Stationary Oxygen Vacancy Construction toward a Superior-Performance Ultrahigh Nickel Single-Crystal Cathode.

Abstract

Oxygen vacancies exert a complex and profound influence on the layered cathodes, especially those with ultrahigh nickel content. They can facilitate lithium-ion transport and enhance electronic conductivity, while aggressive oxygen vacancy formation causes structural degradation and electrolyte decomposition. Herein, taking ultrahigh nickel single-crystal LiNi_0.92Co_0.06Mn_0.02O₂ (SC-Ni92) as a model material, we propose a pinning strategy to harness the benefits of oxygen vacancies while mitigating their detrimental effects. Through a carefully controlled thermal process, both oxygen vacancies and pinning atoms are successfully introduced into the surface region. The resulting anchored oxygen vacancies, capitalizing on their inherent advantages, improve conductivity and lithium-ion diffusion. Simultaneously, the neighboring pinning atoms effectively increase the migration barrier and suppress the adverse effects of these vacancies, including electrolyte decomposition and structural degradation during long-term electrochemical cycling. Consequently, oxygen vacancy-anchored single-crystal LiNi_0.92Co_0.06Mn_0.02O₂ (SC-Ni92-OV) demonstrates significantly improved high-voltage electrochemical performance, with 86.16% capacity retention after 200 cycles at 4.6 V and 1 C in a half-cell and 90.71% after 300 cycles at 4.5 V and 1 C in a full cell. This study not only provides valuable insights into the chemistry of oxygen vacancy but also introduces a viable strategy for leveraging oxygen vacancies to achieve stable high-voltage performance in ultrahigh nickel single-crystal cathodes.