固体氟导电相BaxPb0.86-xSn1.14F4的电导率

Ukrainian Chemistry Journal Pub Date : 2022-12-23 DOI:10.33609/2708-129x.88.11.2022.39-54

A. Nahornyi, Yulia Voloshanovska, Anatolii Omelchuk

{"title":"固体氟导电相BaxPb0.86-xSn1.14F4的电导率","authors":"A. Nahornyi, Yulia Voloshanovska, Anatolii Omelchuk","doi":"10.33609/2708-129x.88.11.2022.39-54","DOIUrl":null,"url":null,"abstract":"This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them. \nIt was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated. \nWe register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86. \nThe fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2022-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"CONDUCTIVITY OF SOLID FLUORIDE-CONDUCTING PHASES BaxPb0.86-xSn1.14F4\",\"authors\":\"A. Nahornyi, Yulia Voloshanovska, Anatolii Omelchuk\",\"doi\":\"10.33609/2708-129x.88.11.2022.39-54\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them. \\nIt was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated. \\nWe register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86. \\nThe fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.\",\"PeriodicalId\":23394,\"journal\":{\"name\":\"Ukrainian Chemistry Journal\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2022-12-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Ukrainian Chemistry Journal\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.33609/2708-129x.88.11.2022.39-54\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Ukrainian Chemistry Journal","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.33609/2708-129x.88.11.2022.39-54","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}

引用次数: 0

摘要

本文介绍了基于氟化铅和氟化锡的复合固体氟离子导电相的研究成果。研究了PbSnF4固溶体的结构和导电性能。用Pb0.86Sn1.14F4结构的钡离子取代铅离子，合成了一系列浓度范围为0≤x≤0.86的样品。钡离子具有较大的半径，没有立体活性的孤对电子，这对合成相的电导率和氟离子在其中的输运特性有重要的贡献。结果表明，在pb0.86 - sn1.14 f4中氟离子导电相中，铅阳离子部分或全部被钡阳离子取代，形成了x值为0≤x≤0.86的BaxPb0.86 - xSn1.14F4固溶体。在0≤x≤0.43的浓度范围内，合成相的晶格对称性对应于β-PbSnF4(空间群P4/ nmm)的结构类型。进一步增加氟化钡的含量，使其晶格重排，接近于BaSnF4的结构类型，同时保持了空间群对称。研究了合成相的导电性能。在0≤x≤0.43的范围内，随着钡离子含量的增加，样品的电导率增加。随着钡离子含量的增加，样品电导率在0.43≤x≤0.86范围内达到峰值后逐渐降低。氟离子导电相Pb0.43Ba0.43Sn1.14F4，同结构为β-PbSnF4，与目前已知的氟离子导电相相比，在较宽的温度范围内具有最高的导电性。其电导率比β-PbSnF4高出近两个数量级，在373 K时为0.12 S/cm。通过19FNMR方法，确定了电导率主要是由节间氟阴离子提供的，这些阴离子位于钡和钡阳离子层之间。合成相中氟离子的转移数与理论相一致。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

CONDUCTIVITY OF SOLID FLUORIDE-CONDUCTING PHASES BaxPb0.86-xSn1.14F4

This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them. It was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated. We register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86. The fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Ukrainian Chemistry Journal

自引率

0.00%

发文量