Granted Patent
B2
US 12,218,315 · App. 17/395,087 · Granted Feb 4, 2025
Barium-doped composite electrode materials for fluoride-ion electrochemical cells
Inventors:
Nam Hawn Chou (New Berlin, WI); Kaoru Omichi (Tochigi, JP); Ryan McKenney (Roseville, MN); Qingmin Xu (Dublin, OH); Christopher Brooks (Dublin, OH); Simon C. Jones (Whittier, CA); Isabelle M. Darolles (Azusa, CA); Hongjin Tan (Pasadena, CA)
H01M10/36C01F17/265C01F17/30H01M4/136H01M4/366H01M10/054B82Y30/00B82Y40/00C01F11/22C01P2002/54C01P2002/72C01P2002/85C01P2004/03C01P2004/04C01P2004/80C01P2006/40H01M4/38H01M2300/0034
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Abstract
The present disclosure relates to a method of making core-shell and yolk-shell nanoparticles, and to electrodes comprising the same. The core-shell and yolk-shell nanoparticles and electrodes comprising them are suitable for use in electrochemical cells, such as fluoride shuttle batteries. The shell may protect the metal core from oxidation, including in an electrochemical cell. In some embodiments, an electrochemically active structure includes a dimensionally changeable active material forming a particle that expands or contracts upon reaction with or release of fluoride ions. One or more particles are at least partially surrounded with a fluoride-conducting encapsulant and optionally one or more voids are formed between the active material and the encapsulant using sacrificial layers or selective etching. The fluoride-conducting encapsulant may comprise one or more metals. When the electrochemically active structures are used in secondary batteries, the presence of voids can accommodate dimensional changes of the active material.
Claims (10)
1. An electrode comprising:
a core comprising copper nanoparticles, and
a fluoride-containing shell at least partially surrounding the core,
wherein the fluoride-containing shell comprises a fluoride of barium and lanthanum, and wherein an empirical formula of the fluoride-containing shell comprises Ba x La 1−x , wherein x is from about 0.03 to about 0.15.
2. The electrode of claim 1 , wherein the fluoride-containing shell is directly attached to the core.
3. The electrode of claim 1 , wherein the fluoride-containing shell is spaced from the core so as to define a void space therebetween.
4. The electrode of claim 1 , wherein x is about 0.03.
5. A fluoride shuttle battery comprising the electrode of claim 1 and a liquid electrolyte.
6. The fluoride shuttle battery of claim 5 , wherein the liquid electrolyte comprises a fluoride salt and a solvent.
7. The fluoride shuttle battery of claim 5 , wherein the liquid electrolyte comprises a fluoride salt, a polymer, and an organic liquid.
Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Aug 10, 2021
From: JONES, SIMON C.; DAROLLES, ISABELLE M.
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 057130/0021 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Aug 10, 2021
From: CHOU, NAM HAWN; OMICHI, KAORU; MCKENNEY, RYAN; XU, QINGMIN; BROOKS, CHRISTOPHER
To: HONDA MOTOR CO., LTD.
Reel/Frame 057130/0070 →
EMPLOYMENT AGREEMENT
Recorded Aug 10, 2021
From: TAN, HONGJIN
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 057434/0934 →
Continuity (6)
Provisional Application
62676693
· May 25, 2018
Provisional Application
62453295
· Feb 1, 2017
Provisional Application
62434611
· Dec 15, 2016
References Cited (154)
US 4052539A
· Shropshire et al.
· 1977
[cited by applicant]
US 4931172A
· Kobos et al.
· 1990
[cited by applicant]
US 7007972B1
· Radhakrishnan et al.
· 2006
[cited by applicant]
US 7722993B2
· Potanin
· 2010
[cited by examiner]
US 9166249B2
· Darolles et al.
· 2015
[cited by applicant]
US 9705124B2
· Walker et al.
· 2017
[cited by applicant]
US 20030008145A1
· Goldstein
· 2003
[cited by applicant]
US 20060070491A1
· Yang et al.
· 2006
[cited by applicant]
US 20070209475A1
· Sakaue et al.
· 2007
[cited by applicant]
US 20090269269A1
· White et al.
· 2009
[cited by applicant]
US 20100285358A1
· Cui et al.
· 2010
[cited by applicant]
US 20130078510A1
· Reynolds et al.
· 2013
[cited by applicant]
US 20130115484A1
· Li et al.
· 2013
[cited by applicant]
US 20130133934A1
· Flores et al.
· 2013
[cited by applicant]
US 20140377457A1
· Liu et al.
· 2014
[cited by applicant]
US 20150118496A1
· Cho et al.
· 2015
[cited by applicant]
US 20160017180A1
· Schmidt et al.
