sofc technology development, in connection to ffi project improved life time for sofc ... · 2015....

SOFC technology development, in

connection to FFI project Improved life

time for SOFC-APU

Jan-Erik Svensson, Hannes Falk

Windisch and Jan Froitzheim

Chalmers University of Technology

Improving Lifetime Performance of

SOFC for Truck APUs (Förbättringar av livslängden av fastoxidbränsleceller-APU

för tunga fordons applikationer)

Jan-Erik Svensson, Jan Froitzheim and Hannes Falk Windisch

Energy and Materials

Chemistry and Chemical Engineering

Chalmers University of Technology

Why trucks are idling?

• Electricity is needed during breaks for

– Cooling

– Heating

– Fridge

– Lighting

– Radio, PC, TV

– Etc.

Rolling homes that need electricity

Advantages with SOFC-APU

SOFC-APU can operate on diesel

• No extra tank required

• No new infrastruktur required

• An SOFC-APU is quiet…

• More effecitve than diesel engine (Efficiency 35%)

There are several types of fuel cells, the most common are:

•PEM (Polymer Electrolyte Membrane Fuel cells)

Operate at 80 C, high efficiency, fast start up, high sensitivity for fuel impurities

•SOFC (Solid oxide fuel cells)

Operate at 600-900 C, high efficiency, fuel flexibility, high-temperature corrosion

Projectpartners

Objectives

This project tries to mitigate three main causes of stack degradation in

relation to the interconnects,

– cathode side oxidation

– chromium evaporation and

– anode side oxidation, that diminishes power output and can lead to

stack failure

The idea behind the proposal is to resolve these issues in a cost-effective way,

using standard ferritic FeCr strip steel protected by multi-layered nano coatings

Improving Lifetime and Performance of SOFC for Truck APUs

- In a cost efficient way

Metallic Interconnect is the key! (Up to 40% of the cost of a stack!

Outline

Part I: Overview SOFC Technology

Part II: Recent results from the FFI project

Solid Oxide Fuel Cell (SOFC)

CathodeAnode Electrolyte

O2

O2-

The electrolyte is a oxygen ion conducting material (600-900 ºC)

H2 (fuel)

H2O (product)

Advantages

• High electrical efficiency

• O2- conductive electrolyte Fuel flexibility (H2, natural gas,

biogas.. diesel)

• High operating temperature No need for expensive catalysts

such as Pt

Solid Oxide Fuel Cell (SOFC)

Electrolyte supported Anode supported

>800C 650-800C

Metal supported

<700C

Solid Oxide Fuel Cell (SOFC)

Electrolyte supported

>800C

Mainly military applications (APU)

military ground vehicle APU

unmanned under water vehicle unmanned aerial systems

power systems for lunar

and Martian landers.

Hexis (Viessmann)

Elektrolyte supported design

1 kWel

1.8 kWheat

46.5% is achieved — with an overall energy

efficiency of 90.0%

Bloom Energy

• Bloom: ~100 MW installed

• Sunfire bought Staxera

• Located in Dresden/Germany

• Focus on both SOFC and SOEC

• rSOC Reversible SOC

SOEC Power to liquid process:

Process efficiency 70%

SOEC efficiency >90%

Cost (500t/day) ~1€/liter

Solid Oxide Fuel Cell (SOFC)

Anode supported

650-800C

Solid Power

(SOFCpower and Ceramic Fuel Cells)

60% electric =Record!

(74% DC single pass)

Courtesy of Elcogen

Courtesy of Elcogen

Versa Power/ Fuel Cell Energy

33 x 33cm cellsIncorporated the larger-scale SOFC

components into fuel cell stacks as large

as 60 kilowatts (kW).

Metal supported

<700C

Ceres Power

Source:http://www.cerespower.com/ProductOverview/ResidentialCHP/)

Ceres Power:

• Low temperature (<600C),

low cost approach

• 97% of the stack is steel –

3% ceramics

The steel cell

Metal supported FC

50% electrical efficiency (goal is 55%)

Natural Gas, steam reforming

< 600 ˚C => low cost materials

Start up time < 30 min

Outline

Part I: Overview SOFC Technology

Part II: Recent results from the FFI project

Cost analysis 1kW Stack

1kW Stack Manufacturing Cost (50 000Units)

Cells Interconnects

Sealing, End plate etc Assembly Hardware

Source: Battelle study prepared for US DOE (2014)

35%

• Similar thermal expansion as the ceramics used in SOFC

• Good electrical and thermal conductivity

• Form conductive oxide scales (Cr2O3)

• Formability

• Cheap to produce

Ferritic Cr2O3-forming steels as interconnect

material in SOFC

However

Steel (FeCr) Steel (FeCr)

Cr2O3

CrO2(OH)2(g)

oxidation

O2 + H2O

600-900 °C

Oxide scale growth → increased electrical resistance

→ Cathode poisoning

Cr vaporization: Cr2O3(s) + O2(g) + H2O(g) → CrO2(OH)2(g)

How to reduce Cr vaporization?

