Mitigating the Kinetic Hysteresis of Co-Free Ni-Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon

Co-free Ni-rich layered oxides are considered a promising cathode material for next-generation Li-ion batteries due to their cost-effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li-ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si-O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co-free Ni-rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li-ion diffusion kinetics in atomic and electrode particle scales, the as-obtained cathodes (LiNixMn1-xSi0.01O2, 0.6 <= x <= 0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li-ion transport properties, and the concept will inspire more researchers to conduct an intensive study.