<p>Ni-rich layered oxide cathodes derived from LiNiO<sub>2</sub>, including Ni-rich NMC and NCA, enable high specific energy but remain constrained by coupled interfacial and lattice instabilities that intensify at elevated upper-cutoff voltages. This review examines the durability limitations of Ni-rich layered oxide cathodes as an interface-dominated issue governed by CEI evolution, HF-driven interfacial chemistry, oxygen-loss-coupled surface reconstruction, and the resulting impedance growth during high-voltage operation. We summarize ceramic interphases and Li⁺-permissive interlayers that regulate contact chemistry, suppress parasitic reactions, and preserve ionic percolation while maintaining electronic insulation. We then examine lattice substitution across transition-metal, Li, and O/anion sites, highlighting how site selectivity and dopant chemistry suppress cation disorder, stabilize the oxygen framework, and sustain Li⁺ transport at high states of charge. Finally, we discuss bulk–surface integration strategies and implications for solid-state battery interfaces, where solid–solid contact and chemo-mechanical compatibility can dominate polarization growth. By consolidating recent studies, we establish a unified design framework linking interfacial chemistry, lattice stability, and transport kinetics, thereby connecting materials chemistry and processing to practical stability targets for next-generation Ni-rich cathodes.</p> Graphical abstract <p></p>

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Interfacial engineering and lattice substitution in Ni-rich layered oxide cathodes for high-voltage stability

  • Ha Eun Kang,
  • Seong-Do Kim,
  • Dong-Joo Kim,
  • Young Soo Yoon,
  • Sang-Jin Lee

摘要

Ni-rich layered oxide cathodes derived from LiNiO2, including Ni-rich NMC and NCA, enable high specific energy but remain constrained by coupled interfacial and lattice instabilities that intensify at elevated upper-cutoff voltages. This review examines the durability limitations of Ni-rich layered oxide cathodes as an interface-dominated issue governed by CEI evolution, HF-driven interfacial chemistry, oxygen-loss-coupled surface reconstruction, and the resulting impedance growth during high-voltage operation. We summarize ceramic interphases and Li⁺-permissive interlayers that regulate contact chemistry, suppress parasitic reactions, and preserve ionic percolation while maintaining electronic insulation. We then examine lattice substitution across transition-metal, Li, and O/anion sites, highlighting how site selectivity and dopant chemistry suppress cation disorder, stabilize the oxygen framework, and sustain Li⁺ transport at high states of charge. Finally, we discuss bulk–surface integration strategies and implications for solid-state battery interfaces, where solid–solid contact and chemo-mechanical compatibility can dominate polarization growth. By consolidating recent studies, we establish a unified design framework linking interfacial chemistry, lattice stability, and transport kinetics, thereby connecting materials chemistry and processing to practical stability targets for next-generation Ni-rich cathodes.

Graphical abstract