WO2021093296A1 - 电池电解液用添加剂、锂离子电池电解液、锂离子电池 - Google Patents

电池电解液用添加剂、锂离子电池电解液、锂离子电池 Download PDF

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WO2021093296A1
WO2021093296A1 PCT/CN2020/091053 CN2020091053W WO2021093296A1 WO 2021093296 A1 WO2021093296 A1 WO 2021093296A1 CN 2020091053 W CN2020091053 W CN 2020091053W WO 2021093296 A1 WO2021093296 A1 WO 2021093296A1
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electrolyte
lithium ion
ion battery
additive
battery
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French (fr)
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林�建
占孝云
安伟峰
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深圳市比克动力电池有限公司
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Priority to JP2022522353A priority patent/JP7371246B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • 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
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    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • 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

  • the invention belongs to the technical field of lithium ion batteries, and in particular relates to an additive for battery electrolyte, a lithium ion battery electrolyte and a lithium ion battery.
  • Lithium-ion secondary batteries are the most competitive new generation of batteries, known as "green energy sources", and are the preferred technology to solve contemporary environmental pollution and energy problems.
  • lithium-ion secondary batteries have achieved great success in the field of high-energy batteries, but consumers still expect batteries with higher comprehensive performance to come out, and this depends on the research and development of new electrode materials and electrolyte systems.
  • electronic digital products such as smart phones and tablet computers have increasingly higher requirements for battery energy density, making it difficult for commercial lithium ion secondary batteries to meet the requirements.
  • the theoretical gram capacity of pure silicon anode is as high as 4200mAh/g, which is an ideal high-capacity anode material for lithium ion secondary batteries.
  • pure silicon is used as the negative electrode of a lithium ion secondary battery, due to the volume effect, the battery swells and the pole pieces are severely powdered, and the cycle performance is poor.
  • the conductivity of silicon-based materials is not good, resulting in poor low-temperature performance of the battery. People consider combining silicon and carbon materials to form a silicon-carbon composite material, which can greatly increase the specific capacity and conductivity of the material, and reduce the volume effect of silicon-based materials to a certain extent.
  • Silicon-carbon composite materials are matched with high-capacity high-nickel cathodes, and the energy density can reach more than 300Wh/Kg. An electrolyte that matches this has also emerged and has become a hot spot in the study of lithium-ion secondary battery electrolytes.
  • Fluorinated ethylene carbonate can form a uniform and stable SEI film on the surface of the silicon-carbon negative electrode. Due to the particularity of the silicon-carbon negative electrode material (battery swelling and pole piece pulverization), the electrolyte system often needs more than the graphite negative electrode system.
  • the film-forming additives usually require the use of a large amount of fluoroethylene carbonate.
  • fluoroethylene carbonate is easy to decompose in a high-temperature environment or a high-nickel positive battery system, and cannot meet the requirements of high-temperature battery use.
  • the use of fluoroethylene carbonate alone has many disadvantages.
  • NC-(CH 2 )n-CN organic dinitriles
  • US 2008/0311481 Al discloses an ether/aryl compound containing two nitrile groups, which can improve battery swelling under high voltage and high temperature conditions, and improve high temperature storage performance.
  • the application of nitrile compounds to the ternary high nickel cathode material system will increase battery polarization and severely degrade cycle performance and low-temperature characteristics.
  • the purpose of the present invention is to provide an additive for battery electrolyte, which aims to solve the problem that the electrolyte oxidizes and decomposes under high temperature conditions in existing lithium-ion batteries, which causes the battery's high-temperature storage performance and low-temperature discharge performance to be inconsistent.
  • Another object of the present invention is to provide a lithium ion battery electrolyte containing the above additives, and a lithium ion battery.
  • the first aspect of the present invention provides an additive for battery electrolyte, the additive includes at least one of the compounds represented by the following structural formulas (1)-(7),
  • the second aspect of the present invention provides an electrolyte for a lithium ion battery, the electrolyte includes a non-aqueous organic solvent, a lithium salt and an additive, wherein the additive includes at least one of the compounds represented by the following structural formulas (1)-(7) One kind,
  • At least one of the compounds represented by the structural formulas (1)-(7) is used as the first type of additive, and based on the total mass of the electrolyte as 100%, the mass of the first type of additive is 100%.
  • the sub-content is 0.05% to 2%.
  • the additive further includes selected from fluoroethylene carbonate, vinylene carbonate, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, A second type additive of at least one of vinyl sulfate and propylene sulfate.
  • the total mass percentage of the additives is less than or equal to 15%.
  • the non-aqueous organic solvent includes ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate , Propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ - At least one of caprolactone.
  • the total mass percentage of the non-aqueous organic solvent is 55%-75%.
  • a third aspect of the present invention provides a lithium ion battery, the lithium ion battery includes a positive electrode, a negative electrode, a separator, and an electrolyte, and the electrolyte is the above-mentioned lithium ion battery electrolyte.
  • the active material of the positive electrode is a transition metal oxide
  • the active material of the negative electrode is graphite, a Si-containing composite material or lithium titanate.
  • the transition metal oxide is LiNi x Co y Mn z L (1-xyz) O 2 , where L is one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe ,
  • L is one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe ,
  • the values of x, y, z satisfy: 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ x+y+z ⁇ 1.
  • the additive for battery electrolyte provided by the present invention includes at least one of the compounds represented by the following structural formulas (1)-(7).
  • the structures of the compounds shown in structural formulas (1)-(7) all contain a vinyl sulfate (DTD) structure.
