Formation mechanism of insensitive tellurium hexanitride with armchair-like cyclo-N6 anions

Zhao Liu,Fubo Tian,Tian Cui,Defang Duan,Fangfei Li,Quan Zhuang,Da Li

doi:10.1038/s42004-020-0286-1

Zhao Liu, Fubo Tian + Show 5 more

Open Access

https://doi.org/10.1038/s42004-020-0286-1

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Journal: Communications chemistry	Publication Date: Apr 2, 2020
Citations: 15	License type: open-access

Affiliation: Jilin University, Ningbo University

Abstract

The lower decomposition barriers of cyclo-N6 anions hinder their application as high-energy-density materials. Here, first-principles calculations and molecular dynamics simulations reveal that enhancing the covalent component of the interaction between cyclo-N6 anions and cations can effectively improve the stability of cyclo-N6 anions. Taking tellurium hexanitride as a representative, the exotic armchair-like N6 anions of tellurium hexanitride exhibit resistance towards electronic attack and gain extra stability through the formation of covalent bonds with the surrounding elemental tellurium under high pressures. These covalent bonds effectively improve the chemical barrier and insensitivity of tellurium hexanitride during blasting, which prevents the decomposition of solid cyclo-N6 salts into molecular nitrogen. Furthermore, the high-pressure induced covalent bonds between cyclo-N6 anions and tellurium enable the high bulk modulus, remarkable detonation performance, and high-temperature thermodynamic stability of tellurium hexanitride.

Highlights

The lower decomposition barriers of cyclo-N6 anions hinder their application as high-energydensity materials
A typically clean and controllable thermodynamic variable, can be adopted to obtain curious materials that are difficult to synthesize under ambient condition[1,2,3]
The precompression evoked by metal elements can reduce the required external pressure for the synthesis of these materials[4]

Summary

Introduction

The lower decomposition barriers of cyclo-N6 anions hinder their application as high-energydensity materials. Taking tellurium hexanitride as a representative, the exotic armchair-like N6 anions of tellurium hexanitride exhibit resistance towards electronic attack and gain extra stability through the formation of covalent bonds with the surrounding elemental tellurium under high pressures These covalent bonds effectively improve the chemical barrier and insensitivity of tellurium hexanitride during blasting, which prevents the decomposition of solid cyclo-N6 salts into molecular nitrogen. We propose a strategy to maintain the “non-molecular nitrogen phase”, i.e., to enhance its energy barrier and insensitivity via covalent bonds entrapment between metal/nonmetal and cyclo-N6 ions to keep it from breaking down into the molecular phase.

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