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

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 (Tdec) = 238.1 °C, impact sensitivity (IS) = 24 J, friction sensitivity (FS) = 210 N, and detonation product (DP) (CO) NH3OH-2AZTO-Li: D = 9028 m s–1, P = 35.7 GPa, Tdec = 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.