Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4

Mercadier, Briséïs; Coles, Samuel W.; Duttine, Mathieu; Legein, Christophe; Body, Monique; Borkiewicz, Olaf J.; Lebedev, Oleg; Morgan, Benjamin J.; Masquelier, Christian; Dambournet, Damien

doi:10.1021/jacs.3c08232

Title: Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF ₄

Journal Article · Mon Oct 16 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c08232· OSTI ID:2202498

Mercadier, Briséïs ^[1];

^[2]; Duttine, Mathieu ^[3];

^[4];

^[4]; Borkiewicz, Olaf J. ^[5]; Lebedev, Oleg ^[6];

^[2];

^[7];

^[8]

Réseau sur le Stockage Electrochimique de l’Energie, RS2E, FR CNRS 3459, 80039 Amiens Cedex, France, Sorbonne Université, CNRS, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux, UMR CNRS 8234, 75005 Paris, France, Laboratoire de Réactivité et de Chimie du Solides, UMR CNRS 7314, 80039 Amiens Cedex, France
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom, Quad One, Harwell Science and Innovation Campus, The Faraday Institution, Didcot OX11 0RA, United Kingdom
Institut de Chimie de la Matière Condensée de Bordeaux, UMR CNRS 5026, 33608 Pessac, France
Institut des Molécules et Matériaux du Mans, UMR CNRS 6283, Le Mans Université, 72085 Le Mans Cedex 9, France
X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
Laboratoire de Cristallographie et Sciences des Matériaux, CRISMAT, 14000 Caen, France
Réseau sur le Stockage Electrochimique de l’Energie, RS2E, FR CNRS 3459, 80039 Amiens Cedex, France, Laboratoire de Réactivité et de Chimie du Solides, UMR CNRS 7314, 80039 Amiens Cedex, France
Réseau sur le Stockage Electrochimique de l’Energie, RS2E, FR CNRS 3459, 80039 Amiens Cedex, France, Sorbonne Université, CNRS, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux, UMR CNRS 8234, 75005 Paris, France

Introducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F₂ fluorites have previously been proposed to exhibit two forms of disorder within their cationic host frameworks: occupational disorder from randomly distributed M and Sn cations and orientational disorder from Sn(II) stereoactive lone pairs. Here, we characterize the structure and fluoride-ion dynamics of cubic BaSnF₄, using a combination of experimental and computational techniques. Rietveld refinement of the X-ray diffraction (XRD) data confirms an average fluorite structure with {Ba,Sn} cation disorder, and the ¹¹⁹Sn Mössbauer spectrum demonstrates the presence of stereoactive Sn(II) lone pairs. X-ray total-scattering PDF analysis and ab initio molecular dynamics simulations reveal a complex local structure with a high degree of intrinsic fluoride-ion disorder, where 1/3 of fluoride ions occupy octahedral “interstitial” sites: this fluoride-ion disorder is a consequence of repulsion between Sn lone pairs and fluoride ions that destabilizes Sn-coordinated tetrahedral fluoride-ion sites. Variable-temperature ¹⁹F NMR experiments and analysis of our molecular dynamics simulations reveal highly inhomogeneous fluoride-ion dynamics, with fluoride ions in Sn-rich local environments significantly more mobile than those in Ba-rich environments. Our simulations also reveal dynamical reorientation of the Sn lone pairs that is biased by the local cation configuration and coupled to the local fluoride-ion dynamics. We end by discussing the effect of host-framework disorder on long-range diffusion pathways in cubic BaSnF₄.

View Journal Article

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2202498

Alternate ID(s):: OSTI ID: 2204339

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 145 Journal Issue: 43; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (124)

