WO2021146839A1 - 电解液和使用其的电化学装置 - Google Patents

电解液和使用其的电化学装置 Download PDF

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WO2021146839A1
WO2021146839A1 PCT/CN2020/073221 CN2020073221W WO2021146839A1 WO 2021146839 A1 WO2021146839 A1 WO 2021146839A1 CN 2020073221 W CN2020073221 W CN 2020073221W WO 2021146839 A1 WO2021146839 A1 WO 2021146839A1
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substituted
unsubstituted
electrolyte
compound
lithium
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PCT/CN2020/073221
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English (en)
French (fr)
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栗文强
刘建
管明明
郑建明
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宁德新能源科技有限公司
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Priority to US17/059,701 priority Critical patent/US20210408603A1/en
Priority to KR1020227028091A priority patent/KR20220121263A/ko
Priority to JP2022544205A priority patent/JP7457135B2/ja
Priority to EP20915120.8A priority patent/EP4092799A4/en
Priority to PCT/CN2020/073221 priority patent/WO2021146839A1/zh
Publication of WO2021146839A1 publication Critical patent/WO2021146839A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • 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
    • H01M4/48—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
    • H01M4/52—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
    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • 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 technical field of electrochemical devices, and more specifically to an electrolyte and an electrochemical device using the electrolyte.
  • High energy density is a relatively large trend in the development of lithium-ion batteries.
  • 5G the volume left for batteries is getting less and less, but the energy required by the batteries is getting higher and higher.
  • High voltage provides a more effective solution and way to increase energy density, but high voltage is accompanied by severe safety issues. Solving safety issues has become the only way for lithium-ion batteries to develop towards high voltage.
  • This application provides an electrolyte and an electrochemical device using the electrolyte to solve the above-mentioned problems.
  • the embodiments of the present application provide an electrolyte and an electrochemical device using the electrolyte, in an attempt to solve at least one problem in the related field at least to some extent.
  • the embodiments of the present application also provide an electrochemical device and an electronic device using the electrolyte.
  • the present application provides an electrolyte solution comprising a compound of formula I and a carboxylate compound:
  • R 11 , R 12 , R 13 , and R 14 are each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted Or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 3-20 heterocyclic group, substituted or unsubstituted C 6-20 aryl, Substituted or unsubstituted C 6-20 heteroaryl or -R 0 -OR group, substituted or unsubstituted sultone, substituted or unsubstituted sulfite lactone, substituted or unsubstituted sulfuric lactone, Wherein the heteroatom in the heterocyclic group is selected from at least one of O, S, N or P; or R 11 and R 12 together with the carbon atoms to which they are connected form a 5
  • R 0 is selected from C 1-6 alkylene
  • R is selected from sulfone, methylsulfone, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted Or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 6-20 heteroaryl;
  • R 11 , R 12 , R 13 , R 14 , and R are each independently substituted, the substituent is selected from halogen, cyano, sulfone, methylsulfone, C 1-20 alkyl, C 3-20 ring Alkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl, C 6-20 heteroaryl, or any combination thereof.
  • R 11 , R 12 , R 13 and R 14 are each independently selected from the following groups:
  • R 11 and R 12 are connected with the carbon atom to which they are connected to form
  • the weight percentage of the compound of formula I is a wt%, and a is 0.001-5.
  • the compound of formula I includes at least one of the following compounds:
  • the carboxylic acid ester compound includes a compound of formula II:
  • R 21 and R 22 are each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2 -20 alkenyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 6-20 heteroaryl;
  • R 21 and R 22 are each independently substituted, the substituent is selected from halogen, cyano, C 1-20 alkyl, C 3-20 cycloalkyl, C 1-20 alkoxy, C 2-20 alkene Group, C 6-20 aryl group or any combination thereof;
  • the weight percentage of the carboxylate compound is bwt%, and b is 0.05-75.
  • the carboxylate compound includes at least one of the following compounds:
  • the electrolyte further includes a compound of formula III:
  • M is selected from one of C and Si;
  • R 31 , R 32 , and R 33 are each independently selected from substituted or unsubstituted C 1 -C 20 alkylene, substituted or unsubstituted C 2 -C 20 alkenylene, -R 35 -SR 36 -or- R 37 -OR 38 -, R 35 , R 36 , R 37 and R 38 are each independently a single bond, substituted or unsubstituted C 1 -C 20 alkylene or substituted or unsubstituted C 2 -C 20 alkylene Alkenyl
  • R 34 is selected from H, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 2 -C 20 alkenyl;
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 are each independently substituted, the substituents are selected from halogen, cyano, C 1-20 alkyl, C 3- 20 cycloalkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl or any combination thereof;
  • the weight percentage of the compound of formula III is 0.01 wt% to 5 wt%.
  • the compound of formula III includes at least one of the following compounds:
  • the electrolyte further includes a lithium salt additive
  • the lithium salt additive includes at least one of the following lithium salts: LiPO 2 F 2 , lithium bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl) Lithium imide, lithium bisoxalate borate, lithium tetrafluorophosphate oxalate, lithium difluorooxalate borate or lithium hexafluorocesium oxide;
  • the weight percentage of the lithium salt additive is 0.001 wt% to 5 wt%.
  • the present application provides an electrochemical device, which includes a positive electrode, the positive electrode includes a positive electrode active material layer, the positive electrode active material layer includes a positive electrode active material; and according to the embodiments of the present application Of electrolyte.
  • the electrolyte of the electrochemical device further contains copper ions, and the content of the copper ions is 0.01 ppm-50 ppm based on the total weight of the electrolyte.
  • the positive electrode active material contains Ti element, based on the total weight of the positive electrode active material layer, the content of Ti element is t ⁇ 10 2 ppm, t is 2-10, and satisfies (a+ b)/t ⁇ 35.
  • the present application provides an electronic device, which includes the electrochemical device according to the embodiment of the present application.
  • the lithium ion battery prepared from the electrolyte of the present application has reduced storage resistance and improved storage flatulence, overcharge performance and hot box performance.
  • a list of items connected by the terms “one of”, “one of”, “one of” or other similar terms can mean any of the listed items.
  • 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 terms “at least one of”, “at least one of”, “at least one of” or other similar terms may mean the listed items Any combination of. For example, if items A and B are listed, then the phrase “at least one of A and 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” means only A; or only B; only C; A and B (excluding 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.
  • alkyl is expected to be a linear saturated hydrocarbon structure having 1 to 20 carbon atoms.
  • Alkyl is also expected to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms.
  • the alkyl group may be an alkyl group of 1-20 carbon atoms, an alkyl group of 1-10 carbon atoms, an alkyl group of 1-5 carbon atoms, an alkyl group of 5-20 carbon atoms, and an alkyl group of 5-15 carbon atoms. Carbon atom alkyl group or 5-10 carbon atom alkyl group.
  • butyl means to include n-butyl, sec-butyl, isobutyl, and 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.
  • cycloalkyl encompasses cyclic alkyl groups.
  • the cycloalkyl group may be a cycloalkyl group of 3-20 carbon atoms, a cycloalkyl group of 6-20 carbon atoms, a cycloalkyl group of 3-12 carbon atoms, or a cycloalkyl group of 3-6 carbon atoms.
  • the cycloalkyl group may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • cycloalkyl groups may be optionally substituted.
  • alkoxy refers to an L-O- group, where L is an alkyl group.
  • the alkoxy group may be an alkoxy group having 1-20 carbon atoms, an alkoxy group having 1-12 carbon atoms, an alkoxy group having 1-5 carbon atoms, or an alkoxy group having 5-20 carbon atoms. , 5-15 carbon atoms alkoxy group or 5-10 carbon atoms alkoxy group.
  • the alkoxy group may be optionally substituted.
  • alkenyl 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 double bonds. Unless otherwise defined, the alkenyl group usually contains 2-20 carbon atoms, for example, it can be an alkenyl group with 2-20 carbon atoms, an alkenyl group with 6-20 carbon atoms, or an alkenyl group with 2-12 carbon atoms. Group or alkenyl of 2-6 carbon atoms.
  • 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.
  • alkylene means a linear or branched divalent saturated hydrocarbon group.
  • the alkylene group may be an alkylene group of 1-20 carbon atoms, an alkylene group of 1-15 carbon atoms, an alkylene group of 1-10 carbon atoms, and an alkylene group of 1-5 carbon atoms.
  • alkylene groups include, for example, methylene, ethane-1,2-diyl ("ethylene”), propane-1,2-diyl, propane-1,3-diyl, butane -1,4-diyl, pentane-1,5-diyl and so on.
  • the alkylene group may be optionally substituted.
  • alkenylene encompasses straight and branched chain alkenylene groups. When an alkenylene group having a specific carbon number is specified, it is expected to encompass all geometric isomers having that carbon number.
  • the alkenylene group may be an alkenylene group of 2-20 carbon atoms, an alkenylene group of 2-15 carbon atoms, an alkenylene group of 2-10 carbon atoms, or an alkenylene group of 2-5 carbon atoms. , 5-20 carbon atoms alkenylene group, 5-15 carbon atoms alkenylene group, or 5-10 carbon atoms alkenylene group.
  • Representative alkenylene groups include, for example, vinylene, propenylene, butenylene, and the like. In addition, alkenylene groups may be optionally substituted.
  • heterocyclic group encompasses aromatic and non-aromatic cyclic groups. Heteroaromatic cyclic group also means heteroaryl.
