In-situ X-ray absorption spectroscopy investigations of a layered LiNi0.65Co0.25Mn0.1O2 cathode material for rechargeable lithium batteries

In-situ X-ray absorption spectroscopy investigations have been carried out to evaluate the oxidation states and the local structure at the Mn, Co and Ni K-edges for LiNi0.65Co0.25Mn0.1O2 during a charging and discharging process in this study. It was found that only the Ni atom in LiNi0.65Co0.25Mn0.1O2 is electroactive from the evolution of XANES spectra and the bond length variation of Ni–O. We observed that the NiII/NiIV and NiIII/NiIV redox pairs exist and the oxidation states of Mn and Co remain as MnIV and CoIII, respectively, in LiNi0.65Co0.25Mn0.1O2 on a charge and discharge cycle. In addition, the irreversible capacity at the first cycle derives mainly from the appearance of inactive Ni during the first discharging, which is consistent with the energy shift E–E0 of the absorption edge for the Ni absorber and the bond length change of Ni–O. A decrease/increase of Debye–Waller factor of the Ni–O contribution results from a decrease/increase of Jahn–Teller active NiIII concentration on the charge and discharge cycle. The charge ordering between NiII and MnIV may take place in this compound, resulting from the significant difference of the bond length and the Debye–Waller factor for the second shell Mn–M and Ni–M contributions between the starting and fully charged states. A balance of the repulsive force and size effect in the layered compound plays an important role in the inhibition of structure distortion during the delithiation and lithiation cycle.