  • DTD vinyl sulfate
  • at least one carbon atom of the vinyl sulfate ring is connected to a vinyl sulfate group, 2,2-di One of methyl-1,3-dioxocene alkyl, ester group, siloxane group, and fluorine-substituted phenyl ether group, used as an electrolyte additive to form a protective film on the electrode surface during the first charging process to improve the battery Output performance.
  • At least one DTD structure (such as the compound represented by the formula (1) structure, the compound represented by the formula (4) structure, and the compound represented by the formula (6) structure) is connected to the carbon atom of the DTD structure.
  • the DTD structure of molecular copolymerization improves the stability of the molecular structure and reduces the reaction activity.
  • the small current precharge can form a thinner, denser and stable SEI, which comprehensively improves the battery output performance.
  • the -CO 2 CH 3 group Connect the -CO 2 CH 3 group to the carbon atom of the DTD structure, such as the compound shown in the structure of formula (3), the -CO 2 CH 3 group is connected to the CO in the DTD ring structure to form an "ethoxy segment",
  • the ethoxy chain segment in the SEI film component formed by the low current precharging increases, and the lithium conductivity is enhanced, thereby reducing the battery impedance and improving the battery power characteristics.
  • the silicon-containing group can effectively remove HF, active proton hydrogen in the electrolyte, H 2 O also participates in the film formation on the electrode surface, thereby realizing the multifunctional effect of a single additive and comprehensively improving the battery output performance.
  • the compounds represented by structural formulas (1)-(7) have vinyl sulfate groups, 2,2-dimethyl-1,3-dioxocene alkyl groups, esters connected to at least one carbon atom of the vinyl sulfate ring
  • One of the group, siloxane group, and fluorine-substituted phenyl ether group can alleviate the small ring tension of the vinyl sulfate (DTD) structure and reduce the molecular activity.
  • DTD vinyl sulfate
  • the activity of the compounds represented by the structural formulas (1)-(7) is lower, and therefore, it is not easy to change color when added to the electrolyte.
  • the lithium ion battery electrolyte provided by the present invention contains the additive for battery electrolyte of the present invention, which can form a low-impedance protective film on the surface of the electrodes (positive and negative electrodes), inhibit side reactions between the electrode and the electrolyte, and reduce the interface impedance, Taking into account both high and low temperature performance (with good low temperature discharge performance, good cycle performance and high temperature storage performance), the overall output performance of the lithium-ion battery is improved.
  • the lithium ion battery provided by the present invention contains the lithium ion battery electrolyte of the present invention, the cycle performance and low-temperature discharge performance of the lithium ion battery can be significantly improved, and the overall output performance of the lithium ion battery can be improved.
  • Figure 1 is the capacity differential curve diagram of Example 6, Comparative Example 1, and Comparative Example 2 of the present invention
  • FIG. 2 is a diagram of DCR (direct current internal resistance) results of Example 6, Comparative Example 1, and Comparative Example 2 of the present invention at different SOC (state of charge);
  • Fig. 3 is a graph showing the result of storing the electrolyte solution at room temperature (25°C ⁇ 3) for 30 days according to an embodiment of the present invention.
  • first and second are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with “first” and “second” may explicitly or implicitly include one or more of these features.
  • “plurality” means two or more than two, unless otherwise specifically defined.
  • the weight of the relevant components mentioned in the description of the embodiments of the present invention can not only refer to the specific content of each component, but also can indicate the proportion of weight between the components. Therefore, as long as the relevant group is in accordance with the description of the embodiment of the present invention Enlargement or reduction in proportion to the content of the fennel is within the scope disclosed in the specification of the embodiments of the present invention.
  • the weight described in the specification of the embodiment of the present invention may be a mass unit well-known in the chemical industry, such as ⁇ g, mg, g, and kg.
  • the first aspect of the embodiments of the present invention provides an additive for battery electrolyte, the additive includes at least one of the compounds represented by the following structural formulas (1)-(7),
  • the additive for battery electrolyte provided by the embodiment of the present invention includes at least one of the compounds represented by the following structural formulas (1)-(7).
  • the structures of the compounds shown in structural formulas (1)-(7) all contain a vinyl sulfate (DTD) structure.
  • DTD vinyl sulfate
  • at least one carbon atom of the vinyl sulfate ring is connected to a vinyl sulfate group, 2,2-di One of methyl-1,3-dioxocene alkyl, ester group, siloxane group, and fluorine-substituted phenyl ether group, used as an electrolyte additive to form a protective film on the electrode surface during the first charging process to improve the battery Output performance.
  • At least one DTD structure (such as the compound represented by the formula (1) structure, the compound represented by the formula (4) structure, and the compound represented by the formula (6) structure) is connected to the carbon atom of the DTD structure.
  • the DTD structure of molecular copolymerization improves the stability of the molecular structure and reduces the reaction activity.
  • the small current precharge can form a thinner, denser and stable SEI, which comprehensively improves the battery output performance.
  • the -CO 2 CH 3 group Connect the -CO 2 CH 3 group to the carbon atom of the DTD structure, such as the compound shown in the structure of formula (3), the -CO 2 CH 3 group is connected to the CO in the DTD ring structure to form an "ethoxy segment",
  • the ethoxy chain segment in the SEI film component formed by the low current precharging increases, and the lithium conductivity is enhanced, thereby reducing the battery impedance and improving the battery power characteristics.
  • the silicon-containing group can effectively remove HF, active proton hydrogen in the electrolyte, H 2 O also participates in the film formation on the electrode surface, thereby realizing the multifunctional effect of a single additive and comprehensively improving the battery output performance.
