Thermally Induced Reactions between Lithiated Nano-Silicon Electrode and Electrolyte for Lithium-Ion Batteries

Abstract

The thermal stability of nano-silicon electrodes before and after lithiation was studied by means of differential scanning calorimetry (DSC). It was found that pristine Si electrodes heated in presence of ECDEC 1M LiPF 6 electrolyte show exothermic reactions between sodium carboxymethylcellulose (Na CMC binder) and LiPF 6 . The products of thermal decomposition of a lithiated nano-Si electrode with electrolyte at different temperatures were identified using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). SEI layer was found to be responsible for the thermal reactions in the range between 77 and 107°C. Exothermic events between 107 and 140°C were caused by partial decomposition of LiPF 6 salt, which products initiated further transformations of SEI layer compounds and esterification of Na CMC. Interaction between nano-Li x Si and ECDEC 1M LiPF 6 was the reason for the main exothermic peaks at temperatures between 150 and 300°C. Nano-Li x Si heated with ECDEC solvent mixture without LiPF 6 resulted in electrolyte decomposition at much lower temperatures ( > 105°C). Therefore, the important role of LiPF 6 in the thermal stabilization of nano-Li x Si with electrolyte at temperatures < 140°C was confirmed while LiTFSI salt added to ECDEC was ineffective in the prevention of the main exothermic reaction starting at 105°C. © 2012 The Electrochemical Society.