Controlled Isotropic Canalization of Microsized Silicon Enabling Stable High‐Rate and High‐Loading Lithium Storage

Abstract Silicon is attractive for lithium‐ion batteries and beyond but suffers large volume change upon cycling. Hierarchical tactics show promise yet lack control over the unit construction and arrangement, limiting stability improvement at the practical level. Here, a protocol is developed as controlled isotropic canalization of microsized silicon. Distinct from the existing strategies, it involves isotropic canalization by honeycomb‐like radial arrangement of silicon nanosheets, and canal consolidation by controlled dual bonding of silicon with carbon. The proof‐of‐concept nitrogen‐doped carbon dual‐bonded silicon honeycomb‐like microparticles, specifically with a medium density of CNSi and COSi bonds, exhibit stable cycling impressively at high rates and industrial‐scale loadings. Two key issues involve isotropic canalization facilitating ion transport in all directions of individual granules and controlled consolidation conferring selective ion permeation and securing charge transport. The study highlights the configurational isotropy and interfacial bonding density, and provides insight into rational design and manufacture of silicon and others with industry‐viable features.