PERFORMANCE ANALYSIS OF SINGLE STEP

CO-FIRED SOLID OXIDE FUEL CELLS (SOFCS)

KYUNG JOONG YOON, PETER A. ZINK, UDAY B. PAL, SRIKANTH GOPALAN

DEPARTMENT OF MECHANICAL ENGINEERING

DIVISION OF MATERIALS SCIENCE AND ENGINEERING
BOSTON UNIVERSITY
OUTLINE

™ Introduction

™ Single Step Co-

Co-firing Process Development

™ Polarization Modeling

™ Polarization Analysis

™ Fuel Utilization Test

™ Advanced
Ad d Cathode
C h d Investigation
I i i

™ Summary & Future Work

 INTRODUCTION
™ Major Challenges for Commercialization of SOFCs
High Manufacturing Costs Reduced Cell Performance at Low Operating
(SOFC System Costs per Unit of Power ($/kW)) Temperature (Interconnects, Sealing, etc.)

Single Step Co-

Co-Firing Process Polarization Modeling:
Modeling: Systematic Analysis of
with Conventional Material System Cell Performance and Polarization Losses

™ Research
R hGGoals
l
ƒ Manufacture SOFCs with the Lowest Manufacturing Costs
by Single Step Co
Co--Firing of the Entire SOFCs
ƒ Achieve the Highest Cell Performance and Lower Operating Temperature
by Optimization of Materials, Microstructures, and Process Parameters
using Polarization Modeling

Minimize $/kW
SINGLE STEP CO-FIRING PROCESS

Cathode Current Collector:

Collector: Screen Printing
Ca
Ca-
C -doped
d d LaMnO
L M O3 (Porous)
(P )

Cathode Active Layer:

Layer: Screen Printing
Ca--doped LaMnO3 + YSZ (Fine & Porous)
Ca

Electrolyte:: Screen Printing

Electrolyte
YSZ ((Dense)) Co--Firing in Air
Co
(1300--1330oC)
(1300
Anode Active Layer:
Layer: Screen Printing
Ni + YSZ (Fine & Porous)

Anode Support:
Support: Tape Casting
Ni + YSZ (Porous)
 PROCESS DEVELOPMENT
™ Lowered Electrolyte Sintering Temperature
ƒ Density of YSZ : Without Sintering Aid: ~ 94%,
94%, With Sintering Aid: ~ 99+% @1300oC

™ Matched Thermal Expansion Coefficients and Sintering Shrinkages

™ Developed Refractory Cathode Composition
ƒ Doped
Doped--(La,Ca
La,Ca)MnO
)MnO3
Doped-LCM LSM

™ Optimized Thicknesses and Porosities of Electrodes

™ Optimized
p Particle Sizes of Initial Powders

™ Evaluated Pore Former Material

ƒ Carbon Black
Carbon Black Methyl Cellulose

™ Employed Cathode Current Collector Cathode Current Collector

: (La,Ca)MnO
(L C )M O3
50μm thick, 50% porous
PROCESS DEVELOPMENT
o
0.6 Temperature: 900 C Cathode Particle Size Optimization
H2+3% H2O / Air
Cathode Current Collector
0.5
Anode Porosity Optimization
Power Density ((W/cm )
2

0.4
Pore Former Material Optimization
0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
2
Current Density (A/cm )

Cathode Current Collector:

LCM, 50μm thick
LCM 50μ thick, 50% porous

Cathode Active Layer:

LCM--YSZ, 30
LCM μm thick, 31% porous
30μ

15μm thick
Electrolyte: YSZ, 15μ
Anode Support:
Ni--YSZ, 850
Ni μm thick, 32% porous
850μ
BASELINE CELL: POWER DENSITY

0.6 2
Max.=0.55 W/cm ™ Test Condition
W/cm )
2

0.5 ƒ Temperature: 700~800oC

ƒ Fuel: 97% H2+3% H2O
Power Density (W

0.4 2
Max.=0.36 W/cm ƒ Oxidant: Air

0.3
2
Max =0 23 W/cm
Max.=0.23
0.2
o
800 C
o
0.1 750 C
o
700 C
0.0
0.0 0.5 1.0 1.5 2.0
2
Current Density (A/cm )
 POLARIZATION MODEL: THEORY

