WO2024250144A1 - 一种二次电池及用电装置 - Google Patents

一种二次电池及用电装置 Download PDF

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Publication number
WO2024250144A1
WO2024250144A1 PCT/CN2023/098308 CN2023098308W WO2024250144A1 WO 2024250144 A1 WO2024250144 A1 WO 2024250144A1 CN 2023098308 W CN2023098308 W CN 2023098308W WO 2024250144 A1 WO2024250144 A1 WO 2024250144A1
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Prior art keywords
group
positive electrode
atom
optionally
secondary battery
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English (en)
French (fr)
Inventor
任家墨
陈培培
张立美
刘姣
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP23940038.5A priority Critical patent/EP4718561A1/en
Priority to KR1020267000044A priority patent/KR20260018966A/ko
Priority to PCT/CN2023/098308 priority patent/WO2024250144A1/zh
Priority to CN202380090692.0A priority patent/CN120500762A/zh
Publication of WO2024250144A1 publication Critical patent/WO2024250144A1/zh
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of battery technology, and in particular to a secondary battery and an electrical device.
  • lithium-ion secondary batteries have begun to be widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as electric vehicles, military equipment, aerospace and other fields.
  • energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as electric vehicles, military equipment, aerospace and other fields.
  • the electric vehicle field as the main commercial field of lithium-ion secondary batteries, has shown explosive growth since 2015, but consumer anxiety caused by insufficient battery life has greatly hindered the development of the electric vehicle field. Improving the battery life is an urgent problem to be solved in this field.
  • high energy density active materials is one of the important directions for developing high energy density power batteries.
  • Ternary materials have become the first choice for some new energy vehicles that pursue endurance due to their higher platform voltage, higher gram capacity and compaction density.
  • researchers have been continuously increasing the nickel content in ternary materials.
  • the lattice stability of the material gradually decreases.
  • lattice collapse is prone to occur, accompanied by the irreversible formation of rock salt phase and spinel phase and transition metal dissolution on the outside.
  • the rock salt phase and spinel phase have lower lithium ion conductivity, which will increase the polarization of the battery and decay the cycle capacity under long-term circulation.
  • the transition metal After the transition metal is dissolved, it will migrate and deposit on the surface of the negative electrode, resulting in an increase in the surface impedance of the negative electrode and a decrease in the utilization rate, thereby deteriorating the battery performance.
  • the positive electrode sheet containing ternary materials often adopts a higher compaction.
  • higher compaction may cause the spherical positive electrode particles to break into smaller particles, increase the specific surface area of the positive electrode material in contact with the electrolyte, and thus deepen the problem of metal dissolution.
  • One problem to be solved by the present invention is how to reduce the impedance increase and capacity attenuation problems of lithium ion secondary batteries caused by severe polarization and damage to the negative electrode by transition metals during the cycle, so as to obtain lithium ion secondary batteries with excellent cycle performance and long life.
  • the present application provides a secondary battery and an electrical device to solve the above problems.
  • the first aspect of the present application provides a secondary battery, comprising a positive electrode plate and a non-aqueous electrolyte, wherein the non-aqueous electrolyte comprises an additive, and the additive comprises a cyclic sulfate ester compound having a structure represented by general formula (I),
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by general formula (II), a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group,
  • a group having a structure represented by general formula (II) a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyan
  • R5 and R6 are each independently selected from any one of a group having a structure represented by the general formula (II), a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group;
  • a group having a structure represented by the general formula (II) a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a
  • R1 and R2 are not hydrogen atoms at the same time and R3 and R4 are not hydrogen atoms at the same time;
  • the compaction density of the positive electrode sheet is greater than 3.1 cm 3 .
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by general formula (II), a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyano group and a sulfonic acid group;
  • a group having a structure represented by general formula (II) a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyan
  • R5 and R6 are each independently selected from a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1- Any one of a C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyano group and a sulfonic acid group.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by the general formula (II), a hydrogen atom, a halogen atom, a C1-C3 alkyl group and a cyano group.
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom and a C1-C3 alkyl group.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having the structure represented by formula (II), a hydrogen atom, a F atom, a Cl atom, a Br atom, a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyano group.
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the group of the structure represented by the general formula (II) is selected from any one of the following groups:
  • X is a F atom, a Cl atom or a Br atom.
  • the group of the structure represented by the general formula (II) is selected from any one of the following groups:
  • the cyclic sulfate compound is selected from any one or more of the following compounds:
  • the mass content of the cyclic sulfate ester compound in the non-aqueous electrolyte is W1, wherein 0.005% ⁇ W1 ⁇ 10%, optionally 0.05% ⁇ W1 ⁇ 5%.
  • the ternary materials include, but are not limited to, LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and LiNi 0.9 Co 0.055 Mn 0.055 O 2 .
  • the compaction density of the positive electrode sheet is 3.3 to 4.1 g/cm 3 , and optionally 3.4 to 3.8 g/cm 3 .
  • the average particle size Dv50 of the positive electrode active material is 1 to 25 ⁇ m; alternatively, 2 ⁇ m ⁇ Dv50 ⁇ 20 ⁇ m, alternatively 2 ⁇ m ⁇ Dv50 ⁇ 15 ⁇ m.
  • a second aspect of the present application provides an electrical device, comprising a secondary battery, wherein the secondary battery comprises any one of the secondary batteries of the first aspect.
  • the secondary battery provided in the present application has improved cycle performance.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack shown in FIG. 4 according to an embodiment of the present application.
  • FIG. 6 is a schematic diagram of an electric device using a secondary battery as a power source according to an embodiment of the present application.
  • ranges are defined in the form of lower limits and upper limits, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. Ranges defined in this manner can be inclusive or exclusive of the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also expected.
  • the numerical range “ab” represents an abbreviation of any real number combination between a and b, where a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application are open-ended or closed-ended.
  • the “include” and “comprising” may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • the first aspect of the present application provides a secondary battery, comprising a positive electrode plate and a non-aqueous electrolyte, wherein the non-aqueous electrolyte comprises an additive, and the additive comprises a cyclic sulfate ester compound having a structure represented by general formula (I),
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by general formula (II), a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group,
  • a group having a structure represented by general formula (II) a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyan
  • R5 and R6 are each independently selected from any one of a group having a structure represented by the general formula (II), a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group;
  • a group having a structure represented by the general formula (II) a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a
  • R1 and R2 are not hydrogen atoms at the same time and R3 and R4 are not hydrogen atoms at the same time;
  • the compaction density of the positive electrode sheet is greater than 3.1 cm 3 .
  • Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can be used continuously by activating active materials by charging after the battery is discharged.
  • secondary batteries include positive electrode sheets, negative electrode sheets, separators and electrolytes.
  • active ions such as lithium ions
  • the separator is arranged between the positive electrode sheets and the negative electrode sheets, and its main function is to prevent the positive and negative electrodes from short-circuiting, while allowing active ions to pass through.
  • the electrolyte is between the positive electrode sheets and the negative electrode sheets, and its main function is to conduct active ions.
  • the ternary material itself has problems such as increased cycle impedance and transition metal dissolution. After adopting high pressure density to increase energy density, it will also aggravate the damage of transition metal to the negative electrode.
  • the present invention adopts cyclic sulfate as an electrolyte additive, which can participate in the film formation at the positive and negative electrode interfaces during the first charging process.
  • the main component of the film formed on the positive electrode interface is an alkyl lithium sulfate type organic lithium compound
  • the main component of the film formed on the negative electrode interface is lithium sulfite and a polymer similar to polyethylene oxide (PEO).
  • This additive can reduce the film formation impedance at the positive and negative electrode interfaces, generate a more stable inorganic and organic mixed SEI film with stronger barrier ability, protect the negative electrode from being destroyed by transition metals, and at the same time It can also reduce the formation of rock salt phase and spinel on the positive electrode interface, thereby avoiding the increase of battery polarization, and further reducing the impedance growth during the cycle process, which greatly improves the cycle performance of the battery cell.
  • the secondary battery of the present application includes a non-aqueous electrolyte, the non-aqueous electrolyte includes an additive, and the additive includes a cyclic sulfate compound having a structure shown in the above general formula (I).
  • the cyclic sulfate rings in the above general formula (I) are all five-membered rings, which can form a denser SEI film.