Steel

Co

Our approach apply metallic nano coatings:

Steel

(Co,Mn)3O4

Cr2O3

CrO2(OH)2(g)

oxidation

O2 + H2O

600-900 °C

0.E+00

1.E-04

2.E-04

3.E-04

4.E-04

5.E-04

6.E-04

7.E-04

8.E-04

9.E-04

1.E-03

0 100 200 300 400

Ac

cu

mu

late

dC

rva

po

riza

tio

n(k

g/m

2)

Exposure time (h)

x10 reduction

Cr vaporizationAir, 850 ºC

Co coated (600nm)

Uncoated Steel

Cr2O3

(Cr,Mn)3O4

Steel

(Co,Mn)3O4

Cr2O3

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

The pre-coated concept

InterconnectCell

The interconnect material has to be shaped in a way to allow for gas

distribution

Before exposure

Post-coated

Pre-coated

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

0.E+00

1.E-04

2.E-04

3.E-04

4.E-04

5.E-04

6.E-04

7.E-04

8.E-04

9.E-04

1.E-03

0 100 200 300 400

Ac

cu

mu

late

d C

r-va

po

riza

tio

n (

kg

/m2)

Exposure time (h)

Uncoated and undeformed

Undeformed (600nm Co)

x10 reduction

Cr vaporizationAir, 850 ºC

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

0.E+00

1.E-04

2.E-04

3.E-04

4.E-04

5.E-04

6.E-04

7.E-04

8.E-04

9.E-04

1.E-03

0 100 200 300 400

Ac

cu

mu

late

d C

r-va

po

riza

tio

n (

kg

/m2)

Exposure time (h)

Deformed + post-coated (600nm Co)

Uncoated and undeformed

Undeformed (600nm Co)

Cr vaporizationAir, 850 ºC

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

0.E+00

1.E-04

2.E-04

3.E-04

4.E-04

5.E-04

6.E-04

7.E-04

8.E-04

9.E-04

1.E-03

0 100 200 300 400

Ac

cu

mu

late

d C

r-va

po

riza

tio

n (

kg

/m2)

Exposure time (h)

Deformed + Post-coated (600nm Co)

Uncoated and undeformed

Undeformed (600nm Co)

Pre-coated + Deformed (600nm Co)

No signs of increased Cr-vaporization after mechanical deformation/stamping

Cr vaporizationAir, 850 ºC

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

60 µm

├───┤

60 µm

├───┤

60 µm

├───┤

60 µm

├───┤

Cr

Unexposed:

6 minutes:

8 hours:

24 hours:

Mn Co

Mn enrichment within the cracked area

More homogenues Cr, Mn and Co signal after 24 h

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

24 h (Air, 850 ºC):

Thin Co-rich layer within the cracked area

Growth of (Co,Mn)3O4 crystals within cracked area

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

Surface homogenously covered by an oxide rich in Co and Mn

336 h (Air, 850 ºC):

Reference: H. Falk-Windisch et al. / Journal of Power Sources 297 (2015) 217-223

Solid Oxide Fuel Cell (SOFC)

Electrolyte supported Anode supported

>800C 650-800C

Metal supported

<700C

Operating temperature for SOFC systems lies in between 600-900C

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0 100 200 300 400 500 600

Ne

t m

ass

ga

in(m

g c

m-2

)

Exposure time (h)

850 ºC

650 ºC

750 ºC

Negative mass gains after 500 h at lower temperatures

The effect of temperature on mass gain

Reference: H. Falk-Windisch et al. / Journal of Power Sources 287 (2015) 25-35

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0 100 200 300 400 500 600

Accu

mu

late

d C

r-va

po

riza

tio

n (

mg

cm

-2)

Expsure time (h)

850 ºC

650 ºC

750 ºC

Small effect of temperatur for Cr vaporization

The effect of temperature on Cr vaporization

=> Coatings are necessary also at lower temperatures (650 ºC)

Reference: H. Falk-Windisch et al. / Journal of Power Sources 287 (2015) 25-35

How is the metallic Co coating influenced by a lower temperatue?

Steel

Co

Steel

(Co,Mn)3O4

Cr2O3Diffusion of

Mn,Cr and Fe

650-750 °C

Steel

(Co,Cr,Mn,Fe)3O4

Cr2O3

?If not, what is formed instead?

And what is the effect on Cr vaporization

and oxide scale growth?

Do we need to design low-temperature

coatings?

Summary and future work

• Novel nano coatings for superior properties (Cr vaporization and oxidation

rate)

• Pre-coated concept to reduce costs

• Crack formation due to mechanical deformation (stamping)

• Self-healing of the (Co,Mn)3O4 toplayer

• Coatings necessary even at low temperatures

Cr vaporization is less influenced by temperature than oxide scale

growth

• A need for special designed low-temperature coatings?

Microstructure and chemical composition of the coating not the same

at lower temperatures

Stack tests (Elcogen) with novel nano coatings are scheduled to be carried

out beginning of 2016