Fabrication of SOFC Electrodes by Impregnation Methods

R. J. Gorte Chemical & Biomolecular Engineering University of Pennsylvania Collaborators: J. M. Vohs, M. D. Gross, S.W. Jung, and W. Wang Support: ONR, DOE-BES (H2 program)

Solid Oxide Fuel Cell

Fuel H 2O eAnode
O 2- Electrolyte O 2-

H2 + O2- H2O + 2e-

Porous Ni/YSZ cermet YSZ (Y-stabilized ZrO2) Porous YSZ/Sr-LaMnO3

eO2 + 4e- 2O2-

Cathode

Air

Operating temperature: 600 to 800C

YSZ is a conductor for O2- but an insulator for electrons.

1.2

350

Electrolyte Electrodes

300 250 200 150

Open Circuit: V = Nernst Potential = G/nF Power output: P = V*i Electrolyte Losses: V = i*Relectrolyte Electrode Losses: V = overpotential = i*Relectrode Relectrode is composed of diffusion, surface kinetics, etc.

Voltage (V)

0.8 0.6 0.4 0.2 0 0

0.8 0.6

100 50 0 0.2 0.4 0.6

Current Density (A/cm )

0.8

Z", (ohm*cm2)

(Relectrolyte+Relectrode) Relectrolyte
4 Hz 1 kHz

0.4 0.2 0 -0.2 0 0.2

0.4

0.6

0.8

1.2

1.4

1.6

Z', (ohm*cm2)

Power Density (mW/cm )

Performance Analysis:

Research Goals at Penn:

1) Anodes for direct utilization of hydrocarbons
Reforming leads to system complexity and to energy losses at high temperatures: Consider: C4H10 + 2O2 = 4CO + 5H2 C4H10 + 6 O2 = 4CO2 + 5H2O 4CO + 5H2 + 4 O2 = 4CO2 + 5H2O At 700C H (kJ/mol) G -2,660 -2,810 -2,370 -1,760 -11% -37% #electrons 26 18 -31%

2) High-performance cathodes
LSM-based cathodes used today limit SOFC performance.

Ni-based anodes cannot be exposed to hydrocarbons: Ni catalyzes carbon formation

Ni in methane for 3 hrs, 800C

Ni in toluene for 3 hrs, 700C

This can be avoided with other metals

Cu in methane for 3 hrs, 800C

Cu in toluene for 3 hrs, 700C

Carbon formation is in, not just on, Ni:

20% CO/7% H2 550C.

Ni Particles

(M. L. Toebes, et al., Catalysis Today, 2002)

Note: Fe, Co, and Ru will all form catalyze carbon formation

Traditional electrode fabrication limits materials that can be used because of high-temperature processing
Pressed NiO/YSZ powder

1400C

NiO/YSZ composite

Porous Ni/YSZ cermet Reduce in H2 800C

YSZ Powder YSZ Powder

in air

Dense YSZ

Dense YSZ

Cathodes: (Sr-doped LaMnO3/YSZ)

Screen print LSM-YSZ and fire to 1200C
Dense YSZ Dense YSZ

High temperatures restrict choices of materials:

1) Cannot use materials that will melt at sintering temp. (Ex: CuO melts at 1235C) 2) High-temperatures can cause solid-state reactions (Ex: LaCoO3 reacts rapidly with YSZ above 1000C.) 3) Must be able to form the correct phase (Ex: Alloys and layered structures are not possible.)

Electrode Fabrication by Impregnation:

YSZ+pore formers YSZ YSZ+pore formers Anode Electrolyte Cathode Impregnation & Calcination at 450 ~ 700C Lamination 70C, 8 MPa Firing 1400 1550C Porous YSZ

Both Anodes & Cathodes formed by impregnation.

