Dual-Modified Compact Layer and Superficial Ti Doping for Reinforced Structural Integrity and Thermal Stability of Ni-Rich Cathodes

Nickel-rich layered oxides have been regarded as a potential cathode material for high-energy-density lithium-ion batteries because of the high specific capacity and low cost. However, the rapid capacity fading due to interfacial side reactions and bulk structural degradation seriously encumbers its commercialization. Herein, a highly stable hybrid surface architecture, which integrates an outer coating layer of TiO₂&Li₂TiO₃ and a surficial titanium doping by incorporated Ti₂O₃, is carefully designed to enhance the structural stability and eliminate lithium impurity. Meanwhile, the surficial titanium doping induces a nanoscale cation-mixing layer, which suppresses transition-metal-ion migration and ameliorates the reversibility of the H2 → H3 phase transition. Also, the Li₂TiO₃ coating layer with three-dimensional channels promotes ion transportation. Moreover, the electrochemically stable TiO₂ coating layer restrains side reactions and reinforces interfacial stability. With the collaboration of titanium doping and TiO₂&Li₂TiO₃ hybrid coating, the sample with 1 mol % modified achieves a capacity retention of 93.02% after 100 cycles with a voltage decay of only 0.03 V and up to 84.62% at a high voltage of 3.0-4.5 V. Furthermore, the ordered occupation of Ni ions in the Li layer boosts the thermal stability by procrastinating the layered-to-rock salt phase transition. This work provides a straightforward and economical modification strategy for boosting the structural and thermal stability of nickel-rich cathode materials.