Chemistry, Structure, and Function of Lone Pairs in Extended Solids Laurita, Geneva; Seshadri, Ram Accounts of Chemical Research, Vol. 55, Issue 7 https://doi.org/10.1021/acs.accounts.1c00741	journal	March 2022
Lone Pair Rotation and Bond Heterogeneity Leading to Ultralow Thermal Conductivity in Aikinite Carnevali, Virginia; Mukherjee, Shriparna; Voneshen, David J. Journal of the American Chemical Society, Vol. 145, Issue 16 https://doi.org/10.1021/jacs.3c02536	journal	April 2023
Etude par diffraction neutronique des solutions solides K1−xBixF1+2xetRb1−xBixF1+2x Soubeyroux, J.; Reau, J.; Matar, S. Solid State Ionics, Vol. 6, Issue 1 https://doi.org/10.1016/0167-2738(82)90102-3	journal	February 1982
Dynamics of defects in superionic fluorites Gillan, Michael J. Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 8 https://doi.org/10.1039/ft9908601177	journal	January 1990
Covalent Bonds in α-SnF2 Monitored by J-Couplings in Solid-State NMR Spectra Bräuniger, Thomas; Ghedia, Stefan; Jansen, Martin Zeitschrift für anorganische und allgemeine Chemie, Vol. 636, Issue 13-14 https://doi.org/10.1002/zaac.201000176	journal	August 2010
Batteries based on fluoride shuttle Anji Reddy, M.; Fichtner, M. Journal of Materials Chemistry, Vol. 21, Issue 43, p. 17059-17062 https://doi.org/10.1039/c1jm13535j	journal	October 2011
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Electronic properties of random alloys: Special quasirandom structures Wei, S. -H.; Ferreira, L. G.; Bernard, James E. Physical Review B, Vol. 42, Issue 15 https://doi.org/10.1103/PhysRevB.42.9622	journal	November 1990
Maximally localized Wannier functions: Theory and applications Marzari, Nicola; Mostofi, Arash A.; Yates, Jonathan R. Reviews of Modern Physics, Vol. 84, Issue 4 https://doi.org/10.1103/RevModPhys.84.1419	journal	October 2012
Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra Massiot, Dominique; Fayon, Franck; Capron, Mickael Magnetic Resonance in Chemistry, Vol. 40, Issue 1 https://doi.org/10.1002/mrc.984	journal	December 2001
PbSn4F10: A new disordered fluorite-type fast ion conductor De´ne`s, Georges Journal of Solid State Chemistry, Vol. 74, Issue 2 https://doi.org/10.1016/0022-4596(88)90364-7	journal	June 1988
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
Neutron diffraction study of β-SnF₂ Will, G.; Bargouth, M. O. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 153, Issue 1-4 https://doi.org/10.1524/zkri.1980.153.14.89	journal	December 1980
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures Xiao, Yihan; Jun, KyuJung; Wang, Yan Advanced Energy Materials, Vol. 11, Issue 37 https://doi.org/10.1002/aenm.202101437	journal	September 2021
Dynamic Stereochemical Activity of the Sn ²⁺ Lone Pair in Perovskite CsSnBr ₃ Fabini, Douglas H.; Laurita, Geneva; Bechtel, Jonathon S. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b06287	journal	September 2016
Multinuclear NMR studies of mixedCa1−xSrxF2crystals Youngman, R. E.; Smith, C. M. Physical Review B, Vol. 78, Issue 1 https://doi.org/10.1103/PhysRevB.78.014112	journal	July 2008
Spectroscopic and computer modelling studies of mixed-cation superionic fluorites Netshisaulu, T. T.; Chadwick, A. V.; Ngoepe, P. E. Journal of Physics: Condensed Matter, Vol. 17, Issue 41 https://doi.org/10.1088/0953-8984/17/41/026	journal	September 2005
Exploiting the paddle-wheel mechanism for the design of fast ion conductors Zhang, Zhizhen; Nazar, Linda F. Nature Reviews Materials, Vol. 7, Issue 5 https://doi.org/10.1038/s41578-021-00401-0	journal	January 2022
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C. Physical Review B, Vol. 67, Issue 12 https://doi.org/10.1103/PhysRevB.67.125111	journal	March 2003
The underappreciated lone pair in halide perovskites underpins their unusual properties Fabini, Douglas H.; Seshadri, Ram; Kanatzidis, Mercouri G. MRS Bulletin, Vol. 45, Issue 6 https://doi.org/10.1557/mrs.2020.142	journal	June 2020
Atomistic mechanisms of ionic transport in fast-ion conductors Catlow, C. Richard A. Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 8 https://doi.org/10.1039/ft9908601167	journal	January 1990
Superionics: crystal structures and conduction processes Hull, Stephen Reports on Progress in Physics, Vol. 67, Issue 7 https://doi.org/10.1088/0034-4885/67/7/R05	journal	June 2004
