Achieving high structure and voltage stability in cobalt-free Li-rich layered oxide cathodes via selective dual-cation doping

Lithium-rich layered oxides (LLOs) are regarded as one of the most promising cathode materials for next generation Li-ion batteries (LIBs) due to their high energy density. However, the associated oxygen release and structure collapse resulting from the intrinsic anion and cation redox reactions lead to performance degradation, particularly the characteristic voltage fading which has prohibited the commercialization of LLOs for more than a decade. Herein, we have developed a dual-doping technique to overcome the longstanding structure and voltage instabilities of Co-free Li_1.2Mn_0.533Ni_0.267O₂, through the concurrent introduction of neodymium (Nd) and aluminum (Al) ions. Selective atomic substitution of Ni/Mn with Nd/Al ions and the preconstructed heteroepitaxial interface significantly enhance the voltage and capacity retention by regulating Ni ion activity and suppressing the phase transformation and Mn dissolution, thereby improving rate performance through tuning the electronic structure and promoting Li⁺ migration. The dual-doped material exhibits a superior cycling stability, with over 90% voltage retention and 82% capacity retention after 200 cycles, and excellent rate performance (150 mAh g⁻¹ at 10 C).