The emergence of a robust lithium gallium oxide surface layer on gallium-doped LiNiO 2 cathodes enables extended cycling stability

LiNiO 2 is a promising cobalt-free cathode for lithium-ion batteries due to its high theoretical capacity and low cost. Although intensely studied, the occurrence of several phase transformations and particle pulverization causing capacity fading in cobalt-free LiNiO 2 have yet to be effectively resolved. Herein, a sol–gel synthesis process is utilized for gallium (Ga) doping of LiNiO 2 at 2% (solution-doping) and 5% (excess-doping) molar ratios. Transmission electron microscopy and X-ray diffraction Rietveld refinement reveal the opportune formation of an α-LiGaO 2 shell at 5% doping beyond the solubility limit of 2%. Alongside solution-doping at the Ni and Li crystallographic sites, the emergence of this α-LiGaO 2 , isostructural and lattice-matched to the R 3̄ m LiNiO 2 , is shown to improve capacity retention by a factor of 2.45 after 100 cycles at C/3. Particles with the LiGaO 2 shell experience significantly less pulverization during extended cycling. In contrast, the solution-doped LiNiO 2 with 2% Ga experiences extensive particle fracturing similar to the baseline undoped LiNiO 2 . In turn, no significant electrochemical performance difference is found between the solution-doped and baseline LiNiO 2 . The evidence garnered suggests that a surface gallium oxide phase achievable with excess Ga is key to enabling extended cycling using Ga doping.