Rietveld refinement of Debye–Scherrer synchrotron X-ray data from Al ₂ O ₃ Thompson, P.; Cox, D. E.; Hastings, J. B. Journal of Applied Crystallography, Vol. 20, Issue 2 https://doi.org/10.1107/S0021889887087090	journal	April 1987
Investigating the Li⁺ substructure and ionic transport in Li₁₀GeP_2−xSb_xS₁₂ (0 ≤ x ≤ 0.25) Helm, Bianca; Gronych, Lara M.; Banik, Ananya Physical Chemistry Chemical Physics, Vol. 25, Issue 2 https://doi.org/10.1039/D2CP04710A	journal	January 2023
Sparse Cyclic Excitations Explain the Low Ionic Conductivity of Stoichiometric ${Li}_{7} {La}_{3} {Zr}_{2} O_{12}$ Burbano, Mario; Carlier, Dany; Boucher, Florent Physical Review Letters, Vol. 116, Issue 13 https://doi.org/10.1103/PhysRevLett.116.135901	journal	March 2016
Superionic Diffusion through Frustrated Energy Landscape Di Stefano, Davide; Miglio, Anna; Robeyns, Koen Chem, Vol. 5, Issue 9 https://doi.org/10.1016/j.chempr.2019.07.001	journal	September 2019
Review—Solid Electrolytes in Rechargeable Electrochemical Cells Goodenough, John B.; Singh, Preetam Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0021514jes	journal	January 2015
Inducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li _{6+ x} P _{1– x} Ge _x S ₅ I for All-Solid-State Batteries Kraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana Journal of the American Chemical Society, Vol. 140, Issue 47 https://doi.org/10.1021/jacs.8b10282	journal	October 2018
Fluoride ion batteries – past, present, and future Nowroozi, Mohammad Ali; Mohammad, Irshad; Molaiyan, Palanivel Journal of Materials Chemistry A, Vol. 9, Issue 10 https://doi.org/10.1039/D0TA11656D	journal	January 2021
Correlating lattice distortions, ion migration barriers, and stability in solid electrolytes Kim, Kwangnam; Siegel, Donald J. Journal of Materials Chemistry A, Vol. 7, Issue 7 https://doi.org/10.1039/C8TA10989C	journal	January 2019
Lone pairs in insulating pyrochlores: Ice rules and high-k behavior Seshadri, Ram Solid State Sciences, Vol. 8, Issue 3-4 https://doi.org/10.1016/j.solidstatesciences.2006.02.020	journal	March 2006
Structure, ionic conduction, and giant dielectric properties of mechanochemically synthesized BaSnF4 Ahmad, Mohamad M.; Yamane, Yohei; Yamada, Koji Journal of Applied Physics, Vol. 106, Issue 7 https://doi.org/10.1063/1.3234393	journal	October 2009
Crystal Structural Framework of Lithium Super‐Ionic Conductors He, Xingfeng; Bai, Qiang; Liu, Yunsheng Advanced Energy Materials, Vol. 9, Issue 43 https://doi.org/10.1002/aenm.201902078	journal	October 2019
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
EXAFS and molecular modelling studies of Rb1−xBixF1+2x Cox, P. A.; Catlow, C. R. A.; Chadwick, A. V. Journal of Materials Science, Vol. 29, Issue 10 https://doi.org/10.1007/BF00356824	journal	May 1994
MSnF4 (M = Pb++, Ba++, Sr++) : Thermal expansion and phase transitions Pannetier, J.; Dénès, G.; Lucas, J. Materials Research Bulletin, Vol. 14, Issue 5 https://doi.org/10.1016/0025-5408(79)90045-X	journal	May 1979
Polarization effects in the simulation of lead (II) fluoride Castiglione, Michael J.; Wilson, Mark; Madden, Paul A. Journal of Physics: Condensed Matter, Vol. 11, Issue 46 https://doi.org/10.1088/0953-8984/11/46/304	journal	November 1999
Point Defect Engineering Enabled the High Ionic Conductivity of BaSnF₄ for Solid-State Fluoride-Ion Batteries at Room Temperature Liu, Jiali; Yi, Lingguang; Zeng, Peng Energy & Fuels, Vol. 36, Issue 24 https://doi.org/10.1021/acs.energyfuels.2c03509	journal	November 2022
Diffusion of F− ions in CaF2 Jacucci, G.; Rahman, A. The Journal of Chemical Physics, Vol. 69, Issue 9 https://doi.org/10.1063/1.437091	journal	November 1978
Sn-K and Pb-L3 EXAFS, X-Ray Diffraction, and 119Sn Mössbauer Spectroscopic Studies of Ordered β-PbSnF4 and Disordered Pb1-xSnxF2 (x = 0.3, 0.4) Solid Solutions and PbSn4F10: High Performance Fluoride Ion Conductors Denes, G.; Yu, Y. H.; Tyliszczak, T. Journal of Solid State Chemistry, Vol. 104, Issue 2 https://doi.org/10.1006/jssc.1993.1159	journal	June 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Wannier90 as a community code: new features and applications Pizzi, Giovanni; Vitale, Valerio; Arita, Ryotaro Journal of Physics: Condensed Matter, Vol. 32, Issue 16 https://doi.org/10.1088/1361-648X/ab51ff	journal	January 2020
Born model calculation of defect energies in CaF2 Franklin, A. D. Journal of Physics and Chemistry of Solids, Vol. 29, Issue 5 https://doi.org/10.1016/0022-3697(68)90144-3	journal	May 1968
