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Solid Oxide Fuel Cells

The Power for the 21 st Century

Meilin Liu

Center for Innovative Fuel Cell and Battery Technologies


School of Materials Science and Engineering
Georgia Institute of Technology
Atlanta, GA 30332-0245
What is a Fuel Cell?

Electricity

Hydrogen
Fossil Fuels
(Gas, oil, coal)
Why Fuel Cells?

From: McDermott
TG DG
DG

FC
TG

FC

SSFC: Ship Service Fuel Cell Program; GTG: Gas Turbne Generator
SSDG: Ship Service Diesel Generator
Motives for Fuel Cells

• High efficiency
• Low emissions (no SOx or NOx, half CO2)
• Low operating costs & low maintenance
• Quiet
• Distributed power generation (avoid power outages)
• Stricter transportation emission standards
Applications of Fuel Cells

Stationary power
Hybrid propulsion
Compact power systems
Distributed power systems
Portable power systems
Microturbine combined cycles
Naval power systems
Naval Applications
Driving Force
• US Department of Energy
¾ $70 million for SOFC research 2002-2003
¾ $140 million supporting hydrogen production and
stationary PEM fuel cell technologies
• FreedomCar initiative
¾ To promote development of hydrogen as a primary fuel for
automobiles
¾ Will spend $150 million on PEMFC technologies in 2002
• Private auto and energy companies
• European, Japanese, and Chinese governments
US DOE Performance Targets

• 2nd Generation
Efficiency: 50-60% LHV
Cost: $1,000-$1,500/kW
Year: 2003

• 21st Century System


Efficiency: 70-80% LHV
Cost: $400/kW
Year: 2015
Cost and Reliability Issues

• Moving parts (pumps, compressors) unable to


perform for thousands of continuous hours
• Stationary fuel cells must operate continuously for
40,000 hours
• Automotive fuel cells require 5000-hour lifetime
• Catalyst costs (platinum, ruthenium, palladium)
• For automotive applications fueling infrastructure is
an issue
Proton Exchange Membrane Fuel Cells
Load
e’

Fuel in Oxidant in

O2
H2

H+
H2 H 2O

Proton
Exchange
Depleted fuel Membrane Depleted oxidant
Anode Cathode
Proton Exchange Membrane (PEMFC)
• Specialty power (small stationary)
• Buses/Vehicles
• Gemini space program

• Dow Chemical (MI, AR)


• Electrochem (MA)
• Energy Partners (FL)
• H-Power (NJ, CA)
• UTC Technologies Corp.(CT)

• 1000 PEMFCs (each averaging 5 kW per unit) were put


into service on an experimental basis
PEMFC
• Solid state (No liquid to circulate)
• Flexible membrane won’t leak or crack
• Produce high power density at temperatures below
100°C; allows fast start-ups and immediate response to
changes in power demand

• Fuels must be purified to avoid catalyst poisoning by


CO and sulfur
• Platinum accounts for 20% of total costs of a 50-kW
PEMFC system for vehicles
– 200 grams of Pt required based on a loading of 0.5
mg/cm2 in the MEA
PEMFC

• Goal is to bring system cost down to $2500 per vehicle;


current cost is about $14,000 per fuel cell engine

• Stationary PEMFCs cost more than $3600 per KW


installed; must bring system cost down to $1200-$1500
per kilowatt to be competitive
Direct Methanol (DMFC)

• No need for fuel reformer


• Operate at 120-190 F
• 40% efficiencies are expected

anode: CH3OH + H2O → CO2 + 6H+ + 2e-


cathode: 3/2O2 + 6H+ + 6e- → 3H2O

overall: CH3OH + 3/2O2 → CO2 + 2H2O


Challenges & Opportunities

¾ Catalysts insensitive to contaminants in the fuel


such as CO;
¾ Novel membranes with minimal MeOH across-over
and high H+ conductivity at 120-180°C ;

