WO2020119803A1 - 锂离子电池及装置 - Google Patents

锂离子电池及装置 Download PDF

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WO2020119803A1
WO2020119803A1 PCT/CN2019/125321 CN2019125321W WO2020119803A1 WO 2020119803 A1 WO2020119803 A1 WO 2020119803A1 CN 2019125321 W CN2019125321 W CN 2019125321W WO 2020119803 A1 WO2020119803 A1 WO 2020119803A1
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substituted
unsubstituted
additive
ion battery
lithium ion
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PCT/CN2019/125321
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English (en)
French (fr)
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钭舒适
胡春华
伊天成
蒋耀
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 US17/056,740 priority Critical patent/US11239500B2/en
Priority to EP19894749.1A priority patent/EP3783723B1/en
Publication of WO2020119803A1 publication Critical patent/WO2020119803A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/04—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C07F9/092—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl substituted by B, Si or a metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the field of energy storage materials, in particular, to a lithium ion battery and device.
  • Lithium ion batteries are widely used in electric vehicles and consumer electronic products due to their advantages such as 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.
  • LiCoO 2 is currently widely used as a positive electrode active material for lithium ion batteries. Its performance is relatively stable when cycling between fully discharged LiCoO 2 and semi-charged Li 0.5 CoO 2 (4.2V vs. Li), so it is actually truly The lithium ion used is only 1/2 of its actual lithium ion content. When the voltage is greater than 4.2V, the remaining 1/2 content of lithium ions in LiCoO 2 can continue to be extracted, but in the process of deep delithiation, Co 3+ will be oxidized to very unstable Co 4+ , and the loss of a lot of electrons Oxygen on the surface co-oxidizes the electrolyte. At this time, a large amount of gas will be generated inside the battery to cause the battery to swell.
  • Co 4+ is dissolved in the electrolyte and deposited on the surface of the negative electrode, which catalyzes the reduction of the electrolyte, and also generates a large amount of gas to cause the battery to swell.
  • the object of the present application is to provide a lithium-ion battery and a device, the lithium-ion battery has excellent cycle performance and storage performance, especially in the case of high temperature and high voltage with excellent cycle performance and Storage performance.
  • the present application provides a lithium-ion battery including an electrode assembly and an electrolyte, the electrode assembly including a positive pole piece, a negative pole piece, and a separator.
  • the positive active material in the positive pole piece includes Li x1 Co y1 M 1-y1 O 2-z1 Q z1 , 0.5 ⁇ x1 ⁇ 1.2, 0.8 ⁇ y1 ⁇ 1.0, 0 ⁇ z1 ⁇ 0.1, M is selected from Al and Ti , Zr, Y, one or more of Mg, Q is selected from one or more of F, Cl, S.
  • the electrolyte contains an additive A, an additive B, and an additive C.
  • the additive A is selected from one or more of the compounds represented by Formula I-1, Formula I-2, and Formula I-3.
  • the additive B is selected from one or more of the compounds represented by Formula II-1 and Formula II-2, and the additive C is selected from one or more of the compounds represented by Formula III-1.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , and R 39 are each independently selected from halogen-substituted or unsubstituted C 1 -C 6 alkane base.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , and R 49 are each independently selected from halogen-substituted or unsubstituted C 1 to C 6 alkane base.
  • R 21 is selected from halogen-substituted C 1 -C 6 alkylene and halogen-substituted C 2 -C 6 alkenylene.
  • the present application provides a device, which includes the lithium ion battery described in the first aspect of the present application.
  • the present application includes at least the following beneficial effects:
  • This application uses a positive electrode active material containing lithium cobalt oxide material Li x1 Co y1 M 1-y1 O 2-z1 Q z1 doped with metal ions M.
  • the doping element M acts as a skeleton in the lithium cobalt oxide material, which can reduce cobalt
  • the lattice shape variation during the deep delithiation of the lithium acid material delays the degradation of the bulk structure of the lithium cobaltate material and improves the structural stability of the lithium ion battery when it is used at a high voltage greater than 4.2V.
  • the electrolyte of the present application contains a combination of additive A, additive B, and additive C.
  • Additive A is a polynitrile six-membered nitrogen heterocyclic compound with a low oxidation potential. When the battery is formed, it can form a stable complex layer on the surface of the cathode active material, effectively passivate the surface of the cathode active material, and reduce the surface activity of the cathode active material.
  • additive B is a silane phosphite compound or a silane phosphate compound or a mixture of both, which has a flame retardant effect and can be added Effectively improve the thermal safety of the electrolyte, so when the lithium ion battery is stored at high temperature or thermal runaway under other extreme conditions, the additive B can reduce the risk of lithium ion battery burning, thereby improving the overall safety of the lithium ion battery ;
  • Additive C halogen-substituted cyclic carbonate compound which can form a uniform and dense protective film on the surface of the negative electrode (especially the surface of the negative electrode containing Si), isolate the electron conduction between the negative electrode and the electrolyte, and effectively reduce the negative electrode and the electrolysis
  • the side reaction between the liquid can not only protect the negative electrode from damage, suppress the continuous increase of the negative electrode resistance, but also reduce the electrolyte consumption during the use of the lithium-
  • the lithium ion battery of the present application can have excellent cycle performance and storage performance, especially under high temperature and high voltage conditions.
  • the device of the present application includes the lithium ion battery described in the first aspect of the present application, and thus has at least the same advantages as the lithium ion battery.
  • Figure 1 shows the NMR carbon spectrum of compound A1.
  • Figure 2 shows the NMR carbon spectrum of the A2 compound.
  • Figure 3 is the NMR carbon spectrum of A3 compound.
  • FIG. 4 is a schematic diagram of an embodiment of a lithium ion battery.
  • FIG. 5 is a schematic diagram of an embodiment of a battery module.
  • FIG. 6 is a schematic diagram of an embodiment of a battery pack.
  • FIG. 7 is an exploded view of FIG. 6.
  • FIG. 8 is a schematic diagram of an embodiment of a device using a lithium ion battery as a power source.
  • the lithium-ion battery and device according to the present application will be described in detail below.
  • the lithium ion battery according to the present application includes an electrode assembly and an electrolyte, and the electrode assembly includes a positive pole piece, a negative pole piece, and a separator.
  • the positive active material in the positive pole piece includes Li x1 Co y1 M 1-y1 O 2-z1 Q z1 , 0.5 ⁇ x1 ⁇ 1.2, 0.8 ⁇ y1 ⁇ 1.0, 0 ⁇ z1 ⁇ 0.1, M is selected from Al , Ti, Zr, Y, Mg one or more, Q is selected from F, Cl, S one or more.
  • the electrolyte contains an additive A, an additive B, and an additive C.
  • the additive A is selected from one or more of the compounds represented by Formula I-1, Formula I-2, and Formula I-3.
  • the additive B is selected from one or more of the compounds represented by Formula II-1 and Formula II-2
  • the additive C is selected from one or more of the compounds represented by Formula III-1.
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a halogen atom, and a substituted or unsubstituted C 1 to C 12 alkane Group, substituted or unsubstituted C 1 -C 12 alkoxy group, substituted or unsubstituted C 1 -C 12 amine group, substituted or unsubstituted C 2 -C 12 alkenyl group, substituted or unsubstituted C 2 ⁇ C 12 alkynyl, substituted or unsubstituted C 6 to C 26 aryl, substituted or unsubstituted C 2 to C 12 heterocyclic, wherein the substituent (in this application means “substituted or unsubstituted” occurs Substitution)
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , and R 39 are each independently selected from halogen-substituted or unsubstituted C 1 -C 6 alkane base.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , and R 49 are each independently selected from halogen-substituted or unsubstituted C 1 to C 6 alkane base.
  • R 21 is selected from halogen-substituted C 1 -C 6 alkylene and halogen-substituted C 2 -C 6 alkenylene.
  • the lithium ion battery of the present application has excellent cycle performance and storage performance, especially under high temperature and high voltage conditions.
  • this application uses a positive electrode active material containing a lithium cobaltate material doped with metal ions M, Li x1 Co y1 M 1-y1 O 2-z1 Q z1 , and the doping element M serves as a skeleton in the lithium cobaltate material. Reduce the lattice deformation of lithium cobalt oxide materials during the deep delithiation process, delay the degradation of the bulk phase structure of lithium cobalt oxide materials, and improve the structural stability of lithium ion batteries when used at high voltages greater than 4.2V.
  • additives of additive A, additive B and additive C are added to the electrolyte of the present application at the same time, the three can play a synergistic role to jointly protect the lithium ion battery, so that the lithium ion battery has excellent cycle performance and storage performance, especially It has excellent cycle performance and storage performance under high temperature and high voltage.
  • Additive A is a polynitrile six-membered nitrogen heterocyclic compound with a low oxidation potential.
  • the nitrogen atom in the nitrile group contains a lone pair of electrons. It has a strong complexation with the transition metal in the positive electrode active material, and the battery becomes It can be adsorbed on the surface of the positive electrode active material to form a loose and porous complex layer and effectively passivate the surface of the positive electrode active material.
  • the complex layer can isolate the direct contact between the surface of the positive electrode active material and the electrolyte and reduce the surface activity of the positive electrode active material, and can also reduce a large number of side reactions on the surface of the positive electrode active material and inhibit the dissolution of transition metals into the electrolyte to ensure the positive electrode active material
  • the structural integrity during the use of lithium-ion batteries thereby effectively improving the cycle capacity retention rate of lithium-ion batteries at high voltage and reducing the high-temperature storage gas production of lithium-ion batteries.
  • Additive A has a special six-membered nitrogen heterocyclic structure, and the distance between the nitrile group and the nitrile group is closer to the distance between the transition metal and the transition metal on the surface of the positive electrode active material, which can maximize the complexation of the nitrile group and make more A large number of nitrile groups exert a complexing effect, so the polynitrile six-membered nitrogen heterocyclic compound of the present application can have a better passivation effect than conventional linear nitrile compounds.
  • Additive B is a silane phosphite compound or a silane phosphate compound or a mixture of the two, which has a flame retardant effect and can effectively improve the thermal safety of the electrolyte after being added. Therefore, when the lithium ion battery is stored at high temperature or When thermal runaway occurs under other extreme conditions, additive B can reduce the risk of lithium ion battery burning, thereby improving the overall safety of the lithium ion battery.
  • Additive C is a halogen-substituted cyclic carbonate compound, which can form a uniform and dense protective film on the surface of the negative electrode (especially the surface of the negative electrode containing Si) to isolate the electron conduction between the negative electrode and the electrolyte and effectively reduce
  • the side reaction between the negative electrode and the electrolyte can not only protect the negative electrode from damage, suppress the continuous increase of the negative electrode impedance, but also reduce the electrolyte consumption during the use of the lithium-ion battery.
  • the protective film formed by the additive C in the negative electrode has excellent mechanical properties. When the expansion and contraction of the negative electrode charge and discharge occurs, this layer of protective film can maintain integrity without damage, which can continue to effectively protect the negative electrode and improve lithium ions. The cycling performance of the battery.
  • the C 1 -C 12 alkyl group may be a chain alkyl group or a cyclic alkyl group.
  • the chain alkyl group may also be a linear or branched alkyl group.
  • the hydrogen on the ring of the cyclic alkyl group is also It may be further substituted with alkyl.