Fluoride-Ion Conductors Derived from the Fluorite Type Dénès, G.; Madamba, M. C.; Muntasar, A. Mössbauer Spectroscopy in Materials Science https://doi.org/10.1007/978-94-011-4548-0_3	book	January 1999
Superionic Conduction in the Plastic Crystal Polymorph of Na₄P₂S₆ Scholz, Tanja; Schneider, Christian; Terban, Maxwell W. ACS Energy Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acsenergylett.1c02815	journal	March 2022
Ion Migration Mechanisms in the Sodium Sulfide Solid Electrolyte Na_3–xSb_1–xW_xS₄ Smith, Jeffrey G.; Siegel, Donald J. Chemistry of Materials, Vol. 34, Issue 9 https://doi.org/10.1021/acs.chemmater.2c00526	journal	April 2022
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Coupled Cation–Anion Dynamics Enhances Cation Mobility in Room-Temperature Superionic Solid-State Electrolytes Zhang, Zhizhen; Roy, Pierre-Nicholas; Li, Hui Journal of the American Chemical Society, Vol. 141, Issue 49 https://doi.org/10.1021/jacs.9b09343	journal	November 2019
Computation of pair distribution functions and three-dimensional densities with a reduced variance principle Borgis, Daniel; Assaraf, Roland; Rotenberg, Benjamin Molecular Physics, Vol. 111, Issue 22-23 https://doi.org/10.1080/00268976.2013.838316	journal	December 2013
Quantifying the impact of disorder on Li-ion and Na-ion transport in perovskite titanate solid electrolytes for solid-state batteries Symington, Adam R.; Purton, John; Statham, Joel Journal of Materials Chemistry A, Vol. 8, Issue 37 https://doi.org/10.1039/D0TA05343K	journal	January 2020
On the Lithium Distribution in Halide Superionic Argyrodites by Halide Incorporation in Li_7–xPS_6–xCl_x Gautam, Ajay; Ghidiu, Michael; Suard, Emmanuelle ACS Applied Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1021/acsaem.1c01417	journal	July 2021
Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li ₂ OHCl Wang, Fei; Evans, Hayden A.; Kim, Kwangnam Chemistry of Materials, Vol. 32, Issue 19 https://doi.org/10.1021/acs.chemmater.0c02602	journal	September 2020
Lithium superionic conductors with corner-sharing frameworks Jun, KyuJung; Sun, Yingzhi; Xiao, Yihan Nature Materials, Vol. 21, Issue 8 https://doi.org/10.1038/s41563-022-01222-4	journal	March 2022
Packing Structures and Transitions in Liquids and Solids Stillinger, F. H.; Weber, T. A. Science, Vol. 225, Issue 4666 https://doi.org/10.1126/science.225.4666.983	journal	September 1984
Fluoride-ion batteries: State-of-the-art and future perspectives Gopinadh, Sumol V.; Phanendra, Peddinti V. R. L.; John, Bibin Sustainable Materials and Technologies, Vol. 32 https://doi.org/10.1016/j.susmat.2022.e00436	journal	July 2022
Bismuth-Based Oxide Conductors Novel Structural and Electrical Features Mairesse, G. Fast Ion Transport in Solids https://doi.org/10.1007/978-94-011-1916-0_15	book	January 1993
Investigation of anion disorder in PbF ₂ at high temperatures by neutron diffraction Dickens, M. H.; Hayes, W.; Hutchings, M. T. Journal of Physics C: Solid State Physics, Vol. 15, Issue 19 https://doi.org/10.1088/0022-3719/15/19/006	journal	July 1982
Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li ₁₀ Ge _{1– x} Sn _x P ₂ S ₁₂ Culver, Sean P.; Squires, Alexander G.; Minafra, Nicolò Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10735	journal	December 2020
Computing three-dimensional densities from force densities improves statistical efficiency Coles, Samuel W.; Borgis, Daniel; Vuilleumier, Rodolphe The Journal of Chemical Physics, Vol. 151, Issue 6 https://doi.org/10.1063/1.5111697	journal	August 2019
Reduced variance analysis of molecular dynamics simulations by linear combination of estimators Coles, S. W.; Mangaud, E.; Frenkel, D. The Journal of Chemical Physics, Vol. 154, Issue 19 https://doi.org/10.1063/5.0053737	journal	May 2021
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Ionic diffusion within the α ^* and β phases of Ag ₃ SI Hull, S.; Keen, D. A.; Madden, P. A. Journal of Physics: Condensed Matter, Vol. 19, Issue 40 https://doi.org/10.1088/0953-8984/19/40/406214	journal	September 2007
Probing the Mechanism of Fluoride-Ion Conduction in LaF₃ and Strontium-Doped LaF₃ with High-Resolution ¹⁹F MAS NMR Wang, Francis; Grey, Clare P. Chemistry of Materials, Vol. 9, Issue 5 https://doi.org/10.1021/cm970044f	journal	May 1997
