Electrochemistry at Haldor Topsøe SOEC and Battery Materials

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1 Electrochemistry at Haldor Topsøe SOEC and Battery Materials Søren Dahl, Electrochemisty R&D, Haldor Topsoe CINF Summer School Reactivity of nanoparticles for more efficient and sustainable 1 energy conversion - IV

2 Agenda Electrochemistry at Haldor Topsoe Solid Oxide Electrolysis Cells Optimal integration in the Energy system Battery materials Automotive batteries for the next 10 years Na-ion: Layered structure Li-ion: High voltage spinel 2

3 More wind and solar power a challenge to balance A need for technologies to balance fluctuating wind and solar power International integration of energy systems Integration with gas, heat and transport Storage 3

4 Haldor Topsoe projects with conversion and storage of electrical energy Hydrogen/CO production using Solid Oxide Electrolysis Cells Based on many years of experience with developing Solid Oxide Fuel Cells and systems Materials for producing batteries for automotive, energy storage etc. Based on competencies with development and production of heterogeneous catalysts Catalysts for low temperature electrochemical synthesis of chemicals. E.g. CO + 2CH 3 OH = (CH 3 O) 2 CO + 2H + + 2e - instead of CO + 2CH 3 OH O 2 = (CH 3 O) 2 CO + H20 Collaboration with Copenhagen University, Technical University of Denmark, Stockholm University, and HPNow 4

5 5 Solid Oxide Electrolysis Cells Optimal integration in the Energy system

6 Solid Oxide Fuel Cell and Electrolyser H 2 + CO + O 2 SOFC SOEC H 2 O + CO 2 + electric energy ( G) + heat (-T S) SOFC SOEC H 2 H 2 O H 2 O H 2 H 2 + O 2- H 2 O + 2e - O 2- ½O 2 + 2e - O 2- H 2 O + 2e - H 2 + O 2- O 2- O 2-2e - +½O 2 ½O 2 ½O 2 6

7 Solid Oxide Cell Development from 1989 to 2013 ESC ASC MSC LSCF CGO YSZ or SSZ FeCr 3G metallic support LSM YSZ Ni/YSZ LSM YSZ Ni/YSZ 1G 2.XG 2.5G Cell generations with ceramic support LSCF CGO YSZ or SSZ Ni/YSZ 1000 o C 850 o C 750 o C 600 o C Performance Robustness Cost reduction 7

8 Electrolysis with SOEC Very flexible and efficient in continuous operation Power Steam CO 2 Heat SOEC CO CO 2 H 2 Syngas Well-known Catalysis Hydrogen SNG Methanol DME Gasoline Diesel 8

9 Biogas upgrade by means of SOEC CH 4 + CO 2 + 3H 2 O + El 2CH 4 +H 2 O + 2O 2 Biogas: 50-80% CH 4 Rest CO 2

10 Methanation generates a lot of heat CO 2 + 4H 2 CH 4 + 2H 2 O (- H = 165 kj/mol) Syngas = CH 4 + heat Energy: 100% = 80% + 20% Heat 20% 100% CH 4 80%

11 Biogas to SNG via SOEC and methanation of the CO 2 in the biogas: SOEC Oxygen Biogas Steam Methanator Water SNG Condensate

12 Exergy Flows in CO 2 case

13 Idea : Biogas directly to CH 4 via SOEC SOEC Oxygen Biogas Methanator Steam Water SNG Condensate 13

14 Exergy Flows in CO case

15 New EUDP project 50 kw SOEC and 10 Nm 3 /h methane Participants: Haldor Topsøe A/S Aarhus University HMN Naturgas Naturgas Fyn EnergiMidt Xergi DGC PlanEnergi Ea Energianalyse Coordinator: Duration: June March 2017 Project sum: 5.3 mio Location: Foulum

16 16 Battery Materials Automotive batteries for the next 10 years

17 Energy Content of Energy Carriers 17

18 Batteries beyond Li-ion Base on conversion materials Li + e - Lithium-air battery O 2 Li 2 O 2 e Voltage [V] Mixed potential Resistive loses 2.0 Capacity 18

19 Energy Content of Energy Carriers Planned to be used for a lot of BEVs in the next 10 years! 19

20 Li(Na)-ion - Batteries based on insertion materials Electrolyte e - e - Li + Anode Current collector Cathode Current collector Discharge Charge Anode SEI-layer Separator Cathode 20

21 Cathode materials LiFePO 4 LiNi 1/3 Mn 1/3 Co 1/3 O 2 Na-ion material LiMn 2 O 4 LiNi 0.5 Mn 1.5 O 4 21 Production similar to production of heterogeneous catalysts

22 Material properties Battery performance Material properties Which material Metals, anions, structure Phase purity Crystal defects Crystal size and shape Secondary particles Connectivity between crystals Porosity Size and distribution Surface area Doping/Contamination Surface modification/coating Battery performance Energy density (mass/volume) Power density Price Stability Safety... 22

23 Inside a battery Material properties Negative electrode Soaked in Which material electrolyte Metals, anions, structure Phase purity Crystal defects Crystal size and shape Secondary particles Connectivity between crystals Porosity Size and distribution Surface area Doping/Contamination Surface modification/coating Positive electrode Li + Li + Positive electrode Current collector Active material Conductive carbon Binder 23 Separator e -

24 Material properties Battery performance Batteries are meta-stable Side reactions limits life and safety Electrolyte decomposition Electrochemical (Outside stability window) Chemical (In charged state active materials are very reactive) Material corrosion 24

