WO2023133882A1 - 隔膜及其相关的二次电池、电池模块、电池包和用电装置 - Google Patents

隔膜及其相关的二次电池、电池模块、电池包和用电装置 Download PDF

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WO2023133882A1
WO2023133882A1 PCT/CN2022/072330 CN2022072330W WO2023133882A1 WO 2023133882 A1 WO2023133882 A1 WO 2023133882A1 CN 2022072330 W CN2022072330 W CN 2022072330W WO 2023133882 A1 WO2023133882 A1 WO 2023133882A1
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region
battery
secondary battery
polymer
present application
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PCT/CN2022/072330
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English (en)
French (fr)
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唐怀超
李婷
牛少军
***
吴凯
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宁德时代新能源科技股份有限公司
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Priority to EP22896837.6A priority Critical patent/EP4239781A1/en
Priority to PCT/CN2022/072330 priority patent/WO2023133882A1/zh
Priority to CN202280005859.4A priority patent/CN117083741A/zh
Priority to US18/207,162 priority patent/US20230318140A1/en
Publication of WO2023133882A1 publication Critical patent/WO2023133882A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • 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 technical field of secondary batteries, in particular to a diaphragm and related secondary batteries, battery modules, battery packs and electrical devices.
  • secondary batteries have been widely used in energy storage power systems such as hydraulic, thermal, wind and solar power plants, as well as electric tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of secondary batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
  • the present application was made in view of the above-mentioned problems, and an object thereof is to provide a separator from which a secondary battery produced has improved safety performance and cycle performance.
  • the present application provides a separator, a secondary battery containing it, a battery module, a battery pack and an electrical device.
  • the first aspect of the present application provides a diaphragm, comprising
  • a coating on at least one surface of the porous substrate comprising a first region comprising inorganic ceramic particles and a first polymer and a second region comprising a second Two polymers, the first region and the second region have the same thickness, wherein the weight content of the second polymer in the second region is 20%-100%, optionally 50% %-100%, based on the total weight of the second region.
  • the coating of the separator of the present application includes a first region and a second region.
  • the second region When assembled into a secondary battery, the second region is arranged at the corner of the innermost circle of the wound electrode assembly.
  • the The second area forms a protrusion relative to the first area, and the protrusion can make the positive and negative electrodes here in close contact, promote the normal transmission of lithium ions in the process of charging and discharging, thereby improving the cycle performance of the secondary battery and safety performance.
  • the second polymer is selected from polyvinylidene fluoride, polyvinyl alcohol, polyacryl alcohol, chlorinated rubber, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyvinyl butyrate, At least one of polyvinyl chloride, polybutadiene, cyclized rubber, acrylonitrile-methyl acrylate copolymer and sodium carboxymethyl cellulose.
  • the weight content of the inorganic ceramic particles in the first region is 50%-99%, based on the total weight of the first region.
  • the cycle performance and safety performance of the secondary battery can be further improved.
  • the weight content of the first polymer in the first region is 1%-50%, based on the total weight of the first region.
  • the cycle performance and safety performance of the secondary battery can be further improved.
  • a second aspect of the present application provides a secondary battery, including a wound electrode assembly including the separator of the first aspect of the present application, and the second region is disposed on the wound electrode assembly. The corner of the innermost ring of the electrode assembly.
  • a third aspect of the present application provides a battery module including the secondary battery of the second aspect of the present application.
  • a fourth aspect of the present application provides a battery pack, including the battery module of the third aspect of the present application.
  • the fifth aspect of the present application provides an electric device, including at least one selected from the secondary battery of the second aspect of the present application, the battery module of the third aspect of the present application, or the battery pack of the fourth aspect of the present application. kind.
  • the battery module, battery pack, and electric device of the present application include the secondary battery of the present application, and thus have at least the same advantages as the secondary battery.
  • FIG. 1 is a schematic diagram of a diaphragm according to an embodiment of the present application.
  • Fig. 2 is a front view of the diaphragm according to one embodiment of the present application shown in Fig. 1 .
