Separator, secondary battery including same, and device

Abstract

To provide a separator, a secondary battery including the same, and a device.SOLUTION: There are provided a separator, a secondary battery including the separator, and a device including the secondary battery. The separator includes a base material (A) and a coating (B) formed on at least one surface of the base material (A). The coating (B) includes inorganic particles (B2) and first organic particles (B1). The first organic particles (B1) each are fitted to the inorganic particles (B2), and each form a protrusion on a surface of the coating (B). The first organic particles (B1) each have a primary particle shape, and the number average particle diameter of the first organic particles (B1)≥2 μm is satisfied.SELECTED DRAWING: Figure 3-1

Description

[Technical Field]

[0001] The present application belongs to the field of secondary battery technology, and specifically relates to a separator, a secondary battery including the same, and a battery module, a battery pack, and an apparatus related thereto. [Background technology]

[0002] 2. Description of the Related Art Secondary batteries have outstanding characteristics such as light weight, pollution-free, and no memory effect, and are therefore widely used in various consumer electronic products and electric vehicles.

[0003] With the development of the new energy industry, users are placing higher and higher requirements on secondary batteries, for example, secondary batteries are being designed to have higher and higher energy densities, but the improvement in battery energy density tends to be unfavorable to the balance of kinetic performance, electrochemical performance, and safety performance.

[0004] Therefore, how to achieve both cycle performance and safety performance in a battery is an important issue in the field of battery design. Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the technical problems in the background art, the present application aims to provide a separator that provides a secondary battery including the separator with good cycle characteristics and safety performance. [Means for solving the problem]

[0006] To achieve the above object, a first aspect of the present application provides a separator including a substrate and a coating formed on at least one surface of the substrate. The coating includes inorganic particles and first organic particles. The first organic particles are embedded in the inorganic particles and form protrusions on the surface of the coating. The first organic particles are in the form of primary particles, and the number average particle diameter of the first organic particles is 2 μm or greater.

[0007] Compared to the prior art, the present invention has at least the following beneficial effects:

[0008] The separator of the present application contains inorganic particles and first organic particles in the same coating, significantly reducing the overall thickness of the separator and improving the energy density of the battery. Furthermore, by specially designing the shape and number-average particle size of the first organic particles, sufficient and uniformly distributed gaps are formed between the inorganic and organic particles, ensuring good breathability of the separator and reinforcing the adhesion between the separator and the tab, thereby providing the secondary battery with good cycle performance and safety. The device of the present application, which includes the secondary battery of the present application, has at least the same advantages as the secondary battery.

[0009] In any embodiment of the present application, the number average particle diameter of the first organic particles is 2 μm to 10 μm, and optionally, the number average particle diameter of the first organic particles is 3 μm to 8 μm. When the number average particle diameter of the first organic particles is within a predetermined range, the cycle performance and safety performance of the battery can be further improved.

[0010] In any embodiment of the present application, the first organic particles include one or more of a homopolymer or copolymer of an acrylate-based monomer unit, a homopolymer or copolymer of an acrylic acid-based monomer unit, a homopolymer or copolymer of a styrene-based monomer unit, a polyurethane-based compound, a rubber-based compound, and a modifying compound for each of the homopolymers or copolymers described above.

[0011] In any embodiment of the present application, the first organic particles comprise one or more of a copolymer of an acrylate-based monomer unit and a styrene-based monomer unit, a copolymer of an acrylic acid-based monomer unit and a styrene-based monomer unit, a copolymer of an acrylic acid-based monomer unit, an acrylate-based monomer unit and a styrene-based monomer unit, a copolymer of a styrene-based monomer unit and an unsaturated nitrile-based monomer unit, a copolymer of a styrene-based monomer unit, an olefin monomer unit and an unsaturated nitrile-based monomer unit, and modified compounds of the above copolymers.

[0012] In any embodiment of the present application, the first organic particles include one or more of butyl acrylate-styrene copolymer, butyl methacrylate-isooctyl methacrylate copolymer, isooctyl methacrylate-styrene copolymer, methacrylate-methacrylic acid-styrene copolymer, methyl acrylate-isooctyl methacrylate-styrene copolymer, butyl acrylate-isooctyl acrylate-styrene copolymer, butyl acrylate-isooctyl methacrylate-styrene copolymer, butyl methacrylate-isooctyl methacrylate-styrene copolymer, butyl methacrylate-isooctyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, methyl acrylate-styrene-acrylonitrile copolymer, isooctyl methacrylate-styrene-acrylonitrile copolymer, styrene-vinyl acetate copolymer, styrene-vinyl acetate-pyrrolidone copolymer, and modified compounds of the copolymers.

[0013] In any embodiment of the present application, at least some of the first organic particles have a core structure and a shell structure. When at least some of the first organic particles have a core structure and a shell structure, the cycle performance and safety performance of the battery can be further improved.

[0014] In any embodiment of the present application, the glass transition temperature of the shell structure is higher than the glass transition temperature of the core structure.

[0015] In any embodiment of the present application, the glass transition temperature of the core structure is between -30°C and 20°C, optionally between -10°C and 10°C.

[0016] In any embodiment of the present application, the glass transition temperature of the shell structure is between 50°C and 70°C, optionally between 55°C and 65°C.

[0017] When the glass transition temperatures of the shell structure and the core structure satisfy the above conditions, the cycle performance and safety performance of the battery can be further improved.

[0018] In any embodiment of the present application, the core and shell structures both comprise copolymers of acrylate-based monomer units.

[0019] In any embodiment of the present application, the core structure and the shell structure of the first organic particles each include a copolymer of an acrylate-based monomer unit and a styrene-based monomer unit.

[0020] When the core structure and the shell structure of the second organic particles both contain the copolymer, the cycle performance of the battery can be further improved.

[0021] In any embodiment of the present application, the mass ratio of the first organic particles in the coating is ≧10%, and optionally 10% to 30%. When the content of the first organic particles is within a predetermined range, the cycle performance and safety performance of the battery can be further improved.

[0022] In any embodiment of the present application, the coating may further include second organic particles, which are embedded in the inorganic particles and form protrusions on the surface of the coating, and the second organic particles have a secondary particle shape. When the coating includes second organic particles of the above type, the cycle performance and safety performance of the battery can be further improved.

[0023] In any embodiment of the present application, the number average particle diameter of the second organic particles is 12 μm or more, and optionally, the number average particle diameter of the second organic particles is 15 μm to 25 μm. When the number average particle diameter of the second organic particles is within the predetermined range, the cycle performance and safety performance of the battery can be further improved.

[0024] In any embodiment of the present application, the mass ratio of the second organic particles in the coating is equal to or less than the mass ratio of the first organic particles in the coating, and optionally, the mass ratio of the second organic particles in the coating is 1% to 10%, and further optionally, 2% to 8%. When the mass ratio of the second organic particles to the first organic particles satisfies this condition, the cycle performance of the battery can be further improved.

[0025] In any embodiment of the present application, the second organic particles contain one or more of a homopolymer or copolymer of a fluorine-containing alkyl group monomer unit, a homopolymer or copolymer of an olefin monomer unit, a homopolymer or copolymer of an unsaturated nitrile-based monomer unit, a homopolymer or copolymer of an alkylene oxide-based monomer unit, and a modified compound of each of the homopolymers or copolymers, In any embodiment of the present application, the second organic particles comprise one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyethylene, polypropylene, polyacrylonitrile, polyethylene oxide, a copolymer of different fluorine-containing alkyl group monomer units, a copolymer of fluorine-containing alkyl group monomer units and vinyl group monomer units, a copolymer of fluorine-containing alkyl group monomer units and acrylic acid-based monomer units, a copolymer of fluorine-containing alkyl group monomer units and acrylate-based monomer units, and modified compounds of the above-mentioned homopolymers or copolymers.

[0026] In any embodiment of the present application, the second organic particles include one or more of vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-acrylic acid copolymer, vinylidene fluoride-hexafluoropropylene-acrylate copolymer, and modified compounds of the copolymers.

[0027] In some embodiments, the inorganic particles can include one or more of boehmite (γ-AlOOH), alumina (AlO), barium sulfate (BaSO), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)), silicon dioxide (SiO), tin dioxide (SnO), titanium oxide (TiO), calcium oxide (CaO), zinc oxide (ZnO), zirconium dioxide (ZrO), yttrium oxide (YO), nickel oxide (NiO), cerium oxide (CeO), zirconium titanate (SrTiO), barium titanate (BaTiO), and magnesium fluoride (MgF).

