Comprehensive study of Mn/Ni ordering in LiNi0.5-xMn1.5+xO4 using neutron powder diffraction and scanning transmission electron microscopy
In this study, we extensively establish unique relationships between the chemical compositions of LiNi 0.5-x Mn 1.5+x O 4 (LNMO) spinel-type positive electrode materials and the degree of Mn/Ni ordering, which influences their electrochemical performance. To achieve this, in situ temperature-controlled neutron powder diffraction experiments were performed under air or oxygen atmospheres to track the Mn/Ni ordering process during annealing of LNMO samples that contain different Mn/Ni ratios. Systematic in-depth structural analysis of a large number of samples, using both neutron and synchrotron X-ray powder diffractions, revealed clear correlations between the variations in the voltage-composition profiles and the distribution of Mn and Ni atoms between the 4 b and 12 d crystallographic sites of ordered LNMO. Additionally, we employed high-resolution scanning transmission electron microscopy combined with fast Fourier transform analysis that enabled us to visualize the distribution and sizes of Mn/Ni ordered domains at the particle level in excellent agreement with the Rietveld refinement from neutron powder diffraction data.
Authors
- Laurence Croguennec (ORCID: https://orcid.org/0000-0002-3018-0992)
- D. S. Chezganov (ORCID: https://orcid.org/0000-0001-8696-262X)
- Emmanuelle Suard (ORCID: https://orcid.org/0000-0001-5966-5929)
- Christian Masquelier (ORCID: https://orcid.org/0000-0001-7289-1015)
- François Fauth (ORCID: https://orcid.org/0000-0001-9465-3106)
- Pierre‐Etienne Cabelguen (ORCID: https://orcid.org/0000-0002-5953-4213)
- Thomas C. Hansen (ORCID: https://orcid.org/0000-0003-4611-2393)
- Mylène Hendrickx (ORCID: https://orcid.org/0000-0002-2396-4836)
- François Weill (ORCID: https://orcid.org/0000-0001-8331-6075)
- Ilia Tertov
Institutions
- Umicore (Belgium) (BE)
- Centre National de la Recherche Scientifique (FR)
- University of Antwerp (BE)
- Université de Bordeaux (FR)
- Institut Universitaire de France (FR)
- ALBA Synchrotron (Spain) (ES)
- Réseau sur le Stockage Electrochimique de l'énergie (FR)
- Institut de Chimie de la Matière Condensée de Bordeaux (FR)
- Institut Laue-Langevin (FR)
- Laboratoire de Réactivité et Chimie des Solides (FR)
- Institut Polytechnique de Bordeaux (FR)
- Université de Picardie Jules Verne (FR)
Publication Details
- Journal
- Energy storage materials
- Published
- 2025-06-06
- DOI
- https://doi.org/10.1016/j.ensm.2025.104359
- Citations
- 2
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 1.46
Funders
- European Commission
- Agence Nationale de la Recherche