  • R1 , R2 , R3 and R4 can be alkyl or substituents containing F or N.
  • substituents such as alkyl
  • an elastic SEI film with a longer organic chain can be generated at the negative electrode, which can cope with the volume change of the negative electrode during the cycle and avoid the destruction of the SEI film;
  • substituents containing F and N the film formation can be participated in the negative electrode to generate a SEI film rich in more inorganic components such as LiF and Li3N , thereby improving the mechanical strength of the SEI film, thereby improving the stability of the negative electrode SEI film, and achieving the purpose of further improving the battery cycle performance.
  • the above-mentioned alkyl group may be a straight-chain alkyl group, a branched alkyl group or a cycloalkyl group, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, cyclopropyl, cyclobutane, etc.;
  • the alkyl group in the above-mentioned haloalkyl group includes but is not limited to a straight-chain alkyl group, a branched alkyl group or a cycloalkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, cyclopropyl, cyclobutane, etc.
  • the halogen atom may be a fluorine atom, a chlorine atom or a bromine atom, and the halogen atom replaces any one or more hydrogen atoms on
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by general formula (II), a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyano group and a sulfonic acid group;
  • a group having a structure represented by general formula (II) a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyan
  • R5 and R6 are each independently selected from any one of a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, a C2-C3 alkenyl group, a C2-C3 ester group, a cyano group and a sulfonic acid group.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having a structure represented by the general formula (II), a hydrogen atom, a halogen atom, a C1-C3 alkyl group and a cyano group.
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom, a C1-C3 alkyl group, kind.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from any one of a group having the structure represented by formula (II), a hydrogen atom, a F atom, a Cl atom, a Br atom, a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyano group.
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the group of the structure represented by the general formula (II) is selected from any one of the following groups:
  • X is a F atom, a Cl atom or a Br atom.
  • the group of the structure represented by the general formula (II) is selected from any one of the following groups:
  • the cyclic sulfate compound is selected from any one or more of the following compounds:
  • the preparation method of the cyclic sulfate ester compound is simpler, easier to promote and implement in industry, and has a more stable effect on improving the cycle performance of secondary batteries.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 satisfy the following conditions:
  • R1 and R2 are both hydrogen atoms and one of R3 and R4 is a hydrogen atom and the other is any one of a group having a structure represented by the general formula (II), a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group, and R5 and R6 in the group having a structure represented by the general formula (II) are not both hydrogen atoms.
  • R5 and R6 in the group having a structure represented by the general formula (II) are not both hydrogen atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 satisfy the following conditions:
  • R3 and R4 are both hydrogen atoms and one of R1 and R2 is a hydrogen atom and the other is any one of a group having a structure represented by general formula (II), a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 ester group, a cyano group and a sulfonic acid group, and R5 and R6 in the group having a structure represented by general formula (II) are not both hydrogen atoms.
  • R5 and R6 in the group having a structure represented by general formula (II) are not both hydrogen atoms.
  • R 5 and R 6 are each independently selected from groups other than the structural groups represented by the general formula (II).
  • the content of the cyclic sulfate compound in the non-aqueous electrolyte can be arbitrary.
  • the mass content of the cyclic sulfate compound in the non-aqueous electrolyte is W1, wherein 0.005% ⁇ W1 ⁇ 10%, optionally 0.05% ⁇ W1 ⁇ 5%.
  • the cyclic sulfate compound within the above content range has a more obvious effect on improving the cycle performance, and the battery cell can have better performance.
  • W1 can be less than 0.001%, or 0.001% to 0.005%, 0.005% to 0.01%, 0.01% to 0.05%, 0.05% to 1%, 1% to 2%, 2% to 3%, 3% to 5%, 5% to 8%, 8% to 10%, 10% to 15%, or greater than 15%.
  • the non-aqueous electrolyte used in the present invention also includes an electrolyte.
  • the electrolyte can be generally used in non-aqueous electrolytes, it can be considered to be applied to the non-aqueous electrolyte of the present application.
  • Those skilled in the art can make a choice based on the battery system in which the non-aqueous electrolyte is applied, such as selecting a conventional electrolyte suitable for secondary batteries.
  • the electrolyte includes an alkali metal salt electrolyte; optionally, the electrolyte includes a lithium salt; optionally, the lithium salt includes one or more selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(trifluoromethanesulfonyl)imide and lithium bis(trifluoromethanesulfonyl)imide.
  • lithium salts or sodium salts can be used alone. Two or more kinds may also be used in combination.
  • the content of electrolyte in the non-aqueous electrolyte can refer to the electrolyte content in conventional non-aqueous electrolyte.
  • the electrolyte content in the non-aqueous electrolyte is 0.1mol/L-5mol/L, for example, it can be 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 4mol/L or 5mol/L.
  • the non-aqueous electrolyte further comprises a non-aqueous solvent.
  • the non-aqueous solvent comprises any one or more selected from the group consisting of cyclic carbonates, chain carbonates, nitrile solvents, ketone solvents and sulfone solvents; further optionally, the non-aqueous solvent comprises one or more selected from the group consisting of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfon solventsul
  • non-aqueous solvents can be used alone or in combination of two or more.
  • a mixed solvent of cyclic carbonate and chain carbonate can be used.
  • EC+EMC ethylene carbonate+ethyl methyl carbonate
  • a solid solvent such as dimethyl sulfone may be used.
  • the additives may also include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the above-mentioned additives also include, but are not limited to, one or more selected from the group consisting of sulfate compounds, sulfite compounds, sultone compounds, disulfonic acid compounds, nitrile compounds, aromatic compounds, isocyanate compounds, phosphazene compounds, cyclic anhydride compounds, phosphite compounds, phosphate compounds, borate compounds, and carboxylate compounds.
  • the reaction temperature of the first step is controlled at 30-60°C; the reaction temperature of the second step is controlled at 10-30°C.
  • the second step is catalyzed by a catalyst such as ruthenium trichloride trihydrate, and the oxidant may be sodium hypochlorite, ozone, etc.
  • the secondary battery provided by the present invention includes a positive electrode plate, which includes a positive electrode material layer containing a positive electrode active material.
  • the ternary materials include, but are not limited to, LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and LiNi 0.9 Co 0.055 Mn 0.055 O 2 .
  • Adding cyclic sulfate compounds to the system containing the above-mentioned ternary materials can improve the growth of lithium ion cycle impedance and cycle performance.
  • the positive electrode sheets containing ternary materials often adopt higher compaction.
  • higher compaction may cause the spherical positive electrode particles to break into smaller particles, increasing the specific surface area of the positive electrode material in contact with the electrolyte, thereby deepening the problem of metal dissolution.
  • Adding cyclic sulfate compounds to the electrolyte can help solve the above problems.
  • the cyclic sulfate compound additive used in the present invention can be applied to secondary batteries with a high compaction density (for example, a compaction density greater than 3.1 cm 3 ) of the positive electrode plate.
  • the compaction density of the positive electrode sheet is 3.3-4.1 g/cm 3 , optionally 3.4-3.8 g/cm 3 , for example 3.3-3.4 g/cm 3 , 3.4-3.45 g/cm 3 , 3.45-3.5 g/cm 3 , 3.5-3.6 g/cm 3 , 3.6-3.7 g/cm 3 , 3.7-3.8 g/cm 3 , 3.8-3.9 g/cm 3 , 3.9-4.0 g/cm 3 or 4.0-4.1 g/cm 3 .
  • the compacted density can be measured using a compacted density meter, and the measurement method can be a method commonly used in the art or a method given in the compacted density meter manual.
  • the reason why the particle size distribution of ternary materials affects their compaction density is related to the spherical morphology of ternary materials.
  • the particle size of the material can be expressed by Dv50, which refers to the particle size corresponding to when the cumulative volume percentage reaches 50%, that is, the median particle size of the volume distribution.
  • the average particle size Dv50 of the positive electrode active material used in the present invention is 1 to 25 ⁇ m; optionally, 2 ⁇ m ⁇ Dv50 ⁇ 20 ⁇ m, optionally 2 ⁇ m ⁇ Dv50 ⁇ 15 ⁇ m.
  • the positive electrode active material Dv50 is within the above preferred range, the polarization on the positive electrode side can be reduced while ensuring high pressure density, thereby ensuring better battery performance.