[0028] In any embodiment of the present application, the particle size of the inorganic particles is ≦2.5 μm, and optionally, the particle size of the inorganic particles is 0.5 μm to 2.5 μm. When the particle size of the inorganic particles is within the predetermined range, the cycle performance and safety performance of the battery can be further improved.

[0029] In any embodiment of the present application, the weight of the coating on one side of the separator per unit area is ≦3.0 g / m 2 and optionally, the weight of the coating on one side of the separator per unit area is 1.5 g / m 2 ~2.5g / m 2 When the coating weight satisfies the above range, the cycle performance and safety performance of the battery can be further improved.

[0030] In any embodiment of the present application, the separator may have an air permeability of 100s / 100mL to 300s / 100mL, and optionally, the separator may have an air permeability of 150s / 100mL to 250s / 100mL.

[0031] In any embodiment of the present application, the separator has a transverse tensile strength (TD) of 1000 kg / cm 2 ~3500kg / cm 2 and optionally, the separator has a transverse tensile strength of 1200 kg / cm 2 ~3000kg / cm 2 may be.

[0032] In any embodiment of the present application, the separator has a tensile strength in the machine direction (MD) of 1000 kg / cm 2 ~3000kg / cm 2 and optionally, the separator has a longitudinal tensile strength of 1000 kg / cm 2 ~2800kg / cm 2 may be.

[0033] In any embodiment of the present application, the separator may have a transverse elongation at break of 50% to 200%, and optionally, the separator may have a transverse elongation at break of 80% to 150%.

[0034] In any embodiment of the present application, the separator may have a longitudinal elongation at break of 50% to 200%, and optionally, the separator may have a longitudinal elongation at break of 80% to 150%.

[0035] In any embodiment of the present application, the inorganic particles and the organic particles form a non-uniform tunnel structure in the coating.

[0036] In any embodiment of the present application, when the distance between any two adjacent inorganic particles is L1 and the distance between any adjacent inorganic particle and organic particle is L2, L1 <L2である。

[0037] A second aspect of the present application is A method for producing a coating slurry comprising: (1) providing a substrate; and (2) providing a coating slurry including a solvent and component materials including inorganic particles and organic particles including first organic particles. and step (3) applying the coating slurry described in step (2) to at least one side of the substrate described in step (1), forming a coating, and drying to obtain the separator, wherein the separator includes a substrate and a coating formed on at least one surface of the substrate, the coating including inorganic particles and first organic particles, the first organic particles being embedded in the inorganic particles and forming protrusions on the surface of the coating, the first organic particles being in the form of primary particles, and the number average particle diameter of the first organic particles being 2 μm or more.

[0038] In any embodiment of the present application, in step (2), the added mass of the first organic particles is 10% or more, and optionally 10% to 30% of the total dry weight of the component materials.

[0039] In any embodiment of the present application, in step (2), the organic particles further include second organic particles, and the second organic particles are in the form of secondary particles.

[0040] In any embodiment of the present application, in step (2), the added mass of the second organic particles is equal to or less than the added mass of the first organic particles.

[0041] In any embodiment of the present application, in step (2), the added mass of the second organic particles is 1% to 10% of the total dry weight of the component materials, and optionally 2% to 8%.

[0042] In any embodiment of the present application, in step (2), based on the weight of the coating slurry, the solid content of the coating slurry is 28% to 45%, optionally 30% to 38%.

[0043] In any embodiment of the present application, in step (3), the coating is performed using a coater, the coater includes a gravure roll, and the ruling of the gravure roll is 100 LPI to 300 LPI, optionally 125 LPI to 190 LPI.

[0044] In any embodiment of the present application, in step (3), the speed of the application is 30 m / min to 90 m / min, optionally 50 m / min to 70 m / min.

[0045] In any embodiment of the present application, in step (3), the linear velocity ratio of the coating is 0.8 to 2.5, and optionally, 0.8 to 1.5.

[0046] In any embodiment of the present application, in step (3), the drying temperature is 40°C to 70°C, optionally 50°C to 60°C.

[0047] In any embodiment of the present application, in step (3), the drying time is 10 seconds to 120 seconds, optionally 20 seconds to 80 seconds. A third aspect of the present application provides a secondary battery including a separator according to the first aspect of the present application or a separator produced by the method of the second aspect of the present application.

[0048] A fourth aspect of the present application provides a battery module including the secondary battery according to the third aspect of the present application.

[0049] A fifth aspect of the present application provides a battery pack including the battery module according to the fourth aspect of the present application.

[0050] A sixth aspect of the present application provides a device including at least one of the secondary battery according to the third aspect of the present application, the battery module according to the fourth aspect of the present application, or the battery pack according to the fifth aspect of the present application.

[0051] In order to more clearly explain the technical solution of the present application, the drawings used in the present application will be briefly described below. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without expending creative efforts. [Brief explanation of the drawings]

[0052] [Figure 1-1] FIG. 2 is a schematic diagram showing a coating configuration according to one embodiment of the separator of the present application. [Figure 1-2] FIG. 2 is a schematic diagram showing the coating configuration of another embodiment of the separator of the present application. [Figure 2-1] 1 is a photograph of an ion-polished cross section (CP) of an embodiment of a separator of the present application. [Figure 2-2] 1 is a photograph of an ion-polished profile (CP) of another embodiment of a separator of the present application. [Figure 3-1] 1 is a scanning electron microscope (SEM) photograph of an embodiment of a separator according to the present application. [Figure 3-2] 1 is a scanning electron microscope (SEM) photograph of another embodiment of the separator of the present application. [Figure 4-1] 1 is a schematic diagram illustrating the configuration of an embodiment of a separator according to the present invention. [Figure 4-2] FIG. 2 is a schematic diagram illustrating the configuration of another embodiment of the separator of the present application. [Figure 5] FIG. 1 is a schematic diagram illustrating an embodiment of a secondary battery. [Figure 6] FIG. 6 is an exploded view of FIG. 5. [Figure 7] FIG. 1 is a schematic diagram illustrating an embodiment of a battery module. [Figure 8] FIG. 1 is a schematic diagram illustrating an embodiment of a battery pack. [Figure 9] FIG. 9 is an exploded view of FIG. 8. [Figure 10] FIG. 1 is a schematic diagram illustrating an embodiment of an apparatus that uses a secondary battery as a power source. DETAILED DESCRIPTION OF THE INVENTION

[0053] The present application will be further described below with reference to specific embodiments, which should be understood as being for illustrative purposes only and not limiting the scope of the present application.

[0054] For brevity, this specification specifically discloses only a few numerical ranges. However, any lower limit can be combined with any upper limit to form an open range. Also, any lower limit can be combined with another lower limit to form an open range, and similarly, any upper limit can be combined with another upper limit to form an open range. Also, each point or single numerical value disclosed individually can itself be used as a lower or upper limit in combination with any other point or single numerical value or with other lower or upper limits to form an open range.

[0055] In the description of this specification, unless otherwise specified, the terms "more than or equal to" and "less than or equal to" include the number, and "multiple types" in "one or more types" means two types and more than two types.

[0056] In the description herein, unless otherwise specified, the term "or" is inclusive. That is, the phrase [A or B] means "A, B, or both A and B." More specifically, "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) and B is true (or exists), or when both A and B are true (or exist). Unless otherwise specified, terms used herein have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of each parameter referred to in this application can be measured by various measurement methods commonly used in the art (e.g., the methods described in the examples of this application).

[0057] secondary battery A secondary battery is a battery that can be continuously used by activating the active material through charging after discharging.

[0058] A secondary battery typically comprises a positive electrode plate, a negative electrode plate, a separator, and an electrolyte. During the charge and discharge process, active ions are inserted and removed between the positive and negative electrodes. The separator is placed between the positive and negative electrodes to separate them. The electrolyte conducts ions between the positive and negative electrodes.

[0059] [Separator] The separator according to the present application includes a substrate and a coating formed on at least one surface of the substrate. The coating includes inorganic particles and organic particles. The organic particles include first organic particles. The first organic particles are embedded in the inorganic particles and form protrusions on the surface of the coating. The first organic particles have a primary particle shape, and the number average particle diameter of the first organic particles is 2 μm or more.

