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WO2021128205A1 - 一种电解液及电化学装置 - Google Patents

一种电解液及电化学装置 Download PDF

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Publication number
WO2021128205A1
WO2021128205A1 PCT/CN2019/128851 CN2019128851W WO2021128205A1 WO 2021128205 A1 WO2021128205 A1 WO 2021128205A1 CN 2019128851 W CN2019128851 W CN 2019128851W WO 2021128205 A1 WO2021128205 A1 WO 2021128205A1
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Prior art keywords
electrolyte
compound
carbon
formula
substituted
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PCT/CN2019/128851
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English (en)
French (fr)
Inventor
唐超
张丽兰
刘俊飞
郑建明
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to CN201980029147.4A priority Critical patent/CN112055910B/zh
Priority to EP19908073.0A priority patent/EP4084182A4/en
Priority to PCT/CN2019/128851 priority patent/WO2021128205A1/zh
Priority to US16/961,495 priority patent/US12412930B2/en
Publication of WO2021128205A1 publication Critical patent/WO2021128205A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/0568—Liquid materials characterised by the solutes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/05—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing at least three cyano groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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

  • This application relates to the field of energy storage technology, and in particular to an electrolyte and an electrochemical device containing the electrolyte.
  • Lithium-ion batteries have the advantages of high energy density, high working voltage, low self-discharge rate, long cycle life, and no pollution. They have been widely used in computers, smart wearable devices, smart phones, drones, and electric vehicles. With the development of modern information technology and the expansion of the application range of lithium-ion batteries, this field has put forward more performance requirements for lithium-ion batteries. For example, improving the endurance of lithium-ion batteries, avoiding swelling of the battery during continuous charging, improving the high temperature resistance of the battery after cycling, and avoiding thermal runaway of the battery.
  • the present invention provides an electrolyte and an electrochemical device including the electrolyte.
  • the electrolyte of the present invention can significantly improve the cycle capacity retention rate of a lithium ion battery, alleviate battery expansion during the cycle, and improve the high temperature resistance of the battery after the cycle.
  • An aspect of the present invention provides an electrolyte, the electrolyte comprising:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 2 -C 10 alkenyl, substituted or unsubstituted Substituted C 2 -C 10 alkynyl, substituted or unsubstituted C 6 -C 12 aryl, substituted or unsubstituted C 1 -C 10 alkoxy, or substituted or unsubstituted C 6 -C 12 aryloxy When substituted, the substituent is halogen, cyano or C 1 -C 10 alkyl; wherein a, d and f are each independently selected from an integer of 1 to 5, and b, c, e, g, h and i are each Independently selected from an integer from 0 to 5.
  • the compound of formula I comprises: At least one of
  • the compound of formula II comprises: At least one of
  • the compound of formula III includes: At least one of them. In some embodiments, the amount of the compound of formula I accounts for about 0.01% to about 3% by weight of the electrolyte solution.
  • the amount of the compound of formula II, compound of formula III, or a combination thereof accounts for about 0.1% to about 5% by weight of the electrolyte solution.
  • the electrolyte further includes a fluorinated additive including fluoroethylene carbonate, a fluorocarbonate having 2 to 7 carbon atoms, and a fluorine having 2 to 7 carbon atoms. At least one of a substituted carboxylic acid ester or a fluoroether having 2 to 7 carbon atoms.
  • the fluorinated additive accounts for about 1% to about 20% by weight of the electrolyte solution.
  • the fluorinated additive includes at least one of the following: fluoromethyl ethyl carbonate, fluorodimethyl carbonate, fluorodiethyl carbonate, fluoropropionate, fluoro Propyl propionate, methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate, propyl fluoroacetate,
  • the ratio of the mass fraction C of the fluorinated additive in the electrolyte to the mass fraction A of the compound of formula I in the electrolyte is: about 1 ⁇ C/A ⁇ about 50.
  • Another aspect of the present invention provides an electrochemical device, which includes a positive electrode, a negative electrode, and any of the foregoing electrolytes.
  • the negative electrode of the electrochemical device includes a silicon-containing material
  • the silicon-containing material includes a silicon compound SiO x , silicon simple substance, or a mixture of the two, where 0.5 ⁇ x ⁇ 1.5.
  • the negative electrode of the electrochemical device contains carbon nanotubes, and the carbon nanotubes have a tube diameter of about 1 nanometer to about 10 nanometers and a tube length of about 1 micrometer to about 50 micrometers.
  • the silicon-containing material has a carbon layer on the surface, the carbon layer has a thickness of about 1 nanometer to about 500 nanometers, and the carbon layer includes amorphous carbon, graphite, hard carbon, soft carbon, carbon black, Acetylene black, carbon nanotubes or a combination thereof.
  • the negative electrode of the electrochemical device includes graphite, and the mass ratio of the graphite to the silicon-containing material is about 95:5 to about 60:40.
  • Another aspect of the present invention provides an electronic device, which includes the electrochemical device described above.
  • the term "about” is used to describe and illustrate small variations.
  • the term can refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very closely.
  • the term can refer to a range of variation less than or equal to ⁇ 10% of the stated value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, Less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • a list of items connected by the term "one of” may mean any one of the listed items. For example, if items A and B are listed, then the phrase “one of A and B” means only A or only B. In another example, if items A, B, and C are listed, then the phrase "one of A, B, and C" means only A; only B; or only C.
  • Project A can contain a single element or multiple elements.
  • Project B can contain a single element or multiple elements.
  • Project C can contain a single element or multiple elements.
  • a list of items connected by the term "at least one of” can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" or “at least one of A or B” means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" "at least one of A, B, or C” means only A; or only B ; C only; A and B (exclude C); A and C (exclude B); B and C (exclude A); or all of A, B and C.
  • Project A can contain a single element or multiple elements.
  • Project B can contain a single element or multiple elements.
  • Project C can contain a single element or multiple elements.
  • the number after the capital letter “C”, such as “C 1 -C 10 ", “C 3 -C 10 “, etc., after the "C” indicates the number of carbons in a specific functional group. That is, the functional groups may include 1-10 carbon atoms and 3-10 carbon atoms, respectively.
  • C 1 -C 4 alkyl refers to an alkyl group having 1 to 4 carbon atoms, such as CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH- , CH 3 CH 2 CH 2 CH 2 -, CH 3 CH 2 CH(CH 3 )- or (CH 3 ) 3 C-.
  • alkyl is expected to be a linear saturated hydrocarbon structure having 1 to 10 carbon atoms. "Alkyl” is also expected to be a branched or cyclic hydrocarbon structure having 3 to 10 carbon atoms.
  • the alkyl group may be an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 7 carbon atoms, or an alkyl group of 1 to 4 carbon atoms.
  • butyl means to include n-butyl, sec-butyl, isobutyl, tert-butyl And cyclobutyl;
  • propyl includes n-propyl, isopropyl and cyclopropyl.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, Isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl Base and so on.
  • the alkyl group may be optionally substituted.
  • alkenyl refers to a monovalent unsaturated hydrocarbon group that may be straight or branched and has at least one and usually 1, 2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group usually contains 2 to 10 carbon atoms, for example, it may be an alkenyl group of 2 to 7 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms.
  • Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. In addition, alkenyl groups may be optionally substituted.
  • alkynyl refers to a monovalent unsaturated hydrocarbon group that can be straight or branched and has at least one and usually 1, 2, or 3 carbon-carbon triple bonds. Unless otherwise defined, the alkynyl group usually contains an alkynyl group of 2 to 10, 2 to 7, or 2 to 4 carbon atoms. Representative alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like. In addition, alkynyl groups may be optionally substituted.
  • aryl encompasses both monocyclic and polycyclic ring systems.
  • a polycyclic ring may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic, such as others
  • the ring can be a cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl group.
  • the aryl group may contain 6 to 12 or 6 to 10 carbon atoms.
  • Representative aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl and naphth-1-yl, naphth-2-yl, and the like.
  • aryl groups may be optionally substituted.
  • aryloxy means an aryl group having the stated number of carbon atoms connected by an oxygen bridge. Where the aryl group has the meaning as described in the present invention, such examples include but are not limited to phenoxy, p-tolyloxy, p-ethylphenoxy and the like.
  • alkoxy refers to a group formed by connecting an alkyl group to an oxygen atom. Wherein the alkyl group has the meaning as described in the present invention. Representative alkoxy examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, iso Pentyloxy or tert-pentyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, etc.
  • halogen encompasses F, Cl, Br, I.
  • the substituents can be selected from the group consisting of halogen and alkyl.
  • the content of each component in the electrolyte is based on the total weight of the electrolyte.
  • the embodiment of the present application provides an electrolyte, which includes diglycolic anhydride and trinitrile or ether trinitrile compound.