  • Fig. 3 is a front view of the swollen diaphragm according to one embodiment of the present application shown in Fig. 1 .
  • FIG. 4 is a schematic diagram of a wound electrode assembly 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 one 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.
  • FIG. 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 one embodiment of the present application shown in FIG. 8 .
  • FIG. 10 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • ranges disclosed herein are defined in terms of lower and upper limits, and 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 and may be combined arbitrarily, ie 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, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, 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" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • 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 in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (a) and (b) performed in sequence
  • steps (b) and (a) performed in sequence.
  • step (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), also Steps (a), (c) and (b) may be included, and steps (c), (a) and (b) may also be included.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • the inventors of the present application found that when the coating of the separator contains a first region and a second region, in the electrolyte, the second region forms a protrusion at the corner of the innermost circle of the wound electrode assembly,
  • the positive and negative plates can be in close contact, which can promote the normal transmission of lithium ions during charging and discharging, thereby improving the cycle performance and safety performance of the secondary battery.
  • the present application proposes a diaphragm, comprising
  • a coating on at least one surface of the porous substrate comprising a first region comprising inorganic ceramic particles and a first polymer and a second region comprising a second Two polymers, the first region and the second region have the same thickness, wherein the weight content of the second polymer in the second region is 20%-100%, optionally 50% %-100%, based on the total weight of the second region.
  • the coating of the separator of the present application includes a first region and a second region, the first region contains inorganic ceramic particles and the first polymer, and the second region contains the second region.
  • Two polymers, and the weight content of the second polymer in the second region is 20%-100%, optionally 50%-100%, when assembled into a secondary battery, in the electrolyte, the second region
  • the swelling thickness is greater than that of the first region, that is, the second region forms a protrusion relative to the first region.
  • the protrusion can make the positive and negative electrode sheets here in close contact, and promote the normal transmission of lithium ions during the charge and discharge process, thereby improving the secondary battery life.
  • the cycle performance and safety performance of the battery are the same.
  • the first region and the second region have the same thickness, which can ensure production efficiency and assembly efficiency.
  • the separator includes a porous substrate 100 and a coating
  • the coating includes a first region 101 and a second region 102
  • the first region 101 and the second region 102 have the same thickness.
  • the swelling thickness of the second region 102 is greater than that of the first region 101 , that is, the second region 102 forms a protrusion relative to the first region 101 .
  • the weight content of the second polymer in the second region is 50%-99%, based on the total weight of the second region.
  • the second polymer is selected from polyvinylidene fluoride, polyvinyl alcohol, polyacryl alcohol, chlorinated rubber, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyvinyl butyrate, At least one of polyvinyl chloride, polybutadiene, cyclized rubber, acrylonitrile-methyl acrylate copolymer and sodium carboxymethyl cellulose.
  • the second polymer is the same as the first polymer.
  • the second polymer is different from the first polymer.
  • the second region also includes the first polymer.
  • the second polymer is a particle.
  • the particle size range of the second polymer is 1 ⁇ m-20 ⁇ m, optionally 0.1 ⁇ m-10 ⁇ m, further optionally 1 ⁇ m-10 ⁇ m, which can be tested using equipment and methods known in the art , for example, using a scanning electron microscope for direct observation.
  • the weight content of the inorganic ceramic particles in the first region is 50%-99%, based on the total weight of the first region.
  • the weight content of the inorganic ceramic particles in the first region is within the given range, it can ensure that the separator has good heat resistance, thereby further improving the cycle performance and safety performance of the secondary battery.
  • the weight content of the first polymer in the first region is 1%-50%, based on the total weight of the first region.
  • the interface stability between the separator and the pole piece can be improved, thereby further improving the cycle performance and safety performance of the secondary battery.
  • the inorganic ceramic particles are selected from at least one of boehmite, aluminum oxide, silicon oxide, magnesium hydroxide, titanium dioxide, zirconium dioxide, tin dioxide, magnesium oxide and zinc oxide.