Ionic and electronic transport in the fast Ag conductor α*-AgSI Gombotz, M.; Hanghofer, I.; Eisbacher-Lubensky, S. Solid State Sciences, Vol. 118 https://doi.org/10.1016/j.solidstatesciences.2021.106680	journal	August 2021
Nanostructured Fluorite-Type Fluorides As Electrolytes for Fluoride Ion Batteries Rongeat, Carine; Reddy, M. Anji; Witter, Raiker The Journal of Physical Chemistry C, Vol. 117, Issue 10 https://doi.org/10.1021/jp3117825	journal	March 2013
Fast Na diffusion and anharmonic phonon dynamics in superionic Na ₃ PS ₄ Gupta, Mayanak K.; Ding, Jingxuan; Osti, Naresh C. Energy & Environmental Science, Vol. 14, Issue 12 https://doi.org/10.1039/D1EE01509E	journal	January 2021
Fluoride ion disorder and clustering in superionic PbF ₂ Castiglione, Michael J.; Madden, Paul A. Journal of Physics: Condensed Matter, Vol. 13, Issue 44 https://doi.org/10.1088/0953-8984/13/44/311	journal	October 2001
Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li ₆ PS ₅ X (X = Cl, Br, I) Minafra, Nicolò; Kraft, Marvin A.; Bernges, Tim Inorganic Chemistry, Vol. 59, Issue 15 https://doi.org/10.1021/acs.inorgchem.0c01504	journal	July 2020
From ionic to superionic conductivity: The influence of cation order on sodium diffusion in Na3Zr2Si2PO12 Haarmann, L.; Albe, K. Solid State Ionics, Vol. 363 https://doi.org/10.1016/j.ssi.2021.115604	journal	May 2021
Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder Thurber, Kent R.; Tycko, Robert Journal of Magnetic Resonance, Vol. 196, Issue 1 https://doi.org/10.1016/j.jmr.2008.09.019	journal	January 2009
Crystallographic studies of tin(II) compounds. I. Crystal structure of tin(II) fluoride, SnF2 McDonald, Robert C.; Hau, Herbert H. K.; Eriks, Klaas. Inorganic Chemistry, Vol. 15, Issue 4 https://doi.org/10.1021/ic50158a003	journal	April 1976
High-entropy mechanism to boost ionic conductivity Zeng, Yan; Ouyang, Bin; Liu, Jue Science, Vol. 378, Issue 6626 https://doi.org/10.1126/science.abq1346	journal	December 2022
ICET – A Python Library for Constructing and Sampling Alloy Cluster Expansions Ångqvist, Mattias; Muñoz, William A.; Rahm, J. Magnus Advanced Theory and Simulations, Vol. 2, Issue 7 https://doi.org/10.1002/adts.201900015	journal	May 2019
Targeting Superionic Conductivity by Turning on Anion Rotation at Room Temperature in Fast Ion Conductors Zhang, Zhizhen; Li, Hui; Kaup, Kavish Matter, Vol. 2, Issue 6 https://doi.org/10.1016/j.matt.2020.04.027	journal	June 2020
Antiperovskite K ₃ OI for K-Ion Solid State Electrolyte Zheng, Jingfeng; Fang, Hong; Fan, Longlong The Journal of Physical Chemistry Letters, Vol. 12, Issue 30 https://doi.org/10.1021/acs.jpclett.1c01807	journal	July 2021
Recent advances in magnetic structure determination by neutron powder diffraction Rodríguez-Carvajal, Juan Physica B: Condensed Matter, Vol. 192, Issue 1-2 https://doi.org/10.1016/0921-4526(93)90108-I	journal	October 1993
Dynamic Lone Pair Expression as Chemical Bonding Origin of Giant Phonon Anharmonicity in Thermoelectric InTe Zhang, Jiawei; Ishikawa, Daisuke; Koza, Michael M. Angewandte Chemie, Vol. 135, Issue 13 https://doi.org/10.1002/ange.202218458	journal	February 2023
Computer simulation study of defect formation and migration energy in calcium fluoride Li, Kun-Dar; Xiao, H. Y.; Wang, L. M. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 266, Issue 12-13 https://doi.org/10.1016/j.nimb.2008.03.101	journal	June 2008
Cation polarizability from first-principles: Sn2+ Bernasconi, Leonardo; Wilson, Mark; Madden, Paul A. Computational Materials Science, Vol. 22, Issue 1-2 https://doi.org/10.1016/S0927-0256(01)00173-2	journal	November 2001
Study of Fluoride Ion Motions in PbSnF₄ and BaSnF₄ Compounds With Molecular Dynamics Simulation and Solid State NMR Techniques Chaudhuri, Santanu; Castiglione, Michael; Wang, Francis MRS Proceedings, Vol. 658 https://doi.org/10.1557/PROC-658-GG10.9	journal	January 2000
Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li ₃ MCl ₆ (M = Y, Er) Superionic Conductors Schlem, Roman; Muy, Sokseiha; Prinz, Nils Advanced Energy Materials, Vol. 10, Issue 6 https://doi.org/10.1002/aenm.201903719	journal	December 2019
Fast fluoride ion conducting materials in solid state ionics: An overview Patro, L. N.; Hariharan, K. Solid State Ionics, Vol. 239 https://doi.org/10.1016/j.ssi.2013.03.009	journal	May 2013
Origin of fast ion diffusion in super-ionic conductors He, Xingfeng; Zhu, Yizhou; Mo, Yifei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15893	journal	June 2017
