Fuel Cell Technology

Topics
1. A Very Brief History
2. Electrolysis
3. Fuel Cell Basics
- Electrolysis in Reverse
- Thermodynamics
- Components
- Putting It Together
4. Types of Fuel Cells
- Alkali
- Molten Carbonate
- Phosphoric Acid
- Proton Exchange Membrane
- Solid Oxide
5. Benefits
6. Current Initiatives
- Automotive Industry
- Stationary Power Supply Units
- Residential Power Units
7. Future
A Very Brief History
Considered a curiosity in the 1800s. The first fuel cell was built in 1839 by Sir William Grove, a
lawyer and gentleman scientist. Serious interest in the fuel cell as a practical generator did not begin
until the 1960's, when the U.S. space program chose fuel cells over riskier nuclear power and more
expensive solar energy. Fuel cells furnished power for the Gemini and Apollo spacecraft, and still
provide electricity and water for the space shuttle.
(1)
Electrolysis
What does this have to do with fuel cells?
By providing energy from a battery, water (H
2
O)
can be dissociated into the diatomic molecules of
hydrogen (H
2
)
and oxygen (O
2
).
Figure 1
Fuel Cell Basics
Put electrolysis in reverse.
fuel
cell
H
2
O
O
2
H
2
heat
work
The familiar process of electrolysis requires work to proceed, if the process is put in reverse, it should be able to do
work for us spontaneously.
The most basic black box representation of a fuel cell in action is shown below:
Figure 2
Fuel Cell Basics
Thermodynamics
H
2
(g) + O
2
(g) H
2
O(l)
Other gases in the fuel and air inputs (such as N
2
and CO
2
) may be present, but as they are not involved in the
electrochemical reaction, they do not need to be considered in the energy calculations.
69.91
J
/
molK
205.14
J
/
molK
130.68
J
/
molK
Entropy (S)
-285.83
kJ
/
mol
0 0 Enthalpy (H)
H
2
O (l) O
2
H
2
Table 1 Thermodynamic properties at 1Atm and 298K
Enthalpy is defined as the energy of a system plus the work needed to make room for it in an environment with constant
pressure.
Entropy can be considered as the measure of disorganization of a system, or as a measure of the amount of energy that is
unavailable to do work.
Fuel Cell Basics
Thermodynamics
Enthalpy of the chemical reaction using Hess Law:
H = H
reaction
= H
products
H
reactants

