dc.identifier.uri |
http://dx.doi.org/10.15488/15497 |
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dc.identifier.uri |
https://www.repo.uni-hannover.de/handle/123456789/15618 |
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dc.contributor.author |
Bottke, Patrick
|
|
dc.contributor.author |
Hogrefe, Katharina
|
|
dc.contributor.author |
Kohl, Julia
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dc.contributor.author |
Nakhal, Suliman
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dc.contributor.author |
Wilkening, Alexandra
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dc.contributor.author |
Heitjans, Paul
|
|
dc.contributor.author |
Lerch, Martin
|
|
dc.contributor.author |
Wilkening, H. Martin R.
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dc.date.accessioned |
2023-11-24T05:59:02Z |
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dc.date.available |
2023-11-24T05:59:02Z |
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dc.date.issued |
2023 |
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dc.identifier.citation |
Bottke, P.; Hogrefe, K.; Kohl, J.; Nakhal, S.; Wilkening, A. et al.: Energetically preferred Li+ ion jump processes in crystalline solids: Site-specific hopping in β-Li3VF6 as revealed by high-resolution 6Li 2D EXSY NMR. In: Materials Research Bulletin 162 (2023), 112193. DOI: https://doi.org/10.1016/j.materresbull.2023.112193 |
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dc.description.abstract |
The visualization of atomic or ionic jump processes on the Ångström length scale is important to identify the preferred diffusion pathways in solid electrolytes for energy storage devices. Two-dimensional high-resolution 6Li nuclear magnetic resonance (NMR) spectroscopy is highly suited to yield unprecedented site-specific insights into local Li+ exchange processes within a single measurement. Here, the beta-modification of Li3VF6 is used as a model system for such an investigation as it provides a range of important Li+ geometric environments in one and the same crystal structure useful to elucidate qualitatively a ranking of energetic preferences of the Li+ exchange processes. In Li3VF6 the Li+ ions are subject to diffusive exchange processes among five crystallographically and magnetically inequivalent Li sites: LiFn (n = 6, 4). By using a sample with a natural concentration of the 6Li isotope, we suppressed unwanted spin-diffusion processes and visualized the various exchange processes on the ms time scale. We were able to verify the following ranking experimentally: Li+ ion jumps between face-shared polyhedra are preferred, followed by Li+ exchange between edge-shared configurations for which interstitial sites are needed to jump from site to site. Surprisingly, Li+ exchange between corner-shared polyhedra and Li+ hopping involving almost isolated LiF4 polyhedra do contribute to overall Li+ self-diffusion as well. In this sense, the current study experimentally verifies current predictions by theory but also extends our understanding of ion dynamics between corner-shared Li-bearing polyhedra. |
eng |
dc.language.iso |
eng |
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dc.publisher |
New York, NY [u.a.] : Elsevier |
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dc.relation.ispartofseries |
Materials Research Bulletin 162 (2023) |
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dc.rights |
CC BY 4.0 Unported |
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dc.rights.uri |
https://creativecommons.org/licenses/by/4.0 |
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dc.subject |
Cathode materials |
eng |
dc.subject |
Exchange processes |
eng |
dc.subject |
NMR |
eng |
dc.subject |
Self-diffusion |
eng |
dc.subject.ddc |
600 | Technik
|
|
dc.subject.ddc |
670 | Industrielle und handwerkliche Fertigung
|
|
dc.title |
Energetically preferred Li+ ion jump processes in crystalline solids: Site-specific hopping in β-Li3VF6 as revealed by high-resolution 6Li 2D EXSY NMR |
eng |
dc.type |
Article |
|
dc.type |
Text |
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dc.relation.issn |
0025-5408 |
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dc.relation.doi |
https://doi.org/10.1016/j.materresbull.2023.112193 |
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dc.bibliographicCitation.volume |
162 |
|
dc.bibliographicCitation.firstPage |
112193 |
|
dc.description.version |
publishedVersion |
eng |
tib.accessRights |
frei zug�nglich |
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dc.bibliographicCitation.articleNumber |
112193 |
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