¾ Efficient catalysts that promote a high rate


of oxygen reduction;
¾ Alternative catalysts less expensive than
Pt/Ru to reduce the cost.
Solid Oxide (SOFC)

e’

Fuel in Oxidant in

O2
H2
H+
H2 H 2O
Anion
Hydrocarbon H O O2
2 conductor
Fuels

Electrolyte

Depleted fuel (Ionic Depleted oxidant


conductor)
Anode Cathode

CO, H2+O2→CO2, H2O+2e- 4e- + O2 → 2O2-


SOFC Materials

• Electrolyte: YSZ, GDC, LSGM, SrCeO3


• Anode: Porous Ni-ZrO2 or Cu-YSZ cermet
• Cathode: LSM/YSZ, LSCF/GDC, SSC
Why SOFC ?

The cleanest, most efficient &


versatile system for chemical
to electrical energy conversion

50% electrical, 85% overall


Advantages of SOFCs
Efficient – 40-60% efficiency in individual electric systems and up to
80% in hybrid systems
Environmental – Reduces global warming and air pollution

Fuel Flexible – Uses available liquid fuels such as gasoline and


diesel as well as natural gas and propane

Fuel Extending – Extends the use of variety of fossil fuels, including


vast domestic coal reserves

Modular: as the basic building block for multiple applications

Distributive Energy – Brings electricity to remote locations where


no transmission exists

Domestic Security – Reduces dependence on foreign oil

SECA
Applications
Stationary – SOFCs will efficiently provide clean,
economical electricity either in urban settings, or in
remote locations for homes, hospitals, farms,
businesses, or recreation facilities.

Transportation – SOFCs are able to work with all


standard transportation fuels to provide auxiliary
power (AP) for trucks and other vehicles.

Military – Fuel cells are attractive for military use


because they represent quiet, clean, uninterruptible
energy that can be delivered at the point of power
application.

SECA
Honeywell SOFC System Concept

20 IN.

36 IN.

15 IN.
McDermott's
2-kW Technology
Demonstration Unit
Delphi/Battelle’SOFC APU
‹ SOFC system as an AUXILIARY POWER UNIT (APU)
‹ Markets: stationary, passenger automobiles, trucks, recreational vehicles,
military
12V-24V trailer
12V Alternator converter Refrigeration Unit
CAB LIGHTS Refrigeration
CB RADIO 12V Alternator Battery Isolator
AM/FM
HEATER
FRIDGE
SATELLITE

Refrigeration Unit
Lift-gate Battery
Battery

Low Voltage Voltage


Disconnect trailer lights, ABS,..
conditioner for

Delphi Gasoline APU


for passenger automobiles Diesel Truck APU

Stationary applications -
Natural gas or diesel power generators
Delphi Next Generation APU System
Proof of Concept (PoC) APU

Mass reduction:
PoC: 200 + kg
Next Generation: 50 kg

Next Generation
APU Mock-up

Size reduction:
PoC: 152 Liters
Next Generation: 50 Liters
SOFC Obstacles
• Electrolyte conductive only at high temp
• Expensive alloys needed to house the cell
• High temperature causes thermal stresses in
ceramic structures
• Too expensive: $4000-6000/kW
Challenge: Cost Reduction

• Materials selection: inexpensive


materials

• Fabrication processes: simple &


cost-effective
Lower Operating Temp → Material Cost
• Advantages
– Inexpensive metallic components may be used for
interconnect, heat exchanges, and other components
– Greater system reliability & longer optional life
– Potential for mobile applications

• Challenges
– Conductive electrolytes
– Catalytically active electrodes
– Macro- & meso-porous electrodes/interfaces

GT – FC/BT
Cost-Effective Fabrication→Manufacturing Cost

• Fabrication Techniques
– Screen Printing
– Dry Pressing
– Co-Extrusion
• Advantages
– Simple, inexpensive, reproducible