  • the electrolyte can form a stable protective layer on the surface of the positive and negative electrodes, and significantly improve the cycle performance of the battery.
  • the electrolyte of the present application can ensure that the negative electrode protective layer of the battery still has good stability after the battery is cyclically charged and discharged, so as to prevent the battery from being heated and causing safety accidents caused by thermal runaway.
  • the electrolyte includes:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 10 alkyl, substituted
  • a, d, and f are each independently selected from 0, 1, 2, 3, 4, or 5 and b, c, e, g, h, and i are each independently selected from 0, 1, 2, 3, 4, or 5.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 7 alkyl, substituted or unsubstituted C 1 -C 4 alkyl , Substituted or unsubstituted C 2 -C 7 alkenyl, substituted or unsubstituted C 2 -C 4 alkenyl, substituted or unsubstituted C 2 -C 7 alkynyl, substituted or unsubstituted C 2 -C 4 Alkynyl, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted C 1 -C 7 alkoxy, substituted or unsubstituted C 1 -C 4 alkoxy or substituted or unsubstituted C 6 -C 10 aryloxy; when substituted, the substituent is halogen, cyano or C 1 -C 3 alkyl
  • R 1 , R 2 , R 3 and R 4 are each independently selected from H, F, methyl, ethyl, propyl, vinyl, 1-propenyl, 2-propenyl, 1-propenyl Alkynyl, 2-propynyl, methoxy, ethoxy, or phenoxy.
  • the compound of formula I comprises:
  • the compound of formula II comprises:
  • the compound of formula III includes:
  • the amount of the compound of formula I in the electrolyte accounts for about 0.01% to about 3% by weight, about 0.05% to about 2% by weight, or about 0.2% by weight of the electrolyte. % To about 1% by weight. In some embodiments, the amount of the compound of formula I accounts for about 0.08% by weight, about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, about 0.6% by weight of the electrolyte. % By weight, about 0.7% by weight, about 0.8% by weight, about 0.9% by weight, about 1% by weight, about 1.2% by weight, or about 1.5% by weight.
  • the amount of the compound of formula II, the compound of formula III, or a combination thereof in the electrolyte accounts for about 0.1% to about 5% by weight, about 0.25% to about 4% by weight of the electrolyte. % By weight, about 0.5% by weight to about 3% by weight, about 1% by weight to about 2% by weight. In some embodiments, the amount of the compound of formula II, compound of formula III, or a combination thereof in the electrolyte solution accounts for about 1.5% by weight, about 2% by weight, or about 2.5% by weight of the electrolyte solution.
  • the electrolyte further includes a fluorinated additive
  • the fluorinated additive includes fluoroethylene carbonate (FEC), At least one of a fluorocarbonate having 2 to 7 carbon atoms, a fluorocarboxylic acid ester having 2 to 7 carbon atoms, or a fluoroether having 2 to 7 carbon atoms.
  • FEC fluoroethylene carbonate
  • This type of fluoride can be quickly repaired when the protective layer of the silicon negative electrode is damaged, thereby reducing the side reaction between the electrolyte and the silicon negative electrode.
  • the fluorinated additive accounts for about 1% to about 20% by weight of the electrolyte solution. In some embodiments, the fluorinated additive accounts for about 2% to about 18% by weight of the electrolyte solution. In some embodiments, the fluorinated additive accounts for about 3% to about 15% by weight of the electrolyte solution. . In some embodiments, the fluorinated additive accounts for about 5% to about 18% by weight of the electrolyte solution.
  • the fluorinated additive comprises at least one of the following: fluoromethyl ethyl carbonate, fluorodimethyl carbonate, fluorodiethyl carbonate, fluoropropionate, fluoro Propyl propionate, methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate or propyl fluoroacetate.
  • the fluorinated additive includes at least one of the following:
  • the fluorinated additive accounts for the mass fraction C of the electrolyte and the compound of formula I accounts for the mass fraction A of the electrolyte.
  • the ratio is: about 1 ⁇ C/A ⁇ about 50.
  • the electrolyte may further contain selected from vinylene carbonate (VC), 1,3-propane sultone (PS), vinyl sulfate ( At least one additive of DTD), succinonitrile (SN) or adiponitrile (ADN).
  • VC vinylene carbonate
  • PS 1,3-propane sultone
  • PS vinyl sulfate
  • At least one additive of DTD succinonitrile
  • SN succinonitrile
  • ADN adiponitrile
  • the vinylene carbonate accounts for about 0.001% to about 2% by weight of the electrolyte solution.
  • the 1,3-propane sultone accounts for about 0.001% to about 2% by weight of the electrolyte solution. In some embodiments, the 1,3-propane sultone accounts for about 0.001% to about 1% by weight of the electrolyte solution.
  • the vinyl sulfate accounts for about 0.001% to about 3% by weight of the electrolyte solution.
  • the succinonitrile, adiponitrile, or a combination thereof accounts for about 0.1% to about 7% by weight of the electrolyte solution.
  • the succinonitrile, adiponitrile, or a combination thereof accounts for about 0.5% to about 6% by weight of the electrolyte solution.
  • the electrolyte further includes a lithium salt and an organic solvent.
  • the lithium salt is selected from one or more of inorganic lithium salt and organic lithium salt. In some embodiments, the lithium salt contains at least one of fluorine, boron, or phosphorus. In some embodiments, the lithium salt is selected from one or more of the following lithium salts: lithium hexafluorophosphate LiPF 6 , lithium bistrifluoromethanesulfonimide LiN (CF 3 SO 2 ) 2 (abbreviated as LiTFSI), Lithium bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 ) (abbreviated as LiFSI), bis(oxalic acid) borate LiB(C 2 O 4 ) 2 (abbreviated as LiBOB), difluorooxalic acid borate LiBF 2 (C 2 O 4 ) (abbreviated as LiDFOB), at least one of lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO), at least one
  • the concentration of the lithium salt is about 0.5 mol/L to about 1.8 mol/L. In some embodiments, the concentration of the lithium salt is about 0.8 mol/L to about 1.5 mol/L. In some embodiments, the concentration of the lithium salt is about 0.8 mol/L to about 1 mol/L.
  • the organic solvent includes a cyclic ester and a chain ester, and the cyclic ester is selected from at least one of ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone (BL) and butylene carbonate One; the chain ester is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propyl ethyl carbonate, methyl formate (MF), ethyl formate ( At least one of MA), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), methyl propionate, methyl butyrate, and ethyl butyrate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • MF methyl formate
  • MA ethyl formate
  • MA ethyl acetate
  • EP
  • the organic solvent accounts for about 70% to about 90% by weight of the electrolyte solution.
  • the electrochemical device of the present application includes any device that undergoes an electrochemical reaction, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the electrochemical device of the present application is an electrochemical device having a positive electrode having a positive electrode active material capable of occluding and releasing metal ions, and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions. Its characteristics are It consists of any of the above-mentioned electrolytes of the present application.
  • the material, composition, and manufacturing method of the negative electrode used in the electrochemical device of the present application may include any technology disclosed in the prior art.
  • the negative electrode is the negative electrode described in U.S. Patent Application US9812739B, which is incorporated in this application by reference in its entirety.
  • the negative electrode includes a current collector and a negative active material layer on the current collector.
  • the negative electrode active material includes a material that reversibly intercalates/deintercalates lithium ions.
  • the material that reversibly intercalates/deintercalates lithium ions includes a carbon material.
  • the carbon material may be any carbon-based negative active material commonly used in lithium ion rechargeable batteries.
  • the carbon material includes, but is not limited to: crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be amorphous, flake-shaped, flake-shaped, spherical or fibrous natural graphite or artificial graphite.
  • Amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • the negative active material layer includes a negative active material.
  • the negative active material includes at least one of a carbon-containing material, a silicon-containing material, an alloy material, or a tin-containing material.
  • the negative electrode active material includes, but is not limited to: lithium metal, structured lithium metal, natural graphite, artificial graphite, mesophase carbon microspheres (MCMB), hard carbon, soft carbon, silicon, silicon- Carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , spinel structure lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy, or any combination thereof.
  • the negative active material includes a silicon-containing material
  • the silicon-containing material includes a silicon compound SiO x (0.5 ⁇ x ⁇ 1.5), a simple substance of silicon, or a mixture of the two.
  • the mass fraction of the silicon-containing material is about 5 wt% to about 90 wt%, about 10 wt% to about 70 wt%, or about 10 wt% To about 50% by weight.
  • the silicon-containing material in order to further improve the conductivity of the silicon-containing material, has a carbon layer on the surface to promote the formation of a stable protective layer by the diglycolic anhydride additive on the surface of the negative electrode.
  • the carbon layer may be selected from at least one of amorphous carbon, graphite, hard carbon, soft carbon, carbon black, acetylene black or carbon nanotubes.
