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Understanding the thermal stability and bonding characteristic of Li x Ni0.5Mn1.5O4 as cathode materials for lithium-ion battery from first principles

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Abstract

The thermodynamic stability is a very important quantity for the electrode materials, because it is not only related to the electrochemical performances of the materials but also the safety issue of the cells. To evaluate the thermodynamic stability of Li x Ni0.5Mn1.5O4 (x = 0, 1), the formation enthalpies from elemental phases and oxides were obtained. The values for LiNi0.5Mn1.5O4 were calculated to be −1341.10 and −141.84 kJ mol−1, while those for Ni0.5Mn1.5O4 were −949.11 and −49.21 kJ mol−1. These values are much more negative than those of LiCoO2 and LiNiO2 compounds, indicating that the thermodynamic stability of Li x Ni0.5Mn1.5O4 is better than the two classic compounds. To clarify the microscopic origin, the density of states, magnetic moments, and bond orders were systematically investigated. The results showed that the excellent thermodynamic stability of LiNi0.5Mn1.5O4 is attributed to the absence of Jahn-Teller distortions, strong electrostatic interactions of Li–O ionic bond, and strong Ni–O/Mn–O ionic-covalent mixing bonds. After lithium extraction, the disappearance of the pure Li–O bonds leads to an increase of formation enthalpy, indicating a decreasing thermodynamic stability for Ni0.5Mn1.5O4 with respect to LiNi0.5Mn1.5O4.

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Acknowledgments

This work was financially supported by the Anhui Provincial Natural Science Foundation (1508085MB25), National Natural Science Foundation of China (nos. 51274002, 21301052, and 51404002), Anhui Provincial Science Fund for Excellent Young Scholars (gxyqZD2016066), Specialized Research Fund for the Doctoral Program of Higher Education (20132301120001), Postdoctoral science-research developmental foundation of Heilongjiang Province (LBH-Q13138), Natural Science Foundation of Heilongjiang Province (E2016056), and the Applied Technology Research and Development Program of Harbin (2015RAQXJO32).

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Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, People’s Republic of China

    Qing-Shan Song, Hai-Tao Yu, Ying Xie & Zhi-chao Xiong

  2. School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, Anhui, 243002, People’s Republic of China

    Ting-Feng Yi

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Correspondence to Ying Xie or Ting-Feng Yi.

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Song, QS., Yu, HT., Xie, Y. et al. Understanding the thermal stability and bonding characteristic of Li x Ni0.5Mn1.5O4 as cathode materials for lithium-ion battery from first principles. Ionics 23, 559–565 (2017). https://doi.org/10.1007/s11581-016-1846-3

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