Download - Enhancement of SOFC Cathode Electrochemical Performance ... · Perovskite (AO-BO. 2. stacking) Cathode Material. Completed 33/36 months of project. 1. How does this interfacial enhancement

Enhancement of SOFC Cathode Electrochemical Performance Using

Multi-Phase Interfaces

Dane Morgan, Yueh-Lin LeeDepartment of Materials Science and Engineering

University of Wisconsin – Madison, WI USA

Stuart Adler, Timothy (TJ) McDonaldDepartment of Chemical Engineering

University of Washington, Seattle, WA USA

Yang Shao-Horn, Dongkyu (DK) Lee, Xiao (Renshaw) Wang Department of Mechanical Engineering

Massachusetts Institute of Technology, Boston, MA USA

16th Annual SECA WorkshopPittsburgh, PA

July 14 – 16, 2015 1

Acknowledgements

External Collaborators• Briggs White (NETL)• Michael D. Biegalski, H.M. Christen (Oak

Ridge National Laboratory)• Paul Fuoss, Edith Perret, Brian Ingram,

Mitch Hopper, Kee-Chul Chang (Argonne National Laboratory)

• Zhan Zhang, Christian M. Schlepuetz, Lynette Jirik (ID-33 of Advanced Photon Source)

• Paul Salvador (Carnegie Melon University)

MIT Skoltech Center For Electrochemical Energy Storage

King Abdullah University of Science andTechnology

Computing Support

National Energy Research Scientific Computing Center

Oak Ridge National Laboratory

NSF Supercomputing

DE-FE0009435, DESC0001284 2

Oak Ridge National Laboratory

Funding Support

Oxide Heterointerface for SOFC Cathodes

Interface of two oxides: Enhances ORR kinetics by ordersof magnitude compared to individual phases1-4

3

LSC-113: ABO3 Perovskite(AO-BO2 stacking)Cathode Material

LSC-214: K2NiF4 type AO-AO-BO2 stacking, coating

LSC-113LSC-214

Novel Heterostructure

Enhances ORR kinetics at 500-600°C

[1] E. J. Crumlin, et al., The Journal of Physical Chemistry Letters, 1, 3149-3155.[2] M. Sase, et al., Journal of The Electrochemical Society, 2008, 155, B793-B797.[3] M. Sase, et al., Solid State Ionics, 2008, 178, 1843-1852.[4] K. Yashiro, et al., Electrochem. Solid State Lett., 2009, 12, B135-B137.

Oxide Heterointerface for SOFC Cathodes

Interface of two oxides: Enhances ORR kinetics by ordersof magnitude compared to individual phases1-4

4

LSC-214: K2NiF4 type AO-AO-BO2 stacking, coating

[1] E. J. Crumlin, et al., The Journal of Physical Chemistry Letters, 1, 3149-3155.[2] M. Sase, et al., Journal of The Electrochemical Society, 2008, 155, B793-B797.[3] M. Sase, et al., Solid State Ionics, 2008, 178, 1843-1852.[4] K. Yashiro, et al., Electrochem. Solid State Lett., 2009, 12, B135-B137.

LSC-113: ABO3 Perovskite(AO-BO2 stacking)Cathode Material

Completed 33/36 months of project

1. How does this interfacialenhancement work in LSC113?

2. Can it be extended toXYZ214/LSCF113 interfaces?

3. Can we make more active, morestable porous electrodes withthese interfaces?

5

Conclusions1. How does this interfacial enhancement work in

LSC113?

Stabilization of Sr-rich LSC113 surface andsuppression of Sr-rich precipitation

2. Can it be extended to XYZ214/LSCF113 interfaces?

Yes! LSC214/LSC113/LSCF113 enhances LSCF113 10x!

3. Can we make more active, more stable porouscathodes with these interfaces?

Promising initial results but needs more workwith NETL, industry teams, future proposals …

Yang Shao-Horn (MIT)

Dane Morgan (U Wisc.) Stuart Adler (U Wash.)