  • the thickness of the carbon layer is about 1 nanometer to about 500 nanometers, about 10 nanometers to about 300 nanometers, or about 20 nanometers to about 200 nanometers.
  • the negative electrode when the negative electrode includes a silicon-containing material, the negative electrode may further include a carbon nanotube conductive agent, so as to improve the electrical contact failure caused by the expansion and contraction of the silicon negative electrode during charge and discharge, and improve the performance of the silicon negative electrode secondary battery. Cycle capacity retention rate and thermal safety after cycling.
  • the tube diameter of the carbon nanotube is about 1 nanometer to about 10 nanometers; the tube length is about 1 micrometer to about 50 micrometers; the carbon nanotubes are in close contact with the silicon surface or the silicon surface coating layer.
  • the negative active material layer may include a binder, and optionally a conductive material.
  • the binder improves the bonding of the negative active material particles with each other and the bonding of the negative active material with the current collector.
  • the binder includes, but is not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyfluoro Ethylene, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylic (ester) styrene butadiene Rubber, epoxy resin, nylon, etc.
  • conductive materials include, but are not limited to: carbon-based materials, metal-based materials, conductive polymers, or mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, silver.
  • the conductive polymer is a polyphenylene derivative.
  • the negative electrode current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, foamed nickel, foamed copper, conductive metal-coated polymer substrate, and any combination thereof.
  • the negative electrode can be prepared by a preparation method known in the art.
  • the negative electrode can be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
  • the solvent may include water and the like, but is not limited thereto.
  • the material of the positive electrode used in the electrochemical device of the present application can be prepared using materials, structures, and manufacturing methods known in the art.
  • the technology described in US9812739B can be used to prepare the positive electrode of the present application, which is incorporated into the present application by reference in its entirety.
  • the positive electrode includes a current collector and a positive electrode active material layer on the current collector.
  • the positive electrode active material includes at least one lithiated intercalation compound that reversibly intercalates and deintercalates lithium ions.
  • the positive active material includes a composite oxide.
  • the composite oxide contains lithium and at least one element selected from cobalt, manganese, and nickel.
  • the positive electrode active material is selected from one or more of lithium cobaltate, lithium manganate, lithium nickelate, or lithium nickel manganese cobalt ternary materials
  • the positive active material may have a coating on its surface, or may be mixed with another compound having a coating.
  • the coating may include at least one selected from the oxide of the coating element, the hydroxide of the coating element, the oxyhydroxide of the coating element, the oxycarbonate of the coating element, and the hydroxycarbonate of the coating element.
  • the compound used for the coating may be amorphous or crystalline.
  • the coating element contained in the coating may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or any of them. combination.
  • the coating can be applied by any method as long as the method does not adversely affect the performance of the positive electrode active material.
  • the method may include any coating method known in the art, such as spraying, dipping, and the like.
  • the positive active material layer further includes a binder, and optionally a conductive material.
  • the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
  • the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene-containing Oxygen polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylic (ester) styrene butadiene rubber, epoxy resin, Nylon etc.
  • conductive materials include, but are not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, graphene, or any combination thereof.
  • the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive electrode current collector may be aluminum, but is not limited thereto.
  • the positive electrode can be prepared by a preparation method known in the art.
  • the positive electrode can be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
  • the solvent may include N-methylpyrrolidone and the like, but is not limited thereto.
  • the positive electrode is made by forming a positive electrode material using a positive electrode active material layer including lithium transition metal-based compound powder and a binder on a current collector.
  • the positive active material layer can usually be made by the following operations: dry mixing the positive electrode material and the binder (conducting material and thickener used as needed) to form a sheet, The obtained sheet is press-bonded to the positive electrode current collector, or these materials are dissolved or dispersed in a liquid medium to prepare a slurry, which is coated on the positive electrode current collector and dried.
  • the material of the positive active material layer includes any material known in the art.
  • the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuits.
  • the material and shape of the isolation membrane used in the electrochemical device of the present application are not particularly limited, and it may be any technology disclosed in the prior art.
  • the isolation membrane includes a polymer or an inorganic substance formed of a material that is stable to the electrolyte of the present application.
  • the isolation film may include a substrate layer and a surface treatment layer.
  • the substrate layer is a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.
  • a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be selected.
  • the substrate layer can be one layer or multiple layers. When the substrate layer is multiple layers, the polymer composition of different substrate layers can be the same or different. The weight average molecular weight of the polymer of different substrate layers is different. It is exactly the same; when the substrate layer is a multilayer, the closed cell temperature of the polymer of different substrate layers is different.
  • At least one surface of the substrate layer is provided with a surface treatment layer
  • the surface treatment layer may be a polymer layer or an inorganic substance layer, or a layer formed by a mixed polymer and an inorganic substance.
  • the inorganic layer includes inorganic particles and a binder.
  • the inorganic particles are selected from alumina, silica, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, One or a combination of yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
  • the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, One or a combination of polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
  • the polymer layer contains a polymer, and the material of the polymer includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( At least one of vinylidene fluoride-hexafluoropropylene).
  • the electrolyte solution according to the embodiments of the present application can significantly improve the cycle performance of the lithium ion battery and the high temperature stability characteristics under overdischarge conditions, and is suitable for use in electronic equipment including electrochemical devices.
  • the use of the electrochemical device of the present application is not particularly limited, and it can be used for various known uses.
  • notebook computers pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, headsets, video recorders, LCD TVs, portable cleaners, portable CD players, Mini discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, assisted bicycles, bicycles, lighting equipment, toys, game consoles, clocks, power tools, flashlights , Cameras, large household storage batteries or lithium-ion capacitors, etc.
  • ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) in a weight ratio of 20:10:70, and then add the lithium salt LiPF 6 .
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Specific types and amounts of substances are added to the above electrolyte (the types and amounts of the added substances are shown in Table 1, and the content of each substance is calculated based on the total weight of the electrolyte), and the electrolyte is obtained after uniform mixing.
  • the concentration of LiPF 6 in the electrolyte is 1.05 mol/L.
  • a polyethylene (PE) isolation film with a thickness of 7 microns is selected.
  • the electrode assembly is obtained after winding and welding the tabs.
  • the electrode assembly is placed in a packaging bag and dried. , Inject the electrolyte prepared above. Then after vacuum packaging, standing, forming (0.02C constant current charging to 3.3V, and then 0.1C constant current charging to 3.6V), exhaust and test capacity to obtain the finished lithium-ion battery.
  • the electrolytes and lithium ion batteries of Examples 1-21 and Comparative Example 1-2 were prepared according to the above methods (1) to (5).
  • the electrolyte and lithium ion battery of Example 22 were prepared, wherein the negative pole piece was prepared according to the method described in the following paragraph, and the others were prepared according to the above-mentioned methods (2) to (5).
  • the electrolyte and lithium ion battery of Example 23 were prepared, wherein the negative pole piece was prepared according to the method described in the following paragraph, and the others were prepared according to the above-mentioned methods (2) to (5).
  • CMC carboxymethyl cellulose
  • the electrolyte and lithium ion battery of Example 24 were prepared, wherein the negative pole piece was prepared according to the method described in the following paragraph, and the others were prepared according to the above-mentioned methods (2) to (5).
  • the electrolyte and lithium ion battery of Example 25 were prepared, wherein the negative pole piece was prepared according to the method described in the following paragraph, and the others were prepared according to the above-mentioned methods (2) to (5).
  • CMC carboxymethyl cellulose
  • the lithium-ion battery Place the lithium-ion battery at 25°C for 30 minutes, then charge at a constant current of 0.5C to a voltage of 4.45V, then charge at a constant voltage of 4.45V to a current of 0.05C, stand for 5 minutes, and then charge at a constant current of 0.5C.
  • the current is discharged to a voltage of 3.0V, which is a charge-discharge cycle process.
  • the discharge capacity this time is the first discharge capacity of the lithium-ion battery.
  • the lithium ion battery was subjected to 500 cycles of charge and discharge test in the above manner, and the discharge capacity of the Nth cycle was detected. Each example tests 5 batteries.
  • the capacity retention rate of the lithium ion battery after N cycles (%) the discharge capacity of the N cycle/first discharge capacity ⁇ 100%.
  • the battery capacity retention rate decays to 70%, and the battery is placed in an oven; at room temperature, the temperature is increased at 2°C/min until the battery fails to burn, the furnace temperature and the battery surface temperature are monitored, and the battery failure temperature is recorded.
  • Battery size test Take three batteries of Example 1 and Example 24, charge them to 3.9V at a constant current of 0.5C at 25°C, and then charge to 0.05C at a constant voltage to cut off; use a micrometer to test the battery thickness, Width, length.
