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Meilin Liu
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
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
e’
Fuel in Oxidant in
O2
H2
H+
H2 H 2O
Anion
Hydrocarbon H O O2
2 conductor
Fuels
Electrolyte
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.
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
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
• 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 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
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
1.6
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
GT – FC/BT
SOFC: Key Components
FUEL: H2 or Propane e-
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
Jv
TPB1 TPB1
MIEC/O2
MIEC/O2
TPB2
Functionally Graded Electrode
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;
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−
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
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
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
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
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
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
Anode
Electrolyte
Cathode
Bipolar Separator
Repeating
unit Anode
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
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
Inter-Mixed Layer
Highly Catalytic
Electrolyte Adhesion
Matched Thermal Expansion
Electrolyte
The Interfacial Resistances About 10 Times Smaller
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
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.
NSF
DoE/NETL
DARPA/DSO-Palm Power
ONR Grant N00014-99-1-0353