  • the preferred lower limit of the number of carbon atoms in the C 1 to C 12 alkyl group is 1, 2, 3, 4, and 5, and the preferred upper limit is 3, 4, 5, 6, 8, 10, and 12.
  • C 1 ⁇ C 10 alkyl is selected; further preferably, C 1 ⁇ C 6 chain alkyl, C 3 ⁇ C 8 cyclic alkyl is selected; still more preferably, C 1 ⁇ C 4 chain is selected.
  • Alkyl C 5 -C 7 cyclic alkyl.
  • Examples of the C 1 to C 12 alkyl group specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isoamyl, neopentyl, hexyl, 2-methyl-pentyl, 3-methyl-pentyl, 1,1,2-trimethyl-propyl, 3,3-dimethyl-butyl, Heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, isoheptyl, octyl, nonyl, decyl.
  • C 1 -C 12 alkyl group contains an oxygen atom
  • it may be a C 1 -C 12 alkoxy group.
  • C 1 -C 10 alkoxy is selected; further preferably, C 1 -C 6 alkoxy is selected; still more preferably, C 1 -C 4 alkoxy is selected.
  • Examples of C 1 to C 12 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, N-pentyloxy, isopentyloxy, cyclopentyloxy, cyclohexyloxy.
  • the C 2 -C 12 alkenyl group may be a cyclic alkenyl group or a chain alkenyl group, and the chain alkenyl group may be a linear alkenyl group or a branched alkenyl group.
  • the number of double bonds in the C 2 to C 12 alkenyl group is preferably one.
  • the preferred lower limit of the number of carbon atoms in the C 2 to C 12 alkenyl group is 2, 3, 4, and 5, and the preferred upper limit is 3, 4, 5, 6, 8, 10, and 12.
  • C 2 -C 10 alkenyl is selected; further preferably, C 2 -C 6 alkenyl is selected; still more preferably, C 2 -C 5 alkenyl is selected.
  • Examples of C 2 to C 12 alkenyl groups include vinyl, allyl, isopropenyl, pentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.
  • the C 2 -C 12 alkynyl group may be a cyclic alkynyl group or a chain alkynyl group, and the chain alkynyl group may be a linear alkynyl group or a branched alkynyl group.
  • the number of triple bonds in the C 2 to C 12 alkynyl group is preferably one.
  • the preferred lower limit of the number of carbon atoms in the C 2 to C 12 alkynyl group is 2, 3, 4, and 5, and the preferred upper limit is 3, 4, 5, 6, 8, 10, and 12.
  • C 2 to C 10 alkynyl is selected; further preferably, C 2 to C 6 alkynyl is selected; still more preferably, C 2 to C 5 alkynyl is selected.
  • Examples of C 2 to C 12 alkynyl groups include ethynyl, propargyl, isopropynyl, pentynyl, cyclohexynyl, cycloheptynyl, and cyclooctynyl groups.
  • the C 1 ⁇ C 12 amino group can be selected from Wherein R ', R "is selected from C 1 ⁇ C 12 alkyl group.
  • C 6 ⁇ C 26 aryl groups can be phenyl, phenalkyl, biphenyl, fused ring aromatic hydrocarbon groups (such as naphthyl, anthracenyl, phenanthrenyl), biphenyl and fused ring aromatic hydrocarbon groups can be further alkyl Or alkenyl substitution.
  • a C 6 -C 16 aryl group is selected; further preferably, a C 6 -C 14 aryl group is selected; still more preferably, a C 6 -C 9 aryl group is selected.
  • Examples of the C 6 -C 26 aryl group include phenyl, benzyl, biphenyl, p-tolyl, o-tolyl, m-tolyl, naphthyl, anthryl, and phenanthryl.
  • the hetero atom in the C 2 -C 12 heterocyclic group may be selected from one or more of oxygen, nitrogen, sulfur, phosphorus, and boron, and the hetero ring may be an aliphatic hetero ring or an aromatic hetero ring.
  • a C 2 -C 10 heterocyclic group is selected; further preferably, a C 2 -C 7 heterocyclic group is selected; still more preferably, a five-membered aromatic heterocyclic ring, a six-membered aromatic heterocyclic ring, and a benzo heterocyclic ring are selected.
  • C 2 to C 12 heterocyclic group specific examples include ethylene oxide, propylene oxide, ethylene sulfide, aziridine, ⁇ -propiolactone, furyl, Thienyl, pyrrolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolinyl.
  • the halogen atom as a substituent may be one or more selected from a fluorine atom, a chlorine atom, and a bromine atom, preferably a fluorine atom.
  • the compound represented by Formula I-1 is a polycyanopyrimidine compound.
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted C 1 to C 6 linear or branched alkyl group, and a substitution Or unsubstituted C 5 ⁇ C 9 cyclic alkyl, substituted or unsubstituted C 1 ⁇ C 6 alkoxy, substituted or unsubstituted C 1 ⁇ C 6 amino, 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 2 -C 12 heterocyclyl; further preferably, R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a fluorine atom,
  • x is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1, or 2.
  • y is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1 or 2.
  • m is preferably selected from 1 or 2.
  • n is preferably selected from 1 or 2.
  • R 1 and R 3 are the same group; further preferably, R 1 , R 3 and R 4 are all the same group.
  • R 1 and R 3 are all hydrogen atoms; further preferably, R 1 , R 3 and R 4 are all hydrogen atoms.
  • R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, or R 1 , R 3 and R 4 are all hydrogen atoms and R 2 is selected from fluorine atom, chlorine atom, bromine atom, substituted or unsubstituted C 1 -C 6 linear or branched alkyl, substituted or unsubstituted C 1 -C 6 alkoxy.
  • the substituent is selected from one or more of halogen atoms, preferably, the substituent is selected from fluorine atoms.
  • the compound represented by Formula I-1 may be specifically selected from one or more of the following compounds, but the application is not limited thereto:
  • the compound represented by Formula I-2 is a polynitrile piperazine compound.
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted C 1 to C 6 linear or branched alkyl group, and a substitution Or unsubstituted C 5 ⁇ C 9 cyclic alkyl, substituted or unsubstituted C 1 ⁇ C 6 alkoxy, substituted or unsubstituted C 1 ⁇ C 6 amino, 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 2 -C 12 heterocyclyl; further preferably, R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a fluorine atom,
  • x is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1, or 2.
  • y is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1 or 2.
  • m is preferably selected from 1 or 2.
  • n is preferably selected from 1 or 2.
  • R 1 , R 2 , R 3 , and R 4 are the same group, and further preferably, at least three of R 1 , R 2 , R 3 , and R 4 are the same group.
  • R 1 , R 2 , R 3 , and R 4 are hydrogen atoms; further preferably, at least three of R 1 , R 2 , R 3 , and R 4 are hydrogen atoms.
  • R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, or three of R 1 , R 2 , R 3 and R 4 are hydrogen atoms and the remaining one is selected from fluorine atom, chlorine atom and bromine atom , Substituted or unsubstituted C 1 -C 6 linear or branched alkyl, substituted or unsubstituted C 1 -C 6 alkoxy.
  • the substituent is selected from one or more of halogen atoms, preferably, the substituent is selected from fluorine atoms.
  • the compound represented by Formula I-2 may be specifically selected from one or more of the following compounds, but the application is not limited thereto:
  • the compound represented by Formula I-3 is a polynitrile mesitazine compound.
  • R 1 , R 2 and R 3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted C 1 to C 6 linear or branched alkyl group, a substituted or unsubstituted C 5 ⁇ C 9 cyclic alkyl, substituted or unsubstituted C 1 ⁇ C 6 alkoxy, substituted or unsubstituted C 1 ⁇ C 6 amino, 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 2 -C 12 heterocyclyl; further preferably, R 1 , R 2 And R 3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a
  • x is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1, or 2.
  • y is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1 or 2.
  • z is preferably selected from integers of 0 to 6, further preferably selected from integers of 0 to 4, even more preferably selected from 0, 1 or 2.
  • m is preferably selected from 1 or 2.
  • n is preferably selected from 1 or 2.
  • k is preferably selected from 1 or 2.
  • At least two of R 1 , R 2 and R 3 are the same group.
  • At least two of R 1 , R 2 and R 3 are hydrogen atoms.
  • R 1 , R 2 and R 3 are all hydrogen atoms, or two of R 1 , R 2 and R 3 are hydrogen atoms and the remaining one is selected from fluorine atom, chlorine atom, bromine atom, substituted or unsubstituted C 1 -C 6 linear or branched alkyl, substituted or unsubstituted C 1 -C 6 alkoxy.
  • the substituent is selected from one or more of halogen atoms, preferably, the substituent is selected from fluorine atoms.
  • the compound represented by Formula I-3 may be specifically selected from one or more of the following compounds, but the application is not limited thereto:
  • the additive B is a silane phosphite compound or a silane phosphate compound or a mixture of both.
  • the compound represented by Formula II-1 is a silane phosphite compound.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 are each independently selected from halogen substituted or unsubstituted C 1 ⁇ C 4 alkyl.
  • the halogen atom as a substituent may be one or more selected from a fluorine atom, a chlorine atom, and a bromine atom, and is preferably a fluorine atom.
  • the silane phosphite compound may be specifically selected from one or more of the following compounds, but the application is not limited thereto:
  • the compound represented by Formula II-2 is a silane phosphate compound.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 are each independently selected from halogen substituted or unsubstituted C 1 ⁇ C 4 alkyl.
  • the halogen atom as a substituent may be one or more selected from a fluorine atom, a chlorine atom, and a bromine atom, and is preferably a fluorine atom.
  • the silane phosphate compound may be specifically selected from one or more of the following compounds, but the application is not limited thereto:
  • the compound represented by Formula III-1 is a halogen-substituted cyclic carbonate compound.
  • the halogen atom for substituting the alkylene group and the alkenylene group may be one or more kinds selected from a fluorine atom, a chlorine atom, and a bromine atom, preferably a fluorine atom.
  • R 21 is selected from halogen-substituted C 2 -C 4 alkylene and halogen-substituted C 2 -C 4 alkenylene.
  • the additive C may be specifically selected from fluoroethylene carbonate (FEC), fluoropropylene carbonate (FPC), trifluoropropylene carbonate (TFPC), trans or cis-4,5-di One or more of fluoro-1,3-dioxolane-2-one (DFEC).
  • FEC fluoroethylene carbonate
  • FPC fluoropropylene carbonate
  • TFPC trifluoropropylene carbonate
  • DFEC fluoro-1,3-dioxolane-2-one
  • the mass percentage content of the additive A in the electrolyte is 0.1% to 10%. If the content of additive A is too low, the improvement effect on the electrolyte is not obvious; if the content of additive A is too high, the complex layer formed on the surface of the positive electrode active material adsorbed by it is too thick and dense, affecting the diffusion and migration of lithium ions The positive electrode impedance is greatly increased. At the same time, the excessively high content of additive A also causes the overall viscosity of the electrolyte to increase and the ionic conductivity to decrease. Therefore, the excessively high content affects the performance of the lithium-ion battery.
  • the upper limit of the content range of the additive A can be selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5% , 1%, 0.8%
  • the lower limit of the content range of the additive A can be selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2 %.
  • the mass percentage content of the additive A in the electrolyte is 0.1% to 6%. More preferably, the mass percentage of the additive A in the electrolyte is 0.1% to 3.5%.