E = E − iR − η − η
C 0 i act conc

α ne η act F ( 1 − α ) neη act F

ƒ Activation Polarization (ηact)* : i = i 0 exp( ) − i0 exp(- ) (α=1/2, ne=2)
RT RT

η actt = RT ln{ 1 [( i ) + ( i ) + 4 ]}
2
(Anode + Cathode)
F 2 i0 i0
o
RT i pH 2 i
ƒ Concentration Polarization (ηconc)** : ηconc = − RT ln(1 − i ) − ln(1 − ) +
RT
+
ln(1 o )
4F ics 2F ias 2F p
H Oi 2 as

RT 1 i i 2 RT i RT i RT p Ho 2i
EC = Eo − i R i − ln{ [( ) + ( ) + 4 ]} + ln(1 − ) + ln(1 − ) − ln(1 + o )
F 2 io io 4 F ics 2 F ias 2 F p i
H 2 O as

Open Circuit Ohmic Activation Concentration Concentration

Potential Polarization Polarization Polarization (Cathode) Polarization (Anode)

* P.W.Li
P.W.Li,, M.K.Chyu
M.K.Chyu,, J. Heat Transfer,
Transfer, vol.127, 1344 (2005)
** J.W.Kim,
J.W.Kim, A.V.Virkar,
A.V.Virkar, K-
K-Z.Fung
Z.Fung,, K.Mehta,
K.Mehta, S.C.Singhal
S.C.Singhal,, J.Electrochem.Soc
J.Electrochem.Soc.146
.146 (1) (1999) 69
 POLARIZATION MODELING: CURVE-FITTING (EXAMPLE)
™ Test Condition
ƒ Temperature: 800oC
Fitting 21% O2 + 8% O2 +
ƒ Fuel: 97% H2+3% H2O (300cc/min): Fixed 100% O2
Parameters 79% N2 92% N2
ƒ Oxidant: 100%,
100% 21%,
21% 8% O2 + N2 (1000cc/min)
1.2 Ri (Ω·
Ω·cm
cm2) 0.082 0.082 0.082
100% O2
1.0 21% O2 + 79% N2
io (A/cm2) 0.52 0.28 0.097
8% O2 + 92% N2
0.8 Curve-fitted
Curve fitted
ias (A/cm
( / 2) 5.77 5.77 5.77
Voltage (V)

0.6
ics (A/cm2) - 5.42 1.77
0.4

0.2
Assumption: ics >> ias and ηconc,c<< ηconc,a, ηact with 100% O2
0.0
0 1 2 3 4 5 6
2
C
Current
tDDensity
it (A/cm
(A/ )

2 F p Ho 2 D Heff2 − H 2 O
ƒ Anode Limiting Current i as = DeffH2 2
R T la H2--H2O = 0.23 cm /s

4 F`p o D eff

ƒ Cathode Limiting Current i cs = O2 O 2− N 2

DeffO2 2
p − po O2--N2 = 0.037 cm /s
O2
( )RTl
c
p
 POLARIZATION MODELING: VERIFICATION OF ASSUMPTION

Various Polarization Losses @800oC with Cathodic Limiting Current Density

Humidified Hydrogen (3% H2O) and Air @800oC as a Function of pO2 in Oxidant
1000

Limiting Currentt Density (A/cm )

2
o o
0.6 Temperature: 800 C Temperature: 800 C
Fuel: 97% H2+3% H2O
800
0.5 Oxidant: Air
n (V)

0.4 600
Polarization

0.3 n
rizatio 400
iv at ion Pola
Act
0.2 zatio
n
n P olari
tio
entra 200
01
0.1 ic Conc

Cathodic L
Anod
olarization
centration P
Cathodic Con
0.0 0
0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0
2
Current Density (A/cm ) pO2 in oxidant (atm)

ƒ ηconc,c << ηconc,a and ηact except at high ƒ ics rapidly increases as pO2 increases and
current density near ics approaches 100% O2

™ Consistent with assumption that ηconc,c is negligible compared to other polarization

losses when oxygen at the cathode nears 100%
 POLARIZATION MODELING & IMPEDANCE SPECTROSCOPY
ƒ Activation Polarization Resistance at OCV

