On the Beneficial Impact of Li2CO3 as Electrolyte Additive in NCM523 ∥ Graphite Lithium Ion Cells Under High‐Voltage Conditions

Abstract Lithium ion battery cells operating at high‐voltage typically suffer from severe capacity fading, known as ‘rollover’ failure. Here, the beneficial impact of Li 2 CO 3 as an electrolyte additive for state‐of‐the‐art carbonate‐based electrolytes, which significantly improves the cycling performance of NCM523 ∥ graphite full‐cells operated at 4.5 V is elucidated. LIB cells using the electrolyte stored at 20 °C (with or without Li 2 CO 3 additive) suffer from severe capacity decay due to parasitic transition metal (TM) dissolution/deposition and subsequent Li metal dendrite growth on graphite. In contrast, NCM523 ∥ graphite cells using the Li 2 CO 3 ‐containing electrolyte stored at 40 °C display significantly improved capacity retention. The underlying mechanism is successfully elucidated: The rollover failure is inhibited, as Li 2 CO 3 reacts with LiPF 6 at 40 °C to in situ form lithium difluorophosphate, and its decomposition products in turn act as ‘scavenging’ agents for TMs (Ni and Co), thus preventing TM deposition and Li metal formation on graphite.