WO2019006777A1 - 一种电解液及电化学装置 - Google Patents

一种电解液及电化学装置 Download PDF

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WO2019006777A1
WO2019006777A1 PCT/CN2017/093309 CN2017093309W WO2019006777A1 WO 2019006777 A1 WO2019006777 A1 WO 2019006777A1 CN 2017093309 W CN2017093309 W CN 2017093309W WO 2019006777 A1 WO2019006777 A1 WO 2019006777A1
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group
substituted
unsubstituted
electrolyte
formula
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PCT/CN2017/093309
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English (en)
French (fr)
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蒋耀
胡春华
伊天成
苗露
梁成都
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宁德时代新能源科技股份有限公司
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Priority to US16/342,852 priority Critical patent/US11309582B2/en
Priority to EP17917082.4A priority patent/EP3514881B1/en
Priority to JP2019510295A priority patent/JP6765510B2/ja
Publication of WO2019006777A1 publication Critical patent/WO2019006777A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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 an electrochemical device.
  • 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 purpose of the present application is to provide an electrolyte containing the additive A and the additive B, and the additive A is selected from the polynitrile six-membered nitrogen as shown in Formula I-1, Formula I-2 or Formula I-3. At least one of the heterocyclic compounds:
  • 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, k are each independently selected from an integer of 0 to 2;
  • the additive B is selected from at least one of cyclic carbonate compounds having an unsaturated bond.
  • Another object of the present application is to provide an electrochemical device 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, wherein the electrolyte is The electrolyte of the present application.
  • the surface activity of the positive electrode material can be effectively inactivated, and the oxidation of the electrolyte solution can be suppressed. Effectively reduce battery gas production.
  • an anode SEI film can be formed, which hinders the contact of the anode with the electrolyte, thereby significantly reducing the occurrence of side reactions.
  • An electrochemical device using the electrolytic solution of the present application has excellent 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.
  • the electrolyte of the present application may be a liquid electrolyte or a solid electrolyte.
  • the present application is further explained in the present application with a liquid electrolyte as an example.
  • a first aspect of an embodiment of the present application provides an electrolyte comprising an organic solvent, an electrolyte salt, and an additive.
  • the additive comprises the additive A and the additive B
  • the additive A is selected from at least one of the polynitrile six-membered nitrogen heterocyclic compounds
  • the additive B is selected from at least one of the cyclic carbonate compounds having an unsaturated bond.
  • the polynitrile six-membered nitrogen heterocyclic compound as the additive A may be specifically selected from at least one of the compounds represented by the formula I-1, the formula I-2 or the 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; preferably, m, n, and k are each independently selected from 1 or 2.
  • the polynitrile six-membered nitrogen heterocyclic compound has a nitrile group
  • the nitrogen atom in the group has a strong complexation with the transition metal, so when it is applied to the electrolyte, it is adsorbed on the surface of the positive electrode material.
  • a porous protective film can be formed to insulate the surface of the positive electrode material from the electrolyte without affecting the normal transmission of lithium ions, reducing the surface activity of the positive electrode material, and suppressing a large number of surface side reactions occurring on the surface, thereby reducing by-products. And inhibit the role of 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 ⁇ C 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 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 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; alternatively, R 1 , R 3 and R 4 are all the same group.
  • R 1 and R 3 are hydrogen; alternatively, 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; alternatively, R 1 , R 2 , R 3 and R At least three of the four groups are the same group.
  • R 1 , R 2 , R 3 and R 4 are hydrogen; optionally, at least R 1 , R 2 , R 3 and R 4 There are three for 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 additive A in the electrolyte is 0.001% to 10%. If the content of the additive A is too low, the effect of improving the electrolyte is not significant. If the content of the additive A is too high, the thickness of the complex layer formed is too large, and the impedance of the positive and negative electrodes is greatly increased, and the battery is deteriorated. performance.
  • the upper limit of the mass percentage range of the additive A in the electrolyte in the examples of the present application is selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3 %, 2%, 1%, 0.8%, the lower limit is selected from 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8%, 0.9%, 1.0%, 1.2% .
  • the mass percentage of the additive A in the electrolytic solution is from 0.01% to 6%, more preferably from 0.1% to 3.5%.