ƒ Anodic Concentration Polarization Resistance at OCV

ƒ Cathodic Concentration Polarization Resistance at OCV

Impedance Spectroscopy @800oC 0.8

Polarizzation Resistance ((Ohm-cm )

Impedance Spectroscopy

2
100% O2 Polarization Model
Z(Im) (Ohm-cm )
2

0.4
21% O2 + 79% N2 0.6
8% O2 + 92% N2
0.2
0.4

0.0
0.2 0.4 0.6 0.8 1.0 1.2 0.2
2
Z(Re) (Ohm-cm )

High Frequency Intercept = RΩ 0.0

0.0 0.2 0.4 0.6 0.8 1.0

Low Frequency Intercept = Rpolar + RΩ pO2 in oxidant (atm)

POLARIZATION ANALYSIS #1: BASELINE CELL
1.2

Ohmic Loss (Electrolyte)

1.0
Ohmic Loss (Electrode) : Anode + Cathode + Contacts
0.8
Volltage (V)

0.6
Activation Polarization

0.4 Cathodic Concentration Polarization

Anodic Concentration Polarization
o
0.2 Temperature: 800 C
H2-3% H2O / Air
0.0
0.0 0.5 1.0 1.5 2.0
2
Current Density (A/cm )

™ Dominant Polarization Losses

ƒ Ohmic Loss (Electrode)
ƒ Activation
A ti ti Polarization
P l i ti (Cathode)
(C th d )
ƒ Concentration Polarization (Anode)
POLARIZATION ANALYSIS #2: CONTACT RESISTANCE
™ Cathode Current Collection : Ag Mesh vs. Pt Mesh
1.2 2
1.0
o
Temperature: 800 C Max.=0.9W/cm
H2-3% H2O / Air Tm(Ag) = 961oC
1.0
0.8
Relectrode = 0.067 Ω· cm2
Ω·cm

Power Density (W/cm )

0.8
2 0.6
e (V)

Max.=0.55W/cm
06
0.6
Voltage

Tm(Pt) = 1772oC
0.4
0.4 Relectrode = 0.156 Ω· cm2
Ω·cm
0.2
0.2
Ag Mesh

2
Pt Mesh
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
2
Current Density (A/cm )

ƒ Ag is softer than Pt at operating temperature.

⇒ Higher Interfacial Contact Area ⇒ Lower Ohmic Electrode Resistance

ƒ In SOFC stacks, the effect of the contacts between the electrode and interconnects can be
substantial.
POLARIZATION ANALYSIS #3: CATHODE MICROSTRUCTURE
1300oC Sintering
™ Sintering Temperature: 1300oC vs. 1330oC Avg. Grain Size = 2.3 μm
1.2 o
1.6
Temperature: 800 C 2
Max.=1.4W/cm
H2-3% H2O / Air 1.4
10
1.0
1.2

Power Den
0.8
2 1.0
Max.=0.9W/cm
ge (V)

0.6 0.8

nsity (W/cm )
Voltag

0.6
0.4 io = 0.27 A/cm2
0.4
0.2 o
1330oC Sintering
1300 C Sintering

2
0.2
o Avg. 3 2 μm
Avg Grain Size = 3.2
1330 C Sintering
0.0 0.0
0 1 2 3 4
2
Current Density (A/cm )

Impedance Spectroscopy
o
0.3 1300 C Sintering
-IM(Z) (Ω cm )

o
2

1330 C Sintering
0.2
io = 0.16 A/cm2
0.1

0.0
ƒ No Significant Change in Anode Microstructure.
1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.6
Re(Z) (Ω cm )
2
ƒ Less Sintering of Cathode ⇒ Low Activation Polarization
POLARIZATION ANALYSIS #4: ANODE POROSITY
8 wt% Carbon Black
™ Pore Former in Anode: 8 wt% C vs. 5 wt% C Anode Porosity: 37%

12
1.2
o
Temperature: 800 C Max.= 1.5 W/cm
2 1.6
1.0 H2-3% H2O / Air
1.4

Power Density (W
2
Max.= 1.4 W/cm 1.2
0.8
1.0
Voltage (V)

ias = 5.77 A/cm2

0.6
H2--H2O = 0.23 cm s
2 -1
0.8 DeffH2

0.4 0.6 5 wt% Carbon Black

V

W/cm )
0.4 Anode Porosity: 32%
0.2
8 wt% Carbon Black

2
0.2
5 wt% Carbon Black
0.0 0.0
0 1 2 3 4 5
2
Current Density (A/cm )