• Challenges
– How to retain competitive performance

GT – FC/BT
SECA Development:
Progressive Applications

2005
2015
• $800/kW
• Prototype ($- 2010 • Vision 21 Power Plants
Unit) 75% efficient plants
3 - 10 kW
• $400/kW • Propulsion <$200?/kW
• Commercial
Solid Oxide Fuel Cells
Fabricated by
Screen-Printing & Dry-Pressing
Characteristics of GDC Powder by GNP
Large surface area
Compositional homogeneity

Loose agglomerates
4µm Foam-like structure
Fill density 0.059 g/cm3
b 120th of theoretical value

Easy to densify
92% at 1250oC/5 hrs
1µm 95% at 1350oC/5 hrs
Dry Pressing of GNP Powder

The thickness of the


loose powder is
about 120 times that
of the dense film
2400 µm
2.4 mm Loose
Dense Film ~ 0.1”
Powder
20 µm

The thinnest: 8 µm
Microstructures of Dry-Pressed Films

10µm 30µm

cathode
GDC film

electrolyte

Substrate anode

~8 µm ~15 µm
Cross-Sectional View of a Single Cell
A single cell Porous SSC and
10 v%SDC
cathode Cathode

electrolyte

anode 2µm
30µm

Dense SDC Porous Ni-SDC


Anode

2µm
2µm

Changrong Xia, Fanglin Chen and Meilin Liu, Electrochemical and Solid State letters, 4(5) A52-A54 (2001).
Performance of SOFCs

2.0
LBL
-2

1.8 SDC (30 µm), Xia, dry pressing


Power density, Wcm

1.6
YSZ (5-10 µ m), Tsai Utah
YSZ (8 µ m), YDC interlayer, Ghosh
1.4 YSZ (10 µ m), Kim
YSZ (9 µ m), Visco
NW
1.2

1.0 ANL
0.8

0.6
GT
0.4 Dry pressing
0.2

0.0
400 500 600 700 800

Temperature, °C
Significance of Interfacial Resistances
0.4 a 500 C
o

2
Im Z, Ωcm
o
0.2 550 C
o
600 C

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
2
Re Z, Ω cm
10

Interfacial Resistance
8
Resistance, Ω cm2

6 Performance is
determined by Rp at
4
low temperatures!
2
Electrolyte, 30µm

0
400 450 500 550 600

Temperature, °C
Modeling and Design of
Porous Mixed-Conducting Electrodes

Supported by

National Science Foundation

GT – FC/BT
SOFC: Key Components

FUEL: H2 or Propane e-

anode H 2 +O XO → H 2O + VO•• + 2e′

electrolyte VO••
Load
1
cathode O 2 + VO•• + 2 e ′ → O XO
2

OXIDANT: air or O2 e-
Active sites for Electrochemical reactions
Metallic Electrode: TPB
1
2 e′( electrode ) + V (
••
O electrolyt e ) + O2 ( gas ) → OOX
2
O2 (gas)
Metallic Electrode
2e-

Electrolyte Vo..

Reaction Rate
Active sites for Electrochemical reactions
MIEC Electrode: Solid/Gas Interface
1
2 e′( electrode ) + V (
••
O electrolyt e ) + O2 ( gas ) → OOX
2
1
O2 ( gas ) + {VO.. + 2 e′}( MIEC ) → OOX
2
O2
2e-
MIEC Vo
Electrolyte
Vo..

Reaction Rate
Porous MIEC Electrode
Elementary Steps
1
2 e′( electrode ) + VO•• ( electrolyt e ) + O2 ( gas ) → OOX
2
Ionization of Oad Electrolyte

Adsorption O2

Diffusion

e- Oad
O2-
Ionic and Electronic Surface diffusion
Transport

Electrolyte
Modeling of Porous MIEC Electrodes

• In the Solid MIEC


 uk 
J k = − zk F  [(1 − p )ck ](∇µ k + zk F∇φ )
τs 
• Through the Pores of MIEC
  u O2  
N O2 =  −  ∇ µ O + v  ( pcO )
τ  2 2
  g  
• At the MIEC/O2 Interface & TPBs
 * 
1
 α ∆ µ~  
α a ∆ µ e   pO2
~
 cV   2
J V = J 0 ,V   exp − *  exp  c e 
  p   RT  
 cV  
RT
  O2    

Distribution of Reaction Rate
Useful Thickness
CC Porous MIEC El. CC Porous MIEC El.

