3D self-supporting core-shell silicon-carbon nanofibers-based host enables confined Li+ deposition for lithium metal battery

Three-dimensional (3D) porous hosts play pivotal roles in realizing dendrite-free lithium metal anodes (LMAs) owing to their high specific area. However, uneven local electric field and lack of lithiophilic sites on the reactive interface cause nonuniform lithium ion (Li⁺) deposition, leading to Li dendrite growth and parasitic reactions. These issues will inevitably incur short cycling life and severe safety hazards of lithium metal batteries. Herein, a 3D self-supporting host composed of hollow carbon nanofibers incorporated with silicon (Si) nanoparticles inside (Si-HCF) is constructed as Li metal host by a scalable coaxial electrospinning technique. During the first cycle, the Si nanoparticles is alloyed with Li⁺ to form lithiophilic Li-Si alloy, contributing to deliver a low nucleation overpotential and homogeneous surface potential confirmed by Kelvin probe force microscopy, finally guiding Li⁺ flux homogeneously throughout the fibrous mat. As expected, the Li metal can percolate through Si-HCF host reversibly without uncontrollable Li dendrites and the Si-HCF exhibits a stable cycle life of Li plating/stripping over 1400 h. Additionally, the full cell combined with LiFePO₄ cathodes presents steady cycling over 400 cycles with a high average coulombic efficiency of 99.4 %. This work provides new insights for the synthesis of 3D hosts with controllable nucleation sites to homogenize Li⁺ deposition in LMAs.