Classifications

• • 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
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/025—Boronic and borinic acid 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
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/022—Boron compounds without C-boron linkages
• • 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
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/04—Esters of boric acids
• • 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
  • H01M10/0567—Liquid materials characterised by the additives
• • 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 invention relates to a process for the preparation of Metalldifluorochelatoboraten and their use as battery electrolytes or additives in galvanic cells.
• lithium batteries are particularly suitable for these purposes, which have significantly higher energy densities compared to the former systems.
• large-format lithium batteries should also be used e.g. for stationary applications (power back-up) and in the automotive sector for traction purposes (hybrid drives or purely electric drive). Especially in the latter applications, safety is given paramount importance.
• the current generation of lithium-ion batteries uses as the electrolyte a liquid, gel or polymeric electrolyte with LiPF 6 as conductive salt. This salt begins already when it exceeds about 70 ° C according to
• LiPF 6 LiF + PF 5 (1) to form the highly reactive Lewis acid PF 5 to decompose.
• the acid attacks the organic components of the electrolytes (eg alkyl carbonates) used in the prior art. This reaction is exothermic and can lead to runaway self - heating, which at least impairs the ability of the electrochemical cell to function or causes it to be completely destroyed by dangerous concomitants.
• electrolytes inter alia, solutions of lithium salts with fluorochelatoborate anion, z. Lithium difluorooxalatoborate (LiDFOB) (US6849752, Z. Chen, J. Liu, K.
• L is a chelator with two terminal oxygen atoms with the general formula
• a disadvantage of this method is that LiF remains in the product, the ligand 1, 1, 1, 3, 3, 3-hexafluoroisopropanol expensive and the process consuming because it is two-stage.
• lithium tetrafluoroborate anhydrous oxalic acid and SiCl are reacted as auxiliary reagent (EP 1308449):
• LiDFOB forms in the warm storage of equimolar mixtures of LiBF and LiBOB in ethylene carbonate / ethyl methyl carbonate (EC / EMC) in a very slow reaction (B. Lucht, Electrochem., Solid State Lett., 14 (11) A161 -A164 (201 1)).
• the mixed salt LiDFOB is obtained at 100 ° C storage within 10 weeks with about 80% yield.
• the disadvantages of this method are that the conversion is significantly too slow for commercial use and that the raw material LiBF is expensive.
• LiDFOB can be prepared from lithium tetrafluoroborate and bis (thmethylsilyl) oxalate in acetonitrile solution (C. Schreiner, M. Amereller, H. Gores, Chem. Eur. J. 13 (2009) 2270-2):
• the object of the invention has been found to provide a method that forms starting from industrially available, easy to handle raw materials Metalldifluorochelatoborate, in particular LiDFOB in a one-step, simple reaction.
• L is a chelating agent having two terminal oxygen atoms with the general formula
• LiDFOB lithium ö / s (oxalato) borate
• LiBOB lithium fluoride or lithium oxalate and boron trifluoride
• lithium difluoromalonato borate is prepared from lithium oil (malonato) borate and BF 3 as well as LiF or lithium malonate (Li 2 C 3 H 2 O 4 ).
• Further preferred products are: lithium difluorolactatoborate, lithium difluoroglycolate borate, lithium difluorosalicylatoborate, lithium difluoroborate catechinatoborate and the corresponding sodium salts.
• aprotic organic solvents preferably ethers, esters, nitriles, lactones, carbonates, either used in pure form or in any mixture.
• hydrocarbons aromatics or saturated compounds
• solvents which are suitable for use in lithium batteries.
• solvents include: carbonic acid esters (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate), cyclic ethers such as tetrahydropyran or tetrahydrofuran, polyethers such as 1, 2-dimethoxyethane or diethylene glycol dimethyl ether, furthermore nitriles such as acetonitrile, adiponitrile, malononitrile, glutaronitrile and lactones such as ⁇ -butyrolactone.