25 Material properties Battery performance Material properties Which material Metals, anions, structure Phase purity Crystal defects Crystal size and shape Secondary particles Connectivity between crystals Porosity Size and distribution Larger surface area Doping/Contamination Surface modification/coating Battery performance Lower Energy density (mass/volume) Better Power density Higher price Lower Stability Less Safe.. 25 Trade-offs

26 Topsoes goal is to develop optimal battery materials with the optimal production processes

27 Where to focus? Materials For Li-ion New technologies LiNi 0.5 Mn 1.5 O 4 Li + e - Li(Ni 1/3 Co 1/3 Mn 1/3 )O V 140 mahg -1 O 2 Li 2 O 2 e - Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 Sulfur Lithium air 3.6 V 170 mahg V 210 mahg -1 Sodium 27

28 Price is very important! Price and energy capacity 2022-target: 125 $/kwh Kilde: DOE præsentation af David Howell, Source: Axeon, Our guide to batteries, 2012

29 Battery cathode materials at Haldor Topsoe Future drop-in materials with cost perspective Added advantages: Faradion Na-ion: Safety. Can be stored fully discharged High voltage Li-ion: Fast discharge 29

30 It is important to look at price of cell it is not proportional to price of cathode material 150 $/kwh 100 $/kwh Cost of Cell Components 50 $/kwh Other Current collector Electrolyte Anode Cathode 0 $/kwh NMC LFP LNMO NAB 30

31 Cobalt The problem with cobalt 31

32 Increased demand for Lithium can also cause problems Spot market price in China 32

33 33 Battery Materials Na-ion: Layered structure

34 Na x MeO 2 : Layered structure Much more rich structural chemistry than lithium analoges O3 P2 Na\Fe-Mn- Co O3 P3 P3+P2 (10%) 0.7 O3 P2+P3 (5%) P2 0.5 O3 P2 P2+ Fe 2 O 3 (2%) Data from Steinar Birgisson et al. Aarhus University 34

35 Na-ion A collaboration with Faradion a British start-up Lithium Natrium Molar mass 6.9 g/mol 23.0 mol/g Potential vs. Li/Li + 0 V 0.3 V Abundance < 50 ppm 2.6 % Energy density comparable to Li-ion based on LFP Anode compatible with Al lower cost than Cu for Li-ion No Cobalt or Lithium Drop-in material Can be discharged to 0 V safer to transport Low tendency for thermal run away - safe 35

36 Faradion materials 5 4 Cell Voltage [V] Gen#3 Gen#2 Gen# Cathode Specific Capacity [mah/g] 36

37 ARC: Self-heating Rate 37

38 Optimized 418 Wh E-Bike Pack Total Pack Weight = 5.1 kg 82 Wh/kg; fully packaged Pack Dimensions: 36 cm (L) x 14 cm (W) x 5 cm (D); Volume = 2.5 litres

39 39 Battery Materials Li-ion: High voltage spinel

40 Where to focus? New materials For Li-ion New technologies LiNi 0.5 Mn 1.5 O 4 Li + e - Li(Ni 1/3 Co 1/3 Mn 1/3 )O V 140 mahg -1 O 2 Li 2 O 2 e - Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 Sulfur Lithium air 3.6 V 170 mahg V 210 mahg -1 Sodium 40

41 Development Haldor Topsoe LiNi 0.5 Mn 1.5 O 4 High conductivity Relative small and isotropic volume change Problem with electrolyte degradation and materials corrosion. Simple working hypothesis: We must produce, Very dense particles with very low surface area and smooth surface 41

42 The material Phase purity Difractogram and phase purity 42

43 The material Uniform and spherical secondary particles Tap density: 2.3 g/cm3 Tunable size distribution BET surface area: 0.3 m2/g 20 µm 20 µm µm 6 µm < D50 < 25 µm Narrow or broad 10 µm

44 Li 1.0 Ni 0.5 Mn 1.5 O 4 High voltage 0.5C 1C 2C 1C 5C 10C 0.5C charge and 0.5C discharge 44

45 Li 1.0 Ni 0.5 Mn 1.5 O 4 High voltage g kg t kt Fade rate: 0.09% per cycle at 55 C 0.5C charge and 0.5C discharge 45

46 Next generation - Still room for improvement Electrolyte degradation Coulombic efficiency below 100% - electrochemical Chemical reactivity in charged state Corrosion of the material Ni and Mn found on anode Ni:Mn ratio the same as in material 46

47 Strategies for increasing stability/lowering reactivity of Battery Materials Doping Al in NCA (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), Li and Al in LMO (LiMn 2 O 4 ), etc Relative large amounts needed There can be drawbacks, e.g. lower capacity Electorlyte engineering Increase stability by change of solvent Additives that form protective layers Surface coating AlF 3, Li 3 PO 4, ZrO 2... etc 47

48 Example of surface coating Fig. 3. TEM images of (a) pristine LiNi 0.5 Mn 1.5 O 4, (b) ZrP 2 O 7 -coated LiNi 0.5 Mn 1.5 O 4, and (c e) ZrO 2 -coated LiNi 0.5 Mn 1.5 O 4. H.M. Wu et al. / Journal of Power Sources 195 (2010)

49 Inspiration from catalysis Only passivate the most active sites on the surface of the Battery Material to prevent reactions and corrosion Ni 4+ 49

50 Take-home messages By proper process integration high temperature electrolysis can be very exergy efficient in transforming electrical energy into chemical energy Commercial batteries will in the next 10 years be dominated by insertion materials, a huge growth is foreseen due to automotive There can be shortage of Co, that can drive change of preferred battery materials Li ion: high voltage spinel Na ion: layered structure It is a trade off between different performance parameters to design optimal battery materials and batteries 50