Energetic N‐Nitramino‐Substituted 1,2,4‐Triazole and Corresponding Salts: Green Primary Explosives with Excellent Detonation Performance Based on 1,5‐Diamino‐3‐nitro‐1,2,4‐triazole

5‐amino‐3‐nitro‐1‐nitramino‐1,2,4‐triazole was synthesized through the nitration reaction of 1,5‐diamino‐3‐nitro‐1,2,4‐triazole, and several energetic salts were prepared based on the reactivity of the acidic proton in nitramino group (−NHNO₂). These compounds were fully characterized by NMR (¹H and ¹³C), IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. Their thermal stabilities were analyzed by differential scanning calorimetric (DSC) and Impact and friction sensitivities were determined using standard BAM technology. Moreover, the structural differences between individual compounds were studied to investigate the potential structure‐property relationship. All compounds possess positive heats of formation calculated based on isodesmic reaction to be between 173.7~454.6 kJ ⋅ mol⁻¹. Among them, 5‐amino‐3‐nitro‐1‐nitramino‐1,2,4‐triazole (D=8682 m ⋅ s⁻¹, P=33.0 GPa, IS=0.75 J), hydrazine salt (D=8908 m ⋅ s⁻¹, P=34.9 GPa, IS=0.5 J) and hydroxylamine salt (D=9117 m ⋅ s⁻¹, P=36.7 GPa, IS=2 J) exhibits desirable detonation properties similar to RDX (D=8795 m ⋅ s⁻¹, P=34.9 GPa), calculated by Kamlet‐Jacobs equations and features comparable impact sensitivity with DDNP (IS=1 J). The simple synthetic route, free of heavy metals and superior detonation properties of above compounds make them serve as promising candidate for green primary explosives.