  • the compounds represented by structural formulas (1)-(7) have vinyl sulfate groups, 2,2-dimethyl-1,3-dioxocene alkyl groups, esters connected to at least one carbon atom of the vinyl sulfate ring
  • One of the group, siloxane group, and fluorine-substituted phenyl ether group can alleviate the small ring tension of the vinyl sulfate (DTD) structure and reduce the molecular activity.
  • DTD vinyl sulfate
  • the activity of the compounds represented by the structural formulas (1)-(7) is lower, and therefore, it is not easy to change color when added to the electrolyte.
  • the second aspect of the embodiments of the present invention provides an electrolyte for a lithium ion battery, the electrolyte includes a non-aqueous organic solvent, a lithium salt, and an additive, wherein the additive at least includes a compound represented by the following structural formulas (1)-(7) One of
  • the lithium ion battery electrolyte provided by the embodiment of the present invention contains the additive for the battery electrolyte of the present invention, which can form a low-impedance protective film on the surface of the electrode (positive and negative), inhibit side reactions between the electrode and the electrolyte, and reduce the interface Impedance, both high and low temperature performance (with good low temperature discharge performance, and good cycle performance and high temperature storage performance), improve the overall output performance of lithium-ion batteries.
  • the components of the electrolyte of the lithium ion battery are respectively introduced in detail below.
  • the embodiment of the present invention uses a non-aqueous organic solvent as the solvent component of the electrolyte.
  • the non-aqueous organic solvent includes ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate , Propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ - At least one of caprolactone.
  • the total mass percentage of the non-aqueous organic solvent is 55%-75%.
  • the lithium salt may be the lithium salt commonly used in lithium ion batteries, including but not limited to lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bisoxalate, lithium bisfluorooxalate, and bis(trifluoroborate).
  • lithium hexafluorophosphate lithium perchlorate
  • lithium tetrafluoroborate lithium bisoxalate
  • lithium bisfluorooxalate lithium bisfluorooxalate
  • bis(trifluoroborate) bis(trifluoroborate).
  • the amount of the lithium salt is 10%-18% by mass in the electrolyte of the lithium ion secondary battery.
  • the additive is mainly used to improve the film-forming performance during the first charge and discharge.
  • the additives described in the embodiments of the present invention include at least one of the compounds represented by the following structural formulas (1)-(7).
  • the structures of the compounds shown in structural formulas (1)-(7) all contain a vinyl sulfate (DTD) structure.
  • DTD vinyl sulfate
  • at least one carbon atom of the vinyl sulfate ring is connected to a vinyl sulfate group, 2,2-di One of methyl-1,3-dioxocene alkyl, ester group, siloxane group, and fluorine-substituted phenyl ether group, used as an electrolyte additive to form a protective film on the electrode surface during the first charging process to improve the battery Output performance.
  • At least one DTD structure (such as the compound represented by the formula (1) structure, the compound represented by the formula (4) structure, and the compound represented by the formula (6) structure) is connected to the carbon atom of the DTD structure.
  • the DTD structure of molecular copolymerization improves the stability of the molecular structure and reduces the reaction activity.
  • the small current precharge can form a thinner, denser and stable SEI, which comprehensively improves the battery output performance.
  • the -CO 2 CH 3 group Connect the -CO 2 CH 3 group to the carbon atom of the DTD structure, such as the compound shown in the structure of formula (3), the -CO 2 CH 3 group is connected to the CO in the DTD ring structure to form an "ethoxy segment",
  • the ethoxy chain segment in the SEI film component formed by the low current precharging increases, and the lithium conductivity is enhanced, thereby reducing the battery impedance and improving the battery power characteristics.
  • the silicon-containing group can effectively remove HF, active proton hydrogen in the electrolyte, H 2 O also participates in the film formation on the electrode surface, thereby realizing the multifunctional effect of a single additive and comprehensively improving the battery output performance.
  • the compounds represented by structural formulas (1)-(7) have vinyl sulfate groups, 2,2-dimethyl-1,3-dioxocene alkyl groups, esters connected to at least one carbon atom of the vinyl sulfate ring
  • One of the group, siloxane group, and fluorine-substituted phenyl ether group can alleviate the small ring tension of the vinyl sulfate (DTD) structure and reduce the molecular activity.
  • DTD vinyl sulfate
  • the activity of the compounds represented by the structural formulas (1)-(7) is lower, and therefore, it is not easy to change color when added to the electrolyte.
  • At least one of the compounds represented by the structural formulas (1)-(7) is used as the first type of additive, and based on the total mass of the electrolyte as 100%, the mass of the first type of additive is 100%.
  • the sub-content is 0.05% to 2%. If the mass percentage content of the first type of additive is less than 0.05%, a stable protective film cannot be formed on the electrode surface, and it cannot achieve "inhibition of side reactions between the electrode and the electrolyte, reduce the interface impedance, and comprehensively improve the output of the battery.
  • the additive further includes selected from fluoroethylene carbonate, vinylene carbonate, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, A second type additive of at least one of vinyl sulfate and propylene sulfate.
  • the total mass percentage of the additives is less than or equal to 15%.
  • any preferred additives fluoroethylene carbonate, vinylene carbonate, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone , Vinyl sulfate, propylene sulfate
  • any preferred additives fluoroethylene carbonate, vinylene carbonate, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone , Vinyl sulfate, propylene sulfate
  • a third aspect of the embodiments of the present invention provides a lithium ion battery, the lithium ion battery includes a positive electrode, a negative electrode, a separator, and an electrolyte, and the electrolyte is the aforementioned lithium ion battery electrolyte.
  • the lithium ion battery provided by the embodiments of the present invention because it contains the lithium ion battery electrolyte of the present invention, can significantly improve the cycle performance and low-temperature discharge performance of the lithium ion battery, and improve the overall output performance of the lithium ion battery.
