Thermal Decomposition Mechanism of Molecular Perovskite Energetic Material (C6NH14)(NH4)(ClO4)3(DAP‐4)

The recently developed ammonium perchlorate‐based molecular perovskite has been demonstrated to exhibit excellent comprehensive performance as an energetic material. This ABX3‐type molecular perovskite energetic material consists of a high symmetry ternary structure framework stabilized through ionic bonds. In this work, the thermal decomposition mechanism of (C6NH14)(NH4)(ClO4)3 (DAP‐4) was extrapolated by analyzing its thermal decomposition characteristics, gas products, kinetic parameters, and condensed phase change results along with temperature‐varying, with the help of DSC‐TG‐MS‐FTIR and in‐situ FTIR experiment. The results show that a rapid reaction occurs once the decomposition of DAP‐4 starts at 383.7 °C, with the maximum thermal weight loss rate reaches 97.4 %. By using Kissinger's and Ozawa's method, the calculated activation energy of thermal decomposition of DAP‐4 was estimated to be 124.3 kJ/mol and 128.6 kJ/mol, respectively, demonstrating good reliability of our results. The gas products during the thermal decomposition were found mainly include NH3, H2O, HNCO, HCN, CO, HCl, and CO2. The decomposition process of DAP‐4 contains three stages. The first stage involves crystal form changes and H+ transfer of DPA‐4, followed by the collapse of the cage skeleton in the second stage. The third stage mainly involves a rapid redox reaction at high temperatures to generate great heat.