Richard LAUCOURNET Group head in the development of advanced materials for new energies CEA TOWARD A MORE EFFICIENT PROCESS TO RECOVER MATERIALS

Transcription

1 Richard LAUCOURNET Group head in the development of advanced materials for new energies CEA TOWARD A MORE EFFICIENT PROCESS TO RECOVER MATERIALS

2 STATE OF THE ART

3 The directive on recycling for A high environmental protection A restriction of heavy metals in batteries (Hg, Cd) A ban on the disposal of used batteries A collection organization A requirement for batteries recycling processes The Recycling Targets to be achieved are: 65% for lead-acid batteries with 100% for Pb 75% for Nickel-Cadmium batteries with 100% for Cd 50% for other types of waste batteries, amongst others Li-ion and Ni-MH batteries

4 NMC NCA LFP Cell materials 63,0 59,8 53,0 Cables 2,1 5,0 6,4 Frame 11,4 10,1 12,8 Casing (stainless steel) 19,9 24,1 26,7 Others NMC 3,6 1,0 NCA 1,1 % Cathode 31%wt. Electrolyte 17% Separator 8% Anode-Carbon 22% Cathode foil - Al 6% Anode foil - Cu 11% Cell case - Al 3% Others 1% LFP -Lithium -Cobalt -Nickel -Manganese -Aluminum -Iron -Phosphorus -Oxygen -Lithium -Cobalt -Nickel -Manganese -Aluminum -Iron -Phosphorus -Oxygen -Lithium -Cobalt -Nickel -Manganese -Aluminum -Iron -Phosphorus -Oxygen Buchert, M., Jenseit, W., Merz, C., Schüler, D.: Verbundprojekt: Entwicklung eines realisierbaren Recyclingkonzepts für die Hochleistungsbatterien zukünftiger Elektrofahrzeuge LiBRi: Teilprojekt: LCA der Recyclingverfahren. 2011

5 Used Batteries EoL Pyrolysis-Smelting C Dismantling Crushing Screening Slag Magnetic separation Alloys, Carbon & Oxide Exhaust Gas Treatment Acidic leaching Metals Oxides Refining Chemical separation Metals Oxides

6 Process name Enterprise Process Country - Fernwärme Wien No data A Umicore process Umicore Recycling Solutions Pyrometallurgy B Batrec-Sumitomo process Batrec Industrie AG Pyrometallurgy CH - Xstrada Pyrometallurgy CH Vacuum distillation Accurec Recycling GmbH Pyrometallurgy D - DK Recycling und Roheisen GmbH Pyrometallurgy D - Redux Pyrometallurgy D - Pilagest No data E Valibat process Recupyl Hydrometallurgy F - S.N.A.M Pyrometallurgy F - Euro Dieuze Industrie Hydrometallurgy F - AFE Group (Valdi) Pyrometallurgy F Sony-Sumitomo process Sony Corp. & Sumitomo Metals and Mining Pyrometallurgy J Co. - Dowa Pyrometallurgy J - Japan Recycle Center Pyrometallurgy J - Nippon Mining and Metals Pyro- & Hydrometallurgy J - SAFT AB Pyrometallurgy S AEA process AEA Technology Batteries - UK Toxco process Toxco Incorporation Hydrometallurgy USA - Salesco Sytems Pyrometallurgy USA - AERC Pyrometallurgy USA - OnTo Technology Solvent extraction USA - INMETCO Pyrometallurgy USA Ellis, T.W., Mirza, A.H.: Battery Recycling: defining the market and identifying the technology required to keep high value materials in the economy and out of the waste dump

7 Recycling efficiency is limited : For instance electrolyte recovery is not carried out at industrial scale Materials sorting is not really considered to concentrate high value elements at upstream level Alternative materials to LiCoO2 require some strong modifications of processes LFP, complex Li mixed oxides LTO

8 RECOVERY EFFICIENCY

9 Electrolyte recovery on used batteries Complete dissolution of electrolyte solution (EC, DMC, LiPF6) in water 1.Electrolyte extraction by aqueous solvent Reduction of LiPF6 decomposition into HF From 460 ppm to >100 ppm HF emission by using a fluoride absorbent in solution Organic solvent addition is required Several green solvents were evaluated with success 2.Extraction of aqueous phase & Li salt 3.Separation of organic solvents EC/DMC/ organic solvent separation

10 weight distribution Shredding & Materials Screening Particles size Li Ni Co Fe Al Cu C Low temperature pyrolysis Shredding with sieve Particles classification 0 > 5 mm> 2,5 mm> 1 mm> 500 µm> 300 µm> 200 µm> 100 µm< 100 µm High oxide/carbon fraction High metal fraction

11 Electrostatic Separation Experimental design Plates distance Plates inclination Applied voltage Rotor velocity conditions %Carbon powder (Al-Cu) metals/co Upper plate, experimental conditions A 73,8% 0,18 Upper plate, experimental conditions B 42,5% 0,07 Carbon rich fraction Oxide rich fraction Lower plate, experimental conditions B 23,4% 2,12 Metal rich fraction

12 NCA based electrode material Leaching study Temperature, Acid nature & concentration Ratio Solid/Liquid Ni & Co extraction by selective precipitation Precipitate Purity Li Ni Co Al Na Co 2 O 3, 3H 2 O ± ± ± ± ± 0.17 Ni(OH) ± ± ± ± ± 0.02 Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries M. Joulie, R. Laucournet, E. Billy Journal of Power Sources, Volume 247, 1 February 2014, Pages

13 LFP/LTO based material cell Selective dissolution of LFP/LTO by controlling ph value Reduce the amount of chemical products and by products (salts) Make easier the further chemical separation Li and Fe valorization by the synthesis of phosphate components in closed loop Li3PO4 FePO4, Fe3(PO4)2

14 By ELIBAMA project, new concepts of materials recovery/sorting/separation have been shown Electrolyte recovery Sorting of materials Shredding & Screening Electrostatic separation High value elements extraction with high purity Phosphate materials concerns

15 A complete recycling process has been designed including promising technologies from current SNAM process Materials valorisation efficiency up to 70% Production of Carbon Metals Metallic salts Dismantling Low temperature pyrolysis Shredding Screening Electrostatic separation Hydrometallurgy

16 FROM LAB TO PILOT SCALE

17 Development of investigated technologies at pilot scale (xx kg/h) Process flexibility required according to the batteries chemistry and the used batteries volume Evaluation of secondary raw materials recovered in various applicative streams

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19 The ELIBAMA project is granted by the European Commission under the Nanosciences, nanotechnologies, materials & new production technologies (NMP) Theme of the 7th Framework Programme for Research and Technological Development.