Formation of solid solution and its effect on lithium insertion schemes for advanced lithium-ion batteries: X-ray absorption spectroscopy and X-ray diffraction of LiCoO2, LiCo1/2Ni1/2O2 and LiNiO2

The X-ray absorption spectra (XAS) of LiCoO₂, LiCo_1/2Ni_1/2O₂ and LiNiO₂ were examined together with X-ray diffraction (XRD). Co and Ni K-edge XANES spectra of LiCo_1/2Ni_1/2O₂ are quite similar to that of LiCoO₂ or LiNiO₂, suggesting that electronic states of Co and Ni in LiCo_1/2Ni_1/2O₂ are Co³⁺ and Ni³⁺. Analytical results of Co and Ni K-edge EXAFS oscillations on the first coordination shell of nickel and cobalt ions in LiCo_1/2Ni_1/2O₂ indicate that the local environment around the targeted species is the same as that in LiCoO₂ or LiNiO₂. Since there is no doubt about the crystal and electronic structures of LiCoO₂ and LiNiO₂, the results indicate that LiCo_1/2Ni_1/2O₂ consists of low-spin states of Co³⁺ and Ni³⁺ distributed at equivalent positions in triangular lattice of sites forming homogeneous transition metal oxide layers. Thus, XAS complements XRD in describing solid solution LiCo_1/2Ni_1/2O₂ of LiCoO₂ and LiNiO₂. The electrochemical behaviors of LiCoO₂, LiCo_1/2Ni_1/2O₂ and LiNiO₂ are also restated and the effects of the formation of solid solution on the change in lattice dimension during topotactic electrochemical reactions are discussed.