LSC-214/LSCF-113 Films LSCF-113LSC-214

NLEIS + Rate modeling, LSC-214/LSCF-113 porous electrodes

Ab initio EnergeticsThermokinetic Modeling

Project Overview

6

Major Activities• PLD synthesis and physical (SEM, xray, Auger,

COBRA) electrochemical (EIS) characterization of LSC113, LSCF113, LSC214, LSN214, LSC214/LSC113 , LSC214/LSCF113, LSN214/LSC113, LSC113-LSC214/LSCF113.

• NLEIS, kinetic modeling, degradation testing of oxygen reduction for film/porous electrode LSC113and LSCF113.

• Ab initio calculations of defects and Srsegregation in LaSrMO4 (214), LSC113, LSCF113, LSC214/LSC113, LSC214/LSCF113.

7

Major Conclusions• LSC113: Sr segregates strongly to surfaces of LSC113 but is unstable at

these surfaces leading to precipitation and lost performance.

• LSC214/LSC113: Has enhanced performance because Sr is gettered by LSC214, which effectively stabilizes Sr-rich LSC113 surface and suppresses precipitation.

• LSCF113: Sr segregates very strongly to surfaces of LSCF113 and is relatively stable at these surfaces vs. LSC113.

• LSC214/LSCF113: Has little enhanced performance because Sr-rich LSCF214 is already fairly stable.

• LSC214/LSC113/LSCF113: Has enhanced performance due to enhanced activity of LSC214/LSC113 on the LSCF.

8







9

Sr Segregation and Precipitation

Bulk Sr

La Co OSurface segregated Sr

SrOxPrecipitated Sr

10

CoO2

(La,Sr)OCoO2

(La,Sr)O

Surface Terminations of (001) (La,Sr)CoO3

11

What Termination/Segregation is Stable?

12

AO surface is stable over CoO2, and Sr-rich is stable over La-rich. Consistent with data from Auger spectroscopy, LEIS, COBRA, etc.

(001) (La0.75Sr0.25)CoO3, 550°C, 1atm

D Lee, J Mater Chem A 2015

What Precipitation is Stable (SEM)?

13

Surface is unstable with respect to Sr-rich precipitates

(001) (La0.80Sr0.20)CoO3 550°C D Lee, J Mater Chem A 2015

Pristine 70h Anneal

What Precipitation is Stable (COBRA)?

14

Surface is unstable with respect to Sr enriched precipitates

(001) (La0.80Sr0.20)CoO3

Coherent Brag Rod Analysis (COBRA)

Feng et al., Energy Environ. Sci. 2014; Feng et al., J Phys. Chem. Lett. 2014

What Precipitation is Stable (DFT)?

15

Surface is unstable with respect to Sr enriched precipitates

Further Evidence for Segregation/Precipitation Effects

(NLEIS)

16

Non-Linear Electrochemical Impedance Spectroscopy (NLEIS)

C. Kreller et al., JES ‘13

• Excellent agreement with NLEIS data.

• Implies both Sr segregation and lateral Sr inhomogeneity.

• xs(2) ~0.4 for LSC-82, xs

(1) ~ 0.45.

-10.0

-8.0

-6.0

-4.0

-2.0

-5 -4 -3 -2 -1 0

What Surfaces are Active?

17

CoO2 surface best, SrO next best, LaO surface inactiveLog10[PO2 (atm)]

Log

10[k

tr(m

/s)]

van der Haar et al., JES ’02Egger et al. SSI ‘12

M. Gadre et al, Submitted ‘15

LaO Termination

(001) (La0.5Sr0.5)CoO3 650°C

-2

-4

-6

-20

Summary of Stability and Activity

18

(001) (La0.5Sr0.5)CoO3 650°C

CoO2 Termination

Log

10[k

tr(m

/s)]

LaO Termination

SrO Termination

SrO Termination +Sr-rich Precipitates

Increasing stability







19







20

Sr Gettered by LSC214 and Stabilized at LSC214/LSC113Interface

21Sr in interface and LSC214 film and depleted from LSC113

Z. Feng, et al., JPCL ‘14

LSC214 Decoration Suppresses Sr-Rich Phase Precipitation

22

(LaSr)CoO4(La0.80Sr0.20)CoO3 550°C

LSC113

LSC214/LSC113

Pristine 70h AnnealD. Lee, J Mater Chem A 2015

LSC214 Decoration Enhances LSC113Activity and Stability

23


(LaSr)CoO4, (La0.80Sr0.20)CoO3 550°C







24







25

What Termination/Segregation is Stable?