  • the cyclic carbonate compound having an unsaturated bond as the additive B may be selected from at least one of the compounds of the formula II;
  • R 20 is selected from an alkenyl-substituted C 1 -C 6 alkylene group, a substituted or unsubstituted C 2 -C 6 alkenylene group;
  • the substituent is at least one selected from the group consisting of halogen, C 1 -C 3 alkyl, and C 2 -C 4 alkenyl.
  • R 20 is selected from an alkenyl-substituted C 1 -C 4 alkylene group, a substituted or unsubstituted C 2 -C 4 alkenylene group, and the substituent is selected from halogen, C 1 -C 3 alkyl group, C 2 -C 4 alkenyl.
  • the additive B can participate in the formation of the anode SEI film, so that the formed SEI film can hinder the contact of the anode with the electrolyte, thereby effectively reducing the occurrence of side reactions.
  • the cyclic carbonate compound having an unsaturated bond is at least one selected from the group consisting of the following structural formulas:
  • the mass percentage of the additive B in the electrolyte is from 0.1% to 10%. If the content of the additive B is too low, the effect of improving the electrolyte is not significant. If the content of the additive B is too high, the thickness of the formed SEI film is too large, affecting the cycle capacity retention rate of the cell, and deteriorating the battery performance.
  • the upper limit of the mass percentage range of the additive B in the electrolyte in the examples of the present application is selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3 %, 2%, 1.5%, and the lower limit is selected from 0.1%, 0.25%, 0.3%, 0.5%, 0.6%, 0.8%, 0.9%, 1.0%, and 1.2%.
  • the percentage of the additive B in the electrolytic solution is from 0.5% to 6%, more preferably from 1% to 3%.
  • additive C may be added as the additive C to the electrolytic solution of the embodiment of the present application.
  • the additive C may be selected from at least one selected from the group consisting of a sulfate compound and a sulfite compound.
  • Additive C has a higher reduction potential, which is preferentially reduced on the graphite surface in the electrolyte to form a dense sulfur-containing SEI film, which prevents the solvation of lithium ions from destroying the graphite structure, and the oxidation potential of the additive C is also high. It has good oxidative stability and does not cause side reactions on the surface of the positive electrode.
  • the sulfate compound is preferably a cyclic sulfate compound, and the cyclic sulfate compound is at least one selected from the group consisting of compounds represented by formula III-1;
  • R 31 is selected from a substituted or unsubstituted C 1 -C 6 alkylene group, a substituted or unsubstituted C 2 -C 6 alkenylene group;
  • the substituent is at least one selected from the group consisting of halogen, C 1 -C 3 alkyl, and C 2 -C 4 alkenyl.
  • R 31 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 And at least one of C 2 to C 4 alkenyl groups.
  • 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 sulfite compound is preferably a cyclic sulfite compound, and the cyclic sulfite compound is selected from at least one of the compounds of the formula III-2;
  • R 32 is selected from a substituted or unsubstituted C 1 -C 6 alkylene group, a substituted or unsubstituted C 2 -C 6 alkenylene group;
  • the substituent is at least one selected from the group consisting of halogen, C 1 -C 3 alkyl, and C 2 -C 4 alkenyl.
  • R 32 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 And at least one of C 2 to C 4 alkenyl groups.
  • 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 mass percentage of the additive C in the electrolyte is from 0.1% to 10%. If the content of the additive C is too low, the effect of improving the electrolyte solution is not remarkable. If the content of the additive C is too high, the film formed on the surface of the cathode is too thick, affecting the cycle capacity retention ratio of the cell, and deteriorating the battery performance.
  • the upper limit of the mass percentage range of the additive C in the electrolyte in the examples of the present application is selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3 %, 2%, 1.5%, and the lower limit is selected from 0.1%, 0.25%, 0.5%, 0.6%, 0.8%, 0.9%, 1.0%, and 1.2%.
  • the percentage of the additive C in the electrolyte is from 0.5% to 6%, preferably from 1% to 3%.
  • 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, the carbon source is selected.
  • the alkoxy group having a number of 1 to 6 is more preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferably 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.
  • 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.
  • 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.
