Tuning Li occupancy and local structures for advanced Co-free Ni-rich positive electrodes

Structure evolution and surface reactivity have long been regarded as the most crucial points for studying Ni-rich positive electrodes for Li-ion batteries. Unfortunately, the influence of Li occupancy as a single factor on electro-chemomechanical stability has been overlooked and is missing, owing to the challenge of Li determination in the lattice. Here, a comprehensive analysis reveals different Li occupancies and related structural domains (Ni/Li exchange, Li_aXO_b, Li/Mn/X(Ni) ordering domains, X = Nb⁵⁺, W⁶⁺, and Mo⁶⁺) by using a combination of Li-sensitive characterization techniques. By introducing a Li-regulation strategy, the relative ratio of each domain is effectively tuned in the Ni-rich positive electrodes. Through tuning, two specific positive electrodes are designed, exhibiting notable improvement in battery cyclability. The specific Li structural units induce significant changes in redox mechanisms. This Li-occupancy-tuning approach highlights the necessity of focusing on Li distribution and opens up ideas for designing advanced Ni-rich positive electrodes with high durability.