WO2018167477A1 - Sels de calcium - Google Patents

Sels de calcium Download PDF

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Publication number
WO2018167477A1
WO2018167477A1 PCT/GB2018/050636 GB2018050636W WO2018167477A1 WO 2018167477 A1 WO2018167477 A1 WO 2018167477A1 GB 2018050636 W GB2018050636 W GB 2018050636W WO 2018167477 A1 WO2018167477 A1 WO 2018167477A1
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WO
WIPO (PCT)
Prior art keywords
salt
crown
ligand
general formula
ether
Prior art date
Application number
PCT/GB2018/050636
Other languages
English (en)
Inventor
Evan Keyzer
Clare GREY
Dominic Wright
Original Assignee
Dyson Technology Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dyson Technology Limited filed Critical Dyson Technology Limited
Priority to CN201880018658.1A priority Critical patent/CN110446717B/zh
Priority to EP18714016.5A priority patent/EP3596092A1/fr
Publication of WO2018167477A1 publication Critical patent/WO2018167477A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/04—Calcium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/535—Organo-phosphoranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a salt of calcium hexafluorophosphate. Additionally, the present invention relates to a method of making a calcium hexafluorophosphate salt and the use of the calcium hexafluorophosphate salt in an electrolyte in a cell or battery.
  • Lithium-ion batteries are currently used in a variety of electronic devices.
  • the use of lithium-ion cells has prevailed over other battery technologies due to the ability of a lithium-ion cell to be recharged without a loss of a significant charge capacity in the short term.
  • the energy density of a lithium-ion battery enables its use in portable products such as laptop computers and mobile phones. Over time however, lithium batteries are known to suffer from loss of charge capacity. Furthermore, issues of thermal runaway and overheating risks have been widely reported.
  • LiPF 6 is the preferred electrolyte salt in lithium-ion cells due to its balance of several properties that no other lithium salt has been found to possess.
  • there are concerns over the long term use of lithium cells given the relatively low abundance of lithium in the Earth's crust and the current high price of lithium relative to other Alkali and Alkaline Earth metals.
  • the present invention provides salt of the general formula:
  • each L represents a ligand selected from one of the following compounds: an ether or aza macrocyclic; a halomethane or a nitrile of the general formula R-C ⁇ N.
  • alkaline earth metals such as calcium could be used as electrolyte solutions in electrochemical cells and batteries.
  • Calcium is the fifth most Earth- abundant element and therefore has a relatively low cost per ton compared to lithium.
  • calcium has a higher charge capacity than lithium.
  • the large ionic radius of a Ca 2+ ion, and thus lower charge density with respect to Mg 2+ and Al 3+ could permit faster solid-state diffusion into electrode materials, in electrodes with appropriately sized voids within the structure, an issue that has limited the construction of efficient Mg-ion batteries so far.
  • calcium has not been widely adopted as an electrolyte or as a material for anodes because of difficulties in forming electrolytes that are stable over a wide voltage range and also compatible with multiple electrodes.
  • the lithium hexafluorophosphate salt is the preferred electrolyte salt in lithium-ion cells.
  • a barrier for using a calcium hexafluorophosphate based electrolyte in calcium-ion batteries is the fact that the synthesis of an Alkaline Earth metal hexafluorophosphate salt can be costly and more problematic (often resulting in lower purity materials) when compared with the synthesis of a lithium hexafluorophosphate salt. It has been found however that the calcium hexafluorophosphate salt of the present invention can be readily synthesised in an anhydrous solution under relatively mild conditions.
  • L may represent a ligand selected from one only of the following compounds: a cyclic crown ether; an aza macrocyclic compound; a halomethane; or a nitrile of the general formula R-C ⁇ N. That is to say that L may comprise one or more cyclic crown ethers, one or more aza macrocyclic compounds, two or more halomethanes, or two or more nitriles of the general formula R-C ⁇ N.
  • the ether or aza macrocyclic can comprise typical cyclic crown ethers selected from one of the following: [12]-crown-4, [15]-crown-5, [18]-crown-6, [24]-crown-8.
  • the cyclic crown ether may be used to sequester, or partly sequester the calcium cation.
  • the aza macrocyclic compound may be cyclen or cyclam.
  • the use of a multidentate ligand can be favourable since the calcium cation remains in solution but has a lowered reactivity and could also inhibit the decomposition of the PF 6 ion during synthesis; and plating of calcium onto an electrode surface if the salt is used in an electrolyte in a calcium-ion cell.
  • each R may represent an organic group independently selected from the following: methyl, ethyl, propyl, butyl, 'butyl, pentyl, ethylene, propylene, butylene, pentylene, toluene, naphthalene, or phenyl.
  • a sterically bulky ligand could prevent the solvation of the calcium cation. Therefore for the general formula, R may preferably represents a group that would provide a nitrile that is considered to have low sterically hindrance.
  • Each L may be the same nitrile. This renders the synthesis of the salt more straightforward since the same nitrile solution can be used in both the activation and the treatment steps.
  • L may be acetonitrile, which is the least sterically hindered nitrile.
