US20100143806A1 - Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride - Google Patents

Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride Download PDF

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US20100143806A1
US20100143806A1 US12/667,550 US66755008A US2010143806A1 US 20100143806 A1 US20100143806 A1 US 20100143806A1 US 66755008 A US66755008 A US 66755008A US 2010143806 A1 US2010143806 A1 US 2010143806A1
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lithium
borate salt
lithium borate
alkyl
solvent
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Rainer Dietz
Ulrich Wietelmann
Uwe Lischka
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Albemarle Germany GmbH
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Chemetall GmbH
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Publication of US20100143806A1 publication Critical patent/US20100143806A1/en
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    • 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
    • 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
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 provides a process for producing low-acid lithium borate salts for applications in battery electrolytes.
  • Lithium batteries have become established as energy stores above all for applications in portable electronics (laptops, mobile telephones), because of their high energy density and power density in comparison to other battery types.
  • primary lithium batteries which are non-rechargeable batteries having mostly lithium metal anodes, and secondary systems, in other words rechargeable batteries.
  • Both battery types contain anhydrous liquid or gel-like ion-conductive electrolytes, in which supporting electrolytes, for example LiPF 6 , LiBF 4 , lithium imides, lithium methides or lithium borate salts, for example lithium bis(oxalato)borate (LiBOB, corresponding to Li[B(C 2 O 4 ) 2 ]), are present in dissolved form.
  • supporting electrolytes for example LiPF 6 , LiBF 4 , lithium imides, lithium methides or lithium borate salts, for example lithium bis(oxalato)borate (LiBOB, corresponding to Li[B(C 2 O 4 ) 2 ]
  • lithium borate salts such as LiBOB bring about a significant improvement in cycle stability and safety properties in secondary lithium batteries (Cox, S. S. Zhang, U. Lee, J. L. Allen, T. R. Jow, J. Power Sources 46, 2005, 79-85).
  • Lithium borate salts for example having the general formulae I or II are used:
  • L is a chelating agent having two terminal oxygen atoms with the general formula
  • Lithium borate salts are generally produced by reacting an oxidic boron compound (for example boric acid, boron oxide or a boric acid ester) with oxalic acid or an oxalic acid salt or a fluoride donor, for example BF 3 , and optionally further dihydroxy compounds, for example dicarboxyl compounds, diphenols, and a lithium raw material, for example lithium carbonate, lithium hydroxide, lithium alcoholate or similar.
  • an oxidic boron compound for example boric acid, boron oxide or a boric acid ester
  • oxalic acid or an oxalic acid salt or a fluoride donor for example BF 3
  • dihydroxy compounds for example dicarboxyl compounds, diphenols
  • a lithium raw material for example lithium carbonate, lithium hydroxide, lithium alcoholate or similar.
  • the commonest method of producing bis(chelato)borates of type I involves suspending the components in a solvent and separating off the water azeotropically (E. Bessler and J. Weidlein, Z. Naturforsch. 37b, 1020-1025, 1982).
  • Suitable solvents are those which form an azeotrope with water, for example saturated or aromatic solvents such as heptane, octane, toluene or cumene.
  • the alkali metal can also be incorporated via the lithium salt of the ligand (LiHL or Li 2 L) or a metal borate, for example LiBO 2 , for example:
  • a further production possibility is to react a metal tetraalkoxyborate M[B(OR) 4 ] with two equivalents of the ligands in an organic solvent (DE-C-19829030), for example:
  • R is an alkyl radical, for example H 3 C or C 2 H 5 .
  • the alcohol itself (formed in the reaction, ROH), for example methanol or ethanol, or an aprotic, polar solvent, for example acetonitrile, can be used as the organic solvent.
  • DE-A-10108608 discloses the synthesis of alkali metal bis(chelato)borates by means of the reactions listed above without addition of solvents in the heterogeneous phase and removal of the water formed during the reaction. This process has the disadvantage of relatively poor drying results.
  • DE-A-10108608, Example 1 discloses a product having a water content of 0.4%. This water content is well above the values required for supporting electrolytes for batteries.
  • LiDFOB lithium difluorooxalatoborate
  • LiDFOB a complex of boron trifluoride with diethyl ether as solvate
  • Li 2 C 2 O 4 Li 2 C 2 O 4
  • the gaseous products formed during the hydrolysis of fluorine-containing supporting electrolytes are highly caustic and damaging to the other battery components, for example the cathode materials.
  • HF leads to the disintegration of manganese spinels, for example, and destroys the top coating on the electrode materials, which is important for a long operating life.
  • the cycle stability of secondary batteries is impaired as a consequence.
  • Borate electrolytes are also sensitive to water. In this case hydrolysis products, some of them insoluble, are formed, which likewise impair the functional properties of the batteries.
  • Hydrolysis products such as boric acid or oxalic acid are acid-corrosive and similarly impair the formation of the top coating on the cathode or anode materials.