  • Energy density (Wh/L) discharge energy (Wh)/(battery thickness mm ⁇ battery width mm ⁇ battery length mm ⁇ 10 -6 )
  • Example 1 According to the test results of Example 1 and Comparative Examples 1 and 2, it can be seen that adding the compound of formula I and the compound of formula II or formula III to the electrolyte can significantly improve the cycle performance of lithium-ion batteries with silicon-containing negative electrodes and the safety of high temperature resistance after cycling. Sex.
  • the compound of formula II (such as compound 10) is added to the electrolyte while adding the compound of formula I (such as compound 1) of different contents and can significantly improve the lithium content of the silicon-containing negative electrode.
  • a proper amount of the compound of formula I and a proper amount of the compound of formula II work together to have excellent film-forming properties on the surface of the silicon negative electrode and a faster reaction rate.
  • the thicker the protective layer the better the high temperature resistance after cycling . Because the thicker protective layer can better inhibit the side reaction of the electrolyte on the silicon surface, reduce the release of heat, and thus improve the safety of high temperature resistance. Based on the above factors, the effect is particularly ideal when the added compound of formula I accounts for about 0.5% to about 2% by weight of the electrolyte.
  • Example 1 According to the test results of Example 1 and Examples 11 to 13, it can be seen that the various examples of the compound of formula I (for example, compound 1, 2, 3 or 5) and the compound of formula II (for example, compound 10) can be added to the electrolyte in combination to obtain similar results.
  • the various examples of the compound of formula I for example, compound 1, 2, 3 or 5
  • the compound of formula II for example, compound 10
  • Example 1 According to the test results of Example 1, Examples 6 to 9 and Comparative Example 2, it can be seen that when an appropriate amount of the compound of formula I (such as compound 1) is added to the electrolyte, the range of about 0.1% by weight to about 5% by weight of formula II is added.
  • Compounds (such as compound 10) significantly improve the capacity retention rate and thermal safety of lithium-ion batteries after cycling; especially for the high temperature resistance of the battery after cycling, there is a significant improvement; when the battery does not contain trinitrile or ether trinitrile In the case of nitrile additives, the high temperature resistance safety of the battery after cycling is significantly reduced. Taking the above factors into consideration, the effect of adding the compound of formula II in an amount of about 0.5% by weight to about 3% by weight is particularly desirable.
  • Example 10 According to the test results of Example 1 and Example 10, it can be seen that combining a compound of formula II (such as compound 10) or a compound of formula III (such as compound 16) with a compound of formula I (such as compound 1) can achieve similar improvement effects.
  • Example 17 According to the test results of Example 1 and Example 17, it can be seen that adding an appropriate amount of fluorinated additives (such as the combination of compound 23 and compound 21) to the electrolyte can further improve the cycle performance and high temperature resistance of lithium-ion batteries containing silicon anodes. .
  • fluorinated additives such as the combination of compound 23 and compound 21
  • the electrolyte of the present invention is not only suitable for lithium ion batteries whose negative electrode material is silicon negative electrode material coated with amorphous carbon or carbon nanotubes, but also suitable for The negative electrode material is a lithium ion battery with a silicon negative electrode material without a coating layer, and the former has improved cycle performance and high temperature resistance after cycling compared with the latter. This may be due to the poor conductivity of the silicon anode material.
  • the uniformity of the protective layer can be improved, thereby reducing the occurrence of side reactions of the electrolyte on the surface of the silicon anode and improving the lithium ion battery
  • the thickness of the carbon layer is preferably about 20 nanometers to about 200 nanometers. This may be because the carbon material is reactive and consumes active lithium. When the coating layer is too thick, it will cause more loss of active lithium. Thereby reducing the capacity retention rate of the cycle.
