “on site”

Utility Grid

Coal, nuclear

Sub Station

100 - 1000 MW
Natural Gas

Natural Gas
10 - 500 kW
500 - 5000 kW


Ch. 17 - 5
Energy Landscape - Midterm
e- H2
e- e-

Wind Hydrogen PV (Solar)

e- e-

e- PEM e-
e- e-
Fuel Cell
Commercial Residential
Consumer CH4 Consumer


Ch. 17 - 6
Traditional Generation vs.
Distributed Energy Resources


180 Wind
Distributed Energy Resources
160 59.3 GW in 2020 11%

140 Solar
120 Distributed Energy
100 High-Speed
Diesel Recip
Diesel Recip
80 55%
60 Traditional Generation Natural Gas
40 Recip
20 Gas Turbine
0 7%

2000 2005 2010 2015 2020 Emerging

Source: Plug Power Estimate based on IEA data Source: PSR, AD Little, Strategies Unlimited, BTM Consulting

PEM fuel cells are well positioned to capture this growth opportunity

Ch. 17 - 7
Fuel Cells as Viable Electrical Sources

2 ml
360 ml

0.6 ml
0.4 ml
0.2 ml

Hydrogen – Liquid Methanol Li-ion

uncompressed gas Hydrogen
Hydrogen Battery

Ch. 17 - 8
History of Fuel Cell
1839: First publication by
William Grove, not long after the
first metallic battery (Alessandro
Volta‟s zinc-silver „Voltaic pile‟ in
Alternating H2 and O2 electrodes in a „gas battery‟
– W. Grove, Philos. Mag., Ser. 3, 1839, 14, 127

Pressurised, hot alkali fuel cells

were developed during the
1950‟s, and generated useful
power conversion – notably the
Bacon cell which was bought by
Nasa for the Apollo program…

1959: 5 kW alkaline cell

Ch. 17 - 9
Recent Fuel Cell Progress

Present day: Honda, GM, etc.

have prototype fuel cell vehicles
(FCVs) ~ 50 kW

2005: Honda FCV

Prototype hydrogen-
burning machine

Ch. 17 - 10
What Is Fuel Cell

 Reversed Electrolysis

 Pt coated electrodes

 Use air as a source of


Ch. 17 - 11
Fuel Cell

 An energy conversion
device that directly
converts chemical energy
into electrical energy (dc

 Analogous operation to a
natural gas fueled electric
generator: energy in fuel +
and oxygen are converted
to electric power as long as Heat, H2O
fuel and air are supplied

 Six types, each suited for

specific applications

Ch. 17 - 12
What is Fuel Cell?
 DEFINITION. An electrochemical device that continuously
changes the chemical energy of a fuel (hydrogen) and
oxidant (oxygen) directly to electrical energy and heat,
without combustion.

 PRINCIPLE. The electrical process causes hydrogen atoms

to give up their electrons. It is similar to a battery in that it
has electrodes, an electrolyte, and positive and negative

 USAGE. A fuel cell provides a DC (direct current) voltage

that can be used to power motors, lights or any number of
electrical appliances. There are several different types of fuel
cells, each using a different chemistry. Fuel cells are usually
classified by the type of electrolyte they use.

 ADVANTAGES. No combustion therefore few emissions. No

moving parts therefore quiet.

Ch. 17 - 13
How Does it Work
 Electrolyte- proton-
(PEM), Phosphoric Acid

 Combines Fuel and


 Produces H20 (l), heat,



Ch. 17 - 14
Fuel Cell Stack

Ch. 17 - 15
Advantages of Fuel Cell
 Power generation is accomplished without moving
 Higher efficiency than an internal combustion

 Clean - products are water, heat, and electricity

 Does not generate conventional NOx or SOx


 Generates approximately half the amount of CO2


 Co-generation: Combined Heat and Power (CHP)


Ch. 17 - 16
Advantages of Fuel Cells

 Fuel cells can convert as
much as 80% of the
energy stored in the fuel *



Graph Courtesy of Mercedes-Benz

* Berinstein, Paula. Alternative Energy: Facts, Statistics, and Issues. Westport, CT, Oryxpress 2001