  • Dv50 can be less than 0.5 ⁇ m, or 0.5 ⁇ m to 1 ⁇ m, 1 ⁇ m to 1.5 ⁇ m, 1.5 ⁇ m to 2 ⁇ m, 2 ⁇ m to 5 ⁇ m, 5 ⁇ m to 10 ⁇ m, 10 ⁇ m to 15 ⁇ m, 15 ⁇ m to 18 ⁇ m, 18 ⁇ m to 20 ⁇ m, 20 ⁇ m to 22 ⁇ m, 22 ⁇ m to 25 ⁇ m, 25 ⁇ m to 30 ⁇ m, or greater than 30 ⁇ m.
  • Dv50 can be measured using instruments and methods known in the art.
  • a laser diffraction particle size distribution measuring instrument Malvern Instruments Ltd. of the United Kingdom is used for testing.
  • the particle size distribution laser diffraction method GB/T19077-2016 the particle size distribution is measured to obtain Dv50.
  • the positive electrode sheet generally includes a positive electrode current collector and a positive electrode material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode current collector has two surfaces opposite to each other in its thickness direction, and the positive electrode material layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode material layer may further include other positive electrode active materials.
  • Positive electrode active materials for batteries known in the art may be used.
  • the positive electrode active material may include at least one of the following materials: lithium-containing phosphates with an olivine structure, lithium transition metal oxides, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (such as LiCoO 2 ), lithium nickel oxide (such as LiNiO 2 ), lithium manganese oxide (such as LiMnO 2 , LiMn 2 O 4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide
  • the present invention relates to a lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co
  • lithium-containing phosphates having an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (may also be referred to as LFP)), at least one of a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (may also be referred to as LFP)
  • LiMnPO 4 lithium manganese phosphate
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • vinylidene fluoride-tetrafluoroethylene-propylene terpolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer
  • the positive electrode film layer may further include a conductive agent, for example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the secondary battery of the present invention may further include a negative electrode sheet.
  • the negative electrode sheet may include a negative electrode current collector and a negative electrode film layer (negative electrode material layer) disposed on at least one surface of the negative electrode current collector, wherein the negative electrode material layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and other substrates).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
  • the negative electrode active material may include at least one of the following materials: graphite (e.g., artificial graphite, natural graphite), soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further include a binder.
  • the binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may further include a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener eg, sodium carboxymethyl cellulose (CMC-Na)
  • the negative electrode sheet can be prepared in the following manner: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the secondary battery further includes a separator.
  • the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG1 is a secondary battery 5 of a square structure as an example.
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries may be assembled into a battery module.
  • the number of secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space, and the plurality of secondary batteries 5 are received in the receiving space.
  • the battery modules described above may also be assembled into a battery pack.
  • the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG4 and FIG5 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be Arrange them in the battery box in any way.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a secondary battery, a battery module or a battery pack may be selected according to its usage requirements.
  • Fig. 6 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • the reaction temperature of the first step is controlled at 30-60°C; the reaction temperature of the second step is controlled at 10-30°C.
  • the second step is catalyzed by a catalyst such as ruthenium trichloride trihydrate, and the oxidant may be sodium hypochlorite, ozone, etc.
  • Step 1 Add 300 g (2 mol) of solid 1,6-dideoxygalactitol to a 5L three-necked flask, start stirring, and drop 523 g (4.4 mol) of thionyl chloride into the three-necked flask. During the dropwise addition, control the temperature at about 15°C. After the dropwise addition is completed, keep the reaction at 45°C for 4 hours. A large amount of pasty solid precipitates from the reaction solution. After cooling, slowly drop 1L of deionized water, stir quickly to break up the reaction system, and wash the filtered solid with deionized water for multiple times until the pH is neutral. Dry the filter cake at 60°C under reduced pressure to obtain an intermediate product 1.
  • Step 2 Add 184.2 g (0.8 mol) of intermediate 1 to a 3L three-necked flask, add 1000 mL of acetonitrile, add 80 mg of ruthenium trichloride trihydrate catalyst, replace the system with nitrogen, cool the system to 20°C, start stirring, drop 2000 g of 20% sodium hypochlorite aqueous solution within 1 hour, and control the reaction temperature at 10-20°C; after the addition is complete, stir at 10-20°C for 10 minutes, separate the liquids, and quench the organic phase with sodium sulfite aqueous solution until the starch potassium iodide test paper does not turn blue; separate again The organic layer was concentrated and crystallized with acetonitrile to obtain a white powder solid, which was the above-mentioned compound 1. 1H-NMR, CD 3 CN, ⁇ ppm 5.42-5.39 (m, 2H), 5.36-5.34 (m, 2H), 1.67-1.65 (d, 6H).
  • Step 1 Add 356.5 g (2 mol) of solid 3,4,5,6-octanetrol into a 5 L three-necked flask, start stirring, and drop 523 g (4.4 mol) of thionyl chloride into the three-necked flask. During the dropwise addition, control the temperature at about 15°C. After the dropwise addition is completed, keep the reaction at 45°C for 4 hours. A large amount of pasty solid precipitates from the reaction solution. After cooling, slowly drop 1 L of deionized water, stir quickly to break up the reaction system, and wash the filtered solid with deionized water for multiple times until the pH is neutral. Dry the filter cake at 60°C under reduced pressure to obtain an intermediate product 2.
  • Step 2 Add 216.2 g (0.8 mol) of intermediate 2 to a 3L three-necked flask, add 1000 mL of acetonitrile and 80 mg of ruthenium trichloride trihydrate catalyst, replace the system with nitrogen, cool the system to 20°C, start stirring, drop 2000 g of 20% sodium hypochlorite aqueous solution within 1 hour, and control the reaction temperature to 10-20°C; after the addition is complete, stir at 10-20°C for 10 min, separate the liquids, quench the organic phase with sodium sulfite aqueous solution until the starch potassium iodide paper does not turn blue; separate the liquids again, concentrate the organic layer, crystallize with acetonitrile to obtain compound 2.
  • Step 1 Add 328.4 g (2 mol) of solid 2,3,4,5-heptetetrol into a 5 L three-necked flask, start stirring, and drop 523 g (4.4 mol) of thionyl chloride into the three-necked flask. During the dropwise addition, control the temperature at about 15°C. After the dropwise addition is completed, keep the reaction at 45°C for 4 hours. A large amount of pasty solid precipitates from the reaction solution. After cooling, slowly drop 1 L of deionized water, stir quickly to break up the reaction system, and wash the filtered solid with deionized water for multiple times until the pH is neutral. Dry the filter cake at 60°C under reduced pressure to obtain an intermediate product 3.
  • Step 2 Add 205 g (0.8 mol) of intermediate 3 to a 3L three-necked flask, add 1000 mL of acetonitrile, and stir until The solid was completely dissolved, 80 mg of ruthenium trichloride trihydrate catalyst was added, and after nitrogen replacement of the system, the system was cooled to 20 ° C, stirring was started, and 2000 g of 20% sodium hypochlorite aqueous solution was added dropwise within 1 h, and the reaction temperature was controlled at 10-20 ° C; after the addition was completed, the mixture was stirred at 10-20 ° C for 10 min, and the liquid was separated.
  • Step 1 Add 392.4 g (2 mol) of solid 1,2,3,4,5.6-heptanhexaol into a 5 L three-necked flask, start stirring, and drop 784.5 g (6.6 mol) of thionyl chloride into the three-necked flask. During the dropwise addition, control the temperature at about 15°C. After the dropwise addition is completed, keep the reaction at 45°C for 4 hours. A large amount of pasty solid precipitates from the reaction solution. After cooling, slowly drop 1 L of deionized water, stir quickly to break up the reaction system, and wash the filtered solid with deionized water for multiple times until the pH is neutral. Dry the filter cake at 60°C under reduced pressure to obtain intermediate product 4.
  • Step 2 Add 140 g (0.4 mol) of intermediate product 4 to a 4L three-necked flask, add 1000 mL of acetonitrile, add 110 mg of ruthenium trichloride trihydrate catalyst, replace the system with nitrogen, cool the system to 20°C, start stirring, drop 1500 g of 20% sodium hypochlorite aqueous solution within 1 hour, control the reaction temperature at 10-20°C; after the addition is complete, stir at 10-20°C After 10 min, the liquids were separated and the organic phase was quenched with aqueous sodium sulfite solution until the starch potassium iodide test paper did not turn blue; the liquids were separated again, the organic layer was concentrated, and the mixture was crystallized with acetonitrile to obtain compound 5.
