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Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films

The level of oxygen deficiency δ in high-voltage spinels of the composition LiNi(0.5)Mn(1.5)O(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 com...

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Autores principales: Bumberger, Andreas E., Ražnjević, Sergej, Zhang, Zaoli, Friedbacher, Gernot, Fleig, Juergen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10644792/
https://www.ncbi.nlm.nih.gov/pubmed/38014361
http://dx.doi.org/10.1039/d3ta05086f
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author Bumberger, Andreas E.
Ražnjević, Sergej
Zhang, Zaoli
Friedbacher, Gernot
Fleig, Juergen
author_facet Bumberger, Andreas E.
Ražnjević, Sergej
Zhang, Zaoli
Friedbacher, Gernot
Fleig, Juergen
author_sort Bumberger, Andreas E.
collection PubMed
description The level of oxygen deficiency δ in high-voltage spinels of the composition LiNi(0.5)Mn(1.5)O(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 Mn(3+) 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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spelling pubmed-106447922023-11-15 Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films Bumberger, Andreas E. Ražnjević, Sergej Zhang, Zaoli Friedbacher, Gernot Fleig, Juergen J Mater Chem A Mater Chemistry The level of oxygen deficiency δ in high-voltage spinels of the composition LiNi(0.5)Mn(1.5)O(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 Mn(3+) 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. The Royal Society of Chemistry 2023-10-16 /pmc/articles/PMC10644792/ /pubmed/38014361 http://dx.doi.org/10.1039/d3ta05086f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Bumberger, Andreas E.
Ražnjević, Sergej
Zhang, Zaoli
Friedbacher, Gernot
Fleig, Juergen
Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title_full Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title_fullStr Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title_full_unstemmed Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title_short Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi(0.5)Mn(1.5)O(4−δ) thin films
title_sort chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of lini(0.5)mn(1.5)o(4−δ) thin films
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10644792/
https://www.ncbi.nlm.nih.gov/pubmed/38014361
http://dx.doi.org/10.1039/d3ta05086f
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