= (1mol)(-285.83
kJ
/
mol
) (0)
= -285.83 kJ

Entropy of chemical reaction:
S = S
reaction
= S
products
S
reactants

= [(1mol)(69.91
J
/
molK
)] [(1mol)(130.68
J
/
molK
) + (mol)(205.14
J
/
molK
)]
= -163.34
J
/
K
Heat gained by the system:
Q = TS
= (298K)(-163.34
J
/
K
)
= -48.7 kJ
Fuel Cell Basics
Thermodynamics
The Gibbs free energy is then calculated by:
G = H TS
= (-285.83 kJ) (-48.7 kJ)
= -237 kJ
The external work done on the reaction, assuming reversibility and constant temp.
W = G
The work done on the reaction by the environment is:
The heat transferred to the reaction by the environment is:
W = G = -237 kJ
Q = TS = -48.7 kJ
More simply stated:
The chemical reaction can do 237 kJ of work and produces 48.7 kJ of heat to the environment.
Fuel Cell Basics
Components
Anode: Where the fuel reacts or "oxidizes", and releases electrons.
Cathode: Where oxygen (usually from the air) "reduction" occurs.
Electrolyte: A chemical compound that conducts ions from one electrode to the other inside a fuel cell.
Catalyst: A substance that causes or speeds a chemical reaction without itself being affected.
Cogeneration: The use of waste heat to generate electricity. Harnessing otherwise wasted heat boosts the
efficiency of power-generating systems.
Reformer: A device that extracts pure hydrogen from hydrocarbons.
Direct Fuel Cell: A type of fuel cell in which a hydrocarbon fuel is fed directly to the fuel cell stack,
without requiring an external "reformer" to generate hydrogen.
Fuel Cell Basics
Putting it together.
Figure 3
Types of Fuel Cells
The five most common types:
Alkali
Molten Carbonate
Phosphoric Acid
Proton Exchange Membrane
Solid Oxide
Types of Fuel Cells
Vorteil: Keine aufwendige Brenngas-Aufbereitung
Nachteil: Hohe Betriebstemperaturen = Hohe System-Kosten
Starke Material-Beanspruchung
SOFC
Alkali Fuel Cell
compressed hydrogen and oxygen fuel
potassium hydroxide (KOH) electrolyte
~70% efficiency
150C - 200C operating temp.
300W to 5kW output
requires pure hydrogen fuel and platinum catylist ($$)
liquid filled container corrosive leaks
Figure 4
Molten Carbonate Fuel Cell (MCFC)
carbonate salt electrolyte
60 80% efficiency
~650C operating temp.
cheap nickel electrode catylist
up to 2 MW constructed, up to 100 MW designs exist
Figure 5
The operating temperature is too hot for many applications.
carbonate ions are consumed in the reaction inject CO
2
to compensate
Phosphoric Acid Fuel Cell (PAFC)
phosphoric acid electrolyte
40 80% efficiency
150C - 200C operating temp
11 MW units have been tested
sulphur free gasoline can be used as a fuel
Figure 6
The electrolyte is very corrosive
Platinum catalyst is very expensive
Proton Exchange Membrane (PEM)
thin permeable polymer sheet electrolyte
40 50% efficiency
50 250 kW
80C operating temperature
electrolyte will not leak or crack
temperature good for home or vehicle use
platinum catalyst on both sides of membrane $$
Figure 7
Solid Oxide Fuel Cell (SOFC)
hard ceramic oxide electrolyte
~60% efficient
~1000C operating temperature
cells output up to 100 kW
high temp / catalyst can extract the hydrogen from the fuel at the electrode
high temp allows for power generation using the heat, but limits use
SOFC units are very large
solid electrolyte wont leak, but can crack
Figure 8
Benefits
Efficient: in theory and in practice

Portable: modular units

Reliable: few moving parts to wear out or break

Fuel Flexible: With a fuel reformer, fuels such as natural gas, ethanol, methanol,
propane, gasoline, diesel, landfill gas,wastewater, treatment digester gas, or even ammonia can be used


Environmental: produces heat and water (less than combustion in both cases)
near zero emission of CO and NO
x

reduced emission of CO
2
(zero emission if pure H
2
fuel)
Materials challenges of the PEM Fuel Cell
7/11/2014 Fuel Cell Fundamentals 20
Review of Membrane (Nafion) Properties
Chemical Structure
Proton Conduction Process
Water Transport and Interface Reactions
PSSA
poly(styrene-co-
styrenesulfonic acid)
(PSSA)

Nafion,
TM

Membrane C
Dow
PESA
(Polyepoxy-
succinic Acid)

o,|,|-Trifluorostyrene grafted onto
poly(tetrafluoro-ethylene) with post-
sulfonation)
Poly AMPS
Poly(2-acrylamido-
2-methylpropane sulfonate)
Chemical structures of some membrane materials
Nafion Membrane
Chemical Structure
Nafion Membrane
Proton Conduction Process
The water transport through Nafion Membrane
Water flux due to electroosmotic drag (mol/cm
2
s) is: N
w, drag
= I()/F.
Where: I is the cell current, () is the electroosmotic drag coefficient at a
given state of membrane hydration (=N(H
2
O)/N(SO
3
H) and F is the Faraday
constant. This flux acts to dehyddrate the anode side of a cell and to
introduce additional water at the cathode side.
The buildup of water at the cathode (including the product water
from the cathode reaction) is reduced, in turn, by diffusion back down the
resulting water concentration gradient (and by hydraulic permeation of water
in differentially pressurized cells where the cathode is held at higher overall
pressure). The fluxes (mol/cm
2
s) brought about by the latter two mechanisms
within the membrane are:
N
w,diff
= -D()Ac/ Az, N
w,hyd
= -k
hyd
()AP/ Az
where D is the diffusion coefficient in the ionomer at water content , Ac/ Az
is a water concentration gradient along the z-direction of membrane thickness,
k
hyd
is the hydraulic permeability of the membrane, and AP/ Az is a pressure
gradient along z.
The water transport through Nafion Membrane
Many techniques have been introduced to prevent the dehydration of the anode (including the introduction
of liquid water into the anode and/or cathode, etc. which, however, can lead to flooding problems that
inhibit mass transfer).
However, the overall question of water management, including the issue of drag as a central component,
has been solved to a very significant extent by the application of sufficiently thin PFSA membranes (<100
m thick) in PEFCs, combined with humidification of the anode fuel gas stream.
An example of a development specifically enabling this to an extreme degree is the developmental composite
membrane introduced W. L. Gore that provides usable mechanical properties for very thin (20 m and less)
perfluorinated membranes with high protonic conductivity.
Water Transport (& Interface Reactions)
in Nafion Membrane of the PEM Fuel Cell
Materials challenges of the SOFC
SOFC
Solid Oxide Fuel Cell
Air side = cathode: High oxygen partial pressure

