Jingwen Jiang, Tobias Kutsch, Wilhelm Klein, Manuel Botta, Anatoliy Senyshyn, Robert J. Spranger, Volodymyr Baran, Leo van Wüllen, Hubert A. Gasteiger, Thomas F. Fässler
{"title":"钪诱导的Li3Sb结构紊乱和空位工程——Li3−3xScxSb优异的离子电导率","authors":"Jingwen Jiang, Tobias Kutsch, Wilhelm Klein, Manuel Botta, Anatoliy Senyshyn, Robert J. Spranger, Volodymyr Baran, Leo van Wüllen, Hubert A. Gasteiger, Thomas F. Fässler","doi":"10.1002/aenm.202500683","DOIUrl":null,"url":null,"abstract":"Solid-state electrolytes are indispensable for all-solid-state batteries. Sulfide-based solid electrolytes, such as Li<sub>10</sub><i>M</i>P<sub>2</sub>S<sub>12</sub> (<i>M </i>= Ge, Sn) and Li<sub>6</sub>PS<sub>5</sub><i>X</i> (<i>X</i> = Cl, Br, I), exhibit excellent ionic conductivities, with the fastest Li<sup>+</sup> ion conductor, Li<sub>9.54</sub>[Si<sub>0.6</sub>Ge<sub>0.4</sub>]<sub>1.74</sub>P<sub>1.44</sub>S<sub>11.1</sub>Br<sub>0.3</sub>O<sub>0.6</sub>, achieving 32 mS cm<sup>−1</sup> at room temperature. Phosphide-based solid electrolytes have recently shown great potential with diverse structures and variable ionic conductivities. This compound class is expanded to the heavier homolog Li<sub>3</sub>Sb, showing its transformation to a superionic conductor through aliovalent substitution of lithium with scandium. Resulting Li<sub>2.55</sub>Sc<sub>0.15</sub>Sb shows an unexpected high ionic conductivity of 42(6) mS cm<sup>−1</sup> at 298 K under electron-blocking conditions in line with a very low activation energy of 17.6(8) kJ mol<sup>−1</sup>, representing the highest and lowest reported values, respectively, for a solid Li-ion conductor so far. Additionally, the compound exhibits a significant, but two orders of magnitude lower electronic conductivity making it a promising candidate for mixed ionic-electronic conductor (MIEC). The series of new compounds Li<sub>3−3</sub><i><sub>x</sub></i>Sc<i><sub>x</sub></i>Sb, maintains the β-Li<sub>3</sub>Sb structure up to a nominal composition of <i>x</i>(Sc) = 0.15, with Sc<sup>3+</sup> ions occupying the tetrahedral voids of the face-centered cubic Sb anion arrangement and creating vacancies that facilitate efficient Li<sup>+</sup> ion diffusion pathways. This work proposes a general design strategy for vacancy engineering in which replacement of Li with Sc in simple binary compounds has a direct impact on the ion mobility.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"24 1","pages":""},"PeriodicalIF":24.4000,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Scandium Induced Structural Disorder and Vacancy Engineering in Li3Sb – Superior Ionic Conductivity in Li3−3xScxSb\",\"authors\":\"Jingwen Jiang, Tobias Kutsch, Wilhelm Klein, Manuel Botta, Anatoliy Senyshyn, Robert J. Spranger, Volodymyr Baran, Leo van Wüllen, Hubert A. Gasteiger, Thomas F. Fässler\",\"doi\":\"10.1002/aenm.202500683\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Solid-state electrolytes are indispensable for all-solid-state batteries. Sulfide-based solid electrolytes, such as Li<sub>10</sub><i>M</i>P<sub>2</sub>S<sub>12</sub> (<i>M </i>= Ge, Sn) and Li<sub>6</sub>PS<sub>5</sub><i>X</i> (<i>X</i> = Cl, Br, I), exhibit excellent ionic conductivities, with the fastest Li<sup>+</sup> ion conductor, Li<sub>9.54</sub>[Si<sub>0.6</sub>Ge<sub>0.4</sub>]<sub>1.74</sub>P<sub>1.44</sub>S<sub>11.1</sub>Br<sub>0.3</sub>O<sub>0.6</sub>, achieving 32 mS cm<sup>−1</sup> at room temperature. Phosphide-based solid electrolytes have recently shown great potential with diverse structures and variable ionic conductivities. This compound class is expanded to the heavier homolog Li<sub>3</sub>Sb, showing its transformation to a superionic conductor through aliovalent substitution of lithium with scandium. Resulting Li<sub>2.55</sub>Sc<sub>0.15</sub>Sb shows an unexpected high ionic conductivity of 42(6) mS cm<sup>−1</sup> at 298 K under electron-blocking conditions in line with a very low activation energy of 17.6(8) kJ mol<sup>−1</sup>, representing the highest and lowest reported values, respectively, for a solid Li-ion conductor so far. Additionally, the compound exhibits a significant, but two orders of magnitude lower electronic conductivity making it a promising candidate for mixed ionic-electronic conductor (MIEC). The series of new compounds Li<sub>3−3</sub><i><sub>x</sub></i>Sc<i><sub>x</sub></i>Sb, maintains the β-Li<sub>3</sub>Sb structure up to a nominal composition of <i>x</i>(Sc) = 0.15, with Sc<sup>3+</sup> ions occupying the tetrahedral voids of the face-centered cubic Sb anion arrangement and creating vacancies that facilitate efficient Li<sup>+</sup> ion diffusion pathways. 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Scandium Induced Structural Disorder and Vacancy Engineering in Li3Sb – Superior Ionic Conductivity in Li3−3xScxSb
Solid-state electrolytes are indispensable for all-solid-state batteries. Sulfide-based solid electrolytes, such as Li10MP2S12 (M = Ge, Sn) and Li6PS5X (X = Cl, Br, I), exhibit excellent ionic conductivities, with the fastest Li+ ion conductor, Li9.54[Si0.6Ge0.4]1.74P1.44S11.1Br0.3O0.6, achieving 32 mS cm−1 at room temperature. Phosphide-based solid electrolytes have recently shown great potential with diverse structures and variable ionic conductivities. This compound class is expanded to the heavier homolog Li3Sb, showing its transformation to a superionic conductor through aliovalent substitution of lithium with scandium. Resulting Li2.55Sc0.15Sb shows an unexpected high ionic conductivity of 42(6) mS cm−1 at 298 K under electron-blocking conditions in line with a very low activation energy of 17.6(8) kJ mol−1, representing the highest and lowest reported values, respectively, for a solid Li-ion conductor so far. Additionally, the compound exhibits a significant, but two orders of magnitude lower electronic conductivity making it a promising candidate for mixed ionic-electronic conductor (MIEC). The series of new compounds Li3−3xScxSb, maintains the β-Li3Sb structure up to a nominal composition of x(Sc) = 0.15, with Sc3+ ions occupying the tetrahedral voids of the face-centered cubic Sb anion arrangement and creating vacancies that facilitate efficient Li+ ion diffusion pathways. This work proposes a general design strategy for vacancy engineering in which replacement of Li with Sc in simple binary compounds has a direct impact on the ion mobility.
期刊介绍:
Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small.
With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics.
The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.