• carbonic acid esters dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate
• cyclic ethers such as tetrahydropyran or tetrahydrofuran
• polyethers such as 1, 2-dimethoxyethane or diethylene glycol dimethyl ether
• nitriles
• the reaction is carried out at temperatures between 0 and 250 ° C, preferably 20 and 150 ° C and more preferably between 30 and 130 ° C.
• the sparingly soluble starting materials ie the metal fluorides and / or metal chelate salts, are used in pulverized form, preferably ground.
• the average particle size is preferably ⁇ 100 ⁇ m and particularly preferably ⁇ 50 ⁇ m.
• a catalyst is used to accelerate the reaction.
• the catalysts used are Lewis acids or substances which are capable of liberating Lewis acids in the reaction mixture.
• Preferred catalysts are element compounds of the 2nd to 15th group of the Periodic Table, particularly preferably molecular halides, perfluoroalkyls, perfluoroaryls and oxo compounds of boron, aluminum and phosphorus. Examples are: aluminum alcoholates (Al (OR) 3), boric acid esters (B (OR) 3), phosphorus oxides and phosphorus halides.
• Very particularly preferred are super-acidic boron compounds such as B (C 6 F 5 ) 3 (“BARF"), C 6 F 5 BO 2 C 6 F 4 and boric acid esters of trivalent oxygen-based chelating ligands such as
• the catalytic use of LiPF 6 which is in equilibrium with the strong Lewis acid PF 5 under the abovementioned reaction conditions is also very particularly preferred (equation 1).
• the catalysts mentioned are used in amounts of at most 20 mol%, preferably up to 10 mol% and particularly preferably up to 5 mol%, based on the boron trifluoride used.
• boron trifluoride is then either introduced in the gaseous state or condensed or metered in the form of commercially available solvate complexes, for example as BF 3 ⁇ diethyl ether, BF 3 ⁇ THF or BF 3 ⁇ acetonitrile.
• solvate complexes for example as BF 3 ⁇ diethyl ether, BF 3 ⁇ THF or BF 3 ⁇ acetonitrile.
• gaseous BF 3 or a previously prepared with BF 3 gas solution in the desired solvent eg, a carbonate such as dimethyl carbonate or propylene carbonate.
• the BF 3 - dosing takes place in the temperature range between 0 ° C and 150 ° C, preferably between 10 and 100 ° C. After complete addition of the BF 3 is stirred until the reaction is complete. The progress of the reaction can conveniently be monitored, for example, by 11 B NMR measurements.
• the process according to the invention may also deviate slightly from the theoretical stoichiometry (Equations 6 to 9).
• the stoichiometries are preferably selected which lead to a complete consumption of the raw material BF 3 which interferes with the battery.
• the metal salts MF and / or M 2 L are used in excess.
• the metal salts mentioned are preferably used with 0.1 to 100% by weight excess, more preferably with 1 to 20% by weight.
• reaction solution is clarified by filtration (e.g., membrane filtration). As such, it can be used directly as a battery electrolyte or additive if no solvents which disturb the battery performance were used. If interfering solvents should be present, the synthesized Metalldifluorochelatoborat invention is obtained by an evaporation or crystallization process in pure form.
• Example 1 Preparation of LiDFOB from LiBOB, lithium oxalate and BF 3 in
• DMC Dimethyl carbonate
• Example 5 Preparation of LiDFOB from LiBOB, lithium fluoride and BF 3 in
• Lithium fluoride and BF3 in dimethylsulfoxide (DMSO) without catalyst In an inerted GC septum glass with magnetic stirrer, 1.78 g of LiBMB and 0.21 g of lithium fluoride were dissolved or suspended in 10.5 g of DMSO. To the stirred suspension, 1.14 g of boron trifluoride etherate were injected and then stirred at 100 ° C. After a short time, an almost clear reaction solution was formed. Samples were taken at certain time intervals and tested for reaction progress by 11 B-NMR:

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• 2012
  • 2012-11-14 CA CA2856123A patent/CA2856123C/en active Active
  • 2012-11-14 CN CN201280055854.9A patent/CN104185636B/zh active Active
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  • 2012-11-14 WO PCT/EP2012/072603 patent/WO2013072359A1/de not_active Ceased
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