异质阳离子高能低感含能盐的设计及性能调控

As a new kind of green energetic materials, energetic salts have gained more and more attentions as high energy density materials. It is critically difficult to achieve high heat of formation, high density and low sensitivity at the same time. In this project, a method is first proposed to match hetero-cations with anions to get energetic salts with high energy and low sensitivity, which breaks the limit of one-to-one match of cation and anion. The hetero-cationic salts are designed and synthesized by regulating and matching the hetero-cations and dianion. The effects of functional group and ion on heat of formation and density are mainly studied. The influences of hydrogen bond on crystal structures and sensitivity are revealed. Dense packing of hetero-cationic salts is obtained by crystal regulation. The obtained hetero-cationic energetic salts possess high heat of formation, high density, and low sensitivity. The study will be valuable to guide the design and synthesis of new energetic materials with high energy and low sensitivity in experimental and theoretical aspects.

含能盐作为一类新型的绿色含能材料，已成为高能量密度材料研究的重点。如何实现高生成焓、高密度和低感度的统一始终是含能盐研究的难点。本项目首次提出异质阳离子构建高能低感含能盐的方法，突破了含能盐阴阳离子一对一配对的局限；通过异质阳离子和二价阴离子的结构调控和匹配，设计合成新型含能盐；重点研究官能团和离子协同作用对生成焓和密度的调控机制，揭示氢键对含能盐密度和感度的影响规律；通过晶型调控获得阴阳离子的有序致密堆积，实现含能盐高生成焓、高密度和低感度的统一，为高能低感含能盐研究提供理论依据和实验指导。

含能材料是国防工业的命脉，国民经济发展的基石。高能低感是含能材料领域研究开发的重要方向，传统含能材料能量和感度总是相互矛盾的。本项目提出构建异质阳离子含能盐的概念，这种含能盐含多个官能团，有利于形成更多的氢键，降低感度；不同大小离子交替排列可实现晶体的致密堆积提高密度；同时结构本身又具有较高生成焓，因此异质阳离子含能盐可实现高能、高密度、低感度的统一；通过结构设计与优化获得了系列异质阳离子含能盐结构，并对设计的化合物进行了选择性合成，先后合成出4,4’,5,5’-四硝基咪唑（TNBI）、4-R-5-硝基-1,2,3-三唑等系列含能盐，获得了它们的微观结构和理化性质参数，详细揭示了他们的构效关系；本项目制备出的4,5-二硝基-1,2,3-三唑羟胺盐、4-硝酰胺-5-硝基-1,2,3-三唑羟胺盐的综合性能较优，可显著提高固体推进剂的比冲，具有潜在的应用前景。