  • the heteroaromatic ring group and the heteronon-aromatic ring group are C 3 -C 20 heterocyclic groups including at least one heteroatom, C 3 -C 150 heterocyclic groups, C 3 -C 10 Heterocyclic group, C 5 -C 20 heterocyclic group, C 5 -C 10 heterocyclic group, C 3 -C 6 heterocyclic group.
  • morpholinyl for example, morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like.
  • the heterocyclic group may be optionally substituted.
  • aryl encompasses 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 be a C 6 -C 50 aryl group, a C 6 -C 40 aryl group, a C 6 -C 30 aryl group, a C 6 -C 20 aryl group, or a C 6 -C 10 aryl group.
  • aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl and naphth-1-yl, naphth-2-yl, and the like. In addition, aryl groups may be optionally substituted.
  • heteroaryl encompasses monocyclic heteroaromatic groups that may include one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, Pyrazine and pyrimidine, etc.
  • heteroaryl also includes polycyclic heteroaromatic systems having two or more rings shared by two adjacent rings (the rings are "fused") in which two atoms are At least one is heteroaryl, and the other ring may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
  • the heteroatom in the heteroaryl group may be O, S, N, Se, etc., for example.
  • the heteroaryl group can be a C 3 -C 50 heteroaryl group, a C 3 -C 40 heteroaryl group, a C 3 -C 30 heteroaryl group, a C 3 -C 20 heteroaryl group or a C 3 -C 10 heteroaryl group .
  • heteroaryl groups may be optionally substituted.
  • dinitrile compound refers to a compound containing two -CN functional groups.
  • heteroatom encompasses O, S, P, N, B or isosteres thereof.
  • halogen encompasses F, Cl, Br, I.
  • substituents When the above-mentioned substituents are substituted, their substituents may be independently selected from the group consisting of halogen, alkyl, alkenyl, and aryl.
  • substituted or “substituted” means that it can be substituted with 1 or more (eg, 2, 3) substituents.
  • each component is based on the total weight of the electrolyte.
  • the present application provides an electrolyte solution comprising a compound of formula I and a carboxylate compound:
  • R 11 , R 12 , R 13 , and R 14 are each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted Or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 3-20 heterocyclic group, substituted or unsubstituted C 6-20 aryl, Substituted or unsubstituted C 6-20 heteroaryl or -R 0 -OR group, substituted or unsubstituted sultone, substituted or unsubstituted sulfite lactone, substituted or unsubstituted sulfuric lactone, Wherein the heteroatom in the heterocyclic group is selected from at least one of O, S, N or P; or R 11 and R 12 together with the carbon atoms to which they are connected form a 5
  • R 0 is selected from C 1-6 alkylene
  • R is selected from sulfone, methylsulfone, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted Or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 6-20 heteroaryl;
  • R 11 , R 12 , R 13 , R 14 , and R are each independently substituted, the substituent is selected from halogen, cyano, sulfone, methylsulfone, C 1-20 alkyl, C 3-20 ring Alkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl, C 6-20 heteroaryl, or any combination thereof.
  • R 11 , R 12 , R 13 and R 14 are each independently selected from the following groups:
  • R11 and R12 are connected with the carbon atom to which they are connected to form
  • the weight percentage of the compound of formula I is a wt%, and a is 0.001-5. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the compound of formula I is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt% %, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or these
  • the content of the compound of formula I within this range can form a better protective film, and can more effectively prevent the side reaction of the electrolyte with the positive electrode or the negative electrode.
  • the compound of formula I includes or is selected from at least one of the following compounds:
  • the combination of the compound of formula I and the fluorocarboxylate can give full play to the stability of the organic protective film and the oxidation resistance of the electrolyte, and can effectively improve the hot box and overcharge performance.
  • the compound of formula I and the fluorocarboxylic acid ester work together to improve the oxidation resistance of the electrolyte system, which is more conducive to the film formation of the additives on the positive and negative electrodes, which is effective Protect the active material; as the temperature increases, the protection of the active material by the organic protective film will gradually weaken.
  • the combination of the compound of formula I and the fluorocarboxylic acid ester can effectively reduce the chemical heat generation and improve the safety performance of the electrochemical device.
  • the carboxylate compound includes or is selected from a compound of formula II:
  • R 21 and R 22 are each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2 -20 alkenyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 6-20 heteroaryl;
  • R 21 and R 22 are each independently substituted, the substituent is selected from halogen, cyano, C 1-20 alkyl, C 3-20 cycloalkyl, C 1-20 alkoxy, C 2-20 alkene Group, C 6-20 aryl group or any combination thereof;
  • the weight percentage of the carboxylate compound is bwt%, and b is 0.05-75. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the carboxylate compound is 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 10wt%, 15wt% %, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt% or a range of any two of these values . When the carboxylate content is within this range, the electrochemical device has better overcharge performance and hot box performance.
  • the carboxylate compound includes or is selected from at least one of the following compounds:
  • the electrolyte further includes a compound of formula III:
  • M is selected from one of C and Si;
  • R 31 , R 32 , and R 33 are each independently selected from substituted or unsubstituted C 1 -C 20 alkylene, substituted or unsubstituted C 2 -C 20 alkenylene, -R 35 -SR 36 -or- R 37 -OR 38 -, R 35 , R 36 , R 37 and R 38 are each independently a single bond, substituted or unsubstituted C 1 -C 20 alkylene or substituted or unsubstituted C 2 -C 20 alkylene Alkenyl
  • R 34 is selected from H, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 2 -C 20 alkenyl;
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 are each independently substituted, the substituents are selected from halogen, cyano, C 1-20 alkyl, C 3- 20 cycloalkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl, or any combination thereof.
  • the combined action of the compound of formula I, the carboxylate compound and the compound of formula III can further improve the overcharge performance of the electrochemical device and at the same time improve the high temperature storage expansion problem of the electrochemical device.
  • the detailed mechanism of this effect is not clear, it can be considered as follows: the combined action of the compound of formula I, the carboxylate compound and the compound of formula III can further reduce the risk of electrolyte oxidation, while improving the protection of the positive electrode and reducing the active material of the positive electrode.
  • the direct contact between the interface and the electrolyte can reduce the flatulence caused by the contact between the electrolyte and the positive electrode active material during high-temperature storage.
  • the weight percentage of the compound of formula III is 0.01 wt% to 5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the compound of formula III is 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or a range composed of any two of these values. If the weight percentage of the compound of formula III is within this range, better overcharge performance and better high-temperature storage performance can be obtained.
  • the compound of formula III includes or is selected from at least one of the following compounds:
  • the electrolyte further includes a lithium salt additive
  • the lithium salt additive includes at least one of the following lithium salts: LiPO 2 F 2 , lithium bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl) Lithium imide, lithium bisoxalate borate, lithium tetrafluorophosphate oxalate, lithium difluorooxalate borate or lithium hexafluorocesium oxide.
  • the weight percentage of the lithium salt additive is 0.001 wt% to 5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the lithium salt additive is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt% , 1.5wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or any two of these values.
  • the electrolyte further includes a dinitrile compound. Due to the small steric hindrance of the dinitrile compound, the film formation defect of the compound of formula III can be compensated to strengthen the interface protection of the positive electrode active material.
  • the dinitrile compound includes, but is not limited to: succinonitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1 ,7-dicyanoheptane, 1,8-dicyanooctane, 1,9-dicyanononane, 1,10-dicyanodecane, 1,12-dicyanododecane, Tetramethylsuccinonitrile, 2-Methylglutaronitrile, 2,4-Dimethylglutaronitrile, 2,2,4,4-Tetramethylglutaronitrile, 1,4-Dicyanopentane , 1,4-dicyanopentane, 2,5-dimethyl-2,5-hexane dicarbonitrile, 2,6-dicyanoheptane, 2,7-dicyanooctane, 2 , 8-Dicyanononane, 1,6-dicyan
  • the weight percentage of the dinitrile compound is 0.1 wt% to 15 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not less than 0.1 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not less than 0.5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not less than 2 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not less than 4 wt%.
  • the weight percentage of the dinitrile compound is not more than 15 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not more than 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the dinitrile compound is not more than 8 wt%.
  • the electrolyte further includes a cyclic ether.
  • Cyclic ethers can simultaneously form films on the positive and negative electrodes, reducing the reaction between the electrolyte and the active material.
  • the cyclic ether includes, but is not limited to: tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 2-methyl 1,3-dioxolane, 4-methyl Group 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxypropane.
  • the weight percentage of the cyclic ether is 0.1 wt% to 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the cyclic ether is not less than 0.1 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the cyclic ether is not less than 0.5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the cyclic ether is not more than 2 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the cyclic ether is not more than 5 wt%.
  • the electrolyte further includes chain ether.
  • chain ethers include, but are not limited to: dimethoxymethane, 1,1-dimethoxyethane, 1,2-dimethoxyethane, diethoxymethane, 1 , 1-diethoxyethane, 1,2-diethoxyethane, ethoxymethoxymethane, 1,1-ethoxymethoxyethane, 1,2-ethoxymethane Oxyethane.
  • the weight percentage of the chain ether is 0.1 wt% to 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the chain ether is not less than 0.5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the chain ether is not less than 2 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the chain ether is not less than 3 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the chain ether is not more than 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the chain ether is not more than 5 wt%.
  • the electrolyte further includes a phosphorus-containing organic solvent.
