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D09.06.02.presentation D09.06.02.presentation Presentation Transcript

  • Innovative Solid Oxide Electrolyser Stacks for Efficient and Reliable Hydrogen production Towards durable and efficient high temperature steam electrolysis: the RelHy project Florence Lefebvre-Joud
  • Concept of RelHy RelHy Integration of 25-cell stack optimised materials and prototype, innovative design in a operated at reliable and efficient 800°C laboratory electrolyser prototype d te en m 5-cell tru I ns Stacks Design innovations Thermo mechanics, Tightness, SRUs Water management State of the Art • Good cells Cells Materials optimisation • No compromise Durable electrodes/electrolyte, Sealing, Material compatibility and stability, in stacks nor SRUs Cost effective materials and processes between durability and efficiency constituting a bridge between current good performing cells and reliable and efficient SOEC stack prototype operated at 800°C with cost effective materials. 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 2
  • SoA: Main results of Hi2H2 At the single cell level: -High performances obtained on SOFC cells operated in the electrolysis mode (ex: 2 A.cm-2 at 1.4V at 850°C) -Low degradation rate obtained up to 1500 hrs: ~3% per 1000 hrs at -0.25A/cm² and -0.5A/cm² , 800-850°C and absolute humidity up to 70%. -Degradation rate observed to decrease with decreasing the current density and with increasing i-V curves obtained at DTU-Risoe on 5x5cm2 solid oxide cells temperature. Compromise between the cell M. Mogensen, S. H. Jensen, A. Hauch, I. Chorkendorff, and T. Jacobsen. Lucerne (2006). performance and its durability required Jensen, S. H., Larsen, P. H., and Mogensen, M. Inter. J. Hydrogen Energy (2008). 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 3
  • SoA: Main results of Hi2H2 At the Single Repeating Unit and short stack levels: -Degradation rate ~ 10% per 1000hrs obtained with complete SRU at -0.5A/cm² and 850°C (i.e. x3 compared to single cells) -Degradation rate ≥ 15% per 1000hrs obtained with 5-cell SOEC Stack at -0.3A/cm², 800°C, 50% absolute humidity and 50% steam to H2 conversion rate over test duration of 2000 hrs. -Adding a coated interconnect to the O2electrode lower cell performance and lower the degradation rate of the cell Major influence of stack environment on cell performance and durability 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 4
  • SoA: Results at CERAMATEC / INL Ageing curve at 800-830°C Degradation rate ~ 10% per 1000hrs 25-cell Ceramatec Stack Similar trends obtained in the US C. Stoots, J.E. O’Brien, G.L. Hawkes, J.S. Herring, program on larger stacks J.J. Hartvigsen, Workshop on HTE, Roskilde, Denmark, 2006 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 5
  • SoA: What about SOFC performance/durability compromise ? TOFC 75 cell stack concept • SOFC stacks 1 - 10kW currently tested with continuously increasing performances and durability (Real SOFC project, SECA prog., etc.) • Ex: TOFC short stack operated 13000 hrs with an overall voltage degradation rate ~ 1% per 1000 hrs, • Ex: TOFC 50 or 75-cell stacks (≥1 kW) Development of metallic interconnects tested at FU up to 92% with with ceramic coating: ASR~0.5Ω.cm-2 degradation rates below 0.5% per 1000 hrs, especially by improvement of metal alloy interconnects and coatings Major progresses achieved regarding Short stack ageing test performance / durability compromise for 13000hrs in SOFC environment I.C. Vinke, R. Erben, R-H Song, J. Kiviaho Lucerne (2006) N. Christiansen, J.B. Hansen, H. Holm-Larsen, M. Linderoth, P.H. Larsen, P.V. Hendriksen, M. Mogensen Lucerne (2006) 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 6