Jv
TPB1 TPB1

MIEC/O2

MIEC/O2

TPB2
Functionally Graded Electrode

Current collector Layer

Intermediate Layer

Catalytic layer

Electrolyte
In-situ potential-dependent FTIR
Emission Spectroscopy
To understand elementary steps involved in electrode
reactions in SOFCs, such as adsorption, dissociation,
charge transfer, and mass transfer;

To provide surface structural details under conditions


for actual fuel cell operation; and

To rationalize the pd-FTIRES spectra correlated to


electrochemical data with the types of the intermediate
species found at the functional interfaces.

GT – FC/BT
Experimental Arrangements for
Investigations into SOFC Reactions Using
in-situ FTIR-ES, IS, and MS/GC
Process
Control Mass
System Spectrometer Gas
FTIR Chromatograph
Accessory
To Vent
Argon
Fuel/O2
Mass Flow Drier
To Vent
Controllers
Oxygen
Sensor
Impedance Spectroscopy
Electroanalytical measurements

GT – FC/BT
Optical Configuration
for In-Situ pd-FTIR Emission Spectroscopy
Top: Oxygen Reduction
1/ 2O2 +VO•• + 2e− →OOX
(1/ 2O2 + 2e− →O2− )
Bottom: Oxygen Evolution

O2− − 2e− →1/ 2O2


FTIR Spectrometer
(Liquid-N2-Cooled PO2
MCT Detector)

O2−

Thermocouple

Impedance Spect.
DC Overpotential PO2
Heating Cartridge

GT – FC/BT
In-Situ Pd-FTIRES Spectra
-1
- After local baseline correctionw a v e n u m b e r / c m -1
wavenumber / cm
1400 1300 1200 1100 1000 900
4000 3500 3000 2500 2000 1500 1000 500
8

6
0 .0

4
In air
2 (η: 0 to
320 mV) (a )
0
-0 .1

25

0
20

15
In 1%O2
10
(η: 0 to
(b )
760 mV)
5

0 -3

25
0
20

15 In N2
(η: 0 to (c )
10
690 mV)
5
O2−
-3
0
1400 1300 1200 1100 1000 900
4000 3500 3000 2500 2000 1500 1000 500
w a v e n u m b e r / c m -1
wavenumber / cm-1

After local baseline correction


Evolution of Oxygen - SSC/SDC/SSC, in 1% O at 500°C 2

8 6
SSC/SDC/SSC, in 1%O2, at 550 C
o

o
7 -Im{Z} (Ω⋅cm )
2
4
with DC bias, 0~1.1V with 0.2V increment
550 C, with DC bias
6 2

5 m ent
cr e
0
0 2 4 6 8 10 12

V i n
4 0. 2
2
Re{Z} (Ω⋅cm )

ith
3 V,w
1.1
∆E/E0(%)

0~ 930
2
1124
1236
1
0 OCV
-1
-2
0 ~ -1
-3 . 1 V, w
ith -0
. 2V in
-4 crem
ent
-5
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber/cm
Proposed Reaction Mechanism for Oxygen Reduction

Rate-determining step (rds): O2−,ad + e′ → O2=,ad


PO 2 O2(gas) O2(gas)
Gas Mixture

O- O-
O O
e- e-
2− 2− 2−
2−
O LC 2−
VO•• O LC O LC O LC VO•• O LC
MIEC Electrode
2− 2− 2− 2− 2− 2−
O LC O LC O LC VO•• O LC O LC O LC

