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With the rapid growth in the use of lithium - ion batteries, the amount of waste lithium - ion batteries is increasing, posing a threat to the environment and creating a shortage of critical materials (such as lithium, cobalt, nickel, and manganese). Lithium - ion battery material recycling technologies aim to recover these valuable materials from waste batteries, reduce environmental pollution, and promote the circular economy of battery materials.
1. Pretreatment Processes
Disassembly and Sorting: The first step in battery recycling is to disassemble the waste battery packs into individual cells and separate the different components (cells, BMS, case, cables, etc.). This is usually done manually or using automated disassembly equipment. Manual disassembly is suitable for small - scale operations or battery packs with complex structures, while automated equipment (such as robotic arms and conveyor belts) is used for large - scale recycling. After disassembly, the cells are sorted based on their chemistry, form factor, and state of charge. For example, lithium - cobalt oxide cells (used in consumer electronics) are sorted separately from lithium - iron phosphate cells (used in ESS) because they require different recycling processes. Cells with a high state of charge are discharged to a safe level (usually below 3 V) to prevent short - circuits and thermal runaway during subsequent processing.
Crushing and Shredding: The sorted cells are crushed or shredded into small particles (usually 1 - 5 mm in size) to break down the cell case and release the internal components (electrodes, electrolyte, separator). Crushing and shredding can be done using equipment such as hammer mills, jaw crushers, or shredders. To prevent thermal runaway during this process, the crushing and shredding are often carried out in an inert atmosphere (such as nitrogen) or under a vacuum to avoid the ignition of flammable electrolytes. After crushing, the mixture of particles is subjected to sieving to separate the coarse particles (such as cell case fragments) from the fine particles (electrode materials, separator, and electrolyte).
2. Material Recovery Processes
Hydrometallurgical Processes: Hydrometallurgical processes use aqueous solutions to dissolve and extract valuable metals from the crushed battery materials. The main steps include leaching, purification, and precipitation. In the leaching step, the crushed material is mixed with a leaching agent (such as sulfuric acid, hydrochloric acid, or nitric acid) along with oxidants (such as hydrogen peroxide or sodium chlorate) to dissolve the metals (lithium, cobalt, nickel, manganese) from the electrode materials. The leaching conditions (temperature, pH, concentration of leaching agent, and reaction time) are optimized to maximize the leaching efficiency. For example, leaching lithium - nickel - manganese - cobalt oxide (NMC) electrodes with sulfuric acid and hydrogen peroxide at 80 - 90°C for 2 - 4 hours can achieve a metal leaching rate of over 95%. After leaching, the leachate contains a mixture of metal ions, which is purified using methods such as solvent extraction, ion exchange, or precipitation. Solvent extraction uses organic solvents to selectively extract specific metal ions from the leachate. For example, cobalt and nickel can be extracted using extractants such as D2EHPA (di - 2 - ethylhexyl phosphoric acid), while lithium remains in the aqueous phase. Ion exchange uses resins to adsorb metal ions from the leachate, which can then be eluted with a suitable solution. Precipitation involves adding chemicals to the leachate to form insoluble metal compounds (such as hydroxides, carbonates, or sulfates) that can be separated by filtration. Finally, the purified metal solutions are processed to produce metal salts or oxides, which can be reused in the production of new battery electrodes.
Pyrometallurgical Processes: Pyrometallurgical processes use high temperatures to melt and separate the battery materials. The crushed battery material is fed into a furnace (such as a rotary kiln or electric arc furnace) and heated to high temperatures (1200 - 1600°C) in the presence of a reducing agent (such as coke or charcoal). At high temperatures, the organic components (electrolyte, binder) are burned off, and the metal oxides in the electrode materials are reduced to metallic alloys (such as cobalt - nickel - copper alloys). The slag (containing lithium, aluminum, and other impurities) is separated from the metal alloy by density difference. The metal alloy is then further processed using methods such as electrolysis or chemical refining to recover individual metals (cobalt, nickel, copper). Lithium in the slag can be recovered by leaching with water or acid. Pyrometallurgical processes are suitable for large - scale recycling of mixed battery chemistries and can handle batteries with high levels of contamination. However, they have high energy consumption and may generate toxic gases (such as dioxins) if not properly controlled.
Direct Recycling Processes: Direct recycling processes aim to recover the active electrode materials (such as lithium cobalt oxide, lithium nickel - manganese - cobalt oxide) from waste batteries without breaking down the metal ions into individual elements. This approach is more energy - efficient and environmentally friendly compared to hydrometallurgical and pyrometallurgical processes. The main steps of direct recycling include electrode separation, washing, and regeneration. In the electrode separation step, the crushed battery material is treated with solvents (such as N - methyl - 2 - pyrrolidone or acetone) to dissolve the binder, allowing the active electrode materials to be separated from the current collector (aluminum or copper foil). The separated active materials are then washed with water or solvents to remove impurities (such as electrolyte residues and carbon black). Finally, the washed active materials are subjected to heat treatment (sintering) or chemical modification to restore their crystal structure and electrochemical performance. The regenerated active materials can be directly used in the production of new battery electrodes. Direct recycling is still in the development stage but shows great potential for the recycling of high - quality waste batteries with minimal degradation.
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