[0060] The term "primary particles" has the meaning known in the art, and refers to particles that are not in an aggregated state.

[0061] The number-average particle size of the organic particles is the average particle size of the organic particles statistically counted by the number of organic particles in the separator coating. The particle size of the organic particles is the distance between the two most distant points on the organic particles.

[0062] As shown in FIG. 1-1, the separator includes a substrate (A) and a coating (B), and the coating (B) includes first organic particles (B1) and inorganic particles (B2). The first organic particles (B1) are primary particles, and the first organic particles are embedded in the inorganic particles (B2), forming protrusions on the surface of the coating (B).

[0063] Although it is not desired to be limited to any theory, the separator according to the present application contains inorganic particles and first organic particles in the same coating, and compared to a separator having two coatings, an inorganic particle layer and an organic particle layer, the separator has a significantly reduced overall thickness. In addition, the first organic particles are specially designed, and the interaction between the two allows the battery to achieve both better cycle performance and safety performance. Furthermore, because the primary particle-shaped first organic particles have a relatively small specific gravity, the first organic particles can be more easily floated on the coating surface during the separator manufacturing process. After the separator is used in a battery, the first organic particles effectively improve the adhesion between the separator and the electrode plate, and wrinkles are less likely to form on the electrode plate during the battery charge and discharge process, thereby improving the battery's cycle performance. Meanwhile, when the battery is in a steady operating environment (e.g., below 60°C), the specially designed first organic particles of the present application have a low swelling rate in the electrolyte, which effectively reduces the likelihood of forming a dense and large-area gel film structure. This ensures that the separator has a moderate and non-uniform tunnel structure, making it easier for ions to transmit, further improving the battery's cycle performance. In particular, when the battery is in a high-temperature operating environment (e.g., above 100°C), the specially designed first organic particles form a large-area gel film structure at high temperatures, rapidly reducing the ion diffusion paths and delaying the battery's thermal diffusion time, effectively improving the battery's safety performance.

[0064] As a result of intensive research, the present inventors have found that the separator according to the present application satisfies the above design conditions, and optionally satisfies one or more of the following conditions, thereby further improving the performance of the secondary battery:

[0065] In some embodiments, the number-average particle diameter of the first organic particles is 2 μm to 12 μm. For example, the number-average particle diameter of the first organic particles may be 2 μm to 10 μm, 2.5 μm to 10 μm, 2.8 μm to 10 μm, 3 μm to 8 μm, 2.5 μm to 6 μm, or 4 μm to 8 μm. When the number-average particle diameter of the first organic particles is within a predetermined range, the particles have an appropriate swelling ratio in the electrolyte, ensuring smooth ion transmission paths during steady-state battery operation. Furthermore, an appropriate particle diameter range can prevent poor wetting of the electrolyte due to excessively strong adhesion between the separator and electrode plates, further improving the cycle performance of the battery.

[0066] In some embodiments, the first organic particles may include one or more of a homopolymer or copolymer of an acrylate-based monomer unit, a homopolymer or copolymer of an acrylic acid-based monomer unit, a homopolymer or copolymer of a styrene-based monomer unit, a polyurethane-based compound, a rubber-based compound, and a modified compound of each of the homopolymers or copolymers.

[0067] In some embodiments, the first organic particles may include one or more of a copolymer of an acrylate-based monomer unit and a styrene-based monomer unit, a copolymer of an acrylic acid-based monomer unit and a styrene-based monomer unit, a copolymer of an acrylic acid-based monomer unit-acrylate-based monomer unit-styrene-based monomer unit, a copolymer of a styrene-based monomer unit and an unsaturated nitrile-based monomer unit, a copolymer of a styrene-based monomer unit-olefin monomer unit-unsaturated nitrile-based monomer unit, and modified compounds of each of the above materials.

[0068] In some embodiments, the acrylate monomer units can be selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, isooctyl methacrylate, and the like.

[0069] In some embodiments, the acrylic acid-based monomer units can be selected from one or more of acrylic acid, methacrylic acid, and the like.

[0070] In some embodiments, the styrenic monomer units may be selected from one or more of styrene, methylstyrene, and the like.

[0071] In some embodiments, the unsaturated nitrile-based monomer units may be selected from one or more of acrylonitrile, methacrylonitrile, and the like.

[0072] In some embodiments, the first organic particles can comprise one or more of butyl acrylate-styrene copolymer, butyl methacrylate-isooctyl methacrylate copolymer, isooctyl methacrylate-styrene copolymer, methacrylate-methacrylic acid-styrene copolymer, methyl acrylate-isooctyl methacrylate-styrene copolymer, butyl acrylate-isooctyl acrylate-styrene copolymer, butyl acrylate-isooctyl methacrylate-styrene copolymer, butyl methacrylate-isooctyl methacrylate-styrene copolymer, butyl methacrylate-isooctyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, methyl acrylate-styrene-acrylonitrile copolymer, isooctyl methacrylate-styrene-acrylonitrile copolymer, styrene-vinyl acetate copolymer, styrene-vinyl acetate-pyrrolidone copolymer, and modified compounds of each of the above materials.

[0073] In the present application, the modified compound of each homopolymer or copolymer means a modified compound obtained by copolymerizing a monomer unit in each homopolymer or copolymer with a specific functional group-containing monomer unit. For example, a modified compound can be obtained by copolymerizing a fluorine-containing alkyl group monomer unit with a compound having a carboxyl group-containing functional group.

[0074] In some embodiments, at least some of the first organic particles comprise a core structure and a shell structure.

[0075] In some embodiments, the core structure and the shell structure comprise copolymers of the same monomer units, and the glass transition temperatures of the core structure and the shell structure materials can be adjusted by adjusting the copolymerization ratio of each monomer unit or the polymerization process.

[0076] In some embodiments, the glass transition temperature of the shell structure is higher than that of the core structure, which effectively reduces the probability of fusion between organic particles and the formation of a continuous gel film during the separator manufacturing process, improving the ion transmission path of the separator and maintaining good sheet adhesion in the electrolyte, thereby better bonding the electrode plate and separator, thereby further improving the cycle performance of the battery.

[0077] In some embodiments, the glass transition temperature of the core structure may be from -30°C to 20°C, for example, from -10°C to 10°C.

[0078] In some embodiments, the glass transition temperature of the shell structure may be from 50°C to 70°C, for example, from 55°C to 65°C.

[0079] In some embodiments, the core structure and the shell structure both include a copolymer of an acrylate-based monomer unit, for example, a copolymer of an acrylate-based monomer unit and a styrene-based monomer unit, which helps reduce the swelling rate of the first organic particles in the electrolyte during room temperature operation, further reducing the probability of forming a large-area gel film structure, and further improving the cycle performance of the battery.

[0080] In some embodiments, the weight percentage of the first organic particles in the coating is 10% or more (based on the total weight of the coating), for example, the weight percentage of the first organic particles in the coating may be 10% to 30%, 15% to 30%, 10% to 25%, or 10% to 20%. When the weight percentage of the first organic particles is controlled within a predetermined range, it helps the separator coating to have a good tunnel structure while ensuring adhesion, and further improves the cycle performance and safety of the battery.

[0081] In some embodiments, the inorganic particles can include one or more of boehmite (γ-AlOOH), alumina (AlO), barium sulfate (BaSO), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)), silicon dioxide (SiO), tin dioxide (SnO), titanium oxide (TiO), calcium oxide (CaO), zinc oxide (ZnO), zirconium dioxide (ZrO), yttrium oxide (YO), nickel oxide (NiO), cerium oxide (CeO), zirconium titanate (SrTiO), barium titanate (BaTiO), and magnesium fluoride (MgF).

[0082] In some embodiments, the volume average particle diameter Dv 50 ≦2.5 μm, and for example, the volume average particle diameter of the inorganic particles may be 0.5 μm to 2.5 μm, 1.5 μm to 2.5 μm, 0.3 μm to 0.7 μm, etc. When the particle diameter of the inorganic particles is controlled within a predetermined range, it contributes to improving the wettability of the electrolyte to the separator, and further improves the cycle performance of the battery.

[0083] In some embodiments, the weight percentage of the inorganic particles in the coating is ≦90% based on the total weight of the coating, and may be, for example, 70% to 90%, 75% to 85%, etc. When the weight percentage of the inorganic particles is controlled within a predetermined range, the energy density of the battery can be further improved while ensuring the safety performance of the separator.

