Projects per year
Abstract
Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li10Ge1–xSnxP2S12. Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S2– ions. This charge redistribution modifies the Li+ substructure causing Li+ ions to bind more strongly to the host framework S2– anions, which in turn modulates the Li+ ion potential energy surface, increasing local barriers for Li+ ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.
Original language | English |
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Pages (from-to) | 21210-21219 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 50 |
Early online date | 7 Dec 2020 |
DOIs | |
Publication status | Published - 16 Dec 2020 |
Fingerprint
Dive into the research topics of 'Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li10Ge1–xSnxP2S12'. Together they form a unique fingerprint.Projects
- 3 Finished
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Computational Discovery of Conduction Mechanisms in Lithium-Ion Solid Electrolytes
Morgan, B. (PI)
1/10/19 → 30/09/22
Project: Research council
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Faraday Institute Call - Multi-Scale Modelling
Islam, S. (PI) & Morgan, B. (CoI)
Engineering and Physical Sciences Research Council
1/03/18 → 30/06/21
Project: Research council
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Dr B Morgan URF - Modelling Collective Lithium-Ion Dynamics in Battery Materials
Morgan, B. (PI)
1/10/14 → 30/09/19
Project: Research council
Datasets
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Dataset for "Evidence for the existence of an inductive effect in superionic conductors"
Squires, A. G. (Creator) & Morgan, B. (Creator), University of Bath, 7 Dec 2020
DOI: 10.15125/BATH-00798
Dataset