  • Example 1 Comparing the test results of Example 1 and Example 24, it can be seen that adding carbon nanotube conductive agent to the silicon negative electrode material and coating amorphous carbon can improve the cycle performance of the silicon-containing lithium ion battery. This may be due to the large expansion and contraction of the silicon negative electrode during the cycle, and poor electrical contact between the negative electrode material particles is likely to occur.
  • the addition of long-range (for example, 1 micron or more) carbon nanotube conductive agent can improve electrical contact, thereby increasing lithium The cycle capacity retention rate of the ion battery.
  • Example 1 uses a silicon oxide negative electrode
  • Example 25 uses a graphite negative electrode, and the positive electrode materials of the two are the same.
  • the gram capacity of graphite anode is much lower than that of silicon anode active material. Therefore, the loading capacity of the graphite negative electrode of Example 25 is higher than that of the silicon oxide negative electrode of Example 1.
  • the battery obtained in Example 25 has a larger volume, and its energy density is lower than that in Example 1.
  • Example 25 Based on the experimental results of Example 1 and Example 25, it can be known that whether it is a lithium battery containing a graphite negative electrode or a lithium ion battery containing a silicon-oxygen negative electrode, the electrolyte of the present invention can obtain satisfactory improved capacity retention and The thermal safety after cycling is particularly effective in improving lithium batteries containing graphite anodes.
  • references to “some embodiments”, “partial embodiments”, “one embodiment”, “another example”, “examples”, “specific examples” or “partial examples” throughout the specification mean At least one embodiment or example in this application includes the specific feature, structure, material, or characteristic described in the embodiment or example. Therefore, descriptions appearing in various places throughout the specification, such as: “in some embodiments”, “in embodiments”, “in one embodiment”, “in another example”, “in an example “In”, “in a specific example” or “exemplary”, which are not necessarily quoting the same embodiment or example in this application.
  • the specific features, structures, materials, or characteristics herein can be combined in one or more embodiments or examples in any suitable manner.

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Abstract

一种电解液及电化学装置。所述电解液包括二乙醇酸酐和三腈化合物，能显著改善锂离子电池的循环性能及在过放电条件下的高温稳定特性。

Description

一种电解液及电化学装置 技术领域
本申请涉及储能技术领域，尤其涉及一种电解液和包含该电解液的电化学装置。
背景技术
锂离子电池具有高能量密度，工作电压高、自放电率低、循环寿命长、无污染等优点，已被广泛应用于计算机、智能穿戴设备、智能手机、无人机，以及电动汽车等领域。随着现代信息技术的发展和锂离子电池应用范围的拓展，本领域对于锂离子电池提出了更多性能要求。例如，提高锂离子电池的续航能力，避免电池在持续充电过程中发生鼓胀、提升循环后电池的耐高温性能，避免电池发生热失控等。
发明内容
本发明提供了一种电解液和包括该电解液的电化学装置。本发明的电解液能够显著改善锂离子电池的循环容量保持率，缓解循环过程中电池膨胀，提升循环后电池的耐高温性能。
本发明的一方面提供了一种电解液，所述电解液包含：
式I化合物，以及
式II化合物或式III化合物中的至少一种；
Figure PCTCN2019128851-appb-000001
其中，R 1、R 2、R 3和R 4各自独立选自氢、卤素、取代或未取代的C 1-C 10烷基、取代或未取代的C 2-C 10烯基、取代或未取代的C 2-C 10炔基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 10烷氧基、或取代或未取代的C 6-C 12芳氧基；经取代时，取代基为卤素、氰基或C 1-C 10烷基；其中a、d和f各自独立选自1至5的整数，b、c、e、g、h和i各自独立选自0至5的整数。
在一些实施例的电解液中,所述式I化合物包含：
Figure PCTCN2019128851-appb-000002
Figure PCTCN2019128851-appb-000003
Figure PCTCN2019128851-appb-000004
中的至少一种；
所述式II化合物包含：
Figure PCTCN2019128851-appb-000005
Figure PCTCN2019128851-appb-000006
Figure PCTCN2019128851-appb-000007
中的至少一种；
所述式Ⅲ化合物包含：
Figure PCTCN2019128851-appb-000008
Figure PCTCN2019128851-appb-000009
中的至少一种。在一些实施例中，所述式I化合物的量占所述电解液重量的约0.01重量％至约3重量％。
在一些实施例中，所述式II化合物、式III化合物或其组合的量占所述电解液重量的约0.1重量％至约5重量％。
在一些实施例中，所述电解液进一步包含氟代添加剂，所述氟代添加剂包含氟代碳酸乙烯酯、碳原子数为2至7的氟代碳酸酯、碳原子数量为2至7的氟代羧酸酯或碳原子数为2至7的氟代醚中的至少一种。
在一些实施例中，所述氟代添加剂占所述电解液重量的约1重量％至约20重量％。
在一些实施例中，所述氟代添加剂包含下述中的至少一种：氟代碳酸甲乙酯、氟代碳酸二甲酯、氟代碳酸二乙酯、氟代丙酸乙酯、氟代丙酸丙酯、氟代丙酸甲酯、氟代乙酸乙酯、氟代乙酸甲酯、氟代乙酸丙酯、
Figure PCTCN2019128851-appb-000010
Figure PCTCN2019128851-appb-000011
在一些实施例中，所述氟代添加剂占所述电解液的质量分数C与所述式I化合物占电解液的质量分数A的比值为：约1≤C/A≤约50。
本发明另一方面提供了一种电化学装置，其包括正极、负极以及上述任一电解液。
在一些实施例中，所述电化学装置的负极包含含硅材料，所述含硅材料包含硅化合物SiO x、硅单质或二者的混合物，其中0.5<x<1.5。
在一些实施例中，所述电化学装置的负极含有碳纳米管，所述碳纳米管的管径为约1纳米至约10纳米、管长为约1微米至约50微米。
在一些实施例中，所述含硅材料表面有碳层，所述碳层厚度为约1纳米至约500纳米，所述碳层包括无定形碳、石墨、硬碳、软碳、炭黑、乙炔黑、碳纳米管或其组合。
在一些实施例中，所述电化学装置的负极包含石墨，所述石墨与所述含硅材料的质量比为约95:5至约60:40。
本发明的又一方面提供了一种电子装置，所述电子装置包括如上任一所述的电化学装置。
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
具体实施方式
本申请的实施例将会被详细的描示在下文中。本申请的实施例不应该被解释为对本申请要求保护范围的限制。除非另外明确指明，本文使用的下述术语具有下文指出的含义。
如本文中所使用，术语“约”用以描述及说明小的变化。当与事件或情形结合使用时，所述术语可指代其中事件或情形精确发生的例子以及其中事件或情形极近似地发生的例子。举例来说，当结合数值使用时，术语可指代小于或等于所述数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的一者”连接的项目的列表可意味着所列项目中的任一者。例如，如果列出项目A及B，那么短语“A及B中的一者”意味着仅A或仅B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的一者”意味着仅A；仅B；或仅C。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
