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Ammonium dinitramide (ADN) is considered as a potential substitute for ammonium perchlorate in energetic materials due to its high density, positive oxygen balance, and halogen-free characteristics. However, its application has been severely limited because of its strong hygroscopicity, difficult storage, and incompatibility with isocyanate curing agents. In order to better bloom the advantages of the highly energetic and environment-friendly ADN in the fields of energetic materials, an in-depth analysis of the current situation and discussion of key research points are particularly important. In this paper, a detailed overview on the synthesis, thermal decomposition, hygroscopic mechanism, and anti-hygroscopicity of ADN has been discussed, its application in powders and explosives are also presented, and its future research directions are proposed.