  • the mass percentage content of the additive B in the electrolyte is 0.1% to 10%. If the content of additive B is too low, the safety performance of lithium-ion batteries is not significantly improved; if the content of additive B is too high, the product produced by the reaction will greatly increase the overall impedance of the battery, and too high content will cause the electrolyte ion The conductivity drops, which in turn affects the performance of lithium-ion batteries.
  • the upper limit of the content range of the additive B can be selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5% , 1%, 0.8%
  • the lower limit of the content range of the additive B can be selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2 %.
  • the mass percentage content of the additive B in the electrolyte is 0.1% to 5%.
  • the mass percentage content of the additive C in the electrolyte is 0.1% to 30%. If the content of additive C is too low, its protective effect on the negative electrode is not obvious; if the content of additive C is too high, the products produced in the reaction of the negative electrode will be deposited on the surface of the negative electrode in a large amount, significantly improving the negative electrode resistance, and due to its thermal stability Poor, easy to decompose, will also lead to a large amount of gas generated in the lithium-ion battery, causing bubbles inside the battery, electrolyte broken bridge phenomenon, further improve the battery impedance, so the excessively high content affects the performance of the lithium-ion battery.
  • the upper limit of the range of the additive C content can be selected from 30%, 28%, 25%, 22%, 19%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9% , 8%, 7%, 6%, 5%
  • the lower limit of the range of the additive C content can be optionally selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9 %, 1%, 2%, 3%, 4%, 5%.
  • the mass percentage content of the additive C in the electrolyte is 5% to 15%.
  • the electrolyte further includes an organic solvent and an electrolyte salt.
  • the type of organic solvent used in the electrolyte of the examples of the present application is not particularly limited, and preferably may include cyclic carbonates and chain carbonates, which can further improve the cycle performance and storage of lithium ion batteries at high temperature and high voltage Performance, and it is easy to adjust the conductivity of the electrolyte to a suitable range, which is more conducive to additives A, B, and C to achieve a better film-forming effect.
  • the organic solvent used in the electrolyte as an example of the present application may further include a carboxylic acid ester, that is, the organic solvent of the present application may include a mixture of cyclic carbonate, chain carbonate, and carboxylic acid ester.
  • Carboxylic acid esters have the characteristics of large dielectric constant and low viscosity, which can effectively prevent the association of lithium ions and anions in the electrolyte, and at the same time have more advantages in ion conduction than cyclic carbonates and chain carbonates, especially in At low temperatures, it can ensure that the electrolyte has good ion conduction characteristics.
  • the mass percentage content of the cyclic carbonate can be 15% to 55%, preferably 25% to 50%; the mass percentage content of the chain carbonate can be 15% to 74 %, preferably 25% to 70%; the mass percentage content of the carboxylic acid ester may be 0.1% to 70%, preferably 5% to 50%.
  • the cyclic carbonate may be selected from one or more of ethylene carbonate, propylene carbonate, 1,2-butene carbonate, and 2,3-butanediol carbonate. Further preferably, the cyclic carbonate may be one or more selected from ethylene carbonate and propylene carbonate.
  • the chain carbonate may be one or more asymmetric chain carbonates selected from ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, and ethyl propyl carbonate.
  • the chain carbonate can also be selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, one or more symmetric chain carbonate; the chain carbonate can also be the above A mixture of asymmetric chain carbonates and symmetric chain carbonates.
  • the carboxylic acid ester may be selected from methyl pivalate, ethyl pivalate, propyl pivalate, butyl pivalate, methyl butyrate, ethyl butyrate, propyl butyrate, butyric acid
  • butyl ester methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate.
  • the following lithium salts can be suitably cited.
  • Li salts-2 suitably selected from (CF 2 ) 2 (SO 2 ) 2 NLi (cyclic), (CF 2 ) 3 (SO 2 ) 2 NLi (cyclic) and LiC (SO one or more of the 2 CF 3) 3 "methyl imide or lithium salts.”
  • [Li salt-5] suitably selected from bis[oxalate-O,O'] lithium borate (LiBOB), difluoro[oxalate-O,O'] lithium borate, difluorobis[oxalic acid Root-O,O']Lithium Phosphate (LiPFO) and tetrafluoro[oxalate-O,O']Lithium Phosphate, one or more "lithium salt with oxalate ligand as positive ion", Among them, it is more preferably selected from LiBOB and LiPFO.
  • the lithium salt can be used alone or in combination.
  • the lithium salt is selected from LiPF 6 , LiPO 2 F 2 , Li 2 PO 3 F, LiBF 4 , LiSO 3 F, trifluoro((methanesulfonyl)oxy) lithium borate (LiTFMSB), bis[oxalic acid One or more of lithium-O,O'] lithium borate (LiBOB), difluorobis[oxalate-O,O'] lithium phosphate (LiPFO) and tetrafluoro[oxalate-O,O'] lithium phosphate Species.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiSO 3 F, trifluoro((methanesulfonyl)oxy) lithium borate (LiTFMSB), LiPO 2 F 2 , bis[oxalate-O,O'] One or more of lithium borate (LiBOB) and difluorobis[oxalate-O,O'] lithium phosphate (LiPFO). Even more preferably, the lithium salt is LiPF 6 .
  • the concentration of the electrolyte salt is not particularly limited, and can be adjusted reasonably according to actual needs.
  • the electrolyte has a conductivity of 4 mS/cm to 12 mS/cm at 25°C.
  • the preparation method of the electrolyte is not limited, and it can be prepared according to a conventional electrolyte method.
  • Li x1 Co y1 M 1-y1 O 2-z1 Q z1 may be specifically selected from LiCo 0.9 Zr 0.1 O 2 , LiCo 0.9 Ti 0.1 O 2 , Li 1.05 Co 0.8 Mg 0.2 O 2 , Li 1.01 Co 0.98 Mg 0.01 Ti 0.005 Al 0.005 O 2 , Li 1.05 Co 0.98 Mg 0.005 Zr 0.005 Ti 0.01 O 1.9 F 0.1 , Li 1.1 Co 0.95 Mg 0.01 Zr 0.01 Al 0.03 O 2 , Li 1.04 Co 0.95 Mg 0.02 Zr 0.03 O 1.95 F 0.05 , Li 1.06 Co 0.96 Mg 0.02 Ti 0.02 O 2 , Li 1.08 Co 0.97 Mg 0.01 Zr 0.01 Al 0.01 O 1.9 S 0.1 , Li 1.09 Co 0.98 Mg 0.01 Ti 0.005 Al 0.005 O 2 , Li 1.085 Co 0.98 Zr 0.01 Ti 0.005 Al 0.005 O 1.9 Cl 0.1
  • the positive electrode active material may further include lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, the foregoing oxide One or more of the compounds obtained by adding other transition metals or non-transition metals.
  • 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 After the slurry is dried, a positive pole piece is obtained.
  • the types and contents of conductive agent and binder are not specifically limited, and can be selected according to actual needs.
  • the type of the positive electrode current collector is also not specifically limited, and can be selected according to actual needs, and is preferably aluminum foil.
  • the negative electrode active material in the negative electrode sheet includes one or more of Si, SiO x2 , Si/C composite material, and Si alloy, 0 ⁇ x2 ⁇ 2.
  • the negative electrode active material may further include one or more of soft carbon, hard carbon, artificial graphite, natural graphite, lithium titanate, and a metal capable of forming an alloy with lithium.
  • the negative electrode sheet further includes a binder and a conductive agent, and the negative electrode slurry containing the negative electrode active material, the binder and the conductive agent is coated on the negative electrode current collector, and the negative electrode After the slurry is dried, a negative pole piece is obtained.
  • the types and contents of conductive agent and binder are not specifically limited, and can be selected according to actual needs.
  • the type of the negative electrode current collector is also not specifically limited, and can be selected according to actual needs, and is preferably a copper foil.
  • the separator is provided between the positive pole piece and the negative pole piece to play a role of isolation.
  • the specific type of the separator is not specifically limited, and may be any separator material used in existing lithium ion batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, and their multilayer composite films, but not limited to These ones.
  • the charge cut-off voltage of the lithium ion battery is not less than 4.2V, that is, the lithium ion battery can be used in a high voltage state not less than 4.2V.
  • the charging cut-off voltage of the lithium ion battery is not less than 4.35V.
  • the lithium-ion battery of the present application may be either a hard-shell lithium-ion battery or a soft-package lithium-ion battery.
  • the hard shell lithium ion battery preferably uses a metal hard shell.
  • the flexible packaging lithium ion battery preferably uses a packaging bag as a battery case, and the packaging bag generally includes an accommodating portion and a sealing portion, wherein the accommodating portion is used to accommodate the electrode assembly and the electrolyte, and the sealing portion is used to seal the electrode assembly and the electrolyte.
  • the additive A can be synthesized by the following method.
  • P20 aqueous solution with a concentration of 30% to 40% is added dropwise to the raw material P-1 within 20min to 60min and quickly stirred. After the completion of the dropwise addition, the solution is rapidly stirred for 15h to 30h, and stirred at 70°C to 90°C in an oil bath under reflux for 3h. 5h, to obtain colorless fuming viscous liquid intermediate product I-1-1; continue to add K 2 CO 3 , KI, anhydrous acetonitrile, quickly stir to form a solid-liquid mixed phase, quickly add raw materials at 40 °C ⁇ 60 °C P-3, continue to stir for 10h-20h, then cool to room temperature, and separate and purify to obtain the compound represented by Formula I-1.
  • the anhydrous sodium carbonate, the raw material P-4 and the raw material P-3 are mixed in absolute ethanol, and the reaction is stirred for 2h to 5h; the hot ethanol is repeatedly washed several times to obtain a crude product, and the compound represented by the formula I-2 is obtained by recrystallization.
  • the anhydrous sodium carbonate, the raw material P-5 and the raw material P-3 are mixed in absolute ethanol, and the reaction is stirred for 2h to 5h; the hot ethanol is repeatedly washed many times to obtain a crude product, and the compound represented by formula I-3 is obtained by recrystallization.
  • the lithium ion battery may include an outer package for encapsulating the positive pole piece, the negative pole piece, and the electrolyte.
  • the positive pole piece, the negative pole piece and the separator may be laminated or wound to form a laminated structure electrode assembly or a wound structure electrode assembly, and the electrode assembly is encapsulated in an outer package; the electrolyte may use an electrolyte, which is infiltrated by the electrolyte In the electrode assembly.
  • the number of electrode assemblies in a lithium ion battery can be one or several, which can be adjusted according to requirements.
  • the outer package of the lithium-ion battery may be a soft bag, such as a pouch type soft bag.
  • the material of the soft bag may be plastic, such as one or more of polypropylene PP, polybutylene terephthalate PBT, polybutylene succinate PBS, etc.
  • the outer package of the lithium ion battery can also be a hard shell, such as an aluminum shell.
  • the present application has no particular limitation on the shape of the lithium ion battery, which may be cylindrical, square, or any other shape.
  • 4 is a lithium-ion battery 5 having a square structure as an example.
  • the lithium-ion battery may be assembled into a battery module, and the number of lithium-ion batteries contained in the battery module may be multiple, and the specific number may be adjusted according to the application and capacity of the battery module.
  • FIG. 5 is a battery module 4 as an example.