Structure near electrolyte interface:

Electrode I

electrolyte

Electrode II

Add active phase separately:

Ex: La0.8Sr0.2FeO3-YSZ
Porous YSZ 40 wt% LSF-YSZ by impregnation

Advantages:
1. Separate firing temperatures for YSZ and active phase. - Avoids solid-state reactions between LSF & YSZ. - Can use low-melting solids (CuO). 2. Composite is non-random structure.
a) Electrical conductivity of LSM-YSZ
700C in air, composites calcined at 1523 K.
Impregnated LSM Mixed powders

Percolation threshold for random media

b) CTE of LSCo-YSZ
LSCo Weight Fraction in YSZ CTE (10-6/K), 300 to 1073 K CTE of LSCo is 23x10-6/K 0% 10.3 35% 11.7 45% 12.6 55% 12.6

Our past focus: Cu-ceria anodes

a) Cu for electronic conductivity b) Ceria for catalysis C2 H6 Cu Cu CO2 H2 O

eCeO2 O2YSZ

Cu-ceria composites perform in real fuels!

15%CeO2 25%Cu, 24um electrolyte, laminated cell, LSF, Heavy Naph 700 oC

Operation on Heavy Naphtha, 700C; fuel was undiluted.

1.2 1 Voltage, V 0.8 0.6 0.4 0.2 0 0 5 10 15 20 25 30 35 40 45
Voltage Power density

1.2 1 0.8 0.6 0.4 0.2 0 Power density, W/cm2

Time, hour

Power densities can be good with optimized cells:

Fuel: pure n-decane
1200

500
700 C, 1.2 ml/h decane 725 C, 1.2 ml/h decane 750 C, 1.2 ml/h decane 775C, 1.4 ml/h decane 800C, 1.7 ml/h decane

1000

Power Density (mW/cm )

400

800 C

Potential (mV)

800

775 C 300 750 C 725 C 200 700 C 700 C, 30% conversion at peak power 725 C, 40% conversion at peak power 750 C, 44% conversion at peak power 775C, 47% conversion at peak power 800C, 50% conversion at peak power 0 200 400 600 800 1000 2 1200 1400

600

400 700 C 200 725 C 750 C

800 C 775 C

100

0 0 200 400 600 800 1000 1200 1400

Current(mA/cm2)

Current Density (mA/cm )

Data from SRI International Cell area 6.4 cm2

Cu-ceria-YSZ electrodes stable in sulfur: Measure performance in H2-H2O-H2S mixtures

0.4
800 C, Keep at ~0.6V
0

-9

800 C
-10

Power density (W/cm )

log PS (PS in atm)

0.3

Ce2O2S
-11

0.2

0.1

H2 with 10vol% H2O and 50ppm H2S 100ppm H2S 200ppm H2S 300ppm 450ppm 600ppm 900ppm

900 ppm 600 ppm 450 ppm 300 ppm 200 ppm 100 ppm

-12

CeO1.83
-13

50 ppm

0.0

50

100

150

200

250

300

350

Time (h)

-14 -22.0

-21.5

-21.0
2 2

-20.5

-20.0

log PO (PO in atm)

Sulfur poisoning occurs when Ce2O2S is formed. Note: Ni-anodes are poisoned at surface monolayer, ~ 5 ppm.

Cu-based anodes have limitations:

Low catalytic activity (ceria is the catalyst) Limited to use at lower temperatures. 700C
B
B Cu

900C

Cu

Effect of thermal treatment on cell performance:

2

Cu-ceria-YSZ YSZ LSM-YSZ

1.5

3% H2O-97% H2 at 700C

Sintering of Cu: 1) Loss of anode conduction 2) Increased ohmic resistance

-Z im cm 2

After heating to 800C

After heating to 900C

0.5

-0.5 0 0.5 1 1.5 2

Z re cm

2.5

3.5

Solution 1: Electroplate Co onto Cu cermets

DC

e
V

Idea: Coat thermally stable Co with chemically stable Cu:

Cu
Co

e
Cu2+ Cu Anode
Co Cermet Ni

Cu and Co do not form alloys

CuSO4 + H2S04 Solution

Key is to deposit evenly throughout the pores; Co plating is much easier than Cu.