Ch. 17 - 17
More Advantages

 Low Pollution- Fuel cells produce only

water and CO2 depending upon the fuel
 Low Maintenance/Operating cost

 Can use conventional fuels - gasoline,

methane, propane
 Small or large scale uses

Ch. 17 - 18

 Still produce CO2 although with more usable

 Expensive: (Pt) It costs about $40,000 to
make a fuel cell system for a car.*
 (Power plant estimated costs 1999: $800-1200/kWh (The first one in
Austin cost about $4000/kW)**)
 Hydrogen/Reformer Problem
 Clean Fuel

* Berinstein, Paula. Alternative Energy: Facts, Statistics, and Issues. Westport, CT, Oryxpress 2001
** Daily Texan 17.7. 2002

Ch. 17 - 19
Adv./Disadvantages of Fuel Cells

 Advantages
 Water is the only discharge (pure H2)

 Disadvantages
 CO2 discharged with methanol reform
 Little more efficient than alternatives
 Technology currently expensive
 Many design issues still in progress
 Hydrogen often created using “dirty” energy (e.g.,
 Pure hydrogen is difficult to handle
 Refilling stations, storage tanks, …

Ch. 17 - 20
Problems with Fuel Cells
 Obtaining Hydrogen  Storing Hydrogen
 Water  Must be Stored at High
Pressures and Low
 Fossil Fuel (Natural Gas, Temperatures
Coal, Petroleum)  15 lbs of Hydrogen
 Methanol Required to Propel a 3500
 Solar Power lb Vehicle 335 Miles
 Wind Power  15 lbs of Hydrogen Stored
at 36,000psi = 74 Gallons
of Hydrogen
 Infrastructure  Compression Takes
 Few Pipelines for H2, Energy
Unlike Natural Gas
 Volume of Hydrogen Large  Cost
to Transport as is  Average Large Power Plant
Using Coal or Natural Gas
Produces 1 KW for $1,000
 Fuel Cells Produce 1KW
for $3000-$4000

Ch. 17 - 21
Fuel Cell Low Emissions

Average U.S. Utility

Emissions ONSI PC25 200 kW NG Fuel
(lbs per megawatt-hour) Cell
Contaminant (lbs per megawatt-hour)

Nitrogen Oxides 7.65 0.016

Carbon monoxide 0.34 0.023

Reactive organic gases 0.34 0.0004

Sulfur oxides 16.1 0

Particulates (PM10) 0.46 0

Ch. 17 - 22
Current State of Fuel Cell Technology

Innovators / Early Adopters

System Cost ($/kW)

Backup & Standby

1,000 Initial Mass

Remote / Automotive
100 Premium

2000 2005 2010 2015 2020

Ch. 17 - 23
Auto Power Efficiency Comparison

Technology Efficiency
Fuel Cell 24-32%
Electric Battery 26%
Gasoline Engine 20%

Ch. 17 - 24
Why Fuel Cells for the Future?

 Reduction of Pollution

 Two to Three Times More Efficient

Than Today’s Automobile

 Multiple Types of Energy for


 Use Domestic Resources

 Enhance National Security

Ch. 17 - 25
Fuell Cell Power Spectrum

Ch. 17 - 26
The World of Energy
Chapter 17 – Fuel Cells

17.1. Basic Principles & Technology

What is a Fuel Cell?

 Electrochemical Energy
Conversion Device
 Hydrogen + Oxygen =
 Produces Electricity
and Heat

From Ballard Power Systems

Ch. 17 - 28
How Does a Fuel Cell Work??
Proton Exchange Membrane (PEM) Fuel Cell

From IdaTech

Ch. 17 - 29
Fuel Cell Energy Exchange

Ch. 17 - 30
Basis for Fuel Cell Operation
 Electron transfer – chemical reaction
 Voltage determined by difference in chemical
potential of fuel and oxygen
 Current determined by area of cell

 Catalyzed conversion of oxygen and hydrogen into

reactive species O= and H
 H2 + O2 = H2O + 2 electrons + heat

 Electrons are separated from reactants by circuit

 Need to understand electrical circuit background as it

relates to fuel cell

Ch. 17 - 31
Parts of a Fuel Cell
 Anode
 Negative post of the fuel cell.
 Conducts the electrons that are freed from the hydrogen molecules so that they
can be used in an external circuit.
 Etched channels disperse hydrogen gas over the surface of catalyst.