  • the phosphorus-containing organic solvent includes, but is not limited to: trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, phosphoric acid Ethylene ethyl, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphate, tris(2, 2,3,3,3-pentafluoropropyl) ester.
  • the weight percentage of the phosphorus-containing organic solvent is 0.1 wt% to 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the phosphorus-containing organic solvent is not less than 0.1 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the phosphorus-containing organic solvent is not less than 0.5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the phosphorus-containing organic solvent is not more than 2 wt%.
  • the weight percentage of the phosphorus-containing organic solvent is not more than 3 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the phosphorus-containing organic solvent is not more than 5 wt%.
  • the electrolyte further includes an aromatic fluorine-containing solvent.
  • the aromatic fluorine-containing solvent can quickly form a film to protect the active material, and the fluorine-containing substance can improve the infiltration performance of the electrolyte to the active material.
  • the aromatic fluorine-containing solvent includes, but is not limited to: fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, and trifluoromethylbenzene.
  • the weight percentage of the aromatic fluorine-containing solvent is about 0.1 wt% to 10 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the aromatic fluorine-containing solvent is not less than 0.5 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the aromatic fluorine-containing solvent is not less than 2 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the aromatic fluorine-containing solvent is not more than 4 wt%. In some embodiments, based on the total weight of the electrolyte, the weight percentage of the aromatic fluorine-containing solvent is not more than 8 wt%.
  • the electrolyte used in the electrolyte of the embodiment of the present application may be an electrolyte known in the prior art.
  • the electrolyte includes, but is not limited to: inorganic lithium salts, such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiSbF 6 , LiSO 3 F, LiN(FSO 2 ) 2 etc.; fluorine-containing organic lithium salts, such as LiCF 3 SO 3 , LiN(FSO 2 )(CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2.
  • inorganic lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiSbF 6 , LiSO 3 F, LiN(FSO 2 ) 2 etc.
  • fluorine-containing organic lithium salts such as LiCF 3 SO 3 , LiN(FSO 2 )(CF 3 SO 2 ),
  • LiBF 2 (CF 3 ) 2 LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (CF 3 SO 2 ) 2 , LiBF 2 (C 2 F 5 SO 2 ) 2 ; lithium salt containing dicarboxylic acid complex
  • the above-mentioned electrolytes may be used singly, or two or more of them may be used simultaneously.
  • the electrolyte includes a combination of LiPF 6 and LiBF 4.
  • the electrolyte includes a combination of an inorganic lithium salt such as LiPF 6 or LiBF 4 and a fluorine-containing organic lithium salt such as LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , and LiN(C 2 F 5 SO 2 ) 2 .
  • the concentration of the electrolyte is in the range of 0.8-3 mol/L, for example, in the range of 0.8-2.5 mol/L, in the range of 0.8-2 mol/L, in the range of 1-2 mol/L, 0.5- 1.5mol/L, 0.8-1.3mol/L, 0.5-1.2mol/L, and for example 1mol/L, 1.15mol/L, 1.2mol/L, 1.5mol/L, 2mol/L or 2.5mol/L.
  • 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 includes the electrolyte in any of the above-mentioned embodiments of the present application.
  • the electrolyte used in the electrochemical device of the present application is the electrolyte of any of the above-mentioned embodiments in the present application.
  • the electrolyte of the electrochemical device of the present application further includes copper ions, wherein the content of the copper ions is 0.01-50 ppm based on the total weight of the electrolyte. In some embodiments, based on the total weight of the electrolyte, the content of copper ions is 0.01 ppm, 0.05 ppm, 0.1 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 7 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, or a range composed of any two of these values.
  • electrolytic solution used in the electrochemical device of the present application may also include other electrolytic solutions within the scope not departing from the gist 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 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 electrode active material layer can be formed using methods such as vapor deposition method, sputtering method, and plating method.
  • the negative electrode includes lithium metal, for example, a conductive skeleton having a spherical twisted shape and metal particles dispersed in the conductive skeleton are used to form the negative active material layer.
  • the spherical stranded conductive skeleton may have a porosity of 5%-85%.
  • a protective layer may be further provided on the lithium metal negative electrode active material 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, polymers containing ethylene oxide, 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 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 substrates, 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 lithium cobalt oxide (LiCoO 2 ), lithium nickel cobalt manganese (NCM) ternary material, lithium iron phosphate (LiFePO 4 ), lithium manganate (LiMn 2 O 4 ), or their Any combination of.
  • 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, V, Sn, Ge, Ga, B, As, Zr, F, 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 includes Ti element, and based on the total weight of the positive active material layer, the content of Ti element is t ⁇ 10 2 ppm, t is 2-10, and satisfies (a+b)/ t ⁇ 35.
  • t is a range consisting of 2, 3, 4, 5, 6, 7, 8, 9, 10, or any two of these values.
  • (a+b)/t is a range consisting of 35, 30, 25, 20, 15, 10, 15, 10, 5, 1, 0.5, 0.4, 0.3 or any two of these values.
  • 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, 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 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.
  • a surface treatment layer is provided on at least one surface of the substrate layer.
  • the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by a mixed polymer and an inorganic substance.
  • the thickness of the substrate layer and the surface treatment layer The thickness ratio is 1:1 to 20:1, the thickness of the substrate layer is 4 ⁇ m to 14 ⁇ m, and the thickness of the surface treatment layer is 1 ⁇ m to 5 ⁇ m. .
  • 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 according to the embodiments of the present application can be used to improve the storage impedance, storage capacity retention and cycle at room temperature, high-temperature storage performance, overcharge performance and hot box performance of the battery, 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.
  • a lithium ion battery is taken as an example and combined with specific examples of preparing the electrolyte of the present application and the measurement method of the electrochemical device to illustrate the preparation and performance of the lithium ion battery of the present application.
  • the preparation methods described in this application are only examples, and any other suitable preparation methods are within the scope of this application.
  • the cathode material of this application can be used in other suitable electrochemical devices.
  • Such an electrochemical device 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.
  • ethylene carbonate abbreviated as EC
  • DEC diethyl carbonate
  • PC propylene carbonate
  • carboxylic acid ester compounds are as follows:
  • the positive active material containing Ti element lithium cobalt oxide (molecular formula is LiCoO 2 ), acetylene black, binder polyvinylidene fluoride (abbreviated as PVDF) in a weight ratio of 96:2:2 in an appropriate amount of N-methylpyrrolidone (Abbreviated as NMP) Fully stir and mix in the solvent to form a uniform positive electrode slurry; coat the slurry on the positive electrode current collector Al foil, dry and cold press to obtain the positive electrode active material layer, and then cut the sheet , Weld the tabs to obtain the positive electrode.
  • the positive electrode active material lithium cobalt oxide contains Ti element. Unless otherwise specified, in the following examples and comparative examples, the content of Ti element is 400 ppm based on the total weight of the positive electrode active material layer.
  • the following example illustrates the preparation method of the positive electrode active material lithium cobalt oxide with a Ti element content of 400 ppm based on the total weight of the positive electrode active material layer:
  • CoCl 2 and TiCl 4 are respectively configured as aqueous solutions, and the molar ratio of the active material is 1:n( 0 ⁇ n ⁇ 0.00081787), and add NH 3 ⁇ HCO 3 solution to adjust the pH of the mixture to 10.5 to obtain a precipitated material.
  • the obtained precipitation material was calcined at 400° C. for 5 hours to obtain Co 3 O 4 containing Ti element. After the obtained Co 3 O 4 and Li 2 CO 3 are uniformly mixed in a molar ratio of 2:3.15, they are calcined at a temperature of 1000° C.
  • LiCoO 2 molar ratio 1: (0.00081787-n) mixing ratio of TiO 2 was added, the mixed materials sintered at 800 °C 8h, a lithium cobaltate positive electrode active material containing Ti element (formula LiCoO 2 ).
  • SBR binder styrene butadiene rubber
  • CMC thickener sodium carboxymethyl cellulose
  • Isolation membrane a polyethylene (PE) porous polymer film with a thickness of 7.5 ⁇ m-8.5 ⁇ m is used as the substrate, and the Al 2 O 3 particle layer is on the substrate, and the thickness of the Al 2 O 3 particle layer is 2 ⁇ m-4 ⁇ m.
  • PE polyethylene
  • Preparation of lithium-ion battery stack the positive electrode, separator film, and negative electrode in order, so that the separator film is located between the positive electrode and the negative electrode for isolation, and then wound, placed in the outer packaging foil, and prepared the above
  • the electrolyte solution is injected into the dried battery, and the preparation of the lithium-ion battery is completed through the steps of vacuum packaging, standing, forming, and shaping.
  • the electrolyte of a lithium ion battery contains Cu ions. Unless otherwise specified, the content of Cu ions in the following examples and comparative examples is 4 ppm.
  • the thickness of the battery is recorded as a 1 .
  • the thickness after 21 days of testing is recorded as b 1 , and the calculation formula for the thickness expansion rate of the battery: (b 1 -a 1 )/a 1 ⁇ 100%.
  • the solution is evaporated to 1ml to 2ml, remove the digestion tank and cool it to room temperature, rinse the digestion tank 3 times with ultrapure water, pour the liquid into a 50ml plastic volumetric flask after washing, and shake it well after constant volume.
  • a plasma emission spectrometer (ICP) was used to test the sample using the standard curve method, and the concentration of the test sample was recorded as p 1 g/ml.
  • the Cu ion calculation result is: (p 1 ⁇ 50)/c.