But Cu segregates to Co surface

XPS of 250-nm Co film on Cu with heating

Co plated Cu stable in CH4 at 800C for 3 h Cu-Co Co only

Enhanced thermal stability achieved:

Ohmic Resistances of Cells at 900C
() Cu-ceria-YSZ (18-vol% Cu) ( ) Co-ceria-YSZ (18-vol% Co)

(o) Co-Cu-ceria-YSZ (5-vol% Co electroplated; 13-vol% Cu)

Cu-Co composites stable for long times

1. 2 1 0. 6 0. 5 0. 4 0. 3 0. 2 0. 1 0 0 50 100 150 200 250 300 350 400 450 500

0. 8 0. 6 0. 4 0. 2 0

Time , ho ur

Po we r de ns ity, W/c m

vo ltag e po we r de nis ity

Dry CH4, 800C 50:50 Co-Cu

Vo ltag e , V

Solution 2: Ceramic anodes (the Holy Grail?)

Problem: Oxides have either poor conductivity at low P(O2) or poor catalytic activity Separate the two required functions
Anode current collector
Porous ceramic, optimized for conductivity.

Concept:

YSZ electrolyte

Anode functional layer

Optimized for catalytic performance. Thin to avoid need for high conductivity.

Key point: If = 10 m and Rohmic must be < 0.1 .cm2, need only be 0.01 S/cm!

Concept works:
1. Functional layer can provide high performance when Ag used for current collection.
Current collector, Ag paint Anode, Ceria-YSZ (10 m)(Pd doped) YSZ electrolyte (75 m) LSF-YSZ cathode (300 m)
10 m
1.2

H2 (3% H2O)
650C 700C 750C 800C

1.0 0.9 0.8

1.0

Power Density, W/cm2

0.8

0.7 0.6

800C 750C 700C

650C

Voltage, V

0.6

0.5 0.4

0.4

0.3 0.2 0.1

0.2

0.0 0.0 0.5 1.0 1.5 2.0 2.5

0.0

Current Density, A/cm2

2.

Ag can be replaced by La0.3Sr0.7TiO3:

1.2 1

H2 (3% H2O)
800C

0.7 0.6 0.5 0.4 Power Density / W cm -2

Power Density / W cm -2

0.8 Voltage / V

750C

0.6 0.3 0.4 0.2 0.2 0.1 0 0 0.4 0.8 Current Density / A cm -2 1.2 1.6

650C
0

20 m
Porous YSZ-active region YSZ electrolyte

CH4 (3% H2O)

1.4 0.6

La0.3Sr0.7TiO3 current collector

Voltage / V

1.2 1 0.8 0.6

800C 750C

0.5

0.4

0.3

0.2 0.4 0.2 0 0 0.4 0.8 Current Density / A cm -2 1.2 1.6

700C

0.1

Cathode Research: Background

Standard Material: LSM (La0.8Sr0.2MnO3)-YSZ composite LSM is used because
- it has good electronic conductivity. - low reactivity with YSZ, even at 1200C. - good long-term stability. - good CTE match with YSZ.

But,
- it has poor ionic conductivity, so that performance poor below 800C. - activated by cathodic polarization (implications for electrolysis.).

LSCo ((La0.8Sr0.2CoO3): But,

- good electronic and ionic conductivity - can provide outstanding electrode performance at below 700C. - electrode performance is not stable. - it reacts with YSZ, even at 700C (forms La2Zr2O7). - poor CTE match with YSZ.

LSM by impregnation:
Observations

ESSL, 9 (2006) A237-240

We need a minimum of 30 to 40 wt% of LSM. Performance independent of LSM precursor

1.2 1 350

20 wt% in butandiol

Voltage (V)

a) Nano-particles () b) Aqueous solutions ()

1.6 molar, nitrate solution

0.8 0.6 0.4 0.2 0 0 0.2

250 200 150

c)

Molten salts ()

700C Co-ceria|YSZ|LSM-YSZ
Current Density (A/cm2)
0.4 0.6 0.8 1

100 50 0

Fewest steps required by Molten Salt Impregnated LSM indistinguishable from screen-printed LSM/YSZ

Power Density (mW/cm2)

300

Understanding LSM-YSZ cathodes: Polarization activation

ESSL, 7 (2004) A111-A114.

