WO2018227689A1 - 一种电解液及电池 - Google Patents

一种电解液及电池 Download PDF

Info

Publication number
WO2018227689A1
WO2018227689A1 PCT/CN2017/093311 CN2017093311W WO2018227689A1 WO 2018227689 A1 WO2018227689 A1 WO 2018227689A1 CN 2017093311 W CN2017093311 W CN 2017093311W WO 2018227689 A1 WO2018227689 A1 WO 2018227689A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
substituted
unsubstituted
formula
Prior art date
Application number
PCT/CN2017/093311
Other languages
English (en)
French (fr)
Inventor
伊天成
胡春华
郝莉
湛英杰
梁成都
Original Assignee
宁德时代新能源科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to JP2019516707A priority Critical patent/JP6903128B2/ja
Priority to US16/343,326 priority patent/US10862170B2/en
Priority to EP17913433.3A priority patent/EP3514879B1/en
Publication of WO2018227689A1 publication Critical patent/WO2018227689A1/zh

Links

Images

Classifications

    • 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
    • H01M10/42—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of energy storage materials, and in particular to an electrolyte and a battery using the same.
  • Lithium-ion batteries are widely used in electric vehicles and consumer electronics due to their high energy density, high output power, long cycle life and low environmental pollution.
  • the current demand for lithium-ion batteries is: high voltage, high power, long cycle life, long storage life and excellent safety performance.
  • Lithium-ion batteries are currently widely used as an electrolyte system in which lithium hexafluorophosphate is used as a conductive lithium salt and a cyclic carbonate and/or a chain carbonate is used as a solvent.
  • the above electrolyte system still has many disadvantages. For example, under high voltage and high temperature conditions, the cycle performance and storage performance of the above electrolyte system need to be improved.
  • the applicant conducted intensive research and found that by adding a polynitrile six-membered nitrogen heterocyclic compound as an electrolyte additive, the surface activity of the positive electrode material can be effectively inactivated, and the oxidation of the electrolyte solution can be suppressed. Reduce battery gas production, which can improve the high temperature and high pressure cycle performance and storage performance of the battery. Thereby completing the application.
  • An object of the present application is to provide an electrolyte containing an additive selected from at least one selected from the group consisting of polynitrile six-membered nitrogen heterocyclic compounds represented by Formula I-1, Formula I-2 or Formula I-3.
  • an additive selected from at least one selected from the group consisting of polynitrile six-membered nitrogen heterocyclic compounds represented by Formula I-1, Formula I-2 or Formula I-3.
  • R 1, R 2, R 3 and R 4 are each independently selected from hydrogen, halo, a substituted or unsubstituted C 1 ⁇ C 12 alkyl group, a substituted or unsubstituted C 1 ⁇ C 12 alkoxy group, a substituted Or unsubstituted C 1 -C 12 amino group, substituted or unsubstituted C 2 -C 12 alkenyl group, substituted or unsubstituted C 2 -C 12 alkynyl group, substituted or unsubstituted C 6 -C 26 aryl group a substituted or unsubstituted C 4 -C 12 heterocyclic group;
  • the substituent is at least one selected from the group consisting of halogen, nitrile group, C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, and C 1 -C 6 alkoxy group;
  • x, y, z are each independently selected from an integer of 0-8;
  • n, and k are each independently selected from an integer of 0 to 2.
  • Another object of the present application is to provide a battery comprising a positive electrode tab, a negative electrode tab, a separator disposed between the positive electrode tab and the negative electrode tab, and an electrolyte, which is the electrolyte of the present application.
  • the electrolyte of the present application by adding a polynitrile-based six-membered nitrogen heterocyclic compound as an additive, the surface activity of the positive electrode material can be effectively inactivated, the oxidation of the electrolyte solution can be suppressed, and the gas production of the battery can be reduced.
  • the battery using the electrolyte of the present application has better high temperature and high pressure cycle performance and storage performance.
  • Figure 1 is a nuclear magnetic resonance carbon spectrum of the A2 compound
  • Figure 2 is a nuclear magnetic resonance carbon spectrum of the A8 compound
  • Figure 3 is a nuclear magnetic resonance carbon spectrum of the A13 compound.
  • a first aspect of the embodiments of the present application provides an electrolyte comprising an organic solvent, an electrolyte salt, and an additive.
  • the additive includes a polynitrile six-membered nitrogen heterocyclic compound.
  • the polynitrile six-membered nitrogen heterocyclic compound of the examples of the present application is selected from at least one of the compounds represented by Formula I-1, Formula I-2 or Formula I-3:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted Or unsubstituted C 1 -C 12 amino group, substituted or unsubstituted C 2 -C 12 alkenyl group, substituted or unsubstituted C 2 -C 12 alkynyl group, substituted or unsubstituted C 6 -C 26 aryl group a substituted or unsubstituted C 4 -C 12 heterocyclic group;
  • the substituent is at least one selected from the group consisting of halogen, nitrile group, C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, and C 1 -C 6 alkoxy group;
  • x, y, z are each independently selected from an integer of 0-8;
  • n, and k are each independently selected from an integer of 0 to 2.
  • the polynitrile six-membered nitrogen heterocyclic compound has a nitrile group
  • the nitrogen atom in the group The transition metal has strong complexation. Therefore, when it is applied to the electrolyte, it can be adsorbed on the surface of the positive electrode material to form a porous porous protective film.
  • the surface of the positive electrode material is in contact with the electrolyte without affecting the lithium ion.
  • the normal transmission, reducing the surface activity of the positive electrode material can inhibit a large number of surface side reactions occurring on the surface, thereby reducing by-products and inhibiting gas production.
  • the polynitrile six-membered nitrogen heterocyclic compound of the present application is a nitrile compound, since it has a special six-membered nitrogen heterocyclic structure, it can affect the film formation potential of the nitrile group and the surface of the positive electrode material.
  • the film forming effect and the like can further improve the electrochemical performance of the entire battery system, such as reducing gas production, increasing high temperature and high pressure cycle life, and the like.
  • the compound represented by the formula I-1 is a polynitrile pyrimidine compound.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 6 straight or branched alkane a substituted, unsubstituted C 5 -C 9 cycloalkyl group, a substituted or unsubstituted C 1 -C 6 alkoxy group, a substituted or unsubstituted C 1-6 amino group, a substituted or unsubstituted C 2 ⁇ 6 alkenyl, substituted or unsubstituted C 2 -C 6 alkynyl, substituted or unsubstituted C 6-12 aryl, substituted or unsubstituted C 4 -C 12 heterocyclic; the substituent is selected from halogen.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 3 straight or branched alkane a substituted, unsubstituted C 5 -C 7 cycloalkyl group, a substituted or unsubstituted C 1 -C 3 alkoxy group, a substituted or unsubstituted C 1 -C 3 amine group, a substituted or unsubstituted C 2 group a C 3 alkenyl group, a substituted or unsubstituted C 2 -C 3 alkynyl group, a substituted or unsubstituted C 6 -C 8 aryl group, a substituted or unsubstituted C 4 -C 7 heterocyclic group; the substituent is selected from halogen.
  • alkyl group, the alkenyl group and the alkynyl group may be a chain substituent or a cyclic substituent, wherein the chain substituent includes a linear substituent and a branched substituent.
  • x is preferably selected from an integer of 0 to 6, further preferably an integer of 0 to 4; more preferably selected from 1 or 2; and y is preferably selected from an integer of 0 to 6, Further preferably an integer of 0 to 4; more preferably selected from 1 or 2.
  • R 1 and R 3 are the same group; preferably, R 1 , R 3 and R 4 are all the same group.
  • R 1 and R 3 are hydrogen; preferably, R 1 , R 3 and R 4 are all hydrogen.
  • R 1 to R 4 are all hydrogen; or R 1 , R 3 and R 4 are all hydrogen, and R 2 is selected from halogen, substituted or unsubstituted C 1 - C 6 straight or branched alkyl, substituted or unsubstituted C 1 -C 6 alkoxy; the substituent is selected from halogen, preferably fluorine.
  • the compound represented by the formula I-1 is specifically selected from the following compounds and is not limited thereto:
  • the formula I-2 is a polynitrile piperazine compound.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 6 straight or branched alkane a substituted, unsubstituted C 5 -C 9 cycloalkyl group, a substituted or unsubstituted C 1 -C 6 alkoxy group, a substituted or unsubstituted C 1 -C 6 amine group, a substituted or unsubstituted C 2 group a C 6 alkenyl group, a substituted or unsubstituted C 2 -C 6 alkynyl group, a substituted or unsubstituted C 6 -C 12 aryl group, a substituted or unsubstituted C 4 -C 13 heterocyclic group; the substituent is selected from halogen.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 3 straight or branched alkane a substituted, unsubstituted C 5 -C 7 cycloalkyl group, a substituted or unsubstituted C 1 -C 3 alkoxy group, a substituted or unsubstituted C 1 -C 3 amine group, a substituted or unsubstituted C 2 group a C 3 alkenyl group, a substituted or unsubstituted C 2 -C 3 alkynyl group, a substituted or unsubstituted C 6 -C 8 aryl group, a substituted or unsubstituted C 4 -C 7 heterocyclic group; the substituent is selected from halogen.
  • alkyl group, the alkenyl group and the alkynyl group may be a chain substituent or a cyclic substituent, wherein The chain substituent includes a linear substituent and a branched substituent.
  • x is preferably an integer of 0 to 6, further preferably an integer of 0 to 4; more preferably selected from 1 or 2; y is preferably selected from an integer of 0 to 6, further preferably 0 An integer of ⁇ 4; more preferably 1 or 2.
  • R 1 , R 2 , R 3 and R 4 are the same group; preferably, R 1 , R 2 , R 3 and R 4 At least three of them are the same group.
  • At least two of R 1 , R 2 , R 3 and R 4 are hydrogen; preferably, at least three of R 1 , R 2 , R 3 and R 4 One is hydrogen.
  • R 1 to R 4 are all hydrogen; or at least three of R 1 , R 2 , R 3 and R 4 are hydrogen and the other group is selected from halogen, a substituted or unsubstituted C 1 -C 6 linear or branched alkyl group, a substituted or unsubstituted C 1 -C 6 alkoxy group; the substituent is selected from halogen, preferably fluorine.
  • the compound represented by the formula I-2 is specifically selected from the following compounds and is not limited thereto:
  • the formula I-3 is a polynitrile-based s-triazine compound.
  • R 1 , R 2 and R 3 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 6 straight or branched alkyl, substituted Or unsubstituted C 5 -C 9 cycloalkyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 1 -C 6 amine, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 alkynyl, substituted or unsubstituted C 6 -C 12 aryl, substituted or unsubstituted C 4 -C 13 heterocyclic; the substituent is selected from halogen.
  • R 1 , R 2 and R 3 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 3 straight or branched alkyl, substituted Or unsubstituted C 5 -C 7 cycloalkyl, substituted or unsubstituted C 1 -C 3 alkoxy, substituted or unsubstituted C 1 -C 3 amine, substituted or unsubstituted C 2 -C 3 Alkenyl, substituted or unsubstituted C 2 -C 3 alkynyl, substituted or unsubstituted C 6 -C 8 aryl, substituted or unsubstituted C 4 -C 7 heterocyclyl; substituent selected from halogen.
  • alkyl group, the alkenyl group and the alkynyl group may be a chain substituent or a cyclic substituent, wherein the chain substituent includes a linear substituent and a branched substituent.
  • x is preferably selected from an integer of 0 to 6, further preferably an integer of 0 to 4; more preferably 1 or 2; y is preferably selected from an integer of 0 to 6, further preferably 0 An integer of ⁇ 4; more preferably 1 or 2.
  • R 1 , R 2 and R 3 are the same group.
  • R 1 , R 2 and R 3 are hydrogen.
  • R 1 , R 2 and R 3 are all hydrogen; or at least two of R 1 , R 2 and R 3 are hydrogen and the other group is selected from halogen a substituted or unsubstituted C 1 -C 6 linear or branched alkyl group, a substituted or unsubstituted C 1 -C 6 alkoxy group; the substituent is selected from halogen, preferably fluorine.
  • the compound represented by the formula I-3 is specifically selected from the following compounds and is not limited thereto:
  • the polynitrile six-membered nitrogen heterocyclic compound may also be selected from the following compounds and is not limited thereto:
  • the mass percentage of the polynitrile six-membered nitrogen heterocyclic compound in the electrolytic solution is from 0.001% to 10%. If the content of the polynitrile six-membered nitrogen heterocyclic compound is too low, the effect of improving the electrolyte is not significant. If the content of the polynitrile six-membered nitrogen heterocyclic compound is too high, the thickness of the complex layer formed is too large. Further, the positive and negative impedances are greatly increased, and the battery performance is deteriorated.
  • the upper limit of the mass percentage range of the polynitrile six-membered nitrogen heterocyclic compound in the electrolyte solution of the present application is selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4 %, 3.5%, 3%, 2%, 1%, 0.8%, and the lower limit is selected from 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%. Still more preferably, the polynitrile six-membered nitrogen heterocycle is present in the electrolyte in an amount of from 0.1% to 3.5%.
  • additive A other additives may be added to the electrolytic solution of the examples of the present application, and the following additives (a) to (o) may be suitably exemplified.
  • the unsaturated cyclic carbonate-containing compound is at least one selected from the group consisting of compounds of the formula II-0;
  • R 20 is selected from alkenyl-substituted C 1 ⁇ C 6 alkylene group, a substituted or unsubstituted C 2 ⁇ C 6 alkenylene group.
  • the cyclic carbonate compound containing an unsaturated bond is at least one selected from the group consisting of the following structural formulas:
  • a halogen-substituted cyclic carbonate compound selected from at least one of the compounds of formula II-1;
  • R 21 is selected from a halogen-substituted C 1 -C 6 alkylene group or a halogen-substituted C 2 -C 6 alkenylene group.
  • the halogen-substituted cyclic carbonate compound is selected from the group consisting of fluoroethylene carbonate (abbreviated as FEC), fluorocarbonate (abbreviated as FPC), and propylene trifluorocarbonate (abbreviated as TFPC).
  • FEC fluoroethylene carbonate
  • FPC fluorocarbonate
