The Integrated Project SOFC600 - Europa · 2018. 10. 22. · The Integrated Project SOFC600 Low-Temperature SOFC development General Assembly FCH-JU, Brussels, 26/27 October 2009

The Integrated Project SOFC600

Low-Temperature SOFC development

General Assembly FCHGeneral Assembly FCH--JU, Brussels, 26/27 October 2009 JU, Brussels, 26/27 October 2009

Bert RietveldBert Rietveld

Energy Research centre of the Netherlands (ECN)Energy Research centre of the Netherlands (ECN)

FCH-JU General Assembly, Brussels, 26/27 October 2009 SES6-2006-020089 2

Project dataProject data

FW6 Integrated Project FW6 Integrated Project SES6SES6--20062006--020089020089

Priority 6.1 Sustainable Energy Systems (SUSTDEVPriority 6.1 Sustainable Energy Systems (SUSTDEV--1) 1)

Research activities medium and longResearch activities medium and long--term (SUSTDEVterm (SUSTDEV--1.2)1.2)

Fuel cells and their applications (SUSTDEVFuel cells and their applications (SUSTDEV--1.2.1)1.2.1)

Duration 1Duration 1stst March 2006 March 2006 –– 28 February 201028 February 2010

21 participants21 participants

Research and development project with emphasis on development ofResearch and development project with emphasis on development of novel novel materials, (nearmaterials, (near--nano) microstructures and manufacturing processes nano) microstructures and manufacturing processes

Relatively high level of basic R&D, less application targeted (gRelatively high level of basic R&D, less application targeted (generic)eneric)


EU SOFC600 Project Consortium

7 Universities7 UniversitiesBasic researchBasic research

11 R&D organisations11 R&D organisationsBasic research + developmentBasic research + development

3 Industrial companies, all 3 Industrial companies, all SMEsSMEsDevelopment + implementationDevelopment + implementation

ECNECN NetherlandsNetherlands

HTceramixHTceramix SwitzerlandSwitzerland

CEACEA FranceFrance

EMPAEMPA SwitzerlandSwitzerland

FZJFZJ GermanyGermany

Imperial CollegeImperial College United KingdomUnited Kingdom

UniUni KarlsruheKarlsruhe GermanyGermany

UniUni St.AndrewsSt.Andrews United KingdomUnited Kingdom

UniUni OxfordOxford United KingdomUnited Kingdom

UniUni LeobenLeoben AustriaAustria

CNRS BordeauxCNRS Bordeaux FranceFrance

TOFCTOFC Denmark Denmark

AECA (NTDAAECA (NTDA--SOFC) SpainSOFC) Spain

NRCNRC CanadaCanada

DICPDICP ChinaChina

IPMSIPMS UkraineUkraine

SJTU SJTU ChinaChina

BICBIC RussiaRussia

PMI PMI BelarusBelarus

VTTVTT FinlandFinland

DTUDTU DenmarkDenmark


Project objectivesProject objectives and scope

Specification of stack components for operation at 600Specification of stack components for operation at 600ooC aiming for C aiming for endurance and costendurance and cost

Anodes, cathodes and electrolytesAnodes, cathodes and electrolytesInterconnect materials Interconnect materials Contact and barrier/protective coatingsContact and barrier/protective coatingsSealsSeals

Components are demonstrated by integration in the current cell aComponents are demonstrated by integration in the current cell and stack nd stack technology of the developerstechnology of the developers

The development and delivery of full cells and stacks itself is The development and delivery of full cells and stacks itself is outside the outside the scope of the project scope of the project

Non technical objectives (WP6)Non technical objectives (WP6)Dissemination and communication project achievementsDissemination and communication project achievementsProject websiteProject websiteWorkshops (internal and external)Workshops (internal and external)Initiate and contribute to European HFPInitiate and contribute to European HFP--SOFCnet SOFCnet


