WO2018167477A1 - Sels de calcium - Google Patents
Sels de calcium Download PDFInfo
- 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
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- 159000000007 calcium salts Chemical class 0.000 title description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 150000002825 nitriles Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910004060 NOPF6 Inorganic materials 0.000 claims abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- 229940003871 calcium ion Drugs 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000013557 residual solvent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- -1 cyclic crown ether Chemical class 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 26
- 239000011575 calcium Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 claims description 3
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 claims description 3
- QNTPNTFBQZBRCK-UHFFFAOYSA-N 1,5,9,13-tetraoxacyclohexadecane Chemical compound C1COCCCOCCCOCCCOC1 QNTPNTFBQZBRCK-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 229910014495 Ca(PF6)2 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (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)
- Geology (AREA)
- Materials Engineering (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.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18714016.5A EP3596092A1 (fr) | 2017-03-14 | 2018-03-13 | Sels de calcium |
CN201880018658.1A CN110446717B (zh) | 2017-03-14 | 2018-03-13 | 钙盐 |
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 |
Family
ID=58605345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2018/050636 WO2018167477A1 (fr) | 2017-03-14 | 2018-03-13 | Sels de calcium |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3596092A1 (fr) |
CN (1) | CN110446717B (fr) |
GB (1) | GB2560534B (fr) |
WO (1) | WO2018167477A1 (fr) |
Citations (2)
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)
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 |
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2017
- 2017-03-14 GB GB1704038.7A patent/GB2560534B/en active Active
-
2018
- 2018-03-13 WO PCT/GB2018/050636 patent/WO2018167477A1/fr unknown
- 2018-03-13 CN CN201880018658.1A patent/CN110446717B/zh active Active
- 2018-03-13 EP EP18714016.5A patent/EP3596092A1/fr not_active Withdrawn
Patent Citations (2)
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)
Title |
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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 * |
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Publication number | Publication date |
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CN110446717B (zh) | 2022-09-27 |
CN110446717A (zh) | 2019-11-12 |
EP3596092A1 (fr) | 2020-01-22 |
GB2560534B (en) | 2019-12-04 |
GB2560534A (en) | 2018-09-19 |
GB201704038D0 (en) | 2017-04-26 |
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