Density Functional Theory Research into the Reduction Mechanism for the Solvent/Additive in a Sodium‐Ion Battery

Abstract The solid–electrolyte interface (SEI) film in a sodium‐ion battery is closely related to capacity fading and cycling stability of the battery. However, there are few studies on the SEI film of sodium‐ion batteries and the mechanism of SEI film formation is unclear. The mechanism for the reduction of ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), ethylene sulfite (ES), 1,3‐propylene sulfite (PS), and fluorinated ethylene carbonate (FEC) is studied by DFT. The reaction activation energies, Gibbs free energies, enthalpies, and structures of the transition states are calculated. It is indicated that VC, ES, and PS additives in the electrolyte are all easier to form organic components in the anode SEI film by one‐electron reduction. The priority of one‐electron reduction to produce organic SEI components is in the order of VC>PC>EC; two‐electron reduction to produce the inorganic Na 2 CO 3 component is different and follows the order of EC>PC>VC. Two‐electron reduction for sulfites ES and PS to form inorganic Na 2 SO 3 is harder than that of carbonate ester reduction. It is also suggested that the one‐ and two‐electron reductive decomposition pathway for FEC is more feasible to produce inorganic NaF components.