(Invited) Generation and Evolution of Materials in the Anode Solid Electrolyte Interphase (SEI) of Lithium Ion Batteries

Abstract

A solid electrolyte interphase is generated on the anode of lithium ion batteries during the first few charging cycles. The presence and stability of the solid electrolyte interphase (SEI) is critical to the performance of the battery. Despite thorough investigation of the SEI for over 20 years, the mechanism of formation and function are still relatively poorly understood. We have investigated the structure of the initial SEI on graphite and silicon electrodes along with changes which occur to the SEI upon additional cycling via a combination of ex-situ surface analysis techniques. The investigation of SEI provides significant insight into the structure and properties of the anode SEI. The one electron reducing agent, lithium napthalenide has been used to independently prepare the reduction products which constitute the SEI. The initial reduction product of ethylene carbonate is lithium ethylene dicarbonate (LEDC). However, the thermal decomposition of LEDC and related lithium alkyl carbonates in the presence of LiPF6 generates a intricate mixture of compounds which greatly complicates the structure of the SEI. The reduction products and their subsequent thermal decomposition products have been thoroughly investigated via a combination of NMR, XPS, IR-ATR, TGA, and GC-MS. Mechanisms for the generation of the complicated mixture of products will be discussed. Thermal behavior of the SEI on a silicon electrode for Lithium ion batteries has been investigated by TGA. In order to provide a better understanding of the thermal decomposition of the SEI on silicon, the thermal decomposition behavior of independently synthesized lithium ethylene dicarbonate (LEDC) was investigated as a model SEI. The model SEI (LEDC) has three stages of thermal decomposition. Over the temperature range of 50~300oC, LEDC decomposes to evolve CO2 and C2H4 gasses leaving lithium propanoate (CH3CH2CO2Li) and Li2CO3 as solid residues. The lithium propanoate decomposes over the temperature range of 300~600oC to evolve pentanone leaving Li2CO3 as a residual solid. Finally, the Li2CO3 decomposes over 600oC to evolve CO2 leaving Li2O as a residual solid. A very similar thermal decomposition process is observed for the SEI generated on cycled silicon electrodes. However, two additional thermal decomposition reactions were observed characteristic of LixPOyFz at 300oC and the polyimide binder at 550oC. TGA measurements of Si electrodes after various numbers of cycles suggest that the LEDC on Si electrodes thermally decomposes during cycling to form lithium propanoate and Li2CO3, resulting in increased complexity of the SEI.