  • DE-A-10049097 discloses the separation of water and protic contaminants from an organic liquid electrolyte by bringing it into contact with insoluble alkali-metal hydrides and separating off the insoluble secondary reaction products.
  • the disadvantage of the process described is that the drying times are relatively long and the amounts of drying agent to be used are very high; thus approx. 0.4 to 6 g of lithium hydride are used per kg of electrolyte solution, corresponding to about 2 to 25 g per kg of lithium borate salt content.
  • the object of the present invention is to provide a simple, cost-effective process for producing anhydrous and acid-free (or low-water and low-acid) solid lithium borate salts and solutions thereof in aprotic organic solvents.
  • the object is achieved by mixing crude lithium borate salts contaminated with water and/or acid, abbreviated below to crude lithium borate salt, in the solid phase, or suspended in a solvent which does not dissolve the crude lithium borate salt, with lithium hydride and stirring them together, preferably at elevated temperature.
  • This treatment preferably takes place either under vacuum or in a dry atmosphere, most particularly preferably in an inert-gas atmosphere.
  • the compounds represented by the generic formulae I and II are used as lithium borate salts:
  • L is a chelating agent having two terminal oxygen atoms with the general formula
  • lithium bis(oxalato)borate LiBOB
  • lithium malonato-oxalato-borate LiMOB
  • lithium glycolato-oxalatoborate LiGOB
  • lithium salicylato-oxalatoborate LiSOB
  • lithium lactato-oxalatoborate LiLOB
  • lithium catecholato-oxalatoborate LiBZOB
  • lithium difluorooxalatoborate LiDFOB
  • lithium difluoro-malonatoborate lithium difluoroglycolatoborate
  • lithium difluorosalicylatoborate lithium difluorolactatoborate
  • lithium difluorocatecholatoborate lithium difluorocatecholatoborate.
  • the lithium hydride is particularly preferably used in finely dispersed form, i.e. ground.
  • the average particle size D 50 is preferably 100 ⁇ m or below.
  • LiBOB lithium bis(oxalato)borate
  • LiBOB undergoes thermal decomposition with formation of gases as follows:
  • the mixing of lithium borate salt and lithium hydride can take place in pure form or with addition of an aprotic solvent or solvent blend which does not dissolve the lithium borate salt, with a boiling point or range of at least 100° C. under normal pressure (referred to below as aprotic solvent).
  • aprotic solvent preferably boils in the range between 110 and 280° C.
  • Suitable aprotic solvents are aromatic or saturated hydrocarbons, perfluorinated or partially fluorinated hydrocarbons or dialkyl ethers.
  • aromatic hydrocarbons examples include: toluene, ethyl benzene, xylenes, cumene; examples of saturated hydrocarbons: heptane, octane, nonane, decane, undecane and dodecane and mixtures thereof. Most particularly suitable too are commercially obtainable hydrocarbon blends such as for example Shellsol D70 or D100 or Halpasols.
  • fluorinated hydrocarbons are: perfluoro(methyldecalin), perfluorononane, perfluorooctane, perfluorotridecane, perfluorodecalin or commercially obtainable perfluorocarbon blends such as perfluorokerosene with a boiling range between 210 and 240° C.
  • High-boiling dialkyl ethers such as dibutyl ether, diamyl ether or diphenyl ether or mixtures thereof are also suitable.
  • the amount of lithium hydride to be used is governed by the concentration of protic contaminants in the crude lithium borate salt. As a general rule, a minimum of 0.001 wt. % and a maximum of 10 wt. %, relative to the weight of lithium borate salt used, should be used.
  • the preferred amount of LiH is between 0.01 and 1 wt. %.
  • the reaction between lithium borate salt and lithium hydride in the absence of an aprotic solvent or solvent blend takes place under an inert-gas atmosphere or under vacuum at temperatures of between 40 and 280° C., particularly preferably under pressures of less than 50 mbar and at temperatures of between 110 and 220° C.
  • the duration of the reaction is between 10 min and 24 hours, preferably between 0.5 and 10 hours.
  • drying and neutralisation preferably take place at a temperature at which the solvent boils.
  • the boiling process brings about an acceleration of the drying process through cavitation effects.
  • the aprotic solvents used for the process according to the invention form azeotropic mixtures with water, i.e. water that is present forms a low-boiling-point mixture with the solvent.
  • Water and aprotic solvent separate in the condensate.
  • the water phase can be separated off using suitable prior art apparatus so that only the aprotic solvent returns to the lithium borate salt/LiH/aprotic solvent blend. A most particularly efficient drying can take place in this way.
  • the necessary drying times in the presence of an aprotic solvent which does not dissolve the lithium borate salt are dependent on the drying temperature, the amount of lithium hydride used, etc.
  • the concentration of lithium hydride, relative to the weight of crude lithium borate salt, is at least 0.001 and at most 10 wt. % and the concentration of solids (i.e. lithium borate salt and lithium hydride) in the solvent is at least 5 and at most 95% in total.
  • drying is carried out in the preferred temperature range of between 110 and 220° C., 0.5 to 10 hours are generally found to be sufficient.