ƒ Increased Anode Porosity ias = 4.97 A/cm2

H2--H2O = 0.19 cm s
DeffH2 2 -1

⇒ Low Anode Concentration Polarization

 CELL PERFORMANCE IMPROVEMENT CHART

1.6
m)

o 1.5 W/cm2
2

Temperature: 800 C
wer Density (W/cm

1.4 97% H2+3% H2O - Air Comparable to the State-

State-of
of--
the--Art Cells Fabricated with
the
1.2
Multiple
p Firing
g Steps
p
1.0

0.8
mum Pow

0.6

0.4
Maxim

0.2

0.0
11/4/0511/30 12/231/30/06 2/15 4/10 4/27 5/3 5/8 6/15 6/19 6/29 7/14 7/20 9/28

Date
FUEL UTILIZATION TEST : BACKGROUND
ƒ Fuel Utilization
&
Molar flow rate of reactants consumed in a cell Nconsumed
Ut = =
Molar flow rate of reactants supplied into the cell &
Nin

ƒ Fuel utilization increases along the flow path over the electrode surface.
⇐ Fuels are consumed and products are formed along the flow path.

ƒ Cell Performance Loss near Exit (High Fuel Utilization)

• Loss of Nernst Potential
• Anodic Activation Polarization
• Anodic Concentration Polarization

ƒ Simulate the effect of practical fuel utilization on single cell performance

by increasing H2O content in fuel
FUEL UTILIZATION TEST : EFFECT OF ANODE ACTIVE LAYER

With Anode Active Layer Without Anode Active Layer

o o
1.4 Temperature: 800 C 1.4 Temperature: 800 C

1.2 1.2
ensity (W/cm )

ensity (W/cm )
2

2
1.0 1.0

0.8 H2-3% H2O / Air 0.8 H2-3% H2O / Air

H2-30% H2O / Air H2-30% H2O / Air
0.6 0.6
Power De

Power De
H2-40% H2O / Air H2-40% H2O / Air
0.4 H2-50% H2O / Air 0.4 H2-50% H2O / Air

0.2 H2-60% H2O / Air 0.2 H2-60% H2O / Air

H2-70% H2O / Air H2-70% H2O / Air
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
2 2
Current Density (A/cm ) Current Density (A/cm )

Max. Power Density

Fuel (W/cm2)
Porosity = 26% Compositions
p
Anode Active Layer With Without
Avg. Grain Size = 1.3 μm AAL AAL
Avg. Pore Size = 0.7 μm
H2 – 3% H2O 1.41 1.40

Porosity = 37% H2 – 30% H2O 1.27 1.25

Anode Support
Avg. Grain Size = 4.3 μm
H2 – 50% H2O 1.17 0.91
Avg. Pore Size = 2.6 μm
H2 – 70% H2O 0.84 0.45
 FUEL UTILIZATION TEST : POLARIZATION MODELING

Ri, DeffO2-N2 : Independent of Fuel Composition

DeffH2-H2O : Independent of H2/H2O ratio (Kinetic Theory of Gases)*

With Anode Active Layer Without Anode Active Layer Exchange Current
Fuel Density (A/cm2)
97% H2-3% H2O 97% H2-3% H2O Compositions With Without
1.2 1.2 70% H2-30% H2O
70% H2-30% H2O AAL AAL
60% H2-40% H2O 60% H2-40% H2O
1.0 1.0 50% H2-50% H2O
50% H2-50% H2O H2 – 3% H2O 0.87 0.98
40% H2-60% H2O 40% H2-60% H2O
0.8 0.8 30% H2-70% H2O
30% H2-70% H2O
H2 – 30% H2O 0.84 0.78
Voltage (V)
Volttage (V)

---- Curve-fitted ---- Curve-fitted

0.6 0.6
H2 – 40% H2O 0.82 0.70
0.4 0.4

H2 – 50% H2O 0.79 0.57

0.2 0.2 o
Temperature: 800 C
o Temperature: 800 C

0.0 0.0 H2 – 60% H2O 0.75 0.43

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
2
Current Density (A/cm )
2
Current Density (A/cm ) H2 – 70% H2O 0.53 0.22