  • Step 1 Add 484g (2mol) of solid octitol to a 5L three-necked flask, start stirring, and add 1046g (8.8mol) of thionyl chloride dropwise to the three-necked flask. Control the temperature at about 15°C during the addition process. After the addition is completed, keep the reaction at 45°C for 4h. A large amount of pasty solid precipitates from the reaction solution. After cooling, slowly add 1L of deionized water dropwise, stir quickly to break up the reaction system, and wash the filtered solid with deionized water for multiple times until the pH is neutral. Dry the filter cake at 60°C under reduced pressure to obtain an intermediate product 5.
  • Step 2 Add 183.2 g (0.4 mol) of intermediate product 5 to a 4L three-necked flask, add 1000 mL of acetonitrile, add 150 mg of ruthenium trichloride trihydrate catalyst, and after nitrogen replacement of the system, cool the system to 20°C, start stirring, and drop 2000 g of 20% sodium hypochlorite aqueous solution within 1 hour, and control the reaction temperature to 10-20°C; after the addition is completed, stir at 10-20°C for 10 minutes, separate the liquids, and quench the organic phase with sodium sulfite aqueous solution until the starch potassium iodide paper does not turn blue; separate the liquids again, concentrate the organic layer, and crystallize with acetonitrile to obtain compound 7.
  • Electrolyte composition Compound 1 is used as an additive, and its mass content in the electrolyte is 2%; LiPF 6 is used as an electrolyte, and its content in the electrolyte is 10%, and a mixture of EC+EMC (ethylene carbonate+ethyl methyl carbonate) with a volume ratio of 3:7 is used as a solvent.
  • EC+EMC ethylene carbonate+ethyl methyl carbonate
  • the positive electrode active material LiNi 0.5 Co 0.3 Mn 0.2 O 2 (average particle size Dv50 is 8 ⁇ m), the conductive agent acetylene black, and the binder polyvinylidene fluoride (PVDF) are dissolved in the solvent N-methylpyrrolidone (NMP) at a weight ratio of 97:1:2, and the positive electrode slurry is obtained after being fully stirred and mixed; then the positive electrode slurry is evenly coated on the positive electrode collector, and then dried, cold pressed, and cut to obtain the positive electrode sheet.
  • the compacted density of the positive electrode sheet is 3.45 g/cm 3 .
  • the Dv50 of the positive electrode active material refers to the particle size corresponding to when the cumulative volume percentage of the positive electrode active material reaches 50%, that is, the median particle size of the volume distribution, in ⁇ m.
  • Dv50 can be measured using instruments and methods known in the art. For example, the laser diffraction particle size distribution measuring instrument (Malvern Mastersizer 3000) of Malvern Instruments Ltd. of the United Kingdom is used for testing. According to the particle size distribution laser diffraction method GB/T19077-2016, the particle size distribution is measured to obtain Dv50.
  • the compaction density of the positive electrode sheet can be measured using a compaction density meter.
  • the negative electrode active material graphite, the conductive agent carbon black, the binder styrene-butadiene rubber (SBR), and the thickener sodium carboxymethyl cellulose (CMC-Na) are dissolved in the solvent deionized water in a weight ratio of 90:4:4:2, and mixed evenly to prepare a negative electrode slurry; the negative electrode slurry is evenly coated on the negative electrode collector copper foil once or multiple times, and the negative electrode sheet is obtained after drying, cold pressing, and slitting.
  • Lithium-ion battery assembly
  • the positive electrode sheet, the separator, and the negative electrode sheet are stacked in order, so that the separator is placed between the positive and negative electrode sheets to play an isolating role, and then they are wound to obtain an electrode assembly; the electrode assembly is placed in a battery casing, and after drying, the electrolyte is injected, and then a lithium-ion battery is obtained through processes such as formation and standing.
  • the positive electrode active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 was used to replace the positive electrode active material LiNi 0.5 Co 0.3 Mn 0.2 O 2 , and the rest was the same as in Example 1.
  • the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 was used to replace the positive electrode active material LiNi 0.5 Co 0.3 Mn 0.2 O 2 , and the rest was the same as in Example 1.
  • the positive electrode active material LiNi 0.9 Co 0.055 Mn 0.055 O 2 is used to replace the positive electrode active material LiNi 0.5 Co 0.3 Mn 0.2 O 2 .
  • the rest is the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 0.5 ⁇ m, and the rest was the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 1.5 ⁇ m, and the rest was the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 5 ⁇ m, and the rest was the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 18 ⁇ m, and the rest was the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 22 ⁇ m, and the rest was the same as in Example 1.
  • the average particle size of the positive electrode active material was adjusted to 30 ⁇ m, and the rest was the same as in Example 1.
  • the lithium-ion battery is charged at a constant current of 1C to a voltage of 4.25V, then charged at a constant voltage of 4.25V to a current of ⁇ 0.05C, and after standing for 5 minutes, the lithium-ion battery is discharged at a constant current of 1C to a voltage of 2.8V.
  • This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the first cycle.
  • the lithium-ion battery is subjected to multiple cycle charge and discharge tests according to the above method until the discharge capacity of the lithium-ion secondary battery decays to 80%, and the number of cycles of the lithium-ion battery is recorded.
  • the capacity retention rate (%) of the battery after N cycles at 45° C. (discharge capacity of the battery at the Nth cycle/discharge capacity of the battery at the first cycle) ⁇ 100%.
  • the lithium-ion battery is charged to 4.25V at a constant current of 1C, and then charged to a current of 0.05C at a constant voltage of 4.25V. After the battery is fully charged, it is left to stand for 5 minutes, discharged at 1C for 30 minutes (the battery cell is charged to 50% SOC), and then left to stand for 5 minutes. Adjust the temperature to 25°C, let it stand for 1 hour, and record the voltage V1 of the battery cell at this time. Discharge at 4C for 30 seconds, and record the voltage V2 after pulse discharge.
  • the cyclic sulfate compound can form a film on the positive and negative electrode sides, reduce the film formation impedance of the positive and negative electrode interfaces, and generate a more stable, inorganic and organic mixed SEI film with stronger barrier capacity, thereby avoiding the increase of battery polarization, thereby reducing the impedance growth during the cycle process, and greatly improving the cycle performance of the battery cell.
  • the SEI generated by the additive used in this application at the negative electrode has higher stability and better effect.

