Operando Monitoring of F– Formation in Lithium Ion Batteries

Online electrochemical mass spectrometry (OEMS) was applied to study the influence of tris­(trimethylsilyl)­phosphate (TMSPa) as an additive in 1 M LiPF6 (fluoroethylene carbonate/diethylene carbonate (DEC)) electrolyte on the gas evolution in Li-rich/NCM full cells during cycling. The results indicate that TMSPa neither influences the solid electrolyte interphase (SEI) formation on the anode nor the surface reconstruction on the cathode but acts as a chemical scavenger for HF and LiF. TMSPa thus lowers the electrolyte acidity and suppresses further LiPF6 decomposition, resulting in lower impedance and higher lithium ion battery (LIB) performance. Furthermore, the selective reactivity of TMSPa toward fluorides leads to the formation of Me3SiF enabling the additive to act as a chemical probe and to study HF/LiF formation operando by OEMS. By this methodology, we were able to identify contributions from SEI formation, proton and reactive oxygen formation >4.2 V, cross-talk between the anode and cathode, and the polyvinylidene fluoride binder to the fluoride formation in LIBs.