1
conductance
d
o =
Fuel side= anode: H
2
+ H
2
O= low oxygen partial pressure

H
2
+ 1/2O
2
D H
2
O

H
2

O
2

H
2
O
SOFC
Electromotive Force (EMF)
Chemical Reactions in 2 separated compartements:
- Cathode (Oxidation):
- Anode (Reduction):
O
2
+ 2e
-
D O
2-
H
2
+ O
2-
D H
2
O + 2e
-
EMF of a galvanic Cell:
(1) EMF = AG
r
/-z F
AG = Free Enthalpie
z = number of charge carriers
F = Faraday Constant
AG
0
= Free Enthalpie in
standart state
R = Gas Constant

SOFC:
O
2
+ H
2
D H
2
O

( )
2
0
0.5
2 2
ln
( ) ( )
a H O
G G RT
a H a O
A = A +
(2)
difference of AG between anode und cathode
( )
( )
2
2
ln
4
p O
RT
EMK
F p O
=
K
A
Nernst Equation:
SOFC
Elektrochemische Potential
Oxygen ions migrate due to an electrical
and chemical gradient


2 2
( ) ( ) 2 O O F

A = A A
2
( ) O

A
Chemical
Potential
Electrical
Potential
Electrochemichal
Potential
Driving force for the O
2-
Diffusion through the electrolyte are the
different oxygen partial pressures at the anode and the cathode
side:


2
( )
2
i
i
j O
F
o

= A
j
i
= ionic current
o
i
= ionic conductivity
SOFC
engl. Open Circuit Voltage (OCV)
2
( )
2
i
i
j O
F
o

= A
2 2
( ) ( ) 2 O O F

A = A A
2
( ) 0 O

A =
What happems in case :







0
i
j =
No current
Electrical potential difference = chemical potetial
OCV
SOFC
Leistungs-Verluste
Under load decrease of cell voltage
and internal losses

U(I) = OCV - I(R
E
+ R
C
+R
A
) - q
C
- q
A
(R
E
+ R
C
+R
A
)
OCV
q
C

q
A

cell current I [mA/cm
2
]
c
e
l
l

v
o
l
t
a
g
e

U
(
I
)

[
V
]

Ohmic resistances
Non ohmic resistances=
over voltages
SOFC
berspannungen
Over voltages exist at interfaces of
Elektrolyte - Cathode
Elektrolyte - Anode



Reasons:


Kinetic hindrance of the electrochemical reactions
Bad adheasion of electrode and electrolyte
Diffusion limitations at high current densities





SOFC
Ohms losses
800nm
Kathode
Anode
Reduce electrolyte thickness

Past
Future
SOFC
Leistungs-Verluste
(1) Open circuit voltage (OCV), I = 0
(2) SOFC under Load U-I curve
(3) Short circuit, V
cell
= 0
0.0 0.5 1.0 1.5 2.0
0.0
0.2
0.4
0.6
0.8
1.0
900C
in Luft/Wasserstoff
Stromdichte [A/cm
2
]
Z
e
l
l
s
p
a
n
n
u
n
g

