Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes

Abstract The high-voltage oxygen redox activity of Li-rich layered oxides enables additional capacity beyond conventional transition metal (TM) redox contributions and drives the development of positive electrode active materials in secondary Li-based batteries. However, Li-rich layered oxides often...

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Main Authors: Hao Liu, Weibo Hua, Sylvia Kunz, Matteo Bianchini, Hang Li, Jiali Peng, Jing Lin, Oleksandr Dolotko, Thomas Bergfeldt, Kai Wang, Christian Kübel, Peter Nagel, Stefan Schuppler, Michael Merz, Bixian Ying, Karin Kleiner, Stefan Mangold, Deniz Wong, Volodymyr Baran, Michael Knapp, Helmut Ehrenberg, Sylvio Indris
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54312-z
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author Hao Liu
Weibo Hua
Sylvia Kunz
Matteo Bianchini
Hang Li
Jiali Peng
Jing Lin
Oleksandr Dolotko
Thomas Bergfeldt
Kai Wang
Christian Kübel
Peter Nagel
Stefan Schuppler
Michael Merz
Bixian Ying
Karin Kleiner
Stefan Mangold
Deniz Wong
Volodymyr Baran
Michael Knapp
Helmut Ehrenberg
Sylvio Indris
author_facet Hao Liu
Weibo Hua
Sylvia Kunz
Matteo Bianchini
Hang Li
Jiali Peng
Jing Lin
Oleksandr Dolotko
Thomas Bergfeldt
Kai Wang
Christian Kübel
Peter Nagel
Stefan Schuppler
Michael Merz
Bixian Ying
Karin Kleiner
Stefan Mangold
Deniz Wong
Volodymyr Baran
Michael Knapp
Helmut Ehrenberg
Sylvio Indris
author_sort Hao Liu
collection DOAJ
description Abstract The high-voltage oxygen redox activity of Li-rich layered oxides enables additional capacity beyond conventional transition metal (TM) redox contributions and drives the development of positive electrode active materials in secondary Li-based batteries. However, Li-rich layered oxides often face voltage decay during battery operation. In particular, although Li-rich positive electrode active materials with a high nickel content demonstrate improved voltage stability, they suffer from poor discharge capacity. Here, via physicochemical and electrochemical measurements, we investigate the correlation between oxygen redox activity and superstructure units in Li-rich layered oxides, specifically the fractions of LiMn6 and Ni4+-stabilized LiNiMn5 within the TM layer. We prove that an excess of LiNiMn5 hinders the extraction/insertion of lithium ions during Li metal coin cell charging/discharging, resulting in incomplete oxygen redox activity at a cell potential of about 3.3 V. We also demonstrate that lithium content adjustment could be a beneficial approach to tailor the superstructure units. Indeed, we report an improved oxygen redox reversibility for an optimized Li-rich layered oxide with fewer LiNiMn5 units.
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spelling doaj-art-a5d51fa39c5c4b6c84662f48996f5eca2024-11-24T12:32:27ZengNature PortfolioNature Communications2041-17232024-11-0115111410.1038/s41467-024-54312-zTailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodesHao Liu0Weibo Hua1Sylvia Kunz2Matteo Bianchini3Hang Li4Jiali Peng5Jing Lin6Oleksandr Dolotko7Thomas Bergfeldt8Kai Wang9Christian Kübel10Peter Nagel11Stefan Schuppler12Michael Merz13Bixian Ying14Karin Kleiner15Stefan Mangold16Deniz Wong17Volodymyr Baran18Michael Knapp19Helmut Ehrenberg20Sylvio Indris21Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1University of Bayreuth, Bavarian Center for Battery Technology (BayBatt), Universitätsstraße 30University of Bayreuth, Bavarian Center for Battery Technology (BayBatt), Universitätsstraße 30Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Karlsruhe Nano Micro Facility, Karlsruhe Institute of Technology (KIT), Kaiserstraße 12Karlsruhe Nano Micro Facility, Karlsruhe Institute of Technology (KIT), Kaiserstraße 12Karlsruhe Nano Micro Facility, Karlsruhe Institute of Technology (KIT), Kaiserstraße 12Münster Electrochemical Energy Technology (MEET), University of Münster (WWU)Münster Electrochemical Energy Technology (MEET), University of Münster (WWU)Institute for Photon Science and Synchrotron Radiation (IPS), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Dynamics and Transport in Quantum Materials, Helmholtz-Zentrum Berlin für Materialen und Energie, GmbH, Albert-Einstein-Strasse 15Deutsches Elektronen-Synchrotron (DESY), Notkestrasse 85Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1Abstract The high-voltage oxygen redox activity of Li-rich layered oxides enables additional capacity beyond conventional transition metal (TM) redox contributions and drives the development of positive electrode active materials in secondary Li-based batteries. However, Li-rich layered oxides often face voltage decay during battery operation. In particular, although Li-rich positive electrode active materials with a high nickel content demonstrate improved voltage stability, they suffer from poor discharge capacity. Here, via physicochemical and electrochemical measurements, we investigate the correlation between oxygen redox activity and superstructure units in Li-rich layered oxides, specifically the fractions of LiMn6 and Ni4+-stabilized LiNiMn5 within the TM layer. We prove that an excess of LiNiMn5 hinders the extraction/insertion of lithium ions during Li metal coin cell charging/discharging, resulting in incomplete oxygen redox activity at a cell potential of about 3.3 V. We also demonstrate that lithium content adjustment could be a beneficial approach to tailor the superstructure units. Indeed, we report an improved oxygen redox reversibility for an optimized Li-rich layered oxide with fewer LiNiMn5 units.https://doi.org/10.1038/s41467-024-54312-z
spellingShingle Hao Liu
Weibo Hua
Sylvia Kunz
Matteo Bianchini
Hang Li
Jiali Peng
Jing Lin
Oleksandr Dolotko
Thomas Bergfeldt
Kai Wang
Christian Kübel
Peter Nagel
Stefan Schuppler
Michael Merz
Bixian Ying
Karin Kleiner
Stefan Mangold
Deniz Wong
Volodymyr Baran
Michael Knapp
Helmut Ehrenberg
Sylvio Indris
Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
Nature Communications
title Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
title_full Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
title_fullStr Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
title_full_unstemmed Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
title_short Tailoring superstructure units for improved oxygen redox activity in Li-rich layered oxide battery’s positive electrodes
title_sort tailoring superstructure units for improved oxygen redox activity in li rich layered oxide battery s positive electrodes
url https://doi.org/10.1038/s41467-024-54312-z
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