component technologies for automotive sofc · 2016-02-05 · 3 and lacro 3 as dbl materials show...

This document is the property of PLANSEE SE and shall not be communicated to 3rd parties and/orreproduced without prior written agreement. Its contents shall not be disclosed. PLANSEE SE – © 2007

Component Technologies for Automotive SOFC

K.Rissbacher / PLANSEE SE

A3PS conference / TECHGATE Vienna

Vienna, October 16, 2009

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This document is the property of PLANSEE SE and shall not be communicated to 3rd parties and/orreproducedwithout prior written agreement. Its contents shall not be disclosed. PLANSEE SE – © 2007

SOFC-APU for automotive applicationsAn (automotive) revolution

takes it course

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PLANSEE GroupFacts & figures and its mission for the emerging SOFC marketPlansee Group is a private, family owned company

– Worldwide leading company in powder metallurgical materials and components

– 1.6 Bn € sales– 70 manufacturing sites worldwide– approx. 7.000 employees – Competence in mass production of

materials and components for automotive, electronic and lighting industries

Plansee contributes to the SOFC market by means of

– Development and manufacturing of high performance, powder metallurgical stack components

– Competitive stack performance through designed alloys based on powder metallurgy

– Cost effective production by means of net shape technologies and mass production competences

Leading metallic componentsupplier for SOFC stacks

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PLANSEE GroupCompany Headquarter in Reutte, Austria

Pilot fabrication of SOFC components

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Produktportfolio Brennstoffzelle

Passive components –Energy from the heart of the SOFC

Active components –Into the heart of the SOFC

MSC Zelle – Stationary

ITM / MSC Zelle Repeat unit -Automotive

CFY Interkonnektor

ITM Interkonnektor

PLANSEE Product Portfolio for SOFC - stacks

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Metal supported cell Gas separator and catalyst

for the electrochemical reaction

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Metal supported cell (MSC-cell) technology is the next step in SOFC

Cathode

ElectrolyteSupportAnode Anode Support

ElectrolyteCathode

Anode

Metall Support

CathodeElectrolyte

AnodeAnode

1G 2G 3G

Anode Support

Electrolyte SSZ

Cathode LSCF

Anode

CGO Reduced cost

Higher robustness

Higher reliability

Better performance

Lower Stack mnfct cost

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PLANSEE SE - Facts and Figures

FeCr

YSZ/SSZ

LSCF CGO

YSZ/NiLSM/LSCR

MSC-cell Technology Roadmap at PLANSEE

SinteredMSC

Plasma-Sprayed MSC

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FeCr

YSZ/SSZ

LSCF

CGO

YSZ/Ni

LSM/LSCR

Metal Substrate– Long-term corrosion

stability– Adapted CTE– High porosity– Fine porous surface

Diffusion Barrier Layer (DBL)– High electronical

conductivity– Chemical stability– Adapted CTE

Functional cell layers– same requirements as in

other cell concepts

Set-up of PLANSEE MSC Special Requirements

MSC Product Development Requirements to a MSC concept

Cathode

Protective CoatingElectrolyte

AnodeDiffusion Barrier LayerMetal support

PLANSEE focuses the development on key technologies:

1. Porous metallic substrate

2. Diffusion barrier layers (DBL)

3. Functional cell layers (electrodes, electrolyte)

PLANSEE focuses the development on key technologies:

1. Porous metallic substrate

2. Diffusion barrier layers (DBL)

3. Functional cell layers (electrodes, electrolyte)

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Corrosion behavior in anode gas atmosphere at 800°CP/M ITMFe26Cr (Mo, Mn, Ti, Y2O3)

MSC Product Development Porous Metallic Substrate made of P/M ITM alloy

Low Al + Si content due to high purity P/M processing

Anode gas: H2-20% H2O

Enhanced life time of P/M ITM FeCr alloy in anode gas compared to I/M ferritic FeCr alloys due to:

– Lower oxidation rate constant

– 26 % instead of typical 22 % Cr

Porous ferritic P/M ITM alloys shows an adequate long-term oxidation stability

0,000

0,010

0,020

0,030

0,040

0,050

0,060

0 200 400 600 800 1000

Fe22Cr

ITM

Exposure time t [h]

Wei

ght G

ain

Δm

/A [m

g/cm

2 ]

P/M ITM

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Facts

Interdiffusion of Ni, Fe and Cr take place during cell operation

Cr and Fe in the Ni-phase of anode causes a significant reduction of catalytic activity

Ni in the FeCr-phase of substrate causes a decrease of corrosion stability and a significant increase of CTE

M. Brandner, PhD-Thesis, Ruhruniversität Bochum, 2006, Jül-Bericht 4238

Solution:

A Diffusion Barrier Layer (DBL) at substrate/anode-interface is needed

Interdiffusion of Ni, Cr and Fe at anode side

Metallicsubstrate

Anode Ni

Cr Fe

200 µm 20 µm

Fe, Cr, Mn-Oxide

Ni

MSC Product Development Diffusion Barrier Layer (DBL)

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PVD-DBL based on doped LaMnO3/LaCrO3-perovskites Facts

MSC Product Development Diffusion Barrier Layer (DBL)

DBL

ITM substrate

Physical Vapor Deposition (PVD) seems to be an adequate coating technology for the fabrication of DBL layers

Doped LaMnO3 and LaCrO3 as DBL materials show good barrier effect for Ni, Fe and Cr as well as its species

Chemical stability of doped LaMnO3 could be a problem under long-term operation conditions

PVD-DBL based on doped LaMnO3/LaCrO3-perovskites enables a long-term cell operation of MSC

Sample exposure in Air at 850°C, 1000 hrs.

