{"title":"利用电模谱数据提取超离子导体Ba0.5La0.5F2.5中可移动氟离子的跳频","authors":"N.I. Sorokin","doi":"10.1016/j.ssi.2025.117017","DOIUrl":null,"url":null,"abstract":"<div><div>The spectra of the complex electrical modulus <em>M</em>*(<em>ν</em>) = <em>M</em> <sup>/</sup>+<em>iM</em> <sup>//</sup> for a single crystal of the superionic conductor Ba<sub>0.5</sub>La<sub>0.5</sub>F<sub>2.5</sub> with a fluorite-type structure (sp. gr. <span><math><mi>Fm</mi><mover><mn>3</mn><mo>¯</mo></mover><mi>m</mi></math></span>) were studied in the frequency range of 10<sup>−1</sup>–10<sup>7</sup> Hz at temperatures of 210–407 K. The diagrams of the complex modulus <em>M</em> <sup>/</sup>(<em>ν</em>), <em>M</em> <sup>//</sup>(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus <em>M</em> <sup>//</sup>(<em>ν</em>), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy Δ<em>H</em><sub>h</sub> and the average frequency ν<sub>h</sub> of carrier jumps. The calculated values of Δ<em>H</em><sub>h</sub> and ν<sub>h</sub> are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μ<sub>mob</sub> and mobile ion concentration <em>n</em><sub>mob</sub> were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117017"},"PeriodicalIF":3.3000,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The extraction of hopping frequencies of mobile fluorine ions in the superionic conductor Ba0.5La0.5F2.5 from electrical modulus spectroscopy data\",\"authors\":\"N.I. Sorokin\",\"doi\":\"10.1016/j.ssi.2025.117017\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The spectra of the complex electrical modulus <em>M</em>*(<em>ν</em>) = <em>M</em> <sup>/</sup>+<em>iM</em> <sup>//</sup> for a single crystal of the superionic conductor Ba<sub>0.5</sub>La<sub>0.5</sub>F<sub>2.5</sub> with a fluorite-type structure (sp. gr. <span><math><mi>Fm</mi><mover><mn>3</mn><mo>¯</mo></mover><mi>m</mi></math></span>) were studied in the frequency range of 10<sup>−1</sup>–10<sup>7</sup> Hz at temperatures of 210–407 K. The diagrams of the complex modulus <em>M</em> <sup>/</sup>(<em>ν</em>), <em>M</em> <sup>//</sup>(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus <em>M</em> <sup>//</sup>(<em>ν</em>), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy Δ<em>H</em><sub>h</sub> and the average frequency ν<sub>h</sub> of carrier jumps. The calculated values of Δ<em>H</em><sub>h</sub> and ν<sub>h</sub> are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μ<sub>mob</sub> and mobile ion concentration <em>n</em><sub>mob</sub> were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.</div></div>\",\"PeriodicalId\":431,\"journal\":{\"name\":\"Solid State Ionics\",\"volume\":\"431 \",\"pages\":\"Article 117017\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-09-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Solid State Ionics\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S016727382500236X\",\"RegionNum\":4,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Solid State Ionics","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S016727382500236X","RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
在210 ~ 407 K的频率范围内,研究了具有荧光型结构的超离子导体Ba0.5La0.5F2.5 (sp. gr. Fm3¯M)单晶的复电模量M*(ν) = M /+iM //的光谱。复模量M /(ν)和M //(ν)的图采用Cole-Cole形式,其特征是存在一个移动离子载流子的弛豫时间分布。在复模量M //(ν)虚部的频率依赖上,观察到由移动间隙氟离子(载流子)的跳变率引起的弛豫峰。根据弛豫最大值位置的温度变化,计算了活化焓ΔHh和载流子跳变的平均频率νh。该晶体的ΔHh和νh的计算值与Almond-West法的计算结果吻合得很好。在晶体物理模型的框架内,计算了载流子迁移率μmob和迁移离子浓度nmob。使用模光谱方法的研究无疑对进一步寻找和创造氟导电固体电解质具有重要意义。
The extraction of hopping frequencies of mobile fluorine ions in the superionic conductor Ba0.5La0.5F2.5 from electrical modulus spectroscopy data
The spectra of the complex electrical modulus M*(ν) = M/+iM// for a single crystal of the superionic conductor Ba0.5La0.5F2.5 with a fluorite-type structure (sp. gr. ) were studied in the frequency range of 10−1–107 Hz at temperatures of 210–407 K. The diagrams of the complex modulus M/(ν), M//(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus M//(ν), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy ΔHh and the average frequency νh of carrier jumps. The calculated values of ΔHh and νh are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μmob and mobile ion concentration nmob were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.
期刊介绍:
This interdisciplinary journal is devoted to the physics, chemistry and materials science of diffusion, mass transport, and reactivity of solids. The major part of each issue is devoted to articles on:
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