New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

Allan J. Jacobson
Texas Center for Superconductivity, University of Houston

Charles A. Mims
University of Toronto

Peter Rieke
Pacific Northwest National Laboratories

Project Manager: Dr. Lane Wilson

DOE National Energy Technology Laboratory
A. J. Jacobson 1

Objectives
The specific objectives are to develop cathode materials that meet the electrode performance targets
1.0 W/cm2 at 0.7 V in combination with YSZ at 700 C and with GDC at 600 C.

The research strategy is to:

investigate both established classes of materials and new candidates as cathodes; determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer; couple these parameters to performance in single cell tests; use model thin film structures to isolate specific features of oxygen reactivity and transport at surfaces and interfaces

A. J. Jacobson

Overview
New Materials Model Systems Bulk Properties Surfaces/ Interfaces Electrode Performance Electrode Polarization Electrode/ Electrolyte Structure Modeling

Optimized electrode /electrolyte combinations

A. J. Jacobson

SOFC Cathode Performance

1 / 2O2 ( g ) + S ( II )
VO ( II ) + Os ( II ) VO ( Y ,II VO ( Y ,II
fads k

krdes k

Os ( II )

fex krex

S ( II ) + 2h ( II ) + OO ( II )
fTBP krTBP k

) + Otbp ( II ,Y ) )
fDBP krDBP k

S( II ) + 2h ( II ) + OO ( Y )

VO ( II ,Y )

DO ( II ),Ds ( II )

Both surface and bulk diffusion considered

from Coffey et al. JECS 150, A1139 (2003)

A. J. Jacobson 4

SOFC Cathodes
A model that does not consider surface diffusion gives the cathode resistance in terms of the diffusion coefficient (DO*) and the surface exchange rate (kO0 )
R cathode RT = 2 2 * 0 2 F ( 1 )Sc O DO kO
1/ 2

where , and S are the electrode tortuosity, porosity and surface area
DO and kO can be measured by: Isotope exchange and depth profiling (IEDP) Electrical conductivity relaxation (ECR)
(Adler et al. J. Electrochem. Soc. (1996) 143 3554)
A. J. Jacobson 5

Materials Classes
perovskite ferrites
oxygen vacancies
La1-xSrxFeO3-x, x= 0.2, 0.3 La0.7Sr0.3Cu0.2Fe0.8O3-x

perovskite related structures

oxygen interstitials
La2NiO4+x Pr2NiO4+x

perovskite oxides with ordered A cations

2 dimensional vacancies
PrBaCo2O5+x LaBaCuFeO5+x,
A. J. Jacobson 6

Experimental Methods
Stoichiometry measurements Conductivity and Conductivity relaxation Photoelectron spectroscopy / Kelvin probe AC impedance on symmetric cells Isotope exchange and depth profiling (IEDP) Half cell measurements Thin film synthesis of model structures

A. J. Jacobson

Materials Classes
perovskite ferrites
oxygen vacancies
La1-xSrxFeO3-x, x= 0.2, 0.3 La0.7Sr0.3Cu0.2Fe0.8O3-x
Stoichiometry Interfacial chemistry Extensive measurements of DO, kex, and

A. J. Jacobson

La0.7Sr0.3Fe0.8Cu0.2O3-x Electrochemistry
0.0

LSF20

-0.2

Cathodic Current, A/cm

-0.4

LSF30
-0.6

In O2

LSCuF7328
-0.8

-1.0 -0.15 -0.10 -0.05 Potential vs Pt/PtO, Volts 0.00

Linear Scan Voltammetry

Charge under peak corresponds to ~ 1 electron reduction of B site metal
A. J. Jacobson

Peter C. Rieke
9

La0.7Sr0.3Fe0.8Cu0.2O3-x Stoichiometry
0.18 0.28 1000 C 0.15 0.24
o

Relative Nonstoichiometry ( )

Relative Nonstoichiometry ( )

900 C 0.20 800 C 0.16

o

0.12

0.09

0.12

0.06 1 cell at 850 C Run 3_HL Run 4_LH 2 0.00 cell at 850 C Run 7_HL Run 8_LH Criteria: 0.08%/min
nd o st o

0.08 Closed: high to low pO2 0.04 Open: low to high pO2 The data above 850 C are offset for clarity
-10 -8 -6 -4 -2 0

0.03

0.00

10-9

10-7

10-5

10-3

10-1

10

10

10

10

10

10

log pO 2 (atm)

log pO 2 (atm)