  • TFPC propylene trifluorocarbonate
  • the sulfate compound is preferably a cyclic sulfate compound, and the cyclic sulfate compound is selected from at least one of the compounds of the formula II-2;
  • R 22 is selected from substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 2 -C 6 alkenylene; the substituent is selected from halogen, C 1 -C 3 alkyl, C 2 ⁇ C 4 alkenyl.
  • R 22 is selected from a substituted or unsubstituted C 1 -C 4 alkylene group, a substituted or unsubstituted C 2 -C 4 alkenylene group; the substituent is selected from halogen, C 1 -C 3 alkyl group, C 2 -C 4 alkenyl.
  • the cyclic sulfate compound is at least one selected from the group consisting of vinyl sulfate (DTD for short), propylene sulfate (abbreviated as TMS), and 4-methylsulfuric acid (abbreviated as PLS), and the specific structural formula is as follows;
  • the cyclic sulfate compound may also be selected from:
  • the sultone compound is selected from at least one of the compounds of formula II-3;
  • R 23 is selected from substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 2 -C 6 alkenylene; the substituent is selected from halogen, C 1 -C 3 alkyl, C 2 ⁇ C 4 alkenyl.
  • the sultone compound is at least one selected from the group consisting of 1,3-propane sultone (abbreviated as PS) and 1,3-propene sultone (referred to as PES), and the specific structural formula is as follows;
  • the sultone compound can also be selected from:
  • the disulfonic acid compound is a compound containing two sulfonic acid groups, and more preferably, it is selected from disulfonic acid.
  • a methylene ester compound specifically selected from at least one of the compounds of formula II-4;
  • R 24 , R 25 , R 26 , R 27 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 2 -C 10 alkenyl; substituent It is selected from the group consisting of halogen, C 1 -C 3 alkyl, and C 2 -C 4 alkenyl.
  • the methylene disulfonate compound is selected from methane methane disulfonate (abbreviated as MMDS);
  • the methylene disulfonate compound may also be selected from methyl 3-methyl-methane disulfonate and one or more of the following structural formulas:
  • the sulfite compound is preferably a cyclic sulfite compound, and may be specifically selected from at least one of the compounds of the formula II-5;
  • R 28 is selected from substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 2 -C 6 alkenylene; the substituent is selected from halogen, C 1 -C 3 alkyl, C 2 ⁇ C 4 alkenyl.
  • the sulfite compound may be selected from the group consisting of vinyl sulfite (abbreviated as ES), propylene sulfite (abbreviated as PS), and butylene sulfite (abbreviated as BS).
  • ES vinyl sulfite
  • PS propylene sulfite
  • BS butylene sulfite
  • the nitrile compound may be selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimeliconitrile, xin One or more than one nitrile of dinitrile and sebaconitrile.
  • one or more selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, and pimeliconitrile are more preferable.
  • the aromatic compound may be selected from the group consisting of cyclohexylbenzene, fluorocyclohexylbenzene compounds (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), tert-butyl
  • An aromatic compound having a branched alkyl group such as benzene, tert-amylbenzene or 1-fluoro-4-tert-butylbenzene, biphenyl, terphenyl (ortho, meta, para), diphenyl Ether, fluorobenzene, difluorobenzene (ortho, meta, para), anisole, 2,4-difluoroanisole, partial hydride of terphenyl (1,2-dicyclohexylbenzene, An aromatic compound such as 2-phenylbicyclohexyl, 1,2-diphenylcyclohe
  • one or more selected from the group consisting of biphenyl, terphenyl (ortho, meta, and para), fluorobenzene, cyclohexylbenzene, t-butylbenzene, and t-amylbenzene are more preferable. It is particularly preferably one or more selected from the group consisting of biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene, and t-amylbenzene.
  • the isocyanate compound may be selected from the group consisting of methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene di
  • hexamethylene diisocyanate octamethylene diisocyanate
  • 2-isocyanatoethyl acrylate 2-isocyanatoethyl methacrylate are more preferable.
  • the phosphazene compound may preferably be exemplified by methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene or ethoxysevocyclotetracycline. Phosphazene compound.
  • a cyclic phosphazene compound such as methoxypentafluorocyclotriphosphazene, ethoxy pentafluorocyclotriphosphazene or phenoxy pentafluorocyclotriphosphazene is preferred, and methoxypentafluorocyclotriphosphate is more preferred. Nitrile or ethoxy pentafluorocyclotriphosphazene.
  • the cyclic acid anhydride compound may suitably be a chain carboxylic anhydride such as acetic anhydride or propionic anhydride.
  • a cyclic anhydride such as succinic anhydride, maleic anhydride, 2-allyl succinic anhydride, glutaric anhydride, itaconic anhydride or 3-sulfo-propionic anhydride.
  • succinic anhydride, maleic anhydride, and 2-allyl succinic anhydride are preferable, and succinic anhydride and 2-allyl succinic anhydride are more preferable.
  • the phosphite compound may be selected from a silane phosphite compound, and may be specifically selected from at least one of the compounds represented by formula II-6;
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 are each independently selected from a substituted or unsubstituted C 1 -C 6 alkyl group; From halogen.
  • the silanous phosphite compound may be selected from at least one of the following compounds,
  • the phosphate compound may be selected from a silane phosphate compound, and may be specifically selected from at least one of the compounds of the formula II-7;
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 are each independently selected from substituted or unsubstituted C 1 -C 6 alkyl groups; From halogen.
  • the silane phosphate compound may be selected from at least one of the following compounds,
  • the borate compound may be selected from a silane borate compound, and may be specifically selected from at least one of the compounds of formula II-8;
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 are each independently selected from a substituted or unsubstituted C 1 -C 6 alkyl group; From halogen.
  • the silane boronate compound may be selected from at least one of the following compounds,
  • the carboxylic acid ester may be selected from the group consisting of a chain carboxylic acid ester and a cyclic carboxylic acid ester.
  • the chain carboxylic acid ester or cyclic carboxylic acid ester may contain an unsaturated bond or a halogen atom.
  • EA ethyl acetate
  • MB methyl butyrate
  • EB ethyl butyrate
  • TFEA ethyl trifluoroacetate
  • MPFP trifluoroethyl acetate
  • the mass percentage of the additive A in the electrolyte is 0.01% to 30%.
  • alkyl group having 1 to 12 carbon atoms may be a chain alkyl group or a cycloalkyl group, and the hydrogen group on the ring of the cycloalkyl group may be substituted by an alkyl group, and the number of carbon atoms in the alkyl group Preferred lower limit values are 1, 2, 3, 4, 5, and preferred upper limit values are 3, 4, 5, 6, 8, 10, 12.
  • an alkyl group having 1 to 10 carbon atoms is selected, and more preferably, a chain alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 8 carbon atoms are selected, and still more preferably, A chain alkyl group having 1 to 4 carbon atoms and a cycloalkyl group having 5 to 7 carbon atoms are selected.
  • Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and new.
  • the above-mentioned alkyl group having 1 to 12 carbon atoms contains an oxygen atom, it may be an alkoxy group.
  • an alkoxy group having 1 to 10 carbon atoms is selected, and more preferably, an alkoxy group having 1 to 6 carbon atoms is selected, and more preferably, an alkoxy group having 1 to 4 carbon atoms is selected.
  • Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a t-butoxy group, and a n-pentyloxy group. Isovaleryloxy, cyclopentyloxy, cyclohexyloxy.
  • the alkenyl group having 2 to 12 carbon atoms may be a cyclic alkenyl group or a chain alkenyl group. Further, the number of double bonds in the alkenyl group is preferably one.
  • the lower limit of the number of carbon atoms in the alkenyl group is preferably 3, 4, and 5.
  • the preferred upper limit is 3, 4, 5, 6, 8, 10, and 12.
  • an alkenyl group having 2 to 10 carbon atoms is selected, and more preferably an alkenyl group having 2 to 6 carbon atoms is selected, and more preferably an alkenyl group having 2 to 5 carbon atoms is selected.
  • alkenyl group examples include a vinyl group, an allyl group, an isopropenyl group, a pentenyl group, a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group.
  • An amine group having 1 to 12 carbon atoms is selected from or Wherein R' and R" are an alkyl group having 1 to 12 carbon atoms.
  • the alkynyl group having 2 to 12 carbon atoms may be a cyclic alkynyl group or a chain alkynyl group. Further, the number of the triple bonds in the alkynyl group is preferably one.
  • the lower limit of the number of carbon atoms in the alkynyl group is preferably 3, 4, and 5. The preferred upper limit is 3, 4, 5, 6, 8, 10, 12.
  • an alkynyl group having 2 to 10 carbon atoms is selected, and an alkynyl group having 2 to 6 carbon atoms is more preferably selected, and an alkynyl group having 2 to 5 carbon atoms is more preferably selected.
  • alkenyl group examples include an ethynyl group, a propargyl group, an isopropynyl group, a pentynyl group, a cyclohexynyl group, a cycloheptynyl group, and a cyclooctynyl group.
  • An aryl group having 6 to 26 carbon atoms such as a phenyl group, a phenylalkyl group, an aryl group containing at least one phenyl group such as a biphenyl group, a fused ring aromatic hydrocarbon group such as naphthalene, anthracene or phenanthrene, a biphenyl group and a thick group.
  • the cycloaromatic hydrocarbon group may also be substituted by an alkyl group or an alkenyl group.
  • an aryl group having 6 to 16 carbon atoms is selected, and more preferably, an aryl group having 6 to 14 carbon atoms is selected, and even more preferably an aryl group having 6 to 9 carbon atoms is selected.
  • Specific examples of the aryl group include a phenyl group, a benzyl group, a biphenyl group, a p-tolyl group, an o-tolyl group, and an m-tolyl group.
  • a heterocyclic group having 4 to 12 carbon atoms a hetero atom may be selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, boron, etc., and the heterocyclic ring may be an alicyclic or aromatic heterocyclic ring; and may be a 5-membered and a 6-membered heterocyclic ring; Benzocycloheterocyclic compound.
  • a heterocyclic group having 4 to 10 carbon atoms is selected, and more preferably, a heterocyclic group having 4 to 7 carbon atoms is selected.
  • it may be selected from the group consisting of furyl, thienyl, pyrrolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, fluorenyl, quinolyl and the like.
  • the halogen is selected from the group consisting of fluorine, chlorine, bromine, and preferably fluorine.
  • the alkylene group having 1 to 6 carbon atoms is a linear or branched alkylene group, and the lower limit of the number of carbon atoms in the alkylene group is preferably 2 or 3, and the preferred upper limit is 4 or 5. 6.
  • an alkylene group having 1 to 4 carbon atoms is selected.
  • Specific examples of the alkyl group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a sec-butylene group, a pentylene group, and a hexylene group.
  • the alkenylene group having 2 to 6 carbon atoms is a linear or branched alkenylene group, and the number of double bonds in the alkenyl group is preferably one.
  • the lower limit of the number of carbon atoms in the alkenylene group is preferably 3 or 4, and the preferred upper limit is 3, 4, 5, and 6.
  • an alkenylene group having 2 to 5 carbon atoms is selected.
  • Specific examples of the alkenylene group include a vinylidene group, an allylene group, an isopropenylene group, an iylene group, and an allylene group.
  • the halogen is selected from the group consisting of fluorine, chlorine, bromine, and preferably fluorine.
  • the organic solvent to be used in the electrolytic solution of the embodiment of the present invention may preferably be one or more selected from the group consisting of a cyclic carbonate, a chain ester, a lactone, an ether, and an amide. From the viewpoint of further improving high-temperature high-pressure cycle performance and storage performance, it is preferred to contain a cyclic carbonate and a chain carbonate.
  • chain ester is used as a concept including a chain carbonate and a chain carboxylate.
  • the cyclic carbonate may be selected from the group consisting of ethylene carbonate (abbreviated as EC), propylene carbonate (abbreviated as PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and vinylene carbonate. (referred to as VC), vinyl ethylene carbonate (referred to as VEC), 4-ethynyl-1,3-dioxolane-2-one (referred to as EEC), etc.
  • EC ethylene carbonate
  • PC propylene carbonate
  • PC 1,2-butylene carbonate
  • VEC vinyl ethylene carbonate
  • EEC 4-ethynyl-1,3-dioxolane-2-one
  • Cyclic carbonate having carbon-carbon unsaturated bonds Cyclic carbonate; and 4-fluoro-1,3-dioxol-2-one (abbreviated as FEC), trans or cis-4,5-difluoro-1,3-dioxo
  • FEC 4-fluoro-1,3-dioxol-2-one
  • FEC 4-fluoro-1,3-dioxol-2-one
  • DFEC heterocyclic pentan-2-one
  • EEC 4-ethynyl-1,3-dioxolane-2-one
  • the chain ester may suitably be selected from the group consisting of ethyl methyl carbonate (abbreviated as MEC), methyl propyl carbonate (abbreviated as MPC), methyl isopropyl carbonate (abbreviated as MIPC), methylbutyl carbonate and carbonic acid.
  • MEC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • MIPC methyl isopropyl carbonate
  • methylbutyl carbonate methylbutyl carbonate
  • One or more asymmetric chain carbonates of ethylene propyl ester selected from dimethyl carbonate (abbreviated as DMC), diethyl carbonate (abbreviated as DEC), dipropyl carbonate, and dibutyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • One or more symmetrical chain carbonates selected from pivalic acid esters such as methyl pivalate, ethyl pivalate, propyl pivalate, methyl propionate, ethyl propionate,
  • One or more chain carboxylic acid esters of methyl acetate and ethyl acetate selected from dimethyl carbonate (abbreviated as DMC), diethyl carbonate (abbreviated as DEC), dipropyl carbonate, and dibutyl carbonate
  • One or more symmetrical chain carbonates selected from pivalic acid esters such as methyl pivalate, ethyl pivalate, propyl pivalate, methyl prop
  • a cyclic ether selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane, 1,2-dimethoxyethane, and 1,2-diethyl can be suitably used.
  • Chain ether such as oxyethane or 1,2-dibutoxyethane; amide such as dimethylformamide; sulfone such as sulfolane, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -angelica lactone, etc.
  • lactones and the like One or more of lactones and the like.
  • the following lithium salt can be suitably exemplified.
  • LiN(SO 2 F) 2 LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , (CF 2 ) 2 (SO 2 ) 2 NLi (ring)
  • LiN (SO is preferred) 2 F) 2 LiN(SO 2 CF 3 ) 2 or LiN(SO 2 C 2 F 5 ) 2
  • LiN(SO 2 F) 2 LiN(SO 2 CF 3 ) 2 or LiN(SO 2 C 2 F 5 ) 2
  • LiN(SO 2 F) 2 or LiN(SO 2 CF 3 ) 2 LiN(SO 2 F) 2 or LiN(SO 2 CF 3 ) 2 .