700C, H2/3%H2O, OCV after applying current

2
LSM-YSZ

1.5

0.8 Hz 1.6 Hz
CeO2 Pd- C - YSZ

-Z Im, .cm2

1 0.5 0

3 Hz

-0.5 -1

2 kHz

4 Hz

- 0 mA/cm2 - 60 mA/cm2

- 150 mA/cm2 - 850 mA/cm2

0.5

1.5

2.5

3.5

Z Re, .cm2

Note: These changes are reversible. ~ 120 minutes.

What we believe is happening:

Electrode before activation
LSM

Activated Electrode
YSZ

YSZ

1) Dense LSM covers YSZ 2) Performance limited by oxygen diffusion.

Gaps in LSM film caused by reduction Gas can get to YSZ interface.

Process driven by surface interactions between LSM & YSZ

LSM Particles on YSZ (100): Effect of calcination temperature

ESSL, 9 (2006) A237-240 A237-

850C

1050C

1150C

Movement of particles is reversible:

Calcination at 1150C Reduced in H2 (10%H2O) at 700C 2 m x 2 m

1) LSM is stable in 10%H2O-90% H2 at 700C. 2) Reducing LSM-YSZ electrode activate it.

Consequences for electrolysis (anode environment is oxidizing):

JECS, in press.

285 mA/cm2; 700C; 85%H2-15%H2O| air LSM-YSZ anode

1.45 3.5 3 1.4 Cell potential (V) 2.5 Electrode impedance ( -cm2)

LSF-YSZ anode
1.4 1.2 Cell potential (V) 1.0 0.8 0.6 0.4 0.2 0.0 0 50 100 150 200 250 300

1.35

1.5 1.3 1

1.25 -20 10 40 70 100 130 160 Time (min)

0.5 190

Time (min)

LSF-YSZ (this cannot be made by screen printing) Observations:

1) See no additional phases with calcination temperature (Very different from LaCoO3) 2) Formation of Zr-doped LaFeO3 only above 1200C 3) Zr doping is not a deactivation process.

-0.15

Z'' (ohm.cm2)

-0.1

700C, symmetric cell

10%Zr-LSF+YSZ

-0.05
LSF+YSZ

0 0 0.05 0.1 0.15 2 Z' (ohm.cm ) 0.2 0.25

Time & calcination temperature have similar effect: Symmetric Cells R = expected value for

Calcine @ 850C t = 0 h @700 C

YSZ electrolyte independent of i

RP = 0.12 cm2 @ 700C R = expected value for YSZ electrolyte

Calcine @ 850C t = 2500 h @700C

RP = 0.6 to 0.1 cm2, depends strongly on i No hysteresis! Not like LSM. R = expected value for YSZ electrolyte RP = 2.5 to 0.1 cm2, depends strongly on i No hysteresis.

Calcine @ 1100C t=0h

Effect of Calcination Temperature, Performance @ 700C

Anode: metal-doped ceria-YSZAg, 50 m YSZ electrolyte metalceria-

Calcine
-Z Im, ohm*cm2

0.3
450 mA/cm2 OCV - 450 mA/cm2

@ 850C t=0h

0.2

0.1

0 0.3 0.4 0.5 0.6 0.7 0.8 Z Re, ohm*cm2

-Z Im, ohm*cm2

Calcine @ 1100C

0.8 0.6 0.4 0.2 0 0.3

450 mA/cm2 100 mA/cm2 OCV - 100 mA/cm2 - 450 mA/cm2

0.5

0.7

0.9 1.1 Z Re, ohm*cm2

1.3

1.5

Proposed deactivation mechanism:

850C calcination
LSF

1100C
YSZ

YSZ

1 m

1 m

Implications:

1. Deactivation is structural, not associated with interfacial reactions 2. Interlayers will probably not be effective 3. With LSM, activation of very good electrodes less important use same concepts for stabilizing LSF?

