Exploring the Relationship Between Halide Substitution, Structural Disorder, and Lithium Distribution in Lithium Argyrodites (Li6-xPS5-xBr1+x)
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| Titel: | Exploring the Relationship Between Halide Substitution, Structural Disorder, and Lithium Distribution in Lithium Argyrodites (Li6-xPS5-xBr1+x) |
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| Autoren: | Gautam, A. (author), Al-Kutubi, H.A.A. (author), Famprikis, T. (author), Ganapathy, S. (author), Wagemaker, M. (author) |
| Verlagsinformationen: | 2023 |
| Publikationsart: | Electronic Resource |
| Abstract: | Lithium argyrodite superionic conductors have recently gained significant attention as potential solid electrolytes for all-solid-state batteries because of their high ionic conductivity and ease of processing. Promising aspects of these materials are the ability to introduce halides (Li6-xPS5-xHal1+x, Hal = Cl and Br) into the crystal structure, which can greatly impact the lithium distribution over the wide range of accessible sites and the structural disorder between the S2- and Hal- anion on the Wyckoff 4d site, both of which strongly influence the ionic conductivity. However, the complex relationship among halide substitution, structural disorder, and lithium distribution is not fully understood, impeding optimal material design. In this study, we investigate the effect of bromide substitution on lithium argyrodite (Li6-xPS5-xBr1+x, in the range 0.0 ≤ x ≤ 0.5) and engineer structural disorder by changing the synthesis protocol. We reveal the correlation between the lithium substructure and ionic transport using neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and electrochemical impedance spectroscopy. We find that a higher ionic conductivity is correlated with a lower average negative charge on the 4d site, located in the center of the Li+ “cage”, as a result of the partial replacement of S2- by Br-. This leads to weaker interactions within the Li+ “cage”, promoting Li-ion diffusivity across the unit cell. We also identify an additional T4 Li+ site, which enables an alternative jump route (T5-T4-T5) with a lower migration energy barrier. The resulting expansion of the Li+ cages and increased connections between cages lead to a maximum ionic conductivity of 8.55 mS/cm for quenched Li5.5PS4.5Br1.5 having the highest degree of structural disorder RST/Storage of Electrochemical Energy RID/TS/Instrumenten groep |
| Index Begriffe: | journal article |
| DOI: | 10.1021.acs.chemmater.3c01525 |
| URL: | Chemistry of Materials--0897-4756--7b0ba94d-3f40-4afd-b923-6401299ef465 |
| Verfügbarkeit: | Open access content. Open access content © 2023 A. Gautam, H.A.A. Al-Kutubi, T. Famprikis, S. Ganapathy, M. Wagemaker |
| Anmerkung: | English |
| Other Numbers: | NLTUD oai:tudelft.nl:uuid:556402c9-be00-4de0-8051-2abc6c48e323 doi:10.1021/acs.chemmater.3c01525 1408381467 |
| Originalquelle: | DELFT UNIV OF TECHNOL From OAIster®, provided by the OCLC Cooperative. |
| Dokumentencode: | edsoai.on1408381467 |
| Datenbank: | OAIster |
Nájsť tento článok vo Web of Science | Abstract: | Lithium argyrodite superionic conductors have recently gained significant attention as potential solid electrolytes for all-solid-state batteries because of their high ionic conductivity and ease of processing. Promising aspects of these materials are the ability to introduce halides (Li6-xPS5-xHal1+x, Hal = Cl and Br) into the crystal structure, which can greatly impact the lithium distribution over the wide range of accessible sites and the structural disorder between the S2- and Hal- anion on the Wyckoff 4d site, both of which strongly influence the ionic conductivity. However, the complex relationship among halide substitution, structural disorder, and lithium distribution is not fully understood, impeding optimal material design. In this study, we investigate the effect of bromide substitution on lithium argyrodite (Li6-xPS5-xBr1+x, in the range 0.0 ≤ x ≤ 0.5) and engineer structural disorder by changing the synthesis protocol. We reveal the correlation between the lithium substructure and ionic transport using neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and electrochemical impedance spectroscopy. We find that a higher ionic conductivity is correlated with a lower average negative charge on the 4d site, located in the center of the Li+ “cage”, as a result of the partial replacement of S2- by Br-. This leads to weaker interactions within the Li+ “cage”, promoting Li-ion diffusivity across the unit cell. We also identify an additional T4 Li+ site, which enables an alternative jump route (T5-T4-T5) with a lower migration energy barrier. The resulting expansion of the Li+ cages and increased connections between cages lead to a maximum ionic conductivity of 8.55 mS/cm for quenched Li5.5PS4.5Br1.5 having the highest degree of structural disorder<br />RST/Storage of Electrochemical Energy<br />RID/TS/Instrumenten groep |
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| DOI: | 10.1021.acs.chemmater.3c01525 |