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Thermodynamics of graphite intercalation binary alloys of Li-Na, Na-K, and Li-K from van der Waals density functionals

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Abstract

Graphite may store lithium or potassium, but not sodium, in its interlayer space under ambient conditions. It is, however, unclear whether binary alkali alloys of Li-Na, Li-K, and Na-K may substitute pure Li or K to form binary alkali alloy-graphite intercalation compounds. We investigate thermodynamics of the binary alloy-graphite intercalation compounds using density functional theory with van der Waals density functionals. We find Li-rich co-intercalation compounds and K-rich ones are associated with negative formation energies, and the Na-K alloy has the broadest domain of co-intercalation (approximately up to 36% Na). Because of convexity of the formation-energy functions, these compounds are metastable and tend to decompose even when formation energies are negative. Na metal is among the decomposition products. Binary Li-K alloys in graphite form segregated phases of LiC6 and KC8, and this allows one to fabricate Li-K mixed-ion batteries using graphite anodes, whereas Li-Na and Na-K alloys are thermodynamically unfavorable. The study highlights the importance of convexity of formation-energy functions in thermodynamics of alloy-graphite intercalation compounds.

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Funding

This work is supported by Doctoral Fund of Ministry of Education of China (20133108120021), the National Natural Science Foundation of China for Youths (51302166), and Municipal Natural Science foundation of Shanghai. The computations are performed on Compmat cluster and Ziqiang4000 supercomputer of the High Performance Computing Center of Shanghai University.

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  1. School of Materials Science and Engineering, Shanghai University, Shanghai, China

    Tao Song, Yaoping Xie, Yigang Chen & Haibo Guo

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  1. Tao Song
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Correspondence to Haibo Guo.

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Song, T., Xie, Y., Chen, Y. et al. Thermodynamics of graphite intercalation binary alloys of Li-Na, Na-K, and Li-K from van der Waals density functionals. J Solid State Electrochem 23, 2825–2834 (2019). https://doi.org/10.1007/s10008-019-04383-6

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