[
V
]
0.0
0.1
0.2
0.3
0.4
0.5
L
e
i
s
t
u
n
g

[
W
/
c
m
2
]
(1)
(2)
(3)
(R
E
+ R
C
+R
A
)
OCV
q
C
q
A
cell current I [mA/cm
2
]
c
e
l
l
v
o
l
t
a
g
e
U
(
I
)

[
V
](R
E
+ R
C
+R
A
)
OCV
q
C
q
A
cell current I [mA/cm
2
]
c
e
l
l
v
o
l
t
a
g
e
U
(
I
)

[
V
]
1
2
3
SOFC
( )
*
U L
R f T
I A o
A
= = =
0
log( )
a
E
T kT
o
o =
1
.
a
T vs E
T
o
Electrical resistance:
Electrical conductivity:
U : voltage [V]
I : current [A]
R : resistivity [ohm]
AL : distance between both
inner wires [cm]
A : sample surface [cm2]
o : conductivity [S/m]
E
a
: activation energy [eV]
T : temperature [K]
K : Boltzmann constant
How to determine the electrical conductance
I
i
n
p
u
t

U
m
e
a
s
u
r
e
d

SOFC
SOFC-Designs
SOFC
Tubular design
i.e. Siemens-Westinghouse design
Planar design
i.e. Sulzer Hexis, BMW design
Segment-type tubular design
SOFC Design
SOFC
Tubular Design Siemens-Westinghouse
air flow
anode (fuel)
cathode
interconnection
cathode
(air)
Why was tubular design
developed in 1960s by
Westinghouse?
Planar cell: Thermal
expansion mismatch
between ceramic and
support structures leads to
problems with the gas
sealing tubular design
was invented

Advantages of tubular
design:
At cell plenum: depleted air
and fuel react heat is
generated incoming
oxidant can be pre-heated.
No leak-free gas
manifolding needed in this
design !

Drawback of tubular
design:
Electric current flows along
circumference of anode and
cathode high cell losses

SOFC
anode (fuel)
cathode
(air)
electrolyte
Tubular Design Siemens-Westinghouse
To overcome problems new
Siemens-Westinghouse HPD-
SOFC design:

New: Flat cathode tube with
ligaments

Advantages of HPD-SOFC:
Ligaments within cathode short
current pathways decrease of
ohmic resistance
High packaging density of cells
compared to tubular design
Siemens-Westinghouse shifted from
basic technology to cost reduction and
scale up.

Power output: Some 100 kW can be
produced.
SOFC
Planar Design Sulzer Hexis
anode (fuel)
electrolyte
cathode (air)
interconnect

Advantages of planar
design:
Planer cell design of bipolar
plates easy stacking no
long current pathways
Low-cost fabrication
methods, i.e. Screen printing
and tape casting can be
used.

Drawback of tubular
design:
Life time of the cells 3000-
7000h needs to be
improved by optimization of
mechanical and
electrochemical stability of
used materials.


Power output: 1 kW is aimed.

SOFC
Planar Design BMW
electrolyte
anode
porous metallic substrate
Fe-26Cr-(Mo, Ti, Mn, Y2O3) alloy
cathode
Cathode current collector
bipolar plate
bipolar plate
Air channel
Fuel channel
20-50 m
5-20 m
15-50 m
Plasma spray
Plasma spray
Plasma spray

Application
Batterie replacement in the
BMW cars of the 7-series.

Power output: 135 kW is
aimed.

