powerpoint presentation · title: powerpoint presentation author: heather created date: 7/28/2011...

Electrodeposition of SOFC

Interconnect Coatings

1H. McCrabb, 1T.D. Hall, 1J. Kell, 1S. Snyder, 2H. Zhang, 2X. Liu, 1E.J.Taylor

1Faraday Technology, Inc. 315 Huls Dr., Clayton, OH 453152West Virginia University, Dept. of Mechanical Aerospace Eng. ESB, Morgantown, WV

26506

12th Annual SECA Workshop

July 26 – 28, 2011

PSI Employees

by Education

PSI Locations

Faraday Technology, Inc.

• Faraday Technology specializes

in electrochemical engineering

• www.faradaytechnology.com

• Faraday is a wholly-owned

subsidiary of Physical Sciences,

Inc. (Boston, MA)

• www.psicorp.com

• Collectively, the company

staffs ~185 employees - ~100

with PhDs

• Annual revenue of ~ $50M

12th Annual SECA Workshop Pittsburgh, PA, July 27, 2011 slide 2

• Faraday’s R&D efforts

augment client company R&D

needs

• Open innovation leverages

government R&D dollars to

solve current industrial issues.

• Faraday’s strong IP portfolio

reinforces our open innovation

position and provides a

competitive advantage for

strategic partners.

26 Issued Electrochemical Patents

25 Pending Electrochemical Patents

Investment

Dollars

Discovery

ResearchKnowledge

Innovation Market

Dollars

Investment

Dollars

Discovery

ResearchKnowledge

Innovation Market

Dollars

Faraday Embraces Open Innovation


Platform Technology:Pulse/Pulse

Reverse Processing

Core Competency:Design and Engineer of Novel Electrochemical

Hardware

Total Manufacturing

Solution

• Electronics

• Edge and Surface Finishing

• Engineered Coatings

• Battery and Fuel Cell Power

• Environmental Systems

• Corrosion and Monitoring

Services

• Enables uniform processing

• Applicable for additive or

subtractive electrochemical

processes

• Uniform processing is

achieved over entire substrate,

improving end product

reliability

Either may be applied independently to

improve current industrial practices or may be

combined for a total manufacturing solution

Faraday Technology, Inc.


Objective of Program

slide 5

• Develop, optimize & validate an inexpensive

manufacturing process for coating metallic SOFC

interconnects with Co and Mn

– Demonstrate the process’s flexibility to 4”x4” and 10” x 10”

single and dual-sided patterned interconnect substrates

– Control coatings nanostructure and composition to prevent

T441 exposure to O2 and Cr diffusion to coating surface

– Mitigate Cr diffusion by identifying diffusion mechanism via

in-situ high temperature XRD and ex-situ XPS depth

profiling

– Develop a comprehensive economic assessment

– Work closely with our the SOFC industry to enhance the

commercialization plan for the program.

12th Annual SECA Workshop Pittsburgh, PA, July 27, 2011

Program Summary

slide 6

• FARADAYIC Process allows for non-line-of-sight deposition of a wide

range of compositions and surface structures using a single plating bath

• Coatings prepared using the FARADAYIC Process have uniform

surface composition and thickness on 2” x 2” flat panels

• Coatings exhibit adequate adhesion

• Initial ASR and crystallinity analysis showed that the as-deposited

thickness/composition had little effect on performance after a 500 hr

heat cycle

• 3µm thickness is capable of minimizing Cr diffusion for 500 hr testing

• Capability to coat dual-sided 1” buttons, 4” x 4”, and up to 11” x 14”

panels

• Based on batch manufacturing, the DOE’s high volume target of

1,600,000 plates per annum at a cost of ~$1.23 per 25 x 25 cm

interconnect


Coating Process

slide 7

• Surface pretreatment to

remove oxide and enhance

coating adhesion

• Electrodeposition to coat

interconnects with Mn-Co

alloy

– Pulse and pulse reverse

electric fields to control

deposit properties

• Elevated thermal treatment

to convert alloy to spinel

Acetone&

ScrubGrit Blast

Rinse&

Scrub

PickleDip RinsePlate

Acetone&

ScrubGrit Blast

Rinse&

Scrub

PickleDip RinsePlate


FARADAYIC Processing

slide 8

“Tuned” to remove

adverse effects of H2

H2 = 2H+ + 2e-

“Tuned” to:

1. allow replenishment of

reacting species on electrode

surface

2. & allow transport of

undesirable byproducts from

electrode surface

“Tuned” to:

1. enhance mass transfer

2. control current

distribution

tcAp

pli

ed i

( + )Anodic

Cathodic( - )

