A study of the correlations between the stoichiometry, secondary phases and transition metal ordering of LiNi0.5Mn1.5O4 was undertaken by characterizing samples synthesized at different temperatures. Insight into the composition of the samples was obtained by electron microscopy, neutron diffraction and X-ray absorption spectroscopy. In turn, analysis of cationic ordering was performed by combining neutron diffraction with Li MAS NMR spectroscopy. Under the conditions chosen for the synthesis, all samples systematically showed an excess of Mn, which was compensated by the formation of a secondary rock salt phase and not via the creation of oxygen vacancies. Local deviations from the ideal 3:1 Mn:Ni ordering were found, even for samples that show the superlattice ordering by diffraction, with different disordered schemes also being possible. The magnetic behavior of the samples was correlated with the deviations from this ideal ordering arrangement. The in-depth crystal-chemical knowledge generated was employed to evaluate the influence of these parameters on the electrochemical behavior of the materials.
Several members of the compositional series Li[Ni x Mn x Co(1–2x)]O2 (0.01 ≤ x ≤ 1/3) were synthesized and characterized. X-ray diffraction results confirm the presence of the layered α-NaFeO2-type structure, while X-ray absorption near-edge spectroscopy experiments verify the presence of Ni2+, Mn4+, and Co3+. Their local environment and short-range ordering were investigated by using a combination of 6Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and neutron pair distribution function (PDF) analysis, associated with reverse Monte Carlo (RMC) calculations. The 6Li MAS NMR spectra of compounds with low Ni/Mn contents (x ≤ 0.10) show several well-resolved resonances, which start to merge when the amount of Ni and Mn increases, finally forming a broad resonance at high Ni/Mn contents. Analysis of the 6Li MAS NMR 6Li[Ni0.02Mn0.02Co0.96]O2 spectrum, is consistent with the formation of Ni2+ and Mn4+ clusters within the transition-metal layers, even at these low-doping levels. The oxidation state of Ni in this high Co content sample strongly depends upon the Li/transition metal ratio of the starting materials. Neutron PDF analysis of the highest Ni/Mn content sample Li[Ni1/3Mn1/3Co1/3]O2 shows a tendency for Ni cations to be close to Mn cations in the first coordination shell; however, the Co3+ ions are randomly distributed. Analysis of the intensity of the “LiCoO2” resonance, arising from Li surrounded by Co3+ in its first two cation coordination shells, for the whole series provides further evidence for a nonrandom distribution of the transition-metal cations. The presence of the insulator-to-metal transition seen in the electrochemical profiles of these materials upon charging correlates strongly with the concentration of the “LiCoO2” resonance.
The growth of lithium microstructures during battery cycling has, to date, prohibited the use of Li metal anodes and raises serious safety concerns even in conventional lithium-ion rechargeable batteries, particularly if they are charged at high rates. The electrochemical conditions under which these Li microstructures grow have, therefore, been investigated by in situ nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) and susceptibility calculations. Lithium metal symmetric bag cells containing LiPF 6 in EC: DMC electrolytes were used. Distinct 7 Li NMR resonances were observed due to the Li metal bulk electrodes and microstructures, the changes in peak positions and intensities being monitored in situ during Li deposition. The changes in the NMR spectra, observed as a function of separator thickness and porosity (using Celgard and Whatmann glass microfiber membranes) and different applied pressures, were correlated with changes in the type of microstructure, by using SEM. Isotopically enriched 6 Li metal electrodes were used against natural abundance predominantly 7 Li metal counter electrodes to investigate radiofrequency (rf) field penetration into the Li anode and to confirm the assignment of the higher frequency peak to Li dendrites. The conclusions were supported by calculations performed to explore the effect of the different microstructures on peak position/broadening, the study showing that Li NMR spectroscopy can be used as a sensitive probe of the both the amount and type of microstructure formation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.