WO2024011350A1 - 复合材料及其制备方法、电极、二次电池及用电装置 - Google Patents

复合材料及其制备方法、电极、二次电池及用电装置 Download PDF

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Publication number
WO2024011350A1
WO2024011350A1 PCT/CN2022/104890 CN2022104890W WO2024011350A1 WO 2024011350 A1 WO2024011350 A1 WO 2024011350A1 CN 2022104890 W CN2022104890 W CN 2022104890W WO 2024011350 A1 WO2024011350 A1 WO 2024011350A1
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Prior art keywords
coupling agent
dielectric material
binder
composite material
particles
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PCT/CN2022/104890
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English (en)
French (fr)
Inventor
白文龙
吴益扬
叶永煌
游兴艳
武宝珍
吴凯
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN202280005932.8A priority Critical patent/CN116802835B/zh
Priority to JP2024568081A priority patent/JP2025516025A/ja
Priority to CN202411294608.XA priority patent/CN118943342B/zh
Priority to EP22950482.4A priority patent/EP4510222A4/en
Priority to KR1020247038016A priority patent/KR20250002523A/ko
Priority to PCT/CN2022/104890 priority patent/WO2024011350A1/zh
Publication of WO2024011350A1 publication Critical patent/WO2024011350A1/zh
Priority to US18/981,699 priority patent/US20250118763A1/en
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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 composite material and its preparation method, electrode, secondary battery and electrical device.
  • secondary batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields.
  • energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields.
  • secondary batteries have achieved great development, higher requirements have been placed on their energy density, cycle performance, etc.
  • this application provides a new composite material and its preparation method, electrode, secondary battery and power device, which are described separately below.
  • the present application provides a composite material including:
  • the surface of the dielectric material particles is covered with a coupling agent, and the coupling agent bridges the dielectric material particles and the binder.
  • the dielectric material particles in the composite material of the present application are bridged to the binder resin through a coupling agent, which can bring the following beneficial effects:
  • the dielectric material particles are evenly dispersed in the electrode slurry and will not all settle at the bottom of the slurry;
  • the dielectric material particles can be bonded to the surface of the negative active material through the binder, and are close to the surface of the negative active material, giving full play to the modification effect;
  • lithium-ion batteries due to the embedding of lithium ions in the negative active material of lithium-ion batteries during the fast charging process, the difference in the desolvation rate of solvated lithium at the SEI film interface will lead to a wider concentration gradient distribution. Between the SEI film and the negative electrode, The enrichment of lithium ions at the interface will lead to excessive local lithium content. When the enrichment of lithium ions exceeds the insertion amount of lithium ions, lithium ions will combine with electrons and cause lithium dendrites locally in the negative electrode. Due to the conductivity of lithium dendrites, The resistance is much higher than that of the negative electrode piece, so subsequent lithium ions will preferentially gather at the lithium dendrite ends, causing macroscopic lithium precipitation.
  • High dielectric constant materials have a dielectric constant similar to that of the electrolyte, which is beneficial to reducing the desolvation barrier, improving the desolvation level of lithium, and improving fast charging performance. This material is affected by the electric field and will generate a counter electric field.
  • the thin SEI film produced at the three-phase interface of dielectric constant material, graphite or silicon, and solvent reduces the loss of active lithium and shortens the migration path of lithium ions in the SEI film, thereby improving fast charging performance and reducing electrolyte consumption.
  • the composite material of this application is used in the negative electrode of secondary batteries, and the secondary batteries can show one or more of the following improved properties: increased specific capacity, increased first-cycle Coulombic efficiency, and improved fast-charge cycle life.
  • the negative active material will expand/contract in volume during the charge and discharge process. During this process, because the dielectric material particles are bridged on the binder resin, the dielectric material particles will not expand/shrink with the negative active material. And when it falls off, it will not lose contact with the negative active material. The dielectric material particles can maintain stable contact with the negative active material during battery operation, and thus can stably exert a modification effect.
  • the binder bonds the dielectric material particles to the negative active material.
  • the dielectric material particles have a relative dielectric constant of 80 to 200. Based on this solution, the relative dielectric constants of the dielectric material particles and the electrolyte are relatively close, resulting in better fast charging performance.
  • the dielectric material is selected from one or more of the following: barium titanate, lead titanate, lithium niobate, lead zirconate titanate, lead metaniobate, barium lithium lead niobate.
  • the binder is an organic binder.
  • the binder is selected from one or more of the following: polyacrylic acid (PAA), styrene-butadiene rubber (SBR), polyamide-imide (PAI), polyvinyl alcohol (PVA) , polyethyleneimine (PEI), polyimide binder (PI), polytert-butyl acrylate-triethoxyvinylsilane (TBATEVS).
  • PAA polyacrylic acid
  • SBR styrene-butadiene rubber
  • PAI polyamide-imide
  • PVA polyvinyl alcohol
  • PEI polyethyleneimine
  • PEI polyimide binder
  • TBATEVS polytert-butyl acrylate-triethoxyvinylsilane
  • the coupling agent is selected from one or more of the following: silane coupling agent, titanate coupling agent.
  • the coupling agent is selected from the group consisting of silane coupling agent KH590, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH792, silane coupling agent DL602, silane coupling agent One or more of the coupling agent DL171, chelating 100 titanate coupling agent, and chelating 200 titanate coupling agent.
  • the coupling agent is connected to the dielectric material through a first terminal functional group, and the first terminal functional group includes -O-.
  • the coupling agent is connected to the binder through a second terminal functional group, and the second terminal functional group includes -S-.
  • the coupling agent is connected to the dielectric material through a first terminal functional group, and the first terminal functional group includes -Si-O-.
  • the coupling agent is connected to the binder through a second terminal functional group, and the second terminal functional group includes -C-S-.
  • the binder has a number average molecular weight of 1 million to 2 million.
  • the dielectric material particles are zero-dimensional particles.
  • the dielectric material particles are tetragonal barium titanate particles.
  • the dielectric material particles have a volume median diameter of 50 nm to 200 nm. Based on this, the dielectric material particles and the negative electrode active material can be well combined, and the dielectric material particles are not easily detached from the surface of the negative electrode active material.
  • the negative active material has a volume median particle size of 4-10 ⁇ m. Based on this, the dielectric material can adhere well to the surface of the negative active material and is not easy to fall off.
  • the ratio of the volume median diameter of the negative active material to the dielectric material particles is 200:1 to 20:1. Based on this, the dielectric material easily adheres to the surface of the negative active material and is not easy to fall off.
  • the mass ratio of the dielectric material to the binder is 0.1:100 ⁇ 1:100.
  • this application provides a method for preparing a composite material, where the composite material is the composite material described in any one of the above;
  • the preparation method includes:
  • the coupling agent on the dielectric material particles contains thiol end groups
  • the binder contains alkenyl end groups
  • the coupling agent and the binder Connection via thiol-alkenyl click chemistry contains thiol end groups
  • the thiol-alkenyl click chemistry reaction is performed under the action of a photoinitiator and ultraviolet light.
  • an electrode is provided, containing the composite material according to any one of the above.
  • the present application provides a secondary battery including the electrode described in any one of the above.
  • the present application provides an electrical device including the above-mentioned secondary battery.
  • Composite materials are used in secondary battery electrodes, and secondary batteries exhibit improved negative electrode capacity
  • the composite material is used in secondary battery electrodes, and the secondary battery exhibits improved first-cycle Coulombic efficiency
  • Figure 1 is a schematic diagram of a styrene-butadiene rubber-barium titanate particle composite according to an embodiment of the present application.
  • Figure 2 is an infrared spectrum chart of a styrene-butadiene rubber-barium titanate particle composite, styrene-butadiene rubber, and barium titanate particles according to an embodiment of the present application.
  • Figure 3 is a schematic diagram of a composite material according to an embodiment of the present application.
  • Figure 4 is a schematic diagram of an adhesive force test according to an embodiment of the present application.
  • FIG. 5 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 6 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 5 .
  • FIG. 7 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 8 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 9 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 8 .
  • FIG. 10 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges as disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may 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, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • 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.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: 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).
  • Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can be recharged to activate active materials and continue to be used after the battery is discharged.
  • a secondary battery normally includes a positive electrode plate, a negative electrode plate, a separator and an electrolyte.
  • active ions such as lithium ions
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows active ions to pass through.
  • the electrolyte is between the positive electrode piece and the negative electrode piece and mainly plays the role of conducting active ions.
  • the present application provides a composite material including:
  • the surface of the dielectric material particles is covered with a coupling agent, and the coupling agent bridges the dielectric material particles and the binder.
  • the dielectric material particles in the composite material of the present application are bridged to the binder resin through a coupling agent, which can bring the following beneficial effects:
  • the dielectric material particles are evenly dispersed in the electrode slurry and will not all settle at the bottom of the slurry;
  • the dielectric material particles can be bonded to the surface of the negative active material through the binder, and are close to the surface of the negative active material, giving full play to the modification effect;
  • the negative active material will expand/contract in volume during the charge and discharge process. During this process, because the dielectric material particles are bridged on the binder resin, the dielectric material particles will not expand/shrink with the negative active material. And when it falls off, it will not lose contact with the negative active material. The dielectric material particles can maintain stable contact with the negative active material during battery operation, and thus can stably exert a modification effect.
  • the term "bridging" means that one end of the coupling agent is connected to the dielectric material particle and the other end is connected to the adhesive through a chemical bond.
  • connection refers to being connected by a chemical bond, such as by an ionic or covalent bond.
  • the coupling agent is chemically bonded to the dielectric material particles.
  • the coupling agent is chemically bonded to the binder.
  • Coupler refers to a substance capable of coupling to both dielectric materials and adhesives, respectively.
  • a “coupling agent” can have two functional groups with different properties. For example, one is an inorganic-friendly functional group that easily reacts chemically with the surface of inorganic substances; for example, the other is an organic-philic agent that can chemically react with synthetic resins or other polymers. React, physically entangle, or form hydrogen bonds dissolved in it.
  • the binder bonds the dielectric material particles to the negative active material.
  • the dielectric material particles have a relative dielectric constant of 80 to 200 (eg, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200).
  • the dielectric material is selected from one or more of the following: barium titanate, lead titanate, lithium niobate, lead zirconate titanate, lead metaniobate, barium lithium lead niobate.
  • the general chemical formula of lead zirconate titanate is Pb x Zr 1-x TiO 3 , 0 ⁇ x ⁇ 1.
  • the general chemical formula of barium lithium lead niobate is (Pb x Ba 1-x ) 4 Li 2 Nb 10 O 30 , 0 ⁇ x ⁇ 1.
  • the binder is an organic binder.
  • the binder has one or more (such as one, two or three) selected from the monomer units represented by Formula 1, Formula 2, and Formula 3;
  • the binder is selected from one or more of the following: polyacrylic acid (PAA), styrene-butadiene rubber (SBR), polyamide-imide (PAI), polyvinyl alcohol (PVA) , polyethyleneimine (PEI), polyimide binder (PI), polytert-butyl acrylate-triethoxyvinylsilane (TBATEVS).
  • PAA polyacrylic acid
  • SBR styrene-butadiene rubber
  • PAI polyamide-imide
  • PVA polyvinyl alcohol
  • PEI polyethyleneimine
  • PEI polyimide binder
  • TBATEVS polytert-butyl acrylate-triethoxyvinylsilane
  • the coupling agent is selected from one or more of the following: silane coupling agent, titanate coupling agent.
  • the coupling agent is selected from the group consisting of silane coupling agent KH590, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH792, silane coupling agent DL602 , one or more of silane coupling agent DL171, chelating 100 titanate coupling agent, and chelating 200 titanate coupling agent.
  • the coupling agent is a silane coupling agent with the general formula RSiX3, in which R represents groups such as amino, mercapto, vinyl, epoxy, cyano and methacryloyloxy, These groups have strong reactivity with different matrix resins, and X represents an alkoxy group that can be hydrolyzed (such as methoxy, ethoxy, etc.).
  • the silane coupling agent is one or more of KH550, KH560, KH590, KH570, KH792, DL602, and DL171.
  • the coupling agent is a chelating titanate coupling agent. Specifically, it can be one or more of chelation type 100 and type 200.
  • the chelating 100 type is a titanate coupling agent containing an oxyacetic acid chelating group
  • the chelating 200 type is a titanate coupling agent containing an ethylene glycol chelating agent.
  • the chelating 100-type titanate coupling agent is, for example, di(octyl pyrophosphate) glycolate titanate CTDPP-138S (KR-138S).
  • the chelating 200 titanate coupling agent is, for example, di(dioctyl phosphate) ethylene glycol titanate ETDOP-212S (KR-212S).
  • the coupling agent is selected from the group consisting of silane coupling agent KH590, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH792, silane coupling agent DL602, silane coupling agent One or more of the coupling agent DL171, chelating 100 titanate coupling agent, and chelating 200 titanate coupling agent.
  • the coupling agent is connected to the dielectric material through a first terminal functional group, and the first terminal functional group includes -O-.
  • the coupling agent is connected to the binder through a second terminal functional group, and the second terminal functional group includes -S-.
  • the coupling agent is connected to the dielectric material through a first terminal functional group, and the first terminal functional group includes -Si-O-.
  • the coupling agent is connected to the binder through a second terminal functional group, and the second terminal functional group includes -C-S-.
  • the binder has a number average molecular weight of 1 million to 2 million, such as 1.3 million to 1.7 million, such as 1.5 million.
  • the term "number average molecular weight” refers to the common arithmetic mean of the molecular weights of individual polymers.
  • the dielectric material particles are zero-dimensional particles.
  • Zero-dimensional materials refer to point-like materials that are in the nanoscale range (1-100nm, such as 1-50nm, such as 1-10nm) in three dimensions.
  • the dielectric material particles are tetragonal barium titanate particles.
  • the dielectric material particles have a volume median diameter of 50 nm to 200 nm, such as 50 nm to 100 nm, 100 nm to 150 nm, 150 nm to 200 nm.
  • the advantage of having the volume median particle size of the dielectric material particles within the above range is that they are easily mixed with negative active materials such as graphite and are not easy to fall off from the surface of the graphite.
  • volume median particle size Dv50 refers to the particle size corresponding to 50% of the volume with respect to the cumulative particle distribution ordered from smallest size to largest size.
  • the "volume median particle size” can be observed and measured using a scanning electron microscope or measured using a laser diffraction method.
  • the negative active material has a volume median particle size of 4 to 10 ⁇ m.
  • the ratio of the volume median diameter of the negative active material to the dielectric material particles is 200:1 to 20:1, such as 200:1 to 150:1, 150:1 to 100: 1. 100:1 ⁇ 50:1, 50:1 ⁇ 20:1.
  • the advantage of having the ratio of the volume median diameter of the negative active material to the dielectric material particles within the above range is that the dielectric material is easily attached to the graphite surface and is not easy to fall off.
  • the mass ratio of the dielectric material to the binder is 0.1:100-1:100 (for example, 0.1:100-0.2:100, 0.2:100-0.3:100, 0.3:100- 0.4:100, 0.4:100-0.5:100, 0.5:100-0.6:100, 0.6:100-0.7:100, 0.7:100-0.8:100, 0.8:100-0.9:100, 0.9:100-1: 100).
  • the term “zero dimension” refers to a state of particles in which the particle size is extremely small and has essentially no length, such as a nanoparticle state of particles.
  • the term “three-dimensional” refers to a bulk state with volume
  • the term “two-dimensional” refers to a thin film state
  • the term “one-dimensional” refers to a nanotube state.
  • the term "zero dimension" may refer to particles with a diameter of 1 nm to about 100 nm (1-10 nm, 10-20 nm, 20-30 nm, 30-40 nm, 40-50 nm, 50-60 nm, 60-70 nm, 70-80nm, 80-90nm, 90-100nm).
  • the term "tetragonal” refers to a crystal structure having a unit cell containing three axes, two of which are of the same length and at right angles to each other, and a third axis that is perpendicular to the other two axes.
