EP2877450A1 - Als elektrolytlösungsmittel für lithiumbatterien verwendbare spezifische sulfonatverbindungen - Google Patents

Als elektrolytlösungsmittel für lithiumbatterien verwendbare spezifische sulfonatverbindungen

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Publication number
EP2877450A1
EP2877450A1 EP13756603.0A EP13756603A EP2877450A1 EP 2877450 A1 EP2877450 A1 EP 2877450A1 EP 13756603 A EP13756603 A EP 13756603A EP 2877450 A1 EP2877450 A1 EP 2877450A1
Authority
EP
European Patent Office
Prior art keywords
group
compound
formula
butyl
tert
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13756603.0A
Other languages
English (en)
French (fr)
Inventor
Hervé GALIANO
Stéphane CADRA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Renault SAS
Original Assignee
Renault SAS
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 Renault SAS filed Critical Renault SAS
Publication of EP2877450A1 publication Critical patent/EP2877450A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 fluorinated compounds, to their process of preparation and to their use as solvents capable, in particular, to allow the dissolution of lithium salts.
  • Lithium batteries are particularly interesting for areas where autonomy is a key criterion, as is the case in the fields of computer science, video, mobile telephony, transport such as electric vehicles, cars and cars. hybrid vehicles, or medical, space, microelectronics.
  • the lithium batteries are based on the principle of intercalation-deintercalation of lithium within the constituent materials of the electrodes of the electrochemical cells of the battery.
  • the reaction at the origin of the current output involves the IEC 60050 - International Electrotechnical Vocabulary - Details for IEV number 845-02-23 Electron microscopy / Electrochemistry and electroweening / Electromagnetic transfer from a negative electrode into the acceptor network of the positive electrode negative electrode will feed the external circuit, to which are connected the positive and negative electrode.
  • These electrolytes may consist of a mixture comprising at least one organic solvent and at least one lithium salt for conduction of said lithium ions, which requires that the lithium salt be dissolved in said organic solvent.
  • This organic solvent may be a solvent belonging to the family of carbonates, carboxylates, linear or cyclic ethers, to which it is added additives:
  • siloxane compounds in combination with sulphonate compounds comprising a 1,3-dioxane group as described in US 2012/0034532, intended to limit the degradation phenomena of the capacity of batteries used in the long term.
  • the electrolytes may be relatively complex in nature, in that they involve, in addition to the presence of one or more organic solvents and one or more lithium salts, the presence of one or more several additives.
  • viscosity for example, a viscosity of less than 0 mPa ⁇ s
  • conductivity for example, conductivity greater than 1 mS / cm
  • temperature of melting for example, melting temperature below -20 ° C
  • R 1 is a branched acyclic hydrocarbon group comprising at least 4 carbon atoms.
  • branched acyclic hydrocarbon group is meant a non-cyclic hydrocarbon group whose chain comprises one or more branching points. It may be, in particular, a branched alkyl group comprising at least 4 carbon atoms.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group
  • R 3 is an isopropyl group, an isobutyl group, a tert-butyl group, a 2-butyl group, an isopentyl group or a 3-pentyl group;
  • R 3 is n-propyl, isopropyl, tert-butyl, 2-butyl, isopentyl or 3-pentyl;
  • R when R is an ethyl group, R is an ethyl group, R is an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a 2-butyl group, an isopentyl group or a 3-pentyl group.
  • a family of compounds within the definition of the invention is that, wherein R 2 is H or CH 3 and R 3 is a group selected from tert-butyl or 3-pentyl.
  • the sulfonate compounds of the invention may be prepared by carrying out a process comprising a reaction step between an alcoholic compound of the formula R 1 -OH, wherein R 1 is as defined above with a propane sulfonyl halide compound. , more specifically a propanesulfonyl chloride compound, in a medium comprising at least one base and an organic solvent, more specifically an aprotic organic solvent.
  • Said base can be:
  • an amine compound trimethylamine, triethylamine, tri (n-butyl) amine
  • a pyridine compound such as pyridine
  • imidazole compound such as imidazole.
  • the organic solvent may be an aliphatic hydrocarbon solvent, an aromatic solvent, or a cyclic or acyclic ether solvent.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group
  • R 3 is an isopropyl group, an isobutyl group, a group tert-butyl, 2-butyl, isopentyl or 3-pentyl;
  • R 2 when R 2 is methyl, R 3 is n-propyl, isopropyl, tert-butyl, 2-butyl, isopentyl or 3-pentyl; or
  • R when R is an ethyl group, R is an ethyl group, R is an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a 2-butyl group, an isopentyl group or a 3-pentyl group.
  • the reaction between the alcoholic compound and the propanesulfonyl halide compound is conventionally carried out at room temperature, after bringing these compounds into contact at a subambient temperature.
  • the process for preparing the compounds in accordance with the invention may comprise a step of purifying the compound obtained, this purification step possibly consisting of:
  • the compounds of the invention have, among other properties, an oxidation potential greater than 5 V relative to the Li + / Li pair, a low viscosity (less than 10 mPa.s), a high dielectric constant (greater than 20 ) and a sub-ambient melting temperature. What is more, the compounds of the invention have a good ability to solubilize lithium salts.
  • the invention also relates to:
  • composition more specifically a liquid composition, which may be a conductive electrolyte of lithium ions, comprising at least one fluorinated compound as defined above and at least one lithium salt; and
  • a lithium battery comprising at least one electrochemical cell comprising an electrolyte as defined above disposed between a positive electrode and a negative electrode.
  • the lithium salt may be chosen from the group consisting of LiPF 6, LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 3, LiN (C 2 F 5 SO 2 ), lithium bistrifluoromethylsulfonylimide (known by the abbreviation LiTFSI) LiN [S0 2 CF 3 ] 2 and mixtures thereof.
  • LiPF 6 LiClO 4
  • LiBF 4 LiAsF 6
  • LiCF 3 SO 3 LiN (CF 3 SO 2 ) 3
  • LiN (C 2 F 5 SO 2 ) LiN (C 2 F 5 SO 2 )
  • LiTFSI lithium bistrifluoromethylsulfonylimide
  • compositions may further comprise an aprotic cosolvent, such as a carbonate solvent, a nitrile solvent or a sulfone solvent.
  • an aprotic cosolvent such as a carbonate solvent, a nitrile solvent or a sulfone solvent.
  • the aforementioned liquid electrolyte can be led into the electrochemical cells of the lithium batteries to impregnate a separator, which is disposed between the positive electrode and the negative electrode of the electrochemical cell.
  • This separator may be of a porous material, such as a polymeric material, capable of accommodating in its porosity the liquid electrolyte. More specifically, it may be a Celguard 2400 type membrane.
  • positive electrode is meant conventionally, in what precedes and what follows, the electrode which acts as a cathode, when the generator delivers current (that is to say when it is in the process of discharge) and which acts as anode when the generator is in charging process.
  • negative electrode is meant conventionally, in what precedes and what follows, the electrode which acts as anode, when the generator delivers current (that is to say when it is in the process of discharge ) and which acts cathode, when the generator is in process of charge.
  • the negative electrode may be based on a lithiated oxide of titanium, such as Li 4 Ti 5 O 12 , which constitutes the lithium insertion material, which oxide may be dispersed in a binder.
  • a lithiated oxide of titanium such as Li 4 Ti 5 O 12
  • polymeric for example, a polyvinylidene fluoride binder.
  • 1 / positive electrode for its part, may be based on a lithiated transition metal oxide (the metal may be, for example, nickel, manganese), more specifically LiMn2- z Ni z 04 (with 0 ⁇ z ⁇ 2), which oxide may be dispersed in a polymeric binder, for example a polyvinylidene fluoride binder.
  • a lithiated transition metal oxide the metal may be, for example, nickel, manganese
  • LiMn2- z Ni z 04 with 0 ⁇ z ⁇ 2
  • a polymeric binder for example a polyvinylidene fluoride binder.
  • each of them is advantageously associated with a metal current collector, for example, an aluminum current collector.
  • the mixture is filtered and the filtrate is extracted with a 1M hydrochloric acid solution.
  • the organic phase is recovered, dried and evaporated (under 400 mbar). The residue is distilled under reduced pressure.
  • the resulting product is a colorless liquid.
  • This compound has the following properties:
  • Viscosity (mPa.s): 7.8; -Dielectric constant: 28.7.
  • the mixture is filtered and the filtrate is extracted with a 1M hydrochloric acid solution.
  • the organic phase is recovered, dried and evaporated (under 400 mbar).
  • the residue is purified on a chromatographic column (silica gel, eluent heptane / ether 60:40). The resulting product is a translucent liquid.
  • This compound has the following properties:
  • the mixture is filtered and the filtrate is extracted with a 1M hydrochloric acid solution.
  • the organic phase is recovered, dried and evaporated (under 400 mbar).
  • the residue is purified on a chromatographic column (silica gel, eluent heptane / ether 60:40). The resulting product is a translucent liquid.
  • This compound has the following properties:
  • Viscosity (mPa.s): 4.4;
  • the mixture is filtered and the filtrate is extracted with a solution of hydrochloric acid 1.
  • the organic phase is recovered, dried and evaporated (under 400 mbar).
  • the residue is purified on a chromatographic column (silica gel, eluent heptane / ether 60:40). The resulting product is a translucent liquid.
  • This compound has the following properties:
  • Viscosity (mPa.s): 5.7;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP13756603.0A 2012-07-26 2013-07-26 Als elektrolytlösungsmittel für lithiumbatterien verwendbare spezifische sulfonatverbindungen Withdrawn EP2877450A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1257248A FR2993886B1 (fr) 2012-07-26 2012-07-26 Composes sulfonates specifiques utilisables comme solvant d'electrolyte pour batteries au lithium
PCT/FR2013/051806 WO2014016530A1 (fr) 2012-07-26 2013-07-26 Composes sulfonates specifiques utilisables comme solvant d'electrolyte pour batteries au lithium

