To　meet　the　demand　for　higher　energy　density　in　lithium-ion　batteries,　extensive　research　has　focused　on　advanced　cathodes　and　metallic　lithium　anodes.　However,　Ni-rich　cathodes　suffer　from　the　inactive　phase-transition　and　side　reactions　at　the　cathode-electrolyte　interfaces　(CEI).　In　this　study,　we　propose　a　novel　approach　to　enhance　the　solubility　of　LiNO3　in　carbonate　electrolyte　systems　using　a　local　high-concentrated　addition　strategy　with　triethyl　phosphate　as　a　co-solvent.　Rather　than　the　traditional　solvent-dominated　solvation　clusters,　the　NO3−　dominated　electrolyte　is　examined　to　elucidate　unique　complexation　phenomena.　Two　distinct　clusters　in　NO3−　dominated　electrolyte　arising　from　as　a　consequence　of　intramolecular　interactions　intrinsic　to　the　constituents.　This　promotes　the　formation　of　a　homogeneous　oxynitride　interphase　and　facilitates　more　expeditious　lithium　ion　diffusion　kinetics.　Hence,　the　less　stress　fragmentation　and　irreversible　phase　transformation　occur　on　the　cathode　surface　with　the　homogeneous　oxynitridation　interface.　This　innovative　design　enables　efficient　cycling　of　the　Li　||　NCM811　cell,　offering　a　promising　strategy　to　improve　lithium-ion　batteries　performance.　©　2024　Elsevier　B.V.