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Pyrometallurgy uses high temperature to fa- cilitate the oxidation and reduction reactions in which transition metals like Co and Ni are re- duced from oxides to metals, and recovered in a mixed metal alloy. The metals can then be sepa- rated (by hydrometallurgy) and used to make new cathode material. Other materials, including the aluminum, anode, and electrolyte, are oxidized in the smelter, supplying much of the process en- ergy. The aluminum and lithium oxides end up in the slag and are not generally recovered. Hydro- metallurgy uses acids to dissolve the ions out of a solid like the cathode, producing a mixture of ionic species in solution. These can be recovered by precipitation or solvent extraction and reacted with other recovered materials to produce new cathode material. Other techniques like mem- brane separation have been proposed [11]. Direct recycling separates the different components of the black mass (active material powder from shredding of cells) by physical processes, like gravity separation, which recover separated ma- terials without causing chemical changes, ena- bling recovery of cathode material that is reusable with minimal treatment. (See, for example [12].) Historically, the main objective of Li-ion bat- tery recycling has been recovery of cobalt, be- cause of its high value. Everything else has been secondary. However, as cobalt content in the bat- teries decreases and mandatory recycling regula- tions requiring recovery of over 50% of the ma- terials come into effect in the European Union [13], interest has grown in recovery of additional materials. Materials make up over half of the ini- tial cell cost, and cathode material is the largest contributor to material cost (Fig. 3), so there is a financial incentive to recover cathode material. Further, the value of cathode material is greater than that of its constituent elements, so recovery of reusable cathode provides more revenue than recovery of its constituents. Figure 4 compares cathode prices to the value of elements or key pre- cursors that could be recovered. Recovery of co- balt from LCO cathode by smelting or leaching recovers about 70% of the cathode value, a per- centage that falls drastically for other cathode chemistries containing less cobalt. This could be a considerable advantage for direct recycling, also called cathode-to-cathode recycling, because of the importance of cathode value recovery. The recovered cathode must be of assured quality, however, and must not be contaminated or de- graded. Very specialized structural features, such as dopants in specific locations, might not be re- tained. 4 Fig. 3. Cost breakdowns for Li-ion batteries showing materials as part of total costs, (left), and components of material cost (right). Data from K. Gallagher [14].PDF Image | Lithium-Ion Battery Recycling Processes
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