  • cyclic carbonate examples include cyclic carbonates selected from the group consisting of ethylene carbonate (abbreviated as EC) and propylene carbonate (abbreviated as PC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • 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, In methyl acetate and ethyl acetate
  • One or more chain carboxylic acid esters selected from dimethyl carbonate (abbreviated as DMC), diethyl carbonate (abbreviated as DEC), dipropyl carbonate, and dibutyl carbonate
  • pivalic acid esters such as methyl pivalate, ethyl pivalate, propyl pivalate, methyl propionate, ethyl propionate
  • 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 (LiPFO) and tetrafluoro [oxalate-O, O'] One or two or more kinds of "lithium salts in which an oxalate ligand is an anion", among which LiBOB and LiPFO are more preferable. One or more of them may be mixed and used.
  • 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, an additive A, and an additive B thereto, and further adding at least one of the above-mentioned addition C.
  • 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.
  • An electrochemical device 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 electrochemical device of the embodiment of the present application may be a lithium ion secondary battery, a lithium primary battery, or a lithium ion capacitor.
  • the positive electrode includes a positive electrode active material capable of deintercalating and intercalating lithium ions
  • the negative electrode includes a negative electrode active material capable of intercalating and deintercalating 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, and lithium.
  • Nickel-cobalt aluminum oxide a compound obtained by adding other transition metal or non-transition metal to these lithium transition metal oxides, a mixture of one or more of the above.
  • a layered lithium-containing oxide, a spinel-type lithium-containing oxide, an olivine-type lithium-containing phosphate compound, or the like can be used.
  • the negative electrode active material may be soft carbon, hard carbon, artificial graphite, natural graphite, silicon, a silicon oxide compound, a silicon carbon composite, lithium titanate, a metal capable of forming an alloy with lithium, or the like.
  • 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 electrochemical device is a lithium primary battery
  • the negative electrode material of the lithium primary battery is metallic lithium or a lithium alloy
  • the positive active material of the lithium primary battery is commonly used: a solid halide such as copper fluoride (CuF 2 ), chlorine Copper (CuCl 2 ), silver chloride (AgCl), polyfluorocarbon ((CF) 4 ), solid sulfides such as copper sulfide (CuS), iron sulfide (FeS), iron disulfide (FeS 2 ), solid Oxides such as manganese dioxide (MnO 2 ), copper oxide (CuO), molybdenum trioxide (MoO 3 ), vanadium pentoxide (V 2 O 5 ), solid oxyacid salts such as silver chromate (Ag 2 CrO 4 ) ), lead citrate (Pb 2 Bi 2 O 5 ).
  • a solid halide such as copper fluoride (CuF 2 ), chlorine Copper (CuCl 2 ), silver chloride (
  • the negative electrode material of the lithium ion capacitor is graphite, a polyacene type material, and the positive electrode material is activated carbon.
  • the specific type of the separator is not specifically limited, and may be Any of the separator materials used in existing batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite films thereof, are not limited thereto.
  • 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 the positive electrode slurry containing the positive electrode active material, the binder, and the conductive agent is coated on the positive electrode current collector, and the positive electrode slurry is dried.
  • Positive electrode sheet 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 electrochemical device charging cutoff voltage of the embodiment of the present application is not less than 4.2V, and can operate in the range of 4.2V to 4.9V, and further optionally, in 4.3. Working in the range of V ⁇ 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 a corresponding protective effect to a greater extent.
  • lithium ion battery an embodiment of a lithium ion secondary battery (hereinafter referred to as a lithium ion battery). It is to be understood that the examples are not intended to limit the scope of the application. In the following examples and comparative examples, the reagents, materials, and instruments used were commercially available unless otherwise specified.
  • 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.
  • the additives used are as follows:
  • 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 additive A, the additive B, and the additive C is a weight percentage calculated based on the total weight of the electrolytic solution.
  • the high-voltage and high-temperature cycle performance of the lithium-ion battery was evaluated by the cycle capacity retention rate, and the high-temperature storage performance was evaluated by the thickness expansion ratio of the lithium ion battery.
  • Battery 1 to battery 25 were tested as follows:
  • 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. At this time, the thickness of the lithium ion battery was tested and recorded as h0; The ion battery was placed in an incubator at 85 ° C, and stored after 24 hours of storage. The thickness of the lithium ion battery was measured and recorded as h1.
