WO2012069554A1 - Procédé de fabrication de sels organiques de lithium - Google Patents

Procédé de fabrication de sels organiques de lithium Download PDF

Info

Publication number
WO2012069554A1
WO2012069554A1 PCT/EP2011/070859 EP2011070859W WO2012069554A1 WO 2012069554 A1 WO2012069554 A1 WO 2012069554A1 EP 2011070859 W EP2011070859 W EP 2011070859W WO 2012069554 A1 WO2012069554 A1 WO 2012069554A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
borate
range
carbonate
salt
Prior art date
Application number
PCT/EP2011/070859
Other languages
German (de)
English (en)
Inventor
Miriam Kunze
Alexandra Lex-Balducci
Sascha Nowak
Stefano Passerini
Raphael Wilhelm Schmitz
Martin Winter
Original Assignee
Westfälische Wilhelms-Universität Münster
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 Westfälische Wilhelms-Universität Münster filed Critical Westfälische Wilhelms-Universität Münster
Publication of WO2012069554A1 publication Critical patent/WO2012069554A1/fr

Links

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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C01B35/063—Tetrafluoboric acid; Salts thereof
    • C01B35/066—Alkali metal tetrafluoborates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium 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
    • C07F5/04—Esters of boric acids
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • 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
    • 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 lithium salts with organic borate and / or phosphate anion. Due to their high energy and power density, lithium-ion batteries are now the favorite among energy storage devices, especially for portable applications
  • Lithium-ion batteries comprise two electrodes, which are spatially separated by a separator.
  • the charge transport takes place via an electrolyte.
  • positively charged lithium ions migrate through the electrolyte from the positive to the negative electrode, while the charging current supplies the electrons via the external circuit.
  • the electrolyte is a lithium salt dissolved in a mixture of nonaqueous solvent.
  • Conducting salts are, for example, lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (L1CIO 4 ) or lithium borate salts, for example lithium tetrafluoroborate (L1BF 4 ), lithium bis (oxalato) borate (LiBOB) and, more recently, lithium difluoroxalatoborate (LiDFOB).
  • LiPF 6 lithium hexafluorophosphate
  • LiCIO 4 lithium perchlorate
  • lithium borate salts for example lithium tetrafluoroborate (L1BF 4 ), lithium bis (oxalato) borate (LiBOB) and, more recently, lithium difluoroxalatoborate (LiDFOB).
  • LiPF 6 lithium hexafluorophosphate
  • LiBOB lithium bis (oxalato) borate
  • LiDFOB lithium difluoroxalatoborate
  • the lithium difluorooxalatoborat is
  • LiDFOB lithium difluorooxalatoborate
  • a disadvantage of these synthesis methods is that handling starting materials such as trifluoroborate etherate or silicon tetrachloride is cumbersome or dangerous. Furthermore, HCl is released during the synthesis and chloride or HCl partly remain in the product. This leads to serious problems. On the one hand, the product reacts acidly and on the other hand contains chloride impurities, which are particularly troublesome for the application, since this causes corrosion problems, especially in electrochemical applications.
  • document WO 2009/004059 discloses a purification by removal of acids or water by mixing with lithium hydride.
  • the present invention was therefore based on the object to provide a method which overcomes at least one of the aforementioned disadvantages of the prior art.
  • the present invention was based on the object to provide a method that allows production without impurities.