Motivation for LTMotivation for LT--SOFC = FCHSOFC = FCH--JU relevant topicsJU relevant topics

Lifetime/degradationLifetime/degradationReduced degradation rate of thermally activated cell degradationReduced degradation rate of thermally activated cell degradationmechanismsmechanismsReduced corrosion rate of preferably cheap steels for interconneReduced corrosion rate of preferably cheap steels for interconnectsctsMetal, metalMetal, metal--ceramic (compressible) seals and non crystallizing glassceramic (compressible) seals and non crystallizing glassStability of contact coatingsStability of contact coatingsLower sensitivity for combined thermalLower sensitivity for combined thermal--redox cyclesredox cycles

CostsCostsLifetimeLifetimeCheap interconnect steels and BOP materialsCheap interconnect steels and BOP materialsIndustrial, cost effective manufacturing processesIndustrial, cost effective manufacturing processes

Fuel flexibility and high efficiencyFuel flexibility and high efficiencyHH22 and reformatesand reformatesInternal reforming of NG (simplest and most efficient system)Internal reforming of NG (simplest and most efficient system)

-- Low catalytic activity for C depositionLow catalytic activity for C deposition


Project targets

SOFC cell at 600SOFC cell at 600ooCCArea Specific Resistance (ASR) below 0,5 Area Specific Resistance (ASR) below 0,5 ΩΩ.cm.cm22

Degradation rate below 1.5 mDegradation rate below 1.5 mΩΩ.cm.cm22.khr.khr--1 1 (0.05 %V.khr(0.05 %V.khr--11) ) For ISR at S/C = 2: 0.8 For ISR at S/C = 2: 0.8 ΩΩ.cm.cm22 and 3 mand 3 mΩΩ.cm.cm22.khr.khr--11

Robustness: 5 ppm S, 100 redox cycles, internal reforming capabiRobustness: 5 ppm S, 100 redox cycles, internal reforming capability, lity, reduced coke formation activityreduced coke formation activity

Single repeating unit (cell + coatings + interconnect)Single repeating unit (cell + coatings + interconnect)ASR below 0.7 ASR below 0.7 ΩΩ.cm.cm22

Degradation rate below 3 mDegradation rate below 3 mΩΩ.cm.cm22.khr.khr--11

For ISR at S/C = 2: 1.0 For ISR at S/C = 2: 1.0 ΩΩ.cm.cm22 and 5 mand 5 mΩΩ.cm.cm22.khr.khr--11

Gas tightness sealsGas tightness sealsExternal leakage below 0.5% of fuel/oxidant flow at External leakage below 0.5% of fuel/oxidant flow at ∆∆P = 20 mbarP = 20 mbarInternal leakage below 0.5% at Internal leakage below 0.5% at ∆∆P = 20 mbarP = 20 mbar

Main precondition: projected stack costs < 2500 Euro/kWMain precondition: projected stack costs < 2500 Euro/kWeeDevelopments based on costDevelopments based on cost--effective materials and manufacturingeffective materials and manufacturing


Phases and time scheduleEvaluation StateEvaluation State--ofof--thethe--Art componentsArt components

Identification of most critical componentsIdentification of most critical componentsReference for monitoring progressReference for monitoring progress

Basic componentsBasic components‘‘EasyEasy’’ fuels like Hfuels like H22 and reformateand reformateFocus is performance and endurance; subFocus is performance and endurance; sub--focus thermal and redox focus thermal and redox cyclingcycling

Advanced componentsAdvanced componentsComponents for internal reforming of natural gasComponents for internal reforming of natural gasFocus is reforming catalysis; subFocus is reforming catalysis; sub--focus S tolerance and low catalytic focus S tolerance and low catalytic activity for C depositionactivity for C deposition

