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Where the extraordinaries meet : a cascade of isosymmetrical superionic phase transitions and negative thermal expansion in a novel silver salt-inclusion borate halide. / Volkov, Sergey N.; Charkin, Dmitri O.; Arsentev, Maxim Yu; Aksenov, Sergey M.; Manelis, Lev S.; Krzhizhanovskaya, Maria G.; Sinelshchikova, Olga Yu; Ugolkov, Valery L.; Povolotskiy, Alexey V.; Shilovskikh, Vladimir V.; Antonov, Andrey A.; Bubnova, Rimma S.

In: CrystEngComm, Vol. 24, No. 23, 18.05.2022, p. 4174-4179.

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

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@article{e356c2bb46c0403f9619be5cafc6899f,

title = "Where the extraordinaries meet: a cascade of isosymmetrical superionic phase transitions and negative thermal expansion in a novel silver salt-inclusion borate halide",

abstract = "A new silver iodide borate, Ag3B6O10I, is presented as a promising solid-state electrolyte with a δ ↔ γ ↔ β ↔ α cascade of the isosymmetric superionic phase transitions. Its crystal structure is composed of two sublattices, the “host” B-O covalent part from B6O13 6B:3Δ3□:[φ]<Δ2□>|<Δ2□>|<Δ2□>| corner-sharing hexaborate groups, and the “guest” Ag-I ionic part. The transitions are associated with structural re-arrangements of the latter with a stepwise “melting” of silver sublattice and give rise to an increase in conductivity to 0.005 S cm−1 at 99 °C. Exceptionally large room-temperature anharmonicity of silver vibration has been described. The migration of silver ions leads to negative thermal expansion (NTE) at 25-400 °C. The sodium analog, Na3B6O10I, with a “normal” perovskite-like structure was obtained. The structural diversity in the M3B6O10X family can be rationalized considering the difference in the ionic radii of X− anions and M+ cations.",

author = "Volkov, {Sergey N.} and Charkin, {Dmitri O.} and Arsentev, {Maxim Yu} and Aksenov, {Sergey M.} and Manelis, {Lev S.} and Krzhizhanovskaya, {Maria G.} and Sinelshchikova, {Olga Yu} and Ugolkov, {Valery L.} and Povolotskiy, {Alexey V.} and Shilovskikh, {Vladimir V.} and Antonov, {Andrey A.} and Bubnova, {Rimma S.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

month = may,

day = "18",

doi = "10.1039/d2ce00307d",

language = "English",

volume = "24",

pages = "4174--4179",

journal = "CrystEngComm",

issn = "1466-8033",

publisher = "Royal Society of Chemistry",

number = "23",

}

RIS

TY - JOUR

T1 - Where the extraordinaries meet

T2 - a cascade of isosymmetrical superionic phase transitions and negative thermal expansion in a novel silver salt-inclusion borate halide

AU - Volkov, Sergey N.

AU - Charkin, Dmitri O.

AU - Arsentev, Maxim Yu

AU - Aksenov, Sergey M.

AU - Manelis, Lev S.

AU - Krzhizhanovskaya, Maria G.

AU - Sinelshchikova, Olga Yu

AU - Ugolkov, Valery L.

AU - Povolotskiy, Alexey V.

AU - Shilovskikh, Vladimir V.

AU - Antonov, Andrey A.

AU - Bubnova, Rimma S.

PY - 2022/5/18

Y1 - 2022/5/18

N2 - A new silver iodide borate, Ag3B6O10I, is presented as a promising solid-state electrolyte with a δ ↔ γ ↔ β ↔ α cascade of the isosymmetric superionic phase transitions. Its crystal structure is composed of two sublattices, the “host” B-O covalent part from B6O13 6B:3Δ3□:[φ]<Δ2□>|<Δ2□>|<Δ2□>| corner-sharing hexaborate groups, and the “guest” Ag-I ionic part. The transitions are associated with structural re-arrangements of the latter with a stepwise “melting” of silver sublattice and give rise to an increase in conductivity to 0.005 S cm−1 at 99 °C. Exceptionally large room-temperature anharmonicity of silver vibration has been described. The migration of silver ions leads to negative thermal expansion (NTE) at 25-400 °C. The sodium analog, Na3B6O10I, with a “normal” perovskite-like structure was obtained. The structural diversity in the M3B6O10X family can be rationalized considering the difference in the ionic radii of X− anions and M+ cations.

AB - A new silver iodide borate, Ag3B6O10I, is presented as a promising solid-state electrolyte with a δ ↔ γ ↔ β ↔ α cascade of the isosymmetric superionic phase transitions. Its crystal structure is composed of two sublattices, the “host” B-O covalent part from B6O13 6B:3Δ3□:[φ]<Δ2□>|<Δ2□>|<Δ2□>| corner-sharing hexaborate groups, and the “guest” Ag-I ionic part. The transitions are associated with structural re-arrangements of the latter with a stepwise “melting” of silver sublattice and give rise to an increase in conductivity to 0.005 S cm−1 at 99 °C. Exceptionally large room-temperature anharmonicity of silver vibration has been described. The migration of silver ions leads to negative thermal expansion (NTE) at 25-400 °C. The sodium analog, Na3B6O10I, with a “normal” perovskite-like structure was obtained. The structural diversity in the M3B6O10X family can be rationalized considering the difference in the ionic radii of X− anions and M+ cations.

UR - http://www.scopus.com/inward/record.url?scp=85131825029&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3d93b4a9-bb01-37bc-a2b1-664dc38d66d9/

U2 - 10.1039/d2ce00307d

DO - 10.1039/d2ce00307d

M3 - Article

AN - SCOPUS:85131825029

VL - 24

SP - 4174

EP - 4179

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 23

ER -

ID: 96581052

Where the extraordinaries meet: a cascade of isosymmetrical superionic phase transitions and negative thermal expansion in a novel silver salt-inclusion borate halide

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