Determination of diffusion coefficients for sulfide ions in solid electrolytes on the basis of BaSm2S4 and CaGd2S4

Yurlov, I. S.; Ushakova, Yu. N.; Медведева, О. В.; Kalinina, L. A.; Shirokova, G. I.; Ананченко, Б. А.

doi:10.1134/s1023193507060043

Cited by 2 publications

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“…92 According to their reports, several ternary sulfides ALn 2 S 4 (A = Ca, Ba; Ln = Sm, Gd, Yb) exhibited faster S 2− diffusion when doped with the binary sulfides Ln 2 S 3 , and the activation energy of S 2− diffusion could be much lower than 1.0 eV. 91 This possible Ch 2−/− diffusion was corroborated by the recent report from Lei et al; 93 they demonstrated electrochemical (de)intercalation of Se 2−/− anions in between vdW gap of 2D MoSe 2 . Those results encourages further in-depth analyses from methodological and theoretical viewpoints, 94 as well as possible applications to electrochemical devices based on sulfur-ion shuttling, 95 similar to fluoride-ion batteries that have attracted much recent attention.…”

Section: ) Deintercalation Of Sulfur Anionsmentioning

confidence: 99%

“…Except for the few cases described here, sulfur anions are generally reckoned to be an immobile species in solids, and their solid-state diffusion is scarcely documented. Nevertheless, Ushakova and co-workers carried out a series of attempts to evaluate diffusion constants of S 2– anions in solid electrolytes using Hebb-Wagner type cells and other electrochemical setups . According to their reports, several ternary sulfides ALn 2 S 4 (A = Ca, Ba; Ln = Sm, Gd, Yb) exhibited faster S 2– diffusion when doped with the binary sulfides Ln 2 S 3 , and the activation energy of S 2– diffusion could be much lower than 1.0 eV .…”

Section: “Zipper”-type Topochemistry Based On Anionic Redoxmentioning

confidence: 99%

“…Nevertheless, Ushakova and co-workers carried out a series of attempts to evaluate diffusion constants of S 2– anions in solid electrolytes using Hebb-Wagner type cells and other electrochemical setups . According to their reports, several ternary sulfides ALn 2 S 4 (A = Ca, Ba; Ln = Sm, Gd, Yb) exhibited faster S 2– diffusion when doped with the binary sulfides Ln 2 S 3 , and the activation energy of S 2– diffusion could be much lower than 1.0 eV . This possible Ch 2–/– diffusion was corroborated by the recent report from Lei et al; they demonstrated electrochemical (de)intercalation of Se 2–/– anions in between vdW gap of 2D MoSe 2 .…”

Section: “Zipper”-type Topochemistry Based On Anionic Redoxmentioning

confidence: 99%

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Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond

Sasaki,

Clarke,

Jobic

et al. 2023

ACS Org. Inorg. Au

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Topochemistry refers to a generic category of solidstate reactions in which precursors and products display strong filiation in their crystal structures. Various low-dimensional materials are subject to this stepwise structure transformation by accommodating guest atoms or molecules in between their 2D slabs or 1D chains loosely bound by van der Waals (vdW) interactions. Those processes are driven by redox reactions between guests and the host framework, where transition metal cations have been widely exploited as the redox center. Topochemistry coupled with this cationic redox not only enables technological applications such as Li-ion secondary batteries but also serves as a powerful tool for structural or electronic fine-tuning of layered transition metal compounds. Over recent years, we have been pursuing materials design beyond this cationic redox topochemistry that was mostly limited to 2D or 1D vdW systems. For this, we proposed new topochemical reactions of non-vdW compounds built of 2D arrays of anionic chalcogen dimers alternating with redox-inert host cationic layers. These chalcogen dimers were found to undergo redox reaction with external metal elements, triggering either (1) insertion of these metals to construct 2D metal chalcogenides or (2) deintercalation of the constituent chalcogen anions. As a whole, this topochemistry works like a "zipper", where reductive cleavage of anionic chalcogen−chalcogen bonds opens up spaces in non-vdW materials, allowing the formation of novel layered structures. This Perspective briefly summarizes seminal examples of unique structure transformations achieved by anionic redox topochemistry as well as challenges on their syntheses and characterizations.

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Section: ) Deintercalation Of Sulfur Anionsmentioning

confidence: 99%

Section: “Zipper”-type Topochemistry Based On Anionic Redoxmentioning

confidence: 99%