* R. Byron Bird, Warren E. Stewart, Edwin N. Lightfoot, Transport Phenomena, John Wiley & Sons (1960)
FUEL UTILIZATION TEST : PERFORMANCE ANALYSIS
™ Activation Polarization:
ƒ At Low Fuel Utilization (H2-3% H2O)
⇒ Dominated by Cathode
(No Difference in Cell Performance and Exchange Current Density due
to Anode Active Layer at Low Fuel Utilization)

ƒ At High Fuel Utilization

⇒ Anodic Activation Polarization Increases
⇒ Cathodic Activation Polarization: Independent of Fuel Composition
 FUEL UTILIZATION TEST : PERFORMANCE ANALYSIS
™ Anodic Activation Polarization:

Anodic Exchange
Current Density
Fuel (A/cm2)
Compositions
With Anode Active Layer Without Anode Active Layer With Without
AAL AAL
30% H2-70% H2O 30% H2-70% H2O
0.20 40% H2-60% H2O 0.20 40% H2-60% H2O H2 – 30% H2O 26.73 4.18
V)

V)
Anodic Activation Polarization (V

Anodic Activation Polarization (V

50% H2-50% H2O 50% H2-50% H2O

60% H2-40% H2O 60% H2-40% H2O H2 – 40% H2O 15.68 2.70
0.15 0.15
70% H2-30% H2O 70% H2-30% H2O
---- Curve-fitted ---- Curve-fitted
H2 – 50% H2O 9.47 1.53
0.10 0.10

H2 – 60% H2O 6.02 0.88

0.05 0.05

H2 – 70% H2O 1.55 0.34

0.00 0.00
00
0.0 02
0.2 04
0.4 06
0.6 08
0.8 10
1.0 00
0.0 02
0.2 04
0.4 06
0.6 08
0.8 10
1.0 Cathodic
2
Current Density (A/cm )
2
Current Density (A/cm ) Exchange
Current 0.87 0.98
Density
(A/cm2)
FUEL UTILIZATION TEST : PERFORMANCE ANALYSIS
™ Anodic Concentration Polarization:

Determined by Local H2-H2O Equilibrium:

Equilibrium:

Calculation of pi,aO2

In Steady State,
 FUEL UTILIZATION TEST : PERFORMANCE ANALYSIS
™ Anodic Concentration Polarization:

on Polarizattion (V)
0.4
Temperature = 800o C 
2
i = 4.0 A/cm Deff H2-H2O = 0.27cm2//s 
la = 850μm
0.3
i = 3.0 A/cm2

= 2 0 A/cm2
i = 2.0

Concentratio
0.2
i = 1.0 A/cm2 

0.1

Anodic C
i = 0.1 A/cm2 
0.0
0.0 0.2 0.4 0.6 0.8 1.0
p (
(atm)
)
H2O
ƒ Anodic concentration polarization is low when the fuel is in the intermediate H2O
partial pressure region.

ƒ Anode active layer had no significant effect on anodic concentration polarization.

 FUEL UTILIZATION TEST : POLARIZATION ANALYSIS
™ Anodic Electrode Polarization Loss:
With Anode Active Layer Without Anode Active Layer
0.40 Activation+Concentration 0.40 Activation+Concentration
c Electrode Polarization (V)

c Electrode Polarization (V)

Activation Activation
0.35 o 0.35 o
Temperature: 800 C Temperature: 800 C
0.30 Current Density: 1.5A/cm2 0.30 Current Density: 1.5A/cm2

0 25
0.25 0 25
0.25

0.20 0.20 Anodic Activation

Polarization
0.15 0.15
Anodic Activation
0.10 Polarization 0.10
Anodic

Anodic
0.05 Anodic Concentration 0.05 Anodic Concentration
Polarization Polarization
0.00 0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
o o
p H2O
in Fuel (atm) p H2O
in Fuel (atm)

ƒ Activation Polarization: Dominant Loss at High Fuel Utilization

⇒ Significantly Reduced by Anode Active Layer
 ADVANCED CATHODE INVESTIGATION : BACKGROUND
ƒ Cathode Polarization Loss : Major Difficulty in Lowering the Operating Temperature