  • the particle size distribution of the inorganic ceramic particles is 0.05 ⁇ m-5 ⁇ m.
  • the volumetric energy density of the secondary battery can be further improved on the premise that the secondary battery has good cycle performance and safety performance.
  • the particle size distribution of the inorganic ceramic particles is a well-known meaning in the art, and can be measured using instruments and methods known in the art. For example, it can be measured by using a laser particle size analyzer (such as Master Size 3000) with reference to the GB/T19077-2016 particle size distribution laser diffraction method.
  • a laser particle size analyzer such as Master Size 3000
  • the first polymer is selected from polyvinylidene fluoride, guar gum, sodium alginate, carboxymethyl cellulose, gum arabic, xanthan gum, gelatin, starch, cyclodextrin, At least one of chitosan and carrageenan.
  • the width of the second region is 100 ⁇ m-10 mm.
  • said coating includes three of said second regions.
  • other organic compounds may also be included in the coating, for example, polymers for improving heat resistance, dispersants, wetting agents, etc. may be included.
  • the present application has no special limitation on the types of the above-mentioned other organic compounds, and any known materials with good improvement properties can be selected.
  • the present application has no special limitation on the type of the porous substrate, and any known porous substrate with good chemical stability and mechanical stability can be selected.
  • the porous substrate is selected from at least one of polyethylene and polypropylene.
  • the thickness of the porous substrate is 5 ⁇ m-20 ⁇ m; for example, the thickness of the porous substrate may be 5 ⁇ m-10 ⁇ m.
  • the energy density of the secondary battery can be further improved on the premise of ensuring the rate performance and safety performance of the secondary battery.
  • a secondary battery including a wound electrode assembly, the wound electrode assembly includes the separator according to the first aspect of the present application, and the second region is arranged on the wound electrode assembly. The corner of the innermost ring of the type electrode assembly.
  • the second region is disposed at three corners of the innermost circle of the wound electrode assembly.
  • the second region of the separator is disposed at the corner of the innermost circle.
  • a secondary battery typically includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • active ions are intercalated and extracted back and forth between the positive electrode and the negative electrode.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the diaphragm is arranged between the positive pole piece and the negative pole piece, mainly to prevent the short circuit of the positive and negative pole pieces, and at the same time allow ions to pass through.
  • the positive electrode sheet includes a positive electrode collector and a positive electrode film layer arranged on at least one surface of the positive electrode collector, and the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material known in the art for batteries.
  • the positive active material may include at least one of the following materials: olivine-structured lithium-containing phosphate, lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials of batteries can also be used. These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt 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 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also abbreviated as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also abbreviated as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also abbreviated as 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 LiN
  • olivine-structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also abbreviated as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), phosphoric acid At least one of a composite material of lithium manganese and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also abbreviated as LFP)
  • composite materials of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate
  • phosphoric acid At least one of a composite material of lithium manganese and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer may also optionally include 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 in the following manner: the above-mentioned components used to prepare the positive electrode sheet, such as positive electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, and the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the negative electrode current collector can use a metal foil or a composite current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • Composite current collectors can be formed by metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • the negative electrode active material can be a negative electrode active material known in the art for batteries.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of simple tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further optionally include a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • CMC-Na sodium carboxymethylcellulose
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • the electrolyte can be liquid.
  • the electrolyte is an electrolytic solution.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process.
  • the secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • 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 case may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 5 shows a secondary battery 5 having a square structure as an example.
  • the outer package may include a housing 51 and a cover 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 plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the accommodating cavity. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 7 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may also include a case having a housing space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art 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 body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electric devices may include mobile devices (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, etc.) , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • FIG. 10 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • the electric device may be a mobile phone, a tablet computer, a notebook computer, and the like.
  • the electrical device is usually required to be light and thin, and a secondary battery can be used as a power source.
  • a polyethylene substrate is provided, the thickness of the substrate is 7 ⁇ m, and the porosity is 39%;
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523 ), the conductive agent conductive carbon black, and the binder PVDF are mixed uniformly in an appropriate amount of solvent NMP in a weight ratio of 90:7:3 to obtain the positive electrode slurry.
