biostudies-literatureUnknownWang SLayered ultra-high-nickel oxides are promising cathodes for high-energy-density lithium-ion batteries but suffer from severe structural degradation. Although high-valence doping is widely employed to enhance stability, the underlying mechanism-whether dominated by morphological alignment or cation ordering-remains contested. Through systematic investigation of W<sup>6+</sup>-doped LiNi<sub>0.92</sub>Co<sub>0.04</sub>Mn<sub>0.04</sub>O<sub>2</sub> across varied doping concentrations and sintering temperatures, this work demonstrates that cation ordering, rather than morphological alignment, plays the decisive role in electrochemical enhancement. Although W-doping refines primary particles and sustains a radial microstructure even under extreme sintering conditions (up to 850 °C), correlatioChemical sciencehttps://www.ebi.ac.uk/biostudies/studies/S-EPMC12709538biostudies-literatureRevisiting high-valence dopant mechanisms in Ni-rich cathodes: cation ordering dominates over morphological alignment for enhanced stability.PMC12709538Liu XLiu HXing WWang SXiao YFeng GXiang WChen SZhang BfalseRevisiting high-valence dopant mechanisms in Ni-rich cathodes: cation ordering dominates over morphological alignment for enhanced stability.Layered ultra-high-nickel oxides are promising cathodes for high-energy-density lithium-ion batteries but suffer from severe structural degradation. Although high-valence doping is widely employed to enhance stability, the underlying mechanism-whether dominated by morphological alignment or cation ordering-remains contested. Through systematic investigation of W<sup>6+</sup>-doped LiNi<sub>0.92</sub>Co<sub>0.04</sub>Mn<sub>0.04</sub>O<sub>2</sub> across varied doping concentrations and sintering temperatures, this work demonstrates that cation ordering, rather than morphological alignment, plays the decisive role in electrochemical enhancement. Although W-doping refines primary particles and sustains a radial microstructure even under extreme sintering conditions (up to 850 °C), correlatio2025-01-01T00:00:00Z2025 Dec2026-06-08T05:09:57.719Z2026-06-08T03:09:21.528ZS-EPMC127095384141590510.1039/d5sc09030j