Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Davis, Victoria K.; Bates, Christopher M.; Omichi, Kaoru; Savoie, Brett M.; Momčilović, Nebojša; Xu, Qingmin; Wolf, William J.; Webb, Michael A.; Billings, Keith J.; Chou, Nam Hawn; Alayoglu, Selim; McKenney, Ryan K.; Darolles, Isabelle M.; Nair, Nanditha G.; Hightower, Adrian; Rosenberg, Daniel; Ahmed, Musahid; Brooks, Christopher J.; Miller, III, Thomas F.; Grubbs, Robert H.; Jones, Simon C.

doi:10.1126/science.aat7070

Title: Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Journal Article · 05 December 2018 · Science

DOI: https://doi.org/10.1126/science.aat7070 · OSTI ID:1484839

;

; Momčilović, Nebojša;

; Wolf, William J.;

;

; Alayoglu, Selim; McKenney, Ryan K.; Darolles, Isabelle M.;

;

Fluoride ion batteries are potential “next-generation” electrochemical storage devices that offer high energy density. At present, such batteries are limited to operation at high temperatures because suitable fluoride ion–conducting electrolytes are known only in the solid state. We report a liquid fluoride ion–conducting electrolyte with high ionic conductivity, wide operating voltage, and robust chemical stability based on dry tetraalkylammonium fluoride salts in ether solvents. Pairing this liquid electrolyte with a copper–lanthanum trifluoride (Cu@LaF ₃ ) core-shell cathode, we demonstrate reversible fluorination and defluorination reactions in a fluoride ion electrochemical cell cycled at room temperature. Fluoride ion–mediated electrochemistry offers a pathway toward developing capacities beyond that of lithium ion technology.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1484839

Journal Information:: Science, Journal Name: Science Journal Issue: 6419 Vol. 362; ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

