| SPECIAL TOPIC — Structures and properties of materials under high pressure |
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Structural stability and properties of Li2XN6 (X = Be, Mg, Ca) ternary nitrides |
| Rui Wang(王睿)1, Cai-Zi Zhang(张才姿)1, Qi-Wen Jiang(蒋其雯)1, En-Yu Wang(王恩宇)1,†, Jie Wei(魏杰)1,‡, and Hong-Yang Zhu(祝洪洋)1,2,§ |
1 School of Physics and Electronic Engineering, Linyi University, Linyi 276000, China;
2 Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, Oklahoma 74104, United States |
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Abstract Polynitrogen compounds have attracted significant interest as high-energy-density materials (HEDMs), while their extreme synthesis and preservation conditions hinder their practical applications. Metal incorporation into nitrogen frameworks has emerged as an effective strategy to reduce the synthesis and stabilization pressures of polynitrogen compounds. In this study, we theoretically predict three novel lithium-alkaline-earth metal nitrides: cage-like $R$-3$m$ Li$_2$BeN$_6$, cage-like $R$32 Li$_2$MgN$_6$, and layered $P$-62$m$ Li$_2$CaN$_6$. Phonon spectrum calculations indicate that $R$-3$m$ Li$_2$BeN$_6$ remains stable between 50-100 GPa, and that $R$32 Li$_2$MgN$_6$ and $P$-62$m$ Li$_2$CaN$_6$ are stable under ambient pressure conditions. Ab initio molecular dynamics (AIMD) simulations indicate that $R$-3$m$ Li$_2$BeN$_6$, $R$32 Li$_2$MgN$_6$, and $P$-62$m$ Li$_2$CaN$_6$ remain thermally stable up to 2500 K, 1500 K, and 500 K, respectively. Electronic band structure analysis indicates that $R$-3$m$ Li$_2$BeN$_6$ is semiconducting, while $R$32 Li$_2$MgN$_6$ and $P$-62$m$ Li$_2$CaN$_6$ exhibit metallic characteristics. These differences arise from variations in cation radius and electronegativity, which influence the electron distribution within the lattice. The cage-like $R$-3$m$ Li$_2$BeN$_6$ with a chair-shaped N$_6^{6-}$ ring exhibits an energy density of 4.38 kJ/g upon decomposition into Li$_3$N, Be$_3$N$_2$, and N$_2$, indicating its potential as an HEDM. These findings not only highlight the role of metal insertion in stabilizing polymeric nitrogen at lower pressures but also provide novel guidance for the design of energetic materials.
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Received: 21 October 2025
Revised: 11 November 2025
Accepted manuscript online: 13 November 2025
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PACS:
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62.50.-p
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(High-pressure effects in solids and liquids)
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82.40.Fp
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(Shock wave initiated reactions, high-pressure chemistry)
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91.60.Gf
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(High-pressure behavior)
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| Fund: This work was supported by the National Natural Science Foundation of China (Grant No. 11774128) and the Natural Science Foundation of Shandong Province (Grant Nos. ZR2020QA061, ZR2023QA052, ZR2024QA144, and ZR2025QC1496). |
Corresponding Authors:
En-Yu Wang, Jie Wei, Hong-Yang Zhu
E-mail: wangenyu@lyu.edu.cn;weijie@lyu.edu.cn;hongyang-zhu@utulsa.edu
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Cite this article:
Rui Wang(王睿), Cai-Zi Zhang(张才姿), Qi-Wen Jiang(蒋其雯), En-Yu Wang(王恩宇), Jie Wei(魏杰), and Hong-Yang Zhu(祝洪洋) Structural stability and properties of Li2XN6 (X = Be, Mg, Ca) ternary nitrides 2026 Chin. Phys. B 35 036201
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