  • DMC dosage dimethyl carbonate, purity ⁇ 99.99%
  • Table 1-2 shows the test results of the overcharge test and the hot box test of the lithium ion batteries in Examples 1.1-1.19 and Comparative Examples 1.1-1.4.
  • Example 1.11 and Example 3.1 to Example 3.7 Prepare the electrolyte and lithium ion batteries of Example 1.11 and Example 3.1 to Example 3.7 according to the above preparation method, wherein the contents of the compound of formula I, carboxylate compound, and lithium salt additives in the electrolyte are shown in Table 3-1 .
  • Table 3-1 also shows the test results of the hot box test and storage impedance test of Example 1.11 and Examples 3.1-3.7.
  • Example 1.11 and Examples 4.1-4.9 Prepare the electrolytes and lithium ion batteries of Example 1.11 and Examples 4.1-4.9 according to the above preparation method, wherein the content of related substances in the electrolyte is shown in Table 4-1.
  • Table 4-1 also shows the overcharge test and storage impedance test results of the lithium-ion batteries in Example 1.11 and Examples 4.1-4.9.
  • the battery after injection will be left at a high temperature.
  • the electrolyte in the lithium ion battery will participate in some chemical reactions during this process to dissolve the trace Cu metal impurities in the negative electrode of the lithium ion battery and the trace amount of Cu. Ions will enhance the conductivity of the electrolyte, thereby achieving a reduction in impedance. From the test results of Examples 4.1-4.9 and Example 1.11, it can be seen that the electrolyte containing the compound of formula I and the carboxylate compound containing an appropriate amount of Cu ions can significantly reduce the storage impedance of the lithium ion battery.
  • Example 1.11 and Examples 5.1-5.10 Prepare the electrolytes and lithium ion batteries of Example 1.11 and Examples 5.1-5.10 according to the above preparation method.
  • Table 5-1 shows the content of related substances in the electrolytes of Example 1.11 and Examples 5.1-5.10, the Ti element content in the positive electrode active material layer, and the hot box test results.
  • the positive electrode active material contains Ti element, which not only enhances the interface contact between the positive electrode active material and the electrolyte, but also stabilizes the oxygen free radicals of the positive electrode active material, reduces the contact between oxygen radicals and the electrolyte, and reduces the positive electrode active material and the electrolyte. Oxygen free radicals will accelerate the catalytic oxidation of electrolyte, especially during safety testing.
  • This application adopts the combination of the compound of formula I and the fluorocarboxylic acid ester, which has a certain protective effect on the positive electrode interface, and its own oxidation resistance will be enhanced. Combined with the doping of Ti element, the reaction of the positive electrode active material and the electrolyte is further reduced. So as to achieve the effect of improving the safety of the hot box. It can be seen from the test results of Example 1.11 and Examples 5.1-5.10 that with the increase of Ti doping content, the improvement effect of the hot box is significant.
  • Table 6-2 shows the test results of the overcharge test, hot box test, storage expansion test, and storage impedance test of Example 1.11 and Examples 6.1-6.3.
  • 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 “exemplified”, 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

本申请涉及电解液和使用其的电化学装置。本申请的电解液包含式（I）的化合物和羧酸酯化合物。由本申请电解液制备的电化学装置具有降低的存储阻抗以及改善的存储胀气现象以及过充性能和热箱性能。

Description

电解液和使用其的电化学装置 技术领域
本申请涉及电化学装置技术领域，且更具体来说涉及一种电解液和使用其的电化学装置。
背景技术
高能量密度是锂离子电池发展的一个比较大的趋势。随着近几年5G的迅速发展以及智能设备不断向轻薄和小型化发展，留给电池的体积越来越少，需要电池提供的能量却越来越高。高电压为能量密度的提升提供了比较有效的方案和途径，但高电压伴随而来的是严峻的安全问题。解决安全问题成为锂离子电池向高电压发展必经之路。
本申请提供了一种电解液和使用其的电化学装置，以解决上述问题。
发明内容
本申请实施例提供了一种电解液和使用其的电化学装置，以试图在至少某种程度上解决至少一种存在于相关领域中的问题。本申请实施例还提供了使用该电解液的电化学装置以及电子装置。
在本申请的一方面，本申请提供了一种电解液，其包含式I的化合物和羧酸酯化合物：
Figure PCTCN2020073221-appb-000001
其中R 11、R 12、R 13、R 14各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 3-20杂环基团、取代或未取代的C 6-20芳基、取代或未取代的C 6-20杂芳基或-R 0-O-R基团、取代或未取代的磺酸内酯、取代或未取代的亚硫酸内酯、取代或未 取代的硫酸内酯，其中所述杂环基团中的杂原子选自O、S、N或P中的至少一种；或R 11和R 12与其所连接的碳原子一起形成5-10元环状结构，其中所述环状结构任选地含有杂原子，所述杂原子选自O、S、N或P中的至少一种；
其中R 0选自C 1-6亚烷基，R选自砜基、甲基砜基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
其中R 11、R 12、R 13、R 14、R各自独立地经取代时，取代基选自卤素、氰基、砜基、甲基砜基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基、C 6-20杂芳基或其任意组合。
在一些实施例中，所述R 11、R 12、R 13、R 14各自独立地选自以下基团：
H、
Figure PCTCN2020073221-appb-000002
Figure PCTCN2020073221-appb-000003
R 11和R 12与其所连接的碳原子一起连接形成
Figure PCTCN2020073221-appb-000004
在一些实施例中，基于所述电解液的总重量，所述式I化合物的重量百分比为a wt％，a为0.001-5。
在一些实施例中，所述式I化合物包括如下化合物中的至少一种：
Figure PCTCN2020073221-appb-000005
Figure PCTCN2020073221-appb-000006
在一些实施例中，所述羧酸酯化合物包括式II化合物：
Figure PCTCN2020073221-appb-000007