 Cathode
 Positive post of the fuel cell
 Etched channels distribute oxygen to the surface of the catalyst.
 Conducts electrons back from the external circuit to the catalyst
 Recombine with the hydrogen ions and oxygen to form water.

 Electrolyte
 Proton exchange membrane.
 Specially treated material, only conducts positively charged ions.
 Membrane blocks electrons.

 Catalyst
 Special material that facilitates reaction of oxygen and hydrogen
 Usually platinum powder very thinly coated onto carbon paper or cloth.
 Rough & porous maximizes surface area exposed to hydrogen or oxygen
 The platinum-coated side of the catalyst faces the PEM.

Ch. 17 - 32
Fuel Cell Operation
 Pressurized hydrogen gas (H2) enters cell on anode side.

 Gas is forced through catalyst by pressure.

 When H2 molecule comes contacts platinum catalyst, it splits
into two H+ ions and two electrons (e-).

 Electrons are conducted through the anode

 Make their way through the external circuit (doing useful
work such as turning a motor) and return to the cathode
side of the fuel cell.

 On the cathode side, oxygen gas (O2) is forced through

the catalyst
 Forms two oxygen atoms, each with a strong negative
 Negative charge attracts the two H+ ions through the
 Combine with an oxygen atom and two electrons from the
external circuit to form a water molecule (H2O).

Ch. 17 - 33
Fuel Cell Types

Increasing Temperature
Source: U.S. Fuel Cell Council

Ch. 17 - 34
Attributes of Fuel Cells


Electrolyte KOH Phosphoric Sulfonic Molten Y2O3-ZrO2

Acid Acid Carbonate Ceramic
Polymer Salt
Temperature 1000C 2000C 1000C 6500C 800-10000C

Fuel H2 H2 H2 H2/CO H2/CO

Efficiency (H2 fuel) 60% 55% 60% 55% 55%

(NG fuel) -- 40% 35% 50% 50%

Pollution Very low Very low Very low Low Low

Hydrocarbon No Difficult Difficult Yes Yes

Fuel Use

Start-Up Fast Moderate Fast Slow Slow

Ch. 17 - 35
Fuel Cell Stacks
 Operating voltage of a single cell is ~0.7 volts
 Cells are “stacked” in series to increase voltage to
useful levels:

Source: U.S. Fuel Cell Council

Ch. 17 - 36
Fuel Cell Power System
Useful heat


Fuel Fuel cell Stack Power 10 kW
Processor Sub Assembly Conditioner


Ch. 17 - 37
Power System Efficiency Comparison

Ch. 17 - 38
High Efficiency at Reduced Load

Ch. 17 - 39
Fuel Cell Operating Comparison

Fuel Cell Electrolyte Ions Temperature Cell Voltage Size (largest)

Type (oC) (V) (kW)

Alkaline Potassium Hydroxide OH- 80 0.6 - 0.8 100

PAFC Phosphoric Acid H+ 200 0.6 - 0.8 670

MCFC Molten Carbonate CO3= 550 - 650 0.7 - 0.85 250

SOFC Solid Zn-Oxide O= 850 - 1000 0.6 - 0.75 100

PEMFC Solid Polymer H+ 100 0.6 - 0.8 250

Fuel Cell Operating Comparison

Fuel Cell Current Density System Fuel Proc. Stack Power Transient
Type (mA/cm2) Efficiency Complexity Density Capability

Alkaline 60 - 120 35 - 50 Medium Medium High

PAFC 100 - 400 35 - 45 Medium Medium Medium

MCFC 100 - 200 45 - 55 Low Low Low

SOFC 100 - 300 45 - 50 Low Medium Low

PEMFC 400 - 900 32 - 40 High High High

Fuel Cell Types & Efficiencies

Temp. Projected Suitable
Fuel Cell Type (°C) Efficiency Applications
Alkaline (AFC) 80-100 60% Space, Automotive

