High-Temperature Storage Deterioration Mechanism of Cylindrical 21700-Type Batteries Using Ni-Rich Cathodes under...

The safety and energy density of lithium-ion batteries (LIBs) are important concerns. The use of high-capacity cathode materials, such as Ni-rich cathodes, can greatly improve the energy density of LIBs, but it also brings some safety hazards. Cylindrical 21700-type batteries using Ni-rich cathodes were employed here to investigate their high-temperature storage deterioration mechanism under different states of charge (SOCs). Electrolyte decomposition was identified as the main problem. It can be worsened by elevated storage temperatures and battery SOCs, with the latter having a more significant influence. Specifically, the decomposition of the LiPF₆ solute and the carbonate solvent will induce hydrofluoric acid (HF) formation and solid-electrolyte interphase (SEI) film regeneration, respectively. HF erosion will aggravate the dissolution of transition metal ions and structural degradation of cathode materials, while the destruction/regeneration of SEI films will consume active lithium and hinder Li⁺ diffusion at the anode side. Besides, the self-discharge behavior will also enlarge the graphite layer spacing, thus decreasing the graphitization degree of graphite anodes and causing anode failure. These findings will aid in the development of strategies for improving the safety of LIBs with high energy density.