其中R 21、R 22各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
其中R 21、R 22各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合；
在一些实施例中，基于所述电解液的总重量，所述羧酸酯化合物的重量百分比为b wt％，b为0.05-75。
在一些实施例中，所述羧酸酯化合物包括如下化合物中的至少一种：
Figure PCTCN2020073221-appb-000008
在一些实施例至，所述电解液进一步包括式III化合物：
Figure PCTCN2020073221-appb-000009
其中，M选自C、Si中的一种；
R 31、R 32、R 33各自独立地选自取代或未取代的C 1-C 20亚烷基、取代或未取代的C 2-C 20亚烯基、-R 35-S-R 36-或-R 37-O-R 38-，R 35、R 36、R 37和R 38各自独立的为单键、取代或未取代的C 1-C 20亚烷基或取代或未取代的C 2-C 20亚烯基；
R 34选自H、取代或未取代的C 1-C 20烷基、取代或未取代的C 2-C 20烯基；
其中R 31、R 32、R 33、R 34、R 35、R 36、R 37和R 38各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合；
在一些实施例中，基于所述电解液的总重量，所述式III化合物的重量百分比为0.01wt％-5wt％。
在一些实施例中，所述式III化合物包括如下化合物中的至少一者：
Figure PCTCN2020073221-appb-000010
在一些实施例中，所述电解液进一步包含锂盐添加剂，所述锂盐添加剂包括如下锂盐中的至少一者：LiPO 2F 2、双三氟甲烷磺酰亚胺锂、双(氟磺酰)亚胺锂、双草酸硼酸锂、四氟磷酸草酸锂、二氟草酸硼酸锂或六氟铯酸锂；
在一些实施例中，基于所述电解液的总重量，所述锂盐添加剂的重量百分比为0.001wt％-5wt％。
在本申请的另一方面，本申请提供一种电化学装置，其包括正极，所述正极包括正极活性材料层，所述正极活性材料层包含正极活性材料；和根据本申请的实施例所述的电解液。
在一些实施例中，所述电化学装置的电解液中进一步包含铜离子，基于所述电解液的总重量，所述铜离子的含量为0.01ppm-50ppm。
在一些实施例中，所述正极活性材料中包含Ti元素，基于所述正极活性材料层的总重量，所述Ti元素含量为t×10 2ppm，t为2-10，并且满足(a+b)/t≤35。
在本申请的另一方面，本申请提供一种电子装置，其包括根据本申请的实施例所述的电化学装置。
由本申请电解液制备的锂离子电池具有降低的存储阻抗以及改善的存储胀气现象以及过充性能和热箱性能。
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和显示，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的限制。
在具体实施方式及权利要求书中，由术语“中的一者”、“中的一个”、“中的一种”或其他相似术语所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”、“中的至少一个”、“中的至少一种”或其他相似术语所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”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”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。
如本文所用，术语“烷基”预期是具有1至20个碳原子的直链饱和烃结构。“烷基”还预期是具有3至20个碳原子的支链或环状烃结构。例如，烷基可为1-20个碳原子的烷基、1-10个碳原子的烷基、1-5个碳原子的烷基、5-20个碳原子的烷基、5-15个碳原子的烷基或5-10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。
如本文所用，术语“环烷基”涵盖环状烷基。环烷基可为3-20个碳原子的环烷基、6-20个碳原子的环烷基、3-12个碳原子的环烷基、3-6个碳原子的环烷基。例如，环烷基可为环丙基、环丁基、环戊基、环己基等。另外，环烷基可以是任选地被取代的。
如本文所用，术语“烷氧基”是指L-O-基团，其中L为烷基。例如，烷氧基可为1-20个碳原子的烷氧基、1-12个碳原子的烷氧基、1-5个碳原子的烷氧基、5-20个碳原子的烷氧基、5-15个碳原子的烷氧基或5-10个碳原子的烷氧基。另外，烷氧基可以是任选地被取代的。
如本文所用，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2-20个碳原子，例如可以为2-20个碳原子的烯基、6-20个碳原子的烯基、2-12个碳原子的烯基或2-6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。
如本文所用，术语“亚烷基”意指直链或具支链的二价饱和烃基。例如，亚烷基可为1-20个碳原子的亚烷基、1-15个碳原子的亚烷基、1-10个碳原子的亚烷基、1-5个碳原子的亚烷基、5-20个碳原子的亚烷基、5-15个碳原子的亚烷基或5-10个碳原子的亚烷基。代表性亚烷基包括(例如)亚甲基、乙烷-1，2-二基(“亚乙基”)、丙烷-1，2-二基、 丙烷-1，3-二基、丁烷-1，4-二基、戊烷-1，5-二基等等。另外，亚烷基可以是任选地被取代的。
如本文所用，术语“亚烯基”涵盖直链和支链亚烯基。当指定具有具体碳数的亚烯基时，预期涵盖具有该碳数的所有几何异构体。例如，亚烯基可为2-20个碳原子的亚烯基、2-15个碳原子的亚烯基、2-10个碳原子的亚烯基、2-5个碳原子的亚烯基，5-20个碳原子的亚烯基、5-15个碳原子的亚烯基、或5-10个碳原子的亚烯基。代表性亚烯基包括(例如)亚乙烯基、亚丙烯基、亚丁烯基等。另外，亚烯基可以是任选地被取代的。
如本文所用，术语“杂环基团”涵盖芳香族和非芳香族环状基团。杂芳香族环状基团还意指杂芳基。在一些实施例中，杂芳香族环基团和杂非芳香族环基团为包括至少一个杂原子的C 3-C 20杂环基、C 3-C 150杂环基、C 3-C 10杂环基、C 5-C 20杂环基、C 5-C 10杂环基、C 3-C 6杂环基。例如吗啉基、哌啶基、吡咯烷基等，以及环醚，例如四氢呋喃、四氢吡喃等。另外，杂环基可以是任选地被取代的。
如本文所用，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C 6-C 50芳基、C 6-C 40芳基、C 6-C 30芳基、C 6-C 20芳基或C 6-C 10芳基。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。
如本文所用，术语“杂芳基”涵盖可以包括一到三个杂原子的单环杂芳香族基团，例如吡咯、呋喃、噻吩、咪唑、噁唑、噻唑、三唑、吡唑、吡啶、吡嗪和嘧啶等。术语杂芳基还包括具有其中两个原子为两个邻接环(所述环是“稠合的”)共用的两个或更多个环的多环杂芳香族系统，其中所述环中的至少一者是杂芳基，其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。杂芳基中的杂原子例如可以为O、S、N、Se等。例如杂芳基可为C 3-C 50杂芳基、C 3-C 40杂芳基、C 3-C 30杂芳基、C 3-C 20杂芳基或C 3-C 10杂芳基。另外，杂芳基可以是任选地被取代的。
如本文所用，术语“二腈化合物”是指含有二个-CN官能团的化合物。
如本文所用，术语“杂原子”涵盖O、S、P、N、B或其电子等排体。
如本文所用，术语“卤素”涵盖F、Cl、Br、I。
当上述取代基经取代时，它们的取代基可各自独立地选自由以下组成的群组：卤素、 烷基、烯基、芳基。
如本文所用，术语“取代”或“经取代”是指可以经1个或多个(例如2个、3个)取代基取代。
如本文中所使用，各组分的含量均为基于电解液的总重量得到的。
一、电解液
在一些实施例中，本申请提供了一种电解液，其包含式I的化合物和羧酸酯化合物：
Figure PCTCN2020073221-appb-000011
其中R 11、R 12、R 13、R 14各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 3-20杂环基团、取代或未取代的C 6-20芳基、取代或未取代的C 6-20杂芳基或-R 0-O-R基团、取代或未取代的磺酸内酯、取代或未取代的亚硫酸内酯、取代或未取代的硫酸内酯，其中所述杂环基团中的杂原子选自O、S、N或P中的至少一种；或R 11和R 12与其所连接的碳原子一起形成5-10元环状结构，其中所述环状结构任选地含有杂原子，所述杂原子选自O、S、N或P中的至少一种；所述环状结构可以是饱和或不饱和结构。
其中R 0选自C 1-6亚烷基，R选自砜基、甲基砜基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
其中R 11、R 12、R 13、R 14、R各自独立地经取代时，取代基选自卤素、氰基、砜基、甲基砜基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基、C 6-20杂芳基或其任意组合。
在一些实施例中，所述R 11、R 12、R 13、R 14各自独立地选自以下基团：
H、
Figure PCTCN2020073221-appb-000012
Figure PCTCN2020073221-appb-000013
R11和R12与其所连接的碳原子一起连接形成
Figure PCTCN2020073221-appb-000014
在一些实施例中，基于所述电解液的总重量，所述式I化合物的重量百分比为a wt％，a为0.001-5。在一些实施例中，基于所述电解液的总重量，所述式I化合物的重量百分比为0.001wt％、0.005wt％、0.01wt％、0.05wt％、0.1wt％、0.15wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、1wt％、2wt％、3wt％、3.5wt％、4wt％、4.5wt％、5wt％或这些数值中任意两者组成的范围。所述式I化合物的含量在此范围内能够形成更加良好的保护膜，能够更加有效地阻止电解液与正极或负极的副反应。
在一些实施例中，所述式I化合物包括或选自如下化合物中的至少一种：
Figure PCTCN2020073221-appb-000015
式I化合物和氟代羧酸酯的组合能够充分发挥有机保护膜的稳定性和电解液的耐氧化性，能够有效改善热箱和过充性能。得到此效果的详细作用机理虽然不明，但可考虑如下：式I化合物与氟代羧酸酯共同作用，提升了电解液体系的耐氧化性，更有利于添加剂在正负极成膜，从而有效保护活性材料；随着温度的升高，有机保护膜对活性材料的保护会逐渐减弱。式I化合物与氟代羧酸酯共同作用，会有效降低化学产热，提升电化学装置的安全性能。
在一些实施例中，所述羧酸酯化合物包括或选自式II化合物：
Figure PCTCN2020073221-appb-000016
其中R 21、R 22各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