[0084] In some embodiments, the coating may further include second organic particles, which are embedded in the inorganic particles and form protrusions on the surface of the coating, and the second organic particles are secondary particles. When the separator coating contains a certain amount of second organic particles in the form of secondary particles, this helps to form a uniform coating interface, which can effectively alleviate the tab misalignment problem during battery manufacturing after the separator is used in a battery, thereby further improving the safety performance of the battery.

[0085] The term "secondary particles" has the meaning known in the art, and refers to particles in an agglomerated state formed by agglomeration of two or more primary particles.

[0086] As shown in FIG. 1-2, the separator includes a substrate (A) and a coating (B), and the coating (B) includes first organic particles (B1), inorganic particles (B2), and second organic particles (B3), the first organic particles (B1) are primary particles, the second organic particles (B3) are secondary particles, and both the first organic particles and the second organic particles are embedded in the inorganic particles (B2), forming protrusions on the surface of the coating (B).

[0087] In some embodiments, the number average particle diameter of the second organic particles is ≧2 μm, for example, 12 μm to 25 μm, and may be, for example, 15 μm to 25 μm, 12 μm to 23 μm, 13 μm to 22 μm, 15 μm to 20 μm, 12 μm to 18 μm, etc. When the number average particle diameter of the second organic particles is within a predetermined range, sufficient gaps can be formed between the organic particles, and sufficient ion transmission paths can be formed even when the organic particles swell in the electrolyte, thereby further improving the cycle performance of the battery.

[0088] In some embodiments, the second organic particles may include one or more of a homopolymer or copolymer of a fluorine-containing alkyl group monomer unit, a homopolymer or copolymer of an olefin monomer unit, a homopolymer or copolymer of an unsaturated nitrile-based monomer unit, a homopolymer or copolymer of an alkylene oxide-based monomer unit, and a modified compound of each of the homopolymers or copolymers.

[0089] In some embodiments, the fluorine-containing alkyl group monomer unit can be selected from one or more of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.

[0090] In some embodiments, the olefin monomer units may be selected from one or more of ethylene, propylene, butadiene, isoprene, and the like.

[0091] In some embodiments, the unsaturated nitrile-based monomer units may be selected from one or more of acrylonitrile, methacrylonitrile, and the like.

[0092] In some embodiments, the alkylene oxide-based monomer units can be selected from one or more of ethylene oxide, propylene oxide, and the like.

[0093] In some embodiments, the second organic particles can include one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyethylene, polypropylene, polyacrylonitrile, polyethylene oxide, copolymers of different fluorine-containing alkyl group monomer units, copolymers of fluorine-containing alkyl group monomer units and vinyl group monomer units, copolymers of fluorine-containing alkyl group monomer units and acrylic acid-based monomer units, copolymers of fluorine-containing alkyl group monomer units and acrylate-based monomer units, and modified compounds of each of the above homopolymers or copolymers.

[0094] In some embodiments, the second organic particles can include one or more of vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-acrylic acid copolymer, vinylidene fluoride-hexafluoropropylene-acrylate copolymer, and modified compounds of the copolymers.

[0095] In the examples of the present application, the modified compound of each homopolymer or copolymer means a modified compound obtained by copolymerizing a monomer unit in each homopolymer or copolymer with a specific functional group-containing monomer unit. A modified compound can also be obtained by copolymerizing an alkyl group-containing fluorine-containing monomer unit with a compound having a carboxyl group-containing functional group.

[0096] In some embodiments, the number average molecular weight of the first organic particles is 10,000 to 100,000, such as 20,000 to 80,000.

[0097] In some embodiments, the number average molecular weight of the second organic particles is 300,000 to 800,000, such as 400,000 to 650,000.

[0098] In some embodiments, the weight percentage of the second organic particles in the coating is equal to or less than the weight percentage of the first organic particles in the coating. Optionally, the weight percentage of the second organic particles in the coating may be 1% to 10%, 1.5% to 7.5%, 2% to 8%, 2% to 5%, or 3% to 7%. The inventors have found through research that when the weight percentage of the second organic particles in the coating is within a certain range, the cycle performance and safety performance of the battery can be further improved.

[0099] In some embodiments, the weight of the coating on one side of the separator per unit area is ≦3.0 g / m 2 For example, the weight of the coating on one side of the separator per unit area is 1.5 g / m 2 ~3.0g / m 2 , 1.5g / m 2 ~2.5g / m 2 , 1.8g / m 2 ~2.3g / m 2 By controlling the weight of the coating on one side of the separator per unit area within a predetermined range, it is possible to further improve the energy density of the battery while ensuring the battery cycle performance and safety performance.

[0100] In some embodiments, the coating may further include other organic compounds, such as a polymer for improving heat resistance (also referred to simply as a "heat-resistant adhesive"), a dispersant, a wetting agent, or other types of binders. All of the above organic compounds are non-particulate substances in the dried coating. The present application does not particularly limit the type of the other organic compounds, and any known material with good improving properties may be selected and used.

[0101] The present application does not particularly limit the material of the substrate, and any known substrate having good chemical and mechanical stability can be selected and used, such as one or more of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The substrate may be a single-layer film or a multi-layer composite film. When the substrate is a multi-layer composite film, the materials of each layer may be the same or different.

[0102] In some embodiments, the thickness of the substrate is ≦12 μm, and may be, for example, 5 μm to 10 μm, 5 μm to 9 μm, 7 μm to 12 μm, etc. By controlling the thickness of the substrate within a predetermined range, it is possible to further improve the energy density of the battery while ensuring the battery cycle performance and safety performance.

[0103] In some embodiments, the separator may have an air permeability of 100s / 100mL to 300s / 100mL, for example, 150s / 100mL to 250s / 100mL, 170s / 100mL to 220s / 100mL, etc.

[0104] In some embodiments, the separator has a longitudinal tensile strength of 1000 kgf / cm 2 -3500kgf / cm 2 For example, the longitudinal tensile strength of the separator may be 1200 kgf / cm 2 ~2800kgf / cm 2 , 1200kgf / cm 2 ~2000kgf / cm 2 , 1500kgf / cm 2 ~3000kgf / cm 2 may be.

[0105] In some embodiments, the longitudinal breaking elongation of the separator may be 50% to 200%, for example, the longitudinal breaking elongation of the separator may be 80% to 150%.

[0106] In some embodiments, the separator has a transverse tensile strength of 1000 kgf / cm 2 ~3500kgf / cm 2 For example, the separator may have a transverse tensile strength of 1200 kgf / cm 2 ~3000kgf / cm 2 , 1200kgf / cm 2 ~2000kgf / cm 2 , 1500kgf / cm 2 ~3000kgf / cm 2 may be.

[0107] In some embodiments, the separator may have a transverse elongation at break of 50% to 200%, such as a transverse elongation at break of 80% to 150%.

[0108] In some embodiments, the inorganic particles and the organic particles form non-uniform tunnel structures in the coating.

[0109] In some embodiments, when the distance between any two adjacent inorganic particles is L1 and the distance between any one adjacent inorganic particle and one adjacent organic particle is L2, L1 <L2である。

[0110] In some embodiments, the particle size and number-average particle size of organic particles can be measured using equipment and methods known in the art. For example, a scanning electron microscope (e.g., ZEISS Sigma 300) is used to obtain an SEM image of the separator, for example, according to JY / T010-1996. For example, the measurements can be performed as follows: A sample measuring 50 mm x 100 mm is randomly taken from the separator, and multiple measurement areas (e.g., five) are randomly selected from the sample. The particle size of each organic particle in each measurement area is measured at a certain magnification (e.g., 500x for measuring the first organic particles, and 1000x for measuring the second organic particles). (Note: If the organic particles have an irregular shape, the particle size of the organic particle is determined by the distance between the two most distant points on the organic particle). This is the particle size of the organic particles described herein. The number of organic particles and the particle diameter values ​​in each measurement area are counted, and the arithmetic mean value of the particle diameters of the organic particles in each measurement area is calculated, which is the number-average particle diameter of the organic particles in this sample. To ensure the accuracy of the measurement results, multiple samples (e.g., 10 samples) are taken and the above measurement is performed, and the average value of each sample can be calculated as the final measurement result.