  • LiSO 3 F LiCF 3 SO 3 , CH 3 SO 4 Li, C 2 H 5 SO 4 Li, C 3 H 7 SO 4 Li, trifluoro((methanesulfonyl)oxy)boronic acid
  • LiTFMSB lithium pentafluoro((methylsulfonyl)oxy) lithium phosphate
  • LiPFMSP lithium pentafluoro((methylsulfonyl)oxy) lithium phosphate
  • LiPO 2 F 2 Li 2 PO 3 F
  • LiClO 4 LiPO 2 F 2
  • LiPO 2 F 2 is preferable.
  • Li 2 PO 3 F Li 2 PO 3 F.
  • lithium oxalate-O, O'] lithium borate LiBOB
  • difluoro [oxalate-O, O'] lithium borate difluoro bis[oxalate-O, O'] phosphoric acid.
  • LiBOB lithium borate
  • LiPFO tetrafluoro [oxalate-O, O'] lithium phosphate
  • LiBOB lithium salt having an oxalate ligand as an anion
  • LiPF 6 LiPO 2 F 2 , Li 2 PO 3 F, LiBF 4 , LiSO 3 F, trifluoro((methylsulfonyl)oxy)borate (LiTFMSB), LiN(SO 2 F).
  • LiPFO lithium phosphate
  • LiTFMSB trifluoro ((methanesulfonyl) Lithium) lithium borate
  • LiPO 2 F 2 LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , bis[oxalate-O, O'] lithium borate (LiBOB), and One or more of fluorine bis [oxalate-O, O'] lithium phosphate (LiPFO), more preferably LiPF 6 .
  • the electrolytic solution of the embodiment of the present application can be obtained, for example, by mixing the above organic solvent, adding an electrolyte salt thereto and the polynitrile six-membered nitrogen heterocyclic compound of the present application, and further adding at least one of the above additives A. Kind.
  • the anhydrous sodium carbonate, the raw material P-5 and the raw material P-3 were mixed in absolute ethanol, and the reaction was stirred for 2 to 5 hours.
  • the hot ethanol is washed repeatedly several times to obtain a crude product which is recrystallized to give the compound of formula I-3.
  • a battery according to a second aspect of the embodiment of the present application is explained below.
  • a battery according to an embodiment of the present application includes a positive electrode tab, a negative electrode tab, a separator interposed between the positive electrode tab and the negative electrode tab, and an electrolyte. It should be noted that the battery of the embodiment of the present application may be a lithium ion battery, a sodium ion battery or a magnesium ion battery.
  • the positive electrode When the battery is a lithium ion battery, the positive electrode includes a positive active material capable of deintercalating and intercalating lithium ions, and the negative electrode includes a negative active material capable of inserting and extracting lithium ions.
  • the positive active material may be selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
  • a layered lithium-containing oxide, a spinel-type lithium-containing oxide, an olivine-type lithium-containing phosphate compound, or the like can be used.
  • it is not limited to these materials and a conventionally known material which can be used as a positive electrode active material of a lithium ion battery can be used.
  • These positive electrode active materials may be used alone or in combination of two or more.
  • the negative active material may be soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon oxide, silicon carbon composite, lithium titanate, metal capable of forming an alloy with lithium. Wait.
  • a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, or the like can be used.
  • a conventionally known material which can be used as a negative electrode active material of a lithium ion battery can be used.
  • These negative electrode active materials may be used alone or in combination of two or more.
  • the positive electrode comprises a positive active material capable of deintercalating and intercalating sodium ions
  • the negative electrode comprises a negative active material capable of intercalating and desorbing sodium ions.
  • the positive electrode active material may be selected from the group consisting of sodium iron composite oxide (NaFeO 2 ), sodium cobalt composite oxide (NaCoO 2 ), sodium chromium composite oxide (NaCrO 2 ), sodium manganese composite oxide (NaMnO 2 ), and sodium nickel.
  • Composite oxide NaNiO 2
  • sodium nickel titanium composite oxide NaNi 1/2 Ti 1/2 O 2
  • sodium nickel manganese composite oxide NaNi 1/2 Mn 1/2 O 2
  • sodium iron manganese composite Oxide Na 2/3 Fe 1/3 Mn 2/3 O 2
  • sodium nickel cobalt manganese composite oxide NaNi 1/3 Co 1/3 Mn 1/3 O 2
  • sodium iron phosphate compound NaFePO 4
  • NaMnPO 4 sodium manganese phosphate compound
  • NaCoPO 4 sodium cobalt phosphate compound
  • the negative electrode active material may be selected from carbon materials such as hard carbon, natural graphite, artificial graphite, soft carbon, carbon black, acetylene black, carbon nanotubes, graphene, carbon nanofibers, and the like.
  • carbon materials such as hard carbon, natural graphite, artificial graphite, soft carbon, carbon black, acetylene black, carbon nanotubes, graphene, carbon nanofibers, and the like.
  • an element of an element which is alloyed with sodium such as Si, Ge, Pb, In, Zn, H, Ca, Sr, Ba, Ru, Rh, or the like, and oxidation of these elements may be mentioned.
  • carbides carbides.
  • it is not limited to these materials and a conventionally known material which can be used as a negative electrode active material of a sodium ion battery can be used.
  • These negative electrode active materials may be used alone or in combination of two or more.
  • the positive electrode comprises a positive active material capable of deintercalating and intercalating magnesium ions
  • the negative electrode comprises a negative active material capable of intercalating and removing magnesium ions.
  • the positive electrode active material may be selected from the group consisting of V 2 O 5 , MoO 3 , MnO 2 , TiS 2 , MoS 2 , etc.
  • the negative electrode active material may be selected from the group consisting of magnesium metal, magnesium alloy, graphite, and the like.
  • it is not limited to these materials and a conventionally known material which can be used as a positive and negative electrode active material of a magnesium ion battery can be used.
  • These positive and negative electrode active materials may be used alone or in combination of two or more.
  • the specific kind of the separator is not particularly limited, and may be any separator material used in the existing battery, such as polyethylene, polypropylene, polyvinylidene fluoride, and a multilayer composite film thereof, but is not limited thereto. These ones.
  • the electrolytic solution is the electrolytic solution described in the above first aspect.
  • the positive electrode sheet further includes a binder and a conductive agent, and a positive electrode slurry containing a positive electrode active material, a binder, and a conductive agent is coated on the positive electrode current collector, and a positive electrode sheet is obtained after the positive electrode slurry is dried.
  • an anode slurry containing a negative electrode active material, a binder, and a conductive agent was coated on the anode current collector, and a negative electrode sheet was obtained after the anode slurry was dried.
  • the battery charging cutoff voltage of the embodiment of the present application is not less than 4.2V, that is, operating in the range of 4.2V to 4.9V, and further preferably operating in the range of 4.3V to 4.8V.
  • the higher the valence state of the transition metal on the surface of the positive electrode material the stronger the Coulomb interaction with the nitrile group in the additive, that is, the additive can exert the corresponding protective effect to a greater extent.
  • electrolyte a mixture of ethylene carbonate (abbreviated as EC), ethyl methyl carbonate (abbreviated as EMC) and diethyl carbonate (referred to as DEC) as solvent, wherein the weight ratio of EC, EMC and DEC It is 1:1:1.
  • the lithium salt was LiPF 6 and the total content of LiPF 6 was 12.5% of the total weight of the electrolyte.
  • the electrolyte composition shown in Table 1 was added to the additive, wherein the proportion of the additive was a ratio of the total weight of the electrolyte.
  • positive electrode tab The positive active material LiCoO 2 , the binder PVDF and the conductive agent acetylene black were mixed at a mass ratio of 98:1:1, N-methylpyrrolidone was added, and the mixture was stirred until stable and uniform under the action of a vacuum mixer.
  • the positive electrode slurry was uniformly coated on the aluminum foil; the aluminum foil was air-dried at room temperature, transferred to a blast oven at 120 ° C for 1 hour, and then cold pressed and slit to obtain a positive electrode sheet.
  • the negative electrode tab Preparation of the negative electrode tab : the negative active material graphite, the conductive agent acetylene black, the thickener sodium carboxymethyl cellulose (CMC) solution, the binder styrene-butadiene rubber emulsion are mixed according to the mass ratio of 97:1:1:1. Add deionized water, stir to a stable and uniform under the action of a vacuum mixer to obtain a negative electrode slurry; uniformly apply the negative electrode slurry to the copper foil; dry the copper foil at room temperature, transfer it to a blast oven at 120 ° C to dry After 1 h, the negative electrode sheets were obtained by cold pressing and slitting.
  • CMC carboxymethyl cellulose
  • the positive electrode piece, the negative electrode piece and the PP/PE/PP separator are wound to obtain a battery core, and after the battery core is placed in the package, the electrolyte is injected, and then the sealing is sequentially performed, and the mixture is allowed to stand still and cool.
  • Lithium-ion batteries are obtained by processes such as pressing, chemical formation, exhaust, and test capacity.
  • the content of the polynitrile six-membered nitrogen heterocyclic compound is a weight percentage calculated based on the total weight of the electrolytic solution.
  • the lithium ion secondary battery is first charged at a constant current of 1 C to a voltage of 4.35 V, further charged at a constant voltage of 4.35 V until the current is 0.05 C, and then discharged at a constant current of 1 C to a voltage of 3.0 V, which is a During the charge and discharge cycle, this discharge capacity is the discharge capacity of the first cycle.
  • the lithium ion battery was subjected to 200 cycles of charge/discharge test in accordance with the above method, and the discharge capacity at the 200th cycle was detected.
  • Capacity retention ratio (%) after lithium battery cycle 200 times (discharge capacity of 200 cycles of lithium ion battery cycle / discharge capacity of first cycle of lithium ion battery) ⁇ 100%.
  • the lithium-ion battery is first charged at a constant current of 1 C to a voltage of 4.35 V, further charged at a constant voltage of 4.35 V until the current is 0.05 C, and then discharged at a constant current of 1 C to a voltage of 3.0 V, which is a charge.
  • the discharge capacity of this time is the discharge capacity of the first cycle.
  • the lithium ion battery was subjected to 200 cycles of charge/discharge test in accordance with the above method, and the discharge capacity at the 200th cycle was detected.
  • Capacity retention ratio (%) after lithium battery cycle 200 times (discharge capacity of 200 cycles of lithium ion battery cycle / discharge capacity of first cycle of lithium ion battery) ⁇ 100%.
  • the lithium ion battery was charged at a constant current of 0.5 C to a voltage of 4.35 V, and then charged at a constant voltage of 4.35 V until the current was 0.05 C.
  • the thickness of the lithium ion battery was tested and recorded as h0; Ion battery is placed in an 85 ° C incubator, stored for 24 hours, removed, tested at this time lithium ion The thickness of the battery is recorded as h1.
  • the thickness expansion ratio (%) of the lithium ion battery after 24 hours of storage [(h1 - h0) / h0] ⁇ 100%.
  • the above table uses lithium ion battery cycle capacity retention rate to evaluate its high voltage and high temperature cycle performance, and uses lithium ion battery thickness expansion rate to evaluate its high temperature storage performance.
  • each polynitrile six-membered aza The ring molecule has two or more nitrile groups at the same time.
  • the lone pair electrons contained in the nitrogen atoms in these nitrile groups can be strongly enhanced with the 3d empty orbit of the transition metal on the surface of the positive electrode material.
  • Geocomplexation while reducing the surface activity of the positive electrode (especially at high SOC), isolates the direct contact between the electrolyte and the surface of the positive electrode, so that the surface side reaction is greatly reduced, and the lithium ions consumed in the side reaction are correspondingly reduced. That is to say, the consumption rate of reversible lithium ions is greatly slowed down, and the actual effect finally manifested is that the cycle capacity retention rate is greatly improved.
  • some surface side reactions can generate gas, and the reduction of surface side reactions means a decrease in gas production. The actual effect that appears is that the battery thickness expansion effect at high temperatures is significantly reduced.
  • the batteries 1 to 16 and the battery 17 that after adding 0.001% of the polynitrile six-membered nitrogen heterocyclic compound to the lithium ion battery electrolyte, the high-temperature storage performance is improved compared with the battery 17; when the lithium ion battery electrolyte When the mass percentage of the polynitrile six-membered nitrogen heterocyclic compound is increased to 2%, the high temperature, high voltage cycle performance and storage performance of the lithium ion battery can be effectively improved; when the lithium ion battery electrolyte is polynitrile When the mass percentage of the elemental nitrogen heterocyclic compound is 10%, a thick complex layer can be formed, thereby greatly suppressing the occurrence of side reaction on the surface of the positive electrode material, further reducing the thickness expansion ratio, and high-temperature storage performance.
  • the improvement is very obvious; when the content of the polynitrile six-membered nitrogen heterocyclic compound in the lithium ion battery electrolyte is further increased to 11% by mass, the formation on the surface of the positive electrode material is on the one hand due to the large amount of addition.
  • the layer is too thick and dense, affecting the diffusion and migration of lithium ions, and on the other hand, the overall viscosity of the electrolyte is increased, the ionic conductivity is lowered, and the lithium ion battery is heated. High voltage cycle with a downward trend.
  • the distance between the nitrile group and the nitrile group is closer to the layered positive electrode in the polynitrile six-membered nitrogen heterocyclic molecule due to the adjustment of the cyclic structure.
  • the distance between the transition metal of the material surface and the transition metal enables all the nitrile groups in the molecule to maximize the complexation, so that the efficiency of the passivation surface is greatly increased, so the coverage of the surface transition metal is much stronger than that.
  • Adiponitrile so the improvement of cycle and storage performance is more outstanding.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