  • the term "relative permittivity” refers to the relative permittivity ( ⁇ r ), which is the relative permittivity of the material divided by the relative permittivity of vacuum ( ⁇ 0 ).
  • the dielectric constant refers to the dielectric constant at room temperature (25 ⁇ 5°C), which has a meaning known in the art and can be tested using instruments and methods known in the art.
  • C represents the capacitance, in Farad (F);
  • d represents the sample thickness, in cm;
  • A represents the sample area, in cm 2 ;
  • the test conditions can be 1KHz, 1.0V, 25 ⁇ 5°C.
  • the test standard can be based on GB/T 11297.11-2015.
  • the relative dielectric constant of the present application can be measured by a relative dielectric constant tester.
  • a relative dielectric constant tester For details, refer to GB/T5594.4-1985.
  • the instrument can be the ZJD-C relative dielectric constant of Beijing AVIC Times Instrument Equipment Co., Ltd. Dielectric constant tester.
  • this application provides a method for preparing a composite material, where the composite material is the composite material described in any one of the above;
  • the preparation method includes:
  • the coupling agent on the dielectric material particles contains thiol end groups
  • the binder contains alkenyl end groups
  • the coupling agent and the binder Connection via thiol-alkenyl click chemistry contains thiol end groups
  • the thiol-alkenyl click chemistry reaction is performed under the action of a photoinitiator and ultraviolet light.
  • an electrode is provided, containing the composite material according to any one of the above.
  • the present application provides a secondary battery including the electrode described in any one of the above.
  • the present application provides an electrical device including the above-mentioned secondary battery.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode film layer includes a negative electrode active material, and the negative electrode active material adopts any one of the negative electrode active materials of the present application.
  • the negative electrode current collector has two opposite surfaces in its own 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.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
  • 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 battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative electrode film layer optionally further includes a binder.
  • the binder may be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), At least one of polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer optionally further includes 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 optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • the positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film 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.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • Composite current collectors can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, 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 of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/5 n 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon.
  • At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene tripolymer. At least one of a meta-copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • 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 by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the type of electrolyte in this application can be selected according to needs.
  • the electrolyte can be liquid, gel, or completely solid.
  • the electrolyte is liquid and includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte optionally also includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the secondary battery further includes a separator film.
  • a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • 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 film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and 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 bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 5 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into 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 can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 7 shows the 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 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric 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, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Figure 10 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • SBR-BTO styrene-butadiene rubber-barium titanate particle composite
  • at least part of the surface of the barium titanate particles is covered with ⁇ -mercaptopropyltrimethoxysilane, and ⁇ -mercaptopropyltrimethoxysilane bridges the titanium Barium acid particles and styrene-butadiene rubber.
  • Figure 1 shows a schematic diagram of a styrene-butadiene rubber-barium titanate particle composite. As shown in the figure, at least a portion of the surface of the dielectric material particles 101 is covered with a coupling agent 102. The coupling agent 102 bridges the dielectric material particles 101 and Binder 103.
  • Figure 2 shows the infrared spectrum of barium titanate particles grafted with styrene-butadiene rubber (BTO-SBR). It can be seen from the figure that the infrared spectra of Si-C and Si-O are observed at wave numbers of 1200 and 1100 cm -1 The absorption peak shows that ⁇ -mercaptopropyltrimethoxysilane bridges the barium titanate particles and styrene-butadiene rubber together.
  • BTO-SBR barium titanate particles grafted with styrene-butadiene rubber
  • Example 1 An artificial graphite, conductive agent (acetylene black), barium titanate particles grafted with styrene-butadiene rubber (SBR-BTO for short) and dispersant (sodium carboxymethyl cellulose, CMC for short) according to the weight ratio.
  • the mixture was mixed at 97:1:1:1 to obtain the composite material of Example 1.
  • the composite material is subsequently used to prepare negative electrode slurry for lithium-ion batteries.
  • the ratio of the volume median particle diameter of the negative active material to the dielectric material particles is controlled to 50:1, that is, the volume average particle diameter of the negative active material in Example 1 is 2.5 ⁇ m.
  • Figure 3 shows a schematic diagram of a composite material.
  • the composite material includes a negative active material 100, dielectric material particles 101 and a binder 103.
  • the binder 103 binds the dielectric material particles 101 to the negative active material 100.
  • the above solution of the present application prepares a composite material with a "chain spherical structure". By connecting the binder 103 and the dielectric material particles 101 through sulfhydryl groups, the hydroxyl groups on the surface of the binder 103 can be connected with the negative electrode.
  • the surface of the active material 100 is connected through hydrogen bonds, so that the dielectric material particles 101 can be evenly distributed on the surface of the negative active material 100.
  • this composite material is connected point-to-face at the negative terminal, which improves the performance of high dielectric constant materials. Utilization, it can give full play to its desolvation effect and thin SEI performance without blocking the migration channel of lithium ions.
  • the schematic diagram shown in Figure 3 is only a schematic diagram for the convenience of showing the connection relationship, and the dimensional relationship shown in Figure 3 does not represent the real dimensional relationship.
  • Example 1 The ratio of raw material components (artificial graphite, acetylene black, SBR-BTO, CMC) for preparing composite materials, the ratio of SBR to BTO in SBR-BTO, the volume median particle size Dv50 and relative dielectric of barium titanate Constant, the number average molecular weight of SBR is shown in Table 1.
  • Example 1 The difference between Examples 2 to 15 and Example 1 lies in the different raw material parameters or process parameters for preparing composite materials. The specific parameter differences are shown in Table 1.
  • Example 11 lead titanate (PTO) is used to replace the barium titanate (BTO) in Example 1.
  • Example 12 lithium niobate (PPLN) is used to replace the barium titanate (BTO) in Example 1.
  • PPLN lithium niobate
  • BTO barium titanate
  • Example 13 lead zirconate titanate (PZT) is used to replace the barium titanate (BTO) in Example 1.
  • Example 14 a chelating 100 titanate coupling agent (CTDPP-138S) is used to bridge the dielectric material particles and the binder to replace ⁇ -mercaptopropyltrimethoxysilane in Example 1.
  • CTDPP-138S a chelating 100 titanate coupling agent
  • Example 15 a chelating 200 titanate coupling agent (ETDOP-212S) is used to bridge the dielectric material particles and the binder to replace ⁇ -mercaptopropyltrimethoxysilane in Example 1.
  • ETDOP-212S a chelating 200 titanate coupling agent
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the composite material formula is different.
  • the composite material of Comparative Example 1 does not contain dielectric material particles BTO.
  • the formula of the composite material in Comparative Example 1 is as follows: negative active material (artificial graphite), conductive agent (acetylene black), styrene-butadiene rubber and dispersant (sodium carboxymethyl cellulose) in a weight ratio of 97:1:1:1 mix.
  • the difference between Comparative Example 2 and Example 1 is that the composite material formula is different.
  • the composite material of Comparative Example 2 does not contain dielectric material particles BTO.
  • the formula of the composite material of Comparative Example 2 is as follows: negative active material (artificial graphite), conductive agent (acetylene black), styrene-butadiene rubber, dielectric material particles (barium titanate particles) and dispersant (sodium carboxymethyl cellulose) Mix according to the weight ratio of 97:1:0.95::0.05:1.
  • the positive active material lithium nickel cobalt manganate (NCM523, LiNi 0.5 Co 0.2 Mn 0.3 O 2 ), polyvinylidene fluoride PVDF, and conductive agent acetylene black SP are used in a weight ratio of 98:1:1 Mix, add N-methylpyrrolidone (NMP) as solvent, and stir the slurry under vacuum until uniform.
  • NMP N-methylpyrrolidone
  • the obtained slurry is coated on a 13 ⁇ m aluminum foil with a doctor blade, then dried at 140°C, cold pressed, and cut to obtain a positive electrode sheet with a positive electrode film layer.
  • the surface density of the positive electrode film layer is 13.7 mg/cm. 2 .
