A. F. Baumann, D. Mutter, D. F. Urban, C. Elsässer
{"title":"First-principles study of strain behavior in iron-based fluorides of tungsten bronze type as cathode materials for alkali-ion batteries","authors":"A. F. Baumann, D. Mutter, D. F. Urban, C. Elsässer","doi":"10.1103/physrevmaterials.8.095401","DOIUrl":null,"url":null,"abstract":"Mechanical stresses and strains in the microstructure of cathode materials evolving during charge/discharge cycles can reduce the long-term stability of intercalation type alkali-metal-ion batteries. In this context, crystalline compounds exhibiting zero-strain (ZS) behavior are of particular interest. Near-ZS sodiation was experimentally measured in the tetragonal tungsten bronze (TTB) type compound <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow><msub><mi>Na</mi><mi>x</mi></msub><msub><mi>FeF</mi><mn>3</mn></msub></mrow></math>. Using a first-principles method based on density functional theory, we investigate the potential of iron-based fluoride compounds with tungsten bronze (TB) structures as ZS cathode materials. Simulations were conducted to study the intercalation of the alkali metal ions <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msup><mi>Li</mi><mo>+</mo></msup><mo>,</mo><mo> </mo><msup><mi>Na</mi><mo>+</mo></msup></math>, and <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msup><mi mathvariant=\"normal\">K</mi><mo>+</mo></msup></math> into the TTB and two related TB structures of the cubic perovskite and hexagonal types. We describe compensating local volume effects that can explain the experimentally measured low volume change of <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow><msub><mi>Na</mi><mi>x</mi></msub><msub><mi>FeF</mi><mn>3</mn></msub></mrow></math>. We discuss the structural and chemical prerequisites of the host lattice for a ZS insertion mechanism for alkali ions in TB structures and present a qualitative descriptor to predict the local volume change, which provides a way for faster screening and discovery of novel ZS battery materials.","PeriodicalId":20545,"journal":{"name":"Physical Review Materials","volume":"49 1","pages":""},"PeriodicalIF":3.1000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Review Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1103/physrevmaterials.8.095401","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Mechanical stresses and strains in the microstructure of cathode materials evolving during charge/discharge cycles can reduce the long-term stability of intercalation type alkali-metal-ion batteries. In this context, crystalline compounds exhibiting zero-strain (ZS) behavior are of particular interest. Near-ZS sodiation was experimentally measured in the tetragonal tungsten bronze (TTB) type compound . Using a first-principles method based on density functional theory, we investigate the potential of iron-based fluoride compounds with tungsten bronze (TB) structures as ZS cathode materials. Simulations were conducted to study the intercalation of the alkali metal ions , and into the TTB and two related TB structures of the cubic perovskite and hexagonal types. We describe compensating local volume effects that can explain the experimentally measured low volume change of . We discuss the structural and chemical prerequisites of the host lattice for a ZS insertion mechanism for alkali ions in TB structures and present a qualitative descriptor to predict the local volume change, which provides a way for faster screening and discovery of novel ZS battery materials.
期刊介绍:
Physical Review Materials is a new broad-scope international journal for the multidisciplinary community engaged in research on materials. It is intended to fill a gap in the family of existing Physical Review journals that publish materials research. This field has grown rapidly in recent years and is increasingly being carried out in a way that transcends conventional subject boundaries. The journal was created to provide a common publication and reference source to the expanding community of physicists, materials scientists, chemists, engineers, and researchers in related disciplines that carry out high-quality original research in materials. It will share the same commitment to the high quality expected of all APS publications.