Measurements made in an electrochemical cell with Pt|YSZ|Pt as sensor and pump

A. J. Jacobson 10

Materials Classes

perovskite related structures

oxygen interstitials
La2NiO4+x Pr2NiO4+x

A. J. Jacobson

11

Conductivity and Stoichiometry

circle : 100 % O 2 triangle : 10 % O 2 diamond : 1 % O 2

4.13

Conductivity (S/cm)

100 90 80 70 60 closed : high to low pO 2 open : low to high pO 2

4.11

5% 2 -O 3% 2 -O 2% 2 -O 1% 2 -O

LNO

4.09

4.07

50

40 0.5

4.05 400
1 1.5 2
-1

500

600

700

800

900

1000

2.5

3.5

1000/T (K )

Temperature (C)
4.2

Conductivity (S/cm)

1% O2 100 90 80 70 60 closed : High to low pO 2 50 open : low to high pO 2 0.1% O2

4.18 4.16

7%- O2 5%- O2 3%- O2

PNO

4.14 4.12 4.1 4.08 400 500 600 700 800 900 1000

40 0.5

1.5

2
-1

2.5

3.5

1000/T (K )

A. J. Jacobson

Temperature (C)

12

Electrical Conductivity Relaxation

1.2

0.04 0.03

The normalized conductivity data g(t) are fit to a model that includes Dchem and kchem as variables The surface exchange coefficient (kex) and the self diffusion coefficient (DO) were obtained using the relationships below :

0.02 0.8 a line : data fit diamond : experimental 0.01

error

g(t)

0.6

0 -0.01

0.4 -0.02 La NiO 0.2

2 o 4+

Thermodynamic factor Self diffusion coefficient Surface exchange coefficient

O =

1 ln pO2 2 ln CO 2

at 800 C pO : 0.01 to 0.02 atm

2

-0.03 -0.04 200

0 0 50 100 150

DO 2 Dchem O

Time (s)

kex = kchem O
A. J. Jacobson 13

Oxygen Diffusion Coefficients for La2NiO4 and Pr2NiO4

10
-3

10

-6

Pr NiO
2

4+

Pr NiO
2

4+x

(cm /s)

chem

10

-4

3-7 % 3-5 % 1-3 %

D cm /s

10

-7

La NiO
2

4+

3-5 % 2-3 % 1-2 % 0.5-1 %

05-1% 1-2% 2-3% 3-5% 1-3% 3-5% 3-7%

La NiO
2

4+x

10

-8

0.85

0.9

0.95

1
-1

1.05

1.1

0.85

0.9

0.95

1 -1

1.05

1.1

1000/T (K )

1000/T(K )

A. J. Jacobson

14

Oxygen Diffusion Coefficients for LNO and PNO

10
-6 Imperial Imperial Bordeaux

10

-6 Imperial-LSNO Houston-LNO Houston-PNO Bordeau-PNO Bordeau-LNO

D (cm sec )

Bordeaux

D (cm sec )

-1

-1

10

-7

Houston

10

-7

10

-8

10

-8

10

-9

10

-9

0.8

0.9

1.1
-1

1.2

1.3

1.4

0.8

0.9

1.1
-1

1.2

1.3

1.4

1000/T (K )

1000/T K

A. J. Jacobson

15

Surface Exchange Rates

10
-4 Bordeaux Imperial Houston Houston Bordeaux

10

700 C R ohms cm
10
2
2

k (cm/sec)

10

-5

D=10 La0.75Sr0.25FeO3-x D=10 cm /s La0.8Sr0.2CoO3-x

-7 2

-10

cm /s

ex

10

10

-6

10

10

-7

0.88

0.96

1.04 1000/T (K )
-1

1.12

1.2

10 -10 10

-1

10

-9

10

-8

10

-7

10

-6

10

-5

k cm/s

A. J. Jacobson

16

TOF- SIMS Profile in Cross-section

Cross section after O-18 infusion of La2NiO4+ 700 C, 5 min, pO2 = 0.2 atm

La2NiO4+

100 micrometers

A fit of the 18O profile to kO and DO gives values in agreement with the ECR data
A. J. Jacobson 17

Symmetric cells LNO|YSZ|LNO and LNO|CGO|LNO

-7
-40 1% 5% air 100%

La NiO /CGO/La NiO

2 4 2

-6

527 C

pO = 0.01 atm
-5
2

-30

-4 Z''