  • the thickness expansion ratio (%) of the lithium ion battery after 24 hours of storage [(h1 - h0) / h0] ⁇ 100%.
  • the polynitrile six-membered nitrogen heterocyclic molecule in the additive A has two or more nitrile groups at the same time, and the lone pair electrons contained in the nitrogen atom in the nitrile group can be 3d with the transition metal of the surface of the positive electrode material.
  • the empty orbital is strongly complexed, and the direct contact between the electrolyte and the surface of the positive electrode is isolated while reducing the surface activity of the positive electrode (especially at high SOC), so that the surface side reaction is greatly reduced, and the lithium ions consumed in the side reaction are also The corresponding reduction, that is, the consumption rate of reversible lithium ions is greatly slowed down, and 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, thereby significantly reducing the battery thickness expansion effect at high temperatures.
  • the nitrile group in the additive A can complex Li + in addition to the transition metal on the surface of the positive electrode material. Therefore, when the additive amount of the additive A is excessively large, on the one hand, the excess additive A (except for adsorbing on the surface of the LCO) consumes Li + , resulting in a decrease in the Li + circulated in the cell; on the other hand, it also causes electrolysis. The overall viscosity of the liquid is increased, and the ionic conductivity is lowered, so that the cycle capacity retention rate of the cell is lowered. When the amount of the additive A added is too small, the effect is not remarkable.
  • additive B can participate in the formation of the anode SEI film as an anode film-forming additive, and the SEI film can hinder the contact of the anode with the electrolyte, thereby effectively reducing the occurrence of side reactions.
  • Additive A and Additive B act synergistically to protect both the cathode and the anode.
  • the continued addition of the additive C in the electrolyte further improves the high voltage, high temperature cycle performance and high temperature storage performance of the battery.
  • the increase of the additive amount of additive C (0.1% to 10%)
  • the cycle capacity retention rate of the cell at 25 ° C and 45 ° C reached the best and then decreased, and the high-temperature storage performance continued to improve.
  • Additive A mainly relies on its nitrile group to complex with the cobalt atom in the positive electrode material, so additive A will not protect it in the absence of exposed surface of cobalt atom.
  • Additive C can form a denser film on the surface of the cathode, which can effectively protect the cathode and reduce side reactions in the cycle and storage process. Therefore, the synergy of additive A, additive B and additive C can further enhance the cycle and storage performance of the cell.
  • the amount of additive C is preferably from 1% to 2%.
  • additive amount of additive A, additive B and additive C are 2%, 2%, and 2%, respectively, the best synergistic effect is achieved.
  • the lithium ion battery was continuously prepared by the method of the above examples, and the composition of the electrolyte was as shown in Table 3.