Static disorder from lone-pair electrons in pyrochlores Avdeev, M.; Haas, M. K.; Jorgensen, J. D. Journal of Solid State Chemistry, Vol. 169, Issue 1 https://doi.org/10.1016/S0022-4596(02)00007-5	journal	November 2002
Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity? Düvel, Andre; Heitjans, Paul; Fedorov, Pavel Journal of the American Chemical Society, Vol. 139, Issue 16 https://doi.org/10.1021/jacs.7b00502	journal	April 2017
Excitations Are Localized and Relaxation Is Hierarchical in Glass-Forming Liquids Keys, Aaron S.; Hedges, Lester O.; Garrahan, Juan P. Physical Review X, Vol. 1, Issue 2 https://doi.org/10.1103/PhysRevX.1.021013	journal	November 2011
Exploring the potential energy landscape of glass-forming systems: from inherent structures via metabasins to macroscopic transport Heuer, Andreas Journal of Physics: Condensed Matter, Vol. 20, Issue 37 https://doi.org/10.1088/0953-8984/20/37/373101	journal	August 2008
Paradigms of frustration in superionic solid electrolytes Wood, Brandon C.; Varley, Joel B.; Kweon, Kyoung E. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 379, Issue 2211 https://doi.org/10.1098/rsta.2019.0467	journal	October 2021
Mixed Alkaline-Earth Effect in the Metastable Anion Conductor Ba_1–xCa_xF₂ (0 ≤ x ≤ 1): Correlating Long-Range Ion Transport with Local Structures Revealed by Ultrafast ¹⁹F MAS NMR Düvel, A.; Ruprecht, B.; Heitjans, P. The Journal of Physical Chemistry C, Vol. 115, Issue 48 https://doi.org/10.1021/jp208472f	journal	November 2011
Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li ₆ PS ₅ CN Maughan, Annalise E.; Ha, Yeyoung; Pekarek, Ryan T. Chemistry of Materials, Vol. 33, Issue 13 https://doi.org/10.1021/acs.chemmater.1c01170	journal	June 2021
Advances on fluorine ion conductors, basic and applied research Portier, J.; Reau, J. M.; Matar, S. Solid State Ionics, Vol. 11, Issue 1 https://doi.org/10.1016/0167-2738(83)90067-X	journal	September 1983
Double Paddle‐Wheel Enhanced Sodium Ion Conduction in an Antiperovskite Solid Electrolyte Tsai, Ping‐Chun; Mair, Sunil; Smith, Jeffrey Advanced Energy Materials, Vol. 13, Issue 7 https://doi.org/10.1002/aenm.202203284	journal	December 2022
Solid oxide fuel cells: fundamental aspects and prospects Yamamoto, Osamu Electrochimica Acta, Vol. 45, Issue 15-16 https://doi.org/10.1016/S0013-4686(00)00330-3	journal	May 2000
Classification of chemical bonds based on topological analysis of electron localization functions Silvi, B.; Savin, A. Nature, Vol. 371, Issue 6499 https://doi.org/10.1038/371683a0	journal	October 1994
Synthese et etude des proprietes de conductivite ionique des phases appartenant aux systemes KBiF4  BiF3 et RbBiF4  BiF3 Matar, Samir; Réau, Jean-Maurice; Lucat, Claude Materials Research Bulletin, Vol. 15, Issue 9 https://doi.org/10.1016/0025-5408(80)90034-3	journal	September 1980
SciPy 1.0: fundamental algorithms for scientific computing in Python Virtanen, Pauli; Gommers, Ralf; Oliphant, Travis E. Nature Methods https://doi.org/10.1038/s41592-019-0686-2	journal	February 2020
Site distortions created by the stereoactive lone pair of Tin(II) in highly symmetric structures Dénès, Georges; Madamba, M. Cecilia; Merazig, Hocine AIP Conference Proceedings https://doi.org/10.1063/1.4966002	conference	January 2016
Design principles for solid-state lithium superionic conductors Wang, Yan; Richards, William Davidson; Ong, Shyue Ping Nature Materials, Vol. 14, Issue 10 https://doi.org/10.1038/nmat4369	journal	August 2015
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
A new perspective on lone pair dynamics in halide perovskites Remsing, Richard C.; Klein, Michael L. APL Materials, Vol. 8, Issue 5 https://doi.org/10.1063/5.0001908	journal	May 2020
Cooperative excitations in superionic PbF ₂ Mohn, Chris E.; Krynski, Marcin; Kob, Walter Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 379, Issue 2211 https://doi.org/10.1098/rsta.2019.0455	journal	October 2021
Engineering the Site‐Disorder and Lithium Distribution in the Lithium Superionic Argyrodite Li ₆ PS ₅ Br Gautam, Ajay; Sadowski, Marcel; Ghidiu, Michael Advanced Energy Materials, Vol. 11, Issue 5 https://doi.org/10.1002/aenm.202003369	journal	December 2020
Mismatch in cation size causes rapid anion dynamics in solid electrolytes: the role of the Arrhenius pre-factor Breuer, Stefan; Wilkening, Martin Dalton Transactions, Vol. 47, Issue 12 https://doi.org/10.1039/C7DT04487A	journal	January 2018
