Electrochemical hydrogen production and utilization for a sustainable society

Transcription

1 1/ 재벨과협춘계학술대회 Electrochemical hydrogen production and utilization for a sustainable society Centre for Surface Chemistry and Catalysis KU Leuven Kim MinJoong

2 Research experiences 2/38 Design of electrochemical materials for electrodes PEMFC Water electrolysis Li/Na ion batteries CO 2 conversion

3 Research experiences 3/38 Hydrogen production On-board hydrogen production from reactive metals (Al, Mg) Design of efficient catalysts for water electrolysis Hydrogen utilization Design of Non-precious metal catalysts for PEMFCs Fabrication and optimization of MEAs PEMFCs Corrosion-resistant coating for STS bipolar plate for MCFCs

4 Global Warming 4/38 Global warming consequences source: Job One for Humanity

5 Renewable Energy 5/38 Renewable Energy 2014, IEA

6 Hydrogen based sustainable society 6/38 Vision of a hydrogen based sustainable society source: Toyota

7 Electrochemical Hydrogen Cycle 7/38 Renewable energy Water electrolysis H 2 + O 2 Fuel Cell electricity electricity Hydrogen as an energy storage medium H 2 O Clean energy conversion device

8 Electrochemical Cell 8/38 x e - Z Z x+ + x e - Y x+ + x e - Y Anode : oxidation reaction Ion conducting medium Cathode : reduction reaction

9 Fuel Cells Fuel cell e - e - Load e - PEMFC PAFC Load e - e - 9/38 Oxidation reaction H 2 O 2 Anode Ion channel Electrolyte H 2 O Cathode Reduction reaction H 2 O 2 Anode Cathode Anode H + Electrolyte Cathode H 2 O : H 2 2H + + 2e - : 1/2O 2 + 2H + + 2e - H 2 O MCFC e - e - Load e - SOFC e - e - Load e - H 2 O 2 CO 2 H 2 O Anode Cathode Anode CO 3 2- Electrolyte Cathode CO 2 : H 2 + CO 3 2- H 2 O + CO 2 + 2e - : 1/2O 2 + CO 2 + 2e - CO 3 2- H 2 O 2 H 2 O Anode Anode Cathode O 2- Electrolyte Cathode : O 2- + H 2 H 2 O + 2e - : 1/2O 2 + 2e - O 2-

10 Li-ion Battery vs. Fuel Cell 10/38 Li-ion battery Fuel cell Cathode : LiCoO 2 Li 1-x CoO 2 + xli + + xe - Cathode : ½ O 2 + 2H + + 2e- H 2 O Anode : C + xli + + xe - LiC x Anode : H 2 2H + + 2e - Electric energy charge discharge Chemical energy ( Energy storage ) Chemical energy ( Fuel supply ) Electric energy Energy storage device Energy conversion device

11 Combustion Engine & Thermal Power Plant 11/38 Internal combustion engine Thermal power plant Gasoline or Diesel (Chemical energy) Mechanical Power (Mechanical energy) Coal or Natural gas (Chemical energy) Electric Power (Electric energy)

12 Internal Combustion Engine vs. Fuel cell 12/38 Internal combustion engine Oxidizer (Air) SO x, NO x ; air pollutant Heat Fuel combustion Thermal energy Mechanical energy (Chemical energy) Electric energy Fuel cell Oxidizer (Air) Heat Fuel (Chemical energy) Electrochemical reaction Electric energy H 2 O High efficiency No air pollutants emission No noise

13 Single Cell of Fuel Cell 13/38 Single cell H 2 e - Air Electrode (cathode, anode) - Electrochemical reaction site Ion channel Electrolyte - Ion conductive channel Bipolar plate Bipolar plate Anode Electrolyte Cathode Bipolar plate - Current collector

14 Types of Fuel Cells 14/38

15 Fuel Cell Stack 15/38 Fuel cell stack O 2 H 2 O 2 H 2 한국과학기술연구원 (7 kw; KIST MEA) Electrolyte Electrolyte Cell Cell Cell Cathode Anode Cathode Anode 1.00 V 1.00 V 2.00 V Cell Cell Cell Battery of laptop

16 Applications of Fuel Cells 16/38 PEMFC PAFC MCFC SOFC Advantages Low operating Temp High power density Various application Long life time Reforming gas uses Fuel flexibility Inexpensive catalyst Waste heat uses Wet - Sealing Fuel flexibility Inexpensive catalyst Waste heat uses No electrolyte vaporization Disadvantages CO poisoning Water management Cooling system Low power density < PEMFC Long warm-up time > PEMFC Cathode polarization Severe corrosion Long warm-up time Limited life time Sealing Thermal stress Long warm-up time Expensive ceramic Micro fuel cell PEMFC PAFC SOFC MCFC ~ mw 3 W 50 W 2 kw 100 kw ~ MW MEMS Cellular phone Lap-top computer RPG Transportation Power plant

17 Fuel Cell Electric Vehicle 17/38 Power Hydrogen Tank Battery Driving Range Max. Speed 100 kw bar 24 kw 415 km 160 km/h 0 to 100 km/h 12.5 s Mileage 76.8 km/kg Nexo 2018

18 Fuel Cell Electric Vehicle 18/38 미국 1838 대판매 미국 2455 대판매

19 Nexo vs. Mirai vs. Clarity 19/38

20 Technical Issues in Fuel Cell Electric Vehicles 20/38 Cost <Automotive FC system cost> (high-volume production, 500,000 units/year) Cost target Source: 2015 DOE Annual Report Fuel cell vehicles equip generally 100 kw system. $3,000 for FC system of a vehicle. Comparable with the price of ICE.

