Stabilizing the Bulk‐Phase and Solid Electrolyte Interphase of Silicon Microparticle Anode by Constructing Gradient‐Hierarchically Ordered Conductive Networks

Abstract The poor bulk‐phase and interphase stability, attributable to adverse internal stress, impede the cycling performance of silicon microparticles (µSi) anodes and the commercial application for high‐energy‐density lithium‐ion batteries. In this work, a groundbreaking gradient‐hierarchically ordered conductive (GHOC) network structure, ingeniously engineered to enhance the stability of both bulk‐phase and the solid electrolyte interphase (SEI) configurations of µSi, is proposed. Within the GHOC network architecture, two‐dimensional (2D) transition metal carbides (Ti 3 C 2 T x ) act as a conductive “brick”, establishing a highly conductive inner layer on µSi, while the porous outer layer, composed of one‐dimensional (1D) Tempo‐oxidized cellulose nanofibers (TCNF) and polyacrylic acid (PAA) macromolecule, functions akin to structural “rebar” and “concrete”, effectively preserves the tightly interconnected conductive framework through multiple bonding mechanisms, including covalent and hydrogen bonds. Additionally, Ti 3 C 2 T x enhances the development of a LiF‐enriched SEI. Consequently, the µSi‐MTCNF‐PAA anode presents a high discharge capacity of 1413.7 mAh g −1 even after 500 cycles at 1.0 C. Moreover, a full cell, integrating LiNi 0.8 Mn 0.1 Co 0.1 O 2 with µSi‐MTCNF‐PAA, exhibits a capacity retention rate of 92.0% following 50 cycles. This GHOC network structure can offer an efficacious pathway for stabilizing both the bulk‐phase and interphase structure of anode materials with high volumetric strain.