· 2016
[cited by applicant]
CA 2781043A1
· 2011
[cited by applicant]
CN 101156260A
· 2008
[cited by applicant]
CN 101341614A
· 2009
[cited by applicant]
CN 101501790A
· 2009
[cited by applicant]
CN 102106025A
· 2011
[cited by applicant]
CN 102612776A
· 2012
[cited by applicant]
CN 102714099A
· 2012
[cited by applicant]
CN 102812586A
· 2012
[cited by applicant]
CN 103087805A
· 2013
[cited by applicant]
CN 103620842A
· 2014
[cited by applicant]
CN 103779533A1
· 2014
[cited by applicant]
CN 104332609A
· 2015
[cited by applicant]
CN 104936728A
· 2015
[cited by applicant]
CN 105006596A
· 2015
[cited by applicant]
CN 105024092A
· 2015
[cited by applicant]
CN 105449280A
· 2016
[cited by applicant]
CN 106063004A
· 2016
[cited by applicant]
CN 107452953A
· 2017
[cited by applicant]
DE 102014211907A1
· 2014
[cited by applicant]
JP H02098659A
· 1990
[cited by applicant]
JP 2007294196A
· 2007
[cited by applicant]
JP 2008021415A
· 2008
[cited by applicant]
JP 2008536285A
· 2008
[cited by applicant]
JP 2010003675A
· 2010
[cited by applicant]
JP 201080221A
· 2010
[cited by applicant]
JP 2010519682A
· 2010
[cited by applicant]
JP 20158136A
· 2015
[cited by applicant]
JP 2015518264A
· 2015
[cited by applicant]
JP 2016505704A
· 2016
[cited by applicant]
JP 2016076499A
· 2016
[cited by applicant]
JP 2016526264A
· 2016
[cited by applicant]
JP 2017091701A
· 2017
[cited by applicant]
JP 2017514988A
· 2017
[cited by applicant]
JP 2017216208A
· 2017
[cited by applicant]
JP 201863905A
· 2018
[cited by applicant]
JP 2020047526A
· 2020
[cited by applicant]
KR 1020150064948A
· 2015
[cited by applicant]
KR 20160047022A
· 2016
[cited by applicant]
WO WO2007146453A2
· 2007
[cited by applicant]
WO WO2008048716A2
· 2008
[cited by applicant]
WO WO2009157033A2
· 2009
[cited by applicant]
WO WO2010107720A2
· 2010
[cited by applicant]
WO WO2011063541A2
· 2011
[cited by applicant]
WO WO2012118446A1
· 2012
[cited by applicant]
WO WO2016047906A1
· 2016
[cited by applicant]
WO WO2016068594A1
· 2016
[cited by applicant]
WO WO2017025957A1
· 2017
[cited by applicant]
WO WO2019226663A1
· 2019
[cited by applicant]
WO WO2019246265A1
· 2019
[cited by applicant]
Communication dated Dec. 7, 2021, from the Japanese Patent Office in related application No. 2019-532014.
[cited by applicant]
Katia Guerin et al., “Core-Shell Ni—NiF2 as Cathode Materials for Secondary Lithium Batteries”, IMLB 2016 (18th International Meeting on Lithium Batteries), (2016) (2 Pages Total), https://ecs.confex.com/ecs/imlb2016/we…
[cited by applicant]
Francois Tanguy et al., “Lowering Interfacial Chemical Reactivity of Oxide Materials for Lithium Batteries. A Molecular Grafting Approach”, Journal of Materials Chemistry, vol. 19, No. 27, 2009, pp. 4771-4777. The Royal…
[cited by applicant]
Office Action dated Apr. 4, 2023, issued by the Japanese Patent Office in related Japanese Application No. 2020-565794.
[cited by applicant]
Communication dated Mar. 28, 2022, from the State Intellectual Property Office of People's Republic of China in Application No. 201780073648.3.
[cited by applicant]
Li, Ting, et al., “Electrochemical Conversion Reactions and Their Applications for Rechargeable Batteries”, Journal of Electrochemistry, vol. 21, No. 2, pp. 115-122, 2015, <http://electrochem.xmu.edu.cn>, (Abstract on p…
[cited by applicant]
Office Action dated Nov. 29, 2022, issued by the Korean Patent Office in related Korean Application No. 10-2019-7019489.
[cited by applicant]
B.P. Sobolev et al., “Mechanochemical Synthesis of Nonstoichiometric Fluorite Ca1—xLaxF2+x Nanocrystals from CaF2 and LaF3 Single Crystals” Crystallography Reports, vol. 50, No. 3, pp. 478-485, 2005.
[cited by applicant]
Charles J. McDonald et al., “Hollow latex particles: synthesis and applications” Advanced in Colloid and Interface Science, vol. 99, pp. 181-213, 2002.