Year 1 Year 2 Year 3 Year 4

1. Evaluation SoA

2. Basic components for 600oC, H2 and NG reformate

3. Internal reforming


Cell development lines

High(estHigh(est) performance and endurance at stationary operating conditions) performance and endurance at stationary operating conditionsLarge scale stationary systemsLarge scale stationary systemsASC: Ni based anode ASC: Ni based anode –– SZ electrolyte SZ electrolyte –– SrSr containing cathodescontaining cathodes

High robustness cellHigh robustness cellRedox, Sulphur and Chromium tolerance, reduced C Redox, Sulphur and Chromium tolerance, reduced C depostiondepostionFor cycling and offFor cycling and off--spec operating conditionsspec operating conditionsSmall scale stationary & transport applicationsSmall scale stationary & transport applicationsASC: titanate anode ASC: titanate anode –– SZ electrolyte SZ electrolyte –– nickelate cathodenickelate cathodeESC: Ni based anode ESC: Ni based anode –– 10Sc1CeSZ electrolyte 10Sc1CeSZ electrolyte –– nickelate cathodenickelate cathode

Performance and robustness Performance and robustness evaluated/demonstrated withevaluated/demonstrated with

HH22 (reformate) (reformate) Internal Steam Reforming of NGInternal Steam Reforming of NG


Main Achievements Main Achievements -- High Performance CellHigh Performance Cell

T 600T 600ooC, Fuel 60 HC, Fuel 60 H22 –– 40 H40 H2200


Cell optimisations / alternatives

200

300

400

500

600

700

800

900

1000

1100

1200

0 500 1000 1500 2000 2500

J (mA/cm2)

Volta

ge (

mV)

ASC*-GCO(PVD)-LSC

ASC-GCO(PVD)-LSC

ASC-GCO(RSDT)-LSC

ASC(impregnated Ni-8YSZ)-GCO(SP)-LSC

ASC(MgO-doped Ni-8YSZ)-GCO(SP)-LSC

ASC-GCO(SP)-LSC

0.33 Ωcm2

0.49 Ωcm2

0.34 Ωcm2

0.54 Ωcm2

0.25 Ωcm2

* improved tortuosity substrate

PVDPVD--GCO by FZJGCO by FZJ RSDTRSDT--GCO by NRCGCO by NRC MgOMgO doped AFL by DICPdoped AFL by DICP


Performance with ISR operation at 600oC

0

100

200

300

400

500

600

700

800

900

1000

1100

0 200 400 600 800 1000 1200 1400

J (mA/cm2)

Vol

tag

e (m

V

ASC-CGO(new, SP)-LSC

ASC-CGO(RSDT, NRC)-LSC

ASC-5%MgO_Ni/YSZ anode-8YSZ-CGO(new, SP)-LSC

0.42 ⎠ cm2

0.52 ⎠ cm2

0.57 ⎠ cm2

S/C = 2

Performance target (0.8 Performance target (0.8 ΩΩ.cm.cm22) ) amply met amply met Further activities will focus degradation at ISR conditionsFurther activities will focus degradation at ISR conditions

First shortFirst short--term results show values similar to Hterm results show values similar to H22 operationoperation

0.57 Ω.cm2

0.42 Ω.cm2

0.52 Ω.cm2


Performance and Endurance at ISR operationPerformance and Endurance at ISR operation

0

200

400

600

800

1000

1200

0 500 1000 1500 2000 2500 3000 3500

Time (hrs)

V(m

V; T

(°C)

; J(

mA/

cm2 )

V(mV)T(°C)J(mA/cm²)

ASC ASC -- MgOMgO--doped Ni/YSZ)/CGO(SP)/LSCdoped Ni/YSZ)/CGO(SP)/LSC

Uf = 20%

H2/H2O

60/40

Uf 20%ISR at S/C = 2, ISR at S/C = 2, UUff = 20%= 20%

20 m20 mΩΩ.cm.cm22/khr/khr4 mΩ.cm2/khr 46 m46 mΩΩ.cm.cm22/khr/khr

power failures


Combined thermal and redox cycle

0

200

400

600

800

1000

1200

1400

0 500 1000 1500 2000 2500 3000 3500

Time (hours)