  • This object is achieved by a process for preparing a lithium salt with organic borate and / or phosphate anion by reacting a fluorinated lithium salt with an organic lithium borate or lithium phosphate salt selected from the group comprising oxalates, malonates, glycolates, salicylates, lactates, catecholates, succinates and / or mixtures thereof in an aprotic solvent or solvent mixture.
  • Reaction aids such as S1CI4 need to be used. In an advantageous manner, this does not cause any impurities.
  • the reaction product of the process of the invention contains no chloride impurities.
  • the inventive method thus does not require separation of impurities.
  • the preparation according to the invention of a lithium salt with organic borate and / or phosphate anion is thus a process wherein no purification is necessary to remove acids or water, for example by reaction with lithium hydride.
  • the process step of drying and / or deacidifying a crude electrolyte with lithium hydride required in known processes is thus advantageously unnecessary. It provides a significant advantage that the reaction product need not be reacted with lithium hydride. As a result, advantageously no further purification or separation steps are required to remove excess lithium hydride and its reaction products.
  • the process according to the invention can therefore, in particular, provide a one-step preparation of lithium salts with organic borate and / or phosphate anion.
  • the process according to the invention can be carried out as a simple one-step synthesis.
  • the cost of the synthesis can be significantly reduced and the conditions can be significantly simplified.
  • Another great advantage is that only the reactants and reaction products are present in the reaction mixture.
  • Lithium borate or lithium phosphate salts used as starting materials are used as starting materials. Furthermore, preference is given to the use of aprotic solvents of a purity which can be used in lithium-ion batteries. As a result, time-consuming and expensive cleaning of the produced lithium salts with organic borate and / or phosphate anion can be avoided.
  • the starting materials, fluorinated lithium salts and organic lithium borate or lithium phosphate salts are used in equimolar amounts. This can do that
  • Reaction equilibrium for example, the reaction LiBF 4 + LiBOB- ⁇ LiBFOB using lithium tetrafluoroborate and lithium bis (oxalato) borate favorably influenced product.
  • a fluorinated lithium salt selected from the group comprising lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ),
  • LiSnF 6 Lithium hexafluorostannate
  • LiTaF 6 lithium hexafluorotanatalate
  • the fluorinated lithium salt is
  • Lithium tetrafluoroborate LiBF 4 .
  • an organic lithium borate or lithium phosphate salt selected from the group comprising lithium bis (oxalato) borate (LiBOB), lithium bis (malonato) borate (LiBMB), lithium malonato oxalate borate (LiMOB), lithium glycolato oxalato borate (LiGOB ), Lithium salicylatooxalatoborate (LiSOB), lithium lactatooxalatoborate (LiLOB), lithium catecholatoalatoborate (LiBZOB), lithium bis (succinato) borate (LiBSB) and / or lithium tris (oxalato) phosphate (LiTOP).
  • LiBOB lithium bis (oxalato) borate
  • LiBMB lithium bis (malonato) borate
  • LiMOB lithium malonato oxalate borate
  • LiGOB lithium glycolato oxalato borate
  • LiSOB Lith
  • Process according to the invention can be obtained or produced in a simple manner and on an industrial scale.
  • Lithiumoxalatoboratsalze by Implementation of an oxide boron compound such as boric acid, boron oxide or
  • Boric acid ester can be prepared with oxalic acid or an oxalic acid salt.
  • the organic lithium borate is lithium bis (oxalato) borate (LiBOB).
  • the yield of the process according to the invention can be favorably influenced by varying the aprotic solvent or the ratio of the solvents of a solvent mixture, the reaction temperature and / or the reaction time.