  • composition of the electrolyte, the selection, content, preferred type and selection basis of each component are as described above, in order to save space, the details are not repeated here.
  • the positive electrode includes a positive electrode active material, and any positive electrode active material conventionally used in lithium ion batteries can be used in the embodiments of the present invention.
  • the active material of the positive electrode is a transition metal oxide.
  • the transition metal oxide is LiNi x Co y Mn z L (1-xyz) O 2 , where L is one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, and Fe.
  • L is one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, and Fe.
  • the values of x, y, z satisfy: 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ x+y+z ⁇ 1.
  • the negative electrode includes a negative active material, and any negative active material conventionally used in lithium ion batteries can be used in the embodiments of the present invention.
  • the active material of the negative electrode is graphite, Si-containing composite material or lithium titanate.
  • the selection of the diaphragm includes, but is not limited to, single-layer polyethylene (PE), single-layer polypropylene (PP), double-layer PP/PE, three-layer PP/PE/PP or ceramic diaphragm.
  • LiPF 6 Lithium hexafluorophosphate
  • a lithium ion secondary battery includes a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode active material is lithium nickel cobalt manganate (NCM811) material; the negative electrode active material is silicon carbon composite material (Si/C).
  • the preparation method of lithium ion secondary battery includes the following steps:
  • the silicon-carbon composite material conductive carbon black, binder styrene-butadiene rubber and carboxymethyl cellulose in a mass ratio of 96:1:1.2:1.8, and disperse them in deionized water to obtain a negative electrode slurry. It is clothed on both sides of the copper foil, dried, calendered and vacuum dried, and then welded with a nickel lead wire with an ultrasonic welder to obtain a negative electrode plate (negative plate), the thickness of the electrode plate is between 135 and 160 ⁇ m;
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a mass ratio of 2:1:7. After mixing, add 12.5% lithium hexafluorophosphate based on the total mass of the electrolyte, and add 1% of the total mass of the electrolyte is D1, and the electrolyte is prepared.
  • a PP base film with a thickness of 14 ⁇ m is used, and a ceramic diaphragm with 2 ⁇ m Al 2 O 3 coated on one side.
  • Example 2 In Examples 2 to 10, except for the different components in the electrolyte, the preparation of the other positive electrode, negative electrode, separator, and lithium ion secondary battery are the same as in Example 1.
  • the first type of additive in each example (compound (1) -The selection and content of at least one of (7)) are shown in Table 2.
  • Comparative Example 1 and Comparative Example 2 except for the difference in the type and content of the additives in the electrolyte (based on the total mass of the electrolyte), the preparation of the other positive electrode, negative electrode, separator, and lithium ion secondary battery is the same as that of Example 1. Comparative Example The types and contents of non-aqueous organic solvents and additives in 1 and Comparative Example 2 are shown in Table 2.
  • Cycle performance test at 25 ⁇ 2°C/45°C ⁇ 2°C, charge the divided battery with 0.5C constant current and constant voltage to 4.2V (cut-off current is 0.01C), and then discharge with 1C constant current To 2.75V. Calculate the capacity retention rate of the Nth cycle after charging/discharging for N cycles. The calculation formula is as follows:
  • Nth cycle capacity retention rate (%) (Nth cycle discharge capacity/first cycle discharge capacity) ⁇ 100%
  • High-temperature storage performance charge the divided battery to 4.2V at room temperature with 0.5C constant current and constant voltage (cut-off current is 0.01C), measure the initial discharge capacity of the battery, and then store it at 60°C for 7 days. C discharge to 2.75V to measure the holding capacity and recovery capacity of the battery. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity/initial capacity ⁇ 100%
  • Battery capacity recovery rate (%) recovered capacity/initial capacity ⁇ 100%.
  • Low-temperature discharge retention rate (%) low-temperature discharge capacity/initial capacity ⁇ 100%.
  • the intensity of the reduction peak of EC is significantly lower.
  • the SEI film component contains more ethoxy chain segments, the lithium-conducting performance is improved, the impedance is low, and the corresponding X-axis integration area is small; while the reduction peak in Comparative Example 1 is around 3.0V, which is attributed to the reduction of EC.