  • the positive electrode slurry is coated on the positive electrode current collector aluminum foil, and the positive electrode sheet is obtained through drying, cold pressing, slitting, and cutting processes.
  • the areal density of the positive electrode sheet is 0.175 mg/mm 2 .
  • Negative electrode active material graphite conductive agent conductive carbon black, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber emulsion (SBR, viscosity 350) in an appropriate amount by weight ratio 96.5:1.0:1.0:1.5
  • the solvent is mixed evenly in deionized water to obtain negative electrode slurry, which is coated on the negative electrode current collector copper foil, and the negative electrode sheet is obtained through drying, cold pressing, slitting and cutting processes.
  • the areal density of the negative electrode sheet is 0.110 mg/mm 2 .
  • the electrolyte is a commercial electrolyte for lithium-ion batteries, wherein the organic solvent is a mixture of ethylene carbonate, diethyl carbonate and propylene carbonate with a weight ratio of 50:40:10, and the concentration of the electrolyte salt lithium hexafluorophosphate is 1mol/L .
  • the above-mentioned positive electrode sheet, separator, and negative electrode sheet are stacked in order, and then wound to obtain an electrode assembly, wherein the second area of the separator is set at the three corners of the innermost circle of the electrode assembly; the electrode assembly is placed outside In the packaging, the above-mentioned prepared electrolyte solution is injected into the dried secondary battery, and the secondary battery is obtained through the processes of vacuum packaging, standing still, chemical formation and shaping.
  • Example 1 The preparation of the diaphragm and the preparation of the secondary battery refer to Example 1 as a whole, the difference is that part of the PVDF in the second slurry is replaced by ethylene-vinyl acetate copolymer microspheres (molecular weight is 24,000, particle size distribution is 1- 10 ⁇ m), so that the weight ratio of ethylene-vinyl acetate copolymer microspheres to PVDF in the second slurry is 99:1.
  • Example 1 The preparation of the diaphragm and the preparation of the secondary battery refer to Example 1 as a whole, the difference is that part of the PVDF in the second slurry is replaced by ethylene-vinyl acetate copolymer microspheres (molecular weight is 24,000, particle size distribution is 1- 10 ⁇ m), so that the weight ratios of ethylene-vinyl acetate copolymer microspheres to PVDF in the second slurry were 3:1, 4:1 and 1:1, respectively.
  • ethylene-vinyl acetate copolymer microspheres molecular weight is 24,000, particle size distribution is 1- 10 ⁇ m
  • Example 1 The preparation of the diaphragm and the preparation of the secondary battery refer to Example 1 as a whole, the difference is that part of the PVDF in the second slurry is replaced by acrylonitrile-methyl acrylate copolymer powder (molecular weight is 100,000, particle size distribution is 0.1 -10 ⁇ m), so that the weight ratio of acrylonitrile-methyl acrylate copolymer powder to PVDF in the second slurry is 99:1.
  • Example 1 The preparation of the diaphragm and the preparation of the secondary battery refer to Example 1 as a whole, the difference is that part of the PVDF in the second slurry is replaced by an acrylonitrile-methyl acrylate copolymer (molecular weight: 50,000) with a weight ratio of 1:1. , particle size distribution is 0.1-10 ⁇ m) and sodium carboxymethyl cellulose (molecular weight distribution is 5-25 ten thousand), so that in the second slurry, acrylonitrile-methyl acrylate copolymer and sodium carboxymethyl cellulose The weight ratio of the mixture to PVDF is 99:1.
  • Example 1 The preparation of the separator and the preparation of the secondary battery refer to Example 1 as a whole, except that the first and second regions are fabricated on both surfaces of the separator substrate.
  • the preparation of the diaphragm and the preparation of the secondary battery refer to Example 1 as a whole, the difference is that the diaphragm only includes a second region with a width of 10mm, and in the preparation of the secondary battery, the second region of the diaphragm is arranged on the electrode assembly The corner of the innermost circle.