  • a plurality of lithium ion batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other way. Further, the plurality of lithium ion batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of lithium ion batteries 5 are accommodated in the accommodation space.
  • the above battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery case includes an upper case 2 and a lower case 3.
  • the upper case 2 can be covered on the lower case 3 and forms an enclosed space for accommodating the battery module 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • a device in a second aspect of the present application, includes the lithium-ion battery of the first aspect of the present application, and the lithium-ion battery provides power for the device.
  • the device may be, but not limited to, mobile equipment (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf balls) Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a lithium ion battery, battery module or battery pack according to its usage requirements.
  • FIG. 8 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, or the like.
  • the device usually requires lightness and thinness, and a lithium ion battery can be used as a power source.
  • additives A1, A2, and A3 are commercially available unless otherwise specified.
  • the specific synthesis process of additives A1, A2, and A3 is as follows.
  • Other types of additives A can be synthesized according to similar methods.
  • additives A1, A2, and A3 are commercially available unless otherwise specified.
  • the specific synthesis process of additives A1, A2, and A3 is as follows.
  • Other types of additives A can be synthesized according to similar methods.
  • lithium-ion batteries were prepared according to the following methods.
  • a mixed solution of ethylene carbonate (abbreviated as EC), ethyl methyl carbonate (abbreviated as EMC) and diethyl carbonate (abbreviated as DEC) is used as an organic solvent, wherein the mass ratio of EC, EMC and DEC is 1:1 :1.
  • the lithium salt is LiPF 6 , and the content of LiPF 6 is 12.5% of the total mass of the electrolyte.
  • Each additive is added according to the electrolyte composition shown in Table 1, wherein the content of each additive component is calculated relative to the total mass of the electrolyte.
  • additives A and B used in the examples and comparative examples are abbreviated as follows:
  • the positive electrode active material shown in Table 1 the binder PVDF, and the conductive agent acetylene black were mixed according to a mass ratio of 98:1:1, N-methylpyrrolidone was added, and stirred under the action of a vacuum mixer until stable and uniform, to obtain a positive electrode slurry ; Evenly coat the positive electrode slurry on the aluminum foil, dry the aluminum foil at room temperature and transfer to a 120°C blast oven for 1 hour, and then cold press and cut to obtain the positive pole piece.
  • the negative electrode active material shown in Table 1 the conductive agent acetylene black, the thickener sodium carboxymethyl cellulose, the binder styrene-butadiene rubber according to the mass ratio of 97:1:1:1, add deionized water, in a vacuum Stir under the action of a stirrer until it is stable and uniform to obtain the negative electrode slurry; apply the negative electrode slurry uniformly on the copper foil, dry the copper foil at room temperature and transfer to a 120°C blast oven for 1 hour, and then pass the cold press, Cut to obtain the negative pole piece.
  • the lithium ion battery is first charged with a constant current of 1C to a voltage of 4.35V, further charged with a constant voltage of 4.35V to a current of 0.05C, and then discharged with a constant current of 1C to a voltage of 3.0V, which is a charge
  • the current discharge capacity is the first cycle discharge capacity.
  • the lithium-ion battery was subjected to 200 cycles of charge/discharge test according to the above method, and the discharge capacity at the 200th cycle was detected.
  • Capacity retention rate (%) after 200 cycles of the lithium ion battery (discharge capacity of the lithium ion battery after 200 cycles/discharge capacity of the first cycle of the lithium ion battery) ⁇ 100%.
  • the lithium ion battery is first charged with a constant current of 1C to a voltage of 4.35V, further charged with a constant voltage of 4.35V to a current of 0.05C, and then discharged with a constant current of 1C to a voltage of 3.0V, which is a charge
  • the current discharge capacity is the first cycle discharge capacity.
  • the lithium-ion battery was subjected to 200 cycles of charge/discharge test according to the above method, and the discharge capacity at the 200th cycle was detected.
  • Capacity retention rate (%) after 200 cycles of the lithium ion battery (discharge capacity of the lithium ion battery after 200 cycles/discharge capacity of the first cycle of the lithium ion battery) ⁇ 100%.
  • Lithium-ion battery thickness expansion rate (%) after storage at 85°C for 24 hours [(h 1 -h 0 )/h 0 ] ⁇ 100%.
  • the examples of the present application use a metal ion M-doped lithium cobaltate material Li x1 Co y1 M 1-y1 O 2-z1 Q z1 as a positive electrode active material, using additives A, B and additives
  • the combined additive of C serves as an electrolyte additive.
  • the doping element M serves as a skeleton in the cathode active material, which can reduce the lattice deformation of the cathode active material during the deep delithiation process, delay the degradation of the bulk structure of the cathode active material, and greatly improve the use of lithium ion batteries under high voltage Structural stability at the time.
  • Additive A is a polynitrile six-membered nitrogen heterocyclic compound with a low oxidation potential, which can form a stable complex layer on the surface of the cathode active material when the battery is formed, effectively passivating the surface of the cathode active material and reducing the cathode active material Surface activity, the direct contact between the isolated electrolyte and the surface of the positive electrode active material makes the side reactions on the surface greatly reduced, and the lithium ions consumed in the side reactions are correspondingly reduced, that is, the consumption rate of reversible lithium ions is greatly slowed down, and finally appears The actual effect is that the cycle capacity retention rate of lithium-ion batteries is greatly improved; some surface side reactions can generate gas, and the reduction of surface side reactions also means that the gas production of the battery is reduced.
