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Phase Engineering Improves the Electrochemical Stability of Lithium-rich Cobalt-free Layered Oxides for Lithium-ion Batteries

Title: Phase Engineering Improves the Electrochemical Stability of Lithium-rich Cobalt-free Layered Oxides for Lithium-ion Batteries
Authors: DE SLOOVERE, Dries; MYLAVARAPU, Satish Kumar; D'HAEN, Jan; Thersleff, Thomas; Jaworski, Aleksander; Grins, Jekabs; Svensson, Gunnar; Stoyanova, Radostina; Jøsang, Leif; Rajappa Prakasha, Kunkanadu; Merlo, M; Martínez, E; Nel-Lo Pascual, M; Jacas Biendicho, Jordi; VAN BAEL, Marlies; HARDY, An
Contributors: DE SLOOVERE, Dries; MYLAVARAPU, Satish Kumar; D'HAEN, Jan; Thersleff, Thomas; Jaworski, Aleksander; Grins, Jekabs; Svensson, Gunnar; Stoyanova, Radostina; Jøsang, Leif; Rajappa Prakasha, Kunkanadu; Merlo, M; Martínez, E; Nel-Lo Pascual, M; Jacas Biendicho, Jordi; VAN BAEL, Marlies; HARDY, An
Publication Year: 2025
Collection: Document Server@UHasselt (Universiteit Hasselt)
Description: The expanding electric vehicle market is largely dependent on LiNixMnyCozO2 (NMC) as positive electrode material for lithium-ion batteries (LIBs). The resulting increased demand for cobalt is a pressing concern, since 65% of its global mining is concentrated in a single region. Also driven by its high cost and toxicity, there is a consensus to diminish cobalt usage in LIBs. This has led academia and industry to prioritize developing innovative positive electrode materials with reduced cobalt content or cobalt-free alternatives, such as lithium-rich cobalt-free layered oxides (xLiMO2*(1-x)Li2MO3 (M = Mn, Ni, etc.)). With both rhombohedral and monoclinic crystal phases, this materials class has theoretical capacities around 250 mAh g-1, has improved thermal stability, and is cost-effective because of the manganese-rich composition. Still, the practical application of these materials is hindered because of the pronounced voltage decay during electrochemical cycling, which is caused by the transition from a layered to a disordered spinel-type structure. Research efforts have focused on mitigating this voltage fade, for instance by including dopants to stabilize the crystal structure. For further optimization, it is crucial to quantify the degree in which doping affects the change in crystal structure during electrochemical cycling. In this study, various post-mortem characterization techniques were used to investigate the impact of aluminum doping on the electrochemical stability of lithium-rich, cobalt-free Li1.26Ni0.15Mn0.61O2. Using statistical analysis based on spectroscopic data, the extent to which Al doping reduces disordered spinel phase formation was quantitatively investigated. The active materials were synthesized via spray pyrolysis followed by calcination. Aluminum doping effectively mitigated voltage fade, enhancing capacity retention from 46% to 67% over 250 cycles at 0.2 C. Structural analysis revealed that doping has a significant effect on the crystalline properties of the materials: the undoped ...
Document Type: conference object
File Description: application/pdf
Language: English
Relation: info:eu-repo/grantAgreement/EC/H2020/875568; https://hdl.handle.net/1942/45463
Availability: https://hdl.handle.net/1942/45463
Rights: info:eu-repo/semantics/openAccess
Accession Number: edsbas.BF0C2DB
Database: BASE