The Integrated Project SOFC600 - Europa · 2018. 10. 22. · The Integrated Project SOFC600...
Transcript of The Integrated Project SOFC600 - Europa · 2018. 10. 22. · The Integrated Project SOFC600...
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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)
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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)
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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
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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
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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
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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
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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
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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
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Main Achievements Main Achievements -- High Performance CellHigh Performance Cell
T 600T 600ooC, Fuel 60 HC, Fuel 60 H22 –– 40 H40 H2200
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Cell optimisations / alternatives
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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
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Performance with ISR operation at 600oC
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J (mA/cm2)
Vol
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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
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Performance and Endurance at ISR operationPerformance and Endurance at ISR operation
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Time (hrs)
V(m
V; T
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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
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Combined thermal and redox cycle
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Time (hours)
V (m
V);
T (°
C);
J (m
A/cm
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V(mV)T(°C)J(mA/cm²)
‘State-of-the-Art’ ASC with LSC cathode
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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
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time (hours)
R (
ohm
.cm
²)
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tem
pera
ture
(°C
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LSC
LNF
LSMC
LSCF
temperature
ET 41-22
Typical behaviour of these coatingsTypical behaviour of these coatings
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Time (hours)
ASR
(ohm
.cm
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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
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HTceramix stack with SOF600 cells
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Time (hours)
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ack
(mV)
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J (m
A/c
m2 )
; T
(°C
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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
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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
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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
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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
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Figure 6.3.1. Phasing and time schedule of the project with superimposed overall project milestones.
Good practices: targeted development approach
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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)
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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
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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