A non-aqueous sodium hexafluorophosphate-based electrolyte degradation study: Formation and mitigation of hydrofluoric acid

Fundamental characterization of battery electrolyte is vital for rechargeable batteries. This work reports the chemical stability of sodium hexafluorophosphate (NaPF₆)-based non-aqueous electrolytes containing different solvent mixtures (e.g., cyclic and acyclic carbonates) in the presence of water for Na-ion batteries. A degradation study is conducted using NaPF₆-based electrolytes, highlighting two electrolyte additives, 2,2,2-trifluoroethoxy-2,2,2-ethoxy phosphazene (FM2) and fluoroethylene carbonate (FEC), on degradation and cell performance of Na-ion batteries. Hydrolysis of NaPF₆ in acidic condition is particularly prone to form hydrofluoric acid (HF), and can be observed in electrolytes made with battery grade carbonate solvents (<20 ppm of water). Degradation mechanisms of NaPF₆-based electrolytes are studied using liquid nuclear magnetic resonance (NMR). Noticeable degradation takes place in high purity electrolytes with the presence of moisture to form HF and organophosphates in timeframes below the current shelf-life of the Na electrolytes. FEC is not efficient to protect the electrodes from being exposed to HF. On the other hand, FM2 is revealed as a “scavenger” of HF, which helps stabilize the shelf life of electrolytes that might contain or become exposed to water. Our study underscores the importance to understanding the degradation of electrolyte and improving stability toward better shelf life for sodium ion batteries.