在具体实施方式及权利要求书中，由术语“中的至少一者”连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”或“A或B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”“A、B或C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
在具体实施方式及权利要求书中，在关于碳数的表述即大写字母“C”后面的数字，例如 “C 1-C 10”、“C 3-C 10”等中，在“C”之后的数字例如“1”、“3”或“10”表示具体官能团中的碳数。即，官能团分别可包括1-10个碳原子和3-10个碳原子。例如，“C 1-C 4烷基”是指具有1-4个碳原子的烷基，例如CH 3-、CH 3CH 2-、CH 3CH 2CH 2-、(CH 3) 2CH-、CH 3CH 2CH 2CH 2-、CH 3CH 2CH(CH 3)-或(CH 3) 3C-。
如本文所用，术语“烷基”预期是具有1至10个碳原子的直链饱和烃结构。“烷基”还预期是具有3至10个碳原子的支链或环状烃结构。例如，烷基可为1～10个碳原子的烷基、1～7个碳原子的烷基、或1～4个碳原子的烷基。当指定具有具体碳数的烷基时，预期涵盖具有该碳数的所有几何异构体；因此，例如，“丁基”意思是包括正丁基、仲丁基、异丁基、叔丁基和环丁基；“丙基”包括正丙基、异丙基和环丙基。烷基实例包括，但不限于甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、异戊基、新戊基、环戊基、甲基环戊基、乙基环戊基、正己基、异己基、环己基、正庚基、辛基、环丙基、环丁基、降冰片基等。另外，烷基可以是任选地被取代的。
术语“烯基”是指可为直链或具支链且具有至少一个且通常1个、2个或3个碳碳双键的单价不饱和烃基团。除非另有定义，否则所述烯基通常含有2-10个碳原子，例如可以为2～7个碳原子的烯基、或2～4个碳原子的烯基。代表性烯基包括(例如)乙烯基、正丙烯基、异丙烯基、正-丁-2-烯基、丁-3-烯基、正-己-3-烯基等。另外，烯基可以是任选地被取代的。
术语“炔基”是指可为直链或具支链且具有至少一个且通常具有1个、2个或3个碳碳三键的单价不饱和烃基团。除非另有定义，否则所述炔基通常含有2个到10个、2至7个、或2至4个碳原子的炔基。代表性炔基包括(例如)乙炔基、丙-2-炔基(正-丙炔基)、正-丁-2-炔基、正-己-3-炔基等。另外，炔基可以是任选地被取代的。
术语“芳基”涵盖单环系统和多环系统。多环可以具有其中两个碳为两个邻接环(所述环是“稠合的”)共用的两个或更多个环，其中所述环中的至少一者是芳香族的，例如其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。例如，芳基可为含有6个到12个或6至10个碳原子的。代表性芳基包括(例如)苯基、甲基苯基、丙基苯基、异丙基苯基、苯甲基和萘-1-基、萘-2-基等等。另外，芳基可以是任选地被取代的。
术语“芳氧基”表示通过氧桥连接的具有所述碳原子数目的芳基。其中芳基基团具有如本发明所述的含义，这样的实例包括但并不限于苯氧基，对甲苯氧基，对乙苯氧基等。
术语“烷氧基”指的是烷基与氧原子相连形成的基团。其中烷基基团具有如本发明所述的含义。代表性烷氧基实例包括(但不限于)甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、戊氧基、异戊氧基或叔戊氧基、庚氧基、辛氧基、异辛氧基、壬氧基、癸氧基等。
术语“卤素”涵盖F、Cl、Br、I。
当上述取代基经取代时，取代基可选自由以下组成的群组：卤素、烷基。
如本文中所使用，电解液中各组分的含量均为基于电解液的总重量得到的。
一、电解液
本申请实施例提供了一种电解液，所述电解液包括二乙醇酸酐和三腈或醚三腈化合物。所述电解液能在正、负极表面形成稳定的保护层，显著的改善电池的循环性能。特别是对于负极含有硅活性材料的体系，本申请电解液能保证电池在循环充放电后，其负极保护层仍具有良好的稳定性，以避免电池受热发生热失控引发安全事故。
在一些实施例中，所述电解液包含：
式I化合物，以及
式II化合物或式III化合物中的至少一种；
Figure PCTCN2019128851-appb-000012
其中，R 1，R 2，R 3和R 4各自独立选自氢、卤素、取代或未取代的C 1-C 10烷基、取代
或未取代的C 2-C 10烯基、取代或未取代的C 2-C 10炔基、取代或未取代的C 6-C 12芳基、取 代或未取代的C 1-C 10烷氧基、或取代或未取代的C 6-C 12芳氧基；经取代时，取代基为卤素、氰基或C 1-C 10烷基。
其中a、d、和f各自独立选自0、1、2、3、4或5，b、c、e、g、h和i各自独立选自0、1、2、3、4或5。
在一些实施例中，R 1，R 2，R 3和R 4各自独立选自氢、卤素、取代或未取代的C 1-C 7烷基、取代或未取代的C 1-C 4烷基、取代或未取代的C 2-C 7烯基、取代或未取代的C 2-C 4烯基、取代或未取代的C 2-C 7炔基、取代或未取代的C 2-C 4炔基、取代或未取代的C 6-C 10芳基、取代或未取代的C 1-C 7烷氧基、取代或未取代的C 1-C 4烷氧基或取代或未取代的C 6-C 10芳氧基；经取代时，取代基为卤素、氰基或C 1-C 3烷基。
在一些实施例中，R 1，R 2，R 3和R 4各自独立选自H、F、甲基、乙基、丙基、乙烯基、1-丙烯基、2-丙烯基、1-丙炔基、2-丙炔基、甲氧基、乙氧基、或苯氧基。
在一些实施例的电解液中,所述式I化合物包含:
Figure PCTCN2019128851-appb-000013
Figure PCTCN2019128851-appb-000014
中的至少一种。
所述式II化合物包含:
Figure PCTCN2019128851-appb-000015
Figure PCTCN2019128851-appb-000016
Figure PCTCN2019128851-appb-000017
中的至少一种。
所述式Ⅲ化合物包含:
Figure PCTCN2019128851-appb-000018
Figure PCTCN2019128851-appb-000019
中的至少一种。
在一些实施例中，所述的电解液中所述式I化合物的量占所述电解液重量的约0.01重量％至约3重量％、约0.05重量％至约2重量％、或约0.2重量％至约1重量％。在一些实施例中，式Ⅰ化合物的量占所述电解液重量的约0.08重量％、约0.1重量％、约0.2重量％、约0.3重量％、约0.4重量％、约0.5重量％、约0.6重量％、约0.7重量％、约0.8重量％、约0.9重量％、约1重量％、约1.2重量％或约1.5重量％。
在一些实施例中，所述的电解液中所述式II化合物、式III化合物或其组合的量占所述电解液重量的约0.1重量％至约5重量％、约0.25重量％至约4重量％、约0.5重量％至约3重量％、约1重量％至约2重量％。在一些实施例中，所述的电解液中所述式II化合物、式III化合物或其组合的量占所述电解液重量的约1.5重量％、约2重量％或约2.5重量％。
在一些实施例中，为了进一步改善硅负极在循环过程中因保护层破坏带来的副反应，所述电解液进一步包含氟代添加剂，所述氟代添加剂包含氟代碳酸乙烯酯(FEC)、碳原子数为2至7的氟代碳酸酯、碳原子数量为2至7的氟代羧酸酯或碳原子数为2至7的氟代醚中的至少一种。这类氟化物可在硅负极保护层发生破坏时快速进行修复，从而减少电解液与硅负极的副反应。
在一些实施例中，所述氟代添加剂占所述电解液重量的约1重量％至约20重量％。在一些实施例中，所述氟代添加剂占所述电解液重量的约2重量％至约18重量％。在一些实施例中，所述氟代添加剂占所述电解液重量的约3重量％至约15重量％。。在一些实施例中，所述氟代添加剂占所述电解液重量的约5重量％至约18重量％。
在一些实施例中，所述氟代添加剂包含下述中的至少一种：氟代碳酸甲乙酯、氟代碳酸二甲酯、氟代碳酸二乙酯、氟代丙酸乙酯、氟代丙酸丙酯、氟代丙酸甲酯、氟代乙酸乙酯、氟代乙酸甲酯或氟代乙酸丙酯。
在一些实施例中，所述氟代添加剂包含下述中的至少一种：
Figure PCTCN2019128851-appb-000020
在一些实施例中，为更好的形成稳定的保护层及对保护层的修复，所述氟代添加剂占所述电解液的质量分数C与所述式I化合物占电解液的质量分数A的比值为：约1≤C/A≤约50。
在一些实施例中，为了进一步改善锂离子电池的循环性能，所述电解液还可进一步包含选 自碳酸亚乙烯酯(VC)、1,3-丙烷磺内酯(PS)、硫酸乙烯酯(DTD)、丁二腈(SN)或己二腈(ADN)中的至少一种添加剂。
在一些实施例中，所述碳酸亚乙烯酯占所述电解液重量的约0.001重量％至约2重量％。
在一些实施例中，所述1,3-丙烷磺内酯占所述电解液重量的约0.001重量％至约2重量％。在一些实施例中，所述1,3-丙烷磺内酯占所述电解液重量的约0.001重量％至约1重量％。
在一些实施例中，所述硫酸乙烯酯占所述电解液重量的约0.001重量％至约3重量％。
在一些实施例中，所述丁二腈、己二腈或其组合占所述电解液重量的约0.1重量％至约7重量％。
在一些实施例中，所述丁二腈、己二腈或其组合占所述电解液重量的约0.5重量％至约6重量％。
在一些实施例中，所述电解液进一步包括锂盐和有机溶剂。
在一些实施例中，所述锂盐选自无机锂盐和有机锂盐中的一种或多种。在一些实施例中，所述锂盐含有氟元素、硼元素或磷元素中的至少一种。在一些实施例中，所述锂盐选自如下锂盐中的一种或多种：六氟磷酸锂LiPF 6、双三氟甲烷磺酰亚胺锂LiN(CF 3SO 2) 2(简写为LiTFSI)、双(氟磺酰)亚胺锂Li(N(SO 2F) 2)(简写为LiFSI)、双草酸硼酸LiB(C 2O 4) 2(简写为LiBOB)、二氟草酸硼酸LiBF 2(C 2O 4)(简写为LiDFOB)、六氟砷酸锂(LiAsF 6)、高氯酸锂(LiClO 4)、三氟甲磺酸锂(LiCF 3SO 3)中的至少一种。
在一些实施例中，所述锂盐的浓度为约0.5mol/L至约1.8mol/L。在一些实施例中，所述锂盐的浓度为约0.8mol/L至约1.5mol/L。在一些实施例中，所述锂盐的浓度为约0.8mol/L至约1mol/L。
所述有机溶剂包含环状酯和链状酯，所述环状酯选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、γ-丁内酯(BL)和碳酸丁烯酯中的至少一种；所述链状酯选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙乙酯、甲酸甲酯(MF)、甲酸乙酯(MA)、乙酸乙酯(EA)、丙酸乙酯(EP)、丙酸丙酯(PP)、丙酸甲酯、丁酸甲酯、和丁酸乙酯中的至少一种。
在一些实施例中，所述有机溶剂占所述电解液重量的约70重量％至约90重量％。
二、电化学装置
本申请的电化学装置包括发生电化学反应的任何装置，它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容器。特别地，该电化学装置是锂二次电池，包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。在一些实施例中，本申请的电化学装置是具备具有能够吸留、放出金属离子的正极活性物质的正极以及具有能够吸留、放出金属离子的负极活性物质的负极的电化学装置，其特征在于，包含本申请的上述任何电解液。