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Abstract

本申请提供了一种电池电解液用添加剂，至少包括文中结构式(1)-(7)所示化合物中的一种。本申请提供的电池电解液用添加剂，可以在电极表面形成低阻抗的保护膜，抑制电极和电解液的副反应，降低界面阻抗，兼顾高低温性能，提升锂离子电池的整体输出性能。

Description

电池电解液用添加剂、锂离子电池电解液、锂离子电池 技术领域
本发明属于锂离子电池技术领域，尤其涉及一种电池电解液用添加剂、一种锂离子电池电解液和一种锂离子电池。
背景技术
锂离子二次电池是新一代最具竞争力的电池，被称为“绿色环保能源”，是解决当代环境污染问题和能源问题的首选技术。近年来，在高能电池领域中锂离子二次电池已取得了巨大成功，但消费者仍然期望综合性能更高的电池面世，而这取决于对新的电极材料和电解质体系的研究和开发。目前智能手机、平板电脑等电子数码产品对电池的能量密度要求越来越高，使得商用锂离子二次电池难以满足要求。提升电池的能量密度可以通过以下两种方式：一是选择高容量和高压实的正负极材料；二是提高电池的工作电压。
纯硅负极理论克容量高达4200mAh/g，是锂离子二次电池的理想高容量负极材料。但纯硅用作锂离子二次电池的负极时，由于体积效应，电池膨胀和极片粉化严重，循环性能差。此外，硅基材料的导电性不好，致使电池低温性能差。人们考虑将硅材料和碳材料复合，形成硅碳复合材料，可以很大程度上提高材料的比容量和导电性，一定程度上降低硅基材料的体积效应。硅碳复合材料同高容量的高镍正极搭配，能量密度能够达到300Wh/Kg以上，与此相匹配的电解液也应运而生，成为锂离子二次电池电解液研究的热点。
氟代碳酸乙烯酯可以在硅碳负极表面形成均匀稳定的SEI膜，由于硅碳负极材料的特殊性(电池膨胀和极片粉化严重)，其电解液体系中往往需要比石墨负极体系更多的成膜添加剂，通常需要使用大量的氟代碳酸乙烯酯。而氟代碳酸乙烯酯在高温环境中或者高镍正极电池体系容易分解，无法满足电池高温使用要求等等，单独使用氟代碳酸乙烯酯，其存在多种弊端。为了解决含有氟代碳酸乙烯酯的锂离子二次电池在高温存储过程中的胀气问题，CN201110157665通过在电解液中添加有机二腈类物质(NC-(CH 2)n-CN，其中n＝2～4)的方法抑制胀气。US 2008/0311481Al公开含有两个腈基的醚/芳基化合物，能够改善电池在高电压和高温条件下的气胀，改善高温存储性能。但是腈类化合物应用于三元高镍正极材料体系会增加电池极化，严重劣化循环性能和低温特性。
技术问题
本发明的目的在于提供一种电池电解液用添加剂，旨在解决现有的锂离子电池，在高温条件下，电解液氧化分解，导致电池的高温存储性能和低温放电性能不能兼顾的问题。
技术解决方案
本发明的另一目的在于提供一种含有上述添加剂的锂离子电池电解液，以及一种锂离子电池。
为实现上述发明目的，本发明采用的技术方案如下：
本发明第一方面提供一种电池电解液用添加剂，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
Figure PCTCN2020091053-appb-000001
本发明第二方面提供一种锂离子电池电解液，所述电解液包括非水有机溶剂、锂盐和添加剂，其中，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
Figure PCTCN2020091053-appb-000002
优选的，所述结构式(1)-(7)所示化合物中的至少一种作为第一类添加剂，且以所述电解液的总质量为100％计，所述第一类添加剂的质量百分含量为0.05％～2％。
优选的，所述添加剂还包括选自氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、硫酸丙烯酯中的至少一种的第二类添加剂。
优选的，以所述电解液的总质量为100％计，所述添加剂的质量百分含量之和小于等于15％。
优选的，所述非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯中的至少一种。
优选的，以所述电解液的总质量为100％计，所述非水有机溶剂的质量百分含量之和为55％～75％。
本发明第三方面提供一种锂离子电池，所述锂离子电池包括正极、负极、隔膜和电解液，且所述电解液为上述的锂离子电池电解液。
优选的，所述正极的活性物质为过渡金属氧化物；所述负极的活性物质为石墨、含Si的复合材料或者钛酸锂。
优选的，所述过渡金属氧化物为LiNi xCo yMn zL (1-x-y-z)O 2，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si和Fe中的一种，x、y、z的取值满足：0≤x＜1，0＜y≤1，0≤z＜1，且0＜x+y+z≤1。
本发明提供的电池电解液用添加剂，至少包括如下结构式(1)-(7)所示化合物中的一种。结构式(1)-(7)所示化合物结构中均含有硫酸乙烯酯(DTD)结构，在此基础上，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，作为电解液添加剂，在首次充电过程中在电极表面形成保护膜，改善电池输出性能。具体的，
在DTD结构的碳原子上连接至少一个DTD结构(如式(1)结构所示化合物、式(4)结构所示化合物、式(6)结构所示化合物)，相比单一的DTD结构，两分子共聚的DTD结构提高了分子结构的稳定性，使反应活性有所降低，小电流预充能形成更薄更致密稳定的SEI，综合提升电池输出性能。
在DTD结构的碳原子上连接含-CO 2CH 3基团，如式(3)结构所示化合物，-CO 2CH 3基团与DTD环结构中的C-O相连组成“乙氧链段”，小电流预充所形成SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
在DTD结构的碳原子上连接-CHCH 2O 2(CH 3) 2，如式(2)结构所示化合物、式(5)结构所示化合物、式(6)结构所示化合物、式(7)结构所示化合物，此基团[CHCH 2O 2(CH 3) 2]本身含乙氧链段，分子结构中的乙氧链段增多，可使得形成的SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