  • Electrolyte In an argon atmosphere glove box (H 2 O ⁇ 0.1ppm, O 2 ⁇ 0.1ppm), mix the organic solvent ethylene carbonate (EC)/ethyl methyl carbonate (EMC) according to the volume ratio of 3: 7. Mix evenly, add 12.5% by weight (based on the total weight of ethylene carbonate/ethyl methyl carbonate solvent) LiPF 6 , dissolve it in the above organic solvent, stir evenly, and obtain an electrolyte. The relative dielectric constant of this electrolyte is 90.
  • Isolation film Use a commercially available PP-PE copolymer microporous film with a thickness of 20 ⁇ m and an average pore diameter of 80 nm (from Zhuogao Electronic Technology Co., Ltd., model 20).
  • Adhesion testing was performed using the peel test method.
  • (a) to (d) of FIG. 4 show a flow chart of the peel test.
  • a steel plate 510 is first provided, with dimensions of 30 mm wide and 100 mm long.
  • a piece of double-sided tape 520 is then provided.
  • the size of the double-sided tape 520 is 20 mm wide ⁇ 30 mm long.
  • the double-sided tape 520 is attached to the steel plate 510.
  • One wide edge of the double-sided tape 520 is Aligned with one wide edge of steel plate 510.
  • a pole piece 530 to be tested is then provided.
  • the size of the pole piece 530 to be tested is 20 mm wide by 180 mm long. Cover the pole piece 530 to be tested on the double-sided tape 520 (align both sides), with the coated surface of the pole piece 530 facing the double-sided tape 520 . Since the length of the pole piece 530 to be tested is greater than the length of the double-sided tape 520, some areas of the pole piece 520 to be tested are not bonded to the double-sided tape. As shown in (d) of Figure 4, fix the steel plate 510 on the base of the tensile testing machine, use a clamp to clamp the end of the pole piece 530 to be tested that is not bonded to the double-sided tape, and then move the clamp to the other end.
  • the direction of the stretching force is perpendicular to the steel plate 510 and is at a certain distance from the surface of the steel plate 510 .
  • the steel plate moves upward to keep the stretching direction perpendicular to the peeling position of the pole piece.
  • the stretching causes the pole piece 530 to be gradually peeled off from the steel plate.
  • the stretching speed of the clamp is 50mm/min.
  • record the tensile force of the clamp After the tensile force stabilizes, continue to peel off a length of 40mm. The average tensile force under this peeling length is the bonding force (unit N).
  • the kinetic performance of the secondary battery is evaluated through the 25°C 4C charging resistance.
  • Embodiment 2 Normalize the experimental results. Taking the charging resistor resistance value of Embodiment 2 as a reference value of 100, the embodiment is scaled accordingly.
  • the capacity retention performance of secondary batteries is evaluated by fast charging cycle life/number of turns.
  • the lithium-ion batteries prepared in the Examples and Comparative Examples were charged at a 2C rate, discharged at a 1C rate, and subjected to continuous cycle testing in the 3%-97% SOC range until the capacity of the lithium-ion battery was less than 80% of the initial capacity. %, record the number of cycles.
  • the relative dielectric constant of the dielectric material particles and the electrolyte in this application can be measured by a dielectric constant tester.
  • a dielectric constant tester for details, please refer to GB/T5594.4-1985.
  • the instrument can be ZJD-C dielectric from Beijing AVIC Times Instrument Equipment Co., Ltd. Electrical constant tester.
  • the volume average particle diameter Dv50 has a well-known meaning in the art and can be measured using instruments and methods well-known in the art. For example, you can refer to the GB/T 19077-2016 particle size distribution laser diffraction method and use a laser particle size analyzer to conveniently measure it, such as the Mastersizer 2000E laser particle size analyzer of Malvern Instruments Co., Ltd. in the United Kingdom.