  • the content of the additive A and the additive B is a weight percentage calculated based on the total weight of the electrolytic solution.

Abstract

一种电解液及电化学装置，涉及储能材料领域。该电解液中含有添加剂A和添加剂B，添加剂A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，添加剂B选自具有不饱和键的环状碳酸酯化合物中的至少一种。所述电化学装置中含有上述电解液。该电解液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，有效地降低电池产气，同时还形成阳极SEI膜，阻碍阳极与电解液的接触，从而显著减少副反应。使用该电解液的电化学装置具有优良的高温高压循环性能和存储性能。

Description

一种电解液及电化学装置 技术领域
本申请涉及储能材料领域，具体地讲，涉及一种电解液及电化学装置。
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，申请人进行锐意研究后发现：通过同时加入多腈基六元氮杂环化合物和具有不饱和键的环状碳酸酯化合物作为电解液的添加剂，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，有效降低电池产气，同时还形成阳极SEI膜，阻碍阳极与电解液的接触，从而有效减轻副反应的发生，从而提高了电化学装置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，所述电解液中含有添加剂A和添加剂B，添加剂A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 PCTCN2017093309-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；
所述添加剂B选自具有不饱和键的环状碳酸酯化合物中的至少一种。
本申请的另一目的在于提供一种电化学装置，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，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同时加入多腈基六元氮杂环化合物和具有不饱和键的环状碳酸酯化合物作为添加剂，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，有效降低电池产气。同时还可形成阳极SEI膜，阻碍阳极与电解液的接触，从而显著减少了副反应的发生。
使用本申请的电解液的电化学装置具有优良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实施例的电解液及电池。
首先说明根据本申请第一方面的电解液。本申请的电解液可以为液态电解液，也可以为固态电解液。在本申请中以液体电解液为实施例进一步解释本申请。
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，添加剂包括添加剂A和添加剂B，添加剂A选自多腈基六元氮杂环化合物中的至少一种，添加剂B选自具有不饱和键的环状碳酸酯化合物中的至少一种。
〔添加剂A〕
作为添加剂A的多腈基六元氮杂环化合物具体可选自如式I-1、式I-2或式I-3所示的化合物中的至少一种：
Figure PCTCN2017093309-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；优选地，m、n、k各自独立的选自1或2。
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～C6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；可选地，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；可选地，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 PCTCN2017093309-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；可选地，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；可选地，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 PCTCN2017093309-appb-000004
Figure PCTCN2017093309-appb-000005
(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，优选为氟。
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 PCTCN2017093309-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 PCTCN2017093309-appb-000007
Figure PCTCN2017093309-appb-000008
作为本申请实施例电解液的一种改进，添加剂A在所述电解液中的质量百分含量为0.001％～10％。如果添加剂A的含量过低，则其对电解液的改善效果不明显，如果添加剂A的含量过高，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。
本申请实施例中添加剂A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％、0.8％、0.9％、1.0％、1.2％。
进一步优选地，添加剂A在电解液中的质量百分含量为0.01％～6％，更优选为0.1％～3.5％。
〔添加剂B〕
作为添加剂B的具有不饱和键的环状碳酸酯化合物可选自如式Ⅱ所示化合物中的至少一种；
Figure PCTCN2017093309-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；
取代基选自卤素、C1～C3烷基、C2～C4烯基中的至少一种。
进一步可选的，R20选自烯基取代的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。
添加剂B可参与阳极SEI膜的形成，从而使得形成的SEI膜可以阻碍阳极与电解液的接触，从而有效减少副反应的发生。
具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 PCTCN2017093309-appb-000010
作为本申请实施例电解液的一种改进，添加剂B在电解液中的质量百分含量为0.1％～10％。如果添加剂B含量过低，则其对电解液的改善效果不明显，如果添加剂B的含量过高，则形成的SEI膜的厚度过大，影响电芯的循环容量保持率，恶化电池性能。
本申请实施例中添加剂B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％、1.5％，下限任选自0.1％、0.25％、0.3％、0.5％、0.6％、0.8％、0.9％、1.0％、1.2％。
进一步优选地，添加剂B在电解液中的百分含量为0.5％～6％，更优选为1％～3％。
〔添加剂C〕