  • Additive B has a flame-retardant effect, which can effectively improve the thermal safety of the electrolyte after being added.
  • additive B can reduce the risk of lithium-ion batteries burning. Furthermore, the overall safety of the lithium ion battery is improved.
  • Additive C can form a uniform and dense protective film on the surface of the Si-containing negative electrode, isolate the electron conduction between the negative electrode and the electrolyte, effectively reduce the side reaction between the negative electrode and the electrolyte, both protect the negative electrode from damage and suppress the negative electrode
  • the continuous increase in impedance can also reduce the electrolyte consumption during the use of lithium-ion batteries.
  • the protective film formed by the additive C in the negative electrode has excellent mechanical properties. This layer of protective film is expanded and contracted during the charge and discharge of the negative electrode. It can maintain the integrity without damage, so as to continue to effectively protect the negative electrode and improve the cycle capacity retention rate of the lithium ion battery.
  • the present application can significantly improve the cycle performance and storage performance of lithium-ion batteries under high-temperature and high-voltage conditions.
  • the polynitrile six-membered nitrogen heterocyclic compound of the present application has a special six-membered nitrogen heterocyclic structure, and the distance between the nitrile group and the nitrile group is closer to the surface transition metal of the positive electrode active material The distance from the transition metal can maximize the complexation of the nitrile group, and allow a greater number of nitrile groups to exert complexation.
  • the polynitrile six-membered nitrogen heterocyclic compound of the present application has a stronger covering effect on the transition metal on the surface of the positive electrode active material, a better passivation effect on the surface of the positive electrode active material, and an improvement effect on the cycle performance and storage performance of the lithium ion battery Also more outstanding.
  • an appropriate amount of the additive A needs to be added, preferably 0.1% to 10%, more preferably 0.1% to 6%, still more preferably 0.1% to 3.5%.
  • Lithium-ion batteries produce a large amount of gas, which causes bubbles inside the battery and the electrolyte to break the bridge, further increasing the battery impedance, which affects the cycle performance and storage performance of the lithium-ion battery. Therefore, an appropriate amount of the additive C needs to be added, preferably 0.1% to 30%, and more preferably 5% to 15%.

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Abstract

一种锂离子电池及装置，所述锂离子电池包括电极组件以及电解液，所述电极组件包括正极极片、负极极片以及隔离膜。所述正极极片中的正极活性材料包括Li x1Co y1M 1-y1O 2-z1Q z1，0.5≤x1≤1.2，0.8≤y1<1.0，0≤z1≤0.1，M选自Al、Ti、Zr、Y、Mg中的一种或几种，Q选自F、Cl、S中的一种或几种。所述电解液中含有添加剂A、添加剂B以及添加剂C。所述添加剂A为氧化电位较低的多腈基六元氮杂环化合物，所述添加剂B为硅烷亚磷酸酯化合物或硅烷磷酸酯化合物或二者的混合物，所述添加剂C为卤素取代的环状碳酸酯化合物。该锂离子电池具有优异的循环性能和存储性能，尤其是在高温高电压情况下具有优异的循环性能和存储性能。

Description

锂离子电池及装置 技术领域
本申请涉及储能材料领域，具体地讲，涉及一种锂离子电池及装置。
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LiCoO 2作为正极活性材料，其在完全放电态的LiCoO 2和半充电态的Li 0.5CoO 2(4.2V vs.Li)之间循环时性能比较稳定，因此实际上真正被利用的锂离子只有其实际锂离子含量的1/2。而当电压大于4.2V时，LiCoO 2中剩余1/2含量的锂离子可以继续脱出，但是深度脱锂过程中，Co 3+会被氧化为很不稳定的Co 4+，与失去大量电子的表面氧共同氧化电解液，此时电池内部将会产生大量气体造成电池鼓胀。同时由于电解液中HF对正极表面的腐蚀作用，导致Co 4+溶于电解液后沉积在负极表面，催化电解液的还原，也会产生大量气体造成电池鼓胀。另外由于Co的3d能级与O的2p能级重叠程度较大，深度脱锂还会导致晶格氧失去大量电子，使LiCoO 2晶胞沿c轴方向剧烈收缩，诱发局部体相结构失稳甚至坍塌，最终引起LiCoO 2活性位点损失，锂离子电池容量迅速降低。因此LiCoO 2在大于4.2V的高电压体系中使用时的性能非常差。
鉴于此，特提出本申请。
发明内容
鉴于背景技术中存在的问题，本申请的目的在于提供一种锂离子电池及装置，所述锂离子电池具有优异的循环性能和存储性能，尤其是在高温高电压情况下具有优异的循环性能和存储性能。
为了达到上述目的，在第一方面，本申请提供了一种锂离子电池，其包括电极组件以及电解液，所述电极组件包括正极极片、负极极片以及隔离膜。所述正极极片中的正极活性材料包括Li x1Co y1M 1-y1O 2-z1Q z1，0.5≤x1≤1.2，0.8≤y1<1.0，0≤z1≤0.1，M选自Al、Ti、Zr、Y、Mg中的一种或几种，Q选自F、Cl、S中的一种或几种。所述电解液中含有添加剂A、添加剂B以及添加剂C，所述添加剂A选自式I-1、式I-2、式I-3所示的化合物中的一种或几种，所述添加剂B选自式II-1、式II-2所示的化合物中的一种或几种，所述添加剂C选自式III-1所示的化合物中的一种或几种。
Figure PCTCN2019125321-appb-000001
在式I-1、式I-2、式I-3中：R 1、R 2、R 3、R 4各自独立地选自氢原子、卤素原子、取代或未取代的C 1～C 12烷基、取代或未取代的C 1～C 12烷氧基、取代或未取代的C 1～C 12胺基、取代或未取代的C 2～C 12烯基、取代或未取代的C 2～C 12炔基、取代或未取代的C 6～C 26芳基、取代或未取代的C 2～C 12杂环基，其中，取代基选自卤素原子、腈基、C 1～C 6烷基、C 2～C 6烯基、C 1～C 6烷氧基中的一种或几种；x、y、z各自独立地选自0～8的整数；m、n、k各自独立地选自0～2的整数。
Figure PCTCN2019125321-appb-000002
Figure PCTCN2019125321-appb-000003
在式II-1中，R 31、R 32、R 33、R 34、R 35、R 36、R 37、R 38、R 39各自独立地选自卤素取代或未取代的C 1～C 6烷基。在式II-2中，R 41、R 42、R 43、R 44、R 45、R 46、R 47、R 48、R 49各自独立地选自卤素取代或未取代的C 1～C 6烷基。
Figure PCTCN2019125321-appb-000004
在式III-1中，R 21选自卤素取代的C 1～C 6亚烷基、卤素取代的C 2～C 6亚烯基。
在本申请的第二方面，本申请提供了一种装置，其包括本申请的第一方面所述的锂离子电池。
相对于现有技术，本申请至少包括如下所述的有益效果：
本申请使用包含金属离子M掺杂的钴酸锂材料Li x1Co y1M 1-y1O 2-z1Q z1的正极活性材料，掺杂元素M在钴酸锂材料中充当骨架，可以减小钴酸锂材料深度脱锂过程中的晶格形变量，延缓钴酸锂材料体相结构的退化，改善锂离子电池在大于4.2V高电压下使用时的结构稳定性。
本申请的电解液中包含添加剂A、添加剂B以及添加剂C的组合添加剂。添加剂A为氧化电位较低的多腈基六元氮杂环化合物，电池化成时便能在正极活性材料表面形成稳定的络合物层，有效钝化正极活性材料表面，降低正极活性材料表面活性，抑制过渡金属溶解到电解液中，从而在减少副反应的同时降低电池产气；添加剂B为硅烷亚磷酸酯化合物或硅烷磷酸酯化合物或二者的混合物，其具有阻燃效果，加入后能够有效提高电解液的热安全性，因此当锂离子电池在高温存储或是在其他极端条件下发生热失控时，添加剂B能够降低锂离子电池发生燃烧的风险，进而提高锂离子电池整体的安全性；添加剂C卤素取代的环状碳酸酯化合物，其能够在负极表面(尤其是含Si负极表面)形成一层均匀致密的保护膜，隔绝负极与电解液之间的电子传导，有效减少负极与电解液之间的副反应，既能保护负极免受破坏，抑制负极阻抗的持续增长，又能减少锂离子电池使用过程中的电解液消耗；此外，添加剂C在负极所成的保护膜具有优良的机械性能，在负极充放电过程发生膨胀收缩时，这层保护膜能够保持完整性而不发生破坏，从而能够持续有效保护负极，提高锂离子电池的循环性能。
本申请的锂离子电池能具有优异的循环性能和存储性能，尤其是在高温高电压情况下具有优异的循环性能和存储性能。本申请的装置包括本申请第一方面所述的锂离子电池， 因而至少具有与所述锂离子电池相同的优势。
附图说明
图1为A1化合物核磁共振碳谱。
图2为A2化合物核磁共振碳谱。
图3为A3化合物核磁共振碳谱。
图4是锂离子电池的一实施方式的示意图。
图5是电池模块的一实施方式的示意图。
图6是电池包的一实施方式的示意图。
图7是图6的分解图。
图8是锂离子电池作为电源的装置的一实施方式的示意图。
其中，附图标记说明如下：
1电池包
2上箱体
3下箱体
4电池模块
5锂离子电池
具体实施方式
下面详细说明根据本申请的锂离子电池及装置。
首先说明根据本申请第一方面的锂离子电池。
根据本申请的锂离子电池包括电极组件以及电解液，所述电极组件包括正极极片、负极极片以及隔离膜。
其中，所述正极极片中的正极活性材料包括Li x1Co y1M 1-y1O 2-z1Q z1，0.5≤x1≤1.2，0.8≤y1<1.0，0≤z1≤0.1，M选自Al、Ti、Zr、Y、Mg中的一种或几种，Q选自F、Cl、S中的一种或几种。所述电解液中含有添加剂A、添加剂B以及添加剂C，所述添加剂A选自式I-1、式I-2、式I-3所示的化合物中的一种或几种，所述添加剂B选自式II-1、式II-2所示的化合物中的一种或几种，所述添加剂C选自式III-1所示的化合物中的一种或几种。
Figure PCTCN2019125321-appb-000005
Figure PCTCN2019125321-appb-000006
在式I-1、式I-2、式I-3中：R 1、R 2、R 3、R 4各自独立地选自氢原子、卤素原子、取代或未取代的C 1～C 12烷基、取代或未取代的C 1～C 12烷氧基、取代或未取代的C 1～C 12胺基、取代或未取代的C 2～C 12烯基、取代或未取代的C 2～C 12炔基、取代或未取代的C 6～C 26芳基、取代或未取代的C 2～C 12杂环基，其中，取代基(在本申请中表示“取代或未取代”中发生取代的情况)选自卤素原子、腈基、C 1～C 6烷基、C 2～C 6烯基、C 1～C 6烷氧基中的一种或几种；x、y、z各自独立地选自0～8的整数；m、n、k各自独立地选自0～2的整数。
Figure PCTCN2019125321-appb-000007