  • the negative electrode slurry of Examples 1 to 16 contains the new composite material of the present application, which composite material includes: negative electrode active material (artificial graphite), dielectric material particles (barium titanate particles); and binder resin (styrene-butadiene rubber) ; Wherein, at least part of the surface of the dielectric material particles is covered with a coupling agent ( ⁇ -mercaptopropyltrimethoxysilane), and the coupling agent bridges the dielectric material particles and the binder resin.
  • negative electrode active material artificial graphite
  • dielectric material particles barium titanate particles
  • binder resin styrene-butadiene rubber
  • the dielectric material particles in the composite material of the present application are bridged to the binder resin through a coupling agent, which can bring the following beneficial effects:
  • the dielectric material particles are evenly dispersed in the electrode slurry and will not all settle at the bottom of the slurry;
  • the dielectric material particles can be bonded to the surface of the negative active material through the binder, and are close to the surface of the negative active material, giving full play to the modification effect;
  • the negative active material will expand/contract in volume during the charge and discharge process. During this process, because the dielectric material particles are bridged on the binder resin, the dielectric material particles will not expand/shrink with the negative active material. And when it falls off, it will not lose contact with the negative active material. The dielectric material particles can maintain stable contact with the negative active material during battery operation, and thus can stably exert a modification effect.
  • the battery of this application exhibits one or more of the following properties:

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Abstract

本申请提供一种复合材料，包括：负极活性材料、介电材料颗粒和粘合剂树脂；所述介电材料颗粒的至少一部分表面覆有偶联剂，所述偶联剂桥接所述介电材料颗粒和所述粘合剂树脂。

Description

复合材料及其制备方法、电极、二次电池及用电装置 技术领域
本申请涉及电池技术领域，尤其涉及一种复合材料及其制备方法、电极、二次电池及用电装置。
背景技术
近年来，随着二次电池的应用范围越来越广泛，二次电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于二次电池取得了极大的发展，因此对其能量密度、循环性能等也提出了更高的要求。
锂离子电池工作过程中，在负极存在形成锂枝晶的风险，由于锂枝晶的导电性远高于负极极片，锂离子会优先在锂枝晶端汇集，造成宏观的析锂。宏观的析锂会绕过隔膜，与正极形成微短路，造成诸如存储，自放电，漏电流等问题，甚至会刺穿隔膜，导致短路等严重问题。
发明内容
鉴于上述课题，本申请提供一种新型复合材料及其制备方法、电极、二次电池及用电装置，下面分别描述。
在第一方面，本申请提供一种复合材料，包括：
负极活性材料；
介电材料颗粒；和
粘结剂；
其中，所述介电材料颗粒的至少一部分表面覆有偶联剂，所述偶联剂桥接所述介电材料颗粒和所述粘结剂。
本申请复合材料中的介电材料颗粒通过偶联剂桥接在粘合剂树脂上，能够带来如下的有益效果：
(1)介电材料颗粒在电极浆料中得以分散均匀，不会全部沉降在浆料底部；
(2)介电材料颗粒能够通过粘结剂粘结在负极活性材料的表面，与负极活性材料表面的距离较近，充分发挥改性作用；
以锂离子电池为例，锂离子电池负极活性材料在快速充电过程中由于锂离子的嵌入，溶剂化的锂在SEI膜界面去溶剂化速率差异会导致浓度梯度分布较广，在SEI膜与负极界面处的锂离子富集会导致局部的锂含量过量，由于锂离子富集量超过了锂离子嵌入量的时候，锂离子会结合电子，在负极局部造成锂枝晶，由于锂枝晶的导电性远高于负极极片， 因此会后续的锂离子会优先在锂枝晶端汇集，之后造成宏观的析锂，这些析锂会绕过隔膜，与正极形成微短路，造成诸如存储，自放电，漏电流等问题，甚至会刺穿隔膜，导致短路等严重问题。高介电常数材料，其介电常数与电解液相近，有利于减小去溶剂化壁垒，提升锂的去溶剂化水平，提升快充性能，这种材料受电场的影响，会产生反电场，在介电常数材料，石墨或硅，溶剂三相界面处产生的薄SEI膜，减少活性锂的损耗，同时缩短锂离子在SEI膜的迁移路径，从而可以提升快充性能和减少电解液消耗。
本申请复合材料用于二次电池的负极，二次电池可表现出以下一项或多项改善的性能：提高的比容量、提高的首周库伦效率、改善的快充循环寿命。
(3)负极活性材料在充放电过程中会发生体积膨胀/收缩，在此过程中，由于介电材料颗粒桥接在粘合剂树脂上，介电材料颗粒不会随着负极活性材料膨胀/收缩而脱落，不会与负极活性材料失去接触。介电材料颗粒在电池工作过程中能够与负极活性材料保持稳定的接触，进而能够稳定地发挥改性作用。
在一些实施方案中，所述粘结剂将所述介电材料颗粒粘结在所述负极活性材料上。
在一些实施方案中，所述介电材料颗粒的相对介电常数为80至200。基于此方案，介电材料颗粒与电解液的相对介电常数较为接近，快充性能更佳。
在一些实施方案中，所述介电材料选自以下一种或多种：钛酸钡，钛酸铅，铌酸锂，锆钛酸铅，偏铌酸铅，铌酸铅钡锂。
在一些实施方案中，所述粘结剂是有机粘结剂。
在一些实施方案中，所述粘结剂选自以下中的一种或多种：聚丙烯酸(PAA)、丁苯橡胶(SBR)、聚酰胺酰亚胺(PAI)、聚乙烯醇(PVA)、聚乙烯亚胺(PEI)、聚酰亚胺粘结剂(PI)、聚丙烯酸叔丁酯-三乙氧基乙烯基硅烷(TBATEVS)。
在一些实施方案中，所述偶联剂选自以下一种或多种：硅烷偶联剂、钛酸酯偶联剂。
在一些实施方案中，所述偶联剂选自硅烷偶联剂KH590、硅烷偶联剂KH550，硅烷偶联剂KH560，硅烷偶联剂KH570，硅烷偶联剂KH792，硅烷偶联剂DL602，硅烷偶联剂DL171、螯合100型钛酸酯偶联剂、螯合200型钛酸酯偶联剂中的一种或者多种。
在一些实施方案中，所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-O-。
在一些实施方案中，所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-S-。
在一些实施方案中，所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-Si-O-。
在一些实施方案中，所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-C-S-。
在一些实施方案中，所述粘结剂的数均分子量为100万至200万。
在一些实施方案中，所述介电材料颗粒为零维颗粒。
在一些实施方案中，所述介电材料颗粒为四方晶型的钛酸钡颗粒。
在一些实施方案中，所述介电材料颗粒的体积中值粒径为50nm-200nm。基于此，介电材料颗粒与负极活性材料能够良好地结合，介电材料颗粒不容易从负极活性材料表面脱落。
在一些实施方案中，所述负极活性材料的体积中值粒径为4-10μm。基于此，介电材料能够在负极活性材料表面良好附着，不容易脱落。
在一些实施方案中，所述负极活性材料与所述介电材料颗粒的体积中值粒径的比值为200:1～20:1。基于此，介电材料容易在负极活性材料表面附着，不容易脱落。
在一些实施方案中，所述介电材料与所述粘结剂的质量比为0.1:100～1:100。
在第二方面，本申请提供一种复合材料的制备方法，所述复合材料为以上任一项所述的复合材料；
所述制备方法包括：
(1)对介电材料颗粒进行羟基化处理，获得羟基化的介电材料颗粒；
(2)在所述羟基化的介电材料颗粒上接枝偶联剂，获得接枝有偶联剂的介电材料颗粒；
(3)使介电材料颗粒上接枝的偶联剂与粘结剂通过缩合反应连接；
(4)将上一步产物与负极活性材料混合。