Current Initiatives
Automotive Industry
Most of the major auto manufacturers have fuel cell vehicle (FCV) projects currently under way, which involve all sorts of fuel cells and
hybrid combinations of conventional combustion, fuel reformers and battery power.
Considered to be the first gasoline powered fuel cell vehicle is the H
2
0 by GM:
GMC S-10 (2001)
fuel cell battery hybrid
low sulfur gasoline fuel
25 kW PEM
40 mpg
112 km/h top speed
Figure 9
Fords Adavanced Focus FCV (2002)
fuel cell battery hybrid
85 kW PEM
~50 mpg (equivalent)
4 kg of compressed H
2
@ 5000 psi
Approximately 40 fleet vehicles are planned as a market
introduction for Germany, Vancouver and California for
2004.
Current Initiatives
Automotive Industry
Figure 10
Figure 11
Daimler-Chrysler NECAR 5 (introduced in 2000)
85 kW PEM fuel cell
methanol fuel
reformer required
150 km/h top speed
version 5.2 of this model completed a California to Washington DC drive
awarded road permit for Japanese roads
Current Initiatives
Automotive Industry
Figure 12
Mitsubishi Grandis FCV minivan
fuel cell / battery hybrid
68 kW PEM
compressed hydrogen fuel
140 km/h top speed
Plans are to launch as a production vehicle for Europe in 2004.
Current Initiatives
Automotive Industry
Figure 13
Current Initiatives
Stationary Power Supply Units
A fuel cell installed at McDonalds restaurant, Long Island Power Authority to install 45 more fuel cells across Long Island,
including homes.
(2)
Feb 26, 2003
More than 2500 stationary fuel cell systems have been installed all over the world - in hospitals, nursing homes, hotels,
office buildings, schools, utility power plants, and an airport terminal, providing primary power or backup. In large-scale
building systems, fuel cells can reduce facility energy service costs by 20% to 40% over conventional energy service.
Figure 14
Current Initiatives
Residential Power Units
There are few residential fuel cell power units on the market but many designs are undergoing testing and should be
available within the next few years. The major technical difficulty in producing residential fuel cells is that they must be
safe to install in a home, and be easily maintained by the average homeowner.
Residential fuel cells are typically the size of
a large deep freezer or furnace, such as the
Plug Power 7000 unit shown here, and cost
$5000 - $10 000.
If a power company was to install a residential fuel cell power unit in a home, it would have to charge the homeowner at
least 40 /kWh to be economically profitable.
(3)
They will have to remain a backup power supply for the near future.
Figure 15
Future
...projections made by car companies themselves and energy and automotive experts concur that around 2010, and perhaps
earlier, car manufacturers will have mass production capabilities for fuel cell vehicles, signifying the time they would be
economically available to the average consumer. Auto Companies on Fuel Cells, Brian Walsh and Peter Moores, posted on www.fuelcells.org
Technical and engineering innovations are continually lowering the capital cost of a fuel cell unit as well as the operating
costs, but it is expected that mass production will be of the greatest impact to affordability.
A commercially available fuel cell power plant would cost about $3000/kW, but would have to drop below $1500/kW to
achieve widespread market penetration. http://www.fuelcells.org/fcfaqs.htm
Future
internal combustion obsolete?
solve pollution problems?
common in homes?
better designs?
higher efficiencies?
cheaper electricity?
reduced petroleum dependency?
...winning lottery numbers?
References
(1) FAQ section, fuelcells.org
(2) Long Island Power Authority press release: Plug Power Fuel Cell Installed at McDonalds Restaurant, LIPA to
Install 45 More Fuel Cells Across Long Island, Including Homes,
http://www.lipower.org/newscenter/pr/2003/feb26.fuelcell.html
(3) Proceedings of the 2000 DOE Hydrogen Program Review: Analysis of Residential Fuel Cell Systems & PNGV
Fuel Cell Vehicles, http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/28890mm.pdf
Figures
1, 3 http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/electrol.html
4 8 http://fuelcells.si.edu/basics.htm
10 http://www.moteurnature.com/zvisu/2003/focus_fcv/focus_fcv.jpg
11 http://www.granitestatecleancities.org/images/Hydrogen_Fuel_Cell_Engine.jpg
12 http://www.in.gr/auto/parousiaseis/foto_big/Necar07_2883.jpg
13 http://www3.caradisiac.com/media/images/le_mag/mag138/oeil_mitsubishi_grandis_big.jpg
14 http://www.lipower.org/newscenter/pr/2003/feb26.fuelcell.html
15 http://americanhistory.si.edu/csr/fuelcells/images/plugpwr1.jpg
Table 1 http://hyperphysics.phy-astr.gsu.edu/hbase/tables/therprop.html#c1
Fuel cell data from: Types of Fuel Cells, fuelcells.org
Fuel Cell Vehicle data primarily from: Fuel Cell Vehicles (From Auto Manufacturers) table, fuelcells.org