[0111] In some embodiments, the shape of organic particles (e.g., primary particle shape or secondary particle shape) can be measured using equipment and methods known in the art. Measurements can be made using a scanning electron microscope (e.g., ZEISS Sigma 300). For example, the procedure can be as follows: First, cut the separator into a sample of a certain size (e.g., 6 mm x 6 mm), sandwich the sample between two conductive heat transfer sheets (e.g., copper foil), and secure the sample and the sheets with adhesive (e.g., double-sided tape). Then, press the sample with a strain relief iron block of a certain mass (e.g., about 400 g) for a certain period of time (e.g., 1 hour). The smaller the gap between the sample and the copper foil, the better. Next, trim the edges with scissors and attach the sample to a sample holder with conductive adhesive, so that the sample slightly protrudes from the edge of the holder. Next, place the sample stage in the sample holder and lock it in place. Turn on the argon ion cross-section polishing device (e.g., IB-19500CP) and draw a vacuum (e.g., 10 Pa to 4 Pa). Set the argon gas flow rate (e.g., 0.15 MPa), voltage (e.g., 8 KV), and polishing time (e.g., 2 hours). Adjust the sample stage to oscillation mode and begin polishing. After polishing is complete, use a scanning electron microscope (e.g., ZEISS Sigma 300) to obtain a photograph of the ion-polished cross-section (CP) of the measurement sample.

[0112] Figures 2-1 and 2-2 are photographs of the ion-polished cross-section (CP) of the separator of this example. As can be seen from Figure 2-1, the separator coating contains first organic particles, which are non-agglomerated primary particles with a cross-section of a solid sphere. As can be seen from Figure 2-2, the separator coating contains both first and second organic particles, which are secondary particles composed of multiple primary particles with an irregular cross-section other than a solid sphere.

[0113] According to some embodiments, the type of material of organic particles can be measured using equipment and methods known in the art. For example, the type of material can be identified by measuring the infrared spectrum of the material and determining the characteristic peaks contained therein. Specifically, the organic particles can be subjected to infrared spectroscopy analysis using equipment and methods known in the art, for example, an infrared spectrometer such as the IS10 Fourier transform infrared spectrometer manufactured by Nicolet Corporation, USA, in accordance with GB / T6040-2002 General Rules for Infrared Spectroscopy.

[0114] According to some embodiments, the volume average particle size Dv 50 has a meaning known in the art and can be measured by using instruments and methods known in the art, for example, see GB / T19077-2016 Laser Diffraction Particle Size Distribution Method and can be measured using a laser particle size analyzer (e.g., Master Size 3000).

[0115] In some embodiments, the separator's air permeability, transverse tensile strength (TD), longitudinal tensile strength (MD), transverse breaking elongation, and longitudinal breaking elongation all have meanings known in the art and can be measured by methods known in the art, for example, according to GB / T 36363-2018.

[0116] In some examples, the distance between any two adjacent inorganic particles is determined by arbitrarily taking two adjacent inorganic particles (if the inorganic particles have an irregular shape, circumscribing treatment can be performed on these particles) from the coating in an SEM image of the separator, and measuring the center-to-center distance between the two inorganic particles as the distance between the two inorganic particles, which is designated as L1.

[0117] In some embodiments, the distance between any adjacent inorganic particle and any adjacent organic particle is measured by arbitrarily selecting one adjacent inorganic particle and one adjacent organic particle from the coating in an SEM image of the separator (if the inorganic particle or organic particle has an irregular shape, a circumscribing process can be performed on the particle), and measuring the center-to-center distance between the inorganic particle and the organic particle, which is designated as L2. The organic particle may be a first organic particle or a second organic particle.

[0118] The distance can be measured using tools known in the art, such as a scanning electron microscope. For example, the distance L2 between any adjacent inorganic and organic particles can be measured as follows: A separator is prepared as a test sample measuring 50 mm x 100 mm, and the separator is measured using a scanning electron microscope (e.g., a ZEISS Sigma 300). Measurements can be performed in accordance with JY / T010-1996. Randomly select an area from the sample, perform scanning measurements, and obtain an SEM image of the separator at a certain magnification (e.g., 3000x). In the SEM image, adjacent inorganic and organic particles are randomly selected (if the inorganic or organic particles are irregular, a circumscribing process can be performed on the particles). The distance between the center of the inorganic particle (or its circumscribing circle) and the center of the organic particle (or its circumscribing circle) is measured, and this distance, L2, is the distance between adjacent inorganic and organic particles described herein. To ensure the accuracy of the measurement results, the above measurement is repeated for multiple sets of adjacent particles (for example, 10 sets) in the sample, and the average value of the measurement results for each set is taken as the final result.

[0119] Similarly, the distance L1 between any two adjacent inorganic particles can also be measured by the above method.

[0120] Figs. 3-1 and 3-2 are photographs of a separator of an embodiment of the present application taken with a scanning electron microscope (SEM). As can be seen from Fig. 3-1, the coating of the separator contains inorganic particles and first organic particles. The first organic particles are primary particles, and the first organic particles are embedded in the inorganic particles, forming protrusions on the surface of the coating. As can be seen from Fig. 3-2, the coating of the separator contains inorganic particles, first organic particles and second organic particles. The first organic particles are primary particles, and the second organic particles are secondary particles. Both the first organic particles and the second organic particles are embedded in the inorganic particles, forming protrusions on the surface of the coating. When measured by the method described above, it is found that L1 < L2.

[0121] The present application further provides step (1) of providing a substrate, step (2) of providing a coating slurry containing a component material and a solvent, the component material including inorganic particles and organic particles containing first organic particles, step (3) of applying the coating slurry described in step (2) to at least one side of the substrate described in step (1), forming a coating, drying it, and obtaining the separator, The separator includes a substrate and a coating formed on at least one surface of the substrate. The coating contains inorganic particles and first organic particles. The first organic particles are embedded in the inorganic particles, forming protrusions on the surface of the coating. The first organic particles are in the shape of primary particles, and the number average particle diameter of the first organic particles is ≧ 2 μm. A method for manufacturing a separator is provided.

[0122] The coating may be provided only on one side of the substrate or on both sides of the substrate.

[0123] As shown in Fig. 4-1, the separator includes a substrate (A) and a coating (B), and the coating (B) is provided only on one side of the substrate (A).

[0124] As shown in FIG. 4-2, the separator includes a substrate (A) and a coating (B), and the coating (B) is provided on both sides of the substrate (A).

[0125] In the examples of the present application, the material of the substrate is not particularly limited, and any known substrate having good chemical and mechanical stability can be selected and used, such as one or more of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The substrate may be a single-layer film or a multi-layer composite film. When the substrate is a multi-layer composite film, the materials of each layer may be the same or different.

[0126] In some embodiments, in step (2), the solvent may be water, for example, deionized water.

[0127] In some embodiments, in step (2), the component material may further comprise a second organic particle as described herein.

[0128] In some embodiments, in step (2), the component material may further include other organic compounds, such as a polymer for improving heat resistance (also referred to simply as a "heat-resistant adhesive"), a dispersant, a wetting agent, or other types of binders. Note that all of the organic compounds are non-particulate substances in the dried coating. The present application does not particularly limit the types of the other organic compounds, and any known material with good improving properties may be selected and used.

[0129] In some embodiments, in step (2), the component materials are added to a solvent and stirred uniformly to obtain a coating slurry.

[0130] In some embodiments, in step (2), the added mass of the first organic particles is 10% or more of the total dry weight of the component materials, for example, 10% to 30%, 15% to 30%, 10% to 25%, or 10% to 20%.

[0131] In some embodiments, in step (2), the added mass of the second organic particles is equal to or less than the added mass of the first organic particles. Optionally, the added mass of the second organic particles may be 1% to 10% of the total dry matter weight of the component materials, such as 1.5% to 7.5%, 2% to 8%, 2% to 5%, or 3% to 7%.

[0132] An appropriate content of organic particles can reduce static electricity generated between the separator and the battery winding tool (e.g., winding pin) or stacking tool during the battery manufacturing process, effectively reducing the probability of short-circuiting between the positive and negative electrodes and improving the manufacturing efficiency of the battery.

[0133] If a component material is solid, the dry weight of the component material is the mass of the component material added. If a component material is a suspension, emulsion, or solution, the dry weight of the component material is the product of the mass of the component material added and the solid content of the component material. The total dry weight of the component materials is the sum of the dry weights of each component material.