VO•• VO•• VO•• SDC Electrolyte


2-
2-
O O

MIEC Electrode

+ e- e- +

PO 2 O2(gas) O2(gas)

GT – FC/BT
In-situ FTIRES – Anodes in SOFCs
H2 as background and CH4 as sample 817
CH4(gas)
20 After 5 min in CH4 1050
-1
2143 cm : CO (Adsorbed)
-1
1712 and 1540 cm : Graphite
-1
1070-800 cm : Metal (Ni or Cu)
carbonato (CO3) complexes
16 Ni-S 1712
DC
An CH4(gas) 1540
od
∆E/E0(%)

12
2143
Cu-SDC
Anode

8 1540 1072
807
CO2

4
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber/cm
-1
GT – FC/BT
New Electrode Materials for
Low-Temp SOFCs

Supported by

Department of Energy
Microstructures and Impedances of SSC-SDC10 Cathodes
fired at different temperatures

900oC 950oC 1000oC

2µm 2µm 2µm

0.2
2
Im Z, Ωcm

0.1

o
950 C 900oC o
1000 C
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
2
Re, (Z -Rb), Ωcm
The Best Performance at 400-600°C
0.65
0.60 0.6 W/cm2
0.55
at 600°C
-2

0.50
Power density, Wcm

0.45
0.40
0.35
0.30 W400
0.25 W450
0.20 W500
0.15 W550
0.10 W600
0.05
0.00

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
-2
Current density, Acm
The Best Performance of LT-SOFCs

2.0 GDC (30 µm), Xia, dry pressing LBL


-2

1.8 SDC (30 µm), Xia, dry pressing


Power density, Wcm

1.6
YSZ (5-10 µ m), Tsai Utah
YSZ (8 µ m), YDC interlayer, Ghosh
1.4 YSZ (10 µ m), Kim
YSZ (9 µ m), Visco
NW
1.2

1.0 ANL
0.8

0.6 GT GT
0.4

0.2

0.0
400 500 600 700 800

Temperature, °C
Hybrid Metal/Electrolyte
Monolithic Solid Oxide Fuel Cells

Supported by
DARPA/DSO - Palm Power
(with J. Cochran, J. Lee, D. McDowell, T. Sanders)
Tubular SOFC

Low Power Density


Planar SOFC
End Plate

Anode

Electrolyte
Cathode

Bipolar Separator

Repeating
unit Anode

Difficulties in manifolding and sealing


SOFC: An Extruded Cell
Hybrid Metal/Electrolyte Monolithic Low Temperature SOFCs

FeNiCoMo LCM
_
Fuel
Air Load
Fuel
Air
+
Georgia Institute
of Technology
Hybrid Extrusion - ”In617”/YSZ

Web =
2.5 mm 180 µm

Note that
40% linear
shrinkage
occurs on
sintering.
Webs will
be 110 mm. Lengths can be continuous

GT – FC/BT
Electrolyte Honeycomb
honeycomb fuel cell

Slurry in

Slurry out

Drying
Sintering
Slurry coating
Projections for Hybrid Metal/Ceria Monolithic SOFC

1. Operation Fuels -- Hydrogen, Natural Gas, Propane, Coal Gas, Methanol,


Ethanol, and Reformed Gasoline and Diesel; potentially insensitive to
contaminants such as H2S in reformed fuels.

2. Power Density – 1 Watt/cc in Near Future, 5 Watts/cc in 3-4 Years

3. Operating Temperature – 400-6000C

4. Fuel Cell Size – 6 X 6 mm square by 11cm long. (This Is 4 Watts at 1 W/cc


and 20 watts at 5 W/cc. (This Is Not Palm Power. It Is Finger Power)

5. Materials – Samaria Doped Ceria (SDC) Solid Electrolyte, CoCr Doped Ni


Metal Interconnect, Anode of Porous Ni-SDC, and a Cathode Layer,
Consisting of Sm0.5Sr0.5CoO3 and 10wt.% SDC. Catalysts Will be Added as
Needed Depending on Fuel.

