Ionic Pathways in Li13Si4 investigated by 6Li and 7Li solid state NMR experiments |
| |
| Institution: | 1. Institut für Physikalische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany;2. Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany;3. Institute of Physics in São Carlos, University of São Paulo, Av. Trabalhador Sãocarlense 400, 13590 São Carlos, SP, Brazil;1. Max Planck Institute for Chemical Energy Conversion, Department of Heterogeneous Reactions, 45470 Mülheim an der Ruhr, Germany;2. Forschungszentrum Jülich, IEK-9, 52425 Jülich, Germany;3. Forschungszentrum Jülich, IBI-7 and JuStruct, 52425 Jülich, Germany;4. Fritz Haber Institute of the Max Planck Society, 14195 Berlin, Germany;5. RWTH Aachen University, Institute of Technical and Macromolecular Chemistry, 52074 Aachen, Germany;6. Heinrich Heine Universität Düsseldorf, Institute of Physical Biology, 40225 Düsseldorf, Germany;1. National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive, Tallahassee, FL 32310, USA;2. Department of Chemistry, Queen''s University, 90 Bader Lane, Kingston, Ontario, Canada, K7L 3N6;1. Univ. Lille, CNRS-8181, UCCS: Unit of Catalysis and Chemistry of Solids, F-59000 Lille, France;2. IUF, Institut Universitaire de France, 1 rue Descartes, 75231 Paris, France;3. Bruker France, 34 rue de l’Industrie, F-67166 Wissembourg, France;1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China;2. School of Mechanical, Medical and Process Engineering, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4000, Australia;3. School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4000, Australia;4. Centre of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;5. Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4000, Australia |
| |
| Abstract: | Local environments and dynamics of lithium ions in the binary lithium silicide Li13Si4 have been studied by 6Li MAS-NMR, 7Li spin-lattice relaxation time and site-resolved 7Li 2D exchange NMR measurements as a function of mixing time. Variable temperature experiments result in distinct differences in activation energies characterizing the transfer rates between the different lithium sites. Based on this information, a comprehensive picture of the preferred ionic transfer pathways in this silicide has been developed. With respect to local mobility, the results of the present study suggests the ordering Li6/Li7>Li5>Li1>Li4 >Li2/Li3. Mobility within the z=0.5 plane is distinctly higher than within the z=0 plane, and the ionic transfer between the planes is most facile via Li1/Li5 exchange. The lithium ionic mobility can be rationalized on the basis of the type of the coordinating silicide anions and the lithium-lithium distances within the structure. Lithium ions strongly interacting with the isolated Si4− anions have distinctly lower mobility than those the coordination of which is dominated by Si26− dumbbells. |
| |
| Keywords: | lithium ion conductors 2D-exchange NMR Spin-lattice relaxation Li silicides Li ion batteries |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