特别的，当DTD结构的碳原子上相连的基团进一步含有烷基硅基团如式(5)结构所示化合物，所述含硅基团可以有效去除电解液中含活性质子氢的HF、H 2O，同时参与电极表面成膜，进而实现单一添加剂多功能的效果，全面提升电池输出性能。
此外，结构式(1)-(7)所示化合物，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，可以缓解硫酸乙烯酯(DTD)结构的小环张力，降低份子活性。相比单一DTD，结构式(1)-(7)所示化合物的活性降低，因此，添加到电解液中不易变色。
本发明提供的锂离子电池电解液，含有本发明所述电池电解液用添加剂，可以在电极(正极和负极)表面形成低阻抗的保护膜，抑制电极和电解液的副反应，降低界面阻抗，兼顾高低温性能(具有良好的低温放电性能，以及良好的循环性能和高温存储性能)，提升锂离子电池的整体输出性能。
有益效果
本发明提供的锂离子电池，由于含有本发明的锂离子电池电解液，能够显著提升锂离子电池的循环性能和低温放电性能，提升锂离子电池的整体输出性能。
附图说明
为了更清楚地说明本实用新型实施例中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本实用新型的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例6、对比例1、对比例2的容量微分曲线图；
图2是本发明实施例6、对比例1、对比例2的在不同SOC(荷电状态)的DCR(直流内阻)结果图；
图3是本发明实施例提供的电解液室温(25℃±3)储存30天结果图。
本发明的实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本发明实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本发明实施例说明书相关组分的含量按比例放大或缩小均在本发明实施例说明书公开的范围之内。具体地，本发明实施例说明书中所述的重量可以是μg、mg、g、kg等化工领域公知的质量单位。
本发明实施例第一方面提供一种电池电解液用添加剂，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
Figure PCTCN2020091053-appb-000003
Figure PCTCN2020091053-appb-000004
本发明实施例提供的电池电解液用添加剂，至少包括如下结构式(1)-(7)所示化合物中的一种。结构式(1)-(7)所示化合物结构中均含有硫酸乙烯酯(DTD)结构，在此基础上，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，作为电解液添加剂，在首次充电过程中在电极表面形成保护膜，改善电池输出性能。具体的，
在DTD结构的碳原子上连接至少一个DTD结构(如式(1)结构所示化合物、式(4)结构所示化合物、式(6)结构所示化合物)，相比单一的DTD结构，两分子共聚的DTD结构提高了分子结构的稳定性，使反应活性有所降低，小电流预充能形成更薄更致密稳定的SEI，综合提升电池输出性能。
在DTD结构的碳原子上连接含-CO 2CH 3基团，如式(3)结构所示化合物，-CO 2CH 3基团与DTD环结构中的C-O相连组成“乙氧链段”，小电流预充所形成SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
在DTD结构的碳原子上连接-CHCH 2O 2(CH 3) 2，如式(2)结构所示化合物、式(5)结构所示化合物、式(6)结构所示化合物、式(7)结构所示化合物，此基团[CHCH 2O 2(CH 3) 2]本身含乙氧链段，分子结构中的乙氧链段增多，可使得形成的SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
特别的，当DTD结构的碳原子上相连的基团进一步含有烷基硅基团如式(5)结构所示化合物，所述含硅基团可以有效去除电解液中含活性质子氢的HF、H 2O，同时参与电极表面成膜，进而实现单一添加剂多功能的效果，全面提升电池输出性能。
此外，结构式(1)-(7)所示化合物，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，可以缓解硫酸乙烯酯(DTD)结构的小环张力，降低份子活性。相比单一DTD，结构式(1)-(7)所示化合物的活性降低，因此，添加到电解液中不易变色。
本发明实施例第二方面提供一种锂离子电池电解液，所述电解液包括非水有机溶剂、锂盐和添加剂，其中，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
Figure PCTCN2020091053-appb-000005
本发明实施例提供的锂离子电池电解液，含有本发明所述电池电解液用添加剂，可以在电极(正极和负极)表面形成低阻抗的保护膜，抑制电极和电解液的副反应，降低界面阻抗，兼顾高低温性能(具有良好的低温放电性能，以及良好的循环性能和高温存储性能)，提升锂离子电池的整体输出性能。
下面分别对所述锂离子电池电解液各组分进行详细介绍。
非水有机溶剂
由于水对锂离子电池SEI的形成和电池性能有一定的影响，具体表现为电池容量变小、放电时间变短、内阻增加、循环容量衰减、电池膨胀等。本发明实施例采用非水有机溶剂作为电解液的溶剂成分。
优选的，所述非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯中的至少一种。
进一步优选的，以所述电解液的总质量为100％计，所述非水有机溶剂的质量百分含量之和为55％～75％。
锂盐
本发明实施例中，所述锂盐可以选用锂离子电池常用的锂盐，包括但不限于六氟磷酸锂、高氯酸锂、四氟硼酸锂、双草酸硼酸锂、双氟草酸硼酸锂、双(三氟甲基磺酰)亚胺锂和双氟磺酰亚胺锂中的一种或多种。进一步的，所述锂盐的用量占锂离子二次电池电解液中的质量百分比为10％～18％。
添加剂
本发明实施例中，所述添加剂主要用于在首次充放电时，用于提高成膜性能。
本发明实施例所述添加剂，至少包括如下结构式(1)-(7)所示化合物中的一种。结构式(1)-(7)所示化合物结构中均含有硫酸乙烯酯(DTD)结构，在此基础上，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，作为电解液添加剂，在首次充电过程中在电极表面形成保护膜，改善电池输出性能。具体的，