26

AO surface is stable over CoO2, and 100% Sr is stable for LSCF, vs. ~75% for LSC. Stronger surface segregation of Sr for LSCF!

(001) (La0.75Sr0.25)CoO3, (La0.625Sr0.375)(Co0.2Fe0.8)O3, 550°C, 1atm


Sr = 1.0

Sr= 0.75

Sr=0.5

Sr=0.25

Sr=0.0

LSC113 LSCF113

D. Lee, J Mater Chem A 2015

Is Sr Stable in LSCF Surface (DFT)?

27

Sr is more stable in Sr-rich LSCF surface than Sr-rich LSC surface

LSCF113 Sr-Rich Surface More Stable than LSC113

28

(La0.80Sr0.20)CoO3(La0.6Sr0.4)(Co0.2Fe0.8)O3 550°C

LSC113

LSCF113


Evidence for Segregation/Precipitation Effects in LSCF (NLEIS)

• Inhomogeneous thermodynamics needed to fit data

• ~3 nm of Sr-rich phase at surface• Surface thermodynamics similar to

Sr-rich phase• Total [SrLa

’] < 0.4 (i.e. possible Srprecipitation) 29

Bulk Strontium DistributionPhase 1: [SrLa

’] = 0.15, 87% vol.Phase 2: [SrLa

’] = 0.85, 13% vol.

Surface KineticsRO2

0 ∝ pO2 xv2(1-xh)2

[SrLa’] = 0.9

(La0.6Sr0.4)(Co0.2Fe0.8)O3 Film, 600°C







30







31

Sr More Weakly Attracted by LSC214 form LSCF113 ThanLSC113 (DFT)

32

D. Lee, J Mater Chem A 2015

LSC214 Decoration Has Little Effect on Sr-Rich Phase Precipitation in LSCF

33

(LaSr)CoO4(La0.80Sr0.20)CoO3(La0.6Sr0.4)(Co0.2Fe0.8)O3550°C

LSCF113

LSC214/LSCF113


LSC214 Decoration Has Little Impact on LSCF113 Activity

34D Lee, J Mater Chem A 2015

LSC214/LSC113 LSC214/LSCF113

LSC214 Decoration Has Little Impact on LSCF113 Activity and Stability

35


(LaSr)CoO4, (La0.80Sr0.20)CoO3, (La0.6Sr0.4)(Co0.2Fe0.8)O3 550°C

LSC214/LSC113 LSC214/LSCF113

10~100X ~2X







36







37

Enhancement from Mixed Single Layer [LSC214+LSC113]/LSCF113

550 °C

38

• ~10x enhancement in surface exchange of LSCF113!• From catalytic ability of LSC214+LSC113?

Enhancement from Double Layer StackedLSC214/LSC113/LSCF113

550 °C

39

• ~10x enhancement in surface exchange of LSCF113!• From catalytic ability of LSC214/LSC113?• Strong Sr dependence (qualitatively consistent with previous

observations of Sr being critical) and best for largest Sr content

40

Conclusions1. How does this interfacial enhancement work in

LSC113?

Stabilization of Sr-rich LSC113 surface andsuppression of Sr-rich precipitation

2. Can it be extended to XYZ214/LSCF113 interfaces?

Yes! LSC214/LSC113/LSCF113 enhances LSCF113 10x!

3. Can we make more active, more stable porouscathodes with these interfaces?

Promising initial results but needs more workwith NETL, industry teams, future proposals …

END

Thank you for your attention

41