[cited by applicant]
Hiroyuki Ohno, “Electrochemical Aspects of lonic Liquids” Wiley-Interscience, New York, 2005.
[cited by applicant]
N. I. Sorokin et al., “Nonstoichiometric Fluorides-Solid Electrolytes for Electrochemical Devices: A Review” Crystallography Reports, vol. 52., No. 5., pp. 842-863, 2007.
[cited by applicant]
“Lutensol(R) AO types” [online], Mar. 2014 (Mar. 2014) [retrieved on Jan. 29, 2020], retrieved from the Internet: < https://biakhim.com.ua/index.phpoption=com_k2&Itemid=1174&id=901_f6cc99717606f04a 2abc418ab94 cc6b1&lan…
[cited by applicant]
Benjamin C-K. Tee et al., “An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications”, Nature Nanotechnology, vol. 7, 2012 Macmillan Publish…
[cited by applicant]
Bhatia H. et al., “Conductivity Optimization of Tysonite-type La1—xBaxF3-x Solid Electrolytes for Advanced Fluoride Ion Battery”, ACS Applied Materials & Interfaces, Jun. 2017, [retrieved on Jan. 9, 2020], vol. 9, issue…
[cited by applicant]
Christene A. Smith et al., “N-Heterocyclic Carbenes in Materials Chemistry”, Chem. Rev. 119, 2019 American Chemical Society, pp. 4986-5056, (2019).
[cited by applicant]
Communication dated Jun. 9, 2020, from the European Patent Office in related European Application No. 17880278.1.
[cited by applicant]
David Lou et al., “Hollow Micro-/Nanostructures: Synthesis and Applications”, Advanced Materials, vol. 20, pp. 3987-4019, 2008.
[cited by applicant]
David W. Oxtoby et al., “Electrochemistry”, Principles of Modern Chemistry, 4th Edition, Saunders College Publishing pp. 401-443, 1999.
[cited by applicant]
F. Gschwind et al., Review: Fluoride ion batteries: Theoretical performance, safety, toxicity, and a combinatorial screening of new electrodes, Journal of Fluorine Chemistry, vol. 182, pp. 76-90, (2016).
[cited by applicant]
Fan Cui et al., “Synthesis of Ultrathin Copper Nanowires Using Tris(trimethylsilyl)silane for High-Performance and Low-Haze Transparent Conductors”, American Chemical Society, NANO Letters, D01:10.1021/acs.nanolett.5b03…
[cited by applicant]
Hoe Jin Hah et al. “New synthetic route for preparing rattle-type silica particles with metal cores” Chem. Commun., pp. 1012-1013, 2004.
[cited by applicant]
International Search Report and Written Opinion, issued by International Searching Authority in related International Application No. PCT/US2019/037994, mailed on Sep. 3, 2019, (PCT/ISA/210, PCT/ISA/220 & PCT/ISA/237).
[cited by applicant]
International Search Report and Written Opinion, issued by International Searching Authority in related International Patent Application No. PCT/US19/64736, mailed on Feb. 25, 2020.
[cited by applicant]
International Search Report and Written Opinion, issued by International Searching Authority in related International Patent Application No. PCT/US2019/033334, mailed on Aug. 2, 2019, (PCT/ISA/210, PCT/ISA/220 & PCT/ISA…
[cited by applicant]
International Search Report and Written Opinion, issued by International Searching Authority in related International Patent Application No. PCT/US2019/064792, mailed on Mar. 2, 2020.
[cited by applicant]
J. McBreen et al., “New approaches to the design of polymer and liquid electrolytes for lithium batteries”, Journal of Power Sources, vol. 89, pp. 163-167, 2000.
[cited by applicant]
Kim H. K. et al., “Reduction of the Work Function of Gold by N.Heterocyclic Carbenes”, Chemistry of Materials [online], Apr. 12, 2017 (Apr. 12, 2017) [retrieved on Jan. 30, 2020], vol. 29, issue 8, pp. 3403-3411.
[cited by applicant]
Luiz G. Jacobsohn et al., “Preparation and Characterization of Rare Earth Doped Fluoride Nanoparticles”, Materials, vol. 3, No. 3, (2010), ISSN: 1996-1944, pp. 2053-2068.
[cited by applicant]
Lukasz Gorski et al. “Complexes of tetra-tert-butyl-tetraazaporphine with A1(III) and Zr(IV) cations as fluoride selective ionophores” Analytica Chimica Acta 633, pp. 181-187, 2009.
[cited by applicant]
Lukasz Gorski et al., “Fluoride-selective polymeric membrane electrodes based on Zr(IV)-and A1(III)-salen ionophores of various structures”, Analytica Chimica Acta 655, pp. 39-46, 2010.