本申请涉及储能材料领域，具体讲，涉及一种电解液及应用该电解液的电池，电解液中含有添加剂，添加剂选自如式I-1、式I-2或式I-3所示的多腈基六元氮杂环化合物中的至少一种。本申请的电解液中通过加入多腈基六元氮杂环化合物作为添加剂，能有效钝化正极材料表面活性，抑制其对电解液的氧化作用，使用本申请电解液的电池具有较好的高温高压循环性能和存储性能，同时可以降低电池产气。

Description

一种电解液及电池 技术领域
本申请涉及储能材料领域，具体地讲，涉及一种电解液及应用该电解液的电池。
背景技术
锂离子电池由于具备能量密度大、输出功率高、循环寿命长和环境污染小等优点而被广泛应用于电动汽车以及消费类电子产品中。目前对锂离子电池的需求是：高电压、高功率、长循环寿命、长存储寿命且安全性能优异。
锂离子电池目前广泛使用的是以六氟磷酸锂为导电锂盐以及以环状碳酸酯和/或链状碳酸酯为溶剂的电解液体系。然而上述电解液体系尚存在诸多不足，例如在高电压和高温情况下，上述电解液体系的循环性能和存储性能有待提高。
鉴于此，特提出本申请。
发明内容
为了解决上述问题，本申请人进行锐意研究后发现：通过加入多腈基六元氮杂环化合物作为电解液添加剂，能有效钝化正极材料表面活性，抑制其对电解液的氧化作用，同时可以降低电池产气，从而可提高电池的高温高压循环性能和存储性能。从而完成本申请。
本申请的目的在于提供一种电解液，电解液中含有添加剂，添加剂选自如式I-1、式I-2或式I-3所示的多腈基六元氮杂环化合物中的至少一种：
Figure PCTCN2017093311-appb-000001
其中，R1、R2、R3和R4各自独立的选自氢、卤素、取代或未取代的C1～C12烷基、取代或未取代的C1～C12烷氧基、取代或未取代的C1～C12胺基、取代或未取代的C2～C12烯基、取代或未取代的C2～C12炔基、取代或未取代的C6～C26芳基、取代或未取代的C4～C12杂环基；
取代基选自卤素、腈基、C1～C6烷基、C2～C6烯基、C1～C6烷氧基中的至少一种；
x、y、z各自独立的选自0～8的整数；
m、n、k各自独立的选自0～2的整数。
本申请的另一目的在于提供一种电池，包括正极极片、负极极片、置于正极极片和负极极片之间的隔离膜以及电解液，所述电解液为本申请的电解液。
本申请的技术方案至少具有以下有益的效果：
本申请的电解液中通过加入多腈基六元氮杂环化合物作为添加剂，能有效钝化正极材料表面活性，抑制其对电解液的氧化作用，同时可以降低电池产气。使用本申请的电解液的电池具有较好的高温高压循环性能和存储性能。
附图说明：
图1为A2化合物核磁共振碳谱；
图2为A8化合物核磁共振碳谱；
图3为A13化合物核磁共振碳谱。
具体实施方式
为了使本申请的发明目的、技术方案和有益技术效果更加清晰，以下结合实施例，对本申请进行进一步详细说明。应当理解的是，本说明书中描述的实施例仅仅是为了解释本申请，并非为了限定本申请，实施例的配方、比例等可因地制宜做出选择而对结果并无实质性影响。
下面详细说明根据本申请的电解液及电池。
首先说明根据本申请第一方面的电解液。
为了实现上述发明目的，本申请实施例的第一方面提供了一种电解液，包括有机溶剂、电解质盐和添加剂。其中，添加剂包括多腈基六元氮杂环化合物。
〔多腈基六元氮杂环化合物〕
本申请实施例的多腈基六元氮杂环化合物选自如式I-1、式I-2或式I-3所示的化合物中的至少一种：
Figure PCTCN2017093311-appb-000002
其中，R1、R2、R3和R4各自独立的选自氢、卤素、取代或未取代的C1～C12烷基、取代或未取代的C1～C12烷氧基、取代或未取代的C1～C12胺基、取代或未取代的C2～C12烯基、取代或未取代的C2～C12炔基、取代或未取代的C6～C26芳基、取代或未取代的C4～C12杂环基；
取代基选自卤素、腈基、C1～C6烷基、C2～C6烯基、C1～C6烷氧基中的至少一种；
x、y、z各自独立的选自0～8的整数；
m、n、k各自独立的选自0～2的整数。
由于多腈基六元氮杂环化合物具有腈类基团，该类基团中的氮原子与 过渡金属具有较强的络合作用，因此当其应用于电解液后，吸附在正极材料表面后可生成一层疏松的多孔保护膜，隔绝正极材料表面与电解液接触的同时并不影响锂离子的正常传输、降低正极材料表面活性的同时可抑制表面发生的大量表面副反应，达到减少副产物、抑制产气的作用。
此外，本申请的多腈基六元氮杂环化合物虽然为腈类化合物，然而由于其具有特殊的六元氮杂环结构，因此可影响其中的腈基的成膜电位以及在正极材料表面的成膜效果等，进一步地可改善整个电池体系的电化学性能，诸如降低产气、提高高温高压循环寿命等。
(一)在本申请实施例中，式I-1所示的化合物为多腈基嘧啶类化合物。
作为式I-1所示的化合物的一种改进，R1、R2、R3和R4各自独立地选自氢、卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C5～C9环烷基、取代或未取代的C1～C6烷氧基、取代或未取代的C1～6胺基、取代或未取代的C2～6烯基、取代或未取代的C2～C6炔基、取代或未取代的C6～12芳基、取代或未取代的C4～C12杂环基；取代基选自卤素。
作为式I-1所示的化合物的一种改进，R1、R2、R3和R4各自独立地选自氢、卤素、取代或未取代的C1～C3直链或支链烷基、取代或未取代的C5～C7环烷基、取代或未取代的C1～C3烷氧基、取代或未取代的C1～C3胺基、取代或未取代的C2～C3烯基、取代或未取代的C2～C3炔基、取代或未取代的C6～C8芳基、取代或未取代的C4～C7杂环基；取代基选自卤素。
其中，烷基、烯基和炔基可为链状取代基，也可为环状取代基，其中，链状取代基包括直链取代基和支链取代基。
在式I-1所示的化合物中，x优选地选自0～6的整数，进一步优选0～4的整数；更优选地选自1或2；y优选地选自0～6的整数，进一步优选0～4的整数；更优选地选自1或2。
作为式I-1所示的化合物的一种改进，R1和R3为相同的基团；优选地，R1、R3和R4均为相同的基团。
作为式I-1所示的化合物的一种改进，R1和R3为氢；优选地，R1、 R3和R4均为氢。作为式I-1所示的化合物的一种改进，R1～R4均为氢；或者R1、R3和R4均为氢，R2选自卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C1～C6烷氧基；取代基选自卤素，优选氟。
作为式I-1所示的化合物的一种改进，式I-1所示化合物具体选自以下化合物并不限于此：
Figure PCTCN2017093311-appb-000003
(二)在本申请实施例中，式I-2为多腈基哌嗪类化合物。
作为式I-2所示的化合物的一种改进，R1、R2、R3和R4各自独立地选自氢、卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C5～C9环烷基、取代或未取代的C1～C6烷氧基、取代或未取代的C1～C6胺基、取代或未取代的C2～C6烯基、取代或未取代的C2～C6炔基、取代或未取代的C6～C12芳基、取代或未取代的C4～C13杂环基；取代基选自卤素。
作为式I-2所示的化合物的一种改进，R1、R2、R3和R4各自独立地选自氢、卤素、取代或未取代的C1～C3直链或支链烷基、取代或未取代的C5～C7环烷基、取代或未取代的C1～C3烷氧基、取代或未取代的C1～C3胺基、取代或未取代的C2～C3烯基、取代或未取代的C2～C3炔基、取代或未取代的C6～C8芳基、取代或未取代的C4～C7杂环基；取代基选自卤素。
其中，烷基、烯基和炔基可为链状取代基，也可为环状取代基，其中， 链状取代基包括直链取代基和支链取代基。
在式I-2所示的化合物中，x优选0～6的整数，进一步优选0～4的整数；更优选地选自1或2；y优选地选自0～6的整数，进一步优选0～4的整数；更优选1或2。
作为式I-2所示的化合物的一种改进，R1、R2、R3和R4中至少有两个为相同的基团；优选地，R1、R2、R3和R4中至少有三个为相同的基团。
作为式I-2所示的化合物的一种改进，R1、R2、R3和R4中至少有两个为氢；优选地，R1、R2、R3和R4中至少有三个为氢。
作为式I-2所示的化合物的一种改进，R1～R4均为氢；或者R1、R2、R3和R4中至少有三个为氢，另一个基团选自卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C1～C6烷氧基；取代基选自卤素，优选氟。
作为式I-2所示的化合物的一种改进，式I-2所示化合物具体选自以下化合物并不限于此：
Figure PCTCN2017093311-appb-000004
(三)在本申请实施例中，式I-3为多腈基均三嗪类化合物。
作为式I-3所示的化合物的一种改进，R1、R2和R3各自独立地选自氢、卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C5～C9环烷基、取代或未取代的C1～C6烷氧基、取代或未取代的C1～C6胺基、取代或未取代的C2～C6烯基、取代或未取代的C2～C6炔基、取代或未取代的C6～C12芳基、取代或未取代的C4～C13杂环基；取代基选自卤素。
作为式I-3所示的化合物的一种改进，R1、R2和R3各自独立地选自氢、 卤素、取代或未取代的C1～C3直链或支链烷基、取代或未取代的C5～C7环烷基、取代或未取代的C1～C3烷氧基、取代或未取代的C1～C3胺基、取代或未取代的C2～C3烯基、取代或未取代的C2～C3炔基、取代或未取代的C6～C8芳基、取代或未取代的C4～C7杂环基；取代基选自卤素。
其中，烷基、烯基和炔基可为链状取代基，也可为环状取代基，其中，链状取代基包括直链取代基和支链取代基。
在式I-3所示的化合物中，x优选地选自0～6的整数，进一步优选0～4的整数；更优选1或2；y优选地选自0～6的整数，进一步优选0～4的整数；更优选1或2。
作为式I-3所示的化合物的一种改进，R1、R2和R3中至少有两个为相同的基团。
作为式I-3所示的化合物的一种改进，R1、R2和R3中至少有两个为氢。
作为式I-3所示的化合物的一种改进，R1、R2和R3均为氢；或者R1、R2和R3中至少有两个为氢，另一个基团选自卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C1～C6烷氧基；取代基选自卤素，优选氟。
