Recent Applications of Molecular Structures at Silicon Anode Interfaces

Silicon (Si) is a promising anode material to realize many-fold higher anode capacity in next-generation lithium-ion batteries (LIBs). Si electrochemistry has strong dependence on the property of the Si interface, and therefore, Si surface engineering has attracted considerable research interest to address the challenges of Si electrodes such as dramatic volume changes and the high reactivity of Si surface. Molecular nanostructures, including metal–organic frameworks (MOFs), covalent–organic frameworks (COFs) and monolayers, have been employed in recent years to decorate or functionalize Si anode surfaces to improve their electrochemical performance. These materials have the advantages of facile preparation, nanoscale controllability and structural diversity, and thus could be utilized as versatile platforms for Si surface modification. This review aims to summarize the recent applications of MOFs, COFs and monolayers for Si anode development. The functionalities and common design strategies of these molecular structures are demonstrated.

Lithium Diffusion in Silicon Encapsulated with Graphene

The model of a graphene (Gr) sheet putting on a silicon (Si) substrate is used to simulate the structures of Si microparticles wrapped up in a graphene cage, which may be the anode of lithium-ion batteries (LIBS) to improve the high-volume expansion of Si anode materials. The common low-energy defective graphene (d–Gr) structures of DV5–8–5, DV555–777 and SV are studied and compared with perfect graphene (p–Gr). First-principles calculations are performed to confirm the stable structures before and after Li penetrating through the Gr sheet or graphene/Si-substrate (Gr/Si) slab. The climbing image nudged elastic band (CI-NEB) method is performed to evaluate the diffusion barrier and seek the saddle point. The calculation results reveal that the d–Gr greatly reduces the energy barriers for Li diffusion in Gr or Gr/Si. The energy stability, structural configuration, bond length between the atoms and layer distances of these structures are also discussed in detail.