  • Preferred aprotic solvents are selected from the group comprising cyclic carbonates, preferably ethylene carbonate (EC) and / or propylene carbonate (PC), linear carbonates, preferably diethyl carbonate (DEC), dimethyl carbonate (DMC) and / or ethyl methyl carbonate (EMC), nitriles, preferably acetonitrile (AN) , Dinitriles preferably glutaronitrile (GLN), adiponitrile (ADN) and / or pimelonitrile (PIN), and / or lactones preferably gamma-butyrolactone (GBL) and / or gamma-valerolactone (GVL).
  • cyclic carbonates preferably ethylene carbonate (EC) and / or propylene
  • ethylene carbonate (EC) is preferably usable as the sole solvent or as a constituent of a solvent mixture.
  • the aprotic solvent mixture used is a mixture of ethylene carbonate (EC) with at least one further aprotic solvent selected from the group comprising cyclic carbonates, preferably propylene carbonate (PC), linear carbonates, preferably diethyl carbonate (DEC), dimethyl carbonate (DMC) and / or ethyl methyl carbonate (EMC), nitriles preferably acetonitrile (AN), dinitriles preferably glutaronitrile (GLN), adiponitrile (ADN) and / or pimelonitrile (PIN), and / or lactones preferably gamma-butyrolactone (GBL) and / or gamma-valerolactone (GVL) ,
  • the reaction is carried out in an aprotic solvent mixture of ethylene carbonate (EC) with another aprotic solvent selected from the group comprising cyclic carbonates, preferably propylene carbonate (PC), linear carbonates, preferably diethyl carbonate
  • Solvent selected from the group comprising cyclic carbonates, preferably propylene carbonate (PC), linear carbonates, preferably diethyl carbonate (DEC),
  • PC propylene carbonate
  • DEC diethyl carbonate
  • DMC Dimethyl carbonate
  • EMC ethyl methyl carbonate
  • nitriles preferably acetonitrile (AN), dinitriles preferably glutaronitrile (GLN), adiponitrile (ADN) and / or pimelonitrile (PIN)
  • / or lactones preferably gamma-butyrolactone (GBL) and or gamma-valerolactone (GVL) having a molar ratio of ethylene carbonate to the at least one further aprotic solvent in the range of> 1: 9 to ⁇ 9: 1, preferably in the range of> 3: 7 to ⁇ 7: 3, preferably Range from> 3: 7 to ⁇ 1: 1, by.
  • a molar ratio of ethylene carbonate to the at least one further aprotic solvent in the range of> 1: 9 to ⁇ 9: 1 is preferably suitable.
  • a molar ratio of ethylene carbonate to the at least one further aprotic solvent in the range of> 1: 9 to ⁇ 9: 1 is preferably suitable.
  • At least one further aprotic solvent in the range of> 3: 7 to ⁇ 7: 3, preferably in the range of> 3: 7 to ⁇ 1: 1, the reaction to a good yield
  • Good yields result in an advantageous manner in a range of> 45 ° C to ⁇ 120 ° C.
  • Particularly good yields result in a range of> 60 ° C to ⁇ 100 ° C, especially at temperatures in the range of> 65 ° C to ⁇ 95 ° C.
  • the reaction is carried out in a period in the range of> 48 h to ⁇ 180 h, preferably in the range of> 65 h to ⁇ 170 h, preferably in the range of> 110 h to ⁇ 165 h, by.
  • particularly good yields were obtained over a period in the range from> 65 h to ⁇ 170 h, preferably in the range from> 110 h to ⁇ 165 h.
  • the lithium salt with organic borate and / or phosphate anion is preferably selected from the group consisting of lithium difluorooxalatoborate (LiDFOB), lithium difluoromalonato borate, lithium difluoroglycolate borate, lithium difluorosalicylatoborate, lithium difluorolactatoborate, lithium difluoro-catechinatoborate and / or lithium tetrafluoro (oxalato) phosphate (LTFOP).
  • LiDFOB lithium difluorooxalatoborate
  • LiDFOB lithium difluoromalonato borate
  • lithium difluoroglycolate borate lithium difluorosalicylatoborate
  • lithium difluorolactatoborate lithium difluoro-catechinatoborate
  • LTFOP lithium tetrafluoro (oxalato) phosphate
  • lithium difluorooxalatoborate (LiDFOB) is useful in lithium-ion batteries.