  • the aprotic solvent is removed from the lithium borate salt/lithium hydride mixture. This can take place either via a mechanical liquid/solid separation operation, for example filtration or decanting, or alternatively by means of total evaporation. In total evaporation the condensate is discharged from the distillation apparatus rather than being returned to the distillation vessel. This process can take place under normal pressure or reduced pressure. It is particularly preferable for the final drying to lower the pressure. The final pressure is preferably less than 100 mbar. In this way the aprotic solvent can be removed particularly completely from the lithium borate salt/LiH mixture.
  • lithium borate salts After the drying and neutralisation operation, mixtures of solids are present which are contaminated with excess lithium hydride and reaction products thereof (LiOH, Li 2 CO 3 , Li 2 C 2 O 4 ). They contain a maximum of 100 ⁇ mol of water and a maximum of 10 ⁇ mol of H + per g of crude lithium borate salt. As such mixtures cannot be used directly as supporting electrolytes for lithium batteries, a further object is to separate the cited contaminants from the lithium borate salt. This is achieved most simply through a selective dissolution process. Whereas lithium borate salts generally have a high solubility in many aprotic, polar solvents, the contaminants are scarcely soluble or not at all soluble in the same solvents.
  • the crude lithium borate salt dried and neutralised according to the invention hereinafter simply called the crude salt according to the invention, is brought into contact with a likewise aprotic anhydrous and acid-free solvent or solvent blend which dissolves the crude salt well.
  • Ethers, ketones, carbonic acid esters, ⁇ -lactones, carboxylic acid esters and nitriles either in pure form or blended with one another or mixed with a hydrocarbon, e.g. toluene, ethyl benzene or methyl cyclohexane, are suitable as such crude-salt-dissolving aprotic solvents.
  • Carbonic acid esters in particular cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and the like, nitriles such as acetonitrile and propionitrile and ⁇ -lactones such as ⁇ -butyrolactone and ⁇ -valerolactone, are most particularly suitable.
  • cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and the like
  • nitriles such as acetonitrile and propionitrile
  • ⁇ -lactones such as ⁇ -butyrolactone and ⁇ -valerolactone
  • the concentration of the dissolved crude lithium borate salt is 1 to 50%, preferably 5 to 30%. It was found that the contamination with water is at most 100 ⁇ mol/g and that with acids (H + ) is at most 10 ⁇ mol/g of dissolved crude lithium borate salt.
  • LiBOB is used as a representative of a lithium borate salt.
  • Crude LiBOB produced according to the prior art typically contains 0.1 to 0.2% water and has a relatively high acid content of >100 ⁇ mol/g.
  • the acid content is titrated using a specific method in the anhydrous medium (titration with tertiary amines against bromophenol blue as indicator).
  • 0.1 to 0.5% lithium hydride powder is preferably added to the crude LiBOB and the mixture is then heated with intensive thorough mixing. This operation particularly preferably takes place in the presence of aliphatic hydrocarbons having a boiling range between 110 and 280° C. at temperatures of between 110 and 220° C.
  • the dried and neutralised crude salt isolated from this process either by total evaporation or by a solid/liquid separation process is then introduced with exclusion of air and water, i.e. under vacuum or under an inert-gas atmosphere, into an aprotic solvent which dissolves LiBOB well, preferably ethylene carbonate, propylene carbonate or butylene carbonate, to produce an approx. 10 to 20% solution.
  • the dissolving process can be accelerated by stirring and/or heating. In a stirred system the dissolving process is completed after a few minutes to approx. 5 hours.
  • the crude salt solution containing undissolved residues is then stirred at elevated temperatures, for example at 50 to 200° C., for around 10 minutes to 10 hours. Any remaining traces of water and acid introduced with the aprotic solvent and/or the crude lithium borate salt are removed or neutralised by this measure.
  • the turbid solution treated as described above is then filtered, decanted or centrifuged according to the prior art to separate the sediment.
  • Membrane filtration using filter media having pore diameters of less than 0.5 ⁇ m is most particularly preferred.
  • the product solution can be mixed in this form with other components, in other words solvents, lithium salts (e.g. LiPF 6 ) or special additives (e.g. film-forming substances such as vinylene carbonate or redox shuttle molecules such as for example 1,2-divinyl furoate, 1,3-butadiene carbonate or 2-tert-butyl anisole) and then used as a battery electrolyte.
  • solvents such as for example acetonitrile or butyl acetate, which are not commonly found in batteries, are used for the separation process.
  • the solvent must either be removed by total evaporation or the dissolved lithium borate salt must be isolated by crystallisation (displacement, evaporative or cooling crystallisation).
  • LiBOB/LiH mixture from Example 1 263 g were introduced into 1380 g of dry PC (water content 30 ppm), which had been placed in an inerted 2-litre double-jacketed reactor. Then the stirred turbid mixture was stirred for 3 hours at 120° C. under an argon blanket. After cooling to room temperature the solution was filtered through a membrane filter supplied by Cuno (SCF nylon, pore size 100 nm).
  • the solid was then blown dry with argon and vacuum dried at 100° C.