Synthesis of Fast Fluoride-Ion-Conductive Fluorite-Type Ba_1–xSb_xF_2+x (0.1 ≤ x ≤ 0.4): A Potential Solid Electrolyte for Fluoride-Ion Batteries Mohammad, Irshad; Chable, Johann; Witter, Raiker ACS Applied Materials & Interfaces, Vol. 10, Issue 20 https://doi.org/10.1021/acsami.8b04108	journal	May 2018
Array programming with NumPy Harris, Charles R.; Millman, K. Jarrod; van der Walt, Stéfan J. Nature, Vol. 585, Issue 7825 https://doi.org/10.1038/s41586-020-2649-2	journal	September 2020
Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li ₆ PS ₅ Br Gautam, Ajay; Sadowski, Marcel; Prinz, Nils Chemistry of Materials, Vol. 31, Issue 24 https://doi.org/10.1021/acs.chemmater.9b03852	journal	November 2019
Ionic conductivity of fluorite-type fluorides Hagenmuller, P.; Reau, J.; Lucat, C. Solid State Ionics, Vol. 3-4 https://doi.org/10.1016/0167-2738(81)90110-7	journal	August 1981
Mechanochemically synthesized fluorides: local structures and ion transport Preishuber-Pflügl, Florian; Wilkening, Martin Dalton Transactions, Vol. 45, Issue 21 https://doi.org/10.1039/C6DT00944A	journal	January 2016
Mechanistic Origin of Superionic Lithium Diffusion in Anion-Disordered Li ₆ PS ₅ X Argyrodites Morgan, Benjamin J. Chemistry of Materials, Vol. 33, Issue 6 https://doi.org/10.1021/acs.chemmater.0c03738	journal	March 2021
Special quasirandom structures Zunger, Alex; Wei, S.-H.; Ferreira, L. G. Physical Review Letters, Vol. 65, Issue 3, p. 353-356 https://doi.org/10.1103/PhysRevLett.65.353	journal	July 1990
Understanding fast-ion conduction in solid electrolytes Morgan, Benjamin J. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 379, Issue 2211 https://doi.org/10.1098/rsta.2019.0451	journal	October 2021
Understanding Superionic Conductivity in Lithium and Sodium Salts of Weakly Coordinating Closo -Hexahalocarbaborate Anions Jørgensen, Mathias; Shea, Patrick T.; Tomich, Anton W. Chemistry of Materials, Vol. 32, Issue 4 https://doi.org/10.1021/acs.chemmater.9b04383	journal	January 2020
Fundamentals of inorganic solid-state electrolytes for batteries Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A. Nature Materials, Vol. 18, Issue 12 https://doi.org/10.1038/s41563-019-0431-3	journal	August 2019
Resolving the Different Dynamics of the Fluorine Sublattices in the Anionic Conductor BaSnF ₄ by Using High-Resolution MAS NMR Techniques Chaudhuri, Santanu; Wang, Francis; Grey, Clare P. Journal of the American Chemical Society, Vol. 124, Issue 39 https://doi.org/10.1021/ja026155j	journal	October 2002
Shell model calculations of the energies of formation of point defects in alkaline earth fluorides Catlow, C. R. A.; Norgett, M. J. Journal of Physics C: Solid State Physics, Vol. 6, Issue 8 https://doi.org/10.1088/0022-3719/6/8/002	journal	April 1973
Ab initio study of the stabilities of and mechanism of superionic transport in lithium-rich antiperovskites Zhang, Yi; Zhao, Yusheng; Chen, Changfeng Physical Review B, Vol. 87, Issue 13 https://doi.org/10.1103/PhysRevB.87.134303	journal	April 2013
Substitutional disorder: structure and ion dynamics of the argyrodites Li 6 PS 5 Cl, Li 6 PS 5 Br and Li 6 PS 5 I Hanghofer, I.; Brinek, M.; Eisbacher, S. L. Physical Chemistry Chemical Physics, Vol. 21, Issue 16 https://doi.org/10.1039/C9CP00664H	journal	January 2019
Ionic conductivity and structure of M_1−xPb_xF₂(M = Ca, Sr, Ba) solid solutions prepared by ball milling Düvel, Andre Dalton Transactions, Vol. 48, Issue 3 https://doi.org/10.1039/C8DT03759K	journal	January 2019
Frustration in Super‐Ionic Conductors Unraveled by the Density of Atomistic States Wang, Shuo; Liu, Yunsheng; Mo, Yifei Angewandte Chemie International Edition, Vol. 62, Issue 15 https://doi.org/10.1002/anie.202215544	journal	February 2023
Stereochemistry of post-transition metal oxides: revision of the classical lone pair model Walsh, Aron; Payne, David J.; Egdell, Russell G. Chemical Society Reviews, Vol. 40, Issue 9 https://doi.org/10.1039/c1cs15098g	journal	January 2011
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li_6+xP_1–xGe_xS₅I as Probed by Neutron Diffraction and NMR Hogrefe, Katharina; Minafra, Nicolò; Hanghofer, Isabel Journal of the American Chemical Society, Vol. 144, Issue 4 https://doi.org/10.1021/jacs.1c11571	journal	January 2022