V (m

V);

T (°

C);

J (m

A/cm

2 )

V(mV)T(°C)J(mA/cm²)

‘State-of-the-Art’ ASC with LSC cathode


Steel and contact coatingSteel and contact coating

Steels: 1.4509, Crofer22APU, 1.4016, 1.4521, 1.4435, 1.4845, 1.4Steels: 1.4509, Crofer22APU, 1.4016, 1.4521, 1.4435, 1.4845, 1.4520520

Contact coatings: LSC, LSCF, LSMC, LNF, PrContact coatings: LSC, LSCF, LSMC, LNF, Pr22NiONiO4+4+δδ

0,00

0,04

0,08

0,12

0,16

0,20

0,24

0,28

0,32

0,36

0,40

0 200 400 600 800 1000 1200

time (hours)

R (

ohm

.cm

²)

0

100

200

300

400

500

600

700

800

900

1000

tem

pera

ture

(°C

)

LSC

LNF

LSMC

LSCF

temperature

ET 41-22

Typical behaviour of these coatingsTypical behaviour of these coatings


0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

0 500 1000 1500 2000 2500 3000 3500

Time (hours)

ASR

(ohm

.cm

2 )

SRU Performance & EnduranceSRU Performance & Endurance

5.5 mΩ.cm2/khr; 0.2V%/khr 4.7 mΩ.cm2/khr; 0.2V%/khr

Crofer22APU/LNF/ASC: 3.2 V%/khr

Crofer22APU/Cr-barrier layer/LNF/ASC:

11 mΩ.cm2.khr-1, 0.5 V%/khr (3100 hrs)T = 600T = 600ooCC

Fuel 60 HFuel 60 H22 -- 40 H40 H2200

UUff = 20%= 20%

J = 0.4 A.cmJ = 0.4 A.cm--22Cell = ASC/CGO(SP)/LSCCell = ASC/CGO(SP)/LSC

Targets: ASR 0.7 Targets: ASR 0.7 ΩΩ.cm.cm22 ∆∆ ASR 3.0 mASR 3.0 mΩΩ.cm.cm22.khr.khr--11 equivalent to 0.15 equivalent to 0.15 V%/V%/khrkhr


HTceramix stack with SOF600 cells

0

1000

2000

3000

4000

5000

6000

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000

Time (hours)

V_st

ack

(mV)

0

100

200

300

400

500

600

700

800

J (m

A/c

m2 )

; T

(°C

)

V_STACKJ(mA/cm²)T_fuel in (°C)

1318 hrs - H21.2V%/khr;

732 hrs ISR1.2V%/khr

2000 hrs ISR1.0V%/khr

1st power failure

2nd power failure


Seals

Metal + mica seal for HTceramix stack

Crofer22APU

FillerBS

Bielem.

BMS glass matrix

Glas seals that settle at low temperatures

Mica seals cause corrosion of Crofer;

pre-oxidation seems to prevent this

Untreated steel Pre-oxidised


Powder manufacturing

Flame Spray SynthesisAdvantagesAdvantages

synthesis of synthesis of nanopowdersnanopowders-- high temperature & quenching high temperature & quenching

rate (250 000 K/s)rate (250 000 K/s)-- oonene--step synthesisstep synthesis

nono after treatmentafter treatmenthigh production rates (400 g.hhigh production rates (400 g.h--11))

Powders manufacturedPowders manufacturedCathode and contact coating materialsCathode and contact coating materials-- LSC, LSCF, LNFLSC, LSCF, LNF-- PrPr22NiONiO44, , NiNdNiNd22OO44, NiPr, NiPr22OO44

Electrolyte materialsElectrolyte materials-- CeCe0.0360.036YY0.0140.014ScSc0.6480.648ZrZr3.173.17OO7.57.5