其中R 21、R 22各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合；
在一些实施例中，基于所述电解液的总重量，所述羧酸酯化合物的重量百分比为为b wt％，b为0.05-75。在一些实施例中，基于所述电解液的总重量，所述羧酸酯化合物的重量百分比为0.05wt％、0.1wt％、0.5wt％、1wt％、3wt％、5wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、55wt％、60wt％、65wt％、70wt％、75wt％或这些数值中任意两者组成的范围。当所述羧酸酯含量在此范围内，电化学装置具有更好的过充性能和热箱性能。
在一些实施例中，所述羧酸酯化合物包括或选自如下化合物中的至少一种：
Figure PCTCN2020073221-appb-000017
在一些实施例中，所述电解液进一步包括式III化合物：
Figure PCTCN2020073221-appb-000018
其中，M选自C、Si中的一种；
R 31、R 32、R 33各自独立地选自取代或未取代的C 1-C 20亚烷基、取代或未取代的C 2-C 20亚烯基、-R 35-S-R 36-或-R 37-O-R 38-，R 35、R 36、R 37和R 38各自独立的为单键、取代或未取代的C 1-C 20亚烷基或取代或未取代的C 2-C 20亚烯基；
R 34选自H、取代或未取代的C 1-C 20烷基、取代或未取代的C 2-C 20烯基；
其中R 31、R 32、R 33、R 34、R 35、R 36、R 37和R 38各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合。
式I化合物、羧酸酯化合物和式III化合物共同作用可以进一步改善电化学装置的过充性能，同时改善电化学装置的高温存储膨胀问题。得到此效果的详细作用机理虽然不明，但可考虑如下：式I化合物、羧酸酯化合物和式III化合物共同作用可以进一步降低电解液被氧化的风险，同时提高对正极的保护，降低正极活性材料界面与电解液的直接接触，因此可以降低高温存储时电解液与正极活性材料接触带来的胀气。
在一些实施例中，基于所述电解液的总重量，所述式III化合物的重量百分比为0.01wt％-5wt％。在一些实施例中，基于所述电解液的总重量，所述式III化合物的重量百分比为0.01wt％、0.05wt％、0.1wt％、0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％、4wt％、4.5wt％、5wt％或这些数值中任意两者组成的范围。式III化合物的重量百分比在此范围内能够得到更好的过充性能以及更好的高温存储性能。
在一些实施例中，所式III化合物包括或选自如下化合物中的至少一者：
Figure PCTCN2020073221-appb-000019
在一些实施例中，所述电解液进一步包含锂盐添加剂，所述锂盐添加剂包括如下锂盐中的至少一者：LiPO 2F 2、双三氟甲烷磺酰亚胺锂、双(氟磺酰)亚胺锂、双草酸硼酸锂、四氟磷酸草酸锂、二氟草酸硼酸锂或六氟铯酸锂。
在一些实施例中，基于所述电解液的总重量，所述锂盐添加剂的重量百分比为0.001wt％-5wt％。在一些实施例中，基于所述电解液的总重量，所述锂盐添加剂的重量百分比为0.001wt％、0.005wt％、0.01wt％、0.05wt％、0.1wt％、0.5wt％、1wt％、1.5wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％、4wt％、4.5wt％、5wt％或这些数值中任意两者组成的范围。
在一些实施例中，所述电解液进一步包括二腈化合物。二腈化合物由于空间位阻较小，可以弥补式III化合物的成膜缺陷从而加强对正极活性材料的界面保护。
在一些实施例中，所述二腈化合物包括，但不限于：丁二腈、戊二腈、己二腈、1，5-二氰基戊烷、1，6-二氰基己烷、1，7-二氰基庚烷、1，8-二氰基辛烷、1，9-二氰基壬烷、1，10-二氰基癸烷、1，12-二氰基十二烷、四甲基丁二腈、2-甲基戊二腈、2，4-二甲基戊二腈、2，2，4，4-四甲基戊二腈、1，4-二氰基戊烷、1，4-二氰基戊烷、2，5-二甲基-2，5-己烷二碳腈、2，6-二氰基庚烷、2，7-二氰基辛烷、2，8-二氰基壬烷、1，6-二氰基癸烷、1，2-二氰基苯、1，3-二氰基苯、1，4-二氰基苯、3，5-二氧杂-庚二腈、1，4-二(氰基乙氧基)丁烷、乙二醇二(2-氰基乙基)醚、二乙二醇二(2-氰基乙基)醚、三乙二醇二(2-氰基乙基)醚、四乙二醇二(2-氰基乙基)醚、3，6，9，12，15，18-六氧杂二十烷酸二腈、1，3-二(2-氰基乙氧基)丙烷、1，4-二(2-氰基乙氧基)丁烷、1，5-二(2-氰基乙氧基)戊烷和乙二醇二(4-氰基丁基)醚、1，4-二氰基-2-丁烯、1，4-二氰基-2-甲基-2-丁烯、1，4-二氰基-2-乙基-2-丁烯、1，4-二氰基-2，3-二甲基-2-丁烯、1，4-二氰基-2，3-二乙基-2-丁烯、1，6-二氰基-3-己烯、1，6-二氰基-2-甲基-3-己烯、1，6-二氰基-2-甲基-5-甲基-3-己烯。
在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比为0.1wt％-15wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不小于0.1wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不小于0.5wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不小于2wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不小于4wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不大于15wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不大于10wt％。在一些实施例中，基于所述电解液的总重量，所述二腈化合物的重量百分比不大于8wt％。
在一些实施例中，所述电解液进一步包括环状醚。环状醚可以同时在正负极成膜，降低电解液与活性材料的反应。
在一些实施例中，所述环状醚包括，但不限于：四氢呋喃、2-甲基四氢呋喃、1，3-二氧戊环、2-甲基1，3-二氧戊环、4-甲基1，3-二氧戊环、1，3-二氧六环、1，4-二氧六环、二甲氧基丙烷。
在一些实施例中，基于所述电解液的总重量，所述环状醚的重量百分比为0.1wt％-10wt％。在一些实施例中，基于所述电解液的总重量，所述环状醚的重量百分比不小于0.1wt％。在一些实施例中，基于所述电解液的总重量，所述环状醚的重量百分比不小于0.5wt％。在一些实施例中，基于所述电解液的总重量，所述环状醚的重量百分比不大于2wt％。在一些实施例中，基于所述电解液的总重量，所述环状醚的重量百分比不大于5wt％。
在一些实施例中，所述电解液进一步包括链状醚。在一些实施例中，链状醚包括，但不限于：二甲氧基甲烷、1，1-二甲氧基乙烷、1，2-二甲氧基乙烷、二乙氧基甲烷、1，1-二乙氧基乙烷、1，2-二乙氧基乙烷、乙氧基甲氧基甲烷、1，1-乙氧基甲氧基乙烷、1，2-乙氧基甲氧基乙烷。
在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比为0.1wt％-10wt％。在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比不小于0.5wt％。在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比不小于2wt％。在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比不小于3wt％。在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比不大于10wt％。在一些实施例中，基于所述电解液的总重量，所述链状醚的重量百分比不大于5wt％。
在一些实施例中，所述电解液进一步包括含磷有机溶剂。在一些实施例中，所述含磷有机溶剂包括，但不限于：磷酸三甲酯、磷酸三乙酯、磷酸二甲基乙酯、磷酸甲基二乙酯、磷酸亚乙基甲酯、磷酸亚乙基乙酯、磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三苯酯、磷酸三(2，2，2-三氟乙基)酯、磷酸三(2，2，3，3，3-五氟丙基)酯。
在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂的重量百分比为0.1wt％-10wt％。在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂的重量百分比不小于0.1wt％。在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂的重量百分比不小于0.5wt％。在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂的重量百分比不大于2wt％。在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂 的重量百分比不大于3wt％。在一些实施例中，基于所述电解液的总重量，所述含磷有机溶剂的重量百分比不大于5wt％。
在一些实施例中，所述电解液进一步包括芳香族含氟溶剂。芳香族含氟溶剂可以快速成膜，保护活性材料，且含氟物质可以提升电解液对活性材料的浸润性能。在一些实施例中，所述芳香族含氟溶剂包括，但不限于：氟苯、二氟苯、三氟苯、四氟苯、五氟苯、六氟苯、三氟甲基苯。
在一些实施例中，基于所述电解液的总重量，所述芳香族含氟溶剂的重量百分比为约0.1wt％-10wt％。在一些实施例中，基于所述电解液的总重量，所述芳香族含氟溶剂的重量百分比不小于0.5wt％。在一些实施例中，基于所述电解液的总重量，所述芳香族含氟溶剂的重量百分比不小于2wt％。在一些实施例中，基于所述电解液的总重量，所述芳香族含氟溶剂的重量百分比不大于4wt％。在一些实施例中，基于所述电解液的总重量，所述芳香族含氟溶剂的重量百分比不大于8wt％。
二、电解质
本申请实施例的电解液使用的电解质可以为现有技术中已知的电解质，电解质包括、但不限于：无机锂盐，例如LiClO 4、LiAsF 6、LiPF 6、LiBF 4、LiSbF 6、LiSO 3F、LiN(FSO 2) 2等；含氟有机锂盐，例如LiCF 3SO 3、LiN(FSO 2)(CF 3SO 2)、LiN(CF 3SO 2) 2、LiN(C 2F 5SO 2) 2、环状1，3-六氟丙烷二磺酰亚胺锂、环状1，2-四氟乙烷二磺酰亚胺锂、LiN(CF 3SO 2)(C 4F 9SO 2)、LiC(CF 3SO 2) 3、LiPF 4(CF 3) 2、LiPF 4(C 2F 5) 2、LiPF 4(CF 3SO 2) 2、LiPF 4(C 2F 5SO 2) 2、LiBF 2(CF 3) 2、LiBF 2(C 2F 5) 2、LiBF 2(CF 3SO 2) 2、LiBF 2(C 2F 5SO 2) 2；含二羧酸配合物锂盐，例如双(草酸根合)硼酸锂、二氟草酸根合硼酸锂、三(草酸根合)磷酸锂、二氟双(草酸根合)磷酸锂、四氟(草酸根合)磷酸锂等。另外，上述电解质可以单独使用一种，也可以同时使用两种或两种以上。例如，在一些实施例中，电解质包括LiPF 6和LiBF 4的组合。在一些实施例中，电解质包括LiPF 6或LiBF 4等无机锂盐与LiCF 3SO 3、LiN(CF 3SO 2) 2、LiN(C 2F 5SO 2) 2等含氟有机锂盐的组合。在一些实施例中，电解质的浓度在0.8-3mol/L的范围内，例如0.8-2.5mol/L的范围内、0.8-2mol/L的范围内、1-2mol/L的范围内、0.5-1.5mol/L、0.8-1.3mol/L、0.5-1.2mol/L，又例如为1mol/L、1.15mol/L、1.2mol/L、1.5mol/L、2mol/L或2.5mol/L。