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Abstract

本申请涉及电池技术领域，涉及一种二次电池及用电装置。所述二次电池包括含环状硫酸酯化合物的非水电解液。本申请还涉及包括所述二次电池的用电装置。

Description

一种二次电池及用电装置 技术领域
本申请涉及电池技术领域，特别是涉及一种二次电池及用电装置。
背景技术
随着环境问题日益严峻，世界对于“碳中和”的追求驱使着各行各业向着更加绿色健康的方向发展。锂离子二次电池作为一种更加清洁的储能装置，开始广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动汽车、军事装备、航空航天等多个领域。其中，电动汽车领域作为锂离子二次电池的主要商用领域，自2015年开始呈现爆发式增长，但因为续航不足引起的消费焦虑却大大阻碍了电动汽车领域的发展。提高电池的续航能力是本领域亟待解决的一个问题。
发明内容
高能量密度活性材料的应用是开发高能量密度动力电池的重要方向之一。三元材料由于具有较高的平台电压、更高的克容量和压实密度，因而成为了部分追求续航的新能源汽车的首选。为了进一步提高能量密度，研究者们一直在不断提升三元材料中镍元素的含量，但是随着镍含量的提升，材料的晶格稳定性逐渐下降，在高温或循环过程中，易发生晶格坍塌，同时在外侧伴随不可逆的岩盐相和尖晶石相的生成和过渡金属溶出。岩盐相与尖晶石相具有更低的锂离子传导率，长时间循环下会使电池极化增大和循环容量衰减。过渡金属溶出后，会迁移并沉积在负极表面，导致负极表面阻抗增大与利用率的降低，从而恶化电池性能。此外，为了获得更高的能量密度，含三元材料的正极极片往往采用更高的压密。但是更高的压密可能会使球形的正极颗粒破碎成更小的颗粒，增加了正极材料的与电解液接触的比表面积，从而加深了金属溶出的问题。
本发明要解决的一个问题在于，如何减少锂离子二次电池因极化严重和循环过程中由过渡金属破坏负极等引起的阻抗增大与容量衰减的问题，以获得循环性能优异且长寿命的锂离子二次电池。
本申请提供一种二次电池及用电装置，以解决上述问题。
本申请的第一方面提供了一种二次电池，包括正极极片和非水电解液，其中，所述非水电解液包括添加剂，所述添加剂包括具有通式(I)所示结构的环状硫酸酯化合物，
其中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种，
R5和R6各自独立地选自具有所述通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种；
R1和R2不同时为氢原子且R3和R4不同时为氢原子；
所述正极极片包括含有正极活性材料的正极材料层，所述正极活性材料包含三元正极材料，所述三元正极材料为镍钴锰三元材料，其分子式为Li1+a[NixCoyMnzM1bM2c]O2-dNd，其中M1和M2元素独立地选自Al、Zr、Ti、Mg、Zn、B、Ca、Ce、Te、Fe中的至少一种，N元素选自F、Cl、S中的至少一种，其中0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，-0.1＜a＜0.2，0≤b＜0.3，0≤c＜0.3，0≤d＜0.2，0≤b+c＜0.3，x+y+z+b＝1；
所述正极极片的压实密度大于3.1cm3。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的任意一种；
R5和R6各自独立地选自氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1- C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的任意一种。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3的烷基和氰基中的任意一种。
在一些实施方案中，R5和R6各自独立地选自氢原子、C1-C3的烷基中的任意一种。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、F原子、Cl原子、Br原子、甲基、乙基、丙基、异丙基和氰基中的任意一种。
在一些实施方案中，R5和R6各自独立地选自氢原子、甲基、乙基、丙基和异丙基中的任意一种。
在一些实施方案中，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
其中，X为F原子、Cl原子或Br原子。
在一些实施方案中，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
在一些实施方案中，所述环状硫酸酯化合物选自如下化合物中的任意一种或多种：
在一些实施方案中，所述非水电解液中所述环状硫酸酯化合物的质量含量为W1，其中0.005％≤W1≤10％，可选地0.05％≤W1≤5％。
在一些实施方案中，所述三元材料的分子式为Li[NixCoyMnz]O2，其中，0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，x+y+z＝1。
在一些实施方案中，所述三元材料包括但不限于LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2和LiNi0.9Co0.055Mn0.055O2。
在一些实施方案中，所述正极极片的压实密度为3.3～4.1g/cm3，可选地为3.4～3.8g/cm3。
在一些实施方案中，所述正极活性材料的平均粒径Dv50为1～25μm；可选地，2μm≤Dv50≤20μm，可选地2μm≤Dv50≤15μm。
本申请的第二方面提供了一种用电装置，包括二次电池，其中，所述二次电池包括上述第一方面的任意一种二次电池。
本申请提供的二次电池具有改善的循环性能。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使 用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
在附图中，附图并未按照实际的比例绘制。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组
件；53顶盖组件。
具体实施方式
下面结合附图和实施例对本申请的实施方式作进一步详细描述。以下实施例的详细描述和附图用于示例性地说明本申请的原理，但不能用来限制本申请的范围，即本申请不限于所描述的实施例。
以下，适当地参照附图详细说明具体公开了本申请的非水电解液、二次电池和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、 1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
[二次电池]
本申请的第一方面提供了一种二次电池，包括正极极片和非水电解液，其中，所述非水电解液包括添加剂，所述添加剂包括具有通式(I)所示结构的环状硫酸酯化合物，

其中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种，
R5和R6各自独立地选自具有所述通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种；
R1和R2不同时为氢原子且R3和R4不同时为氢原子；
所述正极极片包括含有正极活性材料的正极材料层，所述正极活性材料包含三元正极材料，所述三元正极材料为镍钴锰三元材料，其分子式为Li1+a[NixCoyMnzM1bM2c]O2-dNd，其中M1和M2元素独立地选自Al、Zr、Ti、Mg、Zn、B、Ca、Ce、Te、Fe中的至少一种，N元素选自F、Cl、S中的至少一种，其中0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，-0.1＜a＜0.2，0≤b＜0.3，0≤c＜0.3，0≤d＜0.2，0≤b+c＜0.3，x+y+z+b＝1；
所述正极极片的压实密度大于3.1cm3。
二次电池又称为充电电池或蓄电池，是指在电池放电后可通过充电的方式使活性材料激活而继续使用的电池。通常情况下，二次电池包括正极极片、负极极片、隔离膜及电解液。在电池充放电过程中，活性离子(例如锂离子)在正极极片和负极极片之间往返嵌入和脱出。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使活性离子通过。电解液在正极极片和负极极片之间，主要起到传导活性离子的作用。
如上文所述，三元材料本身具有循环阻抗增大和过渡金属溶出等问题，在采用高压密提升能量密度后，也会加剧过渡金属对负极的破坏。本发明采用环状硫酸酯作为电解液添加剂，可以在首次充电过程中参与正负极界面成膜，其在正极界面上成膜的主要成分是烷基硫酸锂类有机锂化合物，在负极界面上成膜的主要成分是亚硫酸锂和类似于聚氧化乙烯(PEO)的聚合物。该添加剂既可以降低正负极界面的成膜阻抗，生成更稳定、阻隔能力更强的无机和有机混合的SEI膜，保护负极不被过渡金属破坏，同 时还可以减少正极界面上岩盐相与尖晶石的生成，从而避免电池极化增大，进而减少循环过程中的阻抗增长，对电芯的循环性能有极大的改善。
[非水电解液]
本申请的二次电池包括非水电解液，所述非水电解液包括添加剂，所述添加剂包括具有上述通式(I)所示结构的环状硫酸酯化合物。上述通式(I)中的环状硫酸酯环均为五元环，可以形成更加致密的SEI膜。
上述通式(I)中，R1、R2、R3和R4可以是烷基或含F或含N等取代基，通过引入烷基等取代基可以在负极生成有机链更长的弹性SEI膜，可以应对循环过程中负极产生的体积变化而避免SEI膜的破坏；引入含F和N等取代基，可以在负极参加成膜，生成富含LiF和Li3N等更多无机组分的SEI膜，提高SEI膜的机械强度，进而提高负极SEI膜的稳定性，实现进一步改善电池循环性能的目的。