本申请实施例的电解液中还可添加其他添加剂作为添加剂C。具体的，添加剂C可选自选自硫酸酯化合物、亚硫酸酯化合物中的至少一种。添加剂C具有更高的还原电位，在电解液中会优先在石墨表面还原，形成一层致密的含硫SEI膜，阻止溶剂化锂离子对石墨结构的破坏，而且添加剂C的氧化电位也较高，具有较好的氧化稳定性，不会在正极表面发生副反应。
进一步的，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III-1所示化合物中的至少一种；
Figure PCTCN2017093309-appb-000011
其中，R31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烯基中的至少一种。
进一步可选的，R31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烯基中的至少一种。
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 PCTCN2017093309-appb-000012
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 PCTCN2017093309-appb-000013
亚硫酸酯化合物优选为环状亚硫酸酯化合物，环状亚硫酸酯化合物选自如式III-2所示化合物中的至少一种；
Figure PCTCN2017093309-appb-000014
其中，R32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烯基中的至少一种。
进一步可选的，R32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烯基中的至少一种。
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)。
作为本申请实施例电解液的一种改进，添加剂C在电解液中的质量百分含量为0.1％～10％。如果添加剂C含量过低，则其对电解液的改善效果不明显，如果添加剂C的含量过高，则在阴极表面形成的膜过厚，影响电芯的循环容量保持率，恶化电池性能。
本申请实施例中添加剂C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％、1.5％，下限任选自0.1％、0.25％、0.5％、0.6％、0.8％、0.9％、1.0％、1.2％。
进一步优选地，添加剂C在电解液中的百分含量为0.5％～6％，优选为1％～3％。
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 PCTCN2017093309-appb-000015
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、式III、式IV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)等环状碳酸酯。
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、添加剂A和添加剂B，并还可添加上述添加C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 PCTCN2017093309-appb-000016
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 PCTCN2017093309-appb-000017
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 PCTCN2017093309-appb-000018
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 PCTCN2017093309-appb-000019
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 PCTCN2017093309-appb-000020
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 PCTCN2017093309-appb-000021
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化学装置，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，本申请实施例的电化学装置可为锂离子二次电池、锂一次电池或锂离子电容器。
当电化学装置为锂离子二次电池时，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，当电化学装置为锂离子二次电池时，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。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。
具体的，当电化学装置为锂一次电池时，锂一次电池的负极材料为金属锂或锂合金；锂一次电池的正极活性物质常用的有：固态卤化物如氟化铜(CuF2)、氯化铜(CuCl2)、氯化银(AgCl)、聚氟化碳((CF)4)，固态硫化物如硫化铜(CuS)、硫化铁(FeS)、二硫化铁(FeS2)，固态氧化物如二氧化锰(MnO2)、氧化铜(CuO)、三氧化钼(MoO3)、五氧化二钒(V2O5)，固态含氧酸盐如铬酸银(Ag2CrO4)、铋酸铅(Pb2Bi2O5)。
当电化学装置为锂离子电容器时，锂离子电容器的负极材料为石墨、多并苯类材料，正极材料为活性炭。
在上述电化学装置中，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。
在上述电化学装置中，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，当电化学装置为锂离子二次电池时，本申请实施例的电化学装置充电截止电压不小于4.2V，即可在4.2V～4.9V范围内工作，进一步可选的，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，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，仅示出锂离子二次电池的实施例，但本申请实施例不限于此。
下面结合锂离子二次电池(以下简称锂离子电池)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。
其中，所用到的添加剂如下所示：
添加剂A：
Figure PCTCN2017093309-appb-000022
添加剂B：
Figure PCTCN2017093309-appb-000023
添加剂C：
Figure PCTCN2017093309-appb-000024
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，添加剂A、添加剂B、添加剂C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1～25及对比例电解液中的组分及添加比例
Figure PCTCN2017093309-appb-000025
Figure PCTCN2017093309-appb-000026
其中，“/”表示未添加该添加剂。
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。将电池1至电池25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 PCTCN2017093309-appb-000027