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US12/667,550 2007-07-04 2008-07-03 Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride Abandoned US20100143806A1 (en)

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DE102007031199.2 2007-07-04
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PCT/EP2008/058599 WO2009004059A1 (de) 2007-07-04 2008-07-03 Verfahren zur herstellung säurearmer lithiumboratsalze und mischungen aus säurearmen lithiumboratsalzen und lithiumhydrid

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150110951A1 (en) * 2011-06-01 2015-04-23 Toyota Jidosha Kabushiki Kaisha Method for producing electrode active material and electrode active material
CN105355976A (zh) * 2015-11-13 2016-02-24 华南师范大学 一种含硼酸三丙酯添加剂的电解液及其制备方法与应用
US20160181661A1 (en) * 2014-12-17 2016-06-23 E I Du Pont De Nemours And Company Nonaqueous electrolyte compositions comprising lithium glycolatoborate and fluorinated solvent
US9509014B2 (en) 2009-02-18 2016-11-29 Chemetall Gmbh Galvanic cell having a lithium metal or an alloy comprising a lithium metal as anode material and an electrolyte having lithium . . . complex salt
US10720668B2 (en) * 2015-12-18 2020-07-21 Basf Se Non-aqueous electrolytes for lithium-ion batteries comprising asymmetric borates

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010060770A1 (de) 2010-11-24 2012-05-24 Westfälische Wilhelms Universität Münster Verfahren zur Herstellung organischer Lithiumsalze
CN103840209A (zh) * 2012-11-26 2014-06-04 华为技术有限公司 一种非水有机电解液添加剂及其制备方法、非水有机电解液和锂离子二次电池
CN105870504B (zh) * 2016-05-04 2019-11-22 宁德新能源科技有限公司 一种电解液及锂离子电池
US20180163548A1 (en) * 2016-12-13 2018-06-14 General Electric Company Selective thermal barrier coating repair
CN109627256A (zh) * 2018-11-02 2019-04-16 珠海市赛纬电子材料股份有限公司 一种季戊四醇双硼酸酯二氟化硼的制备方法
CN111825704A (zh) * 2019-04-17 2020-10-27 江苏长园华盛新能源材料有限公司 提纯二氟草酸硼酸锂的方法
CL2020001650A1 (es) 2019-06-18 2021-01-29 Schlumberger Technology Bv Extracción de litio