作为式I-3所示的化合物的一种改进，式I-3所示化合物具体选自以下化合物并不限于此：
Figure PCTCN2017093311-appb-000005
Figure PCTCN2017093311-appb-000006
作为本申请实施例电解液的一种改进，多腈基六元氮杂环化合物还可选自以下化合物并不限于此：
Figure PCTCN2017093311-appb-000007
Figure PCTCN2017093311-appb-000008
作为本申请实施例电解液的一种改进，多腈基六元氮杂环化合物在所述电解液中的质量百分含量为0.001％～10％。如果多腈基六元氮杂环化合物含量过低，则其对电解液的改善效果不明显，如果多腈基六元氮杂环化合物含量过高，则其形成的络合物层厚度过大，进而使正负极阻抗大幅增高，恶化电池性能。
本申请实施例多腈基六元氮杂环化合物在电解液中的质量百分含量范围的上限任选自10％、9％、8％、7％、6％、5％、4.5％、4％、3.5％、3％、2％、1％、0.8％，下限任选自0.001％、0.005％、0.01％、0.05％、0.1％、0.3％、0.5％、0.6％。更进一步优选地，多腈基六元氮杂环在电解液中的百分含量为0.1％～3.5％。
〔添加剂A〕
本申请实施例的电解液中可进一步添加其他添加剂作为添加剂A，添加剂A可合适地列举出以下(a)～(o)的化合物。
(a)含有不饱和键的环状碳酸酯化合物
含有不饱和环状碳酸酯化合物选自如式Ⅱ-0所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000009
其中，R20选自烯基取代的C1～C6亚烷基、取代或未取代的C2～C6亚烯基。
含有不饱和键的环状碳酸酯化合物选自以下化合物中至少一种，具体结构式如下：
Figure PCTCN2017093311-appb-000010
(b)卤素取代的环状碳酸酯化合物
卤素取代的环状碳酸酯化合物选自如式Ⅱ-1所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000011
其中，R21选自卤素取代的C1～C6亚烷基、卤素取代的C2～C6亚烯基。
卤素取代的环状碳酸酯化合物选自氟代碳酸乙烯酯(简称为FEC)、氟代碳酸丙烯酯(简称为FPC)、三氟代碳酸丙烯酯(简称为TFPC)。
(c)硫酸酯化合物
硫酸酯化合物优选为环状硫酸酯化合物，环状硫酸酯化合物选自如式Ⅱ-2所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000012
其中，R22选自取代或未取代的C1～C6亚烷基、取代或未取代的C2～C6亚烯基；取代基选自卤素、C1～C3烷基、C2～C4烯基。
进一步优选的，R22选自取代或未取代的C1～C4亚烷基、取代或未取代的C2～C4亚烯基；取代基选自卤素、C1～C3烷基、C2～C4烯基。
环状硫酸酯化合物选自硫酸乙烯酯(简称为DTD)、硫酸丙烯酯(简称为TMS)、4-甲基硫酸亚乙酯(简称为PLS)中的至少一种，具体结构式如下；
Figure PCTCN2017093311-appb-000013
作为本申请实施例电解液的一种改进，环状硫酸酯化合物还可以选自：
Figure PCTCN2017093311-appb-000014
(d)磺酸内酯化合物
磺酸内酯化合物选自如式Ⅱ-3所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000015
其中，R23选自取代或未取代的C1～C6亚烷基、取代或未取代的C2～C6亚烯基；取代基选自卤素、C1～C3烷基、C2～C4烯基。
具体的，磺酸内酯化合物选自1,3-丙烷磺酸内酯(简称为PS)、1,3-丙烯磺酸内酯(简称为PES)中的至少一种，具体结构式如下；
Figure PCTCN2017093311-appb-000016
磺酸内酯化合物还可以选自：
Figure PCTCN2017093311-appb-000017
(e)二磺酸化合物
二磺酸化合物为含有两个磺酸基的化合物，进一步优选的，选自二磺 酸亚甲酯化合物；具体可选自如式Ⅱ-4所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000018
其中，R24、R25、R26、R27各自独立地选自氢、卤素、取代或未取代的C1～C10烷基、取代或未取代的C2～C10烯基；取代基选自卤素、C1～C3烷基、C2～C4烯基。
二磺酸亚甲酯化合物选自甲烷二磺酸亚甲酯(简称为MMDS)；
Figure PCTCN2017093311-appb-000019
二磺酸亚甲酯化合物还可选自3-甲基-甲烷二磺酸亚甲酯以及如下结构式中的一种或者几种：
Figure PCTCN2017093311-appb-000020
(f)亚硫酸酯化合物
亚硫酸酯化合物优选环状亚硫酸酯化合物，具体可选自如式Ⅱ-5所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000021
其中，R28选自取代或未取代的C1～C6亚烷基、取代或未取代的C2～C6亚烯基；取代基选自卤素、C1～C3烷基、C2～C4烯基。
亚硫酸酯化合物可选自亚硫酸乙烯酯(简称为ES)、亚硫酸丙烯酯(简称为PS)、亚硫酸丁烯酯(简称为BS)。
(g)腈化合物
腈化合物可选自乙腈、丙腈、丁二腈、戊二腈、己二腈、庚二腈、辛 二腈和癸二腈中的一种或二种以上的腈。
其中，更优选选自丁二腈、戊二腈、己二腈和庚二腈中的一种或二种以上。
(h)芳香化合物
芳香化合物可选自环己基苯、氟代环己基苯化合物(1-氟-2-环己基苯、1-氟-3-环己基苯、1-氟-4-环己基苯)、叔丁基苯、叔戊基苯、1-氟-4-叔丁基苯等具有支链烷基的芳香族化合物、联苯、三联苯(邻位体、间位体、对位体)、二苯基醚、氟苯、二氟苯(邻位体、间位体、对位体)、茴香醚、2，4-二氟茴香醚、三联苯的部分氢化物(1，2-二环己基苯、2-苯基双环己基、1，2-二苯基环己烷、邻环己基联苯)等芳香化合物。
其中，更优选为选自联苯、三联苯(邻位体、间位体、对位体)、氟苯、环己基苯、叔丁基苯和叔戊基苯中的一种或二种以上，特别优选为选自联苯、邻三联苯、氟苯、环己基苯和叔戊基苯中的一种或二种以上。
(i)异氰酸酯化合物
异氰酸酯化合物可选自甲基异氰酸酯、乙基异氰酸酯、丁基异氰酸酯、苯基异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、1，4－亚苯基二异氰酸酯、丙烯酸2－异氰酸根合乙酯、和甲基丙烯酸2－异氰酸根合乙酯中的一种或二种以上的异氰酸酯化合物。
其中，更优选为六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、丙烯酸2－异氰酸根合乙酯、和甲基丙烯酸2－异氰酸根合乙酯中的一种或二种以上。
(j)磷腈化合物
磷腈化合物可以优选地列举出甲氧基五氟环三磷腈、乙氧基五氟环三磷腈、苯氧基五氟环三磷腈或乙氧基七氟环四磷腈等环状磷腈化合物。
其中，优选甲氧基五氟环三磷腈、乙氧基五氟环三磷腈、或苯氧基五氟环三磷腈等环状磷腈化合物，更优选甲氧基五氟环三磷腈或乙氧基五氟环三磷腈。
(k)环状酸酐化合物
环状酸酐化合物可以合适地列举出乙酸酐、丙酸酐等链状的羧酸酐、 或琥珀酸酐、马来酸酐、2-烯丙基琥珀酸酐、戊二酸酐、衣康酸酐、3-磺基-丙酸酐等环状酸酐。
其中，优选琥珀酸酐、马来酸酐、2-烯丙基琥珀酸酐，更优选琥珀酸酐、2-烯丙基琥珀酸酐。
(l)亚磷酸酯化合物
亚磷酸酯化合物可选自硅烷亚磷酸酯化合物，具体可选自如式Ⅱ-6所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000022
其中，R31、R32、R33、R34、R35、R36、R37、R38、R39各自独立的分别选自取代或未取代的C1～C6烷基；取代基选自卤素。
硅烷亚磷酸酯化合物可选自以下化合物中的至少一种，
Figure PCTCN2017093311-appb-000023
(m)磷酸酯化合物
磷酸酯化合物可选自硅烷磷酸酯化合物，具体可选自如式Ⅱ-7所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000024
其中，R41、R42、R43、R44、R45、R46、R47、R48、R49各自独立的分别选自取代或未取代的C1～C6烷基；取代基选自卤素。
硅烷磷酸酯化合物可选自以下化合物中的至少一种，
Figure PCTCN2017093311-appb-000025
(n)硼酸酯化合物
硼酸酯化合物可选自硅烷硼酸酯化合物，具体可选自如式Ⅱ-8所示化合物中的至少一种；
Figure PCTCN2017093311-appb-000026
其中，R51、R52、R53、R54、R55、R56、R57、R58、R59各自独立的分别选自取代或未取代的C1～C6烷基；取代基选自卤素。
硅烷硼酸酯化合物可选自以下化合物中的至少一种，
Figure PCTCN2017093311-appb-000027
(o)羧酸酯
羧酸酯可以选自链状羧酸酯、环状羧酸酯。该链状羧酸酯、环状羧酸酯中可以含有不饱和键或卤素原子。
优选地为乙酸乙酯(简称为EA)、丁酸甲酯(简称为MB)、丁酸乙酯(简称为EB)、三氟乙酸乙酯(简称为TFEA)、乙酸三氟乙酯(简称为ETFA)、五氟丙酸甲酯(简称为MPFP)中的至少一种。
作为本申请实施例电解液的一种改进，添加剂A在电解液中的质量百分含量为0.01％～30％。
在本申请实施例的式I-1、式I-2或式I-3所示的通式中：
碳原子数为1～12的烷基，烷基可为链状烷基，也可为环烷基，位于环烷基的环上的氢可被烷基取代，所述烷基中碳原子数优选的下限值为1、2、3、4、5，优选的上限值为3、4、5、6、8、10、12。优选地，选择碳原子数为1～10的烷基，进一步优选地，选择碳原子数为1～6的链状烷基，碳原子数为3～8的环烷基，更进一步优选地，选择碳原子数为1～4的链状烷基，碳原子数为5～7的环烷基。作为烷基的实例，具体可以举出：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、己基、2-甲基-戊基、3-甲基-戊基、1,1,2-三甲基-丙基、3,3,-二甲基-丁基、庚基、2-庚基、3-庚基、2-甲基己基、3-甲基己基、异庚基、辛基、壬基、癸基。