  • Ambition of the RelHy projet RelHy 25-cell stack Integration of optimised materials and • Take advantage of SOFC prototype, innovative design in a reliable and efficient know-how (cell materials, operated at 800°C laboratory electrolyser metallic interconnects and prototype nt ed ceramic coating, seals, etc.) e m 5-cell ru I n st Stacks • Transfer the SOFC Design innovations Thermo mechanics, Tightness, optimisation methodology to SRUs State of the Art Water management SOEC • Good cells Cells Materials optimisation • No compromise Durable electrodes/electrolyte, Sealing, Material compatibility and stability, in stacks nor SRUs Cost effective materials and processes between durability and efficiency Acheive high cell performances at 800°C (~0.03 gH2/cm2/hr, i.e. ~ 1 A/cm2 at ≤1.5V with water conversion >60% ) Decrease degradation rate of SRUs to ~1% per 1000 hr. Integrate most promising materials and design innovations at laboratory scale in a 25-cell electrolyser stack prototype to be operated until the end of the project. 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 7
  • HTSE specifications in 2 cases coupled to nuclear and to renewable energy Nuclear Wind Short Medium Short Medium Degradation (µ/h) 10 5 15 5 0,7% per 1000hrs at 1.5V Lifetime (hrs) 10 000 20 000 16 000 40 000 Thermal cycles/year 2 5 7 14 Voltage/cell (V) 1.5 1.45 1.7 1.55 Current (A/cm2) 1.5 2.0 1.0 1.5 Pressure max (bar) 50 50 20 30 Active Area (cm2) 400 800 300 600 Start up from 600 C <4h < 4h <2 < 1h Turn down to 20 % ? ? < 2 min. < 30 sec. Pertinence of RelHy target: step from current SoA towards industrial application (Under pressure operations to be addressed) 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 8
  • Approach and project structure Testing & Material Prototyping Analysis RelHy Innovative Laboratory Modelling and simulation Electrolyser Prototype Competitiveness assessment Key words: significance and reproducibility of results between partners common single repeating units (SRUs) and short stacks common testing and analysing protocols definition of a reference performance/durability level to compare to 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 9
  • Reference material selection • Cell materials – for the 2 geometries ESC and CSC ESC (ECN) CSC (DTU Risoe) – Electrode H2 : Ni-CGO - Electrode H2 : Ni-YSZ – Electrolyte : 3YSZ - Electrolyte : 8YSZ – Electrode O2 : YDC-LSCF - Electrode O2 : YSZ-LS – Active surface : 100 cm² - Active Surface : 100 cm² •Interconnects and coating • Seals Crofer + LSM coating on the O2 side Pre-sintered glass bars for and NiO coating on the H2 side reproducibility during assembly LSM coating oxidant side NiO coating fuel side 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 10
  • SRU and short stack development Criteria for SRU geometry: • Able to integrate ESC and CSC • « Easy » to assemble • « Easy » to model upper interconnect • Close to standard TOFC geometry cell (120mm by 120mm) pre-sintered Short stack: glass bars • Based on TOFC Alpha standard mica foil design, • Integrates CSC (DTU Risoe) • Modified to integrate ESC from lower interconnect ECN as well (150mm by 150mm by 10mm) metallic bars for current distribution 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 11
  • SRU ready for testing H2/H2O side Air side 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 12
