Tailoring Crystal Facets Enables Scalable Synthesis of Highly Dispersed Single Crystal NCM90

ABSTRACT The single crystal cathodes show significant superiority in cycling stability and safety, but are restricted by high costs, as current preparation strategies often lead to particle agglomeration. Here, we develop a new strategy of surface high‐valence metal doping to prepare the highly dispersed single crystal LiNi 0.90 Mn 0.05 Co 0.05 O 2 (SC‐NCM90) in low‐cost. The surface substitution of Ni 2+/3+ by W 6+ /Mo 6+ facilitates to enhancing the bond with O, suppressing cation interdiffusion, benefiting particle dispersion, and high voltage stability. The surface Mo‐doping lowers the energy of (104) plane and stimulates its prior growth, favoring fast Li + ‐migration and endowing the Mo 6+ ‐doped SC‐NCM90 with the capacity of 111.0 mAh g −1 at 5C, achieving the desired fast charging for SC‐NCM90. W‐doping facilitates the growth of both (003) and (104) planes, benefiting the particle segregation, as (003) plane inhibits ionic fusion. W‐ and Mo‐doped SC‐NCM90 deliver markedly improved cycling life and safety performance than polycrystalline NCM90. This work establishes the strategy of high‐valence elemental surface doping as a dual‐functional paradigm that simultaneously manipulates crystal facet evolution for suppressing particle agglomeration and fortifies transition metal (TM)─O bonding for stabilizing interface, producing highly dispersed SC‐NCM90 with faster charging capability and durability.