Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi0.5Mn1.5O4−δ thin films

Abstract

The level of oxygen deficiency δ in high-voltage spinels of the composition LiNi_0.5Mn_1.5O_4−δ (LNMO) significantly influences the thermodynamic and kinetic properties of the material, ultimately affecting the cell performance of the corresponding lithium-ion batteries. This study presents a comprehensive defect chemical analysis of LNMO thin films with oxygen vacancy concentrations of 2.4% and 0.53%, focusing particularly on the oxygen vacancy regime around 4 V versus Li⁺/Li. A set of electrochemical properties is extracted from impedance measurements as a function of state-of-charge for the full tetrahedral-site regime (3.8 to 4.9 V versus Li⁺/Li). A defect chemical model (Brouwer diagram) is derived from the data, providing a coherent explanation for all important trends of the electrochemical properties and charge curve. Highly resolved chemical capacitance measurements allow a refining of the defect model for the oxygen vacancy regime, showing that a high level of oxygen deficiency not only impacts the amount of redox active Mn^3+/4+, but also promotes the trapping of electrons in proximity to an oxygen vacancy. The resulting stabilisation of Mn³⁺ thereby mitigates the voltage reduction in the oxygen vacancy regime. These findings offer valuable insights into the complex influence of oxygen deficiency on the performance of lithium-ion batteries based on LNMO.