  • the process of the invention comprises reacting a fluorinated lithium salt with an organic lithium borate or lithium phosphate salt.
  • the fluorinated lithium salt for example, lithium tetrafluoroborate, may be the organic lithium borate or
  • Fluoride lithium phosphate salt is therefore in particular a process for the preparation of a lithium salt with fluorinated organic borate and / or phosphate anion.
  • Phosphate anion selected from the group comprising lithium difluorooxalatoborat, lithium difluoromalonatoborat, lithium difluoroglycolatoborat, lithium difluorosalicylatoborat, lithium difluorolactatoborat, lithium difluoro-catecholate and / or lithium tetrafluoro (oxalato) phosphate is lithium difluorooxalatoborat particularly preferred.
  • the process for the preparation of lithium difluorooxalatoborat by reacting lithium tetrafluoroborate (L1BF 4 ) with lithium bis (oxalato) borate (LiBOB).
  • the reaction mixture can be separated by chromatography or by fractional crystallization.
  • the organic lithium fluoro salt is purified
  • Another object of the invention relates to lithium salts with organic borate and / or phosphate anion produced by the novel process.
  • the invention relates to lithium salts with fluorinated organic borate and / or phosphate anion prepared by the process according to the invention.
  • Another object of the invention relates to the use of a lithium salt with organic borate and / or phosphate anion produced by the novel process as a lithium-ion electrolyte in primary and secondary electrochemical energy storage, in particular in lithium-ion batteries.
  • a lithium salt with organic borate and / or phosphate anion produced by the novel process as a lithium-ion electrolyte in primary and secondary electrochemical energy storage, in particular in lithium-ion batteries.
  • the invention relates to the use of a lithium salts with fluorinated organic borate and / or phosphate anion produced by the novel process in primary and secondary electrochemical energy storage, in particular in lithium-ion batteries. Examples which serve to illustrate the present invention are given below.
  • LiBOB Lithium bisoxalatoborate
  • reaction solution was kept for 162 h in an oven (ED 53, BINDER GmbH) at a temperature of 95 ° C.
  • the NMR tube was cooled and the reaction yield determined by U B NMR (Bruker Avance 3, 400 MHz, liquid broadband probe, at 22 ° C-23 ° C). In the U B spectrum only LiDFOB (8.6%), LiBOB (40.7%) and LiBF 4 (50.7%) were found.
  • reaction solution was kept for 162 h in an oven (ED 53, BINDER GmbH) at a temperature of 95 ° C.
  • the NMR tube was cooled and the reaction yield determined by U B NMR (Bruker Avance 3, 400 MHz, liquid broadband probe, at 22 ° C-23 ° C). In the U B spectrum only LiDFOB (7.5%), LiBOB (40.6%) and LiBF 4 (51.9%) were found.
  • LiBOB Lithium bisoxalatoborate
  • LiBF LiBF
  • LiBOB LiBOB
  • EC ethylene carbonate
  • DEC Diethyl carbonate
  • Lithium bisoxalatoborate With 0.94 g (0.01 mol) LiBF 4 (Sigma Aldrich) and 1.93 g (0.01 mol) LiBOB (Chemetal), 10 mL of a 1 M standard solution with an ethylene carbonate (EC, Ferro, 50 wt. %) / Adiponitrile (ADN, Sigma Aldrich, 50% by weight) mixture. 200 ⁇ L of the 1 M LiBF 4 solution and the 1 M LiBOB solution were added to an NMR tube in a glove box (MBraun) with a water and oxygen content of ⁇ lppm. The NMR tube was then evacuated, cooled with liquid nitrogen and sealed with a propane gas burner.
  • EC ethylene carbonate
  • ADN Adiponitrile
  • reaction solution was kept for 162 h in an oven (ED 53, BINDER GmbH) at a temperature of 95 ° C.
  • the NMR tube was cooled and the reaction yield determined by U B NMR (Bruker Avance 3, 400 MHz, liquid broadband probe, at 22 ° C-23 ° C). In the U B spectrum only LiDFOB (2.8%), LiBOB (44.9%) and LiBF (52.3%) were found.