ƒ A site-
site-doped Lanthanum Cobaltite
• High Catalytic Activity and Mixed Electronic
Electronic--Ionic Conductivity
• High Thermal Expansion Coefficient
• Solid State Reaction with YSZ at Low Temperature

ƒ A site-
site-doped Lanthanum Ferrite
• High Catalytic Activity and Mixed Electronic
Electronic--Ionic Conductivity
• Adj t bl Thermal
Adjustable Th l Expansion
E i
• No Solid State Reaction with YSZ up to 1400oC
• Diffusion of Zr4+ into Lanthanum Ferrite : Doped Ceria Interlayer

ƒ Calcium
Calcium--doped Lanthanum Ferrite
• Defect Model pO2 - Weight Relationship
• Thermogravimetry
g y Measurements ⇒ Equilibrium Defect Concentration
• Electrical Conductivity Measurements ⇒ Hole Mobility
ADVANCED CATHODE INVESTIGATION : POINT DEFECT MODEL
™ Point Defect Model for (La0.8Ca0.2)0.95FeO3-δ

A-site B-site O-site

LaxLa   FexFe
Fe•Fe OxO
CaLa  = 0.2×
0.2×0.95
FeFe VO••
≈0
VLa   = 0.05 VFe
≈0

ƒ Oxygen Incorporation Reaction

ƒ Charge
Ch Di
Disproportionation
ti ti Reaction
R ti

ƒ Schottky Equilibrium Reaction

ADVANCED CATHODE INVESTIGATION : POINT DEFECT MODEL
ƒ Charge Neutrality Condition
2 VO•• Fe•Fe CaLa 3 VLa Fe•Fe CaLa 3 VLa 2 VO••
= 0.2 0.95 = 0.05
ƒ A-site Restriction
LaxLa CaLa VLa 1
ƒ B-site
it Restriction
R t i ti

FexFe Fe•Fe 1 FexFe 1 Fe•Fe 1 CaLa 3 VLa 2 VO••

= 0.2×
0.2×0.95 = 0.05
ƒ O-site Restriction
OxO VO•• 3  OxO 3 VO••

ƒ Mass Action Coefficient for Oxygen Exchange Reaction

ADVANCED CATHODE INVESTIGATION : POINT DEFECT MODEL
ƒ Relationship between pO2 and Weight of (La0.8Ca0.2)0.95FeO3-δ
 ADVANCED CATHODE INVESTIGATION : THERMOGRAVIMETRY
™ Thermogravimetry Measurements
o o o o o o o o
900 C 850 C 800 C 750 C 700 C 650 C 600 C 550 C
106.3 o
850 C
1.0 o
800 C
o
750 C
o
106.2 0.8 700 C
o
650 C
ht (μg)

o
600 C
0.6 o

pO2 (atm)
550 C
Weigh

----- Curve-Fitted
C Fitt d
106.1
0.4
pO2=1
pO2=0.21 0.2
106.0 pO2=0.05
pO2=0.001 0.0

0 200 400 600 800 1000 1200 0.1060 0.1061 0.1062 0.1063
Time (min) Weight (g)

n = 0.00049 mol

Temperature 850oC 800oC 750oC 700oC 650oC 600oC 550oC

Kox 186 235 317 376 504 630 813

 ADVANCED CATHODE INVESTIGATION : DEFECT EQUILIBRIUM
ƒ Equilibrium Defect Concentration ƒ ln
ln((Kox) vs. 1/T
0.35 7.0
---- Linear Fit
o
0.30 550oC
650 C
o
750 C
.
[FeFe]
65
6.5
ncentration

0.25 o
850 C
6.0
o
0.20 Slope = -ΔH ox/R

Kox)
5.5
Defect Con

ln(K
0.15

0.10 5.0

0.05
o
850oC
750oC
..
[VO ] 4.5
650oC
550 C
0.00
4.0
-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.9 1.0 1.1 1.2
log(pO2(atm)) -1
1000/T (K )

¾ High pO2 range

• [Vo••]: low
• Charge neutrality is maintained by hole formation.
¾ Low
L pO2 range 37 5 kJ moll-1
∆Hoox = -37.5
• [Vo••]: high ∆Soox = 10.6 J mol-1 K-1
• Hole concentration decreases.
 ADVANCED CATHODE INVESTIGATION : ELECTRICAL CONDUCTIVITY
™ Electrical Conductivity Measurements
ƒ Conductivity vs. Temperature ƒ Mobility vs. Temperature
140
0.6
120
0.5

y (cm V s )
-1 -1
100
vity (S/cm)

