Layered lithium cobalt oxide (LiCoO2, LCO) is the most successful commercial cathode material in lithium-ion batteries. However, its notable structural instability at potentials higher than 4.35 V (versus Li/Li+) constitutes the major barrier to accessing its theoretical capacity of 274 mAh g−1. Although a few high-voltage LCO (H-LCO) materials have been discovered and commercialized, the structural origin of their stability has remained difficult to identify. Here, using a three-dimensional continuous rotation electron diffraction method assisted by auxiliary high-resolution transmission electron microscopy, we investigate the structural differences at the atomistic level between two commercial LCO materials: a normal LCO (N-LCO) and a H-LCO. These powerful tools reveal that the curvature of the cobalt oxide layers occurring near the surface dictates the structural stability of the material at high potentials and, in turn, the electrochemical performances. Backed up by theoretical calculations, this atomistic understanding of the structure–performance relationship for layered LCO materials provides useful guidelines for future design of new cathode materials with superior structural stability at high voltages.
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The data that support the findings of this study are available from the corresponding authors upon reasonable request.
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This research is financially supported by the National Key R&D Programme of China (no. 2016YFB0700600), Guangdong Innovative Team Programme (2013N080), Guangdong Key-lab Project (no. 2017B0303010130), Shenzhen Science and Technology Research Grant (no. ZDSYS20170728102618), National Basic Research Programme of China (nos. 2013CB933402 and 2016YFA0301004) and National Natural Science Foundation of China (nos. 21527803, 21621061 and 21871009).
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Shi Xue Dou, Michael Toney and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Figs. 1–14, Tables 1–5, Notes 1–2 and refs. 1–20.
Data collection and reconstructed reciprocal lattice of cRED for H-LCO-P.
Data collection and reconstructed reciprocal lattice of cRED for N-LCO-P.
Data collection and reconstructed reciprocal lattice of cRED for N-LCO-4.2.
Data collection and reconstructed reciprocal lattice of cRED for H-LCO-4.2.
Data collection and reconstructed reciprocal lattice of cRED for N-LCO-4.5.
Data collection and reconstructed reciprocal lattice of cRED for H-LCO-4.5.
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Li, J., Lin, C., Weng, M. et al. Structural origin of the high-voltage instability of lithium cobalt oxide. Nat. Nanotechnol. (2021). https://doi.org/10.1038/s41565-021-00855-x