上述烷基可以为直链烷基、支链烷基或环烷基，包括但不限于甲基、乙基、丙基、异丙基、正丁基、异丁基、环丙烷基、环丁烷基等；上述卤代烷基中的烷基包括但不限于直链烷基、支链烷基或环烷基，比如甲基、乙基、丙基、异丙基、正丁基、异丁基、环丙烷基、环丁烷基等；卤素原子可以为氟原子、氯原子或溴原子，卤素原子取代烷基上的任意一个或多个氢原子；上述烷氧基包括但不限于环丙烷基、氧杂环丁烷基等；卤代烷氧基中的卤素原子可以为氟原子、氯原子或溴原子，卤素原子取代烷氧基上的任意一个或多个氢原子；烯基包括但不限于-CH＝CH2、-CH＝CH2CH3、-CH2CH＝CH2、-CH2CH＝CH2CH3；酯基包括但不限于甲酸甲酯基、甲酸乙酯基、乙酸乙酯基、丙酸甲酯基、丙酸乙酯基、丙酸丙酯基等。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的任意一种；
R5和R6各自独立地选自氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的任意一种。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3的烷基和氰基中的任意一种。
在一些实施方案中，R5和R6各自独立地选自氢原子、C1-C3的烷基中的任意一 种。
在一些实施方案中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、F原子、Cl原子、Br原子、甲基、乙基、丙基、异丙基和氰基中的任意一种。
在一些实施方案中，R5和R6各自独立地选自氢原子、甲基、乙基、丙基和异丙基中的任意一种。
在一些实施方案中，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
其中，X为F原子、Cl原子或Br原子。
在一些实施方案中，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
在一些实施方案中，所述环状硫酸酯化合物选自如下化合物中的任意一种或多种：

上述环状硫酸酯化合物的制备方法更为简单，工业中更易推广实施，且对二次电池的循环性能改善效果更为稳定。
在一些实施方案中，R1、R2、R3、R4、R5和R6满足以下条件：
R1和R2同时为氢原子且R3和R4一者为氢原子另一者为具有通式(Ⅱ)所示结构的基团、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种，且所述通式(Ⅱ)所示结构的基团中R5和R6不同时为氢原子。
在一些实施方案中，R1、R2、R3、R4、R5和R6满足以下条件：
R3和R4同时为氢原子且R1和R2一者为氢原子另一者为具有通式(Ⅱ)所示结构的基团、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种，且所述通式(Ⅱ)所示结构的基团中R5和R6不同时为氢原子。
在一些实施方案中，R5和R6各自独立地选自除通式(Ⅱ)所示结构基团以外的基团。
本发明中，所述环状硫酸酯化合物在所述非水电解液中的含量可以是任意的。在一些实施方案中，所述非水电解液中所述环状硫酸酯化合物的质量含量为W1，其中0.005％≤W1≤10％，可选地0.05％≤W1≤5％。上述含量范围内的环状硫酸酯化合物对循环性能的改善效果比较明显，电芯能具有较好的性能。
在一些实施方案中，W1可以小于0.001％，或者为0.001％～0.005％、0.005％～0.01％、0.01％～0.05％、0.05％～1％、1％～2％、2％～3％、3％～5％、5％～8％、8％～10％、10％～15％，或大于15％。
在一些实施方式中，本发明采用的非水电解液还包括电解质，只要是通常可以用于非水电解液的电解质都可以考虑应用至本申请的非水电解液中。本领域技术人员可以根据非水电解液应用的电池体系进行选择，比如选择适用于二次电池的常规电解质。在一些实施方式中，电解质包括碱金属盐类电解质；可选地所述电解质包括锂盐；可选地，锂盐包括从六氟磷酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂和双三氟甲磺酰亚胺锂组成的群组中选择的一种或多种。上述各锂盐或钠盐可以单独使用 也可以两种或两种以上混合使用。
非水电解液中电解质的含量可以参考常规非水电解液中的电解质含量，在一些实施方式中，非水电解液中的电解质含量为0.1mol/L-5mol/L，比如可以为0.1mol/L、0.3mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、4mol/L或5mol/L。
在一些实施方式中，上述非水电解液还包括非水溶剂，可选地，非水溶剂包括从环状碳酸酯、链状碳酸酯、腈类溶剂、酮类溶剂和砜类溶剂组成的组中选择的任意一种或多种；进一步可选地非水溶剂包括从碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、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、1,4-丁内酯、环丁砜、二甲砜、甲乙砜、二乙砜、四氢呋喃、乙二醇二甲醚、二氧戊环、丙酮、乙腈以及丁腈组成的群组中选择的一种或多种。上述非水溶剂可以单独使用也可以两种或两种以上混合使用，比如为了提高二次电池的负荷特性、低温特性时，可以采用环状碳酸酯和链状碳酸酯混合溶剂。在一些实施方案中，采用EC+EMC(碳酸亚乙酯+碳酸甲乙酯)作为非水溶剂。
当本申请的非水电解液应用于固体电池时，可以采用二甲砜等固体溶剂。
除了上述添加剂外，添加剂还可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。在一些实施方式中，上述添加剂还包括但不限于从硫酸酯化合物、亚硫酸酯化合物、磺酸内酯化合物、二磺酸化合物、腈化合物、芳香化合物、异氰酸酯化合物、磷腈化合物、环状酸酐化合物、亚磷酸酯化合物、磷酸酯化合物、硼酸酯化合物、羧酸酯化合物组成的群组中选择的一种或多种。
[具有通式(I)所示结构的环状硫酸酯化合物的制备方法]
本申请的具有通式(I)的所示结构的环状硫酸酯化合物的制备方法参考以下合成路线：
其中，第一步骤的反应温度控制在30～60℃；第二步骤的反应温度控制在10～30℃，第二步骤采用催化剂比如三水合三氯化钌进行催化，氧化剂可以为次氯酸钠、臭氧等。
[正极极片]
本发明提供的二次电池包括正极极片，正极极片包括含有正极活性材料的正极材料层，所述正极活性材料包含镍钴锰三元材料，其分子式为Li1+a[NixCoyMnzM1bM2c]O2-dNd，其中M1和M2元素独立地选自Al、Zr、Ti、Mg、Zn、B、Ca、Ce、Te、Fe中的至少一种，N元素选自F、Cl、S中的至少一种，其中0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，-0.1＜a＜0.2，0≤b＜0.3，0≤c＜0.3，0≤d＜0.2，0≤b+c＜0.3，x+y+z+b＝1。
在一些实施方案中，所述三元材料的分子式为Li[NixCoyMnz]O2，其中，0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，x+y+z＝1。
在一些实施方案中，所述三元材料包括但不限于LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2和LiNi0.9Co0.055Mn0.055O2。
在上述三元材料存在的体系中添加环状硫酸酯化合物，均能起到改善锂离子循环阻抗增长和循环性能的作用。
如上文所述，为了获得更高的能量密度，含三元材料的正极极片往往采用更高的压密。但是更高的压密可能会使球形的正极颗粒破碎成更小的颗粒，增加了正极材料的与电解液接触的比表面积，从而加深了金属溶出的问题。向电解液中添加环状硫酸酯化合物有助于解决上述问题。
本发明采用的环状硫酸酯化合物添加剂可以适用于正极极片高压实密度(例如压实密度大于3.1cm3)的二次电池中。
在一些实施方案中，所述正极极片的压实密度为3.3～4.1g/cm3，可选地为3.4～3.8g/cm3，例如3.3～3.4g/cm3、3.4～3.45g/cm3、3.45～3.5g/cm3、3.5～3.6g/cm3、3.6～3.7g/cm3、3.7～3.8g/cm3、3.8～3.9g/cm3、3.9～4.0g/cm3或4.0～4.1g/cm3。
压实密度的测定可以利用压实密度仪测定，测量方法可以是本领域常用的方法或者压实密度仪说明书给出的方法。
三元材料的粒度分布对其压实密度产生影响的原因和三元材料的球形形貌有关，等径球在堆积时，球体和球体之间会有大量的空隙，若没有合适的小粒径来填补这些 空隙，堆积密度就会很低，所以合适的粒度分布能提高材料的压实密度。材料颗粒大小可以用Dv50表示，Dv50指的是累计体积百分数达到50％时所对应的粒径，即体积分布中位粒径。在一些实施方案中，本发明采用的正极活性材料的平均粒径Dv50为1～25μm；可选地，2μm≤Dv50≤20μm，可选地2μm≤Dv50≤15μm。正极活性材料Dv50在上述优选范围时，可以在保证高压密的情况下，减少正极侧的极化，保证较好的电池性能。
在一些实施方案中，Dv50可以是小于0.5μm，或者为0.5μm～1μm、1μm～1.5μm、1.5μm～2μm、2μm～5μm、5μm～10μm、10μm～15μm、15μm～18μm、18μm～20μm、20μm～22μm、22μm～25μm、25μm～30μm，或大于30μm。
Dv50可以用本领域公知的仪器及方法进行测定。例如采用英国马尔文仪器有限公司的激光衍射粒度分布测量仪(Malvern Mastersizer 3000)进行测试，依据粒度分布激光衍射法GB/T19077-2016，测量出粒径分布，得到Dv50。
正极极片通常包括正极集流体以及设置在正极集流体至少一个表面的正极材料层。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极材料层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极材料层还可以包括其他正极活性材料。可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化 物、锂镍钴锰氧化物(如LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)、锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯～四氟乙烯～丙烯三元共聚物、偏氟乙烯～六氟丙烯～四氟乙烯三元共聚物、四氟乙烯～六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N～甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