在式II-1中，R 31、R 32、R 33、R 34、R 35、R 36、R 37、R 38、R 39各自独立地选自卤素取 代或未取代的C 1～C 6烷基。在式II-2中，R 41、R 42、R 43、R 44、R 45、R 46、R 47、R 48、R 49各自独立地选自卤素取代或未取代的C 1～C 6烷基。
Figure PCTCN2019125321-appb-000008
在式III-1中，R 21选自卤素取代的C 1～C 6亚烷基、卤素取代的C 2～C 6亚烯基。
本申请的锂离子电池具有优异的循环性能和存储性能，尤其是在高温高电压情况下还具有优异的循环性能和存储性能。一方面，本申请使用包含金属离子M掺杂的钴酸锂材料Li x1Co y1M 1-y1O 2-z1Q z1的正极活性材料，掺杂元素M在钴酸锂材料中充当骨架，可以减小钴酸锂材料深度脱锂过程中的晶格形变量，延缓钴酸锂材料体相结构的退化，改善锂离子电池在大于4.2V高电压下使用时的结构稳定性。另一方面，本申请的电解液中同时加入添加剂A、添加剂B以及添加剂C三种添加剂，三者能够发挥协同作用共同保护锂离子电池，使锂离子电池具有优异的循环性能和存储性能，尤其是在高温高电压情况下具有优异的循环性能和存储性能。
具体地：
(1)添加剂A为氧化电位较低的多腈基六元氮杂环化合物，腈基中的氮原子含有孤对电子，与正极活性材料中的过渡金属具有较强的络合作用，电池化成时便能吸附在正极活性材料表面生成一层疏松多孔的络合物层并有效钝化正极活性材料表面。该络合物层能隔绝正极活性材料表面与电解液的直接接触以及降低正极活性材料表面活性，还能降低正极活性材料表面发生大量副反应以及抑制过渡金属溶解到电解液中，保证正极活性材料在锂离子电池使用过程中的结构完整性，从而有效提高锂离子电池在高电压下的循环容量保持率并降低锂离子电池的高温存储产气量。此外，添加剂A具有特殊的六元氮杂环结构，腈基与腈基的间距更接近正极活性材料表面过渡金属与过渡金属的间距，可以最大限度地发挥腈基的络合作用，且使更多数量的腈基发挥络合作用，因此与常规线性的腈基化合物相比，本申请的多腈基六元氮杂环化合物可具有更好的钝化效果。
(2)添加剂B为硅烷亚磷酸酯化合物或硅烷磷酸酯化合物或二者的混合物，其具有阻燃效果，加入后能够有效提高电解液的热安全性，因此当锂离子电池在高温存储或是在其他极端条件下发生热失控时，添加剂B能够降低锂离子电池发生燃烧的风险，进而提高锂离子电池整体的安全性。
(3)添加剂C为卤素取代的环状碳酸酯化合物，其能够在负极表面(尤其是含Si负极表面)形成一层均匀致密的保护膜，隔绝负极与电解液之间的电子传导，有效减少负极与电解液之间的副反应，既能保护负极免受破坏，抑制负极阻抗的持续增长，又能减少锂离子电池使用过程中的电解液消耗。此外，添加剂C在负极所成的保护膜具有优良的机械性能，在负极充放电过程发生膨胀收缩时，这层保护膜能够保持完整性而不发生破坏，从而能够持续有效保护负极，提高锂离子电池的循环性能。
在本申请的锂离子电池中，在式I-1、式I-2、式I-3所示的化合物中：
C 1～C 12烷基可为链状烷基，也可为环状烷基，链状烷基又可为直链烷基或支链烷基，位于环状烷基的环上的氢还可进一步被烷基取代。C 1～C 12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C 1～C 10烷基；进一步优选地，选择C 1～C 6链状烷基、C 3～C 8环状烷基；更进一步优选地，选择C 1～C 4链状烷基、C 5～C 7环状烷基。作为C 1～C 12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C 1～C 12烷基中含有氧原子时，可为C 1～C 12烷氧基。优选地，选择C 1～C 10烷氧基；进一步优选地，选择C 1～C 6烷氧基；更进一步优选地，选择C 1～C 4烷氧基。作为C 1～C 12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。
C 2～C 12烯基可为环状烯基，也可为链状烯基，链状烯基又可为直链烯基或支链烯基。另外，C 2～C 12烯基中双键的个数优选为1个。C 2～C 12烯基中碳原子数优选的下限值为2、3、4、5，优选的上限值为3、4、5、6、8、10、12。优选地，选择C 2～C 10烯基；进一步优选地，选择C 2～C 6烯基；更进一步优选地，选择C 2～C 5烯基。作为C 2～C 12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。
C 2～C 12炔基可为环状炔基，也可为链状炔基，链状炔基又可为直链炔基或支链炔基。另外，C 2～C 12炔基中三键的个数优选为1个。C 2～C 12炔基中碳原子数优选的下限值为2、3、4、5，优选的上限值为3、4、5、6、8、10、12。优选地，选择C 2～C 10炔基；进一步优选地，选择C 2～C 6炔基；更进一步优选地，选择C 2～C 5炔基。作为C 2～C 12炔基的实例，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。
C 1～C 12胺基可选自
Figure PCTCN2019125321-appb-000009
其中R’、R”选自C 1～C 12烷基。
C 6～C 26芳基可为苯基、苯烷基、联苯基、稠环芳烃基(例如萘基、蒽基、菲基)，联苯基和稠环芳烃基还可进一步被烷基或烯基取代。优选地，选择C 6～C 16芳基；进一步优选地，选择C 6～C 14芳基；更进一步优选地，选择C 6～C 9芳基。作为C 6～C 26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、萘基、蒽基、菲基。
C 2～C 12杂环基中杂原子可选自氧、氮、硫、磷、硼中的一种或几种，杂环可为脂杂环或芳杂环。优选地，选择C 2～C 10杂环基；进一步优选地，选择C 2～C 7杂环基；更进一步优选地，选择五元芳杂环、六元芳杂环以及苯并杂环。作为C 2～C 12杂环基的实例，具体可以举出：环氧乙烷基、环氧丙烷基、环硫乙烷基、氮杂环丙烷基、β-丙内酯基、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。
作为取代基的卤素原子可选自氟原子、氯原子、溴原子中的一种或几种，优选为氟原子。
(1)具体地，式I-1所示的化合物为多腈基嘧啶类化合物。
在式I-1中：
优选地，R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或未取代的C 5～C 9环状烷基、取代或未取代的C 1～C 6烷氧基、取代或未取代的C 1～C 6胺基、取代或未取代的C 2～C 6烯基、取代或未取代的C 2～C 6炔基、取代或未取代的C 6～C 12芳基、取代或未取代的C 2～C 12杂环基；进一步优选地，R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 3直链或支链烷基、取代或未取代的C 5～C 7环状烷基、取代或未取代的C 1～C 3烷氧基、取代或未取代的C 1～C 3胺基、取代或未取代的C 2～C 3烯基、取代或未取代的C 2～C 3炔基、取代或未取代的C 6～C 8芳基、取代或未取代的C 2～C 7杂环基。其中，取代基选自卤素原子中的一种或几种。
x优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
y优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
m优选地选自1或2。
n优选地选自1或2。
优选地，R 1、R 3为相同的基团；进一步优选地，R 1、R 3、R 4均为相同的基团。
优选地，R 1、R 3均为氢原子；进一步优选地，R 1、R 3、R 4均为氢原子。
优选地，R 1、R 2、R 3、R 4均为氢原子，或者R 1、R 3、R 4均为氢原子而R 2选自氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或未取代的C 1～C 6烷氧基。其中，取代基选自卤素原子中的一种或几种，优选地，取代基选自氟原子。
优选地，式I-1所示的化合物可具体选自以下化合物中的一种或几种，但本申请不限于此：
Figure PCTCN2019125321-appb-000010
Figure PCTCN2019125321-appb-000011
(2)具体地，式I-2所示的化合物为多腈基哌嗪类化合物。
在式I-2中：
优选地，R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或未取代的C 5～C 9环状烷基、取代或未取代的C 1～C 6烷氧基、取代或未取代的C 1～C 6胺基、取代或未取代的C 2～C 6烯基、取代或未取代的C 2～C 6炔基、取代或未取代的C 6～C 12芳基、取代或未取代的C 2～C 12杂环基；进一步优选地，R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 3直链或支链烷基、取代或未取代的C 5～C 7环状烷基、取代或未取代的C 1～C 3烷氧基、取代或未取代的C 1～C 3胺基、取代或未取代的C 2～C 3烯基、取代或未取代的C 2～C 3炔基、取代或未取代的C 6～C 8芳基、取代或未取代的C 2～C 7杂环基。其中，取代基选自卤素原子中的一种或几种。
x优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
y优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
m优选地选自1或2。
n优选地选自1或2。
优选地，R 1、R 2、R 3、R 4中至少有两个为相同的基团，进一步优选地，R 1、R 2、R 3、R 4中至少有三个为相同的基团。
优选地，R 1、R 2、R 3、R 4中至少有两个为氢原子；进一步优选地，R 1、R 2、R 3、R 4中至少有三个为氢原子。
优选地，R 1、R 2、R 3、R 4均为氢原子，或者R 1、R 2、R 3、R 4中有三个为氢原子且剩余一个选自氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或 未取代的C 1～C 6烷氧基。其中，取代基选自卤素原子中的一种或几种，优选地，取代基选自氟原子。
优选地，式I-2所示的化合物可具体选自以下化合物中的一种或几种，但本申请不限于此：
Figure PCTCN2019125321-appb-000012
(3)具体地，式I-3所示的化合物为多腈基均三嗪类化合物。
在式I-3中：
优选地，R 1、R 2、R 3各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或未取代的C 5～C 9环状烷基、取代或未取代的C 1～C 6烷氧基、取代或未取代的C 1～C 6胺基、取代或未取代的C 2～C 6烯基、取代或未取代的C 2～C 6炔基、取代或未取代的C 6～C 12芳基、取代或未取代的C 2～C 12杂环基；进一步优选地，R 1、R 2、R 3各自独立地选自氢原子、氟原子、氯原子、溴原子、取代或未取代的C 1～C 3直链或支链烷基、取代或未取代的C 5～C 7环状烷基、取代或未取代的C 1～C 3烷氧基、取代或未取代的C 1～C 3胺基、取代或未取代的C 2～C 3烯基、取代或未取代的C 2～C 3炔基、取代或未取代的C 6～C 8芳基、取代或未取代的C 2～C 7杂环基。其中，取代基选自卤素原子中的一种或几种。
x优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
y优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
z优选地选自0～6的整数，进一步优选地选自0～4的整数，更进一步优选地选自0、1或2。
m优选地选自1或2。
n优选地选自1或2。
k优选地选自1或2。
优选地，R 1、R 2、R 3中至少有两个为相同的基团。
优选地，R 1、R 2、R 3中至少有两个为氢原子。
优选地，R 1、R 2、R 3均为氢原子，或者R 1、R 2、R 3中有两个为氢原子且剩余一个选自氟原子、氯原子、溴原子、取代或未取代的C 1～C 6直链或支链烷基、取代或未取代的C 1～C 6烷氧基。其中，取代基选自卤素原子中的一种或几种，优选地，取代基选自氟原子。
优选地，式I-3所示的化合物可具体选自以下化合物中的一种或几种，但本申请不限于此：
Figure PCTCN2019125321-appb-000013
在本申请的锂离子电池中，所述添加剂B为硅烷亚磷酸酯化合物或硅烷磷酸酯化合物或二者的混合物。
(1)具体地，式II-1所示的化合物为硅烷亚磷酸酯化合物。
优选地，在式II-1中，R 31、R 32、R 33、R 34、R 35、R 36、R 37、R 38、R 39各自独立地选自卤素取代或未取代的C 1～C 4烷基。
其中，作为取代基的卤素原子可选自氟原子、氯原子、溴原子中的一种或几种，优选为氟原子。
优选地，硅烷亚磷酸酯化合物可具体选自以下化合物中的一种或几种，但本申请不限 于此：
Figure PCTCN2019125321-appb-000014
(2)具体地，式II-2所示的化合物为硅烷磷酸酯化合物。
优选地，在式II-2中，R 41、R 42、R 43、R 44、R 45、R 46、R 47、R 48、R 49各自独立地选自卤素取代或未取代的C 1～C 4烷基。
其中，作为取代基的卤素原子可选自氟原子、氯原子、溴原子中的一种或几种，优选为氟原子。
优选地，硅烷磷酸酯化合物可具体选自以下化合物中的一种或几种，但本申请不限于此：
Figure PCTCN2019125321-appb-000015
在本申请的锂离子电池中，式III-1所示的化合物为卤素取代的环状碳酸酯化合物。
其中，用于对亚烷基、亚烯基进行取代的卤素原子可选自氟原子、氯原子、溴原子中的一种或几种，优选为氟原子。
在式III-1中，优选地，R 21选自卤素取代的C 2～C 4亚烷基、卤素取代的C 2～C 4亚烯基。
优选地，所述添加剂C可具体选自氟代碳酸乙烯酯(FEC)、氟代碳酸丙烯酯(FPC)、三氟代碳酸丙烯酯(TFPC)、反式或顺式-4,5-二氟-1,3-二氧杂环戊烷-2-酮(DFEC)中的一种或几种。
在本申请的锂离子电池中，优选地，所述添加剂A在所述电解液中的质量百分含量为0.1％～10％。如果添加剂A含量过低，则其对电解液的改善效果不明显；如果添加剂A含量过高，则其吸附在正极活性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，正极阻抗大幅增高，同时添加剂A含量过高还导致电解液整体黏度提升、离子电导率下降，因此过高的含量反而影响锂离子电池的性能。所述添加剂A含量范围的上限可任选自10％、9％、8％、7％、6％、5％、4.5％、4％、3.5％、3％、2.5％、2％、1.5％、1％、0.8％，所述添加剂A含量范围的下限可任选自0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.2％。
进一步优选地，所述添加剂A在所述电解液中的质量百分含量为0.1％～6％。更进一 步优选地，所述添加剂A在所述电解液中的质量百分含量为0.1％～3.5％。