[0134] In some embodiments, in step (2), the solid content of the coating slurry can be controlled to 28% to 45%, for example, 30% to 38%, based on the weight of the coating slurry. When the solid content of the coating slurry is in the above range, the probability of occurrence of coating film surface problems and coating unevenness can be effectively reduced, and the cycle performance and safety performance of the battery can be further improved.

[0135] In some embodiments, in step (3), the coating is performed using a coater.

[0136] In the examples of the present application, the type of coater is not particularly limited, and any commercially available coater can be used.

[0137] In some embodiments, in step (3), the coating can be performed using a process such as transfer coating, spin spraying, or dip coating, for example, the coating can be performed using transfer coating.

[0138] In some embodiments, the applicator includes a gravure roll, which is a generally cylindrical steel roll having variously shaped slurry grooves cut into its surface for transferring the coating slurry to the substrate.

[0139] In some embodiments, the gravure roll may have a ruling of 100 LPI to 300 LPI, for example, 125 LPI to 190 LPI (LPI is lines per inch). The higher the ruling of the roller, the less slurry is spread by it. When the ruling of the gravure roll is within the above range, it contributes to controlling the number of the first organic particles and the second organic particles, and further improves the cycle performance and safety performance of the separator.

[0140] In some embodiments, in step (3), the coating speed can be controlled to 30 m / min to 90 m / min, for example, 50 m / min to 70 m / min. When the coating speed is within this range, the coating surface problem can be effectively reduced, the probability of coating unevenness can be reduced, and the cycle performance and safety performance of the battery can be further improved.

[0141] In some embodiments, in step (3), the linear velocity ratio of the coating may be controlled to be 0.8 to 2.5, for example, 0.8 to 1.5, or 1.0 to 1.5.

[0142] In some embodiments, in step (3), the drying temperature may be 40°C to 70°C, for example, 50°C to 60°C.

[0143] In some embodiments, in step (3), the drying time may be 10 seconds to 120 seconds, for example, 20 seconds to 80 seconds, or 20 seconds to 40 seconds.

[0144] By controlling each of the above process parameters within a predetermined range, the performance of the separator of the present invention can be further improved. Those skilled in the art can selectively adjust and control one or more of the above process parameters based on the actual production situation.

[0145] In order to further improve the performance of the secondary battery, the inorganic particles and the organic particles may optionally further satisfy one or more of the above-mentioned parameter conditions, the description of which is omitted here.

[0146] The substrate, the first organic particles, and the second organic particles are all commercially available.

[0147] The method for manufacturing a separator according to the present invention produces a coating in a single application, greatly simplifying the separator production process flow. Furthermore, when the separator manufactured by the above method is applied to a battery, the cycle performance and safety performance of the battery can be effectively improved.

[0148] [Positive electrode] In this secondary battery, the positive electrode plate usually has a positive electrode current collector and a positive electrode film layer that is provided on the positive electrode current collector and contains a positive electrode active material.

[0149] The positive electrode current collector can be a regular metal foil piece or a composite current collector (a composite current collector can be formed by providing a metal material on a polymer substrate.) For example, the positive electrode current collector can be aluminum foil.

[0150] The specific type of the positive electrode active material is not limited, and any active material known in the art that is applicable to the positive electrode of a secondary battery may be used, and those skilled in the art may select the material according to actual requirements.

[0151] For example, the positive electrode active material may include, but is not limited to, one or more of lithium transition metal oxides, olivine-type lithium-containing phosphates, and modified compounds thereof. Examples of lithium transition metal oxides include, but are not limited to, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and modified compounds thereof. Examples of olivine-type lithium phosphates include, but are not limited to, lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon, lithium manganese iron phosphate, a composite of lithium manganese iron phosphate and carbon, and modified compounds thereof. These materials are commercially available.

[0152] In some embodiments, the modified compound for each material may be a doping modification and / or a surface coating modification of the material.

[0153] The positive electrode membrane layer generally optionally includes a binder, a conductive agent, and other optional auxiliary agents.

[0154] By way of example, the conductive agent may be one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, Super P (SP), graphene, and carbon nanofibers.

[0155] By way of example, the binder may be one or more of styrene butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).

[0156] [Negative electrode] In this secondary battery, the negative electrode plate usually has a negative electrode current collector and a negative electrode film layer provided on the negative electrode current collector and containing a negative electrode active material.

[0157] The negative electrode current collector can be a conventional metal foil piece or a composite current collector (for example, a composite current collector can be formed by providing a metal material on a polymer substrate). For example, the negative electrode current collector can be aluminum foil.

[0158] The specific type of the negative electrode active material is not limited, and any active material known in the art that is applicable to the negative electrode of a secondary battery can be used. Those skilled in the art can select the material according to their actual needs. For example, the negative electrode active material can include, but is not limited to, one or more of artificial graphite, natural graphite, hard carbon, soft carbon, silicon-based materials, and tin-based materials. The silicon-based material can be selected from one or more of elemental silicon, silicon oxide (e.g., silicon monoxide), silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. The tin-based material can be selected from one or more of elemental tin, tin oxides, and tin alloys. These materials are commercially available.

[0159] In some embodiments, to further improve the energy density of the battery, the negative electrode active material comprises a silicon-based material.

[0160] The negative electrode membrane layer generally optionally contains a binder, a conductive agent, and other optional auxiliary agents.

[0161] By way of example, the conductive agent may be one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0162] By way of example, the binder may be one or more of styrene butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).

[0163] For example, other optional auxiliary agents may be thickening and dispersing agents (e.g., sodium carboxymethylcellulose CMC-Na), PTC thermistor materials, and the like.

[0164] [Electrolyte] The secondary battery may include an electrolyte that functions to conduct ions between the positive electrode and the negative electrode. The electrolyte may include an electrolyte salt and a solvent.

[0165] By way of example, the electrolyte salt may be selected from one or more of LiPF (lithium hexafluorophosphate), LiBF (lithium tetrafluoroborate), LiClO (lithium perchlorate), LiAsF (lithium hexafluoroarsenate), LiFSI (lithium bis(fluorosulfonyl)imide), LiTFSI (lithium bis(trifluoromethanesulfonylimide), LiTFS (lithium trifluoromethanesulfonate), LiDFOB (lithium difluoro(oxalatoborate), LiBOB (lithium bis(oxalato)borate), LiPOF (lithium difluorophosphate), LiDFOP (lithium difluorobis(oxalato)phosphate), and LiTFOP (lithium tetrafluoro(oxalato)phosphate).

[0166] By way of example, the solvent may be selected from one or more of ethylene carbonate (EC), propylene carbonate (PC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS), and diethyl sulfone (ESE).

[0167] In some embodiments, the electrolyte solution further includes an additive. For example, the additive may include an anode film-forming additive, a cathode film-forming additive, or an additive that can improve some performance of the battery, such as an additive that improves the overcharge performance of the battery, an additive that improves the high-temperature performance of the battery, or an additive that improves the low-temperature performance of the battery.

[0168] In some embodiments, the secondary battery of the present application is a lithium ion secondary battery.

[0169] The secondary battery can be manufactured according to a conventional method in the art. For example, a positive electrode plate, a separator, and a negative electrode plate are sequentially wound (or stacked), a separator is interposed between the positive electrode plate and the negative electrode plate to separate them, a cell is obtained, the cell is placed in an outer casing, an electrolyte is poured in, and the cell is sealed to obtain a secondary battery.

[0170] In the embodiments of the present application, the shape of the secondary battery is not particularly limited, and it may be cylindrical, rectangular, or any other shape. Figure 5 shows a secondary battery 5 having a rectangular structure as an example.

[0171] In some embodiments, the secondary battery can include an outer packaging for packaging the positive electrode plate, the negative electrode plate, and the electrolyte.

[0172] 6, in some embodiments, the exterior may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate together form a surrounding storage chamber. The housing 51 has an opening communicating with the storage chamber, and the cover plate 53 may be fitted over the opening to close the storage chamber.

[0173] The positive electrode plate, the negative electrode plate, and the separator can be wound or stacked to form an electrode assembly 52. ​​The electrode assembly 52 is sealed in the housing. The electrolyte is permeated into the electrode assembly 52. ​​The number of electrode accesses 52 included in the secondary battery 5 can be one or more, and can be adjusted as needed.

[0174] In some embodiments, the exterior of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, etc. The exterior of the secondary battery may be a flexible package, such as a bag-type flexible package. The material of the flexible package may be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.

