Electron density plays an important role in determining the properties of functional materials.Revealing the electron density distribution experimentally in real space can help to tune the properties of materials.Spinel LiMn2O4 is one of the most promising cathode candidates because of its high voltage,low cost,and non-toxicity,but suffers severe capacity fading during electrochemical cycling due to the Mn dissolution.Real-space measurement of electron distribution of LiMn2O4 experimentally can provide direct evaluation on the strength of Mn-O bond and give an explanation of the structure stability.Here,through high energy synchrotron powder x-ray diffraction (SPXRD),accurate electron density distribution in spinel LiMn2O4 has been investigated based on the multipole model.The electron accumulation between Mn and O atoms in deformation density map indicates the shared interaction of Mn-O bond.The quantitative topological analysis at bond critical points shows that the Mn-O bond is relatively weak covalent interaction due to the oxygen loss.These findings suggest that oxygen stoichiometry is the key factor for preventing the Mn dissolution and capacity fading.