  • acetonitrile provides good solvation of the calcium cation, as well as low manufacturing expense since desolvation under high vacuum can be more easily achieved than with other solvents.
  • This desolvated salt could then be re-solvated with, for instance, an ether (such as THF, diethyl ether) or another donor solvent.
  • the halomethane may be a chlorinated methane, such as CH 2 CI 2 , CHCI 3 , CCI4.
  • the chloromethanes represent stable and cost effective dry solvents for the synthesis.
  • Dichloromethane (CH 2 CI 2 ) is particularly suited as a ligand and solvent for the synthesis of the magnesium salt due to its low boiling point and solvating characteristics.
  • a single crystal obtained from the diffusion of Et 2 0 in to a CH 3 CN solution of the salt of the present invention may have the general formula (Cac l5-crown-5) 4 (PF 6 )8(CH3CN)2.
  • the present invention provides a method of making a salt of the general formula:
  • L y represents a ligand independently selected from any one of the following compounds: an ether or aza macrocyclic; a halomethane or a nitrile of the general formula R-C ⁇ N; and L y comprises a mixture of compounds Li and L2; the method comprising: providing Ca metal, washing and activating the Ca metal in a first dry solution comprising a first compound (Li), treating the solution of activated Ca metal and first compound Li with NOPF 6 in a second dry solution comprising a second compound (L 2 ), removing the residual solvent, and recrystallizing the remaining solid to form the salt of Formula (ii).
  • the residual solvent can be removed by evaporation, for example, under vacuum or by heating.
  • the present invention provides an electrolyte comprising a salt in accordance with the above Formula (i) or Formula (ii).
  • the electrolyte may comprise the salt as an additive to a conventional electrolyte, or the salt may be used in a pure solution to form, with an appropriate solvent, an electrolyte by itself.
  • the present invention provides a cell or battery with an electrolyte comprising a salt in accordance with the above Formula (i) or Formula (ii).
  • the salts of the present invention do not suffer from some of the same disadvantages observed with the use of lithium salts in electrochemical cells or batteries.
  • the salt of the present invention may be useful in terms of reducing or limiting the corrosion of cell components.
  • Figure 1 is an X-ray crystal structure of a salt crystal of the present invention selected from bulk solution;
  • Figure 2 is an X-ray crystal structure of another salt crystal falling outside the scope of the present invention.
  • FIG. 3 is a X H NMR spectrum of a salt of the present invention
  • Figure 4 is a 19 F NMR spectrum of a salt of the present invention
  • Figure 5 is a 31 P NMR spectrum of a salt of the present invention.
  • Elemental microanalytical data were obtained from the University of Cambridge, Department of Chemistry microanalytical service. Analysis calculated for C64Hi32Ca4F48N 4 024P8 [(Cac 15-crown-5) 4 (PF 6 ) 8 (CH 3 CN)2 ⁇ (2 CH 3 CN, 4 Et 2 0)]: C, 28.9; H, 5.0; N, 2.1; found: C, 28.5; H, 4.9; N, 2.3.
  • Figure 2 shows the X-ray crystal stuture of another crystal obtained from the diffusion of Et 2 0 in to a CH 3 CN solution.
  • X-ray analysis was carried out on data collected with a Bruker D8 Quest CCD diffractometer and confirmed the complex to be an undesired salt (Figure 2).
  • the structure relates to [(Cac l5-crown- 5) 4 (SiF 6 )2(CH3CN) 2 ] 4+ (PF 6 )4, where the two brid ging ions are SiFg .
  • the elemental analysis (C, H, and N) of this crystal was obtained using elemental microanalytical data obtained from the University of Cambridge, Department of Chemistry microanalytical service. Analysis calculated for C 36 H 69 Ca 2 F 24 N 3 0i 5 P 4 : C, 29.95; H, 4.82; N, 2.91 ; found: C, 29.81 ; H, 4.83; N, 2.48]
  • the 3 ⁇ 4 13 C, 19 F and 31 P NMR spectra of the bulk white crystalline powder of (Cac l5-crown- 5)(PF 6 )2 are shown in Figures 3 to 5, respectively.
  • the 19 F and 31 P NMR spectra exhibited a doublet and heptet, respectively, characteristic of the PF 6 anion.
  • NMR spectra were recorded at 298.0 K on a Bruker 500 MHz AVIII HD Smart Probe Spectrometer ( l at 500 MHz, 31 P 202 MHz, 19 F 471 MHz) or a Bruker 400 MHz AVIII HD Smart Probe spectrometer (*H at 400 MHz, 31 P 162 MHz, 19 F 376 MHz) unless otherwise specified.
  • Chemical shifts ( ⁇ , ppm) are given relative to residual solvent signals for X H, to external 85% H 3 PO4 for 31 P and to CCI 3 F for 19 F.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un sel de formule générale : Ca(L)x(PF6)2 dans laquelle, chaque L représente un ligand choisi parmi un éther ou aza macrocyclique ; un halométhane ou un nitrile de formule générale R-C≡N. Le procédé de fabrication du sel comprend les étapes consistant à : fournir du Ca métallique, activer le Ca métallique dans une première solution sèche comprenant une première solution de ligand (L1), traiter la solution sèche de Ca métallique activé et de L1 avec du NOPF6 dans une seconde solution sèche comprenant une seconde solution de ligand (L2), chauffer la solution de Ca métallique traité, éliminer le solvant résiduel sous vide, et recristalliser le solide restant pour former le sel, L comprenant un mélange de L1 et de L2. Selon l'invention, le sel peut être utilisé comme sel dans un électrolyte ou comme additif à un électrolyte, et l'électrolyte résultant peut être utilisé dans une cellule aux ions calcium ou dans une batterie.
PCT/GB2018/050636 2017-03-14 2018-03-13 Sels de calcium WO2018167477A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880018658.1A CN110446717B (zh) 2017-03-14 2018-03-13 钙盐
EP18714016.5A EP3596092A1 (fr) 2017-03-14 2018-03-13 Sels de calcium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1704038.7 2017-03-14
GB1704038.7A GB2560534B (en) 2017-03-14 2017-03-14 Calcium salts

