Nonhysteretic redox capacity is a critical factor in achieving high energy density without energy loss during cycling for rechargeable battery electrodes, which has been considered a major challenge in oxygen redox (OR) for Li-excess layered oxide cathodes for lithium-ion batteries (LIBs). Until recently, transition metal migration into the Li metal layer and the formation of O-O dimers have been considered major factors affecting hysteretic oxygen capacity. However, Li-excess layered oxides, particularly Ru oxides, exhibit peculiar voltage hysteresis that cannot be sufficiently described by only these factors. Therefore, this study aims to unlock the critical impeding factors in restraining the non-polarizing oxygen capacity of Li-excess layered oxides (herein, Li2RuO3) that exhibit reversible OR reactions. First, Li2RuO3 undergoes an increase in the chemical potential fluctuation as both the thermodynamic material instability and vacancy content increase. Second, the chemical compression of O-O bonds occurs at the early stage of the OR reaction (0.5 ≤ x ≤ 0.75) for Li1-xRu0.5O1.5, leading to flexible voltage hysteresis. Finally, in the range of 0.75 ≤ x ≤ 1.0, for Li1-xRu0.5O1.5, the formation of an O(2p)-O(2p)* antibonding state derived from the structural distortion of the RuO6 octahedron leads to the irreversibility of the OR reaction and enhanced voltage hysteresis. Consequently, our study unlocks the new decisive factor, namely, the structural distortion inducing the O(2p)-O(2p)* antibonding state, of the hysteretic oxygen capacity and provides insights into enabling the full potential of the OR reaction for Li-excess layered oxides for advanced LIBs.
Keywords: Li-excess cathode; anionic redox reactions; first-principles calculations; lithium-ion batteries; thermodynamic phase stability; voltage hysteresis.