-3

pO = 0.25 atm
2

-2

Z'
-1

-20

-10

pO = 1 atm
2

741 C
0

0 0 5 Z'(Ohms) 10 15

10

20

30

40

Data offset for clarity

Z" (ohms)

Interface effects on both YSZ and CGO

A. J. Jacobson 18

Area Resistances on YSZ

100

Area Specific Resistance (Ohms*cm )

100% 25% 1%

10

600

650

700

750
o

800

850

900

Ralph et al., in Solid Oxide Fuel Cells VII, PV 2001-16, p. 466, 2001.

temperature ( C)
A. J. Jacobson 19

Symmetric cells LNO|CGO|LNO and PNO|CGO|PNO

-70

Pr NiO /CGO/ Pr NiO

-60
2 4 2

1% O 5% O

2 2 2

21% O -50

100% O2

-40 Area specific resistance for 1% pO

2

Z''

-30

-20

-10

10 20 30 40 50 60 70 80 90 100

Z'

Representative impedance spectra of the Pr2NiO4 electrochemical cell: Pr2NiO4 /CGO/ Pr2NiO4 (T= 527 C).
A. J. Jacobson 20

Comparisons on CGO
10 Dashed line = La NiO
2 4+

1/ASR (1/(ohms*cm ))

Line =Pr NiO

2

4+

1 634 C 581 C 526 C

0 0 0

0.1

1/ASR=M (pO )
0 2

n= 0.27~0.31 0.01 0.01

2

0.1

1
Ralph et al., in Solid Oxide Fuel Cells VII, PV 2001-16, p. 466, 2001.

pO (atm)

A. J. Jacobson

21

Model materials to study individual steps

Single phase material
Surface and bulk

Two phase (films on single xtals)

Surface, interface and bulk(s)

Patterned materials (masked films, printed patterns)

Surfaces, interface, bulk(s) and TPB Combinatorial investigations

Synthesis: Pulsed Laser Deposition and Ink Jet Printing

A. J. Jacobson 22

Isotope exchange - SIMS analysis

18O

represented by red color

OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO O O O O

Single phase material

Surface and bulk

O2

O2

OO OO OO OO

OO OO OO OO

OO OO OO OO

OO OO OO OO

O O O O

Two phase (films)

Surface, interface and bulk(2)

O2

OO O O OO O O O O

OO OO OO OO

OO OO OO OO

O O O O

Patterned materials (printed films, patterns)

Surfaces (2), interface, bulk(2) and TPB

+ Functioning cathodes?
A. J. Jacobson 23

PLD Film Deposition

(100) LaAlO3 SrTiO3 and YSZ single crystal substrates PBCO at 300 mTorr oxygen partial pressure with a substrate temperature of 880 C. LNO at 300 mTorr and 840 C KrF excimer laser with pulse frequency of 7 Hz. Films 2000 to 5000

A. J. Jacobson

24

Ink - Jet printing on YSZ(100)

TOF-SIMS image - portion of a circle (dia. 4mm, linewidth 500 micron) YSZ ions
(Y+,YO+, Zr+, ZrO+, etc.)

CGO ions
(Ce+,CeO+, Gd+,GdO+,etc.)

100 micrometers

A. J. Jacobson

25

Materials Classes
perovskite oxides with ordered A cations
2 dimensional vacancies PrBaCo2O5+x (PBCO) LaBaCuFeO5+x, LaBaCuxFe1+xO5+x
10
3 1% O 2 air

Conductivity (S/cm)

PrBaCo2O5+x
10
2

0.5

1.5

2
-1

2.5

3.5

1000/T (K )

A. J. Jacobson

26

Thin film PBCO on YSZ (100)

at 700 C, pO2 = 0.2 atm
(PrO-, CoO2-)
1 0.8

18O

PBCO CGO YSZ

PBCO YSZ (YO-, ZrO2-)

fraction ion signal

0.6

0.4

fraction 18O ( 5)

0.2

0 0 100 200 300 400 500 600

nominal depth / nm Insignificant interfacial transfer barriers Exchange limited by surface kO,PBCO and DO, YSZ
A. J. Jacobson

27

Thin films PBCO + CGO on YSZ (100)

18O

at 700 C, pO2 = 0.2 atm

(PrO-, CoO2-)

PBCO CGO YSZ

PBCO YSZ

(CeO-, GdO-)

