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

Literature Information

Publication Date 2023-10-16
DOI 10.1039/D3TA05086F
Impact Factor 12.732
Authors

Andreas E. Bumberger, Sergej Ražnjević, Zaoli Zhang, Gernot Friedbacher, Juergen Fleig


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Abstract

The level of oxygen deficiency δ in high-voltage spinels of the composition LiNi0.5Mn1.5O4−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 Mn3+/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.

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Source Journal

Journal of Materials Chemistry A

Journal of Materials Chemistry A
CiteScore: 19.5
Self-citation Rate: 4.7%
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