[0175] In some embodiments, the secondary batteries can be assembled into a battery module, and the number of secondary batteries included in the battery module can be multiple, and the specific number can be adjusted based on the application and capacity of the battery module.

[0176] 7 shows an example of a battery module 4. In the battery module 4, the plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, they may be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 may be fastened together with fasteners.

[0177] Optionally, the battery module 4 may further include a housing having a storage space for storing a plurality of secondary batteries 5.

[0178] In some embodiments, the battery modules can be further assembled into a battery pack, and the number of battery modules included in the battery pack can be adjusted based on the application and capacity of the battery pack.

[0179] 8 and 9 show an example of a battery pack 1. The battery pack 1 may include a battery case and a plurality of battery modules 4 provided in the battery case. The battery case includes an upper case 2 and a lower case 3, and the upper case 2 is covered by the lower case 3 to form an enclosed space for accommodating the battery modules 4. The plurality of battery modules 4 may be arranged in the battery case in any manner.

[0180] Device The present application further provides a device including at least one of the secondary battery, battery module, or battery pack. The secondary battery, battery module, or battery pack may be used as a power source for the device or as an energy storage means for the device. The device may be, but is not limited to, a mobile device (e.g., a mobile phone, a laptop, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), a train, a ship, a satellite, an energy storage system, etc.

[0181] The device can select a secondary battery, a battery module or a battery pack according to its usage requirements.

[0182] An example device is shown in Figure 10. This device may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. This device can use a battery pack or a battery module to meet the high power and high energy density requirements for secondary batteries.

[0183] Other examples of the device may be a mobile phone, a tablet computer, a laptop computer, etc. These devices are generally required to be lightweight and can employ a secondary battery as a power source.

[0184] The beneficial effects of the present invention will be further illustrated below with reference to examples.

[0185] Example In order to clarify the technical problems, technical solutions, and beneficial effects that the present application aims to solve, the present application will be described in more detail below with reference to examples and drawings. Obviously, the described examples are only some of the examples of the present application, but not all of the examples. The following description of at least one exemplary example is merely illustrative in nature and does not in any way limit the present application and its applications. Any other examples that can be obtained based on the examples of the present application without the need for creative work by those skilled in the art are also within the scope of protection of the present application.

[0186] All materials used in the examples of this application are commercially available, for example: The substrate can be purchased from Shanghai Enjie New Materials Co., Ltd.

[0187] Inorganic particles can be purchased from Yishitong Materials Technology Co., Ltd.

[0188] The first organic particles can be purchased from Akena (Changshu) Chemical Co., Ltd.

[0189] The second organic particles can be purchased from Sichuan IndiLue Technology Co., Ltd.

[0190] The wetting agent can be purchased from Taoshi Chemical Company.

[0191] The dispersant can be purchased from Changshu Weiyi Technology Co., Ltd.

[0192] 1. Separator manufacturing Separator 1: (1) Provide a PE substrate, for example, the thickness of the substrate is 7 μm and the porosity is 36%; (2) A coating slurry was prepared by uniformly mixing inorganic particles (alumina (Al2O3)), first organic particles (butyl methacrylate-isooctyl acrylate-styrene copolymer), dispersant (sodium carboxymethyl cellulose CMC-Na), and wetting agent (organosilicon-modified polyether) in deionized water in a mass ratio of 80:15:3:2 to obtain a coating slurry with a weight-based solid content of 35%. The volume average particle diameter Dv of the inorganic particles (alumina (Al2O3)) was 50 is 1 μm, the number average particle diameter of the first organic particles is 2 μm, the shape of the first organic particles is primary particles, at least some of the first organic particles include a core structure and a shell structure, the glass transition temperature of the shell structure is 55°C, and the glass transition temperature of the core structure is 20°C.

[0193] (3) The coating slurry prepared in step (2) is applied to two surfaces of the PE substrate using a coater, followed by drying and slitting to obtain cell plate 1. The Granvilor line number of the coater is 190 LPI, the coating speed is 70 m / min, the coating linear velocity ratio is 1.3, and the coating weight on one side of the separator per unit area is 2.0 g / m. 2 In the separator, the first organic particles are embedded in the inorganic particles, and protrusions are formed on the surface of the coating.

[0194] Separators 2 to 18 and comparative separators 1 to 4 are manufactured using a method similar to that of separator 1, with the difference being that the number average particle size, mass ratio, type of substance, and particle shape of the first organic particles are adjusted, as shown in Table 1.

[0195] Separators 19 to 35 are manufactured using a method similar to that of separator 1, with the difference being that second organic particles are added to the coating and their number average particle size, mass ratio, and substance type are adjusted, as shown in Table 2 in detail.

[0196] 2. Battery manufacturing Example 1 1. Manufacturing of positive electrode plates LiNi, the positive electrode active material 0.5 Co 0.2 Mn 0.3 O2 (NCM523), carbon black (SuperP) as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder are uniformly mixed in a mass ratio of 96.2:2.7:1.1 in N-methylpyrrolidone (NMP) as a solvent to obtain a positive electrode slurry. The positive electrode slurry is then applied to aluminum foil as a positive electrode current collector, and the positive electrode plate is obtained through heat drying, cold pressing, striping, and cutting processes.

[0197] 2. Manufacturing of negative electrode plates The negative electrode active material, artificial graphite, the conductive agent, carbon black (Super P), the binders, styrene butadiene rubber (SBR) and carboxymethyl cellulose sodium (CMC-Na), are mixed uniformly in a mass ratio of 96.4:0.7:1.8:1.1 with deionized water as the solvent to obtain a negative electrode slurry. This negative electrode slurry is then applied to copper foil as the negative electrode current collector, and the negative electrode plate is obtained after undergoing heat drying, cold pressing, striping, and cutting processes.

[0198] 3. Separator The separator used is the separator 1 manufactured as described above.

[0199] 4. Electrolyte production Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) are mixed in a mass ratio of 30:70 to obtain an organic solvent, and thoroughly dried electrolyte salt LiPF6 is dissolved in the mixed solvent. The electrolyte salt concentration is set to 1.0 mol / L and mixed uniformly to obtain an electrolyte solution.

[0200] 5. Secondary battery manufacturing The positive electrode plate, separator, and negative electrode plate are stacked in this order, and a separator is interposed between the positive and negative electrode plates to serve as an insulator. The electrode assembly is then wound up to obtain an electrode assembly. The electrode assembly is then placed in a casing, and the above-prepared electrolyte is injected into the dried secondary battery assembly. The secondary battery is then obtained by vacuum sealing, leaving it to stand, chemical conversion, and shaping processes.

[0201] The secondary batteries of Examples 2 to 18, Examples 19 to 35 and Comparative Examples 1 to 4 are similar to the secondary battery of Example 1, except that different separators are used.

[0202] 3. Battery performance measurement 1.25℃ cycle performance The secondary batteries manufactured in the examples and comparative examples were charged at a constant current of 1 C at 25°C to a charge cut-off voltage of 4.2 V, then charged at a constant voltage of 0.05 C or less, allowed to stand for 30 minutes, and then discharged at a constant current of 0.33 C to a discharge cut-off voltage of 2.8 V, allowed to stand for 30 minutes, and the battery capacity C0 was recorded. The batteries were charged and discharged 1500 times in this manner, and the battery capacity after 1500 cycles was recorded as C1.

[0203] The cycle capacity retention rate of the battery at 25°C = C1 / C0 x 100%.

[0204] 2.Heat diffusion performance At 25°C, the secondary batteries manufactured in the examples and comparative examples were charged at a constant current of 1C to a charge cut-off voltage of 4.2V, and then charged at a constant voltage of 0.05C or less. After leaving the battery to stand for 10 minutes, a metal heating plate was placed in close contact with the surface of the battery, which was then clamped with a jig. A 3mm insulating gasket was placed between the jig and the battery, and the battery was heated at a constant temperature of 200°C until thermal runaway occurred. The time at which thermal runaway occurred was recorded.

