Graphite　anode　materials　and　carbonate　electrolyte　have　been　the　top　choices　for　commercial　lithium-ion　batteries　(LIBS)　for　a　long　time.　However,　the　uneven　deposition　and　stripping　of　lithium　cause　irreversible　damage　to　the　graphite　structure,　and　the　low　flash　point　and　high　flammability　of　the　carbonate　electrolyte　pose　a　significant　fire　safety　risk.　Here,　we　proposed　a　multifunctional　electrolyte　additive　diphenylphosphoryl　azide　(DPPA),　which　can　construct　a　solid　electrolyte　interphase　(SEI)　with　high　ionic　conductivity　lithium　nitride　(Li3N)　to　ensure　efficient　transport　of　Li+.　This　not　only　protects　the　artificial　graphite　(AG)　electrode　but　also　inhibits　lithium　dendrites　to　achieve　excellent　electrochemical　performance.　Meanwhile,　the　LIBS　with　DPPA　offers　satisfactory　flame　retardancy　performance.　The　AG//Li　half　cells　with　DPPA-0.5M　can　still　maintain　a　specific　capacity　of　about　350　mAh/g　after　200　cycles　at　0.2　C.　Its　cycle　performance　and　rate　performance　were　better　than　commercial　electrolyte　(EC/DMC).　After　cycling,　the　microstructure　surface　of　the　AG　electrode　was　complete　and　flat,　and　the　surface　of　the　lithium　metal　electrode　had　fewer　lithium　dendrites.　Importantly,　we　found　that　the　pouch　cell　with　DPPA-0.5M　had　low　peak　heat　release　rate.　When　exposed　to　external　conditions　of　continuous　heating,　DPPA　significantly　improved　the　fire　safety　of　the　LIBS.　The　research　of　DPPA　in　lithium　electrolyte　is　a　step　towards　the　development　of　safe　and　efficient　lithium　batteries.　©　2024　by　the　authors.