在本申请的锂离子电池中，优选地，所述添加剂B在所述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，则其对锂离子电池安全性能改善不明显；如果添加剂B含量过高，则其反应产生的产物会大幅提高电池整体阻抗，同时过高的含量会导致电解液的离子电导率下降，进而影响锂离子电池性能的发挥。所述添加剂B含量范围的上限可任选自10％、9％、8％、7％、6％、5％、4.5％、4％、3.5％、3％、2.5％、2％、1.5％、1％、0.8％，所述添加剂B含量范围的下限可任选自0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.2％。
进一步优选地，所述添加剂B在所述电解液中的质量百分含量为0.1％～5％。
在本申请的锂离子电池中，优选地，所述添加剂C在所述电解液中的质量百分含量为0.1％～30％。如果添加剂C含量过低，则其对负极的保护作用不明显；如果添加剂C含量过高，则其在负极反应产生的产物会大量沉积在负极表面，显著提高负极阻抗，同时由于自身热稳定性较差、容易分解，还会导致锂离子电池大量产气，造成电池内部出现气泡、电解液断桥现象，进一步提高电池阻抗，因此过高的含量反而影响锂离子电池的性能。所述添加剂C含量范围的上限可任选自30％、28％、25％、22％、19％、16％、15％、14％、13％、12％、11％、10％、9％、8％、7％、6％、5％，所述添加剂C含量范围的下限可任选自0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、2％、3％、4％、5％。
进一步优选地，所述添加剂C在所述电解液中的质量百分含量为5％～15％。
在本申请的锂离子电池中，所述电解液还包括有机溶剂以及电解质盐。
作为本申请实施例的电解液中使用的有机溶剂的种类没有特别的限制，优选可包括环状碳酸酯以及链状碳酸酯，其可进一步提高锂离子电池高温高电压情况下的循环性能和存储性能，且易于将电解液的电导率调节至合适的范围，从而更有利于添加剂A、添加剂B、添加剂C达到更好的成膜效果。
作为本申请实施例的电解液中使用的有机溶剂还可包括羧酸酯，即本申请的有机溶剂可包括环状碳酸酯、链状碳酸酯以及羧酸酯的混合物。羧酸酯具有介电常数大且粘度低的特点，可有效防止锂离子和电解液中阴离子的缔合，同时在离子传导方面比环状碳酸酯和链状碳酸酯更有优势，尤其是在低温下，能可保证电解液具有良好的离子传导特性。
其中，基于有机溶剂的总质量计，环状碳酸酯的质量百分含量可为15％～55％，优选为25％～50％；链状碳酸酯的质量百分含量可为15％～74％，优选为25％～70％；羧酸酯的质量百分含量可为0.1％～70％，优选为5％～50％。
具体地，环状碳酸酯可选自碳酸乙烯酯、碳酸丙烯酯、碳酸1,2-丁烯酯、碳酸-2,3-丁二醇酯中的一种或几种。进一步优选地，环状碳酸酯可选自碳酸乙烯酯、碳酸丙烯酯中的一种或几种。
具体地，链状碳酸酯可选自碳酸甲乙酯、碳酸甲丙酯、碳酸甲基异丙酯、碳酸甲丁酯、碳酸乙丙酯中的一种或几种的非对称链状碳酸酯；链状碳酸酯还可选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯中的一种或几种的对称链状碳酸酯；链状碳酸酯还可为上述非对称链状碳酸酯和对称链状碳酸酯的混合物。
具体地，羧酸酯可选自新戊酸甲酯、新戊酸乙酯、新戊酸丙酯、新戊酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯中的一种或几种。
作为本申请实施方式中使用的电解质盐，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LiPF 6、LiBF 4、LiAsF 6、LiSbF 6、LiPF 4(CF 3) 2、LiPF 3(C 2F 5) 3、LiPF 3(CF 3) 3、LiPF 3(异-C 3F 7) 3和LiPF 5(异-C 3F 7)中的一种或几种的“路易斯酸与LiF的络盐”，其中优选选自LiPF 6、LiBF 4、LiAsF 6，更优选选自LiPF 6、LiBF 4。
〔Li盐－2类〕：可以合适地列举出选自(CF 2) 2(SO 2) 2NLi(环状)、(CF 2) 3(SO 2) 2NLi(环状)和LiC(SO 2CF 3) 3中的一种或几种的“亚胺或甲基化锂盐”。
〔Li盐－3类〕：可以合适地列举出选自LiSO 3F、LiCF 3SO 3、CH 3SO 4Li、C 2H 5SO 4Li、C 3H 7SO 4Li、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、五氟((甲磺酰)氧基)磷酸锂(LiPFMSP)中的一种或几种的“含有S(＝O) 2O结构的锂盐”，其中更优选选自LiSO 3F、CH 3SO 4Li、C 2H 5SO 4Li或LiTFMSB。
〔Li盐－4类〕：可以合适地列举出选自LiPO 2F 2、Li 2PO 3F和LiClO 4中的一种或几种的“含有P＝O或Cl＝O结构的锂盐”，其中优选选自LiPO 2F 2、Li 2PO 3F。
〔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’]磷酸锂中的一种或几种的“以草酸盐配位体为正离子的锂盐”，其中更优选选自LiBOB、LiPFO。
上述锂盐可以单独使用或混合使用。其中，优选地，锂盐选自LiPF 6、LiPO 2F 2、Li 2PO 3F、LiBF 4、LiSO 3F、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、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’]磷酸锂中的一种或几种。进一步优选地，锂盐选自LiPF 6、LiBF 4、LiSO 3F、三氟((甲磺酰)氧基)硼酸锂(LiTFMSB)、LiPO 2F 2、双[草酸根-O,O’]硼酸锂(LiBOB)和二氟双[草酸根-O,O’]磷酸锂(LiPFO)中的一种或几种。更进一步优选地，锂盐为LiPF 6。
在本申请的锂离子电池中，所述电解质盐的浓度没有特别的限制，可根据实际需求进行合理调节。
在本申请的锂离子电池中，优选地，所述电解液25℃的电导率为4mS/cm～12mS/cm。
在本申请的锂离子电池中，所述电解液的制备方法不受限制，可按照常规电解液的方法制备。
在本申请的锂离子电池中，Li x1Co y1M 1-y1O 2-z1Q z1可具体选自LiCo 0.9Zr 0.1O 2、LiCo 0.9Ti 0.1O 2、Li 1.05Co 0.8Mg 0.2O 2、Li 1.01Co 0.98Mg 0.01Ti 0.005Al 0.005O 2、Li 1.05Co 0.98Mg 0.005Zr 0.005Ti 0.01O 1.9F 0.1、Li 1.1Co 0.95Mg 0.01Zr 0.01Al 0.03O 2、Li 1.04Co 0.95Mg 0.02Zr 0.03O 1.95F 0.05、Li 1.06Co 0.96Mg 0.02Ti 0.02O 2、Li 1.08Co 0.97Mg 0.01Zr 0.01Al 0.01O 1.9S 0.1、Li 1.09Co 0.98Mg 0.01Ti 0.005Al 0.005O 2、Li 1.085Co 0.98Zr 0.01Ti 0.005Al 0.005O 1.9Cl 0.1、Li 1.03Co 0.96Mg 0.01Zr 0.01Ti 0.01Al 0.01O 2、Li 1.04Co 0.97Zr 0.01Al 0.02O 1.9F 0.1、Li 1.07Co 0.97Zr 0.01Ti 0.01Al 0.01O 1.9S 0.1、Li 1.02Co 0.96Mg 0.02Zr 0.015Ti 0.005O 1.9S 0.1、Li 1.03Co 0.98Ti 0.01Al 0.01O 1.9Cl 0.1、Li 1.05Co 0.97Mg 0.01Zr 0.01Al 0.01O 1.9Cl 0.1、Li 1.04Co 0.95Zr 0.02Ti 0.03O 1.9F 0.1、 Li 1.09Co 0.97Mg 0.02Ti 0.01O 1.95F 0.05、Li 1.03Co 0.95Mg 0.03Ti 0.02O 1.9S 0.1、Li 1.04Co 0.97Zr 0.01Ti 0.01Al 0.01O 1.9S 0.1中的一种或几种。
在本申请的锂离子电池中，所述正极活性材料还可包含锂镍氧化物、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、前述氧化物添加其他过渡金属或非过渡金属得到的化合物中的一种或几种。
在本申请的锂离子电池中，所述正极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极片。导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。正极集流体的种类也不受具体的限制，可根据实际需求进行选择，优选可为铝箔。
在本申请的锂离子电池中，所述负极极片中的负极活性材料包含Si、SiO x2、Si/C复合材料、Si合金中的一种或几种，0<x2≤2。所述负极活性材料还可包含软碳、硬碳、人造石墨、天然石墨、钛酸锂、能与锂形成合金的金属中的一种或几种。
在本申请的锂离子电池中，所述负极极片还包括粘结剂和导电剂，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极片。导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。负极集流体的种类也不受具体的限制，可根据实际需求进行选择，优选可为铜箔。
在本申请的锂离子电池中，所述隔离膜设置在正极极片和负极极片之间，起到隔离作用。所述隔离膜的具体种类并不受到具体的限制，可以是现有锂离子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。
在本申请的锂离子电池中，所述锂离子电池的充电截止电压不小于4.2V，即锂离子电池可在不小于4.2V的高电压状态下使用。优选地，所述锂离子电池的充电截止电压不小于4.35V。
本申请的锂离子电池既可为硬壳锂离子电池，也可为软包装锂离子电池。硬壳锂离子电池优选使用金属材质的硬壳。软包装锂离子电池优选使用包装袋作为电池壳体，所述包装袋通常包括容纳部和密封部，其中容纳部用于容纳电极组件和电解液，而密封部用于将电极组件和电解液密封。本申请对于软包装锂离子电池性能的改善更明显，原因在于软包装锂离子电池在使用时很容易发生鼓胀，而本申请的电解液可以极大降低电池产气量，避免软包装锂离子电池鼓胀造成寿命缩短。
在本申请的锂离子电池中，所述添加剂A可通过下述方法合成。
(1)式I-1所示的化合物的制备
反应方程式为：
Figure PCTCN2019125321-appb-000016
Figure PCTCN2019125321-appb-000017
具体制备工艺为：
在20min～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，滴加完毕后快速搅拌15h～30h，于70℃～90℃油浴回流搅拌3h～5h，得到无色发烟粘稠状液体中间产物I-1-1；继续加入K 2CO 3、KI、无水乙腈，快速搅拌成固液混合相，于40℃～60℃下快速加入原料P-3，继续搅拌10h～20h后冷却至室温，分离提纯得到式I-1所示的化合物。
(2)式I-2所示的化合物的制备
反应方程式为：
Figure PCTCN2019125321-appb-000018
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2h～5h；热乙醇反复多次冲洗得到粗产物，重结晶得到式I-2所示的化合物。
(3)式I-3所示的化合物的制备
反应方程式为：
Figure PCTCN2019125321-appb-000019
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2h～5h；热乙醇反复多次冲洗得到粗产物，重结晶得到式I-3所示的化合物。
在一些实施例中，锂离子电池可以包括外包装，用于封装正极极片、负极极片和电解质。作为一个示例，正极极片、负极极片和隔离膜可经叠片或卷绕形成叠片结构电极组件或卷绕结构电极组件，电极组件封装在外包装内；电解质可采用电解液，电解液浸润于电极组件中。锂离子电池中电极组件的数量可以为一个或几个，可以根据需求来调节。
在一些实施例中，锂离子电池的外包装可以是软包，例如袋式软包。软包的材质可以是塑料，如可包括聚丙烯PP、聚对苯二甲酸丁二醇酯PBT、聚丁二酸丁二醇酯PBS等中的一种或几种。锂离子电池的外包装也可以是硬壳，例如铝壳等。
本申请对锂离子电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。如图4是作为一个示例的方形结构的锂离子电池5。
在一些实施例中，锂离子电池可以组装成电池模块，电池模块所含锂离子电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
图5是作为一个示例的电池模块4。参照图5，在电池模块4中，多个锂离子电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个锂离子电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的壳体，多个锂离子电池5容纳于该容纳空间。
在一些实施例中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
图6和图7是作为一个示例的电池包1。参照图6和图7，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
接下来说明本申请第二方面的装置。
在本申请的第二方面提供一种装置，所述装置包括本申请第一方面的锂离子电池，所述锂离子电池为所述装置提供电源。所述装置可以但不限于是移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等。
所述装置可以根据其使用需求来选择锂离子电池、电池模块或电池包。
图8是作为一个示例的装置。该装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该装置对锂离子电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用锂离子电池作为电源。
为了使本申请的目的、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。
在实施例、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。其中添加剂A1、A2、A3的具体合成过程如下，其它种类的添加剂A均可根据类似的方法合成。
添加剂A1的合成：
Figure PCTCN2019125321-appb-000020