Molten Carbonate
600-650 45-60% Large Stationary

Phosphoric Acid 200-220 40-45% Large Stationary

Proton Exchange Small Stationary,

70-80 35-45%
Membrane (PEMFC) Automotive, Portable

Solid Oxide (SOFC) 800-1000 50-65% Stationary, Automotive

From Avista (Relion)

Ch. 17 - 42
Hydrogen Fuel Cell Efficiency

 40% efficiency converting methanol to

hydrogen in reformer

 80% of hydrogen energy content

converted to electrical energy

 80% efficiency for inverter/motor

 Converts electrical to mechanical

 Overall efficiency of 24-32%

Ch. 17 - 43
Fuel Processing and Fuel Cells
Under development Fuel Cell Types
Solid Fuel
Coal, Pet Coke Coal-based

500 to 1000 oC


g co

mp l
Gas Cleaning 500 to 1000 oC

exit SOFC
Liquid Fuel
of f u Thermal integrated
el p
S-removal Reformer
500 to 1000 oC

Natural Gas MCFC

Conversion to

Thermal Intergrated

H2/CO Reformer
; de

600 oC

Shift Reaction

(CO<5 %)
g ef

200 oC
CO Selective


Hydrogen (CO<10 ppm)

80 oC
Ref: N.F. Brandon, S. Skinner, B.C.H. Steele, Annu. Rev. Mater. Res. 2003. 33:183-213
Ch. 17 - 44
The World of Energy
Chapter 17 – Fuel Cells

17.2. Proton Exchange Membrane FC (PEMFC)

History of PMFC
 1950’s
 GE development - solid film electrolyte with proton movement
 1960’s
 GE work continues -Membranes unstable -High catalyst
 1970’s
 Development of Nafion, testing of today’s fuel cell version of
membrane. Other Players appear: IFC, Engelhard, Occidental,
Engelhard, US Army………
 1980’s
 Develops monomer and polymerization chemistry, cost, size,
weight reduction, performance improvements
 1990’s to Now
 First attempts to commercialize stationary, early vehicle
utilizing public funding
 Market segmentation: component suppliers, systems
 $/kW major obstacle - shift focus from technical to cost

Ch. 17 - 46
Proton Exchange Membrane

Proton exchange membrane fuel cell uses one of the simplest

reactions of any fuel cell

 Anode side: 2H2 => 4H+ + 4e-

 Cathode side: O2 + 4H+ + 4e- => 2H2O
 Net reaction: 2H2 + O2 => 2H2O

Ch. 17 - 47
Proton Membrane
 The anode conducts the electrons that are freed from the
hydrogen molecules. It disperse the hydrogen gas equally over
the surface of the catalyst.

 The cathode, the positive post of the fuel cell, distributes the
oxygen to the surface of the catalyst. It also conducts the
electrons back from the external circuit to the catalyst, where
they can recombine with the hydrogen ions and oxygen to form

 The electrolyte is the proton exchange membrane. This

specially treated material, which looks something like ordinary
kitchen plastic wrap, only conducts positively charged ions. The
membrane blocks electrons.

 The catalyst is a special material that facilitates the reaction of

oxygen and hydrogen. It is usually made of platinum powder
very thinly coated onto carbon paper or cloth. The catalyst is
rough and porous so that the maximum surface area of the
platinum can be exposed to the hydrogen or oxygen. The
platinum-coated side of the catalyst faces the PEM.