负极
本申请的电化学装置中使用的负极的材料、构成和其制造方法可包括任何现有技术中公开的技术。在一些实施例中，负极为美国专利申请US9812739B中记载的负极，其以全文引用的方式并入本申请中。
在一些实施例中，负极包括集流体和位于该集流体上的负极活性材料层。负极活性材料包括可逆地嵌入/脱嵌锂离子的材料。在一些实施例中，可逆地嵌入/脱嵌锂离子的材料包括碳材料。在一些实施例中，碳材料可以是在锂离子可充电电池中通常使用的任何基于碳的负极活性材料。在一些实施例中，碳材料包括，但不限于：结晶碳、非晶碳或它们的混合物。结晶碳可以是无定形的、片形的、小片形的、球形的或纤维状的天然石墨或人造石墨。非晶碳可以是软碳、硬碳、中间相沥青碳化物、煅烧焦等。
在一些实施例中，负极活性材料层包括负极活性材料。所述负极活性材料包括含碳材料、含硅材料、合金材料或含锡材料中的至少一种。其中在一些实施例中，负极活性材料包括、但不限于：锂金属、结构化的锂金属、天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO 2、尖晶石结构的锂化TiO 2-Li 4Ti 5O 12、Li-Al合金或其任意组合。
在一些实施例中，所述负极活性材料包括含硅材料，所述含硅材料包含硅化合物SiO x(0.5≤x≤1.5)、硅单质或二者的混合物。
在一些实施例中，以所述负极活性材料的总质量计，所述含硅材料的质量分数为约5重量％至约90重量％、约10重量％至约70重量％或约10重量％至约50重量％。
在一些实施例中，为进一步改善含硅材料的导电性，所述含硅材料表面有碳层以促进二乙醇酸酐添加剂在负极表面形成稳定的保护层。所述碳层可选自无定形碳，石墨，硬碳，软碳，炭黑，乙炔黑或碳纳米管中的至少一种。所述碳层厚度为约1纳米至约500纳米、约10 纳米至约300纳米、或约20纳米至约200纳米。
在一些实施例中，当负极包含含硅材料时，所述负极可进一步包含碳纳米管导电剂，从而改进硅负极在充放电膨胀和收缩过程导致的电接触失效，提升硅负极二次电池的循环容量保持率以及循环后的热安全性。在一些实施例中，碳纳米管管径为约1纳米至约10纳米；管长为约1微米至约50微米；碳纳米管与硅表面，或硅表面包覆层紧密接触。
在一些实施例中，所述负极活性材料层可以包括粘合剂，并且可选地包括导电材料。粘合剂提高负极活性材料颗粒彼此间的结合和负极活性材料与集流体的结合。在一些实施例中，粘合剂包括，但不限于：聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
在一些实施例中，导电材料包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物或它们的混合物。在一些实施例中，基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，基于金属的材料选自金属粉、金属纤维、铜、镍、铝、银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施例中，负极集流体包括，但不限于：铜箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜、覆有导电金属的聚合物基底和它们的任意组合。
负极可以通过本领域公知的制备方法制备。例如，负极可以通过如下方法获得：在溶剂中将活性材料、导电材料和粘合剂混合，以制备活性材料组合物，并将该活性材料组合物涂覆在集流体上。在一些实施例中，溶剂可以包括水等，但不限于此。
正极
本申请的电化学装置中使用的正极的材料可以使用本领域公知的材料、构造和制造方法制备。在一些实施例中，可以采用US9812739B中记载的技术制备本申请的正极，其以全文引用的方式并入本申请中。
在一些实施例中，正极包括集流体和位于该集流体上的正极活性材料层。正极活性材料包括可逆地嵌入和脱嵌锂离子的至少一种锂化插层化合物。在一些实施例中，正极活性材料包括复合氧化物。在一些实施例中，该复合氧化物含有锂以及从钴、锰和镍中选择的至少一种元素。
在一些实施例中，正极活性材料选自钴酸锂、锰酸锂、镍酸锂、或锂镍锰钴三元材料中的一种或多种
在一些实施例中，正极活性材料可以在其表面上具有涂层，或者可以与具有涂层的另一化合物混合。该涂层可以包括从涂覆元素的氧化物、涂覆元素的氢氧化物、涂覆元素的羟基氧化物、涂覆元素的碳酸氧盐和涂覆元素的羟基碳酸盐中选择的至少一种涂覆元素化合物。用于涂层的化合物可以是非晶的或结晶的。
在一些实施例中，在涂层中含有的涂覆元素可以包括Mg、Al、Co、K、Na、Ca、Si、Ti、V、Sn、Ge、Ga、B、As、Zr或它们的任意组合。可以通过任何方法来施加涂层，只要该方法不对正极活性材料的性能产生不利影响即可。例如，该方法可以包括对本领域公知的任何涂覆方法，例如喷涂、浸渍等。
正极活性材料层还包括粘合剂，并且可选地包括导电材料。粘合剂提高正极活性材料颗粒彼此间的结合，并且还提高正极活性材料与集流体的结合。
在一些实施例中，粘合剂包括，但不限于：聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
在一些实施例中，导电材料包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维、碳纳米管、石墨烯或其任意组合。在一些实施例中，基于金属的材料选自金属粉、金属纤维、铜、镍、铝、银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施例中，正极集流体可以是铝，但不限于此。
正极可以通过本领域公知的制备方法制备。例如，正极可以通过如下方法获得：在溶剂中将活性材料、导电材料和粘合剂混合，以制备活性材料组合物，并将该活性材料组合物涂覆在集流体上。在一些实施例中，溶剂可以包括N-甲基吡咯烷酮等，但不限于此。
在一些实施例中，正极通过在集流体上使用包括锂过渡金属系化合物粉体和粘结剂的正极活性物质层形成正极材料而制成。
在一些实施例中，正极活性物质层通常可以通过如下操作来制作：将正极材料和粘结剂(根据需要而使用的导电材料和增稠剂等)进行干式混合而制成片状，将得到的片压接于正极集流体，或者使这些材料溶解或分散于液体介质中而制成浆料状，涂布在正极集流体上并进行干燥。在一些实施例中，正极活性物质层的材料包括任何本领域公知的材料。
隔离膜
在一些实施例中，本申请的电化学装置在正极与负极之间设有隔离膜以防止短路。本申请的电化学装置中使用的隔离膜的材料和形状没有特别限制，其可为任何现有技术中公开的技术。在一些实施例中，隔离膜包括由对本申请的电解液稳定的材料形成的聚合物或无机物等。
例如隔离膜可包括基材层和表面处理层。基材层为具有多孔结构的无纺布、膜或复合膜，基材层的材料选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯和聚酰亚胺中的至少一种。具体的，可选用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。基材层可以为一层或多层，当基材层为多层时，不同的基材层的聚合物的组成可以相同，也可以不同，不同的基材层的聚合物的重均分子量不完全相同；当基材层为多层时，不同的基材层的聚合物的闭孔温度不同。
在一些实施例中，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
无机物层包括无机颗粒和粘结剂，无机颗粒选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙和硫酸钡中的一种或几种的组合。粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯和聚六氟丙烯中的一种或几种的组合。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
三、应用
根据本申请实施例的电解液，能够显著改善锂离子电池的循环性能及在过放电条件下的高温稳定特性，适合使用在包含电化学装置的电子设备中。
本申请的电化学装置的用途没有特别限定，可以用于公知的各种用途。例如笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池或锂离子电容器等。
实施例
以下，举出实施例和比较例对本申请进一步具体地进行说明，但只要不脱离其主旨，则本 申请并不限定于这些实施例。
1.锂离子电池的制备
(1)负极的制备
称取1.2kg质量分数为1.5％的羧甲基纤维素钠(CMC)溶液、0.07kg质量分数为50％的丁苯橡胶乳液、2.0kg石墨粉末、0.01Kg碳纳米管(管径为约1至5纳米、管长为约1至30微米)，0.4Kg表面包覆有无定形碳SiO，其中无定形碳包覆层厚度如表1所示；将物料充分混合搅拌得到负极浆料，之后将负极浆料均匀地涂布在厚度为8微米的铜箔上，之后在120℃烘烤1小时，之后经过压实、分切得到负极。
(2)正极的制备
称取1.42kgN-甲基-2-吡咯烷酮(纳米P)、1.2kg质量分数为10％的聚偏二氟乙烯(PVDF)、0.16kg导电石墨以及7.2kg钴酸锂(LiCoO 2)充分混合搅拌得到正极浆料。将正极浆料均匀地涂布在厚度为10微米的铝箔上，再于120℃烘烤1小时，之后经过压实、分切得到正极。
(3)电解液的制备
在干燥的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸二乙酯(DEC)按照20:10:70的重量比充分混合，之后加入锂盐LiPF 6。在上述电解液中加入特定种类和量的物质(添加物质的种类和量如表1所示，各物质的含量为基于电解液的总重量计算得到)，混合均匀后获得电解液。电解液中LiPF 6的浓度为1.05mol/L。
(4)隔离膜的制备
选用7微米厚的聚乙烯(PE)隔离膜。
(5)锂离子电池的制备
将上述正极、隔离膜、负极按顺序叠好，使隔离膜处于正、负极之间起到隔离的作用，然后卷绕、焊接极耳后得到电极组件，将电极组件置于包装袋中，干燥，注入上述制备好的电解液。再经过真空封装、静置、化成(0.02C恒流充电到3.3V，再以0.1C恒流充电到3.6V)、排气并测试容量得到成品的锂离子电池。
实施例1至实施例21，对比例1和对比例2
按照上述方法(1)至(5)制备实施例1-21和对比例1-2的电解液以及锂离子电池。
实施例22
制备实施例22的电解液以及锂离子电池，其中负极极片按照下段所述方法制备，其它按照上述方法(2)至(5)制备。
称取1.2kg质量分数为1.5％的羧甲基纤维素钠(CMC)溶液、0.07kg质量分数为50％的丁苯橡胶乳液、2.0kg石墨粉末、0.01Kg碳纳米管(管径为约1至5纳米、管长为约1至30微米)，0.4Kg表面包覆有碳纳米管(管径为约1至5纳米、管长为约1至30微米)的SiO，其中碳纳米管包覆层的厚度如表1所示；将物料充分混合搅拌得到负极浆料，之后将负极浆料均匀地涂布在厚度为8微米的铜箔上，之后在120℃烘烤1小时得到负极膜片，之后经过压实、分切得到负极。
实施例23