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6506516B1 (en) * 1998-06-30 2003-01-14 Metallgesellschaft Aktiengesellschaft Lithium bisoxalatoborate, the production thereof and its use as a conducting salt
US20040063986A1 (en) * 2001-02-22 2004-04-01 Ulrich Wietelmann Boron chelate complexes
US20040076887A1 (en) * 2001-03-08 2004-04-22 Jan-Christoph Panitz Electrolytes for lithium ion batteries
US20060138056A1 (en) * 2000-09-27 2006-06-29 Ulrich Wietelmann Method of drying organic liquid electrolytes
WO2006087889A1 (ja) * 2005-01-24 2006-08-24 Central Glass Company, Limited イオン性錯体の合成法
US20060269844A1 (en) * 2005-05-26 2006-11-30 Ferro Corporation Triazine compounds for removing acids and water from nonaqueous electrolytes for electrochemical cells
US7674911B2 (en) * 2001-02-22 2010-03-09 Chemetall Gmbh Method for the production of hydrogen-bis (chelato) borates and alkali metal-bis (chelato) borates

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04282563A (ja) * 1991-03-08 1992-10-07 Fuji Elelctrochem Co Ltd 非水電解液電池およびその製造方法
JP3369937B2 (ja) * 1997-11-19 2003-01-20 セントラル硝子株式会社 テトラフルオロホウ酸リチウムの精製方法
DE19827630A1 (de) * 1998-06-20 2000-04-27 Merck Patent Gmbh Aufreinigung von Batterieelektrolyten mittels chemischer Adsorption
US7172834B1 (en) * 2002-07-29 2007-02-06 The United States Of America As Represented By The Secretary Of The Army Additive for enhancing the performance of electrochemical cells
JP2005307083A (ja) * 2004-04-23 2005-11-04 Maruzen Petrochem Co Ltd リサイクル性ポリウレタンおよびその製造法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6506516B1 (en) * 1998-06-30 2003-01-14 Metallgesellschaft Aktiengesellschaft Lithium bisoxalatoborate, the production thereof and its use as a conducting salt
US20060138056A1 (en) * 2000-09-27 2006-06-29 Ulrich Wietelmann Method of drying organic liquid electrolytes
US7666310B2 (en) * 2000-09-27 2010-02-23 Chemetall Gmbh Method of drying organic liquid electrolytes
US20040063986A1 (en) * 2001-02-22 2004-04-01 Ulrich Wietelmann Boron chelate complexes
US7674911B2 (en) * 2001-02-22 2010-03-09 Chemetall Gmbh Method for the production of hydrogen-bis (chelato) borates and alkali metal-bis (chelato) borates
US20040076887A1 (en) * 2001-03-08 2004-04-22 Jan-Christoph Panitz Electrolytes for lithium ion batteries
WO2006087889A1 (ja) * 2005-01-24 2006-08-24 Central Glass Company, Limited イオン性錯体の合成法
US20080125602A1 (en) * 2005-01-24 2008-05-29 Central Glass Company, Limited Method For Synthesizing Ionic Complex
US20060269844A1 (en) * 2005-05-26 2006-11-30 Ferro Corporation Triazine compounds for removing acids and water from nonaqueous electrolytes for electrochemical cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Z. Chen, J. Liu, and K. Amine. Lithium Difluoro(oxalato)borate as Salt for Lithium-Ion Batteries, Electrochemical and Solid-State Letters, 10 (3) A45-A47 (2007). *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9509014B2 (en) 2009-02-18 2016-11-29 Chemetall Gmbh Galvanic cell having a lithium metal or an alloy comprising a lithium metal as anode material and an electrolyte having lithium . . . complex salt
US20150110951A1 (en) * 2011-06-01 2015-04-23 Toyota Jidosha Kabushiki Kaisha Method for producing electrode active material and electrode active material
US10305096B2 (en) * 2011-06-01 2019-05-28 Toyota Jidosha Kabushiki Kaisha Method for producing electrode active material and electrode active material
US20160181661A1 (en) * 2014-12-17 2016-06-23 E I Du Pont De Nemours And Company Nonaqueous electrolyte compositions comprising lithium glycolatoborate and fluorinated solvent
US10199684B2 (en) * 2014-12-17 2019-02-05 Solvay Sa Nonaqueous electrolyte compositions comprising lithium glycolatoborate and fluorinated solvent
CN105355976A (zh) * 2015-11-13 2016-02-24 华南师范大学 一种含硼酸三丙酯添加剂的电解液及其制备方法与应用
US10720668B2 (en) * 2015-12-18 2020-07-21 Basf Se Non-aqueous electrolytes for lithium-ion batteries comprising asymmetric borates

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