在DTD结构的碳原子上连接至少一个DTD结构(如式(1)结构所示化合物、式(4)结构所示化合物、 式(6)结构所示化合物)，相比单一的DTD结构，两分子共聚的DTD结构提高了分子结构的稳定性，使反应活性有所降低，小电流预充能形成更薄更致密稳定的SEI，综合提升电池输出性能。
在DTD结构的碳原子上连接含-CO 2CH 3基团，如式(3)结构所示化合物，-CO 2CH 3基团与DTD环结构中的C-O相连组成“乙氧链段”，小电流预充所形成SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
在DTD结构的碳原子上连接-CHCH 2O 2(CH 3) 2，如式(2)结构所示化合物、式(5)结构所示化合物、式(6)结构所示化合物、式(7)结构所示化合物，此基团[CHCH 2O 2(CH 3) 2]本身含乙氧链段，分子结构中的乙氧链段增多，可使得形成的SEI膜组分中的乙氧链段增多，导锂性增强，进而降低电池阻抗，改善电池功率特性。
特别的，当DTD结构的碳原子上相连的基团进一步含有烷基硅基团如式(5)结构所示化合物，所述含硅基团可以有效去除电解液中含活性质子氢的HF、H 2O，同时参与电极表面成膜，进而实现单一添加剂多功能的效果，全面提升电池输出性能。
此外，结构式(1)-(7)所示化合物，在硫酸乙烯酯环的至少一个碳原子上连接硫酸乙烯酯基、2,2-二甲基-1,3-二恶茂烷基、酯基、硅氧烷基、氟取代苯醚基中的一种，可以缓解硫酸乙烯酯(DTD)结构的小环张力，降低份子活性。相比单一DTD，结构式(1)-(7)所示化合物的活性降低，因此，添加到电解液中不易变色。
优选的，所述结构式(1)-(7)所示化合物中的至少一种作为第一类添加剂，且以所述电解液的总质量为100％计，所述第一类添加剂的质量百分含量为0.05％～2％。若所述第一类添加剂的质量百分含量低于0.05％，则不能在电极表面形成稳定的保护膜，达不到“抑制电极和电解液的副反应，降低界面阻抗，综合提升电池的输出性能”的改善效果，此外，也不能改善高镍搭配硅碳体系的电池输出性能；若所述第一类添加剂的质量百分含量高于2％，则其在电极表面形成的保护膜过厚，电池极化增大，劣化电池性能。
本发明实施例中，在所述结构式(1)-(7)所示化合物中的至少一种作为添加剂的基础上，可以进一步添加其他添加剂来优化锂离子电池性能。优选的，所述添加剂还包括选自氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、硫酸丙烯酯中的至少一种的第二类添加剂。
进一步优选的，以所述电解液的总质量为100％计，所述添加剂的质量百分含量之和小于等于15％。在此基础上，任一优选的添加剂(氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、硫酸丙烯酯)的质量百分含量单独占所述电解液总质量的0.1％～10％。
以及，本发明实施例第三方面提供一种锂离子电池，所述锂离子电池包括正极、负极、隔膜和电解液，且所述电解液为上述的锂离子电池电解液。
本发明实施例提供的锂离子电池，由于含有本发明的锂离子电池电解液，能够显著提升锂离子电池的循环性能和低温放电性能，提升锂离子电池的整体输出性能。
本发明实施例中，所述电解液的组成，各组成成分的选择、含量、优选类型及其选择依据如上文所述，为了节约篇幅，此处不再赘述。
所述正极包括正极活性物质，常规用于锂离子电池的正极活性物质均能用于本发明实施例。但优选的，所述正极的活性物质选用过渡金属氧化物。
具体优选的，所述过渡金属氧化物为LiNi xCo yMn zL (1-x-y-z)O 2，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si和Fe中的一种，x、y、z的取值满足：0≤x＜1，0＜y≤1，0≤z＜1，且0＜x+y+z≤1。
所述负极包括负极活性物质，常规用于锂离子电池的负极活性物质均能用于本发明实施例。但优选的，所述负极的活性物质为石墨、含Si的复合材料或者钛酸锂。
所述隔膜的选择，包括但不限于单层聚乙烯(PE)、单层聚丙烯(PP)、双层PP/PE、三层PP/PE/PP或陶瓷隔膜。
下面结合具体实施例进行说明。
各实施例中，英文简写的中文释义解释如下：
EC：碳酸乙烯酯
EMC：碳酸甲乙酯
DMC：碳酸二甲酯
LiPF 6：六氟磷酸锂
P1:烯丙基磷酸酯
各实施例中，用到的添加剂结构以及其对应的字母编号如下表1所示。
表1
Figure PCTCN2020091053-appb-000006
Figure PCTCN2020091053-appb-000007
实施例1
一种锂离子二次电池，包括正极、负极、隔膜和电解液，其中，正极活性物质为镍钴锰酸锂(NCM811)材料；负极活性物质为硅碳复合材料(Si/C)，所述锂离子二次电池的制备方法包括以下步骤：
按96.8:2.0:1.2的质量比混合正极活性材料NCM811，导电碳黑和粘结剂聚偏二氟乙烯，分散在N-甲基-2-吡咯烷酮中，得到正极浆料，将正极浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板(正极片)，极板的厚度在135～160μm之间；
按96:1:1.2:1.8的质量比混合硅碳复合材料、导电碳黑、粘结剂丁苯橡胶和羧甲基纤维素，分散在去离子水中，得到负极浆料，将负极浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板(负极片)，极板的厚度在135～160μm之间；
将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)按质量比为2:1:7进行混合，混合后加 入基于电解液总质量12.5％的六氟磷酸锂，加入基于电解液总质量1％的D1，制备得到电解液。
采用厚度为14μm的PP基膜，单面涂覆2μm Al 2O 3的陶瓷隔膜。
将制得的正极片、隔膜、负极片放于自动卷绕机上，卷绕得到裸电芯；将裸电芯置于圆柱钢壳中，焊接好负极极耳和盖帽极耳，将上述制备的电解液注入到干燥后的电芯中，封口、静置、预充、老化和分容，完成锂离子二次电池的制备(21700-4.8Ah)。
实施例2～实施例10
实施例2～实施例10，除了电解液中组分不同外，其余正极、负极、隔膜、锂离子二次电池的制备均同实施例1，各实施例中第一类添加剂(化合物(1)-(7)中的至少一种)的选择及其含量如表2所示。
对比例