6. Fuel Cell Cost -- $500/kW in One Year, $50/kW in 3-4 Years

Georgia Institute
of Technology
Functionally Graded Electrodes
on Honeycomb Cells

GT – FC/BT
Functionally Graded Electrodes
YSZ
GDC
LSM
LSCF 1 2 3 4 5
12
2
Interfacial resistance (Ωcm )
2

3
8

4 5

0
650 700 750 800

GT – FC/BT
o
T e m p e ra tu re ( C )
Sample 5: LSM/GDC/LSCF

LSCF

LSCF50+GDC50

LSM25+LSCF25+
GDC50

LSM50+GDC50

YSZ

GT – FC/BT
Graded Composition

High Electronic Conductivity


Interconnect Compatibility

Inter-Mixed Layer
Highly Catalytic
Electrolyte Adhesion
Matched Thermal Expansion
Electrolyte
The Interfacial Resistances About 10 Times Smaller

30 Functional graded cathode


Resistance, Ω cm2

LSM based cathode


25 YSZ (300 µ m thick)

20

15

10

0
550 600 650 700 750 800

Temperature, °C
Cathodes for Zirconia Fuel Cells
oo oo oo oo
850 C 750 C 650 C 550 C
10
Cathode for zirconia 700ºC
2
Interfacial resistance, Ωcm2

1 150ºC

One Order of Magnitude


0.1

Graded cathode, Hart, JPS 106(2002)42


LSM-GDC cathode, Murray, SSI 143(2001)265
Graded cathode,
cathode
YDB cathode
0.85 0.90 0.95 1.00 1.05 1.10 1.15 1.20 1.25
Temperature, 1000/T

GT – FC/BT
Summary - Electrode Development
• Cathodes graded in composition show interfacial
resistances about 10 times lower than that of a
conventional LSM-YSZ cathode;
• The performances are dependent on the microstructures,
and is improved by low-temperature sintering;
• Interfacial resistance of graded cathodes as low as 0.47
Ωcm2 was achieved at 750oC. However, it increased to
4.1 Ωcm2 at 600oC; and
• A new cathode showed much lower interfacial
resistances than the graded cathodes, 0.30 Ωcm2 at
600oC, about 10 times better.
600 mW/cm2 at 600°C
GT – FC/BT
Other Alternative
Advanced Energy Technologies
Future Energy Technology
Renewable, Regenerative Fuel Cells using Solar Energy

Water Water

Courtesy: Aerovironment
The Cleanest Alternative
Solar Energy
Photo-
electrochemical
Cell

H2O H2

Fuel Cell
Electricity
Concluding Remarks
• Solid Oxide Fuel Cells represent the cleanest,
most efficient & versatile system for efficient
use of fossil fuels.

• Recent advances in SOFC R&D suggest that


SOFC technology has the greatest potential
to be the primary energy technology for the
21st century.
Challenges & Opportunities
¾ Cathode development
First-principle calculation to predict best materials and structures
Rational design of functionally graded electrodes and interfaces

¾ Contaminant-Resistant Anodes and reforming


catalysts
Sulfur resistant, Carbon-deposition resistant,
Sulfur removal
¾ Cost-effective fabrication processes to
dramatically reduce the cost
$4,000→$400/KW
Research Team Members
• Bill Rauch
• Alan Burke
• Erik Koep
• Xinyu Lu
• Dr. Changrong Xia (MSE)
• Dr. Siwen Li (MSE)
• Dr. Jessica Bartling (ChE)
Acknowledgements

NSF
DoE/NETL
DARPA/DSO-Palm Power
ONR Grant N00014-99-1-0353

Center for Innovative Fuel Cell and Battery


Technologies, Georgia Tech