Stabilizing Ni-rich layered cathode for high-voltage operation through hierarchically heterogeneous doping with concentration gradient

High-nickel LiNixMnyCo1-x-yO2 (NMC) cathodes have demonstrated superior energy density, yet their stability is compromised under high voltage conditions. To address this, we propose a strategy of heterogeneous doping with a concentration gradient, specifically through Sr-Zr co-modification. We synthesized Ni-rich NMC particles featuring several micron-sized secondary particles composed of micron-sized primary grains. This design aims to harness the structural robustness of single-crystalline grains and the favorable diffusion kinetics of polycrystalline secondary particles. Systematic characterization using a combination of electrochemical measurements and synchrotron analytics reveals an intriguing pattern of hierarchically heterogeneous Sr-Zr co-doping. It demonstrates a depth-dependent concentration gradient at the secondary particle level and competing dopant segregation over the buried grain boundaries. This unique characteristic creates opportunities for enhancing battery performance, particularly by optimizing precursors and implementing advanced modulation techniques. We also investigate the dissolution and precipitation of the cathode's transition metal cations upon high-voltage cycling. These insights suggest that a tailored compositional variation can be a viable approach to effectively design the next-generation high-Ni NMC cathode materials for high-voltage lithium batteries.