Publications (1)

Publication Number Publication Date
WO2018167477A1 true WO2018167477A1 (fr) 2018-09-20

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ID=58605345

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PCT/GB2018/050636 WO2018167477A1 (fr) 2017-03-14 2018-03-13 Sels de calcium

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EP (1) EP3596092A1 (fr)
CN (1) CN110446717B (fr)
GB (1) GB2560534B (fr)
WO (1) WO2018167477A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000149988A (ja) * 1998-09-10 2000-05-30 Sanyo Electric Co Ltd 非水電解液二次電池
WO2016050329A1 (fr) * 2014-10-02 2016-04-07 Toyota Motor Europe Nv/Sa Électrolytes pour batterie rechargeable à base de calcium et batterie rechargeable à base de calcium les comprenant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380803A (en) * 1966-02-03 1968-04-30 Olin Mathieson Process for manufacture of alkali metal and alkaline earth metal hexafluorophosphates
JP3384625B2 (ja) * 1994-08-25 2003-03-10 三洋電機株式会社 非水電解液電池
JP3737729B2 (ja) * 2001-09-26 2006-01-25 株式会社東芝 非水電解液電池および非水電解液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000149988A (ja) * 1998-09-10 2000-05-30 Sanyo Electric Co Ltd 非水電解液二次電池
WO2016050329A1 (fr) * 2014-10-02 2016-04-07 Toyota Motor Europe Nv/Sa Électrolytes pour batterie rechargeable à base de calcium et batterie rechargeable à base de calcium les comprenant

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ALBERT L. LIPSON ET AL: "Rechargeable Ca-Ion Batteries: A New Energy Storage System", CHEMISTRY OF MATERIALS, vol. 27, no. 24, 22 December 2015 (2015-12-22), pages 8442 - 8447, XP055391403, ISSN: 0897-4756, DOI: 10.1021/acs.chemmater.5b04027 *
EVAN N. KEYZER ET AL: "Mg(PF 6 ) 2 -Based Electrolyte Systems: Understanding Electrolyte-Electrode Interactions for the Development of Mg-Ion Batteries", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 138, no. 28, 20 July 2016 (2016-07-20), US, pages 8682 - 8685, XP055348972, ISSN: 0002-7863, DOI: 10.1021/jacs.6b04319 *
EVAN N. KEYZER ET AL: "Synthesis of Ca(PF6)2, formed via nitrosonium oxidation of calcium", CHEMICAL COMMUNICATIONS, vol. 53, no. 33, 31 March 2017 (2017-03-31), GB, pages 4573 - 4576, XP055473794, ISSN: 1359-7345, DOI: 10.1039/C7CC01938F *

Also Published As

Publication number Publication date
GB2560534B (en) 2019-12-04
EP3596092A1 (fr) 2020-01-22
GB2560534A (en) 2018-09-19
CN110446717B (zh) 2022-09-27
CN110446717A (zh) 2019-11-12
GB201704038D0 (en) 2017-04-26

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