[cited by applicant]
M. Anji et al., “Batteries based on fluoride shuttle” , Journal of Materials Chemistry, vol. 21, No. 43, pp. 17059-17062, Nov. 21, 2011.
[cited by applicant]
Michael A. Webb et al., “Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes”, 2015 American Chemical Society, ACS Cent. Sci. 2015, 1, pp. …
[cited by applicant]
Michael A. Webb et al., Supporting Information, Chemically Specific Dynamic Bond Percolation Model for Ion Transport in Polymer Electrolytes, Macromolecules, 48, 7346 (2015), (12 Pages total).
[cited by applicant]
Michelle Lukosi et al., “Recent advances in gold-metal oxide core-shell nanoparticles: Synthesis, characterization, and their application for heterogeneous catalysis”, Frontiers of Chemical Science and Engineering, High…
[cited by applicant]
Nanditha G. Nair et al., “Fluorinated Boroxin-Based Anion Receptors for Lithium Ion Batteries: Fluoride Anion Binding, Ab Initio Calculations, and lonic Conductivity Studies”, The Journal of Physical Chemistry A, vol. 1…
[cited by applicant]
P.J. Gellings et al., “The CRC Handbook of Solid State Electrochemistry”, pp. 195-222, 1997.
[cited by applicant]
Perrin Walker et al., “Handbook of Metal Etchants”, CRC 1991.
[cited by applicant]
Philippe Cordier et al., “Self-healing and thermoreversible rubber supramolecular assembly”, Nature Letters, vol. 451, 2008 Nature Publishing Group, (4 Pages Total), Feb. 21, 2008.
[cited by applicant]
PubChem. Citrate May 27, 2016. Retrieved from Internet: <URL: http://pubchem.ncbi.nlm.nih.gov/compound/citrate>. as viewed on Feb. 6, 2018.
[cited by applicant]
Shinobu Fujihara et al., “Sol-Gel Processiong of LaF3 Thin Films” Journal of the Ceramic Society of Japan vol. 106, pp. 124-126, 1998.
[cited by applicant]
Shlomo Magdassi et al., “Copper Nanoparticles for Printed Electronics: Routes Towards Achieving Oxidation Stability” Materials, vol. 3, pp. 4626-4638, 2010.
[cited by applicant]
Stephan Rudiger et al., “The fluorolytic sol-gel route to metal fluorides—a versatile process opening a variety of application fields”, Dalton Transactions, No. 9, pp. 1117-1127, 2008.
[cited by applicant]
Thomas F. Miller, III, et al., “Designing Polymer Electrolytes for Safe and High Capacity Rechargeable Lithium Batteries”, 2017 American Chemical Society, Acc. Chem. Res. 2017, 50, pp. 590-593, (2017).
[cited by applicant]
V. Trnovcova et al., “Fluoride Solid Electrolytes”, Russian Journal of Electrochemistry, vol. 45, No. 6, pp. 630-639, 2009.
[cited by applicant]
William C. West et al., “Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite”, Journal of the Electrochemical Society, vol. 154, pp. A929-A936, 2007.
[cited by applicant]
Written Opinion and International Search Report of related application No. PCT/US2017/066800 dated Mar. 5, 2018.
[cited by applicant]
Zeb G. et al., “Surface Treatments for Controlling Solid Electrolyte Interphase Formation on Sn/Graphene Composite Anodes for High-Performance Li-Ion Batteries”, Journal of Physical Chemistry C, Jul. 10, 2017 (Jul. 10, …
[cited by applicant]
Action in CN201980035313.1, mailed Oct. 10, 2023, 11 pages.
[cited by applicant]
Office Action and Search Report dated Jan. 2, 2024 issued by the Chinese Patent Office in related Chinese Application No. 201980080733.1.
[cited by applicant]
Barrelet, et al., “Surface Characterization and Electrochemical Properties of Alkyl, Fluorinated Alkyl, and Alkoxy Monolayers on Silicon”, Langmuir, vol. 17, pp. 3460-3465, May 5, 2001.
[cited by applicant]
Chable, Johann, et al., “Fluoride solid electrolytes: investigation of the tysonite-type solid solutions a1-xBaxF3-x (x <0.15)”, Dalton Transactions; 2015, 44, pp. 19625-19635.
[cited by applicant]
Paul, Subir, “Materials and Electrochemistry: Present and Future Battery”, Journal of Electrochemical Science and Technology, 2016, 7(2), pp. 115-131, DOI: http://dx.doi.org/10.5229/JECST.2016.7.2.115.
[cited by applicant]
McKenney, Ryan K., (2017) “Emerging Therapeutics for Organophosphorus Nerve Agent Poisonings. The Development of a Fluoride Ion Battery System Utilizing Nanoparticles”, Dissertation, The Ohio State University.
[cited by applicant]