Ch. 17 - 48
Proton-Exchange Membrane Cell (PEMC)


Ch. 17 - 49
PEM Fuel Cell Schematic

Ch. 17 - 50
Proton Exchange Membrane Fuel Cell

From Ballard Power Systems

Ch. 17 - 51
PEM Fuel Cell

Ch. 17 - 52
PEM Fuel Cell Components

Fuel Fuel
Processor Air Power
Natural Conditioner
Gas or
hydrocarbon DC AC
Hydrogen Power Power


Ch. 17 - 53
PEM Fuel Cell Process
DC Electricity
Hydrogen e e
Electrons Water

Protons Heat

H2 2H+ + 2e- Membrane 1/2O2 + 2e- 1/2O2 - -

0 Volts
H2 + 1/2O2 --> H2O ~1.23 Volts

Approx. 1 volt or less/cell, therefore add cells together

Ch. 17 - 54
Advantages of PEMFC

 PEMFCs operate at a fairly low temperature

(about 176 degrees Fahrenheit, 80 degrees
 Which means they warm up quickly and don't
require expensive containment structures
 Constant improvements in the engineering and
materials used in these cells have increased the
power density to a level where a device about
the size of a small piece of luggage can power a

Ch. 17 - 55
The World of Energy
Chapter 17 – Fuel Cells

17.3. Direct Methanol FC (DMFC)

Direct Methanol Fuel Cell Solution
 Using the hydrogen and methanol from burning
coal and combining it with water we can turn it
into a new form of energy

 Methanol is the most desirable liquid hydrocarbon

fuel for fuel cells and can be effectively utilized in
internal combustion engines using existing

 While all alternative fuels are expected to be

more expensive to the consumer than present-
day gasoline, methanol produced from coal is
likely to be the least expensive of the fuels
considered, if natural gas prices increase as

Ch. 17 - 57
DMFC (Direct Methanol Fuel Cell)
 Uses a membrane
as electrolyte and
produce electricity
directly from liquid

 Efficient of fuel

 Simpler less costly

fuel cell systems

Ch. 17 - 58
Principles of DMFC
 When provided with
current, methanol is
electrochemically oxidized
at the anode electro
catalyst to produce
electrons which travel
through the external
circuit to the cathode and
consumed with oxygen to
form a reaction.

 CH3OH + 3/2O2 CO2 +


Ch. 17 - 59
DMFC Application & Prototype

 Bob Hockaday holds a Motorola cell phone battery for scale in this
photo taken at MHTX H.Q. in Los Alamos, December 1998.

 To his right is his "test rack" micro-DMFC apparatus which provides

the electricity to operate the small black Nokia cell phone in the

 The hypo syringes on top of the rack are used to squirt windshield
washer fluid (blue juice) fuel into the direct methanol fuel cell.

Ch. 17 - 60
DMFCs for
Potential Transportation Applications

 A 5-cell stack operated

at 100 Celsius with 2.8
atm air generated 1 kW
per liter of active stack

 With 0.50 V per cell, the

5-cell achieved a fuel
utilization of 90%; about
37% efficiency

 Catalyst loading was

lowered to 5 gPt per kw,
compared to about 2gPt
per kW (current)

Ch. 17 - 61
The World of Energy
Chapter 17 – Fuel Cells

17.4. Other Types of Fuel Cells

Other Types of Fuel Cells
 Alkaline fuel cell (AFC)
 This is one of the oldest designs. It has been used in the U.S. space
program since the 1960s. The AFC is very susceptible to contamination,
so it requires pure hydrogen and oxygen. It is also very expensive, so
this type of fuel cell is unlikely to be commercialized.

 Phosphoric-acid fuel cell (PAFC)

 The phosphoric-acid fuel cell has potential for use in small stationary
power-generation systems. It operates at a higher temperature than
PEM fuel cells, so it has a longer warm-up time. This makes it unsuitable
for use in cars.

 Solid oxide fuel cell (SOFC)

 These fuel cells are best suited for large-scale stationary power
generators that could provide electricity for factories or towns. This type
of fuel cell operates at very high temperatures (around 1,832 F, 1,000
C). This high temperature makes reliability a problem, but it also has an
advantage: The steam produced by the fuel cell can be channeled into
turbines to generate more electricity. This improves the overall
efficiency of the system.

 Molten carbonate fuel cell (MCFC)

 These fuel cells are also best suited for large stationary power
generators. They operate at 1,112 F (600 C), so they also generate
steam that can be used to generate more power. They have a lower
operating temperature than the SOFC, which means they don't need
such exotic materials. This makes the design a little less expensive.