本发明的二次电池还可以包含负极极片。负极极片可以包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层(负极材料层)，所述负极材料层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯 (PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：石墨(例如人造石墨、天然石墨)、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。作为示例，粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。作为示例，导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次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。例如，图1是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池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二次电池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外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，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为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，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。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(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，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次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。
[实施例]
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品，其余试剂或化合物信息记录在表1中。
表1

合成例
本申请的具有通式(I)的所示结构的环状硫酸酯化合物的制备方法参考以下合成路线：
其中，第一步骤的反应温度控制在30～60℃；第二步骤的反应温度控制在10～30℃，第二步骤采用催化剂比如三水合三氯化钌进行催化，氧化剂可以为次氯酸钠、臭氧等。
合成例1：化合物1的合成
步骤1：将300g(2mol)固体1,6二脱氧半乳糖醇加入到5L三口瓶中，开启搅拌，向三口瓶中滴加523g(4.4mol)氯化亚砜，滴加过程中控制温度在15℃左右，滴加完毕后于45℃下保温反应4h，反应液析出大量糊状固体，冷却后缓慢滴加入去离子水1L，将反应体系快速搅拌打散，过滤得到的固体用去离子水多次打浆洗涤至pH中性，滤饼60℃减压烘干，得到中间产物1。
步骤2：向3L三口瓶中加入184.2g(0.8mol)中间产物1，加入乙腈1000mL，加入80mg三水合三氯化钌催化剂，氮气置换体系后，将体系降温至20℃，开启搅拌，1h内滴入2000g 20％次氯酸钠水溶液，控制反应温度10-20℃；滴加完毕，10-20℃搅拌10min，分液，使用亚硫酸钠水溶液将有机相淬灭至淀粉碘化钾试纸不变蓝；再次分 液，有机层浓缩，乙腈结晶，得到白色粉末固体，即为上述化合物1。1H-NMR,CD3CN,δppm 5.42-5.39(m,2H),5.36-5.34(m,2H),1.67-1.65(d,6H)。
合成例2：化合物2的合成
步骤1：将356.5g(2mol)固体3,4,5,6-辛四醇加入到5L三口瓶中，开启搅拌，向三口瓶中滴加523g(4.4mol)氯化亚砜，滴加过程中控制温度在15℃左右，滴加完毕后于45℃下保温反应4h，反应液析出大量糊状固体，冷却后缓慢滴加入去离子水1L，将反应体系快速搅拌打散，过滤得到的固体用去离子水多次打浆洗涤至pH中性，滤饼60℃减压烘干，得到中间产物2。
步骤2：向3L三口瓶中加入216.2g(0.8mol)中间产物2，加入乙腈1000mL加入80mg三水合三氯化钌催化剂，氮气置换体系后，将体系降温至20℃，开启搅拌，1h内滴入2000g 20％次氯酸钠水溶液，控制反应温度10-20℃；滴加完毕，10-20℃搅拌10min，分液，使用亚硫酸钠水溶液将有机相淬灭至淀粉碘化钾试纸不变蓝；再次分液，有机层浓缩，乙腈结晶，得到化合物2。
合成例3：化合物3的合成
步骤1：将328.4g(2mol)固体2,3,4,5-庚四醇加入到5L三口瓶中，开启搅拌，向三口瓶中滴加523g(4.4mol)氯化亚砜，滴加过程中控制温度在15℃左右，滴加完毕后于45℃下保温反应4h，反应液析出大量糊状固体，冷却后缓慢滴加入去离子水1L，将反应体系快速搅拌打散，过滤得到的固体用去离子水多次打浆洗涤至pH中性，滤饼60℃减压烘干，得到中间产物3。
步骤2：向3L三口瓶中加入205g(0.8mol)中间产物3，加入乙腈1000mL，搅拌至 固体全溶，加入80mg三水合三氯化钌催化剂，氮气置换体系后，将体系降温至20℃，开启搅拌，1h内滴入2000g 20％次氯酸钠水溶液，控制反应温度10-20℃；滴加完毕，10-20℃搅拌10min，分液，使用亚硫酸钠水溶液将有机相淬灭至淀粉碘化钾试纸不变蓝；再次分液，有机层浓缩，乙腈结晶，得到化合物3(163.1g，产率82.8％)。
另外，下列化合物的合成方法参考合成例1，采用表2中对应底物替换1,6二脱氧半乳糖醇。
表2
合成例4：化合物5的合成
步骤1：将392.4g(2mol)固体1,2,3,4,5.6-庚六醇加入到5L三口瓶中，开启搅拌，向三口瓶中滴加784.5g(6.6mol)氯化亚砜，滴加过程中控制温度在15℃左右，滴加完毕后于45℃下保温反应4h，反应液析出大量糊状固体，冷却后缓慢滴加入去离子水1L，将反应体系快速搅拌打散，过滤得到的固体用去离子水多次打浆洗涤至pH中性，滤饼60℃减压烘干，得到中间产物4。
步骤2：向4L三口瓶中加入140g(0.4mol)中间产物4，加入乙腈1000mL，加入110mg三水合三氯化钌催化剂，氮气置换体系后，将体系降温至20℃，开启搅拌，1h内滴入1500g 20％次氯酸钠水溶液，控制反应温度10-20℃；滴加完毕，10-20℃搅拌 10min，分液，使用亚硫酸钠水溶液将有机相淬灭至淀粉碘化钾试纸不变蓝；再次分液，有机层浓缩，乙腈结晶，得到化合物5。
另外，下列化合物的合成方法参考合成例4，采用表3中对应底物替换1,2,3,4,5.6-庚六醇。
表3
合成例5：化合物7的合成
步骤1：将484g(2mol)固体辛糖醇加入到5L三口瓶中，开启搅拌，向三口瓶中滴加1046g(8.8mol)氯化亚砜，滴加过程中控制温度在15℃左右，滴加完毕后于45℃下保温反应4h，反应液析出大量糊状固体，冷却后缓慢滴加入去离子水1L，将反应体系快速搅拌打散，过滤得到的固体用去离子水多次打浆洗涤至pH中性，滤饼60℃减压烘干，得到中间产物5。
步骤2：向4L三口瓶中加入183.2g(0.4mol)中间产物5，加入乙腈1000mL，加入150mg三水合三氯化钌催化剂，氮气置换体系后，将体系降温至20℃，开启搅拌，1h内滴入2000g 20％次氯酸钠水溶液，控制反应温度10-20℃；滴加完毕，10-20℃搅拌10min，分液，使用亚硫酸钠水溶液将有机相淬灭至淀粉碘化钾试纸不变蓝；再次分液，有机层浓缩，乙腈结晶，得到化合物7。
实施例1
电解液组成：化合物1作为添加剂，其在电解液中的质量含量为2％；采用LiPF6作为电解质，其在电解液中的含量为10％，采用体积比为3:7的EC+EMC(碳酸亚乙酯+碳酸甲乙酯)的混合物作为溶剂。
正极极片制备：
正极活性材料LiNi0.5Co0.3Mn0.2O2(平均粒径Dv50为8μm)、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按重量比为97:1:2溶于溶剂N-甲基吡咯烷酮(NMP)中，充分搅拌混合均匀后得到正极浆料；之后将正极浆料均匀涂覆于正极集流体上，再经过烘干、冷压、分切，得到正极极片。正极极片的压实密度为3.45g/cm3。
正极活性材料的Dv50指正极活性材料累计体积百分数达到50％时所对应的粒径，即体积分布中位粒径，单位为μm。Dv50可以用本领域公知的仪器及方法进行测定。例如采用英国马尔文仪器有限公司的激光衍射粒度分布测量仪(Malvern Mastersizer 3000)进行测试，依据粒度分布激光衍射法GB/T19077-2016，测量出粒径分布，得到Dv50。
正极极片的压实密度可以利用压实密度仪测定。
负极极片制备：
将负极活性材料石墨、导电剂碳黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC-Na)按照重量比为90:4:4:2溶于溶剂去离子水中，混合均匀后制备成负极浆料；将负极浆料一次或多次均匀涂覆在负极集流体铜箔上，经过烘干、冷压、分切得到负极极片。
隔膜：
以常规聚丙烯膜作为隔离膜。
锂离子电池组装：
将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于电池壳体中，干燥后注入电解液，再经过化成、静置等工艺制得锂离子电池。
实施例2-1
采用化合物2替换化合物1，其余同实施例1。
实施例2-2
采用化合物3替换化合物1，其余同实施例1。
实施例2-3
采用化合物4替换化合物1，其余同实施例1。
实施例2-4
采用化合物5替换化合物1，其余同实施例1。
实施例2-5
采用化合物6替换化合物1，其余同实施例1。
实施例2-6
采用化合物7替换化合物1，其余同实施例1。
实施例3-1
将化合物1的质量含量调整为0.001％，其余同实施例1。
实施例3-2
将化合物1的质量含量调整为0.01％，其余同实施例1.
