Layered　Li2MnO3　exhibits　great　potential　as　a　high-capacity　cathode　used　in　lithium-ion　batteries,　but　materials　synthesized　by　traditional　solid-phase　methods　exhibit　poor　activity　and　poor　cycling　stability.　In　this　work,　Li2MnO3　nanoparticles　were　synthesized　by　solid　state　method　combined　with　high-energy　ball　milling,　in　which　Fe　was　doped　at　transition　metal　sites　to　obtain　a　Li-rich　cathode　material　(Li1.32Fe0.034Mn0.64O2).　We　systematically　studied　the　effects　of　Fe　doping　and　calcination　temperature　on　the　crystal　structure　and　electrochemical　properties　and　conducted　kinetic　studies　using　the　galvanostatic　intermittent　titration　technique　(GITT),　electrical　impedance　spectroscopy　(EIS)　and　density　functional　theory　(DFT)　calculations.　Our　results　demonstrate　that　the　performance　was　significantly　improved,　its　discharge　capacity　is　about　235　mAh　g−1　after　10　cycles　compared　138　mAh　g−1　of　the　pristine　sample.　The　GITT　and　EIS　results　show　that　the　Fe-doped　sample　had　smaller　charge　transfer　impedance,　larger　lithium-ion　diffusion　coefficient　and　lower　internal　polarization　than　the　pristine.　The　activation　energy　results　show　the　Fe-doped　sample　has　larger　activation　energy　at　the　late　discharging　period　due　to　the　anion　redox　reaction　activation,　indicting　its　O　activation　is　more　active　than　Li2MnO3.　Moreover,　the　DOS　results　showed　that　the　Fe-doped　sample　had　a　narrow　band-gap,　indicating　good　electrical　conductivity.　The　CI-NEB　results　showed　that　the　Fe-doped　sample　had　a　high　transition　metal　ion　migration　energy　barrier,　indicating　that　its　structure　was　stable.　In　conclusion,　Fe　doping　is　helpful　to　active　the　anion　redox　reaction　in　Li2MnO3　and　improve　its　electrochemical　performance　as　a　low　cost　and　high-capacity　cathode　materials.　©　2023