First‐Principles Investigations of Vibration Offsets Towards Efficient Energy Transfer: Case Study of ZnO and ZnS

ABSTRACT While defect engineering is a pivotal strategy for enhancing zinc‐based battery performance, current approaches predominantly focus on electronic state modulation, ignoring the critical role of phonon kinetics and electron–phonon interactions in energy transfer. Herein, we employ first‐principles calculations to investigate the distinct lattice vibrational responses to anion vacancies in ZnO and ZnS systems. Our analysis reveals a fundamental divergence in phonon characteristics despite their crystallographic similarities. In ZnO, oxygen vacancies induce a heterogeneous phonon response characterized by simultaneous redshifts and blueshifts, resulting in a disordered phonon environment prone to incoherent scattering and internal energy dissipation. Conversely, sulfur vacancies in ZnS trigger a uniform and coherent redshift across the sulfur atoms. We propose that this constructive interference of lattice modes establishes a favorable channel for coherent phonon‐electron energy transfer, facilitating carrier transport while minimizing local thermal stress. These findings establish the defect‐induced phonon response as a novel descriptor for the rational design of high‐rate energy storage materials and provide theoretical guidance for the development of battery technologies.