Summary
Electrode fabrication by impregnation allows great flexibility in preparing anodes. Direct utilization of hydrocarbon fuels is possible in Cu-ceria based anodes. The thermal stability of Cu-based anodes can be improved by: 1. Co electrodeposition 2. Using ceramic anodes. High-performance LSF-YSZ cathodes may be possible. http://www.franklinfuelcells.com/ http://www.seas.upenn.edu/cbe/Fuel_Cell_index.htm

Calcination temperature affects activation:

JECS, 152 (2005) A1347-53.

40-wt% impregnated LSM-YSZ, fired to 850C or 1250C LSM/YSZ Measurement at 700C in air at OCV.
( ) Initial spectrum. () After applying 250 mA/cm2 for 10 minutes. ( ) 5 h after applying current.
0.3
5

LSM/YSZ

LSM(850C)
0.2 500 Hz

LSM(1250C)

4 3 0.2 Hz

-Zim .cm2

-Zim .cm2

0.1

2 0.2 Hz 1 0

-0.1 0 0.1 0.2 0.3

2

-1

0.4

0.5

Zre .cm

Zre .cm2

R = 0.5 cm2 Not activated

R = 6.5 cm2 Activated by polarization

BET Surface Areas (40 wt% LSM in YSZ)

Surface Area (m2/g)

Porous YSZ without LSM LSM(850C)-YSZ LSM(1250C)-YSZ LSM(1250oC)-YSZ w/ 700C reduction 0.770.02 2.53 0.380.02 0.780.03

4 [ (1-) ]

= porosity = surface area = YSZ density

= 0.77 m2/g = 1.6 microns = 0.38 m2/g = 0.58 microns dense LSM film on YSZ pores

Gas-phase pyrolysis.
Tony Dean, CO School of Mines

Control requires consideration of flow geometries and coating of surfaces.

Tar formation on a YSZ Slab:

8 7

Wt change of YSZ slab after 4 h in butane:

Weight Gain Percentage (%)

6 5 4 3 2 1

0.3 ml/s 1.0 m/s

1) 2) 3) 4)

Rate depends on flow rate Steam does not affect rate For CH4, negligible tar <900C Butane ~ decane ~ diesel

S:C=1.5

5) .form polyaromatics
TIC 20.0e6

0 925 950 975 1000 1025 1050

3
17.5e6

Temperature (K)

15.0e6

12.5e6

1
10.0e6

6
7500e3

5 2 4 7 8

9 11 10 12

5000e3

2500e3

13

10

15

20

25

30

35

40

45

50

55

10

15

20

25

30

35

40

45

50

55

Time (min)

Perform decreases as anode pores fill with tar:

Performance on un-diluted light naphtha, Saudi-Aramco:
400

Power density (mW/cm )

300

800C
200

750C 700C

100

10

15

20

25

Time (hr)

Most hydrocarbons behave similarly:

Heavy naphtha
500

n-Decane with 20% toluene

350 300 250 200 150 100 50 0

Power density (mW/cm )

400 300 200

800C 700C

Power density (mW/cm )

800C

700C

100 0

10

15

20

25

10

15

20

25

Time (hr)

Time (hr)

Butane and low-sulfur diesel are also similar

Possible Solutions:
1) Prevent gas-phase reactions (radical termination) 2) Remove tar faster than it forms
TPO using 10% H2O in He; tar on YSZ
CeO2/YSZ

H2 CO2
Intensity (a.u.)

CO
YSZ

CO

H2

CO2
800 900 1000 1100 1200 1300

Temperature (K)

Support Layers can be added for strength:

Dense YSZ

Laminated cell

Porous YSZ Dense YSZ Porous YSZ

Final Product

FFC, Inc.