Dual-Layered Interfacial Evolution of Lithium Metal Anode: SEI Analysis via TOF-SIMS Technology

Lithium metal battery has been considered as one of the most promising candidates for the next generation of energy storage systems due to its high energy density. However, the lithium metal may react with the electrolyte, resulting in the instability of the solid/liquid interface. The solid electrolyte interface (SEI) layer was found to affect the interface stability of the lithium metal anode; the real structure of SEI couldn't be accurately analyzed so far. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has been thought as a powerful tool to carry out three-dimensional (3D) characterization and structural reconstruction at a high-resolution nanoscale, as well as detect ionized elements and molecule fragments at the ppb level due to its excellent sensitivity. Herein, we employed TOF-SIMS to investigate the chemical composition of SEI at the surface of the lithium metal anode after electrochemical cycles. We find that SEI is not a completely dense interface layer. The organic phase of SEI can accommodate part of the electrolyte, enhancing the lithium-ion conductivity. Meanwhile, SEI is an interface layer that changes with the state of the electrolyte, and this process of change is expressed by conventional characterization methods. However, the distribution of lithium salt can be analyzed by TOF-SIMS to judge the change degree of SEI. Our work provides significant guidance for accurately characterizing the SEI layer, as well as constructing a more realistic interface layer model.