三、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一实施例中的电解液。
1、电解液
本申请的电化学装置中使用的电解液为本申请中上述任一实施例的电解液。
在一些实施例中，本申请的电化学装置的电解液进一步包括铜离子，其中基于所述电解液的总重量，所述铜离子的含量为0.01-50ppm。在一些实施例中，基于所述电解液的总重量，所述铜离子的含量为0.01ppm、0.05ppm、0.1ppm、0.5ppm、1ppm、2ppm、3ppm、4ppm、5ppm、7ppm、10ppm、15ppm、20ppm、25ppm、30ppm、35ppm、40ppm、45ppm、50ppm或这些数值中任意两者组成的范围。
此外，本申请的电化学装置中使用的电解液还可包含不脱离本申请的主旨的范围内的其它电解液。
2、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。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。
当负极包括硅碳化合物时，基于负极活性材料总重量，硅∶碳＝1∶10-10∶1，硅碳化合物的中值粒径Dv50为0.1μm-100μm。当负极包括合金材料时，可使用蒸镀法、溅射法、镀敷法等方法形成负极活性物质层。当负极包括锂金属时，例如用具有球形绞状的导电骨架和分散在导电骨架中的金属颗粒形成负极活性物质层。在一些实施例中，球形绞状的导电骨架可具有5％-85％的孔隙率。在一些实施例中，锂金属负极活性物质层上还可设置保护层。
在一些实施例中，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，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。
3、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(LiCoO 2)、锂镍钴锰(NCM)三元材料、磷酸亚铁锂(LiFePO 4)、锰酸锂(LiMn 2O 4)或它们的任意组合。
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、V、Sn、Ge、Ga、B、As、Zr、F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。
在一些实施例中，正极活性材料包含Ti元素，基于所述正极活性材料层的总重量，所述Ti元素含量为t×10 2ppm，t为2-10，并且满足(a+b)/t≤35。
在一些实施例中，t为2、3、4、5、6、7、8、9、10或这些数值中任意两者组成的范围。
在一些实施例中，(a+b)/t为35、30、25、20、15、10、15、10、5、1、0.5、0.4、0.3或这些数值中任意两者组成的范围。
在一些实施例中，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，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。
4、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，基材层的厚度与表面处理层的厚度比为1∶1至20∶1，基材层的厚度为4μm至14μm，表面处理层的厚度为1μm至5μm。。
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。
四、应用
根据本申请实施例的电解液，能够用于提高电池的存储阻抗、常温存储容量保持率及循环、高温存储性能、过充性能和热箱性能，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。
下面以锂离子电池为例并且结合具体的制备本申请电解液的实施例及对电化学装置的测式方式以用于说明本申请锂离子电池的制备及效能，本领域的技术人员将理解，本申请中描述的制备方法仅是实例，其他任何合适的制备方法均在本申请的范围内。
虽然以锂离子电池进行了举例说明，但是本领域技术人员在阅读本申请之后，能够想到本申请的正极材料可以用于其他合适的电化学装置。这样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。特别地，所述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。
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、锂离子电池制备
1)电解液的制备：
在含水量＜10ppm的氩气气氛手套箱中，将碳酸乙烯酯(简写为EC)、碳酸二乙酯(简写为DEC)、碳酸丙烯酯(简写为PC)按照3∶4∶3的重量比混合均匀，再将充分干燥的锂盐LiPF 6溶解于上述混合后的溶剂得到基础电解液，其中基础电解液中LiPF 6的浓度为1mol/L。 在基础电解液中加入如下各表中所示的不同含量的物质得到不同实施例和对比例的电解液。如下描述的电解液中各物质的含量均是基于电解液的总重量计算得到。
式I化合物的实例如下：
Figure PCTCN2020073221-appb-000020
羧酸酯化合物的实例如下：
Figure PCTCN2020073221-appb-000021
式III化合物的实例如下：
Figure PCTCN2020073221-appb-000022
2)正极的制备：
将含有Ti元素的正极活性物质钴酸锂(分子式为LiCoO 2)与乙炔黑、粘结剂聚偏二氟乙烯(简写为PVDF)按重量比96∶2∶2在适量的N-甲基吡咯烷酮(简写为NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料；将此浆料涂覆于正极集流体Al箔上，烘干、冷压，得到正极活性材料层，再经过裁片、焊接极耳，得到正极。其中正极活性物质钴酸锂中含有Ti元素，如无特殊说明，以下实施例和对比例中，基于正极活性材料层的总重量，Ti元素的含量为400ppm。
以下举例说明满足基于正极活性材料层的总重量计算Ti元素含量为400ppm的正极活性物质钴酸锂的制备方法：将CoCl 2和TiCl 4分别配置成水溶液，按照活性物质摩尔比为1∶n(0≤n≤0.00081787)的比例混合，并加入NH 3·HCO 3溶液调节混合物的pH值为10.5，得到沉淀物质。将得到的沉淀物质在400℃煅烧5h，得到含有Ti元素的Co 3O 4。将得到的Co 3O 4和Li 2CO 3按照摩尔比2∶3.15的比例混合均匀之后，在1000℃的温度下煅烧8h得到LiCoO 2。将得到的LiCoO 2按照摩尔比为1∶(0.00081787-n)的配比加入TiO 2混匀，将混匀的物质在800 ℃烧结8h，得到含有Ti元素的正极活性物质钴酸锂(分子式为LiCoO 2)。
3)负极的制备：
将负极活性物质石墨、导电剂乙炔黑、粘结剂丁苯橡胶(简写为SBR)、增稠剂羧甲基纤维素钠(简写为CMC)按照重量比95∶2∶2∶1在适量的去离子水溶剂中充分搅拌混合，使其形成均匀的负极浆料；将此浆料涂覆于负极集流体Cu箔上，烘干、冷压，得到负极活性材料层，再经过裁片、焊接极耳，得到负极。
4)隔离膜：以7.5μm-8.5μm的聚乙烯(PE)多孔聚合物薄膜作为基材，基材上有Al 2O 3颗粒层，Al 2O 3颗粒层厚度为2μm-4μm。
5)锂离子电池的制备：将正极、隔离膜、负极按顺序叠好，使隔离膜处于正极和负极之间起到隔离的作用，然后卷绕，置于外包装箔中，将上述制备好的电解液注入到干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。锂离子电池的电解液中含有Cu离子，如无特殊说明，以下实施例和对比例中Cu离子的含量为4ppm。
2、锂离子电池性能测试方法
1)过充测试：
将电池以0.5C的电流放电至3.0V，休息5分钟，之后以3C的电流充电至6.5V，在6.5V电压下恒压充电1h。不起火、不爆炸即通过测试(pass)。每组测试五只电池，记录通过测试的电池数。
2)热箱测试：
将电池以0.5C的电流放电至3.0V，休息5分钟，之后以0.5C的电流充电至4.4V，4.4V电压下恒压至0.05C。将满充的电池放置在140℃的热箱中，恒温60min。不起火、不爆炸即通过测试(pass)。在高温箱固定位置，每组测试五只电池，记录通过测试的电池数。
3)存储膨胀测试：
将电池在25℃下以0.5C的电流放电至4.4V，再以0.5C的电流充电至4.4V，4.4V下恒压充电至电流为0.05C，使用平板轻压测厚计用700g的压力测试满充时电池的厚度记为a 1。将电池放置到60℃烘箱当中，在60℃存储条件下存储21天(21d)，测试21天之后的厚度记为b 1，电池的厚度膨胀率计算公式：(b 1-a 1)/a 1×100％。
4)存储阻抗测试：
将电池在25℃下以0.5C的电流放电至4.4V，再以0.5C的电流充电至4.4V，4.4V下恒压充电至电流为0.05C，放置到60℃烘箱当中，在60℃存储条件下存储21天，使用电阻率测量仪监控存储之后的电阻数值，并记录。
3、锂离子电池物理化学测试方法
1)Cu离子测试
将电池以0.5C电流放电至2.8V，休息5分钟，以0.05C电流放电至2.8V，休息5分钟，采用0.01C电流放电至2.8V。将放电完成的电池除去外层的铝塑膜。采用离心机将锂离子电池中的电解液离心出来。取离心出来的电解液，将样品置于编好号的消解罐中，使用电子天平称重，精确到0.0001g，记为样品重量为c(c≤10)g。缓慢加入10mL浓HNO 3(质量分数为68％)，将内壁上的样品冲入罐底，并轻轻晃动消解罐。将消解罐外面的水珠用无尘纸擦拭干净，放入赶酸仪中180℃消解20分钟。待溶液蒸至1ml至2ml时，取下消解罐冷却至室温，用超纯水冲洗消解罐3次，冲洗后将液体倒入50ml塑料容量瓶中，定容后摇匀。采用等离子发射光谱仪(ICP)使用标准曲线法对样品进行测试，测试样品的浓度记为p 1g/ml。Cu离子计算结果为：(p 1×50)/c。
2)Ti元素测试
将电池以0.5C电流放电至2.8V，休息5分钟，以0.05C电流放电至2.8V，休息5分钟，采用0.01C电流放电至2.8V，休息5分钟，使用0.01C电流重复放电三次。戴干净的手套将电池拆解，小心地将正极和负极分开，不互相接触。在手套箱中，用高纯的DMC(碳酸二甲酯，纯度≥99.99％)浸泡正极10分钟，然后取出，晾干30分钟。(DMC用量：＞15ml/1540mm 2圆片面积)。在干燥环境中，使用陶瓷刮刀，刮粉＞0.4g，用称量纸包好。使用电子天平称重，精确到0.0001g，记为样品重量为d(d≤0.4)g。缓慢加入10mL浓硝酸与浓盐酸的质量比为1∶1的王水，将内壁上的样品冲入罐底，并轻轻晃动消解罐。将消解罐外面的水珠用无尘纸擦拭干净，组装消解装置，置于微波消解仪中消解。卸下消解罐，用超纯水冲洗盖子3次，冲洗液倒入消解罐中。摇动样品溶液，缓慢倾入漏斗流入容量瓶，并冲洗消解罐3次，定容100ml，摇匀。采用等离子发射光谱仪(ICP)使用标准曲线法对样品进行测试，测试样品的浓度记为p 2g/ml。Ti离子计算结果为：(p 2×100)/d。