对比例1和对比例2中，除了电解液中添加剂的类型与含量(基于电解液总质量)不同外，其余正极、负极、隔膜、锂离子二次电池的制备均同实施例1，对比例1和对比例2中非水有机溶剂、添加剂的类型与含量如表2所示。
将实施例1～实施例10、对比例1和对比例2制备的锂离子二次电池进行评估，测试方法如下：
1)容量微分曲线
电池完成注液封口，静置48h后，取电池于abin测试柜以0.1C恒流预充至4.2V，后放电至2.75V，导出容量电压曲线，筛点和微分处理，得到d Q/d V～V曲线。
2)循环性能测试：在25±2℃/45℃±2℃下，将分容后的电池用0.5C恒流恒压充至4.2V(截止电流为0.01C)，然后用1C恒流放电至2.75V。充/放电N次循环后计算第N次循环容量的保持率，计算公式如下：
第N次循环容量保持率(％)＝(第N次循环放电容量/第1次循环放电容量)×100％；
3)高温储存性能：将分容后的电池在常温下用0.5C恒流恒压充至4.2V(截止电流为0.01C)，测量电池初始放电容量，然后在60℃储存7天后，以0.5C放电至2.75V测量电池的保持容量和恢复容量。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％；
电池容量恢复率(％)＝恢复容量/初始容量×100％。
4)低温放电：在室温以0.5C恒流恒压充电至4.2V，搁置5min，0.2C放电至2.75V，检测电池初始容量。搁置5min，0.5C恒流恒压充电至4.2V(截止电流为0.01C)。把电池放入-20℃的低温箱中搁置6h，并在此条件下以0.2C放电至2.75V，检测低温下的放电容量。
低温放电保持率(％)＝低温放电容量/初始容量×100％。
测试结果见下表2所示。
表2
Figure PCTCN2020091053-appb-000008
Figure PCTCN2020091053-appb-000009
Figure PCTCN2020091053-appb-000010
将电池体系为NCM811搭配硅碳复合材料的实施例1-10、对比例1和对比例2进行对比分析。由表2可见，采用本发明技术方案的实施例1至实施例10具有良好的循环性能、高温储存性能和低温放电性能；而采用对比例1和对比例2电解液的锂离子电池输出性能差，不能兼顾高低温和循环性能。
具体的，各实施例和对比例1比较，含有上述结构化合物的实施例1至实施例10，各实施例的低温放电性能、高温循环、常温循环和高温储存性能均明显优于对比例1。说明D1、D2、D4、D4、D5、D6、D7、D1+D7的存在，能够有效地提升电池的综合输出性能。
绘制对比例1、对比例2和实施例6电池首次充电的容量微分曲线图，如图1所示：对比例2中出现2.7V和2.9V两个还原峰，2.7V是添加剂P1在负极的还原峰，2.9V的还原峰归因于溶剂EC的还原，P1能优先溶剂EC还原，且对EC的还原有一定的抑制。P1结构中含有3个双键，活性高，其同X轴的积分面积大，推知其成膜阻抗大；实施例6中出现了2.4V和2.9V两个还原峰，2.4V的还原峰与DTD相似，2.9V的还原峰归因于溶剂EC的还原，EC还原峰强度相比对比例1和对比例2明显降低，说明D6的存在，优先溶剂EC还原，抑制了溶剂EC的还原分解，SEI膜组分中含有更多的乙氧链段，导锂性能提高，阻抗低，对应同X轴积分面积小；而对比例1在3.0V左右出现还原峰，归因于EC的还原。
绘制实施例6、对比例1、对比例2的DCR同电池SOC对应结果图，如图2所示(横坐标表示电池的充电状态SOC；纵坐标代表直流阻抗DCR)电池在10％～100％SOC，实施例6(D6)的DCR<对比例1的DCR<对比例2(P1)的DCR。由于D6成膜组分中含PEO基链段，导锂性增强，故降低了电池阻抗。
将实施例6、对比例1、对比例2提供的电解液25℃±3储存30天得到的结果如图3所示，其中，对比例1、对比例2提供的电解液都有明显的颜色变化，而实施例6提供的电解液没有明显变色。说明D6添加剂稳定性较高，常温静置不易氧化变色。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种电池电解液用添加剂，其特征在于，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
    Figure PCTCN2020091053-appb-100001
  2. 一种锂离子电池电解液，其特征在于，所述电解液包括非水有机溶剂、锂盐和添加剂，其中，所述添加剂至少包括如下结构式(1)-(7)所示化合物中的一种，
    Figure PCTCN2020091053-appb-100002
  3. 如权利要求2所述的锂离子电池电解液，其特征在于，所述结构式(1)-(7)所示化合物中的至少一种作为第一类添加剂，且以所述电解液的总质量为100％计，所述第一类添加剂的质量百分含量为0.05％～2％。
  4. 如权利要求3所述的锂离子电池电解液，其特征在于，所述添加剂还包括选自氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、硫酸丙烯酯中的至少一种的第二类添加剂。
  5. 如权利要求4所述的锂离子电池电解液，其特征在于，以所述电解液的总质量为100％计，所述添加剂的质量百分含量之和小于等于15％。
  6. 如权利要求2至5任一项所述的锂离子电池电解液，其特征在于，所述非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯中的至少一种。
  7. 如权利要求6所述的锂离子电池电解液，其特征在于，以所述电解液的总质量为100％计，所述非水有机溶剂的质量百分含量之和为55％～75％。
  8. 一种锂离子电池，其特征在于，所述锂离子电池包括正极、负极、隔膜和电解液，且所述电解液为权利要求2-7任一项所述的锂离子电池电解液。
  9. 如权利要求8所述的锂离子电池，其特征在于，所述正极的活性物质为过渡金属氧化物；所述负极的活性物质为石墨、含Si的复合材料或者钛酸锂。
  10. 如权利要求9所述的锂离子电池，其特征在于，所述过渡金属氧化物为LiNi xCo yMn zL (1-x-y-z)O 2，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si和Fe中的一种，x、y、z的取值满足：0≤x＜1，0＜y≤1，0≤z＜1，且0＜x+y+z≤1。
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