Landscapes

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

Abstract

L'invention concerne un procédé de fabrication d'un sel de lithium comportant un anion borate et/ou phosphate organique par réaction d'un sel fluoré de lithium avec un sel organique de borate de lithium ou de phosphate de lithium choisi dans le groupe comprenant l'oxalate, le malonate, le glycolate, le salicylate, le lactate, le pyrocatéchinate, le succinate et/ou leurs mélanges dans un solvant ou mélange de solvants aprotique.
PCT/EP2011/070859 2010-11-24 2011-11-23 Procédé de fabrication de sels organiques de lithium WO2012069554A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010060770.3 2010-11-24
DE102010060770A DE102010060770A1 (de) 2010-11-24 2010-11-24 Verfahren zur Herstellung organischer Lithiumsalze

Publications (1)

Publication Number Publication Date
WO2012069554A1 true WO2012069554A1 (fr) 2012-05-31

Family

ID=45218680

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/070859 WO2012069554A1 (fr) 2010-11-24 2011-11-23 Procédé de fabrication de sels organiques de lithium

Country Status (2)

Country Link
DE (1) DE102010060770A1 (fr)
WO (1) WO2012069554A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557995A (zh) * 2013-10-12 2015-04-29 陈琛 一种二氟草酸硼酸锂的制备方法
CN107226821A (zh) * 2017-06-12 2017-10-03 上海如鲲新材料有限公司 一种用双草酸硼酸锂制备二氟草酸硼酸锂的合成工艺
CN109678694A (zh) * 2018-12-21 2019-04-26 东莞东阳光科研发有限公司 一种四氟草酸磷酸锂的制备方法
CN110003277A (zh) * 2019-05-05 2019-07-12 上海如鲲新材料有限公司 一种四氟草酸磷酸锂及其制备方法
CN114349775A (zh) * 2022-01-12 2022-04-15 王怀英 一种双草酸硼酸锂和二氟草酸硼酸锂的联合生产的方法
KR20230127777A (ko) 2022-02-25 2023-09-01 명지대학교 산학협력단 리튬 디플루오로(옥살라토)보레이트의 제조방법, 이로부터 제조된 리튬 디플루오로(옥살라토)보레이트, 리튬이온전지용 전해액 및 이를 포함하는 리튬이온전지

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE102018201548A1 (de) * 2018-02-01 2019-08-01 Robert Bosch Gmbh Elektrolytzusammensetzung für elektrochemische Zelle für Hochtemperaturanwendungen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004059A1 (fr) 2007-07-04 2009-01-08 Chemetall Gmbh Procédé pour produire des borates de lithium, à faible teneur en acide, et mélanges de borates de lithium à faible teneur en acide et d'hydrures de lithium

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10111410C1 (de) * 2001-03-08 2002-07-25 Chemetall Gmbh Elektrolyt, enthaltend Lithium-bis(oxalato)borat und dessen Verwendung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004059A1 (fr) 2007-07-04 2009-01-08 Chemetall Gmbh Procédé pour produire des borates de lithium, à faible teneur en acide, et mélanges de borates de lithium à faible teneur en acide et d'hydrures de lithium