当前述所提到的碳原子数为1～12的烷基中含有氧原子时，可为烷氧基。优选地，选择碳原子数为1～10的烷氧基，进一步优选地，选择碳原子数为1～6的烷氧基，更进一步优选地，选择碳原子数为1～4的烷氧基。作为烷氧基的实例，具体可以举出：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、正戊氧基、异戊氧基、环戊氧基、环己氧基。
碳原子数为2～12的烯基可为环状烯基，也可为链状烯基。另外，烯基中双键的个数优选为1个。所述烯基中碳原子数优选的下限值为3、4、5，优选的上限值为3、4、5、6、8、10、12。优选地，选择碳原子数为2～10的烯基，进一步优选地，选择碳原子数为2～6的烯基，更进一步优选地，选择碳原子数为2～5的烯基。作为烯基的实例，具体可以举出：乙烯基、烯丙基、异丙烯基、戊烯基、环己烯基、环庚烯基、环辛烯基。
碳原子数为1～12的胺基选自
Figure PCTCN2017093311-appb-000028
或
Figure PCTCN2017093311-appb-000029
其中R’、R”为碳原子数为1～12的烷基。
碳原子数为2～12的炔基可为环状炔基，也可为链状炔基。另外，炔基中三键的个数优选为1个。所述炔基中碳原子数优选的下限值为3、4、5，优选的上限值为3、4、5、6、8、10、12。优选地，选择碳原子数为2～10的炔基，进一步优选地，选择碳原子数为2～6的炔基，更进一步优选地，选择碳原子数为2～5的炔基。作为烯基的实例，具体可以举出：乙炔基、炔丙基、异丙炔基、戊炔基、环己炔基、环庚炔基、环辛炔基。
碳原子数为6～26的芳基，例如苯基、苯烷基、至少含有一个苯基的芳基如联苯基、稠环芳烃基如萘、蒽、菲均可，联苯基和稠环芳烃基还可被烷基或是烯基所取代。优选地，选择碳原子数为6～16的芳基，进一步优选地，选择碳原子数为6～14的芳基，更进一步优选地，选择碳原子数为6～9的芳基。作为芳基的实例，具体可以举出：苯基、苄基、联苯基、对甲苯基、邻甲苯基、间甲苯基。
碳原子数为4～12的杂环基，杂原子可选自氧、氮、硫、磷、硼等，杂环可为脂杂环或芳杂环；可为五元和六元杂环及苯并杂环化合物。优选地，选择碳原子数为4～10的杂环基，进一步优选地，选择碳原子数为4～7的杂环基。具体可选自：呋喃基、噻吩基、吡咯基、噻唑基、咪唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、吲哚基、喹啉基等。
卤素选自氟、氯、溴，并优选氟。
在本申请实施例的式Ⅱ-0～式Ⅱ-8所示的通式中：
碳原子数为1～6的亚烷基为直链或支链亚烷基，所述亚烷基中碳原子数优选的下限值为2、3，优选的上限值为4、5、6。优选地，选择碳原子数为1～4的亚烷基。作为烷基的实例，具体可以举出：亚甲基、亚乙基、亚丙基、亚异丙基、亚丁基、亚异丁基、亚仲丁基、亚戊基、亚己基。
碳原子数为2～6的亚烯基为直链或支链亚烯基，烯基中双键的个数优选为1个。所述亚烯基中碳原子数优选的下限值为3、4，优选的上限值为3、4、5、6。优选地，选择碳原子数为2～5的亚烯基。作为亚烯基的实例，具体可以举出：亚乙烯基、亚烯丙基、亚异丙烯基、亚烯丁基、亚烯戊基。
卤素选自氟、氯、溴，并优选氟。
〔有机溶剂〕
作为本申请实施例的电解液中使用的有机溶剂，可以优选地列举出选自环状碳酸酯、链状酯、内酯、醚和酰胺中的一种或二种以上。从进一步提高高温高压循环性能和存储性能的角度出发，优选含有环状碳酸酯和链状碳酸酯。
此外，“链状酯”这一用语是作为包括链状碳酸酯和链状羧酸酯在内的概念来使用的。
作为上述环状碳酸酯，可以列举出选自碳酸乙烯酯(简称为EC)、碳酸丙烯酯(简称为PC)、碳酸1，2-亚丁酯、碳酸2，3-亚丁酯、碳酸亚乙烯酯(简称为VC)、碳酸乙烯基亚乙酯(简称为VEC)、4-乙炔基-1，3-二氧杂环戊烷-2-酮(简称为EEC)等具有碳－碳不饱和键的环状碳酸酯；和4-氟-1，3-二氧杂环戊烷-2-酮(简称为FEC)、反式或顺式-4，5-二氟-1，3-二氧杂环戊烷-2-酮(以下将两者统称为“DFEC”)等具有氟原子的环状碳酸酯中的一种或二种以上，更优选选自碳酸乙烯酯、碳酸丙烯酯、4-氟-1，3-二氧杂环戊烷-2-酮、碳酸亚乙烯酯和4-乙炔基-1，3-二氧杂环戊烷-2-酮(简称为EEC)中的一种或二种以上。
作为链状酯，可以合适地列举出选自碳酸甲乙酯(简称为MEC)、碳酸甲丙酯(简称为MPC)、碳酸甲基异丙酯(简称为MIPC)、碳酸甲丁酯和碳酸乙丙酯中的一种或二种以上的非对称链状碳酸酯；选自碳酸二甲酯(简称为DMC)、碳酸二乙酯(简称为DEC)、碳酸二丙酯和碳酸二丁酯中的一种或二种以上的对称链状碳酸酯；选自新戊酸甲酯、新戊酸乙酯、新戊酸丙酯等新戊酸酯、丙酸甲酯、丙酸乙酯、乙酸甲酯和乙酸乙酯中的一种或二种以上的链状羧酸酯。
作为其它的有机溶剂，可以合适地列举出选自四氢呋喃、2-甲基四氢呋喃、1，4-二噁烷等环状醚、1，2-二甲氧基乙烷、1，2-二乙氧基乙烷、1，2-二丁氧基乙烷等链状醚、二甲基甲酰胺等酰胺、环丁砜等砜、γ-丁内酯、γ-戊内酯、α-当归内酯等内酯等中的一种或二种以上。
〔电解质盐〕
作为本申请中使用的电解质盐，可以合适地列举出下述的锂盐。
〔Li盐－1类〕
可以合适地列举出选自LiPF6、LiBF4、LiAsF6、LiSbF6、LiPF4(CF3)2、LiPF3(C2F5)3、LiPF3(CF3)3、LiPF3(异-C3F7)3和LiPF5(异-C3F7)中的一种或二种以上的“路易斯酸与LiF的络盐”，其中优选LiPF6、LiBF4、LiAsF6，更优选LiPF6、LiBF4。
〔Li盐－2类〕
可以合适地列举出选自LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、(CF2)2(SO2)2NLi(环状)、(CF2)3(SO2)2NLi(环状)和LiC(SO2CF3)3中的一种或二种以上的“亚胺或甲基化锂盐”，其中优选LiN(SO2F)2、LiN(SO2CF3)2或LiN(SO2C2F5)2，更优选LiN(SO2F)2或LiN(SO2CF3)2。
〔Li盐－3类〕
可以合适地列举出选自LiSO3F、LiCF3SO3、CH3SO4Li、C2H5SO4Li、C3H7SO4Li、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、和五氟((甲磺酰)氧基)磷酸锂(LiPFMSP)中的一种或二种以上的“含有S(＝O)2O结构的锂盐”，其中更优选LiSO3F、CH3SO4Li、C2H5SO4Li或LiTFMSB。
〔Li盐－4类〕
可以合适地列举出选自LiPO2F2、Li2PO3F和LiClO4中的一种或二种以上的“含有P＝O或Cl＝O结构的锂盐”，其中优选LiPO2F2、Li2PO3F。
〔Li盐－5类〕
可以合适地列举出选自双[草酸根-O,O’]硼酸锂(LiBOB)、二氟[草酸根-O,O’]硼酸锂、二氟双[草酸根-O,O’]磷酸锂(LiPFO)和四氟[草酸根-O,O’]磷酸锂中的一种或二种以上的“以草酸盐配位体为阴离子的锂盐”，其中更优选LiBOB、LiPFO。可以混合它们中的一种或二种以上来使用。
其中，优选为选自LiPF6、LiPO2F2、Li2PO3F、LiBF4、LiSO3F、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、双[草酸根-O,O’]硼酸锂(LiBOB)、二氟双[草酸根-O,O’]磷酸锂(LiPFO)和四氟[草酸根-O,O’]磷酸锂中的一种或二种以上，更优选为选自LiPF6、 LiBF4、LiSO3F、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、LiPO2F2、LiN(SO2CF3)2、LiN(SO2F)2、双[草酸根-O,O’]硼酸锂(LiBOB)、和二氟双[草酸根-O,O’]磷酸锂(LiPFO)中的一种或二种以上，进一步优选为LiPF6。
〔电解液的制造〕
本申请实施例的电解液例如可以通过下述方法获得：混合上述有机溶剂，向其中添加电解质盐和本申请的多腈基六元氮杂环化合物，并还可添加上述添加剂A中的至少一种。
〔多腈基六元氮杂环化合物的合成〕
(一)通式I-1化合物的制备：
其反应方程式为：
Figure PCTCN2017093311-appb-000030
具体制备工艺为：
1、在20～60min内向原料P-1中滴加浓度为30～40％的P-2水溶液并快速搅拌，滴加完毕快速搅拌15～30h，70～90℃油浴回流搅拌3～5h，得到无色发烟粘稠状液体中间产物I-1-1；
2、继续加入K2CO3、KI、无水乙腈；快速搅拌成固液混合相，40～60℃下快速加入原料P-3，继续搅拌10～20h后冷却至室温，分离提纯得到式I-1 所示化合物。
(二)通式I-2化合物的制备：
其反应方程式为：
Figure PCTCN2017093311-appb-000031
具体制备工艺为：
将无水碳酸钠、原料P-4与原料P-3在无水乙醇中混合，反应搅拌2～5h。热乙醇反复多次冲洗得到粗产物，重结晶得到式I-2所示化合物。
(三)通式I-3化合物的制备：
其反应方程式为：
Figure PCTCN2017093311-appb-000032
具体制备工艺为：
将无水碳酸钠、原料P-5与原料P-3在无水乙醇中混合，反应搅拌2～5h。热乙醇反复多次冲洗得到粗产物，重结晶得到式I-3所示化合物。
合成例1：
Figure PCTCN2017093311-appb-000033
1、在0.5h内向1，3-丙二胺中滴加37％甲醛水溶液并快速搅拌，滴 加完毕快速搅拌20h，80℃油浴回流搅拌4h，得到无色发烟粘稠状液体中间产物六氢嘧啶；
2、继续加入K2CO3、KI、无水乙腈；快速搅拌成固液混合相，60℃下0.5h内加入β-氯丙腈，继续搅拌17h后冷却至室温，分离提纯得到式A2化合物。
核磁共振碳谱如图1所示。
合成例2：
Figure PCTCN2017093311-appb-000034
将无水碳酸钠、哌嗪与β-氯丙腈在无水乙醇中混合，反应搅拌4h。热乙醇反复多次冲洗得到粗产物，重结晶得到式A8化合物。
核磁共振碳谱如图2所示。
