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

超交换相互作用调控Ni/Mn自旋态,引发Ni-t(2g)/O-2p还原耦合,从而实现稳定的富锂正极材料。

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Abstract

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 Li(1.2)Mn(0.6)Ni(0.2)O(2) by Be doping, which generates the superexchange interaction and activates Ni-t(2g) orbitals. The activation of Ni-t(2g) orbitals triggers the reductive coupling mechanism between Ni/O, which improves the reversibility and kinetics of anionic redox. The strong π-type Ni-t(2g)/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(-1)), with a rate performance of 187 mAh/g at 10 C (6 min, 2500 mA g(-1)), providing a strategy for stabilising oxygen redox chemistry and designing high performance lithium-rich cathodes.

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