Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High-Voltage Ultrahigh-Ni Cathode.

High-voltage ultrahigh-Ni cathodes (LiNixCoyMn1-x-yO2, x≥0.9) can significantly enhance the energy density and cost-effectiveness of Li-ion batteries beyond current levels. However, severe Li-Ni antisite defects and their undetermined dynamic evolutions during high-voltage cycling limit the further development of these ultrahigh-Ni cathodes. In this study, we quantify the dynamic evolutions of the Li-Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh-Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li-Ni antisite defects and controlled Ni migrations are essential for achieving stable high-voltage cycling structures in ultrahigh-Ni cathodes. This is further demonstrated by the optimized ultrahigh-Ni cathode, where reduced dynamic evolutions of the Li-Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.

Localizing Oxygen Lattice Evolutions Eliminates Oxygen Release and Voltage Decay in All-Mn-Based Li-Rich Cathodes.

All-Mn-based Li-rich cathodes Li2 MnO3 have attracted extensive attention because of their cost advantage and ultrahigh theoretical capacity. However, the unstable anionic redox reaction (ARR), which involves irreversible oxygen releases, causes declines in cycling capacity and intercalation potential, thus hindering their practical applications. Here, it is proposed that introducing stacking-fault defects into the Li2 MnO3 can localize oxygen lattice evolutions and stabilize the ARR, eliminating oxygen releases. The thus-made cathode has a highly reversible capacity (320 mA h g-1 ) and achieves excellent cycling stability. After 100 cycles, the capacity retention rate is 86% and the voltage decay is practically eliminated at 0.19 mV per cycle. Attributing to the stable ARR, samples show reduced stress-strain and phase transitions. Neutron pair distribution function (nPDF) measurements indicate that there is a structure response of localized oxygen lattice distortion to the ARR and the average oxygen lattice framework is well-preserved which is a prerequisite for the high cycle reversibility.

Diffusion-Optimized Long Lifespan 4.6 V LiCoO2: Homogenizing Cycled Bulk-To-Surface Li Concentration with Reduced Structure Stress.

Increasing the charging cut-off voltage (e.g., 4.6 V) to extract more Li ions are pushing the LiCoO2 (LCO) cathode to achieve a higher energy density. However, an inhomogeneous cycled bulk-to-surface Li distribution, which is closely associated with the enhanced extracted Li ions, is usually ignored, and severely restricts the design of long lifespan high voltage LCO. Here, a strategy by constructing an artificial solid-solid Li diffusion environment on LCO's surface is proposed to achieve a homogeneous bulk-to-surface Li distribution upon cycling. The diffusion optimized LCO not only shows a highly reversible capacity of 212 mA h g-1 but also an ultrahigh capacity retention of 80% over 600 cycles at 4.6 V. Combined in situ X-ray diffraction measurements and stress-evolution simulation analysis, it is revealed that the superior 4.6 V long-cycled stability is ascribed to a reduced structure stress leaded by the homogeneous bulk-to-surface Li diffusion. This work broadens approaches for the design of highly stable layered oxide cathodes with low ion-storage structure stress.