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHRISTIAN SCHREINER ET AL: "Chloride-Free Method to Synthesise New Ionic Liquids with Mixed Borate Anions", CHEMISTRY - A EUROPEAN JOURNAL, vol. 15, no. 10, 23 February 2009 (2009-02-23), pages 2270 - 2272, XP055017100, ISSN: 0947-6539, DOI: 10.1002/chem.200802243 *
LEX-BALDUCCI, A. ET AL.: "Lithium borates for lithium-ion battery electrolytes", ECS TRANSACTIONS, vol. 25, no. 36, 9 October 2009 (2009-10-09), XP009155699 *
ZUGMANN S ET AL: "Electrochemical characterization of electrolytes for lithium-ion batteries based on lithium difluoromono(oxalato)borate", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 196, no. 3, 17 August 2010 (2010-08-17), pages 1417 - 1424, XP027450469, ISSN: 0378-7753, [retrieved on 20100817], DOI: 10.1016/J.JPOWSOUR.2010.08.023 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557995A (zh) * 2013-10-12 2015-04-29 陈琛 一种二氟草酸硼酸锂的制备方法
CN104557995B (zh) * 2013-10-12 2017-02-15 陈琛 一种二氟草酸硼酸锂的制备方法
CN107226821A (zh) * 2017-06-12 2017-10-03 上海如鲲新材料有限公司 一种用双草酸硼酸锂制备二氟草酸硼酸锂的合成工艺
CN109678694A (zh) * 2018-12-21 2019-04-26 东莞东阳光科研发有限公司 一种四氟草酸磷酸锂的制备方法
CN110003277A (zh) * 2019-05-05 2019-07-12 上海如鲲新材料有限公司 一种四氟草酸磷酸锂及其制备方法
CN114349775A (zh) * 2022-01-12 2022-04-15 王怀英 一种双草酸硼酸锂和二氟草酸硼酸锂的联合生产的方法
KR20230127777A (ko) 2022-02-25 2023-09-01 명지대학교 산학협력단 리튬 디플루오로(옥살라토)보레이트의 제조방법, 이로부터 제조된 리튬 디플루오로(옥살라토)보레이트, 리튬이온전지용 전해액 및 이를 포함하는 리튬이온전지

Also Published As

Publication number Publication date
DE102010060770A1 (de) 2012-05-24

Similar Documents

Publication Publication Date Title
WO2012069554A1 (fr) Procédé de fabrication de sels organiques de lithium
DE19829030C1 (de) Lithium-bisoxalatoborat, Verfahren zu dessen Herstellung und dessen Verwendung
JP5974181B2 (ja) リチウムビス（フルオロスルホニル）イミドの製造方法
EP2780346B1 (fr) Procédé pour la production de difluoro-chélatoborates de métal et leur utilisation comme électrolytes de batterie ou additifs dans des cellules galvaniques
WO1998007729A1 (fr) Procede de preparation de complexes lithium-borate
EP0698301B1 (fr) Electrolyte pour pile galvanique
EP1205480B1 (fr) Sels de tétrakisfluoroalkylborate et leur utilisation comme sels électrolytes
WO2013014180A1 (fr) Lithium-2-méthoxy-1,1,2,2-tétrafluoro-éthanesulfonate et son utilisation comme sel conducteur dans des accumulateurs d'énergie à base de lithium
EP1178050A2 (fr) Phosphates de fluoroalkyl pour cellules électrochimiques
EP1726061B1 (fr) Sels conducteurs pour cellules galvaniques, leur production et leur utilisation
WO2002068432A1 (fr) Complexes de chelate de bore
DE10228201A1 (de) Verfahren zur Herstellung von Lithiumiodidlösungen
EP1027744B1 (fr) Ester s'utilisant comme solvant dans des systemes d'electrolyte pour accumulateurs aux ions de lithium
DE10119278C1 (de) Verfahren zur Herstellung von Fluoralkylphosphaten
WO2010094467A1 (fr) Cellule galvanique comprenant du lithium métal ou un alliage contenant du lithium métal comme matériau d'anode et un électrolyte contenant du lithium-bis(oxalato)borate ainsi qu'au moins un autre sel complexe de lithium
EP1048648A1 (fr) Méthode pour la purification de méthanide-électrolytes
DE102012006897A1 (de) Lithiumsilikate
JP5029353B2 (ja) 四フッ化ホウ素塩の製造方法、該方法により得られる四フッ化ホウ素塩、これを用いる電気二重層キャパシタ用電解液およびその製造方法
WO2002011229A1 (fr) Nouvelle utilisation d'esters d'acide difluoromalonique
WO2014079887A1 (fr) Solution d'électrolyte à faible teneur en acide
EP1173416A1 (fr) Procede de purification d'electrolytes (ii) de methanide
WO2001039313A1 (fr) Utilisation nouvelle de diesters a ponts methylene
WO2001038319A1 (fr) Nouvelle utilisation de dioxolones

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11793709

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11793709

Country of ref document: EP

Kind code of ref document: A1