0.4

2
80
0.3

Hole Mobility
Conductiv

60
pO2=1 atm pO2=1 atm
0.2 pO2=0.21 atm
40 pO2=0.21 atm
pO2=0.05 atm pO2=0.05 atm
20 0.1
pO2=0.001 atm pO2=0.001 atm

0 00
0.0
550 600 650 700 750 800 850 550 600 650 700 750 800 850
o o
Temperature ( C) Temperature ( C)

ƒ pO2↑ ⇒ σe ↑ : p-type conductor ƒ pO2↓, T ↑ ⇒ [VO··] ↑

ƒ Low Temperature:
p Thermally
y Activated Behavior ƒ Hopping Conduction Via Fe4+-O-Fe3+ Chain
(Small Polaron Hopping) ƒ VO·· : Scattering Centers or Random Traps
ƒ High Temperature: Decrease in Hole Concentration for Electrons
ADVANCED CATHODE INVESTIGATION : CONDUCTION MECHANISM
ƒ Adiabatic Small Polaron Hopping ƒ Non
Non--adiabatic Small Polaron Hopping

10.0
6.4
9.8
6.2
9.6
.

ln(μpT /(1-[FeFe]))
.
ln(μpT/(1-[FeFe]))

6.0
9.4
5.8 9.2
pO2=1 atm pO2=1 atm

3/2
5.6 pO2=0.21 atm 9.0 pO2=0.21 atm
pO2=0.05
=0 05 atm pO2=0.05 atm
5.4 8.8
pO2=0.001 atm pO2=0.001 atm
---- Linear Fit 8.6 ---- Linear Fit
5.2
0.9 1.0 1.1 1.2 0.9 1.0 1.1 1.2
-1
-1
1000/T (K ) 1000/T (K )

Adiabatic Case Non

Non--adiabatic Case
pO2 (atm
atm))
Activation Energy ((eV
eV)) R2 Activation Energy ((eV
eV)) R2
1 0.108 0.99353 0.149 0.99788
0.21 0.111 0.99344 0.152 0.99776
0.05 0.195 0.99423 0.235 0.99673
0.001 0.272 0.98927 0.310 0.99801
 SUMMARY
ƒ Successfully developed single-
single-step un
un--constrained co
co--firing of the solid oxide
fuel cell @ 1300oC.
ƒ Modeled cell performance.
ƒ Achieved maximum power density of 1.50 W/cm2 at 800oC and 0.87 W/cm2 at
700oC with humidified hydrogen (3% H2O) and air.
ƒ Simulated the effect of practical fuel utilization on single cell performance.
ƒ Improved cell performance at high fuel utilization by employing anode active
layer.
ƒ Investigated defect chemistry and electrical conduction mechanism of novel
cathode material (calcium-
(calcium-doped lanthanum ferrite).