合成例3：
Figure PCTCN2017093311-appb-000035
将无水碳酸钠、1,3,5-均三嗪与氯乙腈在无水乙醇中混合，反应搅拌4h。热乙醇反复多次冲洗得到粗产物，重结晶得到式A13化合物。
核磁共振碳谱如图3所示。
下面说明根据本申请实施例第二方面的电池。
根据本申请实施例的电池，包括正极极片、负极极片、置于正极极片和负极极片之间的隔离膜以及电解液。需要说明的是，本申请实施例的电池可为锂离子电池、钠离子电池或镁离子电池。
当电池为锂离子电池时，正极包含能脱出、嵌入锂离子的正极活性材料，负极包含能嵌入、脱出锂离子的负极活性材料。
具体的，当电池为锂离子电池时，正极活性材料可选自锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物、这些锂过渡金属氧化物添加其他过渡金属或非过渡金属得到的化合物，上述物质的一种或几种的混合物。具体可以采用层状含锂氧化物、尖晶石型含锂氧化物、橄榄石型含锂磷酸盐化合物等。但并不限定于这些材料，可以使用可被用作锂离子电池正极活性物质的传统公知的材料。这些正极活性物质可以仅单独使用一种，也可以将两种以上组合使用。
具体的，当电池为锂离子电池时，负极活性材料可为软碳、硬碳、人造石墨、天然石墨、硅、硅氧化合物、硅碳复合物、钛酸锂，能与锂形成合金的金属等。具体可以采用碳基负极、硅基负极、锡基负极等。但并不限定于这些材料，可以使用可被用作锂离子电池负极活性物质的传统公知的材料。这些负极活性物质可以仅单独使用一种，也可以将两种以上组合使用。
当电池为钠离子电池时，正极包含能脱出、嵌入钠离子的正极活性材料，负极包含能嵌入、脱出钠离子的负极活性材料。例如，正极活性材料可以选自钠铁复合氧化物(NaFeO2)、钠钴复合氧化物(NaCoO2)、钠铬复合氧化物(NaCrO2)、钠锰复合氧化物(NaMnO2)、钠镍复合氧化物(NaNiO2)、钠镍钛复合氧化物(NaNi1/2Ti1/2O2)、钠镍锰复合氧化物(NaNi1/2Mn1/2O2)、钠铁锰复合氧化物(Na2/3Fe1/3Mn2/3O2)、钠镍钴锰复合氧化物(NaNi1/3Co1/3Mn1/3O2)、钠铁磷酸化合物(NaFePO4)、钠锰磷酸化合物(NaMnPO4)、钠钴磷酸化合物(NaCoPO4)等。但并不限定于这些材料，可以使用可被用作钠离子电池正极活性物质的传统公知的材料。这些正极活性物质可以仅单独使用一种，也可以将两种以上组合使用。
负极活性材料可以选自硬碳、天然石墨、人造石墨、软碳、炭黑、乙炔黑、碳纳米管、石墨烯、碳纳米纤维等碳材料。此外，作为其他负极活性物质，还可以列举出例如Si、Ge、Pb、In、Zn、H、Ca、Sr、Ba、Ru、Rh等与钠发生合金化的元素的单质、含这些元素的氧化物以及碳化物等。 但并不限定于这些材料，可以使用可被用作钠离子电池负极活性物质的传统公知的材料。这些负极活性物质可以仅单独使用一种，也可以将两种以上组合使用。
当电池为镁离子电池时，正极包含能脱出、嵌入镁离子的正极活性材料，负极包含能嵌入、脱出镁离子的负极活性材料。例如，正极活性材料可以选自V2O5、MoO3、MnO2、TiS2、MoS2等，负极活性材料可以选自金属镁、镁合金、石墨等。但并不限定于这些材料，可以使用可被用作镁离子电池正负极活性物质的传统公知的材料。这些正负极活性物质可以仅单独使用一种，也可以将两种以上组合使用。
在上述电池中，隔膜的具体种类并不受到具体的限制，可以是现有电池中使用的任何隔膜材料，例如聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜，但不仅限于这些。
电解液为上述第一方面所述的电解液。
在上述中，正极片还包括粘结剂和导电剂，将包含有正极活性材料、粘结剂和导电剂的正极浆料涂覆在正极集流体上，待正极浆料干燥后获得正极片。同样的，将包含有负极活性材料、粘结剂和导电剂的负极浆料涂覆在负极集流体上，待负极浆料干燥后获得负极片。
进一步地，本申请实施例的电池充电截止电压不小于4.2V，即在4.2V～4.9V范围内工作，进一步优选的，在4.3V～4.8V范围内工作。在高电压状态下，正极材料表面过渡金属的价态越高，与添加剂中腈类基团的库仑相互作用便越强，也即添加剂能够越大程度地发挥相应的保护作用。
实施例
在本申请实施例的下述具体实施例中，仅示出锂离子电池的实施例，但本申请实施例不限于此。下面结合锂离子电池的实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。在下述实施例、对比例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得。
电解液的制备：采用碳酸乙烯酯(简称为EC)、碳酸甲乙酯(简称为EMC)和碳酸二乙酯(简称为DEC)的混合液为溶剂，其中，EC、EMC和DEC的重量比为1:1:1。锂盐为LiPF6，LiPF6的总含量为电解液的总重量的12.5％。如表1所示的电解液组成加入添加剂，其中添加剂的比例为占电解液的总重量的比例。
正极极片的制备：将正极活性材料LiCoO2、粘结剂PVDF、导电剂乙炔黑按照质量比98:1:1混合，加入N-甲基吡咯烷酮，在真空搅拌机作用下搅拌至稳定均一，获得正极浆料；将正极浆料均匀涂覆于铝箔上；将铝箔在室温晾干后转移至120℃的鼓风烘箱中干燥1h，然后经过冷压、分切得到正极片。
负极极片的制备：将负极活性材料石墨、导电剂乙炔黑、增稠剂羧甲基纤维素钠(CMC)溶液、粘结剂丁苯橡胶乳液按照质量比97:1:1:1混合，加入去离子水，在真空搅拌机作用下搅拌至稳定均一，获得负极浆料；将负极浆料均匀涂覆于铜箔上；将铜箔在室温晾干后转移至120℃的鼓风烘箱中干燥1h，然后经过冷压、分切得到负极片。
电池的制备：将正极极片、负极极片以及PP/PE/PP隔离膜进行卷绕得到电芯，将电芯放入包装壳后，注入电解液，再依次封口，经静置、热冷压、化成、排气、测试容量等工序，获得锂离子电池。
在表1中，多腈基六元氮杂环化合物的含量为基于电解液的总重量计算得到的重量百分数。
表1：电池1～18电解液中的组分及添加比例
Figure PCTCN2017093311-appb-000036
Figure PCTCN2017093311-appb-000037
将电池1至电池18进行如下的测试：
(1)锂离子电池在高电压情况下的循环性能测试
在25℃下，将锂离子次电池先以1C恒流充电至电压为4.35V，进一步以4.35V恒压充电至电流为0.05C，然后以1C恒流放电至电压为3.0V，此为一个充放电循环过程，此次的放电容量为首次循环的放电容量。将锂离子电池按照上述方法进行200次循环充电/放电测试，检测得到第200次循环的放电容量。
锂离子电池循环200次后的容量保持率(％)＝(锂离子电池循环200次的放电容量/锂离子电池首次循环的放电容量)×100％。
(2)锂离子电池在高温、高电压情况下的循环性能测试
在45℃下，将锂离子电池先以1C恒流充电至电压为4.35V，进一步以4.35V恒压充电至电流为0.05C，然后以1C恒流放电至电压为3.0V，此为一个充放电循环过程，此次的放电容量为首次循环的放电容量。将锂离子电池按照上述方法进行200次循环充电/放电测试，检测得到第200次循环的放电容量。
锂离子电池循环200次后的容量保持率(％)＝(锂离子电池循环200次的放电容量/锂离子电池首次循环的放电容量)×100％。
(3)锂离子电池在高温情况下的存储性能测试
在85℃下，将锂离子电池以0.5C恒流充电至电压为4.35V，然后以4.35V恒压充电至电流为0.05C，此时测试锂离子电池的厚度并记为h0；之后将锂离子电池放入85℃的恒温箱，储存24h后取出，测试此时锂离子 电池的厚度并记为h1。
锂离子电池存储24h后的厚度膨胀率(％)＝[(h1-h0)/h0]×100％。
表2：循环容量保持率、厚度膨胀率实验结果
Figure PCTCN2017093311-appb-000038
上表采用锂离子电池循环容量保持率评价其高电压、高温循环性能，采用锂离子电池的厚度膨胀率评价其高温存储性能。
从电池1-16和电池17的对比中可以看出：在锂离子电池的电解液中加入多腈基六元氮杂环化合物可有效提高锂离子电池的高电压、高温循环性能。多腈基六元氮杂环化合物加入锂离子电池的电解液中，能够明显改善锂离子电池的高温、高电压循环性能以及高温存储性能，其机理主要为：每个多腈基六元氮杂环分子同时具备两个或多个腈类基团，这些腈类基团中氮原子含有的孤对电子可与正极材料表面过渡金属的3d空轨道强有力 地络合，在降低正极表面活性的同时(尤其是在高SOC下)隔绝了电解液与正极表面的直接接触，使得表面副反应大为减少，副反应中消耗的锂离子也就相应减少，也就是可逆锂离子的消耗速度大大减慢，最终显现出来的实际效果即是循环容量保持率大幅提升。另外，部分表面副反应可产生气体，表面副反应的减少意味着产气量的减少，显现出来的实际效果即高温下电池厚度膨胀效应明显减轻。
从电池1～16和电池17可以看出：在锂离子电池电解液中加入0.001％的多腈基六元氮杂环化合物后，高温存储性能较电池17有一定提高；当锂离子电池电解液中多腈基六元氮杂环化合物的质量百分含量增加到2％时，可有效地提高锂离子电池的高温、高电压循环性能以及存储性能；当锂离子电池电解液中多腈基六元氮杂环类化合物的质量百分含量为10％时，可形成较厚的络合物层，从而大大抑制了正极材料表面副反应的发生，使厚度膨胀率进一步降低，对高温存储性能的改善非常明显；当锂离子电池电解液中多腈基六元氮杂环类化合物的含量进一步增加到质量百分含量为11％时，由于加入量较多，一方面在正极材料表面形成的络合物层过于厚和致密，影响锂离子的扩散迁移，另一方面还导致了电解液整体黏度提升、离子电导率下降，使锂离子电池的高温、高电压循环性能具有下降的趋势。
与电池18中采用的线性的己二腈比较，由于环状结构的调节，多腈基六元氮杂环类分子中，腈类基团与腈类基团间的距离更加贴近于层状正极材料表面过渡金属与过渡金属间的距离，使得其分子中的所有腈类基团能够最大限度地发挥络合作用，使得钝化表面的效率大大增加，因此对表面过渡金属的覆盖作用远强于己二腈，故对循环和存储性能的改善效果更加出众。
根据上述说明书的揭示和教导，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本申请构成任何限制。