Figure PCTCN2017093309-appb-000028
从电池1-25和对比1的对比中可以看出：在锂离子电池的电解液中加入本申请的组合添加剂后可显著提高锂离子电池的高电压、高温循环性能和 高温存储性能。
从电池1-9可以看出，随着添加剂A的增加(0.001％增至10％)，在充电截止电压4.35V的情况下，电芯在25℃和45℃时的循环容量保持率达到最佳后又出现了下降的趋势，85℃存储24小时电芯膨胀率一直减小。
这是由于，添加剂A中的多腈基六元氮杂环分子同时具备两个或多个腈类基团，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，最从而使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，从而使高温下电池厚度膨胀效应明显减轻。
添加剂A中的腈基除了可以络合正极材料表面过渡金属之外，还可以络合Li+。因此，当添加剂A的添加量过大时，一方面过量的添加剂A(除了吸附在LCO表面之外的)会消耗Li+，导致电芯中循环的Li+减少；另一方面还导致了电解液整体黏度提升、离子电导率下降，从而使电芯的循环容量保持率下降。而当添加剂A的添加量过小时，则效果不明显。
从电池1-16与对比2的对比可以看出：相对于单独添加添加剂A的电池来讲，同时添加添加A和添加剂B可有效降低电芯85℃存储时的膨胀率，并可有效提升25℃和45℃时的循环性能。
这是由于添加剂B作为阳极成膜添加剂可参与阳极SEI膜的形成，SEI膜可以阻碍阳极与电解液的接触，从而有效减轻副反应的发生。添加剂A和添加剂B协同作用，既可保护阴极，又可将阳极更好地保护起来。
当添加剂A和添加剂B的添加量均在2％时，可同时达到最佳的高电压、高温循环性能和高温存储性能。
从电池17-25可以看出，在电解液中继续添加添加剂C可进一步提高电池的高电压、高温循环性能和高温存储性能。随着添加剂C的添加量的增加(0.1％增至10％)，电芯25℃和45℃的循环容量保持率达到最佳后又出现了下降的趋势，高温存储性能持续获得提升。
添加剂A主要依靠其腈基与正极材料中的钴原子络合，因此在没有钴原子裸露的表面，添加剂A将无法对其起到保护作用。添加剂C可在阴极表面形成较致密的膜，可有效地保护阴极，减轻循环和存储过程中的副反应，因此添加剂A、添加剂B与添加剂C协同作用可进一步增强电芯的循环和存储性能。
但当添加剂C添加量进一步增加时，在阴极表面形成的膜随之增厚，尽管高温存储性能可获得进一步提升，但随着膜厚的增加，阴极的阻抗也会显著增长，可能会影响锂离子的扩散迁移。因此，当添加剂C的含量过大时，使电芯的高电压、高温循环性能产生下降的趋势。因此，添加剂C的添加量优选为1％～2％。
综上，添加剂A、添加剂B和添加剂C添加剂量分别为2％、2％、2％时，达到最佳的协同作用。
其他实施例
采用上述实施例的方法继续制备锂离子电池，其电解液的组成如表3所示。
在表3中，添加剂A和添加剂B的含量为基于电解液的总重量计算得到的重量百分数。
表3：电池26～42电解液中的组分及添加比例
Figure PCTCN2017093309-appb-000029
Figure PCTCN2017093309-appb-000030
采用表3所示的电解液的电池26～42的高压、高温条件下的循环性能与电池5、13相似，限于篇幅不再赘述。
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 (14)

  1. 一种电解液，其特征在于，所述电解液中含有添加剂A和添加剂B，
    所述添加剂A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 PCTCN2017093309-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；优选地，m、n、k各自独立的选自1或2；
    所述添加剂B选自具有不饱和键的环状碳酸酯化合物中的至少一种。
  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，
    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。
  4. 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。
  5. 根据权利要求1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0.001％～10％，优选为0.01％～6％，更优选为0.1％～3.5％。
  6. 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 PCTCN2017093309-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 PCTCN2017093309-appb-100003
    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 PCTCN2017093309-appb-100004
  7. 根据权利要求1所述的电解液，其特征在于，所述具有不饱和键的环状碳酸酯化合物选自如式Ⅱ所示化合物中的至少一种；
    Figure PCTCN2017093309-appb-100005
    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，
    取代基选自卤素、C1～C6烷基、C2～C6烯基中的至少一种。
  8. 根据权利要求7所述的电解液，其特征在于，所述添加剂B在所 述电解液中的质量百分含量为0.1％～10％，优选为0.5％～6％，更优选为1％～3％。
  9. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括添加剂C，所述添加剂C选自硫酸酯化合物、亚硫酸酯化合物中的至少一种。
  10. 根据权利要求9所述的电解液，其特征在于，
    所述硫酸酯化合物为环状硫酸酯化合物，所述环状硫酸酯化合物选自如式III-1所示化合物中的至少一种；
    Figure PCTCN2017093309-appb-100006
    其中，R31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烯基中的至少一种；
    所述亚硫酸酯化合物为环状亚硫酸酯化合物，所述环状亚硫酸酯化合物选自如式III-2所示化合物中的至少一种；
    Figure PCTCN2017093309-appb-100007
    其中，R32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烯基中的至少一种。
  11. 根据权利要求9所述的电解液，其特征在于，所述添加剂C在所述电解液中的质量百分含量为0.1％～10％，优选为0.5％～6％，更优选为1％～3％。
  12. 一种电化学装置，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1～11任一权利要求所述的电解液。
  13. 根据权利要求12所述的电化学装置，其特征在于，所述电化学装置为锂离子二次电池、锂一次电池或锂离子电容器。
  14. 根据权利要求12所述的电化学装置，其特征在于，当所述电化学装置为锂离子二次电池时，所述电化学装置的充电截止电压不小于4.2V。
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