Understanding of the Mechanism Enables Controllable Chemical Prelithiation of Anode Materials for Lithium-Ion Batteries.

By compensating the irreversible loss of lithium ions during the first cycle, prelithiations can solve the issue of insufficient initial Coulombic efficiency for various anodes. Recently, the chemical prelithiation using organolithium compounds has attracted increasing attention because of its uniform and fast reaction, safety, and easily adjustable degree of prelithiation. However, the nature and activity of organolithium involved in chemical prelithiations have not been deeply explored yet. Here, by monitoring the electrical conductivity change in the lithiation solution in the duration of its formation, we have demonstrated the essential role of lithium radical anions for chemical prelithiation and compared the prelithiation activity of dissociated species and aggregates of lithium radical anions. The mechanistic understanding of the nature of the lithiation solution leads to controllable chemical prelithiation, as demonstrated in full cells of prelithiated hard carbon and LiFePO.