The recently developed ammonium perchloratebased molecular perovskite has been demonstrated to exhibit excellent comprehensive performance as an energetic material. This ABX 3 -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 (C 6 NH 14 )(NH 4 )(ClO 4 ) 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 NH 3 , H 2 O, HNCO, HCN, CO, HCl, and CO 2 . 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.
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