Publications (1)

Publication Number Publication Date
EP2877450A1 true EP2877450A1 (de) 2015-06-03

Family

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EP13756603.0A Withdrawn EP2877450A1 (de) 2012-07-26 2013-07-26 Als elektrolytlösungsmittel für lithiumbatterien verwendbare spezifische sulfonatverbindungen

Country Status (5)

Country Link
EP (1) EP2877450A1 (de)
JP (1) JP2015528807A (de)
CN (1) CN104684890A (de)
FR (1) FR2993886B1 (de)
WO (1) WO2014016530A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6570858B2 (ja) * 2015-03-25 2019-09-04 住友化学株式会社 ナトリウム二次電池用非水電解液およびナトリウム二次電池
CN108075187B (zh) * 2016-11-10 2020-09-11 宁德时代新能源科技股份有限公司 电解液及二次电池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4876495B2 (ja) * 2005-09-13 2012-02-15 ソニー株式会社 リチウムイオン二次電池用電解液およびリチウムイオン二次電池
JP4951913B2 (ja) * 2005-09-27 2012-06-13 ソニー株式会社 リチウムイオン二次電池
CN102197024A (zh) * 2008-10-24 2011-09-21 住友精化株式会社 砜化合物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO2014016530A1 *
YOFFI SEGALL ET AL: "Oxide Intermediates with Alcohols", PHOSPHORUS AND SULFUR AND THE RELATED ELEMENTS., vol. 18, no. 1-3, 1 January 1983 (1983-01-01), CH, pages 209 - 212, XP055403892, ISSN: 0308-664X, DOI: 10.1080/03086648308076003 *

Also Published As

Publication number Publication date
JP2015528807A (ja) 2015-10-01
FR2993886B1 (fr) 2014-08-01
FR2993886A1 (fr) 2014-01-31
WO2014016530A1 (fr) 2014-01-30
CN104684890A (zh) 2015-06-03

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