High-Temperature Behavior of Spent Li-Ion Battery Black Mass in Inert Atmosphere

Abstract The increased demand for Li-ion batteries has prompted the scientific community to improve recycling routes in order to reuse the valuable materials in batteries. After their end-of-life, the batteries are collected, discharged, and mechanically disintegrated, generating plastic and metallic streams that are recycled directly; this leaves behind a small particle size fraction known as black mass (BM). BM is composed mainly of graphite and Li-metal complex oxides. Pyrometallurgy is a route known for recycling of BM, in which identifying the BM’s behavior at high temperatures is essential. In this study, two types of BM are characterized in two fractions of 150–700 µm and smaller than 150 µm. The thermal behavior of the BM is studied with thermal analysis techniques. The analyses demonstrate that the mineralogical and morphological properties of the two fractions do not significantly differ, while the amounts of C and organic materials might vary. When the BM was thermally treated, the binders decomposed until a temperature of 500 ℃ was reached, where the volatilization of hydrocarbons was observed, although F mostly persisted in the BM. The Li-metal oxide was partially reduced to lower oxides and Li carbonate at ⁓ 600 ℃, and the main mass loss was caused by carbothermic reduction immediately thereafter. As the products of this process, metallic Co and Ni phases were formed, and part of the graphite remained unreacted. Regarding the Li behavior, it was observed that in the presence of Al, AlLiO 2 is the most likely composition to form, and it changes to LiF by increasing the F concentration in the composition. Graphical Abstract