Forward

modulation

Time off

ta

ic

Reverse

modulation

ia

toff

Eliminates H2 embrittlement

Maintain uniform

concentration &

hydrodynamic conditions

Controls deposit

composition & properties

DC: only iavg can be chosen

FARADAYIC: ia, ta, ic, tc, toff

can be varied independently to

achieve a desired rate


As-deposited

800oC 2hr

800oC 1200hr

14%Mn

~50%Mn

Initial Coating Development

ASR prediction (40,000h, 0.0460 Ohm cm2)

J. Wu, et al., Electrochimica Acta 54 (2008) 793–800

0 200 400 600 800 1000 12000.00

0.01

0.02

0.03

0.04

0.05

++

(1200, 0.0244)

(0, 0.0189)

AS

R (

Oh

m.c

m2)

Time (Hour)

ASR

ASR measurement



slide 1012th Annual SECA Workshop Pittsburgh, PA, July 27, 2011

Good adhesion with

substrate

0 1 2 3 4 50

50

100

150

200

250

5

4

3

2

1

Inte

nsity

(Arb

. u

nit)

Distance ( m)

1 O 2 Cr

3 Mn 4 Fe

5 Co

No Cr penetrate

through the coatings

Significant Mn diffusion

from substrate

Cross section after ASR

0 200 400 600 8000

50

100

150

200

250

3002

Po

we

r d

en

sity (

mW

cm

-2)

Time (h)

1 cell with uncoated 430Desi

2 cell with MnCo coated 430F

Contact

problem

2nd TC1st TC

V/I curve

1

With electrodeposited MnCo coating, cell performance degradation reduced



Interconnect on button cell test

Objective of Phase I

• Demonstrate the technical and economic feasibility of

MnCo electrodeposited on SOFC interconnect

materials by answering the following questions:

1. What range of coating percent compositions can the

electrodeposition process deposit?

2. Can the electrodeposition process deposit Mn-Co alloy

coatings with a thickness range of 3 – 10 um?

3. How well does the coating perform at varying alloy

compositions and coating thickness?

4. Is the electrodeposition process economically viable?


Laboratory Scale Electrodeposition

Equipment

slide 13

Flow cell for plating onto 2”x2” planar T441 substrates


Coating UniformityThe electrodeposited coating exhibits a virtually uniform coating composition

and thickness across the 2”x2” surface

Top

Bot

Flo

w D

irec

tio

n

As Plated


Coating Porosity and Adhesion

*Rockwell test with 1/16” steel ball used to quantify adhesion after

spinel growth after 72 hr. at 800°C

60kgf 100kgf 150kgf

*Sun, X., et. al. JPS, 176 (2008) 167

Feroxyl Porosity Test Results (AMS 2460 3.4.4.2)

SS Without Coating Mn-Co Coating As Deposited

Mn-Co Coating After 72 hour

Thermal Treatment at 800 C

Without Grit Blast With Grit Blast


Cr Ion Diffusion and Coating Porosity


• Cross-sections of samples that

underwent a soak treatment at

800 C for 500 hrs

– Coating thickness was as

deposited

– Indicates that a 3 micron layer

is adequate to produce Cr

complexing and minimize Cr

diffusion due to minimal

porosity

SubstrateCoating surface

Coating Crystal Structure


10 20 30 40 50 60 70

334

2 theta (degrees)

Inte

ns

ity

(a

.u.)

MnCo2O

4

Mn1.5

Co1.5

O4

Mn1.5

CrO4

332

333

40%Co 3µm

40%Co 7µm

40%Co 10µm

Crystal Structure after 500 hrs at 800°CIn

ten

sit

y (

a.u

.)

2 theta (degrees)

Effect of Thickness and Composition on

Performance


The ASR is 75 mΩ cm2 regardless of compositions and thickness

after 500 hrs at 800 C

500 600 700 800

0

500

1000

1500

Temperature ( )

AS

R (

m c

m2)

336

337

ASR Behavior after 500hrs

85%Co 7µm

85%Co 10µm

mΩ cm

2 100 hr 200 hr 500 hr

3 μm 40% Co 35 57 49

7 μm 40% Co 62 7 32

10 μm 40% Co 22 - 36

3 μm 85% Co 31 75 20

7 μm 85% Co 59 40 54

10 μm 85% Co 37 23 22

3 μm 57% Co - 34 26

7 μm 57% Co - - 12

10 μm 57% Co - - 12

ASR at 800 C

Phase II Program Milestones


Milestones

Fiscal

YearTitle

Planned

Completion

Percent

Complete

20111. Design/modification of 10” x 10”

electrodeposition cellMay 2011 100%

20112. Long-term high temperature, thermal

evaluation

September

201133%

20113. Process development for 4”x4” planar

interconnects

September

201115%

20124. Process development for 4”x4” pattern

interconnectsJune 2012 0%

20125. Long-term on-cell performance

evaluationAugust 2012 0%

20126. Qualification/demonstration of IC in

single cell test rig

September

20120%

Extended Thermal Treatment Time Study

• Six samples were prepared using

varying deposition parameters

and placed into a tube furnace at

850 C.

– 2 samples with higher Mn content

and 4 with high Co content

– Target alloy thickness of 5 um

• An air flow of at least 500 sccm

flows through the furnace tube (to

simulate air in SOFC systems)

