Oxygen redox at high voltage has emerged as a transformative paradigm for high-energy battery cathodes such as layered transition-metal oxides by offering extra capacity beyond conventional transition-metal redox. However, these cathodes suffer from voltage hysteresis, voltage fade and capacity drop upon cycling. Single-crystalline cathodes have recently shown some improvements, but these challenges remain. Here we reveal the fundamental origin of oxygen redox instability to be from the domain boundaries that are present in single-crystalline cathode particles. By investigating single-crystalline cathodes with different domain boundaries structures, we show that the elimination of domain boundaries enhances the reversible lattice oxygen redox while inhibiting the irreversible oxygen release. This leads to significantly suppressed structural degradation and improved mechanical integrity during battery cycling and abuse heating. The robust oxygen redox enabled through domain boundary control provides practical opportunities towards high-energy, long-cycling, safe batteries.

The degradation of Ni-rich cathodes during long-term operation at high voltage has garnered significant attention from both academia and industry. Despite many post-mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X-ray probes, electron microscopy, and post-galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi_0.83Mn_0.1Co_0.07O₂ cathode during long-term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three-order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic-free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock-salt phases at high voltage. These findings deepen the degradation mechanism of high-voltage cathodes to achieve long-cycling and fast-charging performance.