Crystal Engineering of Silica Anode Achieving Intrinsic Zero‐Strain

Si-based anodes have large intrinsic volume expansion, which hinders their practicality and commercialization. To address this challenge, the design principle of intrinsic zero-strain anodes (① large intracrystalline cavities and ② strong bonds) is proposed, and silica with large intracrystalline cavities (SLIC) established by strong Si─O bonds ([SiO₄ ] coordinate structures) is obtained and acts as an anode, achieving the intrinsic zero-strain feature first in silicon-based anodes. The phase structure of SLIC is maintained and the [SiO₄ ] coordinate structure merely shows slight disorder during cycling. The feature stems from lithiation taking place by the solid-solution insertion reaction rather than the conventional conversion/alloying addition reactions, because the solid-solution insertion reaction for the SLIC has the lowest change in the Gibbs free energy. The SLIC anode demonstrates excellent cycling stability and high initial Coulombic efficiency (≈85%). Moreover, owing to the low working voltage (≈0.28 V) and relatively high specific capacity, the SLIC anode presents the highest gravimetric energy density among reported zero-/quasi-zero-strain anodes and high volumetric energy density (around twice as much as graphite). The universality of the designing principle is also validated. This work provides design guidelines for zero-strain anodes in next-generation batteries.