[0205] The measured battery performance of each of the examples and comparative examples is shown in Tables 1 and 2. [Table 1-1] [Table 1-2] [Table 2-1] [Table 2-2] [Table 2-3]

[0206] As is clear from Table 1, the use of first organic particles having a specific number-average particle size and particle shape significantly improves the cycle performance and safety performance of the battery. In particular, further optimization of the number-average particle size, additive amount, or type of substance of the first organic particles can further improve the cycle performance and safety performance of the battery. In contrast, Comparative Examples 1 and 2, which used first organic particles outside the number-average particle size range of the present application, were inferior in cycle performance and safety performance to Examples 1 to 18 of the present application. Comparative Example 4 used first organic particles whose number-average particle size of secondary particle shape was outside the range limited by the present application, and the resulting battery performance was significantly inferior to Examples 1 to 18 of the present application. Comparative Example 3 used first organic particles within the number-average particle size range limited by the present application, but because the particle shape was secondary particles, the resulting battery was slightly better in cycle performance and safety performance than Comparative Examples 1, 2, and 4, but did not achieve the same level of improvement as Examples 1 to 18 of the present application.

[0207] As is clear from Table 2, the safety performance and cycle performance of the resulting battery can be further improved by further adding second organic particles of a specific amount, a specific type and a specific number average particle size range.

[0208] The inventors further conducted experiments using other amounts and materials of the inorganic particles, first organic particles, and second organic particles within the scope of the present application, other substrates, other coating process parameters, and other process conditions, and obtained improvements in the cycle performance and safety performance of the battery similar to those of Examples 1 to 35.

[0209] The above content is merely a specific embodiment of the present application, and the scope of protection of the present application is not limited thereto. Those skilled in the art can easily devise various equivalent modifications and replacements within the technical scope disclosed in the present application, and all of these modifications and replacements fall within the scope of protection of the present application. Therefore, the scope of protection of the present application should be determined based on the scope of protection of the claims. [Explanation of symbols]

[0210] 1 battery pack 2 Upper case 3 Lower case 4 Battery Module 5 Secondary battery 51 Housing 52 Electrode Assembly 52 Electrode Access 53 Lid plate

Claims

1. A substrate; a coating formed on at least one surface of the substrate, the coating including inorganic particles and first organic particles, the first organic particles embedded in the inorganic particles and forming protrusions on the surface of the coating; the first organic particles are in the form of primary particles, and the number average particle diameter of the first organic particles is 2 μm to 10 μm; the first organic particles include a copolymer containing an isooctyl acrylate-based monomer unit and a styrene-based monomer unit; the isooctyl acrylate-based monomer unit is selected from at least one of isooctyl acrylate and isooctyl methacrylate, and the styrene-based monomer unit is selected from at least one of styrene and methylstyrene; Separator.

2. 2. The separator according to claim 1, wherein the number average particle size of the first organic particles is 3 μm to 8 μm.

3. 3. The separator according to claim 1, wherein the first organic particles comprise one or more of an isooctyl methacrylate-styrene copolymer, a methyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl acrylate-isooctyl acrylate-styrene copolymer, a butyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl acrylate-styrene copolymer, an isooctyl methacrylate-styrene-acrylonitrile copolymer, and modified compounds of the copolymers.

4. The separator according to any one of claims 1 to 3, wherein at least some of the first organic particles include a core structure and a shell structure.

5. 5. The separator according to claim 4, wherein the glass transition temperature of the shell structure is higher than the glass transition temperature of the core structure.

6. the glass transition temperature of the core structure is −30° C. to 20° C.; 6. The separator according to claim 4, wherein the shell structure has a glass transition temperature of 50°C to 70°C.

7. The separator according to any one of claims 1 to 6, wherein a mass ratio of the first organic particles in the coating is 10% or more.

8. 3. The separator according to claim 1, wherein the coating further comprises second organic particles, the second organic particles being embedded in the inorganic particles and forming protrusions on the surface of the coating, and the second organic particles having a secondary particle shape.

9. The separator according to claim 8, wherein the number average particle size of the second organic particles is 12 μm or more.

10. The separator according to claim 8 or 9, wherein the mass proportion of the second organic particles in the coating is equal to or less than the mass proportion of the first organic particles in the coating.

11. The separator according to any one of claims 8 to 10, wherein the second organic particles contain one or more of a homopolymer or copolymer of a fluorine-containing alkyl group monomer unit, a homopolymer or copolymer of an olefin monomer unit, a homopolymer or copolymer of an unsaturated nitrile-based monomer unit, a homopolymer or copolymer of an alkylene oxide-based monomer unit, and a modified compound of each of the homopolymers or copolymers.

12. The separator according to any one of claims 8 to 10, wherein the second organic particles comprise one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyethylene, polypropylene, polyacrylonitrile, polyethylene oxide, a copolymer of different fluorine-containing alkyl group monomer units, a copolymer of a fluorine-containing alkyl group monomer unit and a vinyl group monomer unit, a copolymer of a fluorine-containing alkyl group monomer unit and an acrylic acid-based monomer unit, a copolymer of a fluorine-containing alkyl group monomer unit and an acrylate-based monomer unit, and a modified compound of each of the homopolymers or copolymers.

13. 13. The separator according to claim 8, wherein the second organic particles comprise one or more of vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-acrylic acid copolymer, vinylidene fluoride-hexafluoropropylene-acrylate copolymer, and modified compounds of the copolymers.

14. The inorganic particles include boehmite (γ-AlOOH), alumina (Al ２ O ３ ), barium sulfate (BaSO ４ ), magnesium oxide (MgO), magnesium hydroxide (Mg(OH) ２ ), silicon dioxide (SiO ２ ), tin dioxide (SnO ２ ), titanium oxide (TiO ２ ), calcium oxide (CaO), zinc oxide (ZnO), zirconium dioxide (ZrO ２ ), yttrium oxide (Y ２ O ３ ), nickel oxide (NiO), cerium oxide (CeO ２ ), zirconium titanate (SrTiO ３ ), barium titanate (BaTiO ３ ), magnesium fluoride (MgF ２ 3. The separator according to claim 1, comprising one or more of the following:

15. 3. The separator according to claim 1, wherein the inorganic particles have a volume average particle size of 2.5 μm or less.

16. Weight of coating on one side of separator per unit area ≦3.0 g / m ２ The separator according to claim 1 or 2,

17. The separator is (1) The separator has an air permeability of 100 s / 100 mL to 300 s / 100 mL; (2) The separator has a transverse breaking elongation of 50% to 200%; (3) The longitudinal breaking elongation of the separator is 50% to 200%; (4) The separator has a transverse tensile strength (MD) of 1000 kgf / cm ２ ~3500kgf / cm ２ That is, (5) The separator has a longitudinal tensile strength (TD) of 1000 kgf / cm ２ ~3500kgf / cm ２ The separator according to claim 1 or 2, further satisfying one or more of the following:

18. 3. The separator according to claim 1, wherein L1<L2 is satisfied, where L1 is the distance between any two adjacent inorganic particles and L2 is the distance between any adjacent inorganic particle and organic particle.

19. A method for producing a separator according to claim 1 or 2, comprising: (1) providing a substrate; (2) providing a coating slurry including component materials including inorganic particles and organic particles including first organic particles, and a solvent; and step (3) applying the coating slurry described in step (2) to at least one side of the substrate described in step (1) to form a coating, followed by drying to obtain the separator; The separator includes a substrate and a coating formed on at least one surface of the substrate, the coating includes inorganic particles and first organic particles, the first organic particles are embedded in the inorganic particles and form protrusions on the surface of the coating, the first organic particles have a primary particle shape, and the number average particle diameter of the first organic particles is 2 μm to 10 μm.

20. 20. The method of claim 19, wherein in step (2), the organic particles further include second organic particles, and the second organic particles are in a secondary particle form.

21. the added mass of the second organic particles is equal to or less than the added mass of the first organic particles; 21. The method of claim 20, wherein the added mass of the second organic particles is 1% to 10% of the total dry weight of the component materials.

22. (1) In the step (2), the added mass of the first organic particles is 10% or more of the total dry weight of the component materials; (2) In the step (2), the solid content of the coating slurry is 28% to 45%; (3) In the step (3), the coating is performed using a coating machine, the coating machine is equipped with a gravure roll, and the number of lines of the gravure roll is 100 LPI to 300 LPI; (4) In the step (3), the coating speed is 30 m / min to 90 m / min; (5) In the step (3), the linear velocity ratio of the coating is 0.8 to 2.5; (6) In the step (3), the drying temperature is 40°C to 70°C; (7) In the step (3), the drying time is 10 seconds to 120 seconds.

23. A secondary battery comprising a separator according to claim 1 or 2.

24. An apparatus comprising the secondary battery described in claim 23.

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