Research progress on recovering the components of spent Li-ion batteries
摘要: 随着近年来电动汽车的蓬勃发展，锂离子电池的使用量以及退役量都在逐年增长，随之而来的是废旧锂离子电池带来的环境污染以及资源浪费问题。目前商用锂离子电池多由过渡金属氧化物或磷酸盐基正极、石墨基负极、含有害锂盐的有机电解质、聚合物隔膜以及塑料或金属外壳组成，在电池退役后，其中的诸多贵金属以及石墨等都具有较高的回收价值。本文对锂离子电池工作原理及组成结构、废旧锂离子电池全组分回收等研究现状进行了综述，着重介绍废旧锂离子电池中正极材料、负极材料以及电解液回收的研究进展，从回收成本和二次污染等方面概述了不同方法所遇到的问题，最后对未来的发展提供了一些思路。Abstract: With the recent rapid development of electric vehicles, the use and decommissioning of Li-ion batteries have increased, causing environmental pollution and the waste of valuable materials in spent batteries. Commercial Li-ion batteries are mostly composed of transition metal oxide or phosphate-based cathodes, graphite-based anodes, organic electrolytes containing harmful lithium salts, polymer separators, and plastic or metal shells. After the battery is retired, many precious metals and graphite have a high recycling value. We review the current status of research on recovering these components with an emphasis on the leaching and separation of cathode and anode materials, and electrolytes in these batteries. The problems encountered in the different methods are outlined in terms of recycling cost and secondary pollution. Future research trends are outlined for the commercial full recovery of spent Li-ion batteries.
Figure 1. (a) Inventory of electric vehicles in various countries in recent years and (b) registered number of electric vehicles in various countries in recent years.
Figure 2. The components of LIBs and the weight distribution of each part (Reprinted with permission).
Figure 6. (a) Working principle of the Falcon centrifugal separator (Reprinted with permission). (b) TG-DSC curve of cathode active powder baked at different temperatures (Reprinted with permission). (c) Process of separating positive electrode material and aluminum foil with deep eutectic solvent (Reprinted with permission).
Figure 7. (a) Schematic diagram of the leaching mechanism of reducing agent LiFePO4 (Reprinted with permission). (b) Comparison of the concentration of inorganic acid and organic acid on the leaching rate of spent LIBs (Reprinted with permission). (c) The influence of the oxalic acid concentration on the reaction efficiency of LiCoO2 (Reprinted with permission).
Figure 8. (a) Comparison of H2SO4 produced by pH adjustment and without measuring pH change in MS-MC biological leaching system (Reprinted with permission). (b) Metal leaching rates of various strains. (c) Glucosidase oxidation process (Reprinted with permission). (d) Final product leaching efficiencies of precious metals by gluconic acid (Reprinted with permission).
Figure 9. The mechanism of ultrasonic cavitation on the leaching process (Reprinted with permission).
Figure 10. (a) Preparation process of ion imprinted membrane. (b) Adsorption capacity of ion imprinted membrane for lithium ions at different pH values. (c) Selective adsorption of Li+ by the imprinted membrane (Reprinted with permission).
Table 1. Usage of various electric vehicle cathode and anode materials.
Vehicle Battery supplier Cathode Anode Renault Fluence Automotive Energy (Nissan NEC JV) LMO C Nissian Leaf EV Automotive Energy (Nissan NEC JV) LMO C Chevrolet Volt Compact Power (subsidiary of LG Chem) LMO C BYD E6 BYD LFP C Tesla Model S Panasonic Energy Nickel-type C Tesla Roadster Panasonic Energy NCA C Subaru G4e Subaru LVP C Honda Fit EV Toshiba Corporation NCM LTO
Table 2. Harmful components in the main components of LIBs and their hazards.
Component Harmful ingredient Main hazard Cathode material Heavy metals such as Co and Ni Easily causing dermatitis, respiratory disorder, lung disease,
and gastrointestinal damage; carcinogenic
Anode material Carbon materials such as graphite and acetylene black The combustion of the materials produces CO, CO2,
and other gases and solid dust to pollute the air.
Lithium salt in electrolyte LiBF4, LiAsF6, LiPF6, etc. Strongly corrosive; it will decompose in water to produce highly
toxic HF, and produce P2O3 and other toxic substances during
combustion, which will pollute the environment.
Electrolyte solvent EC, DMC, PC, DMSO, etc. The combustion of the materials produces CO, CO2, and other gases,
and aldehydes, ketones, and other organic pollutants.
Separator Polypropylene (PP), polyethylene (PE) Naturally difficult to degrade, causing organic pollution
Table 3. Summary of the research status of leaching spent LIB cathode materials with acids as the leaching agents.
Materials Leaching agent Leaching condition Reduction agent Solid-liquid ratio(g/L) Leaching rate Ref. LiCoO2 2 M H2SO4 80 °C + 1.5 h 0.11 M ascorbic acid 200 Li 95.7%, Co 93.8%  LiCoO2 2 M H2SO4 60 °C + 2 h 2% H2O2 (v/v) 33 Li 87.5%, Co 96.3%  LiCoO2 4 M H2SO4 85 °C + 2 h 10% H2O2 (v/v) 0.1 Li 96%, Co 95%  LNCM 2 M H2SO4 60 °C + 1 h 3% H2O2 (v/v) 50 Li: 99%; Co: 99%; Ni: 99%; Mn:99%  LNCM 1.5 M H2SO4 25 °C + 1 h 8% H2O2 (v/v) 30 Li: 80%; Co: 93%; Ni: 92%; Mn:90%  LNCM 0.5 M HNO3 70 °C +0.15 h 0.5 M ascorbic acid 20 Li, Co, Ni, and Mn～100%  LiFePO4 2.5 M H2SO4 60 °C +4 h N/A 100 Li: 97%; Fe: 98%  LiCoO2 3 M HCl 80 °C +40 min 3.5% H2O2 (v/v) 0.05 Li: 81%; Co: 79%  LiCoO2 0.7 M H3PO4 40 °C +1 h 4% H2O2 (v/v) 50 Co: 99.7%; Li: 99.9%  LiCoO2 1 M oxalic acid 80 °C +2 h N/A 50 Co, Li: >98%  LiCoO2 1.25 M ascorbic acid 70 °C +20 min N/A 25 Co: 94.8%; Li: 98.5%  LiCoO2 1.25 M citric acid 90 °C +0.5 h 1% H2O2 (v/v) 16.7 Co: 90%; Li: 98%  LiCoO2 1.5 M malic acid 90 °C +40 min 2% H2O2 (v/v) 20 Co: >90%; Li: ~100%  LiCoO2 0.5 M naphthalene disulfonic acid 60 °C +0.5 h 3% H2O2 (v/v) 25 Co: 97%; Li: 99%  LNCM 1.2 M DL-malic acid 90 °C +0.5 h 1.5% H2O2 (v/v) 40 Li: 98.9%; Co: 94.3%;
Ni: 95.1%; Mn: 96.4%
 LNCM 2 M L-Tartaric acid 70 °C +0.5 h 4% H2O2 (v/v) 17 Li: 99%; Co: 99%;
Ni: 99%; Mn: 99%
 LNCM 0.2 M H3PO4+0.4 M C6H8O7 90 °C +0.5 h N/A 20 Li: 100%; Co: 91.63%;
Ni: 93.38%; Mn: 92%
 Note: M: mol L−1
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