Ni-rich　layered　oxides,　like　LiNi0.8Co0.1Mn0.1O2　(NCM811),　have　been　widely　investigated　as　cathodes　due　to　their　high　energy　density.　However,　gradual　structural　transformation　during　cycling　can　lead　to　capacity　degradation　and　potential　decay　of　cathode　materials.　Herein,　we　doped　high-valence　transition　metal　(TM)　ions　(V5+,　Nb5+,　and　Zr4+)　at　the　Ni　site　of　NCM811　by　first　principles　simulations　and　explored　the　mechanism　of　doping　TMs　in　NCMs　for　enhancing　the　electrochemical　performance.　Analysis　of　the　calculations　shows　that　doping　V,　Nb　and　Zr　has　an　efficient　influence　on　alleviating　the　Ni　oxidation,　reducing　the　loss　of　oxygen,　and　facilitating　Li+　migration.　Moreover,　V　doping　can　further　suppress　the　lattice　distortion　due　to　the　radius　of　V5+　being　close　to　the　radius　of　Mn4+.　In　particular,　compared　with　the　barrier　of　the　pristine　NCM　in　Li　divacancy,　the　barrier　of　V-doped　NCM　reaches　the　lowest.　In　conclusion,　V　is　the　most　favorable　dopant　for　NCM811　to　improve　the　electrochemical　properties　and　achieve　both　high　capacity　and　cycling　stability.　©　2021　the　Owner　Societies.