DBL

ITMITM

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Facts

High kinetic energy and large plasma allows coating of thin and dense layer (10-50 µm)

Uniform coating thickness distribution on thin and larger substrates (repeat units) without any substrate deformation

Low gas leakage rates of electrolyte (< 10-3 mbar * l/(cm2 * s), He)

Heat management of substrate with online temperature monitoring

Source: Sulzer Metco, Wohlen

The LPPS-TF is applicable for large scale mass production with economical benefits

LPPS-TF Process for Electrolyte Fabrication

50µm

1st Gen MSC – IntroductionMSC Product Development Electrolyte layer via Plasma spraying

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Facts:

Improvement of micro structure of both electrodes by increasing the TPB (e.g. by using nano powders)

Use of improved plasma powders with better stoichiometry

Change to LSCF instead LSM for cathode fabrication

Decreasing of the cell leakage rate by improved electrolyte structures

Source: German Aerospace Center (DLR), Stuttgart

Performance Data MSC-cells at Button Cells level

1st Gen MSC – Latest results

Cell area: 12.56 cm2

Operating temperature: 800°C

Fuel gas: 0.5 slpm H2 and 0.5 slpm N2

Oxidizing gas: 2 slpm Air

Plasma spray technology provides a high performance MSC with small button cells

MSC Product Development Electrode and electroyte via Plasma spraying

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Facts

Cell up-scaling and integration into metal stamped light weight cassettes could be demonstrated successfully

Repeat units show a power density of 380 mW/cm2 and a FU of > 30 mol.%

By a systematic development operation with high FU (48 mol.%) with adequate performance could be demonstrated (280 mW/cm2)


Performance data MSC-cell at Single Repeat Unit level

1st Gen MSC – Latest resultsMSC Product Development Electrode and electroyte via Plasma spraying

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Facts

Redox-cycleability could be improved significantly by novel anode structures

20 redox cycles with no degradation of OCV and low degradation of power density(< 2.5 %) is possible

The rate of oxidation and re-oxidation in each cycle was 100%


Redox-cycleability of Button cells

1st Gen MSC – Latest results

Gen 1

Gen 2

Gen 3

The MSC- cell provides a high redox stability

MSC – cell RobustnessRedox-cycleability is a key advantage of MSC-cells

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MSC- cell Cost AdvantageLow cost manufacturing of Repeat unit (Energy Chip) by means of Metal supported Cell (MSC-cell) Technology

Current manfacturing of Current manfacturing of Repeat unit: Repeat unit: Complex and expensive Complex and expensive integrationintegration

Future manufacturing of Repeat Future manufacturing of Repeat unit with MSCunit with MSC--Cells:Cells:Less components and cost effective Less components and cost effective integration integration

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Basic Requirements:

Operating Hours (I>0A): 12000 hOperating Hours (T>100°C): 36000 hDeep Thermal Cycles (T<100°C): 300 -Medium Themal Cycles (T>100°C): 3000 -RedOx Cycles @Operat. Temp (1) 30 -RedOx Cycles to Ambient Temp. (2) 5 -Heat up Time: 30 minMaximum electrical Power: 3000 WMinimum electrical Power: 300 WSulphur Tolerance US (fuel): 15 ppmMass: 100 kgVolume: 100 LAPU Costs (for Integrator): 2000 US$Stack Costs (for Integrator): 600 US$(1) knowingly introduced for oxidation of deposits (S, C)(2) System malfunction, shut down under oxygen environment

Summary:Requirements of Truck SOFC- APU can be best fulfilled by Metal supported cell (MSC-cell) Technology

Requirements for MSC-cell technology

Robustness of MSC cell– Redox-stable MSC cell– Capability of themal cycling

Fast heat up rate – Lowest weight for metallic interconnectors– Metal supported cell with low thermal resistivity– Lower temperture operation

High performance cell– Metal supported cell in same range as ASC cell

Low cost component– Metal supported cell– Integrated design of repeat unit

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Fertigungsroute – MSC-ZelleSummary:PLANSEE technologies as key to establish a superior solution for the Repeat „element“ of SOFC-APU stack.

FeCr YCFY powder

Fe Cr Y MoTi

ITM powder

CFY Interconnects ITM Interconnects MSC-Zelle

H2

Powderpressing

H2sintering

Coating

H2H2sintering

Hot/cold Rolling Stamping/Welding

+ +

++

Coating

H2H2sintering

Greentape

Coating

Joining

CFY- Stack

JoiningITM / MSC-Zelle/

Repeat „Element“

Joining

Fe Cr Y MoTi

ITM powder

X, Y Z

H2 H2 H2

ITM / MSC-Zelle/ Repeat „Element“

ITM-alloy composition

P/M processing technology

Electrochemical layer technology

Performance advantages of MSC-cell based Repeat element

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Three more argument for PLANSEE MSC-cell technology

Cost/Unit, Cost/Hour , Cost/CO²

[email protected]

Tel: +43 5672 600 2778

PLANSEE SE

A-6600 Reutte

component technologies for automotive sofc · 2016-02-05 · 3 and lacro 3 as dbl materials show...

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