LiNiO${}_2$ as a high-entropy charge- and bond-disproportionated glass

Abstract

Understanding microscopic properties of LiNiO${}_2$, a Li-ion battery cathode material with extraordinarily high reversible capacity, has remained a challenge for decades. Based on extensive electronic structure calculations, which reveal a large number of nearly degenerate phases involving local Jahn-Teller effect as well as bond and oxygen-based charge disproportionation, we propose that LiNiO${}_2$ exists in a high-entropy charge-glass like state at and below ambient temperatures. Recognizing the glassy nature of LiNiO${}_2$ does not only explain its key experimental features, but also opens a new path in designing entropy-stabilized battery cathodes with superb capacities.

8 pages, 7 figures

References in corpus (4)

• Ground state oxygen holes and the metal-insulator transition in the negative charge transfer rare-earth nickelates
• Bond disproportionation and dynamical charge fluctuations in the perovskite rare earth nickelates
• Hybridization effects and bond-disproportionation in the bismuth perovskites
• Ground-state valency and spin configuration of the Ni-ions in nickelates

Cited by in corpus (7)

• Understanding the role of entropy in high entropy oxides
• Oxygen Hole Formation Controls Stability in LiNiO${}_2$ Cathodes: DFT Studies of Oxygen Loss and Singlet Oxygen Formation in Li-Ion Batteries
• A fundamental correlative spectroscopic study on LixNiO2 and NaNiO2
• Distinct electridelike nature of infinite-layer nickelates and the resulting theoretical challenges to calculate their electronic structure
• Self-regulated ligand-metal charge transfer upon lithium ion de-intercalation process from LiCoO2 to CoO2
• Temperature-Dependent Dynamic Disproportionation in LiNiO${}_2$
• Direct Evidence of Metal-Ligand Redox in Li-ion Battery Positive Electrodes