Enhancing the Structural Stability of Ni-Rich Layered Oxide Cathodes with a Preformed Zr-Concentrated Defective Nanolayer

Nickel-rich layered oxides (NLOs) exhibit great potential to meet the ever-growing demand for further increases in the energy density of Li-ion batteries because of their high specific capacities. However, NLOs usually suffer from severe structural degradation and undesired side reactions when cycled above 4.3 V. These effects are strongly correlated with the surface structure and chemistry of the active NLO materials. Herein, we demonstrate a preformed cation-mixed (Fm3̅m) surface nanolayer (∼5 nm) that shares a consistent oxygen framework with the layered lattice through Zr modification, in which Ni cations reside in Li slabs and play the role of a “pillar”. This preformed nanolayer alleviates the detrimental phase transformations upon electrochemical cycling, effectively enhancing the structural stability. As a result, the Zr-modified Li(Ni0.8Co0.1Mn0.1)0.985Zr0.015O2 material exhibits a high reversible discharge capacity of ∼210 mA h/g at 0.1 C (1 C = 200 mA/g) and outstanding cycling stability with a capacity retention of 93.2% after 100 cycles between 2.8 and 4.5 V. This strategy may be further extended to design and prepare other high-performance layered oxide cathode materials.