New Insight into Li+ Dynamics in Lithium Bimetal Phosphate. Issue 1 (12th January 2022)

• Record Type: Journal Article
• Authors: Savignac, Laurence; Griffin, John M.; Schougaard, Steen B.
• Is Part Of: Journal of the Electrochemical Society. Volume 169:Issue 1(2022)
• Publication Date: 2022-01-12
• Subjects: Batteries - Li-ion -- LiMnFePO4 -- Li+ dynamics -- MAS NMR -- olivine; Electrochemistry -- Periodicals; 541.3705
• DOI: 10.1149/1945-7111/ac4544
• Languages: English
• ISSNs: 0013-4651

Abstract

Abstract : Substitution of iron by other transition metals within the remarkably stable olivine framework is of interest considering the expected gain in energy density. However, manganese rich olivine materials suffer from sluggish redox kinetics, leading to electrochemical performances at high current densities which are below expectations. The source of the kinetic limitations is not clear, with multiple processes having been proposed, including low bulk electronic conductivity, structural instability of Mn 3+ and a phase transition mechanism. This study employed 7 Li MAS NMR relaxation techniques to indirectly probe Li + dynamics using various stoichiometry of chemically prepared Li x Mny Fe1-y PO4 (0 ≤ ( x, y ) ≤ 1). Focusing on the particle level, the aim was to understand how the different crystal phases, alongside the Mn structural contribution, influence Li + transport at each stage of the oxidation process. Significantly, the formation of an olivine solid solution with vacancies within this progression gave rise to a faster 7 Li transverse relaxation derived from superior Li + motion.