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Phase Engineering via Aluminum Doping Enhances the Electrochemical Stability of Lithium-Rich Cobalt-Free Layered Oxides for Lithium-Ion Batteries
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-0999-3569
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Number of Authors: 162024 (English)In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 20, no 31, p. 2400876-, article id 2400876Article in journal (Refereed) Published
Abstract [en]

Lithium-rich, cobalt-free oxides are promising potential positive electrode materials for lithium-ion batteries because of their high energy density, lower cost, and reduced environmental and ethical concerns. However, their commercial breakthrough is hindered because of their subpar electrochemical stability. This work studies the effect of aluminum doping on Li1.26Ni0.15Mn0.61O2 as a lithium-rich, cobalt-free layered oxide. Al doping suppresses voltage fade and improves the capacity retention from 46% for Li1.26Ni0.15Mn0.61O2 to 67% for Li1.26Ni0.15Mn0.56Al0.05O2 after 250 cycles at 0.2 C. The undoped material has a monoclinic Li2MnO3-type structure with spinel on the particle edges. In contrast, Al-doped materials (Li1.26Ni0.15Mn0.61-xAlxO2) consist of a more stable rhombohedral phase at the particle edges, with a monoclinic phase core. For this core-shell structure, the formation of Mn3+ is suppressed along with the material's decomposition to a disordered spinel, and the amount of the rhombohedral phase content increases during galvanostatic cycling. Whereas previous studies generally provided qualitative insight into the degradation mechanisms during electrochemical cycling, this work provides quantitative information on the stabilizing effect of the rhombohedral shell in the doped sample. As such, this study provides fundamental insight into the mechanisms through which Al doping increases the electrochemical stability of lithium-rich cobalt-free layered oxides.

Place, publisher, year, edition, pages
2024. Vol. 20, no 31, p. 2400876-, article id 2400876
Keywords [en]
aluminium, Co-free, cycle life, Li-rich, voltage fade
National Category
Materials Chemistry Condensed Matter Physics
Identifiers
URN: urn:nbn:se:su:diva-227965DOI: 10.1002/smll.202400876ISI: 001174108400001PubMedID: 38429239Scopus ID: 2-s2.0-85186182480OAI: oai:DiVA.org:su-227965DiVA, id: diva2:1849979
Available from: 2024-04-09 Created: 2024-04-09 Last updated: 2024-09-05Bibliographically approved

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Thersleff, ThomasJaworski, AleksanderGrins, JekabsSvensson, Gunnar

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Mylavarapu, Satish KumarThersleff, ThomasJaworski, AleksanderGrins, JekabsSvensson, Gunnar
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Materials ChemistryCondensed Matter Physics

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