在一些实施方案中，步骤(3)中，所述介电材料颗粒上的偶联剂含有巯基端基，所述粘结剂含有烯基端基，所述偶联剂与所述粘结剂通过巯基-烯基点击化学反应连接。
在一些实施方案中，所述巯基-烯基点击化学反应在光引发剂和紫外光的作用下进行。
在第三方面，提供一种电极，含有上述任一项所述的复合材料。
在第四方面，本申请提供一种二次电池，包括上述任一项所述的电极。
在第五方面，本申请提供一种用电装置，包括上述的二次电池。
有益效果
本申请一个或多个实施方式具有以下一项或多项有益效果：
(1)复合材料用于二次电池电极，二次电池表现出改善的负极容量；
(2)复合材料用于二次电池电极，二次电池表现出改善的首周库伦效率；
(3)复合材料用于二次电池电极，二次电池表现出降低的充电电阻；
(4)复合材料用于二次电池电极，二次电池表现出较长的循环寿命。
附图说明
图1是本申请一实施方式的丁苯橡胶-钛酸钡颗粒复合物的示意图。
图2是本申请一实施方式的丁苯橡胶-钛酸钡颗粒复合物、丁苯橡胶、钛酸钡颗粒的红外光谱图。
图3是本申请一实施方式的复合材料的示意图。
图4是本申请一实施方式的粘结力测试示意图。
图5是本申请一实施方式的二次电池的示意图。
图6是图5所示的本申请一实施方式的二次电池的分解图。
图7是本申请一实施方式的电池模块的示意图。
图8是本申请一实施方式的电池包的示意图。
图9是图8所示的本申请一实施方式的电池包的分解图。
图10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。
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；100负极活性材料；101介电材料颗粒；103粘结剂；510钢板；520双面胶；530待测试极片
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的负极活性材料及其制造方法、正极极片、负极极片、二次电池、电池模块、电池包和装置的实施方式。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]
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。
[复合材料]
在第一方面，本申请提供一种复合材料，包括：
负极活性材料；
介电材料颗粒；和
粘结剂；
其中，所述介电材料颗粒的至少一部分表面覆有偶联剂，所述偶联剂桥接所述介电材料颗粒和所述粘结剂。
本申请复合材料中的介电材料颗粒通过偶联剂桥接在粘合剂树脂上，能够带来如下的有益效果：
(1)介电材料颗粒在电极浆料中得以分散均匀，不会全部沉降在浆料底部；
(2)介电材料颗粒能够通过粘结剂粘结在负极活性材料的表面，与负极活性材料表面的距离较近，充分发挥改性作用；
(3)负极活性材料在充放电过程中会发生体积膨胀/收缩，在此过程中，由于介电材料颗粒桥接在粘合剂树脂上，介电材料颗粒不会随着负极活性材料膨胀/收缩而脱落，不会与负极活性材料失去接触。介电材料颗粒在电池工作过程中能够与负极活性材料保持稳定的接触，进而能够稳定地发挥改性作用。
在一些实施方案中，术语“桥接”是指偶联剂的一端与介电材料颗粒连接，另一端通过化学键与粘结剂连接。
在一些实施方案中，在一些实施方案中，术语“连接”是指通过化学键连接，例如通过离子键或共价键连接。
在一些实施方案中，偶联剂与介电材料颗粒通过化学键键合。
在一些实施方案中，偶联剂与粘结剂通过化学键键合。
术语“偶联剂”指的是能够与介电材料和粘结剂二者分别连接的物质。“偶联剂”可以具有两种不同性质官能团，例如一个是亲无机物的官能团，易与无机物表面起化学反应；例如另一个是亲有机物的剂，能与合成树脂或其它聚合物发生化学反应、物理缠绕或生成氢键溶于其中。
在一些实施方案中，所述粘结剂将所述介电材料颗粒粘结在所述负极活性材料上。
在一些实施方案中，所述介电材料颗粒的相对介电常数为80至200(例如80,90,100,110,120,130,140,150,160,170,180,190或200)。
在一些实施方案中，所述介电材料选自以下一种或多种：钛酸钡，钛酸铅，铌酸锂，锆钛酸铅，偏铌酸铅，铌酸铅钡锂。
在一些实施方案中，锆钛酸铅的化学通式为Pb xZr 1-xTiO 3，0＜x＜1。
在一些实施方案中，铌酸铅钡锂的化学通式为(Pb xBa 1-x) 4Li 2Nb 10O 30，0＜x＜1。
在一些实施方案中，所述粘结剂是有机粘结剂。
在一些实施方案中，所述粘结剂具有选自式1、式2、式3表示的单体单元中的一种或多种(例如一种、两种或三种)；
Figure PCTCN2022104890-appb-000001
Figure PCTCN2022104890-appb-000002
在一些实施方案中，所述粘结剂选自以下中的一种或多种：聚丙烯酸(PAA)、丁苯橡胶(SBR)、聚酰胺酰亚胺(PAI)、聚乙烯醇(PVA)、聚乙烯亚胺(PEI)、聚酰亚胺粘结剂(PI)、聚丙烯酸叔丁酯-三乙氧基乙烯基硅烷(TBATEVS)。
在一些实施方案中，所述偶联剂选自以下一种或多种：硅烷偶联剂、钛酸酯偶联剂。
在一些实施方案中，所述偶联剂选自选自硅烷偶联剂KH590、硅烷偶联剂KH550，硅烷偶联剂KH560，硅烷偶联剂KH570，硅烷偶联剂KH792，硅烷偶联剂DL602，硅烷偶联剂DL171、螯合100型钛酸酯偶联剂、螯合200型钛酸酯偶联剂中的一种或者多种。
在一些实施方案中，所述偶联剂为通式为RSiX3的硅烷偶联剂，式中R代表氨基、巯基、乙烯基、环氧基、氰基及甲基丙烯酰氧基等基团，这些基团和不同的基体树脂均具有较强的反应能力，X代表能够水解的烷氧基(如甲氧基、乙氧基等)。硅烷偶联剂为KH550，KH560，KH590，KH570，KH792，DL602，DL171中的一种或者多种。
在一些实施方案中，所述的偶联剂为螯合型钛酸酯偶联剂。具体可以为螯合100型，200型中的一种或者多种。螯合100型是含有氧乙酸螯合基的钛酸酯偶联剂，螯合200型是含有乙二醇螯合剂的钛酸酯偶联剂。螯合100型钛酸酯偶联剂例如是二(焦磷酸辛酯)羟乙酸钛酸酯CTDPP-138S(KR-138S)。螯合200型钛酸酯偶联剂例如是二(磷酸二辛酯)钛酸乙二(醇)酯ETDOP-212S(KR-212S)。
在一些实施方案中，所述偶联剂选自硅烷偶联剂KH590、硅烷偶联剂KH550，硅烷偶联剂KH560，硅烷偶联剂KH570，硅烷偶联剂KH792，硅烷偶联剂DL602，硅烷偶联剂DL171、螯合100型钛酸酯偶联剂、螯合200型钛酸酯偶联剂中的一种或者多种。
在一些实施方案中，所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-O-。
在一些实施方案中，所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-S-。
在一些实施方案中，所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-Si-O-。
在一些实施方案中，所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-C-S-。
在一些实施方案中，所述粘结剂的数均分子量为100万至200万，例如130万至170万，例如150万。
在一些实施方案中，术语“数均分子量”是指各个聚合物的分子量的普通算术平均值。
在一些实施方案中，所述介电材料颗粒为零维颗粒。零维材料是指在三维均处于纳米尺度范围(1-100nm，例如1-50nm，例如1-10nm)的点状材料。
在一些实施方案中，所述介电材料颗粒为四方晶型的钛酸钡颗粒。
在一些实施方案中，所述介电材料颗粒的体积中值粒径50nm-200nm，例如50nm-100nm，100nm-150nm，150nm-200nm。介电材料颗粒的体积中值粒径在上述范围的优点是容易与石墨等负极活性材料混合且不容易从石墨表面脱落。
在一些实施方案中，术语“体积中值粒径”Dv50指就从最小尺寸到最大尺寸排序的累积颗粒分布而言，对应于50％的体积的粒径。“体积中值粒径”可以采用扫描电子显微镜观察并测量获得，也可以采用激光衍射法测量获得。
在一些实施方案中，所述负极活性材料的体积中值粒径为4～10μm。
在一些实施方案中，所述负极活性材料与所述介电材料颗粒的体积中值粒径的比值为200:1～20:1，例如200:1～150:1、150:1～100:1、100:1～50:1、50:1～20:1。负极活性材料与所述介电材料颗粒的体积中值粒径的比值在上述范围的优点是介电材料容易在石墨表面附着，不容易脱落。
在一些实施方案中，所述介电材料与所述粘结剂的质量比为0.1:100～1:100(例如0.1:100-0.2:100、0.2:100-0.3:100、0.3:100-0.4:100、0.4:100-0.5:100、0.5:100-0.6:100、0.6:100-0.7:100、0.7:100-0.8:100、0.8:100-0.9:100、0.9:100-1:100)。
在一些实施方案中，术语“零维”指其中颗粒尺寸极小且基本上不具有长度的颗粒状态，例如纳米颗粒状态的颗粒。与术语“零维”相比，术语“三维”指具有体积的大体积状态，术语“二维”指薄膜状态，并且术语“一维”指纳米管状态。
在一些实施方案中，术语“零维”可以指直径为1nm至约100nm的颗粒(1-10nm、10-20nm、20-30nm、30-40nm、40-50nm、50-60nm、60-70nm、70-80nm、80-90nm、90-100nm)。
在一些实施方案中，术语“四方晶型”表示具有包含三个轴的晶胞的晶体结构，其中两个轴具有相同的长度并且彼此成直角，第三个轴垂直于另外两个轴。
在一些实施方案中，术语“相对介电常数”是指相对介电常数(ε r)，其为材料的相对介电常数除以真空的相对介电常数(ε 0)。