  • Testing protocol definition • Heating, Sealing and Ni reduction following cell manufacturer recommendations • Test start-up – OCV stabilisation at 800°C under H2 with 3 vol.% H2O • Operation in fuel cell mode at 800°C to check SRU performance – EIS at OCV , j-V curves and EIS = f(j) • Operation in Electrolysis Mode at 800°C: – Change of humidity 50 vol.% Hum (H2 10%/N2 40%) and stabilisation at OCV, – EIS at OCV, j-V curves V≤1.5V, EIS = f(j), – Change of humidity 70 vol.% Hum (H2 10%/N2 40%) and stabilisation at OCV, – EIS at OCV, j-V curves V≤1.5V, EIS = f(j), – Change of humidity 90 vol.% Hum (H2 10%/N2 40%) and stabilisation at OCV, – EIS at OCV, j-V curves V≤1.5V, EIS = f(j), – Back to 50 vol.% Hum to change operation temperature to 750°C • Operation in Electrolysis Mode at 750°C • Operation in Electrolysis Mode at 850°C: • Durability test at 800°C (-1 A/cm2 under 90 vol.% Hum/10 vol.% H2) 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 13
  • Test matrix Partner 1 Partner 2 Partner 3 Partner 4 Reference test Campaign (on going) - Reference ESC - Reference ESC - Reference CSC - Short stack with - Reference CSC + ageing - Reference CSC CSC + ageing + ageing - with Sh. Stack - Short stack with - - coating ESC + ageing - Reference ESC with Sh. Stack coating Optimisation test campaign: with effect and reproducibility measurement on: - Cathode material - Electrolyte material - Coating material - Sealing material 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 14
  • ESC – Results in the SOFC mode 1,2 0,35 0,3 1 0,25 0,8 P (W.cm-2) 0,2 E (V) 0,6 0,15 0,4 0,1 800°C, 0,2 Air=1200 mL/min, 0,05 H2=1200 mL/min 0 0 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 i (A.cm-2) Satisfactory tightness Satisfactory cell ASR (0.9 Ω.cm2 @ 0.7 V) 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 15
  • ESC – First Results in the HTE mode 1,6 50% H2O-10% H2-40% N2 1,5 70% H2O-10% H2-20% N2 1,4 1,3 90% H2O-10% H2 E (V) 1,2 1,1 1 800°C, Air=1200 mL/min, 0,9 H2O/H2/N2=1200 mL/min 0,8 I ( A.cm-2) -0,8 -0,6 -0,4 -0,2 0 i (A.cm-2) OCV in agreement with pH2O ASR ranging between 0.8 and 0.9 Ω.cm2 @ 1.32 V First results not far from RelHy target on performance 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 16
  • ESC – Summary of First results in the HTE mode at 800°C Fuel Utilization / ASR (ohm.cm2) Water conversion Mélange @ H2 Production Production H2 Qtot=1200 @ 0.7V SOFC @ 1.32V @ 1.5V mL/min 0.7V SOFC, 1.32V EHT 1.32V et 1.5V SOFC 100% H2 0.9 ± 0.01 25% 50%H2O - 50 A 70 A EHT 0.86 ± 0.03 62% - 87% 10%H2- 40%N2 18.7 mg/cm2/h 26.2 mg/cm2/h 70%H2O - 53 A 75 A EHT 0.84 ± 0.01 47% - 67% 10%H2- 20%N2 19.8 mg/cm2/h 28 mg/cm2/h 90%H2O - 56 A 80 A EHT 0.77 ± 0.02 39% - 55% 10%H2 20.9 mg/cm2/h 29.9 mg/cm2/h 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 17
  • Conclusions RelHy project: aims at reaching a pertinent compromise between performance and durability Quantified targets in agreement with industrial specifications in two cases (nuclear and renewable coupling) Experimental tools (SRUs and short stacks), protocols and test matrix developed and available Reference performances and reproducibility being established Modelling tools from the microstructure level to the complete SRU level under construction Material developments (cathode, electrolyte, interconnect coating and seals) for second iteration under progress 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 18
  • ☺Acknowledgment to the « RelHy team » Gislaine Ehora and Jacob Bowen at DTU Risoe Jan Peter Ouweltjes and Bert Rietveld at ECN Annabelle Brisse and Mohsine Zahid at EIfER Qiong Cai and Nigel Brandon at Imperial College Thomas Nietsch at Helion Jens Ulrik Nielsen at TOFC and John Boegild Hansen at Haldor Topsoe Marie Petitjean, Hervé Sassoulas, Gatien Fleury, ….. at CEA 3rd International Workshop on High Temperature Water Electrolysis / Karlsruhe Germany / 9-10 June 2009 19