Our　study　shows　that　3,　3′-sulfonyldipropionitrile　(SDPN),　as　an　electrolyte　additive,　can　dramatically　enhance　the　performance　of　LiNi1/3Co1/3Mn1/3O2/graphite　lithium-ion　batteries　(LIBs)　at　high　voltages　(3.0-4.6　V　vs.　Li/Li+).　After　adding　0.2　wt%　SDPN　to　the　electrolytes;　i.-e.,　1.0　M　LiPF6-EC/DMC/EMC,　the　capacity　for　the　LiNi1/3Co1/3Mn1/3O2/graphite　cell　to　retain　power　was　significantly　increased　from　59.5%　to　77.3%　after　only　100　cycles,　which　shows　the　promising　application　of　SDPN　at　higher　voltages.　Density　functional　theory　calculation　results　indicate　that　SDPN　had　reduced　oxidative　constancy　compared　to　ethylene　carbonate　(EC),　dimethyl　carbonate　(DMC)　and　ethyl　methyl　carbonate　(EMC).　The　effects　of　SDPN　on　cell　performance　are　characterized　by　scanning　electron　microscopy　(SEM),　transmission　electron　microscopy　(TEM),　electrochemical　impedance　spectroscopy　(EIS)　and　X-ray　photoelectron　spectroscopy　(XPS).　The　testing　results　indicate　that　the　improvement　in　cycling　activity　could　be　ascribed　to　the　thinner　cathode　electrolyte　interface　film　originated　from　SDPN　on　the　LIB　using　LiNi1/3Co1/3Mn1/3O2,　which　reduced　the　interfacial　resistance　at　a　high　voltage,　but　also　protected　the　decomposition　of　electrolytes　and　suppressed　transition　metal　dissolution.　©　2016　Elsevier　B.V.　All　rights　reserved.