在一些实施方案中，的介电常数是指室温(25±5℃)下的介电常数，其具有本领域公知的含义，可以用本领域已知的仪器及方法进行测试。例如可以将铁电材料制备成圆形试样后，采用LCR测试仪测试电容量C并根据公式：介电常数ε＝(C×d)/(ε 0×A)计算得到。C表示电容量，单位为法拉(F)；d表示试样厚度，单位为cm；A表示试样面积，单位为cm 2；ε 0表示真空介电常数，ε 0＝8.854×10-14F/cm。在本申请中，测试条件可以为1KHz、1.0V、25±5℃。测试标准可依据GB/T 11297.11-2015。制备试样时可参考中国专利申请CN114217139A。
在一些实施方案中，本申请的相对介电常数可以通过相对介电常数测试仪来测定，具体可参照GB/T5594.4-1985，仪器可以选择北京中航时代仪器设备有限公司的ZJD-C相对介电常数测试仪。
在第二方面，本申请提供一种复合材料的制备方法，所述复合材料为以上任一项所述的复合材料；
所述制备方法包括：
(1)对介电材料颗粒进行羟基化处理，获得羟基化的介电材料颗粒；
(2)在所述羟基化的介电材料颗粒上接枝偶联剂，获得接枝有偶联剂的介电材料颗粒；
(3)使介电材料颗粒上接枝的偶联剂与粘结剂通过缩合反应连接；
(4)将上一步产物与负极活性材料混合。
在一些实施方案中，步骤(3)中，所述介电材料颗粒上的偶联剂含有巯基端基，所述粘结剂含有烯基端基，所述偶联剂与所述粘结剂通过巯基-烯基点击化学反应连接。
在一些实施方案中，所述巯基-烯基点击化学反应在光引发剂和紫外光的作用下进行。
在第三方面，提供一种电极，含有上述任一项所述的复合材料。
在第四方面，本申请提供一种二次电池，包括上述任一项所述的电极。
在第五方面，本申请提供一种用电装置，包括上述的二次电池。
[负极极片]
负极极片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，所述负极膜层包括负极活性材料，负极活性材料采用本申请任一项的负极活性材料。
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：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。
[正极极片]
在一些实施方式中，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膜层，正极膜层包括正极活性材料。
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，正极膜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LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、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LiNi 1/3Co 1/5n 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)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LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、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。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，电解质为液态的，且包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、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、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，电解液还可选地包括添加剂。作为示例，添加剂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。
[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5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6，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7是作为一个示例的电池模块4。参照图7，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8和图9是作为一个示例的电池包1。参照图8和图9，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10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。
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。
实施例1：
取100g介电材料颗粒(钛酸钡颗粒，四方晶型)加入到1L H 2O 2溶液中(H 2O 2浓度为3％)，再加入50ml的氯化铵溶液，在90℃回流温度下，加热搅拌3小时，得到羟基改性钛酸钡颗粒。
取100g羟基改性钛酸钡颗粒浸入到乙醇水溶液中(乙醇和水体积比例为8:1)，加入10ml的偶联剂(γ-巯丙基三甲氧基硅烷)，加热至50℃，反应4h，得到接枝有偶联剂的钛酸钡颗粒。
将200g的粘结剂(丁苯橡胶，数均分子量150万)共聚物溶于1L的DMF中，超声搅拌，加入10g接枝有偶联剂的钛酸钡颗粒，再加入9g的安息香双甲醚，获得混合物。将上述混合物在波长为360nm的紫外灯下照射30min，再30℃下加热至DMF挥发，得到丁苯橡胶-钛酸钡颗粒复合物。
在丁苯橡胶-钛酸钡颗粒复合物(简称SBR-BTO)中，钛酸钡颗粒的至少一部分表面覆有γ-巯丙基三甲氧基硅烷，γ-巯丙基三甲氧基硅烷桥接钛酸钡颗粒和丁苯橡胶。
图1示出一个丁苯橡胶-钛酸钡颗粒复合物的示意图，如图所示，介电材料颗粒101的至少一部分表面覆盖有偶联剂102，偶联剂102桥接介电材料颗粒101与粘结剂103。
图2示出接枝有丁苯橡胶的钛酸钡颗粒(BTO-SBR)的红外光谱图，图中可以看出，在波数为1200、1100cm -1处观察到Si-C与Si-O的吸收峰，可证明γ-巯丙基三甲氧基硅烷将钛酸钡颗粒和丁苯橡胶桥接在了一起。
将负极活性材料(人造石墨)、导电剂(乙炔黑)、接枝有丁苯橡胶的钛酸钡颗粒(简称SBR-BTO)和分散剂(羧甲基纤维素钠，简称CMC)按照重量比为97:1:1:1混合，获得实施例1的复合材料。后续将该复合材料用于制备成锂离子电池负极浆料。负极活性材料与所述介电材料颗粒的体积中值粒径的比值被控制为50:1，即实施例1中负极活性材料的体积平均粒径为2.5μm。
图3示出复合材料的示意图，如图所示，复合材料包括负极活性材料100、介电材料颗粒101和粘结剂103，粘结剂103将介电材料颗粒101粘结在负极活性材料100上。如图3所示，本申请上述方案制备了一种具有“链球状结构”的复合材料，通过将粘结剂103与介电材料颗粒101通过巯基相连，粘结剂103表面的羟基可以与负极活性材料100表面通 过氢键相连，使得介电材料颗粒101可以均匀的分布在负极活性材料100的表面，同时，这种复合材料在负极端进行点对面的连接，提高了高介电常数材料的利用率，可以充分发挥其去溶剂化作用和薄SEI的性能，且不会堵塞锂离子的迁移通道。需要特别说明的是，图3示出的仅是为了便于呈现连接关系而作的示意图，图3中示出的尺寸关系不代表真实的尺寸关系。
实施例1制备复合材料的原料组分(人造石墨、乙炔黑、SBR-BTO、CMC)的比例，SBR-BTO中SBR与BTO的比例，钛酸钡的体积中值粒径Dv50和相对介电常数，SBR的数均分子量如表1所示。
实施例2～15
实施例2～15与实施例1的区别在于制备复合材料的原料参数或工艺参数不同。具体参数区别如表1所示。
实施例11采用钛酸铅(PTO)替换实施例1的钛酸钡(BTO)。
实施例12采用铌酸锂(PPLN)替换实施例1的钛酸钡(BTO)。
实施例13采用锆钛酸铅(PZT)替换实施例1的钛酸钡(BTO)。
实施例14采用螯合100型钛酸酯偶联剂(CTDPP-138S)用于桥接介电材料颗粒和粘结剂，以替换实施例1中的γ-巯丙基三甲氧基硅烷。
实施例15采用螯合200型钛酸酯偶联剂(ETDOP-212S)用于桥接介电材料颗粒和粘结剂，以替换实施例1中的γ-巯丙基三甲氧基硅烷。
对比例1
对比例1与实施例1的区别在于复合材料配方不同。对比例1的复合材料中不含有介电材料颗粒BTO。对比例1的复合材料的配方如下：负极活性材料(人造石墨)、导电剂(乙炔黑)、丁苯橡胶和分散剂(羧甲基纤维素钠)按照重量比为97:1:1:1混合。
对比例2
对比例2与实施例1的区别在于复合材料配方不同。对比例2的复合材料中不含有介电材料颗粒BTO。对比例2的复合材料的配方如下：负极活性材料(人造石墨)、导电剂(乙炔黑)、丁苯橡胶、介电材料颗粒(钛酸钡颗粒)和分散剂(羧甲基纤维素钠)按照重量比为97:1:0.95::0.05:1混合。
全电池的制备
(1)负极极片的制备：将上述实施例和对比例的复合材料分别加入到去离子水中，搅 拌混合均匀后制备成负极浆料。将负极浆料按涂覆在7μm的负极集流体铜箔上，经过烘干、冷压、分切得到具有负极膜层的负极极片，负极膜层的面密度为9.7mg/cm 2。
(2)正极极片的制备：正极活性材料镍钴锰酸锂(NCM523即LiNi 0.5Co 0.2Mn 0.3O 2)、聚偏氟乙烯PVDF、导电剂乙炔黑SP按照重量比98：1：1进行混合，加入N-甲基吡咯烷酮(NMP)作为溶剂，在真空状态下搅拌浆料至均匀。将所得的浆料用刮刀涂布在13μm的铝箔上，之后在140℃下烘干，冷压，分切后得到具有正极膜层的正极极片，正极膜层的面密度为13.7mg/cm 2。