CuF ₂ as Reversible Cathode for Fluoride Ion Batteries Thieu, Duc Tho; Fawey, Mohammed Hammad; Bhatia, Harshita Advanced Functional Materials, Vol. 27, Issue 31 https://doi.org/10.1002/adfm.201701051	journal	May 2017
Reactions of the “Naked” Fluoride Ion: Syntheses and Structures of SeF62− and BrF6− Mahjoub, Ali Reza; Zhang, Xiongzhi; Seppelt, Konrad Chemistry - A European Journal, Vol. 1, Issue 4 https://doi.org/10.1002/chem.19950010410	journal	July 1995
Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis Breneman, Curt M.; Wiberg, Kenneth B. Journal of Computational Chemistry, Vol. 11, Issue 3 https://doi.org/10.1002/jcc.540110311	journal	April 1990
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
The solubility of alkali-metal fluorides in non-aqueous solvents with and without crown ethers, as determined by flame emission spectrometry Wynn, D. Talanta, Vol. 31, Issue 11 https://doi.org/10.1016/0039-9140(84)80244-1	journal	November 1984
Rechargeable batteries with aqueous electrolytes Beck, Fritz; Rüetschi, Paul Electrochimica Acta, Vol. 45, Issue 15-16 https://doi.org/10.1016/S0013-4686(00)00344-3	journal	May 2000
Reaction of the fluoride anion with acetonitrile. Chloroform and methylene chloride Christe, Karl O.; Wilson, William W. Journal of Fluorine Chemistry, Vol. 47, Issue 1 https://doi.org/10.1016/S0022-1139(00)80453-4	journal	April 1990
Implementing molecular dynamics on hybrid high performance computers – Particle–particle particle-mesh Brown, W. Michael; Kohlmeyer, Axel; Plimpton, Steven J. Computer Physics Communications, Vol. 183, Issue 3 https://doi.org/10.1016/j.cpc.2011.10.012	journal	March 2012
Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes Shin, J. Electrochemistry Communications, Vol. 5, Issue 12 https://doi.org/10.1016/j.elecom.2003.09.017	journal	December 2003
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Fluoride based electrode materials for advanced energy storage devices Amatucci, Glenn G.; Pereira, Nathalie Journal of Fluorine Chemistry, Vol. 128, Issue 4, p. 243-262 https://doi.org/10.1016/j.jfluchem.2006.11.016	journal	April 2007
Mechanical synthesis and structural properties of the fast fluoride-ion conductor PbSnF4 Fujisaki, Fumika; Mori, Kazuhiro; Yonemura, Masao Journal of Solid State Chemistry, Vol. 253 https://doi.org/10.1016/j.jssc.2017.06.007	journal	September 2017
Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes Savoie, Brett M.; Webb, Michael A.; Miller, Thomas F. The Journal of Physical Chemistry Letters, Vol. 8, Issue 3 https://doi.org/10.1021/acs.jpclett.6b02662	journal	January 2017
Charge–Discharge Behavior of Bismuth in a Liquid Electrolyte for Rechargeable Batteries Based on a Fluoride Shuttle Okazaki, Ken-ichi; Uchimoto, Yoshiharu; Abe, Takeshi ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00320	journal	May 2017
Equilibrium acidities in dimethyl sulfoxide solution Bordwell, Frederick G. Accounts of Chemical Research, Vol. 21, Issue 12 https://doi.org/10.1021/ar00156a004	journal	December 1988
Core/Shell Nanoparticles: Classes, Properties, Synthesis Mechanisms, Characterization, and Applications Ghosh Chaudhuri, Rajib; Paria, Santanu Chemical Reviews, Vol. 112, Issue 4 https://doi.org/10.1021/cr100449n	journal	December 2011
Nonaqueous Li–Air Batteries: A Status Report Luntz, Alan C.; McCloskey, Bryan D. Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500054y	journal	October 2014
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations Rappe, A. K.; Casewit, C. J.; Colwell, K. S. Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035 https://doi.org/10.1021/ja00051a040	journal	December 1992
Syntheses, properties, and structures of anhydrous tetramethylammonium fluoride and its 1:1 adduct with trans-3-amino-2-butenenitrile Christe, Karl O.; Wilson, William W.; Wilson, Richard D. Journal of the American Chemical Society, Vol. 112, Issue 21 https://doi.org/10.1021/ja00177a025	journal	October 1990
Ion pairing and reactivity of enolate anions. 5. Thermodynamics of ionization of .beta.-di- and tricarbonyl compounds in dimethyl sulfoxide solution and ion pairing of their alkali salts Arnett, Edward M.; Maroldo, Stephen G.; Schilling, Steven L. Journal of the American Chemical Society, Vol. 106, Issue 22 https://doi.org/10.1021/ja00334a049	journal	October 1984
Anhydrous Tetrabutylammonium Fluoride Sun, Haoran; DiMagno, Stephen G. Journal of the American Chemical Society, Vol. 127, Issue 7 https://doi.org/10.1021/ja0440497	journal	February 2005
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Preference for Eclipsed Conformations in Acyclic Neopentyldialkylamines and the Stereodynamical Consequences: An NMR and Molecular Mechanics Investigation ¹ Anderson, J. Edgar; Casarini, Daniele; Ijeh, Anthony I. Journal of the American Chemical Society, Vol. 119, Issue 34 https://doi.org/10.1021/ja9710363	journal	August 1997
Conformational studies by dynamic NMR. 39. Clefts in simple acyclic organic molecules. Correlated stereodynamics of N-tert-alkylbenzylamines studied by dynamic NMR spectroscopy, x-ray diffraction, and molecular mechanics calculations Anderson, J. E.; Tocher, D. A.; Casarini, D. The Journal of Organic Chemistry, Vol. 56, Issue 5 https://doi.org/10.1021/jo00005a016	journal	March 1991
