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The research developments of high-nitrogen energetic materials are reviewed. The synthesis and properties of some new compounds derivated from tetrazole and tetrazine,especially 3,6-dihydrazino-1,2,4,5-tetrazine(DHT),3,3′-azobis(6-amino-1,2,4,5-tetrazine)(DAAT),3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino) -1,2,4,5-tetrazine(BTATz) and 5,5′-bitetrazole(BHT) are discussed. Because of their much more positive heats of formation and higher density，these high-nitrogen compounds are unique in their gas generating ability with a little or without smoke and produced residue. They may have a great future for applications in insensitive explosives,low signature propellants,gas generants and low-smoke pyrotechnics.