Claims (12)

  1. 一种电解液，其特征在于，所述电解液中含有添加剂，所述添加剂选自如式I-1、式I-2或式I-3所示的多腈基六元氮杂环化合物中的至少一种：
    Figure PCTCN2017093311-appb-100001
    其中，R1、R2、R3和R4各自独立的选自氢、卤素、取代或未取代的C1～C12烷基、取代或未取代的C1～C12烷氧基、取代或未取代的C1～C12胺基、取代或未取代的C2～C12烯基、取代或未取代的C2～C12炔基、取代或未取代的C6～C26芳基、取代或未取代的C4～C12杂环基；
    取代基选自卤素、腈基、C1～C6烷基、C2～C6烯基、C1～C6烷氧基中的至少一种；
    x、y、z各自独立的选自0～8的整数；
    m、n、k各自独立的选自0～2的整数。
  2. 根据权利要求1所述的电解液，其特征在于，
    R1、R2、R3和R4各自独立地选自氢、卤素、取代或未取代的C1～C3直链或支链烷基、取代或未取代的C5～C7环烷基、取代或未取代的C1～C3烷氧基、取代或未取代的C1～C3胺基、取代或未取代的C2～C3烯基、取代或未取代的C2～C3炔基、取代或未取代的C6～C8芳基、取代或未取代的C4～C7杂环基；
    其中，取代基选自卤素。
  3. 根据权利要求1或2中任一项所述的电解液，其特征在于，m、n、k各自独立的选自1或2。
  4. 根据权利要求1或2中任一项所述的电解液，其特征在于，
    在式I-1中，R1和R3为相同的基团；优选地，R1、R3和R4为相同的基团；
    在式I-2中，R1、R2、R3和R4中至少有两个为相同的基团；优选地，R1、R2、R3和R4中至少有三个为相同的基团；
    在式I-3中，R1、R2和R3中至少有两个为相同的基团。
  5. 根据权利要求4所述的电解液，其特征在于，
    在式I-1中，R1和R3为氢；优选地，R1、R3和R4均为氢；
    在式I-2中，R1、R2、R3和R4中至少有两个为氢；优选地，R1、R2、R3和R4中至少有三个为氢；
    在式I-3中，R1、R2和R3中至少有两个为氢。
  6. 根据权利要求1所述的电解液，其特征在于，所述多腈基六元氮杂环化合物在所述电解液中的质量百分含量为0.001％～10％，优选为0.1％～3.5％。
  7. 根据权利要求1所述的电解液，其特征在于，所述式I-1所示的多腈基六元氮杂环化合物选自如下化合物中的至少一种：
    Figure PCTCN2017093311-appb-100002
    所述式I-2所示的多腈基六元氮杂环化合物选自如下化合物中的至少一种：
    Figure PCTCN2017093311-appb-100003
    Figure PCTCN2017093311-appb-100004
    所述式I-3所示的多腈基六元氮杂环化合物选自如下化合物中的至少一种：
    Figure PCTCN2017093311-appb-100005
  8. 根据权利要求1所述的电解液，其特征在于，所述电解液还含有添加剂A，所述添加剂A选自含有不饱和键的环状碳酸酯化合物、卤素取代的环状碳酸酯化合物、硫酸酯化合物、亚硫酸酯化合物、磺酸内酯化合物、二磺酸化合物、腈化合物、芳香化合物、异氰酸酯化合物、磷腈化合物、环状酸酐化合物、亚磷酸酯化合物、磷酸酯化合物、硼酸酯化合物、羧酸酯化合物中的至少一种。
  9. 根据权利要求8所述的电解液，其特征在于，所述添加剂A在所述电解液中的质量百分含量为0.01％～30％。
  10. 一种电池，包括正极极片、负极极片、置于所述正极极片和所述负极极片之间的隔离膜以及电解液，其特征在于，所述电解液为权利要求1～9任一权利要求所述的电解液。
  11. 根据权利要求10所述的电池，其特征在于，所述电池为锂离子电池、钠离子电池或镁离子电池。
  12. 根据权利要求10所述的电池，其特征在于，当所述电池为锂离子电池时，所述电池的充电截止电压不小于4.2V。
PCT/CN2017/093311 2017-06-15 2017-07-18 一种电解液及电池 WO2018227689A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019516707A JP6903128B2 (ja) 2017-06-15 2017-07-18 電解液及び電池
US16/343,326 US10862170B2 (en) 2017-06-15 2017-07-18 Electrolyte and battery
EP17913433.3A EP3514879B1 (en) 2017-06-15 2017-07-18 Electrolyte solution and battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710454471.3 2017-06-15
CN201710454471.3A CN109148950B (zh) 2017-06-15 2017-06-15 一种电解液及电池

Publications (1)

Publication Number Publication Date
WO2018227689A1 true WO2018227689A1 (zh) 2018-12-20

Family

ID=64660766

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/093311 WO2018227689A1 (zh) 2017-06-15 2017-07-18 一种电解液及电池

Country Status (5)

Country Link
US (1) US10862170B2 (zh)
EP (1) EP3514879B1 (zh)
JP (1) JP6903128B2 (zh)
CN (1) CN109148950B (zh)
WO (1) WO2018227689A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11121406B2 (en) * 2018-04-20 2021-09-14 Contemporary Amperex Technology Co., Limited Electrolyte and battery
US11239497B2 (en) * 2018-04-20 2022-02-01 Contemporary Amperex Technology Co., Limited Electrolyte and electrochemical device
CN114204009A (zh) * 2021-12-08 2022-03-18 万华化学(四川)有限公司 一种锂离子电池正极补锂添加剂及包括其的锂离子电池
US11404697B2 (en) 2019-07-16 2022-08-02 Factorial Inc. Solid electrolyte interphase forming composition, battery comprising the solid electrolyte interphase and anode-free battery comprising the solid electrolyte interphase

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109216764B (zh) * 2017-07-05 2020-09-15 宁德时代新能源科技股份有限公司 一种电解液及电化学装置
CN109216765B (zh) * 2017-07-05 2020-05-05 宁德时代新能源科技股份有限公司 一种电解液及电化学装置
CN109256586B (zh) * 2017-07-14 2021-01-12 宁德时代新能源科技股份有限公司 一种电解液及电化学装置
CN111326793B (zh) 2018-12-14 2021-07-13 宁德时代新能源科技股份有限公司 锂离子电池
CN111326734B (zh) 2018-12-14 2021-11-02 宁德时代新能源科技股份有限公司 锂离子电池
CN111326783B (zh) 2018-12-14 2021-07-13 宁德时代新能源科技股份有限公司 锂离子电池
CN111326728B (zh) * 2018-12-14 2021-09-21 宁德时代新能源科技股份有限公司 锂离子电池
CN111755746B (zh) * 2019-03-26 2022-03-18 比亚迪股份有限公司 一种锂离子电池电解液及锂离子电池
CN112349958B (zh) * 2019-08-06 2022-02-11 珠海冠宇电池股份有限公司 一种电解液及其制备方法和锂离子电池
CN110838596B (zh) * 2019-11-19 2021-10-26 苏州凌威新能源科技有限公司 锂电池电解液及锂电池
CN113571774B (zh) * 2021-06-30 2022-10-14 厦门海辰储能科技股份有限公司 锂离子电池
CN116235361B (zh) 2021-09-17 2024-10-01 宁德时代新能源科技股份有限公司 快充长寿命型二次电池、电池模块、电池包、用电装置
CN118136958A (zh) * 2024-02-22 2024-06-04 成都钠诚新能科技有限公司 一种双添加剂钠离子电池电解液及钠离子电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104852087A (zh) * 2015-04-15 2015-08-19 宁德时代新能源科技有限公司 一种电解液添加剂及应用了该添加剂的锂离子电池
CN105322223A (zh) * 2014-06-02 2016-02-10 Sk新技术株式会社 锂二次电池
CN105489935A (zh) * 2016-01-11 2016-04-13 东莞新能源科技有限公司 电解液以及包括该电解液的锂离子电池

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09213348A (ja) * 1996-01-31 1997-08-15 Sanyo Electric Co Ltd 非水系電解液電池
JPH11111332A (ja) * 1997-09-30 1999-04-23 Sanyo Electric Co Ltd 非水電解質電池
JP4815660B2 (ja) * 2000-06-16 2011-11-16 三菱化学株式会社 非水電解液及び非水電解液二次電池
JP4004769B2 (ja) * 2001-10-17 2007-11-07 Ｎｅｃトーキン株式会社 電解液、並びにこれを用いた電気化学セル
JP2010044883A (ja) 2008-08-08 2010-02-25 Mitsui Chemicals Inc 非水電解液及びリチウム二次電池
JP5619412B2 (ja) * 2009-09-04 2014-11-05 三洋電機株式会社 非水電解質二次電池および非水電解質二次電池の製造方法
JP2012104439A (ja) * 2010-11-12 2012-05-31 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いた非水系電解液二次電池
KR20140033539A (ko) * 2012-08-24 2014-03-19 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 첨가제 및 이를 포함하는 리튬 이차 전지
JP6159556B2 (ja) * 2012-09-20 2017-07-05 シャープ株式会社 非水系二次電池、並びに非水系二次電池用難燃剤及び添加剤
CN103022556B (zh) * 2013-01-05 2015-06-03 宁德新能源科技有限公司 锂离子电池及其电解液
CN103078140B (zh) * 2013-02-03 2015-04-08 宁德新能源科技有限公司 锂离子二次电池及其电解液
CN104995784A (zh) * 2013-02-27 2015-10-21 三菱化学株式会社 非水电解液及使用该非水电解液的非水电解质电池
KR102161266B1 (ko) * 2013-08-30 2020-09-29 삼성전자주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
CN107431197B (zh) * 2015-03-31 2020-08-21 株式会社Lg化学 非水电解质及包含该非水电解质的锂二次电池
KR102446364B1 (ko) * 2015-09-03 2022-09-21 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
EP3190208B1 (en) * 2016-01-06 2018-09-12 ATOTECH Deutschland GmbH Electroless nickel plating baths comprising aminonitriles and a method for deposition of nickel and nickel alloys
CN105655639B (zh) * 2016-01-11 2018-10-12 东莞新能源科技有限公司 电解液以及包括该电解液的锂离子电池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105322223A (zh) * 2014-06-02 2016-02-10 Sk新技术株式会社 锂二次电池
CN104852087A (zh) * 2015-04-15 2015-08-19 宁德时代新能源科技有限公司 一种电解液添加剂及应用了该添加剂的锂离子电池
CN105489935A (zh) * 2016-01-11 2016-04-13 东莞新能源科技有限公司 电解液以及包括该电解液的锂离子电池

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11121406B2 (en) * 2018-04-20 2021-09-14 Contemporary Amperex Technology Co., Limited Electrolyte and battery
US11239497B2 (en) * 2018-04-20 2022-02-01 Contemporary Amperex Technology Co., Limited Electrolyte and electrochemical device
US11404697B2 (en) 2019-07-16 2022-08-02 Factorial Inc. Solid electrolyte interphase forming composition, battery comprising the solid electrolyte interphase and anode-free battery comprising the solid electrolyte interphase
CN114204009A (zh) * 2021-12-08 2022-03-18 万华化学(四川)有限公司 一种锂离子电池正极补锂添加剂及包括其的锂离子电池
CN114204009B (zh) * 2021-12-08 2023-12-19 万华化学(四川)有限公司 一种锂离子电池正极补锂添加剂及包括其的锂离子电池

Also Published As

Publication number Publication date
US10862170B2 (en) 2020-12-08
EP3514879B1 (en) 2020-12-16
EP3514879A1 (en) 2019-07-24
JP6903128B2 (ja) 2021-07-14
JP2019530180A (ja) 2019-10-17
CN109148950A (zh) 2019-01-04
US20200052332A1 (en) 2020-02-13
EP3514879A4 (en) 2019-11-06
CN109148950B (zh) 2020-10-02

Similar Documents

Publication Publication Date Title
WO2018227689A1 (zh) 一种电解液及电池
JP6778777B2 (ja) 電解液および電池
CN109103489B (zh) 一种电解液及电池
CN109256585B (zh) 一种电解液及电化学装置
JP5561163B2 (ja) リチウム電池用非水電解液、それを用いたリチウム電池、及びそれに用いられるホルミルオキシ基含有化合物
CN109216764B (zh) 一种电解液及电化学装置
CN111326793B (zh) 锂离子电池
US20190326633A1 (en) Electrolyte and electrochemical device
CN109256586B (zh) 一种电解液及电化学装置
JP2019192637A (ja) 電解液及び電気化学装置
WO2020119809A1 (zh) 电解液、电池及装置
CN109216765B (zh) 一种电解液及电化学装置
WO2020119808A1 (zh) 电解液、电池及装置

Legal Events

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

Ref document number: 17913433

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019516707

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2017913433

Country of ref document: EP

Effective date: 20190417

NENP Non-entry into the national phase

Ref country code: DE