制备实施例23的电解液以及锂离子电池，其中负极极片按照下段所述方法制备，其它按照上述方法(2)至(5)制备。
称取1.2kg质量分数为1.5％的羧甲基纤维素钠(CMC)溶液、0.07kg质量分数为50％的丁苯橡胶乳液、2.0kg石墨粉末、0.01Kg碳纳米管(管径为约1至5纳米、管长为约1至30微米)，0.4Kg的SiO；将物料充分混合搅拌得到负极浆料，之后将负极浆料均匀地涂布在厚度为8微米的铜箔上，之后在120℃烘烤1小时得到负极膜片，之后经过压实、分切得到负极。
实施例24
制备实施例24的电解液以及锂离子电池，其中负极极片按照下段所述方法制备，其它按照上述方法(2)至(5)制备。
称取1.2kg质量分数为1.5％的羧甲基纤维素钠(CMC)溶液、0.07kg质量分数为50％的丁苯橡胶乳液、2.0kg石墨粉末、0.4Kg表面包覆有无定形碳的SiO，其中无定形碳包覆层厚度如表1所示；将物料充分混合搅拌得到负极浆料，之后将负极浆料均匀地涂布在厚度为8微米的铜箔上，之后在120℃烘烤1小时得到之后经过压实、分切得到负极。
实施例25
制备实施例25的电解液以及锂离子电池，其中负极极片按照下段所述方法制备，其它按照上述方法(2)至(5)制备。
称取1.2kg质量分数为1.5％的羧甲基纤维素钠(CMC)溶液、0.07kg质量分数为50％的 丁苯橡胶乳液、2.4kg石墨粉末；将物料充分混合搅拌得到负极浆料，之后将负极浆料均匀地涂布在厚度为8微米的铜箔上，之后在120℃烘烤1小时，之后经过压实、分切得到负极。
表1 实施例和对比例的电池
Figure PCTCN2019128851-appb-000021
注：“/”代表未添加
2.锂离子电池的循环性能测试
(1)锂离子电池的循环性能测试
在25℃下，将锂离子电池静置30分钟，之后以0.5C恒流充电至电压为4.45V，之后以4.45V恒压充电至电流为0.05C，静置5分钟，之后以0.5C恒流放电至电压为3.0V，此为一个充放电循环过程，此次的放电容量为锂离子电池的首次放电容量。将锂离子电池按上述方式进行500次循环充放电测试，检测得到第N次循环的放电容量。每个实施例测试 5颗电池。
锂离子电池N次循环后的容量保持率(％)＝第N次循环的放电容量/首次放电容量×100％。
(2)循环后锂离子电池过放电耐高温性能测试
经过循环，电池容量保持率衰减至70％，取电池放置于烘箱中；在室温下，以2℃/min升温，直至电池燃烧失效，监控炉温和电池表面温度，记录电池失效温度。每个实施例测试5颗电池。
(3)电池的能量密度测试
电池尺寸测试：取实施例1和实施例24各三颗电池，在25℃下，以0.5C恒电流充电至3.9V，然后在恒电压下，充电至0.05C截止；使用千分尺测试电池厚度、宽度、长度。
在25℃下，以0.5C恒电流充电至4.45V，然后在恒电压下，充电至0.025C截止；搁置5min；以0.1C恒电流放电至3.0V；记录锂离子电池的放电能量。
能量密度(Wh/L)＝放电能量(Wh)/(电池厚度mm×电池宽度mm×电池长度mm×10 -6)
A.按照上述方法制备实施例1至23和对比例1至2的电解液以及锂离子电池。测试锂离子电池不同循环次数循环容量保持率及循环后失效温度，测试结果请见表2。
表2 循环容量保持率和耐高温测试结果
Figure PCTCN2019128851-appb-000022
Figure PCTCN2019128851-appb-000023
根据实施例1与对比例1和2的测试结果可知，电解液中同时添加式I化合物及式II或式III化合物可显著改善含硅负极的锂离子电池的循环性能及循环后的耐高温安全性。
根据实施例1至5和对比例2的测试结果可知，电解液中添加式II化合物(如化合物10)的同时添加不同含量的式I化合物(如化合物1)及可显著改善含硅负极的锂离子电池的循环性能及循环后的耐高温安全性。适量的式I化合物与适量的式II化合物共同作用，在硅负极表面的成膜性能优，反应速率较快。如果添加量太多，容易生成较厚的保护层，阻碍锂离子在硅表面的嵌入和脱出，反而不利于循环容量保持率；另一方面，保护层越厚，循环后的耐高温性能越好，因为较厚的保护层能更好的抑制电解液在硅表面的副反应，减少热量的释放，从而可以改善耐高温安全性。综合上述因素，当添加的式I化合物占电解液质量分数为约0.5重量％至约2重量％时效果尤为理想。
根据实施例1与实施例11至13的测试结果可知，式I化合物的各个实例(例如化合物1、2、3或5)与式II化合物(如化合物10)组合添加到电解液均能获得相似的技术效果。
据实施例1，实施例6至9和对比例2的测试结果可知，在电解液中添加适量式I化合物(如化合物1)的同时添加范围在约0.1重量％至约5重量％的式II化合物(如化合物10)对锂离子电池的容量保持率和循环后热安全性都有明显的提升；特别是对于循环后电池耐高温性能，有明显的提升；当电池不含三腈或醚三腈添加剂时，电池循环后的耐高温安全性显著降低。综合上述因素，添加的式II化合物的量在约0.5重量％至约3重量％时效果尤为理想。
根据实施例1和实施例10的测试结果可知，将式II化合物(如化合物10)或者式III化合物(如化合物16)与式I化合物(如化合物1)搭配能起到相似的改善效果。
根据实施例1和实施例17的测试结果可知，电解液中添加适量氟代添加剂(如化合物23与化合物21的组合)可以进一步改善含硅负极的锂离子电池的循环性能及循环后耐高温性能。
根据实施例1及18至22与实施例23测试结果比较可知，本发明的电解液既适用于负极 材料为包覆有无定形碳或碳纳米管的硅负极材料的锂离子电池，也适用于负极材料为无包覆层的硅负极材料的锂离子电池，且前者较后者具有改进的循环性能和循环后耐高温性能。这可能是由于硅负极材料导电性较差，表面包覆有导电的包覆层后，可改善保护层成膜均一性，从而减少电解液在硅负极表面的副反应发生，达到改善锂离子电池的循环性能和循环后耐高温性能。根据测试结果，碳层的厚度优选约20纳米至约200纳米，这可能是因为碳素材料具有反应活性，会消耗活性锂，当包覆层太厚，会带来更多活性锂的损失，从而降低循环的容量保持率。
将实施例1和实施例24的测试结果进行比较可知，在硅负极材料中加入碳纳米管导电剂并包覆无定形碳可改善含硅锂离子电池的循环性能。这可能是由于硅负极循环过程中膨胀和收缩较大，负极材料颗粒间很容易出现电接触不好，加入长程的(例如1微米以上)的碳纳米管导电剂可改善电接触，从而提升锂离子电池的循环容量保持率。
B.按照上述方法制备实施例1和25的电解液以及锂离子电池。测试锂离子电池能量密度，电池循环容量保持率和耐高温测试结果，测试结果请见表3和4。
表3 不同负极活性材料的电池能量密度
Figure PCTCN2019128851-appb-000024
表4 不同负极活性材料的电池循环容量保持率和耐高温测试结果
Figure PCTCN2019128851-appb-000025
实施例1使用硅氧负极、实施例25使用石墨负极，两者的正极材料相同。石墨负极的克容量远低于硅负极活性材料。因此，实施例25石墨负极的负载量较实施例1的硅氧负极高。实施例25得到的电池体积更大一些，其能量密度低于实施例1。
基于实施例1和实施例25的实验结果可知，无论是包含石墨负极的锂电池还是包含硅氧 负极的锂离子电池，采用本发明的电解液都能得到令人满意的改进的容量保持率和循环后热安全性，对于包含石墨负极的锂电池改善效果尤为显著。
以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例”，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性的实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (10)

  1. 一种电解液，其包含：
    式I化合物，以及
    式II化合物或式III化合物中的至少一种；
    Figure PCTCN2019128851-appb-100001
    其中，R 1、R 2、R 3和R 4各自独立选自氢、卤素、取代或未取代的C 1-C 10烷基、取代或未取代的C 2-C 10烯基、取代或未取代的C 2-C 10炔基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 10烷氧基、或取代或未取代的C 6-C 12芳氧基；经取代时，取代基为卤素、氰基或C 1-C 10烷基；其中a、d和f各自独立选自1至5的整数，b、c、e、g、h和i各自独立选自0至5的整数。
  2. 根据权利要求1所述的电解液，其中,
    所述式I化合物包含：
    Figure PCTCN2019128851-appb-100002
    Figure PCTCN2019128851-appb-100003
    中的至少一种；
    所述式II化合物包含：
    Figure PCTCN2019128851-appb-100004
    Figure PCTCN2019128851-appb-100005
    中的至少一种；
    所述式Ⅲ化合物包含：
    Figure PCTCN2019128851-appb-100006
    Figure PCTCN2019128851-appb-100007
    中的至少一种；
    所述式I化合物的量占所述电解液重量的0.01重量％至3重量％，所述式II化合物、式III化合物或其组合的量占所述电解液重量的0.1重量％至5重量％。
  3. 根据权利要求1所述的电解液，其进一步包含氟代添加剂，所述氟代添加剂包含氟代碳酸乙烯酯、碳原子数为2至7的氟代碳酸酯、碳原子数量为2至7的氟代羧酸酯或碳原子数为2至7的氟代醚中的至少一种，所述氟代添加剂的量占所述电解液重量的1重量％至20重量％。
  4. 根据权利要求3所述的电解液，其中所述氟代添加剂包含下述中的至少一种：氟代碳酸甲乙酯、氟代碳酸二甲酯、氟代碳酸二乙酯、氟代丙酸乙酯、氟代丙酸丙酯、氟代丙酸甲酯、氟 代乙酸乙酯、氟代乙酸甲酯、氟代乙酸丙酯、
    Figure PCTCN2019128851-appb-100008
    Figure PCTCN2019128851-appb-100009
  5. 根据权利要求3所述的电解液，其中所述氟代添加剂占所述电解液的质量分数C与所述式I化合物占电解液的质量分数A的比值为：1≤C/A≤50。
  6. 一种电化学装置，其包括正极、负极以及根据权利要求1-5中任一权利要求所述的电解液。
  7. 根据权利要求6所述的电化学装置，其中所述负极包含含硅材料，所述含硅材料包含硅化合物SiO x、硅单质或二者的混合物，其中0.5<x<1.5。
  8. 根据权利要求6所述的电化学装置，其中所述负极含有碳纳米管，所述碳纳米管的管径为1纳米至10纳米、管长为1微米至50微米。
  9. 根据权利要求7所述的电化学装置，其中所述含硅材料表面有碳层，所述碳层厚度为1纳米至500纳米，所述碳层包括无定形碳、石墨、硬碳、软碳、炭黑、乙炔黑、碳纳米管或其组合。
  10. 一种电子装置，其包括根据权利要求6-9中任一权利要求所述的电化学装置。
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