实施例3-3
将化合物1的质量含量调整为3％，其余同实施例1.
实施例3-4
将化合物1的质量含量调整为8％，其余同实施例1.
实施例3-5
将化合物1的质量含量调整为15％，其余同实施例1.
实施例4-1
采用正极活性材料LiNi0.6Co0.2Mn0.2O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2，其余同实施例1。
实施例4-2
采用正极活性材料LiNi0.8Co0.1Mn0.1O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2，其余同实施例1。
实施例4-3
采用正极活性材料LiNi0.9Co0.055Mn0.055O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2， 其余同实施例1。
实施例5-1
正极活性材料的平均粒径调整为0.5μm，其余同实施例1。
实施例5-2
正极活性材料的平均粒径调整为1.5μm，其余同实施例1。
实施例5-3
正极活性材料的平均粒径调整为5μm，其余同实施例1。
实施例5-4
正极活性材料的平均粒径调整为18μm，其余同实施例1。
实施例5-5
正极活性材料的平均粒径调整为22μm，其余同实施例1。
实施例5-6
正极活性材料的平均粒径调整为30μm，其余同实施例1。
对比例1-1
不添加化合物1，其余同实施例1。
对比例1-2
采用化合物8替换化合物1，其余同实施例1。
对比例1-3
不添加化合物1，同时采用正极活性材料LiNi0.6Co0.2Mn0.2O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2，其余同实施例1。
对比例1-4
不添加化合物1，同时采用正极活性材料LiNi0.8Co0.1Mn0.1O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2，其余同实施例1。
对比例1-5
不添加化合物1，同时采用正极活性材料LiNi0.9Co0.055Mn0.055O2替换正极活性材料LiNi0.5Co0.3Mn0.2O2，其余同实施例1。
1)45℃循环性能测试
在45℃下，将锂离子电池以1C恒流充电至电压4.25V，然后以4.25V恒压充电至电流≤0.05C，静置5min之后，将锂离子电池以1C恒流放电至电压为2.8V，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。将锂离子电池按上述方法进行多次循环充放电测试，直至锂离子二次电池的放电容量衰减至80％，记录锂离子电池的循环次数。
电池45℃循环N次后的容量保持率(％)＝(电池第N次循环的放电容量/电池首次循环的放电容量)×100％。
2)45℃循环后DCR增长率
在室温下，锂离子电池以1C恒流充电到4.25V，随后以4.25V的电压恒压充电至电流为0.05C。电池满充后，静置5min，1C放电30min(电芯带电量为50％SOC)，然后静置5min。调节温度为25℃，静置1h，记录此时电芯的电压V1。以4C放电30s，记录脉冲放电后的电压V2，则电芯50％SOC放电30s时的DCR＝(V1-V2)/I，I＝4C。电池45℃循环至80％后的DCR增长率＝(电池存储循环至80％后的DCR/电池循环前DCR)×100％。
测试结果记录在表4中。
表4

由实施例1和2-1～2-6与对比例1-1和对比例1-2的结果可以看出，环状硫酸酯化合物可以通过在正负极侧成膜，降低正负极界面的成膜阻抗，生成更稳定、阻隔能力更强的无机和有机混合的SEI膜，从而避免电池极化增大，进而减少循环过程中的阻抗增长，对电芯的循环性能有极大的改善。同时，与常规磺酸内酯添加剂相比，本申请使用的添加剂在负极生成的SEI具有更高的稳定性和更好的效果。
由实施例3-1～3-5的结果可以看出，过少的环状硫酸酯化合物的改善作用并不明显，过多的环状硫酸酯化合物可能会使正负极生成的膜较厚，导致电芯的极化增大，在一定程度上会影响电芯的循环性能。当本申请使用的环状磺酸酯添加剂在电解液中的质量占比处于上述优选范围时，电芯能具有较好的性能。
由实施例4-1～4-3和对比例1-3～1-5的结果可以看出，通过在不同金属含量的三元体系中添加环状硫酸酯化合物，如LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.9Co0.55Mn0.55O2，均能起到改善锂离子循环阻抗增长和循环性能的作用。
由实施例5-1～5-6的结果可以看出，当正极活性材料的Dv50太小，造成其BET比表面积过大，会使电极与电解液具有更多的接触，造成界面副反应更剧烈，增大电芯循环阻抗。而过高的Dv50会使得颗粒过大，存在较多空隙，使得极片压密过低。因此，正极活性材料Dv50在上述优选范围时，可以在保证高压密的情况下，减少正极侧 的极化，保证较好的电池性能。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (8)

  1. 一种二次电池，包括正极极片和非水电解液，其中，所述非水电解液包括添加剂，所述添加剂包括具有通式(I)所示结构的环状硫酸酯化合物，
    其中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种，
    R5和R6各自独立地选自具有所述通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6酯基、氰基和磺酸基中的任意一种；
    R1和R2不同时为氢原子且R3和R4不同时为氢原子；
    所述正极极片包括含有正极活性材料的正极材料层，所述正极活性材料包含三元正极材料，所述三元正极材料为镍钴锰三元材料，其分子式为Li1+a[NixCoyMnzM1bM2c]O2-dNd，其中M1和M2元素独立地选自Al、Zr、Ti、Mg、Zn、B、Ca、Ce、Te、Fe中的至少一种，N元素选自F、Cl、S中的至少一种，其中0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，-0.1＜a＜0.2，0≤b＜0.3，0≤c＜0.3，0≤d＜0.2，0≤b+c＜0.3，x+y+z+b＝1；
    所述正极极片的压实密度大于3.1cm3。
  2. 根据权利要求1所述的二次电池，所述添加剂中，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的 任意一种，
    R5和R6各自独立地选自氢原子、卤素原子、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C2-C3烯基、C2-C3酯基、氰基和磺酸基中的任意一种；
    可选地，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、卤素原子、C1-C3的烷基和氰基中的任意一种；
    可选地，R5和R6各自独立地选自氢原子、C1-C3的烷基中的任意一种；
    可选地，R1、R2、R3和R4各自独立地选自具有通式(Ⅱ)所示结构的基团、氢原子、F原子、Cl原子、Br原子、甲基、乙基、丙基、异丙基和氰基中的任意一种；
    可选地，R5和R6各自独立地选自氢原子、甲基、乙基、丙基和异丙基中的任意一种；
    可选地，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
    其中，X为F原子、Cl原子或Br原子；
    可选地，所述通式(Ⅱ)所示结构的基团选自以下基团中的任意一种:
  3. 根据权利要求1或2所述的二次电池，所述添加剂中，所述环状硫酸酯化合物选自如下化合物中的任意一种或多种：
  4. 根据权利要求1至3中任一项所述的二次电池，所述非水电解液中所述环状硫酸酯化合物的质量含量为W1，其中0.005％≤W1≤10％，可选地0.05％≤W1≤5％。
  5. 根据权利要求1至4中任一项所述的二次电池，所述三元材料的分子式为Li[NixCoyMnz]O2，其中，0.5≤x＜1，0＜y≤0.3，0≤z≤0.25，x+y+z＝1；
    可选地，所述三元材料包括但不限于LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2和LiNi0.9Co0.055Mn0.055O2。
  6. 根据权利要求1至5中任一项所述的二次电池，所述正极极片的压实密度为3.3～4.1g/cm3，可选地为3.4～3.8g/cm3。
  7. 根据权利要求1至6中任一项所述的二次电池，所述正极活性材料的平均粒径Dv50为1～25μm；可选地，2μm≤Dv50≤20μm，可选地2μm≤Dv50≤15μm。
  8. 一种用电装置，包括二次电池，其中，所述二次电池包括权利要求1-7任一项所述的二次电池。
PCT/CN2023/098308 2023-06-05 2023-06-05 一种二次电池及用电装置 Ceased WO2024250144A1 (zh)

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CN106252710A (zh) * 2015-06-08 2016-12-21 Sk新技术株式会社 锂二次电池用电解质和含有其的锂二次电池
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CN109950621A (zh) * 2017-12-21 2019-06-28 深圳新宙邦科技股份有限公司 一种锂离子电池非水电解液及锂离子电池
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CN106252710A (zh) * 2015-06-08 2016-12-21 Sk新技术株式会社 锂二次电池用电解质和含有其的锂二次电池
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