Ch. 17 - 63
Zinc Air
Fuel cell modules contain 47
individual air-breathing zinc-air cells,
connected in a series they discharge
17.4kWh before being refueled.
Electric fueled transit buses carry
three trays of 6 modules. This yields
312kWh of on-board energy.

Programs in the U.S. and Germany
are currently in place testing Zinc-Air
Electric transit bussing.

A Zinc-Air fuel cell yields a practical

specific energy of around 200Wh/kg
and a specific peak power of 90W/kg.
Lead-acid batteries typically achieve
30 Wh/kg. Nickel-metal hydride
typically achieves 70Wh/kg.

Ch. 17 - 64
Regenerative Fuel Cell
Unitized Regenerative Fuel Cells (URFC)
operate as both a generator and
electrolyzer. When coupled with
lightweight fuel storage, URFCs operate
with an energy density of about 450Wh/kg.

Regenerative Fuel Cells act as energy
storage systems for alternative fuel
systems. Example: Photovoltaic systems
generate more power than what is need to
fly an airplane when the sun high. The
energy storage systems absorbs the
excess power and accumulates it during
the day. The stored energy can then be
released at night.

Possible Applications: automobiles, solar-

powered aircraft, satellites, and
microspace-craft propulsion.
Ch. 17 - 65
Alkaline Fuel Cell
 This is one of the oldest
designs. It has been used
in the U.S. space program
since the 1960s. The AFC
is very susceptible to
contamination, so it
requires pure hydrogen
and oxygen

 High-temperature AFCs
operate at temperatures
between 100ºC and
250ºC (212ºF and 482ºF).
However, more-recent
AFC designs operate at
lower temperatures of
roughly 23ºC to 70ºC
(74ºF to 158ºF).

Ch. 17 - 66
Alkaline Pro/Con
 AFCs are high-performance fuel cells due to the rate at
which chemical reactions take place in the cell. They
are also very efficient, reaching efficiencies of 60
percent in space applications

 The disadvantage of this fuel cell type is that it is easily

poisoned by carbon dioxide (CO2).
 Even the small amount of CO2 in the air can affect the
cell's operation, making it necessary to purify both the
hydrogen and oxygen used in the cell. This purification
process is costly.
 Susceptibility to poisoning also affects the cell's lifetime.

 AFC stacks have been shown to maintain sufficiently

stable operation for more than 8,000 operating hours.

Ch. 17 - 67
Biological Fuel Cells
Chemical Fuel Biological Fuel
Cell Cell

Catalyst Noble Metals Microorganism

 Microorganisms (ie Pt) or enzyme
or enzymes
pH <1 (Acidic) 7-9 (Neutral)
replace catalysts
Temp. (ºC) 200+ 22-25

Electrolyte Phosphoric Phosphate

acid solution

Capacity High Low

Efficiency (%) 40-60 40+

Fuel Type H2 Any

Output (0.5V) ~@300mA/cm ~@3mA/cm2

Ch. 17 - 68
Solid Oxide Fuel Cells
 Based upon ion conductivity of certain ceramic
materials at elevated temperatures (>600 C)
 First observed by Nernst in 1890’s
 Fluorite Structures (e.g. yttria stabilized zirconia)
 Face Centered cubic arrangement
 Transport through crystal lattice vacancies and
oxide ions located between crystal faces
 First SOFC constructed in 1937 by Baur and Preis

 Requires porous electrodes and dense

electrolyte, low electronic conductivity, and high

Ch. 17 - 69
Solid Oxide Fuel Cells


Anode catalyst
layer CH4 + 3O2- CO2 + H2O + 2e-
O2 + 4e- 2O2-

Pt Ink O2- Effluent

Pt Wire


Cathode catalyst

CH4 + CO2 2CO + 2H2

Electrolyte Disc CH4 + H2O CO2 + 3H2
CO + H2O CO2 + H2
Yttrium-stablized Zirconia (>950 °C)
Galladium-doped Ceria (>600°C)
CH4 + 0.5 O2 CO + 2H2

Ch. 17 - 70