Thermodynamic Analysis of the Hydrolysis of Borate-Based Lithium Salts by Density Functional Theory

Here we discuss the thermodynamics of hydrolysis three borate-based lithium salts commonly used in aprotic electrolytes for lithium-ion batteries: tetrafluoroborate (LiBF 4 ), difluoro(oxalate)borate (LiODBF) and bis(oxalate)borate (LiBOB). We performed density functional theory calculations at ω B97M-V/6–31++G** level to compute thermodynamic stability reagents, intermediate products solution phase. The variations Gibbs free energy heterogeneous reactions were evaluated by coupling DFT values with thermochemical cycles. LiBF LiODBF can be easily hydrolyzed direct reaction water room temperature: degradation is driven precipitation LiF(s) release HF. On contrary, LiBOB much more stable only weakly reacts water: it therefore resilient hydrolyzation suitable application Li-ion battery electrolytes.