Lithium-rich layered oxides, despite their potential as high-energy-density cathode materials, are impeded by electrochemical performance deterioration upon anionic redox. Although this deterioration is believed to primarily result from structural disordering, our understanding of how it is triggered and/or occurs remains incomplete. Herein, we propose a theoretical picture that clarifies the irreversible transformation and redox asymmetry of lithium-rich layered oxides by introducing a series of global and local dynamic structural evolution processes involving slab gliding and transition-metal migration. We show that slab gliding plays a key role in trigger/initiating the structural disordering and consequent degradation of the anionic redox reaction. We further reveal that the ‘concerted disordering mechanism’ of slab gliding and transition-metal migration produces spontaneously irreversible/asymmetric lithiation and de-lithiation pathways, causing irreversible structural deterioration and the asymmetry of the anionic redox reaction. Our findings suggest slab gliding as a crucial, yet underexplored, method for achieving a reversible anionic redox reaction.

富锂层状氧化物尽管具有作为高能量密度正极材料的潜力，但由于阴离子氧化还原时电化学性能恶化而受到阻碍。尽管这种恶化被认为主要是由于结构紊乱造成的，但我们对其如何触发和/或发生的理解仍然不完整。在此，我们提出了一个理论图景，通过引入一系列涉及板坯滑动和过渡金属迁移的全局和局部动态结构演化过程，阐明了富锂层状氧化物的不可逆转变和氧化还原不对称性。我们表明，板坯滑动在触发/引发结构紊乱和随后的阴离子氧化还原反应降解中起着关键作用。我们进一步揭示了板片滑移和过渡金属迁移的“协同无序机制”产生自发的不可逆/不对称的锂化和脱锂途径，导致不可逆的结构恶化和阴离子氧化还原反应的不对称。我们的研究结果表明，平板滑移是实现可逆阴离子氧化还原反应的一种关键但尚未充分探索的方法。