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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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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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. |
format | Online Article Text |
id | pubmed-10644792 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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