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Nano Research 2017, 10(12): 4201-4209 https://doi.org/10.1007/s12274-017-1489-3
Research Article | Issue | Published: 26 April 2017

Improving the structural stability of Li-rich cathode materials via reservation of cations in the Li-slab for Li-ion batteries

Show Author's Information Ji-Lei Shi1,3,  Dong-Dong Xiao2,  Xu-Dong Zhang1,3,  Ya-Xia Yin1,  Yu-Guo Guo1,3( ),  Lin Gu2( ),  Li-Jun Wan1( )
CAS Key Laboratory of Molecular Nanostructure and Nanotechnology CAS Research/Education Center for Excellence in Molecular Sciences Institute of Chemistry Chinese Academy of Sciences, Beijing 100190 China
Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of Sciences Beijing 100190 China
School of Chemistry and Chemical Engineering University of Chinese Academy of Sciences Beijing 100049 China
Keywords:
cathode materials, Li-ion batteries, voltage decay, lithium-rich
Cite this article:
Shi J-L, Xiao D-D, Zhang X-D, et al. Improving the structural stability of Li-rich cathode materials via reservation of cations in the Li-slab for Li-ion batteries. Nano Research, 2017, 10(12): 4201-4209. https://doi.org/10.1007/s12274-017-1489-3
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Abstract Full text About this article

High-capacity Li-rich cathode materials can significantly improve the energy density of lithium-ion batteries, which is the key limitation to miniaturization of electronic devices and further improvement of electrical-vehicle mileage. However, severe voltage decay hinders the further commercialization of these materials. Insights into the relationship between the inherent structural stability and external appearance of the voltage decay in high-energy Li-rich cathode materials are critical to solve this problem. Here, we demonstrate that structural evolution can be significantly inhibited by the intentional introduction of certain adventive cations (such as Ni2+) or by premeditated reservation of some of the original Li+ ions in the Li slab in the delithiated state. The voltage decay of Li-rich cathode materials over 100 cycles decreased from 500 to 90 or 40 mV upon introducing Ni2+ or retaining some Li+ ions in the Li slab, respectively. The cations in the Li slab can serve as stabilizers to reduce the repulsion between the two neighboring oxygen layers, leading to improved thermodynamic stability. Meanwhile, the cations also suppress transition metal ion migration into the Li slab, thereby inhibiting structural evolution and mitigating voltage decay. These findings provide insights into the origin of voltage decay in Li-rich cathode materials and set new guidelines for designing these materials for high-energy-density Li-ion batteries.


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About this article

Improving the structural stability of Li-rich cathode materials via reservation of cations in the Li-slab for Li-ion batteries

Show Author's information Ji-Lei Shi1,3, Dong-Dong Xiao2, Xu-Dong Zhang1,3, Ya-Xia Yin1, Yu-Guo Guo1,3( ), Lin Gu2( ), Li-Jun Wan1( )
CAS Key Laboratory of Molecular Nanostructure and Nanotechnology CAS Research/Education Center for Excellence in Molecular Sciences Institute of Chemistry Chinese Academy of Sciences, Beijing 100190 China
Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of Sciences Beijing 100190 China
School of Chemistry and Chemical Engineering University of Chinese Academy of Sciences Beijing 100049 China

Abstract

High-capacity Li-rich cathode materials can significantly improve the energy density of lithium-ion batteries, which is the key limitation to miniaturization of electronic devices and further improvement of electrical-vehicle mileage. However, severe voltage decay hinders the further commercialization of these materials. Insights into the relationship between the inherent structural stability and external appearance of the voltage decay in high-energy Li-rich cathode materials are critical to solve this problem. Here, we demonstrate that structural evolution can be significantly inhibited by the intentional introduction of certain adventive cations (such as Ni2+) or by premeditated reservation of some of the original Li+ ions in the Li slab in the delithiated state. The voltage decay of Li-rich cathode materials over 100 cycles decreased from 500 to 90 or 40 mV upon introducing Ni2+ or retaining some Li+ ions in the Li slab, respectively. The cations in the Li slab can serve as stabilizers to reduce the repulsion between the two neighboring oxygen layers, leading to improved thermodynamic stability. Meanwhile, the cations also suppress transition metal ion migration into the Li slab, thereby inhibiting structural evolution and mitigating voltage decay. These findings provide insights into the origin of voltage decay in Li-rich cathode materials and set new guidelines for designing these materials for high-energy-density Li-ion batteries.

Keywords: cathode materials, Li-ion batteries, voltage decay, lithium-rich

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Publication history
Copyright
Acknowledgements

Publication history

Received: 28 November 2016
Revised: 17 January 2017
Accepted: 19 January 2017
Published: 26 April 2017
Issue date: December 2017

Copyright

© Tsinghua University Press and Springer‐Verlag Berlin Heidelberg 2017

Acknowledgements

Acknowledgements

This work was supported by the National Key Research and Development Program of China (No. 2016YFA0202500), the National Natural Science Foundation of China (Nos. 51225204 and 21127901), and the "Strategic Priority Research Program" of the Chinese Academy of Sciences (No. XDA09010000).

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