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Title: Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

Abstract

Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K + ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.

Authors:
; ; ; ; ORCiD logo; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1349924
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 4
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., and Cabana, Jordi. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.6b04181.
Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., & Cabana, Jordi. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites. United States. doi:10.1021/acs.chemmater.6b04181.
Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., and Cabana, Jordi. Tue . "Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites". United States. doi:10.1021/acs.chemmater.6b04181.
@article{osti_1349924,
title = {Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites},
author = {Yi, Tanghong and Chen, Wei and Cheng, Lei and Bayliss, Ryan D. and Lin, Feng and Plews, Michael R. and Nordlund, Dennis and Doeff, Marca M. and Persson, Kristin A. and Cabana, Jordi},
abstractNote = {Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials AxK1–xFeF3 (A = Li, Na). By starting with KFeF3, approximately 75% of K+ ions were subsequently replaced by Li+ and Na+ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.},
doi = {10.1021/acs.chemmater.6b04181},
journal = {Chemistry of Materials},
number = 4,
volume = 29,
place = {United States},
year = {Tue Feb 07 00:00:00 EST 2017},
month = {Tue Feb 07 00:00:00 EST 2017}
}
  • Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less
  • Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within themore » perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.« less
  • In aqueous suspensions of alkali-metal intercalation compounds of TiS/sub 2/, double relaxation were observed by using the pressure-jump technique with conductivity detection. For all intercalation compounds, the fast relaxation times decrease with particle concentration, while the slow ones are approximately constant. From the kinetic results obtained, the fast and slow relaxations are attributed to association-dissociation of the alkali-metal ions on the surface of the intercalation compounds and intercalation-deintercalation of their ions in the interlayers of the intercalation compounds, respectively. It was found that the order of association of rate constants of alkali-metal ions correspond to that of the mean timemore » of movement of a water molecule between their ions and that deintercalation rate constant of a lithium ion in the interlayer is 1 order of magnitude faster than those of other alkali-metal ions. 12 references, 6 figures, 1 table.« less
  • We present here the topological (Bader) analysis of the electronic structure for 120 cubic perovskites AMX{sub 3} (A denotes Li, Na, K, Rb, Cs; M denotes Be, Mg, Ca, Sr, Ba, Zn; X denotes F, Cl, Br, I). The perovskite being perhaps the simplest and most abundant structure for ternary compounds, we have found up to seven different topological schemes for the electronic density. Those schemes can be simply arranged and explained in terms of ratios of topologically defined ionic radii. However, no set of empirical radii, even of best-fitted radii, can accomplish the same objective. All crystals do presentmore » M-X and A-X bonds, many have X-X too, and only CsSrF{sub 3} and CsBaF{sub 3} have A-A bonds. The topology and geometry of the electronic density has been further analyzed by depicting the shape of the attraction basins of the ions. Basins have polyhedral shapes and can be simply predicted, in most cases, after the knowledge of the bonds that the ion forms. M{sup 2+} basins do present, however, bizarre nearly bidimensional wings on those topological schemes lacking X-X bonds. Lattice energy has been found to be dominated by Coulombic interactions and determined by the crystal size more than by the electronic topological scheme, although the influence of the electronic density at the M-X bond critical point is also observed. The stability of the perovskite structure with respect to the decomposition into MX{sub 2}+AX has been found to be mostly governed by the M{sup 2+} cation, the crystals having small M{sup 2+} and large A{sup +} ions being the most stable ones. There is also a clear tendency for the crystals lacking X-X bonds, and having bizarre M{sup 2+} shapes, to decompose. {copyright} {ital 1997} {ital The American Physical Society}« less