• Samples examined after 750,

1500, and 2000 hr

ASR Test order:C(t=0); D(t=750 hrs);

E(t=1500 hrs); F(t=2000 hrs); and

A(t=2000 hrs) (for Rockwell Test)


As Deposited

Co/Mn = 4

2000 hrsCo/Mn = 1

1

1 2 3

2 3Co/Mn = 4

Co/Mn = 0.5

Co/Mn = 18

Co/Mn = 16



4

4 5 6

5 6As DepositedCo/Mn = 18

2000 hrsCo/Mn = 10

Co/Mn = 44

Co/Mn = 18

Co/Mn = 16

Co/Mn = 15



Cross Section Results - 1001

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%

Chromia layerCo-Mn layer

Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

C K O K AlK CrK MnK FeK CoK NbL TiK


Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

50

100

150

200

0 2 4 6 8 10 12

Distance (microns)

Co

un

ts

O K CrK MnK FeK CoK

1st layer

2nd layer3rd layer

4th

layer

5th layer Substrate

0

50

100

150

200

0 2 4 6 8 10 12

Distance (microns)

Co

un

ts

O K CrK MnK FeK CoK

1st layer

2nd layer3rd layer

4th

layer

5th layer Substrate

0

50

100

150

200

0 2 4 6 8 10 12

Distance (microns)

Co

un

ts

O K CrK MnK FeK CoK

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Distance (microns)

Rela

tiv

e a

t%


Nb-T

i la

yer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

Rel

ativ

e at

Distance (microns)

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18



Nb

-Ti

layer Substrate

~3:4 Co:Mn coating

~7 μm ~5.5 μm ~1.5 μm


0 hours 2000 hours @ 850 C

Pilot Scale Electrodeposition Equipment


Based upon Faraday’s electrochemical cell design that facilitates uniform flow across the surface

of a flat substrate (US patent #7,553,401)

Initial Pilot Scale Experiments


FARADAYIC Electrodeposition parameters varied for experiments conducted in the newly

modified FARADAYIC Electrodeposition Cell

Trial No

Electrode Spacing

(inches)

Electrolyte Flow

(PSI) Vibration Oscillation

2001 3 16 - -

2002 1.5 16 - -

2003 4.5 16 - -

2004 4.5 10 50 50

2005 4.5 16 50 50

2006 3 16 50 50

2008 3 5 50 50

2009 3 10 50 50

$0.52

$0.02

$0.61

$0.03

$0.00

$0.00

$0.65

$0.04$0.00

Plating Line Water Labor Energy Cobalt Managnese Boric Acid Ammonia Sulfate

$0.52

$0.02$1.09

$0.11$0.01

$0.02

$1.23

$0.00

$0.04

Plating Line Water Labor Energy Cobalt Managnese Boric Acid Ammonia SulfatePhase I

Phase II

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

(42%)

(1%)

(51%)

(3%)

(0%)

(0%)

(3%)

(0%)

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

(29%)

(1%)

(60%)

(6%)

(1%)

(1%)

(2%)

(0%)

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

2%

0%

29%

1%60%

6%1%

1%

68%

Plating Line

Water

Labor

Energy

Cobalt

Managnese

Boric Acid

Ammonia Sulfate

Electrodeposition Cost Analysis


High volume manufacturing of 1,600,000 plates per annum at a cost of ~$1.23 per 25 x 25 cm interconnect

• Determine plating parameters effect on chromium

and oxygen diffusion

• Continue scale-up development for large area

planar T441 substrates

• Begin scale-up development for large area pattern

interconnects

– Demonstrate coating uniformity and

composition

• Testing in single cell and short stack SOFC

systems


Future Direction

Acknowledgments


• Briggs White and the entire SECA program management team

• This material is based upon work supported by the Department of Energy under Award Nos. DE-SC0001023 and DE-FE0006165. Any opinions, findings, conclusions and recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the DOE.

• Contact Information:Heather McCrabb

Ph: 937-836-7749

Email: [email protected]

powerpoint presentation · title: powerpoint presentation author: heather created date: 7/28/2011...

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