(YO-, ZrO2-)

fraction ion signal

fraction 18O ( 5)

nominal depth / nm

Insignificant interfacial transfer barriers Exchange limited by surface kO,PBCO and DO, YSZ
A. J. Jacobson 28

Surface Exchange on PBCO Thin Films

10 cm/sec (IEDP)
-3 700

600

500

400 C
k IEDP k1-10% k2-10% k1-5% k2-5% k1-2% k2-2% k1-1% k2-1%

10

-4

PBCO on YSZ

ave

k , k cm/sec (ECR) and k

10

-5

10

-6

PBCO on STO

10

-7

PBCO on YSZ

10

-8

1.1

1.2

1.3

1.4
-1

1.5

1.6

1.7

1000/T (K )

A. J. Jacobson

29

Structural Characterization of La2NiO4 Thin Films on LAO

as synthesized

1400

1200

after ECR
(220)

LAO(220)

1000

CPS

800 LAO(110) 600 (004) Au(111) (006) 400 Au (200)

200 (200) 0 20 30 40

(008)

HRTEM cross section before ECR

50

A. J. Jacobson
60

30

2 T heta

Surface Exchange Kinetics on La2 NiO4 Films

1.2 1 0.8 0.05 0.1
0.5-0.1% 0.1-0.5% 10-2% 2-10% 10-6
10 k (cm/s)
-5

0.5-0.1% 0.1-0.5% 10-2% 2-10%

Error (2-kinetic-region)

g(t)

0.6 0 0.4 0.2 0 -0.2 0 100 (b) -0.05

k (cm/s)

(b)
1

(a)

200

-0.1

1.05

1.1

1.15

1.05

1.1
-1

1.15

1000/T (K-1)

1000/T (K )

time (s)

A single exponential model does not fit the data requires two time constants
g (t ) = c (t ) c ( 0 ) t t = 1 A1 exp( ) A2 exp( ) 1 2 c ( ) c (0)
A. J. Jacobson 31

La2NiO4 Surface Exchange Model

switch

2%-10% A1 0.17 0.42 0.22 0.23 A2 0.83 0.58 0.78 0.77 A1+A2 1.00 1.00 1.00 1.00 A1 0.17 0.19 0.22 0.21

10%-2% A2 0.83 0.81 0.78 0.79 A1+A2 1.00 1.00 1.00 1.00 A1 0.17 0.32 0.22 0.42

0.1-0.5% A2 0.85 0.70 0.78 0.62 A1+A2 1.02 1.02 1.00 1.04 A1 0.20 0.21 0.28 0.46

0.5-0.1% A2 0.81 0.79 0.72 0.61 A1+A2 1.01 1.00 1.00 1.07

T(oC)

592 617 669 723

k1 S1 V1 V2 S2

k2 l
k(cm/s)

10

-1

1-2% ceramic 10-2% k1 10-2% k2

10-2 10
-3

10-4 10
-5

102 kJ/mol 30 kJ/mol

10-6 10
-7

118 kJ/mol 0.9 1

1000/T

film

substrate

10-8 0.8

1.1

1.2

A. J. Jacobson

32

HRTEM on La2NiO4 after ECR

Films show columnar growth c axis oriented on synthesis Reconstructs during ECR experiment but still mainly c axis oriented Two kinetic pathways due to the anisotropy
A. J. Jacobson 33

Some Conclusions
La0.7Sr0.3Cu0.2Fe0.8O3-x shows complex phase behavior Further structural data needed Pr2NiO4 is a promising material appears to be less reactive with YSZ than La2NiO4 PrBaCo2O5+x thin films have: very fast surface kinetics; good interfaces on YSZ and CGO; bulk materials require further study. Anisotropic materials show two surface kinetic pathways in addition to anisotropic bulk diffusion
A. J. Jacobson 34

Future Plans
Further analysis of the stoichiometry behavior of La0.7Sr0.3Cu0.2Fe0.8O3-x Thin film deposition of La0.7Sr0.3Cu0.2Fe0.8O3-x (target prepared) for interface studies Clarify the potential advantage of Pr vs La systems with respect to interface reactivity Symmetric cell tests of Pr2NiO4 on YSZ Evaluation of PBCO and related compositions in bulk form Electrochemical performance studies of LNO, PNO and PBCO
A. J. Jacobson 35

Acknowledgements
University of Houston
Chonglin Chen Susan Wang Chan Young Park Guntae Kim Frank Azzarello

University of Toronto
Leszek Reimus Peter Brodersen

A. J. Jacobson

36