FUTURE WORK
ƒ Employ advanced cathode material in co-
co-firing process.
ƒ Analyze performance at low operating temperature (600-
(600-700oC).
 PUBLICATION LIST
ƒ Journal Papers
1. Kyung Joong Yoon, Wenhua Huang, Guosheng Ye, Srikanth Gopalan, Uday B. Pal, Donald A. Seccombe, Jr., “Electrochemical Performance
of Solid Oxide Fuel Cells (SOFCs) Manufactured by Single Step Co-firing Process,” Journal of the Electrochemical Society, 154 (4) B389 (2007).
2. Kyung Joong Yoon, Srikanth Gopalan, Uday B. Pal, “Effect of Fuel Composition on Performance of Single Step Co-fired Solid Oxide Fuel
Cells (SOFCs),” Journal of the Electrochemical Society, 154 (10) B1080 (2007).
3. Kyung Joong Yoon, Peter Zink, Srikanth Gopalan, Uday B. Pal, “Polarization Measurements on Single Step Co-fired Solid Oxide Fuel Cells
(SOFCs),” Journal of Power Sources, 172 (1) 39 (2007).
4. Kyung Joong Yoon, Srikanth Gopalan, Uday B. Pal, “Effect of Anode Active Layer on Performance of Single Step Co-fired Solid Oxide Fuel
Cells (SOFCs) at High Fuel Utilizations,” Journal of the Electrochemical Society, 155(6) B610 (2008).
5. Kyung Joong Yoon, Srikanth Gopalan, Uday B. Pal, “Analysis of Electrochemical Performance of Solid Oxide Fuel Cells (SOFCs) Using
Polarization Modeling and Impedance Measurements,” Journal of the Electrochemical Society, 156 (3) B311 (2008).
6. Kyung Joong Yoon, Guosheng Ye, Srikanth Gopalan, Uday B. Pal, “Cost-effective Single Step Co-firing Technique for Manufacturing Solid
Oxide Fuel Cells (SOFCs) using High Shear Compaction (HSC) Anode,” Journal of Fuel Cell Science and Technology, Accepted (2008).
7. Soobhankar Pati, Kyung Joong Yoon, Uday B. Pal, “Solid Oxide Electrolyte Electrolyzer with Liquid Metal Anode for Production of Hydrogen
y
and Syn-Gas from Waste and Steam,” , submitted ((2009).
)
8. Kyung Joong Yoon, Peter Zink, Larry Pederson, Srikanth Gopalan, Uday B. Pal, “Defect Chemistry and Electrical Properties of
(La0.8Ca0.2)0.95FeO3-δ,” in preparation (2009).

ƒ Conference Proceedings
1. Kyung Joong Yoon, Peter Zink, Srikanth Gopalan, Uday B. Pal, “Polarization Analysis in Single Step Co-fired Solid Oxide Fuel Cells
(SOFCs),” Materials Research Society Symposium Proceedings of the Fall 2006 Meeting, Vol. 972, AA 10-02
(SOFCs), 10 02 (2007).
2. Peter A. Zink, Kyung Joong Yoon, Wenhua Huang, Srikanth Gopalan, Uday B. Pal, Donald A. Seccombe, Jr., “Refractory Cathode
Investigation for Single Step Co-fired Solid Oxide Fuel Cells (SOFCs),” Materials Research Society Symposium Proceedings of the Fall 2006
Meeting, Vol. 972, AA 03-12 (2007).
3. Kyung Joong Yoon, Peter Zink, Uday B. Pal, Srikanth Gopalan, “High Performance Low Cost Co-fired Solid Oxide Fuel Cells (SOFCs),” ECS
Transactions, Vol. 7 (1) 579 (2007).
4 Kyung Joong Yoon,
4. Yoon Srikanth Gopalan,
Gopalan Uday B.B Pal,
Pal “Anode (SOFCs),” ECS
Anode Polarization Effects in Single Step Co-fired Solid Oxide Fuel Cells (SOFCs)
Transactions, Vol. 7 (1) 565 (2007).
5. Peter Zink, Kyung Joong Yoon, Wenhua Huang, Uday B. Pal, Srikanth Gopalan, “Refractory Cathode Investigation for Single Step Co-fired
Solid Oxide Fuel Cells (SOFCs),” ECS Transactions, Vol. 7 (1) 399 (2007).
6. Kyung Joong Yoon, Srikanth Gopalan, Uday B. Pal, “Effect of Anode Active Layer on Performance of Single Step Co-fired Solid Oxide Fuel
Cells (SOFCs),” ECS Transactions, Vol. 13 (26) 249 (2008).
7 Kyung Joong Yoon,
7. Yoon Srikanth Gopalan,
Gopalan Uday B.B Pal,
Pal “Electrochemical Performance of Single Step Co-Fired
Co Fired Solid Oxide Fuel Cells (SOFCs)
Analyzed Using Polarization Modeling and Impedance Spectroscopy,” Materials Research Society Symposium Proceedings of the Fall 2008
Meeting, Vol. 1126, S10-02 (2008).
8. Peter A. Zink, Kyung Joong Yoon, Uday B. Pal, Srikanth Gopalan, “Electrical Performance of Calcium-doped Lanthanum Ferrite for Use in
Single Step Co-Fired Solid Oxide Fuel Cells (SOFCs),” Materials Research Society Symposium Proceedings of the Fall 2008 Meeting, Vol. 1126,
S11-02 (2008).
Thank you!