21 PEMFC Stack Cost Breakdown 21/38 Pt/C catalyst 49 % 2 3 nm Pt nanoparticles Amorphous carbon support Source: 2015 DOE annual merit review

22 Towards Pt-free Electrodes 22/38 Low Pt catalysts Non-precious metal catalysts PGM-M Alloy PtNi, PtCo, PtFe.. PdIr, PdCu, PdY.. Core-Shell De-alloyed Organometallic Me(Fe,Co..)-N-C Me(Fe,Co..)-polymer Co 9 Se 8, Co 3 S 4 FeS 2, W-Co-Se Chalcolgenide Metal-oxide M = Ni, Co.. NSTF/MSTF Metal oxide / C Perovskite type Metal-free N, B, P, S, etc.. - CNT, CNF - Graphene

23 Non-precious Metal Catalysts for PEMFC 23/38 Non-precious metal catalysts Co-phthalocyanine Highly Porous Me-N-C Nature, 201 (1964) Science, 324 (2009) 71 Iron-porphyrin based PANI derived Me-N-C Electrochimica Acta, 54 (2009) 6622 Science, 332 (2011) 443

24 Co-N-CNF Catalyst for PEMFC 24/38 Co-N-CNF for ORR Electrospinning PAN + Co solution Morphology BET : m 2 g -1 Pyrolysis 900 Inert gas Co ORR activity ORR pathway ΔE 1/2 = 44 mv 0.1 M KOH 1600 rpm J. Mater. Chem. A, 2015, 3,

25 Fe-N-S-Graphene Catalyst for ORR 25/38 Fe-N-S-Graphene for ORR Ball-milled graphene ORR activity ΔE 1/2 = 12 mv 0.1 M KOH 1600 rpm Ball-milling & Pyrolysis 700 Inert gas Work-function vs. ORR N S Mapping image Work-function ORR activity J. Mater. Chem. A, 2016, 4,

26 Technical Issues in Fuel Cell Electric Vehicles 26/38 Durability Current status: 3,500 hr vs target of 5,000 hr Status 2017 Target <Automotive FC system durability 2) > (projected, under real-world conditions) Lifespan target Source: 2015 DOE Annual Report 5,000 hours corresponds to roughly 150,000 miles of driving. vs. 60,000 hours for residential system. Comparable with the lifespan of ICE.

27 Degradation Mechanism of Pt/C Catalyst 27/38 Short-range Ostwald ripening Pt 2+ Pt 2+ Pt dissolution Pt 2+ Carbon corrosion

28 Inorganic Support for Pt Nanoparticles 28/38 Sci. Rep., 2017, 11, Nanoscale, 2015, 7,

29 Hydrogen Stations in Korea 29/38 In operation Out of operation Under construction 11 stations in operation, 2 in construction (700 bar) 지역 기관명 상업용 압력 (bar) 수소공급 정부지원사업명 1 경기, 용인 현대차 부생수소 - 2 인천, 송도 한국가스공사 NG개질 충전소기술개발사업 3 서울, 신촌 GS칼텍스 NG개질 충전소기술개발사업 4 대전, 유성 SK에너지 LPG개질 충전소기술개발사업 5 제주, 김녕 현대차 수전해 연료전지차실증사업 1단계 6 경기, 화성 현대차 울산, 매암 동덕산업가스 연료전지차실증사업 1단계 8 여수, 중흥 SPG케미칼 부생수소 연료전지차실증사업 1단계 9 경기, 화성 KATRI 안전설계연구 10 서울, 양재 현대차 연료전지차실증사업 1단계 11 서울, 상암 서울시 LFG개질 - 12 전북, 부안 KIER 수전해 - 13 울산, 매암 동덕산업가스 700 부생수소 연료전지차실증사업 2단계 14 대구, 서변 이엠코리아 700 수전해 대경광역경제권선도사업 15 광주 부생수소 환경부보급사업 16 충남 환경부보급사업

30 Hydrogen Station Road Map in Japan 30/38 Source: Global auto news

31 Hydrogen Production Paths 31/38

32 Hydrogen Production from Water Electrolysis 32/38 Wind power-assisted water electrolysis system in Germany

33 Hydrogen Production Cost 33/38 source: Ibid.

34 Stack Cost Breakdown 34/38 Catalyst: Pt-group Materials Anode: Ir, Ru Cathode: Pt

35 Co-Mo 2 C Catalyst for Water Electrolysis 35/38 Co-Mo 2 C for OER Co-Mo 2 C complex SEM BET = m 2 g -1 OER activity in alkaline media 0.1 M KOH 0.1 M KOH 10 ma cm -2 = Co-Mo 2 C (358 mv) < RuO 2 < Co << Mo 2 C Appl. Catal. B: Environ., 2018, 227C,

36 Co-P Foam for Water Electrolysis 36/38 CoP Foam for HER CoP Foam fabrication H 2 bubble CoP 1. H 2 production 2H + + 2e - H 2 E o = V SCE 2. CoP deposition Co e - Co H 2 PO H + + 2e - P + 2H 2 O E o = V SCE E o = V SCE Morphology HER activity 0.5 M H 2 SO 4 Highly porous CoP foam 10 ma cm -2 = CoP Foam (50 mv) Pt/C (45 mv) J. Mater. Chem. A, 2016, 4,

37 Renewable Hydrogen Cycle for Sustainable Society 37/38 Source: RH 2 network

38 감사합니다. 38/38