Anode materialsAnode materials-- LaLa0.70.7SrSr0.20.2TiTi1.01.0OO33


Conclusions

Cells and cell componentsCells and cell components

Intermediate and final performance targets achievedIntermediate and final performance targets achieved

Degradation targets achieved, but further research required to eDegradation targets achieved, but further research required to explain xplain scatterscatter

Robust components identifiedRobust components identified

Interconnects and coatingsInterconnects and coatings

Resistivity and corrosion targets met based on 1000 hours testsResistivity and corrosion targets met based on 1000 hours tests

Development lowDevelopment low--temperature seal options on scheduletemperature seal options on schedule

Powder manufacturing fully operational and fulfilling project nePowder manufacturing fully operational and fulfilling project needseds

Independent EWGS establishedIndependent EWGS established

Workshop in Sofia on Development needs for SOFCWorkshop in Sofia on Development needs for SOFC

Possible solution for Luzern SOFC conference created: Swiss AG sPossible solution for Luzern SOFC conference created: Swiss AG supported upported by SOFC stakeholdersby SOFC stakeholders


Figure 6.3.1. Phasing and time schedule of the project with superimposed overall project milestones.

Good practices: targeted development approach


Good practices: targeted development approachBreakdown of overall target and time schedule towards final targBreakdown of overall target and time schedule towards final targetsets

Regular critical assessments based on achieved results (go/noRegular critical assessments based on achieved results (go/no--go)go)


Project flow sheet and go / noProject flow sheet and go / no--gogo

Reference cells and shorts

stacks

WP5 Testing

WP1 Cell components T1 Anode

T2 Cathode T3 Electrolyt

WP4 Powders

WP2 IC & Coatings

WP3 Seals

SRU

Short stack

T4 Cells

Critical assessment go / noCritical assessment go / no--gogo

FCTESTqa procedure


Good practices

Targeted development approachTargeted development approach

Regular/frequent meetings of all consortium partnersRegular/frequent meetings of all consortium partners4 times per year, plus some ad hoc meetings on specific 4 times per year, plus some ad hoc meetings on specific topicstopicsCritical assessments at each meetingCritical assessments at each meeting

-- Insufficient perspective Insufficient perspective --> stop> stop-- Sufficient perspective Sufficient perspective --> continue development> continue development-- Target achieved Target achieved --> integration next phase: cell, SRU, stack> integration next phase: cell, SRU, stack

Internal and Internal and ‘‘publicpublic’’ workshops, in conjunction with progress meetingsworkshops, in conjunction with progress meetingsDegradation (2x)Degradation (2x)Internal reforming Internal reforming Methods for determining performance of cell componentsMethods for determining performance of cell componentsEUEU--ASIA workshop in ChinaASIA workshop in China

Intensive email and telephone contacts of coordinator to partnerIntensive email and telephone contacts of coordinator to partnerssParticular on critical and complex issuesParticular on critical and complex issues

Exchange of staff between Exchange of staff between organisationsorganisations if there is a strong interdependencyif there is a strong interdependency

To keep partners involved and activeTo keep partners involved and active

Not for all of them the project is core businessNot for all of them the project is core business

The Integrated Project SOFC600 Low-Temperature SOFC developmentProject dataEU SOFC600 Project ConsortiumProject objectives and scopeMotivation for LT-SOFC = FCH-JU relevant topicsProject targetsPhases and time scheduleCell development linesMain Achievements - High Performance CellCell optimisations / alternativesPerformance with ISR operation at 600oCSlide 12Combined thermal and redox cycleSteel and contact coatingSlide 15HTceramix stack with SOF600 cellsSealsPowder manufacturingConclusionsGood practices: targeted development approachGood practices: targeted development approachProject flow sheet and go / no-goGood practices

Documents

The Integrated Project SOFC600 - Europa · 2018. 10. 22. · The Integrated Project SOFC600 Low-Temperature SOFC development General Assembly FCH-JU, Brussels, 26/27 October 2009