(3)电解液：在氩气气氛手套箱中(H 2O<0.1ppm，O 2<0.1ppm)，将有机溶剂碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)按照体积比3:7混合均匀，加入12.5重量％(基于碳酸乙烯酯/碳酸甲乙酯溶剂的总重量计)LiPF 6溶解于上述有机溶剂中，搅拌均匀，得到电解液。该电解液的相对介电常数为90。
(4)隔离膜：使用市售的厚度为20μm、平均孔径为80nm的PP-PE共聚物微孔薄膜(来自卓高电子科技公司，型号20)。
(5)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中间起到隔离的作用，并卷绕得到裸电芯。将裸电芯置于外包装中，注入上述电解液并封装，得到二次电池。
半电池的制备
采用与全电池相同的负极极片和电解液，对电极采用锂片，组装为扣式半电池。
分析检测
1、极片的粘结力测试
采用剥离测试法进行粘结力测试。图4的(a)～(d)示出剥离测试的流程图。如图4的(a)所示，首先提供一块钢板510，钢板尺寸宽30mm×长100mm。如图4的(b)所示，然后提供一块双面胶520，双面胶520的尺寸为宽20mm×长30mm，将双面胶520贴在钢板510上，双面胶520的一个宽边与钢板510的一个宽边对齐。如图4的(c)所示，然后提供一块待测试极片530，待测试极片530的尺寸为宽20mm×长180mm。将待测试极片530覆盖在双面胶520上(两边对齐)，极片530的涂布面朝向双面胶520。由于待测试极片530的长度大于双面胶520的长度，故待测试极片520的部分区域未与双面胶粘接。如图4的(d)所示，将钢板510固定在拉伸试验机的基座上，用夹具夹持待测试极片530未与双面胶粘接的一端，然后使夹具向另一端的方向(如箭头所示方向)拉伸，拉伸的力的方向垂直于钢板510，且与钢板510表面存在一定距离。在向纸面外拉伸剥离极片的同时，钢板向上移动，以保持拉伸方向与极片剥离位置垂直。在拉伸过程中，拉伸使极片530从钢板上被逐渐剥离。在拉伸过程中，夹具的拉伸速度为50mm/min。拉伸过程中，记录夹具 的拉力，待拉力稳定后继续剥离40mm长度，以该剥离长度下的平均拉力为粘结力(单位N)。
2、负极克容量(C)
在2.5～4.3V下，将扣式电池按照0.1C充电至4.3V，然后在4.3V下恒压充电至电流小于等于0.05mA，静置5min，然后按照0.1C放电至2.0V，此时的放电容量为初始克容量。用初始克容量除以正极活性材料的重量，得到正极克容量。
3、负极首次库伦效率(ICE)
在25℃、常压环境下，将扣式电池以0.1C倍率恒流放电至电压为0.005V，再以0.05C倍率恒流放电至电压为0.005V，记录此时的放电比容量，即为首次嵌锂容量；之后以0.1C倍率恒流充电至电压为1.5V，记录此时的充电比容量，即为首次脱锂容量。将扣式电池按照上述方法进行50次循环充放电测试，记录每次的脱锂容量。
首次库伦效率(％)＝首次脱锂容量/首次嵌锂容量×100％
5、充电电阻测试
在本申请中，通过25℃4C充电电阻来评估二次电池的动力学性能。在25℃下，将实施例和对比例制备的锂离子电池放电到50％容量状态，静置30min，记录电压值V1，以4C倍率对应的电流A0进行充电10s，记录充电结束对应的电压值V2，充电电阻的计算方式为：R＝(V2-V1)/A0
对实验结果进行归一化处理。以实施例2的充电电阻阻值为基准值为100，其实施例按比例缩放。
4、快充循环寿命/圈数
在本申请中，通过快充循环寿命/圈数来评估二次电池的容量保持性能。在25℃下，将实施例和对比例制备的锂离子电池以2C倍率充电，以1C倍率放电，进行3％-97％SOC区间的连续循环测试，直至锂离子电池的容量小于初始容量的80％，记录循环圈数。
5、相对介电常数测试
本申请中介电材料颗粒和电解液的相对介电常数可以通过介电常数测试仪来测定，具体可参照GB/T5594.4-1985，仪器可以选择北京中航时代仪器设备有限公司的ZJD-C介电常数测试仪。
6、体积平均粒径
体积平均粒径Dv50为本领域公知的含义，可以用本领域公知的仪器及方法进行测定。例如可以参照GB/T 19077-2016粒度分布激光衍射法，采用激光粒度分析仪方便地测定，如英国马尔文仪器有限公司的Mastersizer 2000E型激光粒度分析仪。
Figure PCTCN2022104890-appb-000003
Figure PCTCN2022104890-appb-000004
由以上实验数据可以看出：
实施例1～16的负极浆料含有本申请新型复合材料，该复合材料包括：负极活性材料(人造石墨)，介电材料颗粒(钛酸钡颗粒)；和粘合剂树脂(丁苯橡胶)；其中，介电材料颗粒的至少一部分表面覆有偶联剂(γ-巯丙基三甲氧基硅烷)，偶联剂桥接介电材料颗粒和所述粘合剂树脂。
本申请复合材料中的介电材料颗粒通过偶联剂桥接在粘合剂树脂上，能够带来如下的有益效果：
(1)介电材料颗粒在电极浆料中得以分散均匀，不会全部沉降在浆料底部；
(2)介电材料颗粒能够通过粘结剂粘结在负极活性材料的表面，与负极活性材料表面的距离较近，充分发挥改性作用；
(3)负极活性材料在充放电过程中会发生体积膨胀/收缩，在此过程中，由于介电材料颗粒桥接在粘合剂树脂上，介电材料颗粒不会随着负极活性材料膨胀/收缩而脱落，不会与负极活性材料失去接触。介电材料颗粒在电池工作过程中能够与负极活性材料保持稳定的接触，进而能够稳定地发挥改性作用。
从电池性能上看，本申请的电池表现出以下一项或多项性能：
(1)改善的负极容量；
(2)改善的首周库伦效率；
(3)降低的充电电阻；
(4)较长的循环寿命。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (19)

  1. 一种复合材料，包括
    负极活性材料；
    介电材料颗粒；和
    粘结剂；
    其中，所述介电材料颗粒的至少一部分表面覆有偶联剂，所述偶联剂桥接所述介电材料颗粒和所述粘结剂。
  2. 根据权利要求1所述的复合材料，其中，所述粘结剂将所述介电材料颗粒粘结在所述负极活性材料上。
  3. 根据权利要求1所述的复合材料，其中，所述介电材料颗粒的相对介电常数为80至200。
  4. 根据权利要求1～2中任一项所述的复合材料，其中，所述介电材料选自以下一种或多种：钛酸钡，钛酸铅，铌酸锂，锆钛酸铅，偏铌酸铅，铌酸铅钡锂。
  5. 根据权利要求1～4中任一项所述的复合材料，其中，所述粘结剂是有机粘结剂。
  6. 根据权利要求1～5中任一项所述的复合材料，其中，所述粘结剂选自以下中的一种或多种：聚丙烯酸(PAA)、丁苯橡胶(SBR)、聚酰胺酰亚胺(PAI)、聚乙烯醇(PVA)、聚乙烯亚胺(PEI)、聚酰亚胺粘结剂(PI)、聚丙烯酸叔丁酯-三乙氧基乙烯基硅烷(TBATEVS)。
  7. 根据权利要求1～6中任一项所述的复合材料，其中，所述偶联剂选自以下一种或多种：硅烷偶联剂、钛酸酯偶联剂。
  8. 根据权利要求1～7中任一项所述的复合材料，其中，所述偶联剂选自硅烷偶联剂KH590、硅烷偶联剂KH550，硅烷偶联剂KH560，硅烷偶联剂KH570，硅烷偶联剂KH792，硅烷偶联剂DL602，硅烷偶联剂DL171、螯合100型钛酸酯偶联剂、螯合200型钛酸酯偶联剂中的一种或者多种。
  9. 根据权利要求1～8中任一项所述的复合材料，其具有以下一项或多项特征
    (1)所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-O-；
    (2)所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-S-。
  10. 根据权利要求1～8任一项所述的复合材料，其具有以下一项或多项特征
    (1)所述偶联剂通过第一端官能团与所述介电材料连接，第一端官能团包括-Si-O-；
    (2)所述偶联剂通过第二端官能团与所述粘结剂连接，第二端官能团包括-C-S-。
  11. 根据权利要求1～10中任一项所述的复合材料，其中，所述粘结剂的数均分子量为100万至200万。
  12. 根据权利要求1～11中任一项所述的复合材料，其中，所述介电材料颗粒具有以下一项或多项特征：
    (1)所述介电材料颗粒为零维颗粒；
    (2)所述介电材料颗粒为四方晶型的钛酸钡颗粒；
    (3)所述介电材料颗粒的体积中值粒径为50nm～200nm；
    (4)所述负极活性材料的体积中值粒径为4～10μm；
    (5)所述负极活性材料与所述介电材料颗粒的体积中值粒径的比值为200:1～20:1。
  13. 根据权利要求1～12中任一项所述的复合材料，其中，所述介电材料与所述粘结剂的质量比为0.1:100～1:100。
  14. 一种复合材料的制备方法，所述复合材料的定义如权利要求1-13中任一项所述；
    所述制备方法包括：
    (1)对介电材料颗粒进行羟基化处理，获得羟基化的介电材料颗粒；
    (2)在所述羟基化的介电材料颗粒上接枝偶联剂，获得接枝有偶联剂的介电材料颗粒；
    (3)使介电材料颗粒上接枝的偶联剂与粘结剂通过缩合反应连接；
    (4)将上一步产物与负极活性材料混合。
  15. 根据权利要求14所述的方法，步骤(3)中，所述介电材料颗粒上的偶联剂含有巯基端基，所述粘结剂含有烯基端基，所述偶联剂与所述粘结剂通过巯基-烯基点击化学反应连接。
  16. 根据权利要求15所述的方法，所述巯基-烯基点击化学反应在光引发剂和紫外光的作用下进行。
  17. 一种电极，含有权利要求1～13中任一项所述的复合材料。
  18. 一种二次电池，包括根据权利要求17所述的电极。
  19. 一种用电装置，包括根据权利要求18所述的二次电池。
PCT/CN2022/104890 2022-07-11 2022-07-11 复合材料及其制备方法、电极、二次电池及用电装置 Ceased WO2024011350A1 (zh)

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