By using silicon (Si) as an anode of lithium-ion batteries, the capacity can be significantly increased, but relatively large volume expansion limits the application as an efficient anode material. Huge volume expansion of the silicon anode during lithiation, however, leads to cracking and losing its connection with the current collector. This shortcoming can be improved by the deposition of a nanometric carbon- or nitrogen-doped carbon coating on the silicon surface, resulting in Si/C-layer and Si/C3N4 interfaces. In this work, Li+ diffusion in Si/C-layer and Si/C3N4 composite materials along three Si surfaces and various ion pathways were carefully analyzed by using density functional theory and ab initio molecular dynamic (AIMD) simulations. Both Si/C and Si/C3N4 interfaces and three Si surfaces of (100), (110), and (111) were investigated. The formation of nitrogen holes and monatomic carbon binders in the composite increases ion diffusivity and limits volume expansion. Furthermore, the Bader analysis shows that the type and orientation of the surfaces have important effects on ion distribution. The results indicated that the C3N4 composite increases Li+ diffusion in Si (100) from 7.82 × 10-5 to 3.17 × 10-4 cm2/s. The presented results provide a guide for the appropriate design of stable and safe high-energy-density batteries.
© 2023 The Authors. Published by American Chemical Society.