Lithium-Promoted Formation of M-2AZTO-Li (M = N₂H₅⁺ or NH₃OH⁺ and AZTO = Anion of 1-Hydroxytetrazole-5-hydrazide)-Type “Quaternary” Complexes with Nitrogen-Rich Characteristics: Construction of Novel Insensitive Energetic Materials

Abstract

Lithium-based nitrogen-rich complexes are important research objects in the field of high-energy materials. However, the weak coordination abilities of lithium ions relative to those of other metal ions with greater atomic numbers have hindered their applications in the field of nitrogen-rich complexes. Herein, we successfully prepared novel lithium-based nitrogen-rich complexes (N2H5-2AZTO-Li and NH3OH-2AZTO-Li) by exploiting the structural properties of 1-hydroxytetrazolium-5-hydrazine (HAZTO). Both N2H5-2AZTO-Li and NH3OH-2AZTO-Li were found to exhibit physicochemical parameters (including the density, stability, and energetic properties) that were intermediate between those of the simple ionic compounds (3 and 4) and the complexes (5) that formed them, enabling a favorable balance between high energy, high stability, and environmental friendliness (for N2H5-2AZTO-Li: detonation velocity (D) = 9005 m s–1, detonation pressure (P) = 35.5 GPa, decomposition temperature (T dec) = 238.1 °C, impact sensitivity (IS) = 24 J, friction sensitivity (FS) = 210 N, and detonation product (DP) (CO) < 2%; for NH3OH-2AZTO-Li: D = 9028 m s–1, P = 35.7 GPa, T dec = 211.2 °C, IS = 20 J, FS = 180 N, and DP (CO) < 2%). This study transcends the conventional structural forms of nitrogen-rich complexes, opening new horizons for the design of novel insensitive energetic materials.

Increasing the Energy Limit of Single Triazole–Tetrazole: HNANTT Modified with Its Energetic Coordination Polymers, Co-Crystals, and Energetic Salts

“…Energetic coordination polymers (ECPs), ,− energetic salts, ,− and energetic co-crystals , based on energetic parent molecules can overcome the various shortcomings of EMs such as their high friction or impact sensitivity, low energy, low density, and low thermal stability. Their energetic properties ( D v and P ) can also be modified and improved by combining them.…”

“…Although they do not stand out in any specific aspect, they also have no obvious shortcomings, making them more suitable for general applications. 18,19 Inspired by the design strategies of energetic materials mentioned above, the nitration product of the triazole amino group was obtained based on the HANTT molecule. An energetic parent material with a high ΔH f and superior detonation performance was obtained, (Z)-N-(5-nitro-2-(1Htetrazol-5-yl)-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)nitramide (HNANTT).…”

“…Although BNTD is represented as a potential EM, it has been out of the single triazole-tetrazole system with a poor detonation performance with a packing index of 65.4%. 10 Energetic coordination polymers (ECPs), 7,12−15 energetic salts, 10,15−17 and energetic co-crystals 18,19 based on energetic parent molecules can overcome the various shortcomings of EMs such as their high friction or impact sensitivity, low energy, low density, and low thermal stability. Their energetic properties (D v and P) can also be modified and improved by combining them.…”

“…Combining more than two energetic ligands in an energetic co-crystal gives them more balanced overall performance with moderate detonation performances and sensitivities. Although they do not stand out in any specific aspect, they also have no obvious shortcomings, making them more suitable for general applications. , …”

A multi-fused heat-resistant energetic compound constructed by hydrogen bonds

“…Energetic materials have extensive applications in both military and civilian domains, where they serve as indispensable components in rockets, satellites, weapons, mining, and tunnel engineering. [1][2][3] Notably, heat-resistant energetic materials with a decomposition temperature exceeding 250 1C are particularly prevalent in oil and gas extraction and aerospace exploration engineering. 4 For instance, as drilling depths exceed 7000 m, temperatures within the earth can surpass 300 1C, necessitating the use of heat-resistant explosives with superior thermal stability to meet the perforation requirements for deep oil and gas extraction.…”