Superexchange interaction regulates Ni/Mn spin states triggering Ni-t/O-2p reductive coupling enabling stable lithium-rich cathode.

Lithium-rich layer oxides are expected to be high-capacity cathodes for next-generation lithium-ion batteries, but their performance is hindered by irreversible anionic redox, leading to voltage decay, lag, and slow kinetics. In order to solve these problems, we regulate the Ni/Mn spin state in LiMnNiO by Be doping, which generates the superexchange interaction and activates Ni-t orbitals. The activation of Ni-t orbitals triggers the reductive coupling mechanism between Ni/O, which improves the reversibility and kinetics of anionic redox. The strong π-type Ni-t/O-2p interaction forms a stable Ni-(O-O) configuration, suppressing excessive anion oxidation. In this work, the Be modified cathodes have good cycle stability, 0.04 mAh/g and 0.5 mV decay per cycle over 400 cycles at 1 C (60 min, 250 mA g), with a rate performance of 187 mAh/g at 10 C (6 min, 2500 mA g), providing a strategy for stabilising oxygen redox chemistry and designing high performance lithium-rich cathodes.