Similar Records

Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores

Journal Article · Sat May 05 00:00:00 EDT 2018 · Solid State Sciences · OSTI ID:2202498

Giampaoli, Gabriella; Li, Jun; Hermann, Raphael P.; +2 more

Lessons learned from FeSb2O4 on stereoactive lone pairs as a design principle for anion insertion

Journal Article · Fri Oct 01 00:00:00 EDT 2021 · Cell Reports Physical Science · OSTI ID:2202498

Zaheer, Wasif; Agbeworvi, George; Perez-Beltran, Saul; +11 more

Sn-K and Pb-L[sub 3] EXAFS, X-ray diffraction, and [sup 119]Sn Moessbauer spectroscopic studies of ordered [beta]-PbSnF[sub 4] and disordered Pb[sub 1[minus]x]Sn[sub x]F[sub 2] (x = 0. 3, 0. 4) solid solutions and PbSn[sub 4]F[sub 10]: High performance fluoride ion conductors

Journal Article · Tue Jun 01 00:00:00 EDT 1993 · Journal of Solid State Chemistry; (United States) · OSTI ID:2202498

Denes, G; Yu, Y H; Tyliszczak, T; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Cations
Chemical structure
Diseases and disorders
Ions

Title: Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4

Citation Formats

References (124)

Similar Records

Related Subjects

Title: Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF ₄