A、按照上述制备方法制备实施例1.1-1.19以及对比例1.1-1.4的电解液及锂离子电池，其中电解液中式I化合物和羧酸酯化合物含量如表1-1所示。
表1-1
Figure PCTCN2020073221-appb-000023
其中“-”代表未添加该物质。
表1-2示出了实施例1.1-1.19以及对比例1.1-1.4中锂离子电池的过充测试、热箱测试的测试结果。
表1-2
Figure PCTCN2020073221-appb-000024
Figure PCTCN2020073221-appb-000025
通过实施例1.1-1.19和对比例1.1-1.4的测试结果可以看出，在电解液中同时加入式I化合物和羧酸酯化合物能够显著改善锂离子电池的过充性能和热箱性能。
B、按照上述制备方法制备实施例1.11和实施例2.1-2.12的电解液及锂离子电池，其中电解液中式I化合物、羧酸酯化合物和式III化合物的含量如表2-1所示。表2-1同时示出了实施例1.11和实施例2.1-2.12的锂离子电池的过充测试和存储膨胀测试的测试结果。
表2-1
Figure PCTCN2020073221-appb-000026
其中“-”代表未添加该物质。
通过实施例2.1-2.12与实施例1.11的测试结果可以看出，在含有式I化合物和羧酸酯化合物的电解液中加入式III化合物，可以显著降低锂离子电池的存储膨胀率。原因可能是式I化合物、羧酸酯化合物与式III化合物共同作用可以进一步降低电解液被氧化的风险，同时提高对正极的保护，降低正极活性材料界面与电解液的直接接触，因此可以降低高温存储时电解液与正极活性材料接触带来的胀气。
C、按照上述制备方法制备实施例1.11和实施例3.1-实施例3.7的电解液及锂离子电池，其中电解液中式I化合物、羧酸酯化合物、锂盐添加剂的含量如表3-1所示。表3-1同时示出了实施例1.11和实施例3.1-3.7的热箱测试和存储阻抗测试的测试结果。
表3-1
Figure PCTCN2020073221-appb-000027
其中“-”代表未添加该物质。
通过实施例3.1-3.7与实施例1.11的测试结果可以看出，在含有式I化合物和羧酸酯化合物的电解液中加入锂盐添加剂LiPO 2F 2，可以显著降低锂离子电池的存储阻抗。这可能是由于式I化合物、羧酸酯化合物和LiPO 2F 2共同作用，会增加有机保护膜中的LiF成份，可以增强有机保护膜的稳定性，提升对高温的耐受性，从而改善存储阻抗。
D、按照上述制备方法制备实施例1.11和实施例4.1-4.9的电解液及锂离子电池，其中电解液中相关物质含量如表4-1所示。表4-1同时示出了实施例1.11和实施例4.1-4.9中锂离子电池的过充测试和存储阻抗测试结果。
表4-1
Figure PCTCN2020073221-appb-000028
Figure PCTCN2020073221-appb-000029
其中“-”代表未添加该物质。
锂离子电池制备过程中会对注液之后的电池进行高温静置，锂离子电池中的电解液在此过程中会参与一些化学反应，溶出锂离子电池负极中的微量Cu金属杂质，微量的Cu离子会增强电解液的导电性，从而实现阻抗的降低。通过实施例4.1-4.9与实施例1.11的测试结果可以看出，含有式I化合物和羧酸酯化合物的电解液中含有适量的Cu离子可显著降低锂离子电池的存储阻抗。
E、按照上述制备方法制备实施例1.11以及实施例5.1-5.10的电解液及锂离子电池。表5-1示出了实施例1.11和实施例5.1-5.10的电解液中相关物质含量、正极活性材料层中的Ti元素含量以及热箱测试结果。
表5-1
Figure PCTCN2020073221-appb-000030
正极活性材料包含Ti元素，不仅可以增强正极活性材料与电解液的界面接触，同时Ti元素会稳定正极活性材料的氧自由基，降低氧自由基与电解液的接触，降低正极活性材料与电解液的氧化反应，尤其是在进行安全测试的时候，氧自由基会加速电解液的催化氧化。本申请采用式I化合物和氟代羧酸酯的组合，对正极界面有一定的保护作用，且自身的抗氧化性会增强，结合Ti元素的掺杂进一步降低正极活性材料与电解液的反应，从而实现提升热 箱安全的效果。通过实施例1.11和实施例5.1-5.10的测试结果可以看出，随着Ti掺杂含量的增加，热箱改善效果显著。
F、按照上述制备方法制备实施例1.11和实施例6.1-6.3的电解液及锂离子电池。表6-1示出了实施例1.11和实施例6.1-6.3的电解液中相关物质含量。
表6-1
Figure PCTCN2020073221-appb-000031
其中“-”代表未添加该物质。
表6-2示出了实施例1.11和实施例6.1-6.3的过充测试、热箱测试、存储膨胀测试和存储阻抗测试的测试结果。
表6-2
Figure PCTCN2020073221-appb-000032
通过实施例实施例1.11和实施例6.1-6.3的测试结果可以看出，在含有式I化合物和羧酸酯化合物的电解液中同时加入三腈化合物和LiPO 2F 2、正极活性材料层中含有适量的Ti元素，且电解液中Cu离子含量在一定范围内时，可以显著改善锂离子电池的过充性能和热箱性能，同时显著降低存储膨胀率和存储阻抗。
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 (12)

  1. 一种电解液，其包含式I的化合物和羧酸酯化合物：
    Figure PCTCN2020073221-appb-100001
    其中R 11、R 12、R 13、R 14各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 1-20杂环基团、取代或未取代的C 6-20芳基、取代或未取代的C 6-20杂芳基或-R 0-O-R基团、取代或未取代的磺酸内酯、取代或未取代的亚硫酸内酯、取代或未取代的硫酸内酯，其中所述杂环基团中的杂原子选自O、S、N或P中的至少一种；或R 11和R 12与其所连接的碳原子一起形成5-10元环状结构，其中所述环状结构任选地含有杂原子，所述杂原子选自O、S、N或P中的至少一种；
    其中R 0选自C 1-6亚烷基，R选自砜基、甲基砜基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
    其中R 11、R 12、R 13、R 14、R各自独立地经取代时，取代基选自卤素、氰基、砜基、甲基砜基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基、C 6-20杂芳基或其任意组合。
  2. 根据权利要求1所述的电解液，其中所述R 11、R 12、R 13、R 14各自独立地选自以下基团：
    Figure PCTCN2020073221-appb-100002
    Figure PCTCN2020073221-appb-100003
    或
    R 11和R 12与其所连接的碳原子一起连接形成
    Figure PCTCN2020073221-appb-100004
    其中基于所述电解液的总重量，所述式I化合物的重量百分比为a wt％，a为0.001-5。
  3. 根据权利要求1所述的电解液，其中所述式I化合物包括如下化合物中的至少一种：
    Figure PCTCN2020073221-appb-100005
  4. 根据权利要求1所述的电解液，其中所述羧酸酯化合物包括式II化合物：
    Figure PCTCN2020073221-appb-100006
    其中R 21、R 22各自独立地选自H、卤素、氰基、取代或未取代的C 1-20烷基、取代或未取代的C 3-20环烷基、取代或未取代的C 2-20烯基、取代或未取代的C 1-20烷氧基、取代或未取代的C 6-20芳基或取代或未取代的C 6-20杂芳基；
    其中R 21、R 22各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、 C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合；
    其中基于所述电解液的总重量，所述羧酸酯化合物的重量百分比为b  wt％，b为0.05-75。
  5. 根据权利要求1所述的电解液，其中所述羧酸酯化合物包括如下化合物中的至少一种：
    Figure PCTCN2020073221-appb-100007
  6. 根据权利要求1所述的电解液，其中所述电解液进一步包括式III化合物：
    Figure PCTCN2020073221-appb-100008
    其中，M选自C、Si中的一种；
    R 31、R 32、R 33各自独立地选自取代或未取代的C 1-C 20亚烷基、取代或未取代的C 2-C 20亚烯基、-R 35-S-R 36-或-R 37-O-R 38-，R 35、R 36、R 37和R 38各自独立的为单键、取代或未取代的C 1-C 20亚烷基或取代或未取代的C 2-C 20亚烯基；
    R 34选自H、取代或未取代的C 1-C 20烷基、取代或未取代的C 2-C 20烯基；
    其中R 31、R 32、R 33、R 34、R 35、R 36、R 37和R 38各自独立地经取代时，取代基选自卤素、氰基、C 1-20烷基、C 3-20环烷基、C 1-20烷氧基、C 2-20烯基、C 6-20芳基或其任意组合；
    其中基于所述电解液的总重量，所述式III化合物的重量百分比为0.01wt％-5wt％。
  7. 根据权利要求6所述的电解液，其中所述式III化合物包括如下化合物中的至少一者：
    Figure PCTCN2020073221-appb-100009
  8. 根据权利要求1所述的电解液，其中所述电解液进一步包含锂盐添加剂，所述锂盐添加剂包括如下锂盐中的至少一者：LiPO 2F 2、双三氟甲烷磺酰亚胺锂、双(氟磺酰)亚胺锂、双草酸硼酸锂、四氟磷酸草酸锂、二氟草酸硼酸锂或六氟铯酸锂；
    其中基于所述电解液的总重量，所述锂盐添加剂的重量百分比为0.001wt％-5wt％。
  9. 一种电化学装置，其包括正极，所述正极包括正极活性材料层，所述正极活性材料层包含正极活性材料；和根据权利要求1-8中任一项所述的电解液。
  10. 根据权利要求9所述的电化学装置，其中所述电化学装置的电解液中进一步包含铜离子，其中基于所述电解液的总重量，所述铜离子的含量为0.01ppm-50ppm。
  11. 根据权利要求9所述的电化学装置，其中所述正极活性材料中包含Ti元素，基于所述正极活性材料层的总重量，所述Ti元素含量为t×10 2ppm，t为2-10，并且满足(a+b)/t≤35。
  12. 一种电子装置，其中所述电子装置包括根据权利要求9-11中任一项所述的电化学装置。
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