A composite modulated structure mechanism for Ag+ fast ion conduction in pearceite and polybasite mineral solid electrolytes

R. L. Withers; L. Norén; T. R. Welberry; L. Bindi; M. Evain; S. Menchetti

doi:10.1016/j.ssi.2008.07.008

A composite modulated structure mechanism for Ag⁺ fast ion conduction in pearceite and polybasite mineral solid electrolytes

R. L. Withers^*, L. Norén, T. R. Welberry, L. Bindi, M. Evain, S. Menchetti

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

A careful electron diffraction investigation of pearceite-Tac and polybasite-Tac samples in the Ag⁺ fast ion conducting state reveals that the average hexagonal [Ag^I ₉]⁹⁺ sub-structure in these mineral solid electrolyte systems is mutually incommensurable with respect to the remaining [(Ag^I,Cu^I)₆(As^III,Sb^III)₂S₇]^2-[Cu^IS₄]^7- framework sub-structure. It is shown how the mutual incommensurability of the two component sub-structures can be compatible with crystal chemical commonsense, with previously reported average structure refinements of these phases as well as providing an insight into their Ag⁺ fast ion conductivity at such low temperatures. In addition, Ag⁺/Cu⁺ ion ordering (and associated displacive shifts of the centreing S^2- ions) in the S^2-(Ag,Cu)₆ octahedral sites is shown to provide a mechanism for low temperature superstructure ordering.

Original language	English
Pages (from-to)	2080-2089
Number of pages	10
Journal	Solid State Ionics
Volume	179
Issue number	37
DOIs	https://doi.org/10.1016/j.ssi.2008.07.008
Publication status	Published - 15 Nov 2008

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title = "A composite modulated structure mechanism for Ag+ fast ion conduction in pearceite and polybasite mineral solid electrolytes",

abstract = "A careful electron diffraction investigation of pearceite-Tac and polybasite-Tac samples in the Ag+ fast ion conducting state reveals that the average hexagonal [AgI 9]9+ sub-structure in these mineral solid electrolyte systems is mutually incommensurable with respect to the remaining [(AgI,CuI)6(AsIII,SbIII)2S7]2-[CuIS4]7- framework sub-structure. It is shown how the mutual incommensurability of the two component sub-structures can be compatible with crystal chemical commonsense, with previously reported average structure refinements of these phases as well as providing an insight into their Ag+ fast ion conductivity at such low temperatures. In addition, Ag+/Cu+ ion ordering (and associated displacive shifts of the centreing S2- ions) in the S2-(Ag,Cu)6 octahedral sites is shown to provide a mechanism for low temperature superstructure ordering.",

keywords = "Ag fast ion conduction, Composite modulated structure, Electron diffraction study, Solid electrolyte",

author = "Withers, {R. L.} and L. Nor{\'e}n and Welberry, {T. R.} and L. Bindi and M. Evain and S. Menchetti",

year = "2008",

month = nov,

day = "15",

doi = "10.1016/j.ssi.2008.07.008",

language = "English",

volume = "179",

pages = "2080--2089",

journal = "Solid State Ionics",

issn = "0167-2738",

publisher = "Elsevier B.V.",

number = "37",

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TY - JOUR

T1 - A composite modulated structure mechanism for Ag+ fast ion conduction in pearceite and polybasite mineral solid electrolytes

AU - Withers, R. L.

AU - Norén, L.

AU - Welberry, T. R.

AU - Bindi, L.

AU - Evain, M.

AU - Menchetti, S.

PY - 2008/11/15

Y1 - 2008/11/15

N2 - A careful electron diffraction investigation of pearceite-Tac and polybasite-Tac samples in the Ag+ fast ion conducting state reveals that the average hexagonal [AgI 9]9+ sub-structure in these mineral solid electrolyte systems is mutually incommensurable with respect to the remaining [(AgI,CuI)6(AsIII,SbIII)2S7]2-[CuIS4]7- framework sub-structure. It is shown how the mutual incommensurability of the two component sub-structures can be compatible with crystal chemical commonsense, with previously reported average structure refinements of these phases as well as providing an insight into their Ag+ fast ion conductivity at such low temperatures. In addition, Ag+/Cu+ ion ordering (and associated displacive shifts of the centreing S2- ions) in the S2-(Ag,Cu)6 octahedral sites is shown to provide a mechanism for low temperature superstructure ordering.

AB - A careful electron diffraction investigation of pearceite-Tac and polybasite-Tac samples in the Ag+ fast ion conducting state reveals that the average hexagonal [AgI 9]9+ sub-structure in these mineral solid electrolyte systems is mutually incommensurable with respect to the remaining [(AgI,CuI)6(AsIII,SbIII)2S7]2-[CuIS4]7- framework sub-structure. It is shown how the mutual incommensurability of the two component sub-structures can be compatible with crystal chemical commonsense, with previously reported average structure refinements of these phases as well as providing an insight into their Ag+ fast ion conductivity at such low temperatures. In addition, Ag+/Cu+ ion ordering (and associated displacive shifts of the centreing S2- ions) in the S2-(Ag,Cu)6 octahedral sites is shown to provide a mechanism for low temperature superstructure ordering.

KW - Ag fast ion conduction

KW - Composite modulated structure

KW - Electron diffraction study

KW - Solid electrolyte

UR - http://www.scopus.com/inward/record.url?scp=56449124027&partnerID=8YFLogxK

U2 - 10.1016/j.ssi.2008.07.008

DO - 10.1016/j.ssi.2008.07.008

M3 - Article

SN - 0167-2738

VL - 179

SP - 2080

EP - 2089

JO - Solid State Ionics

JF - Solid State Ionics

IS - 37

ER -

A composite modulated structure mechanism for Ag⁺ fast ion conduction in pearceite and polybasite mineral solid electrolytes

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