The richness of anionic redox chemistry in the solid state offers new opportunities and a possible paradigm shift in energy storage. The excess capacity that goes beyond conventional theoretical values is attributed to the anionic redox in Li-rich transition metal oxide cathodes for Li-ion batteries. Their electrochemical behavior is thermodynamically determined by structural evolution. To better understand the electrochemical dependence on structural factors, we have induced structural modifications in pristine and electrochemically activated Li_1.144Ni_0.136Co_0.136Mn_0.544O₂ through high-pressure treatment. A unique cyclical change of structural reordering is observed in the anionic redox-activated material during operando pressure sweep, characterized by a periodic evolution of superlattice peak intensity in synchrotron X-ray diffraction patterns. During the structural reordering period, the bulk compressibility of the material decreases, even becoming negative. These insights elucidate the structural flexibility and metastability of anionic redox-based materials, which can undergo large compressions and structural modifications while delivering good electrochemical properties.

固态阴离子氧化还原化学的丰富性为储能提供了新的机遇和可能的范式转变。超出常规理论值的过剩容量归因于锂离子电池的富锂过渡金属氧化物阴极中的阴离子氧化还原。它们的电化学行为是通过结构演变热力学确定的。为了更好地理解电化学对结构因素的依赖性，我们对原始和电化学活化的Li _1.144 Ni _0.136 Co _0.136 Mn _0.544 O ₂进行了结构修饰。通过高压处理。在操作压力扫描期间，在阴离子氧化还原激活的材料中观察到独特的周期性结构变化，其特征在于同步加速器X射线衍射图中超晶格峰强度的周期性演化。在结构重新排序期间，材料的整体可压缩性降低，甚至变为负压。这些见解阐明了基于阴离子氧化还原的材料的结构灵活性和亚稳定性，这些材料在经受良好压缩和结构修饰的同时还具有良好的电化学性能。