Instability of anhydrous tetra-n-alkylammonium fluorides Sharma, Ramesh K.; Fry, James L. The Journal of Organic Chemistry, Vol. 48, Issue 12 https://doi.org/10.1021/jo00160a041	journal	June 1983
Acidities of carbon and nitrogen acids: the aromaticity of the cyclopentadienyl anion Bordwell, Frederick G.; Drucker, George E.; Fried, Herbert E. The Journal of Organic Chemistry, Vol. 46, Issue 3 https://doi.org/10.1021/jo00316a032	journal	January 1981
Comparison of various tetraalkylammonium salts as supporting electrolytes in organic electrochemical reactions House, Herbert O.; Feng, Edith; Peet, Norton P. The Journal of Organic Chemistry, Vol. 36, Issue 16 https://doi.org/10.1021/jo00815a038	journal	August 1971
Eliminations from 2-butyl halides induced by halide ions in dimethylformamide and dimethyl sulfoxide Bartsch, Richard A. The Journal of Organic Chemistry, Vol. 35, Issue 4 https://doi.org/10.1021/jo00829a035	journal	April 1970
Carbon acids. 8. The trimethylammonio group as a model for assessing the polar effects of electron-withdrawing groups Bordwell, F. G.; Van der Puy, Michael.; Vanier, Noel R. The Journal of Organic Chemistry, Vol. 41, Issue 10 https://doi.org/10.1021/jo00872a049	journal	May 1976
Safe and Convenient Procedure for Solvent Purification Pangborn, Amy B.; Giardello, Michael A.; Grubbs, Robert H. Organometallics, Vol. 15, Issue 5, p. 1518-1520 https://doi.org/10.1021/om9503712	journal	January 1996
Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
A fluoride-doped PEG matrix as an electrolyte for anion transportation in a room-temperature fluoride ion battery Gschwind, Fabienne; Zao-Karger, Zhirong; Fichtner, Maximilian J. Mater. Chem. A, Vol. 2, Issue 5 https://doi.org/10.1039/C3TA13881J	journal	January 2014
Parametric investigation of room-temperature fluoride-ion batteries: assessment of electrolytes, Mg-based anodes, and BiF ₃ -cathodes Gschwind, Fabienne; Bastien, Joshua Journal of Materials Chemistry A, Vol. 3, Issue 10 https://doi.org/10.1039/C4TA06625A	journal	January 2015
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
1H, 7Li, and 19F nuclear magnetic resonance and ionic conductivity studies for liquid electrolytes composed of glymes and polyetheneglycol dimethyl ethers of CH3O(CH2CH2O)nCH3 (n=3–50) doped with LiN(SO2CF3)2 Hayamizu, Kikuko; Akiba, Etsuo; Bando, Toshinori The Journal of Chemical Physics, Vol. 117, Issue 12 https://doi.org/10.1063/1.1501279	journal	September 2002
Constant pressure molecular dynamics algorithms Martyna, Glenn J.; Tobias, Douglas J.; Klein, Michael L. The Journal of Chemical Physics, Vol. 101, Issue 5 https://doi.org/10.1063/1.467468	journal	September 1994
Nonstoichiometric fluorides—Solid electrolytes for electrochemical devices: A review Sorokin, N. I.; Sobolev, B. P. Crystallography Reports, Vol. 52, Issue 5, p. 842-863 https://doi.org/10.1134/S1063774507050148	journal	September 2007
High Resolution Nuclear Magnetic Resonance Spectra of Bifluoride Ion and its Homologues Martin, John S.; Fujiwara, Fred Y. Canadian Journal of Chemistry, Vol. 49, Issue 18 https://doi.org/10.1139/v71-515	journal	September 1971
High Li[sup +] Self-Diffusivity and Transport Number in Novel Electrolyte Solutions Videa, Marcelo; Xu, Wu; Geil, Burkhard Journal of The Electrochemical Society, Vol. 148, Issue 12 https://doi.org/10.1149/1.1415030	journal	January 2001
Fluoride-Conducting Solid Electrolytes in Galvanic Cells Schoonman, J. Journal of The Electrochemical Society, Vol. 126, Issue 5 https://doi.org/10.1149/1.2129125	journal	January 1979
A Solid-State Galvanic Cell with Fluoride-Conducting Electrolytes Schoonman, J. Journal of The Electrochemical Society, Vol. 123, Issue 12 https://doi.org/10.1149/1.2132694	journal	January 1976
Thin-Film Galvanic Cell Pb∕PbF[sub 2]∕PbF[sub 2],CuF[sub 2]∕Cu Kennedy, John H. Journal of The Electrochemical Society, Vol. 123, Issue 1 https://doi.org/10.1149/1.2132740	journal	January 1976
Unbiased Assessment of Electrochemical Windows: Minimizing Mass Transfer Effects on the Evaluation of Anodic and Cathodic Limits Olson, Eric J.; Bühlmann, Philippe Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.068302jes	journal	December 2012
Electrochemical Performance of a Bismuth Fluoride Electrode in a Reserve-Type Fluoride Shuttle Battery Konishi, Hiroaki; Minato, Taketoshi; Abe, Takeshi Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0931714jes	journal	January 2017
Magnesium batteries: Current state of the art, issues and future perspectives Mohtadi, Rana; Mizuno, Fuminori Beilstein Journal of Nanotechnology, Vol. 5 https://doi.org/10.3762/bjnano.5.143	journal	January 2014

Similar Records

Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Journal Article · 2018 · Science · OSTI ID:1501644

Davis, Victoria K.; Bates, Christopher M.; Omichi, Kaoru; +18 more

Methods for manufacturing electrodes including fluoropolymer-based solid electrolyte interface layers

Patent · 2022 · OSTI ID:1892513

Xiao, Xingcheng

A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

Journal Article · 2015 · Journal of Power Sources · OSTI ID:1265852

Fears, Tyler M.; Sacci, Robert L.; Winiarz, Jeffrey G.; +3 more

Title: Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Citation Formats

References (47)

Similar Records

Related Subjects