在0.5h内向1,3-丙二胺中滴加37％甲醛水溶液并快速搅拌，滴加完毕后继续快速搅拌20h，之后于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；继续加入K 2CO 3、KI、无水乙腈，快速搅拌成固液混合相，之后于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A1。核磁共振碳谱如图1所示。
添加剂A2的合成：
Figure PCTCN2019125321-appb-000021
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A2。核磁共振碳谱如图2所示。
添加剂A3的合成：
Figure PCTCN2019125321-appb-000022
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A3。核磁共振碳谱如图3所示。
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。
在实施例、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。其中添加剂A1、A2、A3的具体合成过程如下，其它种类的添加剂A均可根据类似的方法合成。
添加剂A1的合成：
Figure PCTCN2019125321-appb-000023
在0.5h内向1,3-丙二胺中滴加37％甲醛水溶液并快速搅拌，滴加完毕后继续快速搅拌20h，之后于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；继续加入K 2CO 3、KI、无水乙腈，快速搅拌成固液混合相，之后于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A1。核磁共振碳谱如图1所示。
添加剂A2的合成：
Figure PCTCN2019125321-appb-000024
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A2。核磁共振碳谱如图2所示。
添加剂A3的合成：
Figure PCTCN2019125321-appb-000025
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A3。核磁共振碳谱如图3所示。
在实施例1-30和对比例1-2中，锂离子电池均按照下述方法制备。
(1)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)的混合液为有机溶剂，其中，EC、EMC和DEC的质量比为1:1:1。锂盐为LiPF 6，LiPF 6的含量为电解液总质量的12.5％。按照如表1所示的电解液组成加入各添加剂，其中各添加剂组分的含量均为相对于电解液的总质量计算得到。
其中，在实施例和对比例中所使用的添加剂A、添加剂B分别简写如下：
Figure PCTCN2019125321-appb-000026
(2)正极极片的制备
将表1所示的正极活性材料、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、分切得到正极极片。
(3)负极极片的制备
将表1所示的负极活性材料、导电剂乙炔黑、增稠剂羧甲基纤维素钠、粘结剂丁苯橡胶按照质量比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、分切得到负极极片。
(4)锂离子电池的制备
将正极极片、负极极片以及PP/PE/PP隔离膜进行卷绕得到电极组件，将电极组件放入包装袋铝塑膜中，之后注入电解液，再依次经过封口、静置、热冷压、化成、排气、测试容量等工序，获得锂离子电池。
表1实施例1-30和对比例1-2的参数
Figure PCTCN2019125321-appb-000027
Figure PCTCN2019125321-appb-000028
下面说明锂离子电池的测试过程。
(1)锂离子电池在常温、高电压情况下的循环性能测试
在25℃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％。
(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25℃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h 0；之后将锂离子电池放入85℃的恒温箱，存储24h后取出，测试此时锂离子电池的厚度并记为h 1。
锂离子电池85℃存储24h后的厚度膨胀率(％)＝[(h 1-h 0)/h 0]×100％。
表2实施例1-30和对比例1-2的性能测试结果
Figure PCTCN2019125321-appb-000029
Figure PCTCN2019125321-appb-000030
从实施例1-30和对比例1-2的对比中可以看出：本申请的锂离子电池在高温高电压情况下具有优异的循环性能和存储性能。
与对比例1相比，本申请的实施例使用金属离子M掺杂的钴酸锂材料Li x1Co y1M 1-y1O 2-z1Q z1作为正极活性材料，使用添加剂A、添加剂B以及添加剂C的组合添加剂作为电解液添加剂。掺杂元素M在正极活性材料中充当骨架，可以减小正极活性材料深度脱锂过程中的晶格形变量，延缓正极活性材料体相结构的退化，大大改善锂离子电池在高电压情况下使用时的结构稳定性。添加剂A为氧化电位较低的多腈基六元氮杂环化合物，其在电池化成时便能在正极活性材料表面形成稳定的络合物层，有效钝化正极 活性材料表面，降低正极活性材料表面活性，隔绝电解液与正极活性材料表面的直接接触，使得表面副反应大大减少，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是锂离子电池循环容量保持率大幅提升；部分表面副反应可产生气体，表面副反应的减少还意味着电池产气量减少，最终显现出来的实际效果是高温下锂离子电池厚度膨胀明显减轻。添加剂B具有阻燃效果，加入后能够有效提高电解液的热安全性，当锂离子电池在高温存储或是在其他极端条件下发生热失控时，添加剂B能够降低锂离子电池发生燃烧的风险，进而提高锂离子电池整体的安全性。添加剂C能够在含Si负极表面形成一层均匀致密的保护膜，隔绝负极与电解液之间的电子传导，有效减少负极与电解液之间的副反应，既能保护负极免受破坏，抑制负极阻抗的持续增长，又能减少锂离子电池使用过程中的电解液消耗；此外，添加剂C在负极所成的保护膜具有优良的机械性能，在负极充放电过程发生膨胀收缩时，这层保护膜能够保持完整性而不发生破坏，从而持续有效保护负极，提高锂离子电池的循环容量保持率。由此，本申请能显著提高锂离子电池在高温高电压情况下的循环性能和存储性能。
与对比例2采用线性的腈基化合物相比，本申请的多腈基六元氮杂环化合物具有特殊的六元氮杂环结构，腈基与腈基的间距更接近正极活性材料表面过渡金属与过渡金属的间距，可以最大限度地发挥腈基的络合作用，且使更多数量的腈基发挥络合作用。因此本申请的多腈基六元氮杂环化合物对正极活性材料表面过渡金属的覆盖作用更强，对正极活性材料表面的钝化效果更好，对锂离子电池循环性能和存储性能的改善效果也更加出众。
从实施例1-7可以看出，随着添加剂A加入量的增加(0.1％增至10.0％)，在充电截止电压固定为4.35V的情况下，锂离子电池在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24h厚度膨胀率一直减小。这是由于当添加剂A的加入量较多时，首先添加剂A吸附在正极活性材料表面形成的络合物层容易更厚和致密，影响锂离子的扩散迁移，正极阻抗大幅增高；其次添加剂A在形成络合物层的同时会消耗锂离子，导致可用于循环的锂离子减少；最后添加剂A较高的加入量会引起电解液整体黏度提升、离子电导率下降，最终锂离子电池在25℃和45℃时的循环容量保持率达到最佳后出现了下降的趋势。因此，添加剂A的加入量需要适量，优选为0.1％～10％，进一步优选为0.1％～6％，更进一步优选为0.1％～3.5％。
从实施例8-14可以看出，随着添加剂B加入量的增加(0.1％增至10％)，在充电截止电压固定为4.35V的情况下，锂离子电池在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24h厚度膨胀率先降低后又出现了增加的趋势。这是由于当添加剂B的加入量较多时，其反应产生的产物一方面会大幅提高电池整体阻抗，另一方面会导致电解液的离子电导率下降，进而影响了锂离子电池性能的发挥。因此，添加剂B的加入量需要适量，优选为0.1％～10％，进一步优选为0.1％～5％。
从实施例15-21还可以看出，随着添加剂C加入量的增加(0.1％增至30％)，在充电截止电压固定为4.35V的情况下，锂离子电池在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24h厚度膨胀率先降低后又出现了增加的趋势。这是由于当添加剂C的加入量较多时，其在负极反应产生的产物会大量沉积在负极表面，不断提高负极阻抗，同时由于自身热稳定性较差、容易分解，加入量较多时还会导致锂离 子电池大量产气，造成电池内部出现气泡、电解液断桥现象，进一步增加电池阻抗，从而影响了锂离子电池的循环性能和存储性能。因此，添加剂C的加入量需要适量，优选为0.1％～30％，进一步优选为5％～15％。
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 (11)

  1. 一种锂离子电池，包括电极组件以及电解液，所述电极组件包括正极极片、负极极片以及隔离膜；
    其特征在于，
    所述正极极片中的正极活性材料包括Li x1Co y1M 1-y1O 2-z1Q z1，0.5≤x1≤1.2，0.8≤y1<1.0，0≤z1≤0.1，M选自Al、Ti、Zr、Y、Mg中的一种或几种，Q选自F、Cl、S中的一种或几种；
    所述电解液中含有添加剂A、添加剂B以及添加剂C，所述添加剂A选自式I-1、式I-2、式I-3所示的化合物中的一种或几种，所述添加剂B选自式II-1、式II-2所示的化合物中的一种或几种，所述添加剂C选自式III-1所示的化合物中的一种或几种；
    Figure PCTCN2019125321-appb-100001
    在所述的式I-1、式I-2、式I-3中：R 1、R 2、R 3、R 4各自独立地选自氢原子、卤素原子、取代或未取代的C 1～C 12烷基、取代或未取代的C 1～C 12烷氧基、取代或未取代的C 1～C 12胺基、取代或未取代的C 2～C 12烯基、取代或未取代的C 2～C 12炔基、取代或未取代的C 6～C 26芳基、取代或未取代的C 2～C 12杂环基，其中，取代基选自卤素原子、腈基、C 1～C 6烷基、C 2～C 6烯基、C 1～C 6烷氧基中的一种或几种；x、y、z各自独立地选自0～8的整数；m、n、k各自独立地选自0～2的整数；
    Figure PCTCN2019125321-appb-100002
    在所述的式II-1中，R 31、R 32、R 33、R 34、R 35、R 36、R 37、R 38、R 39各自独立地选自卤素取代或未取代的C 1～C 6烷基；在所述的式II-2中，R 41、R 42、R 43、R 44、R 45、R 46、R 47、R 48、R 49各自独立地选自卤素取代或未取代的C 1～C 6烷基；
    Figure PCTCN2019125321-appb-100003
    在所述的式III-1中，R 21选自卤素取代的C 1～C 6亚烷基、卤素取代的C 2～C 6亚烯基。
  2. 根据权利要求1所述的锂离子电池，其特征在于，
    在所述的式I-1、式I-2、式I-3中：R 1、R 2、R 3和R 4各自独立地选自氢原子、卤素原子、取代或未取代的C 1～C 3直链或支链烷基、取代或未取代的C 5～C 7环状烷基、取代或未取代的C 1～C 3烷氧基、取代或未取代的C 1～C 3胺基、取代或未取代的C 2～C 3烯基、取代或未取代的C 2～C 3炔基、取代或未取代的C 6～C 8芳基、取代或未取代的C 2～C 7杂环基，其中，取代基选自卤素原子；
    x、y、z各自独立地选自0、1或2；
    m、n、k各自独立地选自1或2；
    R 31、R 32、R 33、R 34、R 35、R 36、R 37、R 38、R 39各自独立地选自卤素取代或未取代的C 1～C 4烷基；
    R 41、R 42、R 43、R 44、R 45、R 46、R 47、R 48、R 49各自独立地选自卤素取代或未取代的C 1～C 4烷基；
    R 21选自卤素取代的C 2～C 4亚烷基、卤素取代的C 2～C 4亚烯基。
  3. 根据权利要求1所述的锂离子电池，其特征在于，
    在所述的式I-1中，R 1、R 3均为氢原子；优选地，R 1、R 3、R 4均为氢原子；
    在所述的式I-2中，R 1、R 2、R 3、R 4中至少有两个为氢原子；优选地，R 1、R 2、R 3、R 4中至少有三个为氢原子；
    在所述的式I-3中，R 1、R 2、R 3中至少有两个为氢原子。
  4. 根据权利要求1所述的锂离子电池，其特征在于，所述添加剂A选自如下化合物中的一种或几种：
    Figure PCTCN2019125321-appb-100004
    Figure PCTCN2019125321-appb-100005
  5. 根据权利要求1所述的锂离子电池，其特征在于，所述添加剂B选自如下化合物中的一种或几种：
    Figure PCTCN2019125321-appb-100006
  6. 根据权利要求1所述的锂离子电池，其特征在于，所述添加剂C选自氟代碳酸乙烯酯、氟代碳酸丙烯酯、三氟代碳酸丙烯酯、反式或顺式-4,5-二氟-1,3-二氧杂环戊烷-2-酮中的一种或几种。
  7. 根据权利要求1所述的锂离子电池，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0.1％～10％，优选为0.1～6％，进一步优选为0.1％～3.5％；
    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0.1％～5％；
    所述添加剂C在所述电解液中的质量百分含量为0.1％～30％，优选为5％～15％。
  8. 根据权利要求1所述的锂离子电池，其特征在于，所述电解液的电导率为4mS/cm～12mS/cm。
  9. 根据权利要求1所述的锂离子电池，其特征在于，所述负极极片中的负极活性材料包含Si、SiO x2、Si/C复合材料、Si合金中的一种或几种，0<x2≤2。
  10. 根据权利要求1所述的锂离子电池，其特征在于，所述锂离子电池的充电截止电压不小于4.2V，优选不小于4.35V。
  11. 一种装置，其特征在于，包括根据权利要求1～10中任一项所述的锂离子电池。
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