  • the preparation of the separator and the preparation of the secondary battery refer to Example 1 as a whole, except that in the preparation of the separator, the first slurry is only coated on one surface of the substrate.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same function and effect are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请涉及一种隔膜，包括多孔基材，和在所述多孔基材的至少一个表面上的涂层，所述涂层包括第一区域和第二区域，所述第一区域包含无机陶瓷颗粒和第一聚合物，所述第二区域包含第二聚合物，所述第一区域与所述第二区域具有相同的厚度，其中，所述第二聚合物在所述第二区域中的重量含量为20％-100％，可选地为50％-100％，基于所述第二区域的总重量计。本申请还涉及包含所述隔膜的二次电池、电池模块、电池包和用电装置。

Description

隔膜及其相关的二次电池、电池模块、电池包和用电装置 技术领域
本申请涉及二次电池技术领域，尤其涉及一种隔膜及其相关的二次电池、电池模块、电池包和用电装置。
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***，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、循环性能和安全性能等也提出了更高的要求。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种隔膜，使得由其制备的二次电池具有改善的安全性能和循环性能。
为了达到上述目的，本申请提供了一种隔膜、包含其的二次电池、电池模块、电池包和用电装置。
本申请的第一方面提供了一种隔膜，包括
多孔基材，和
在所述多孔基材的至少一个表面上的涂层，所述涂层包括第一区域和第二区域，所述第一区域包含无机陶瓷颗粒和第一聚合物，所述第二区域包含第二聚合物，所述第一区域与所述第二区域具有相同的厚度，其中，所述第二聚合物在所述第二区域中的重量含量为20％-100％，可选地为50％-100％，基于所述第二区域的总重量计。
本申请的隔膜的涂层包括第一区域和第二区域，当组装成二次电池时，所述第二区域设置在卷绕型电极组件最内圈的拐角处，在电解液中，所述第二区域相对于所述第一区域形成凸起，所述凸起可以使 此处的正负极片紧密接触，促进锂离子在充放电过程中的正常传输，从而改善二次电池的循环性能和安全性能。
在任意实施方式中，所述第二聚合物选自聚偏二氟乙烯、聚乙烯醇、聚丙烯醇、氯化橡胶、乙烯-醋酸乙烯共聚物、聚醋酸乙烯酯、聚丁酸乙烯酯、聚氯乙烯、聚丁二烯、环化橡胶、丙烯腈-丙烯酸甲酯共聚物与羧甲基纤维素钠中的至少一种。
在任意实施方式中，所述无机陶瓷颗粒在所述第一区域中的重量含量为50％-99％，基于所述第一区域的总重量计。当无机陶瓷颗粒在第一区域中的重量含量在所给范围内时，能够进一步提高二次电池的循环性能和安全性能。
在任意实施方式中，所述第一聚合物在所述第一区域中的重量含量为1％-50％，基于所述第一区域的总重量计。当第一聚合物在第一区域中的重量含量在所给范围内时，能够进一步改善二次电池的循环性能和安全性能。
本申请的第二方面提供一种二次电池，包括卷绕型电极组件，所述卷绕型电极组件包含本申请的第一方面的隔膜，并且所述第二区域设置在所述卷绕型电极组件最内圈的拐角处。
本申请的第三方面提供一种电池模块，包括本申请的第二方面的二次电池。
本申请的第四方面提供一种电池包，包括本申请的第三方面的电池模块。
本申请的第五方面提供一种用电装置，包括选自本申请的第二方面的二次电池、本申请的第三方面的电池模块或本申请的第四方面的电池包中的至少一种。
本申请的电池模块、电池包和用电装置包括本申请的二次电池，因而至少具有与所述二次电池相同的优势。
附图说明
图1是本申请一实施方式的隔膜的示意图。
图2是图1所示的本申请一实施方式的隔膜的前视图。
图3是图1所示的本申请一实施方式的隔膜溶胀后的前视图。
图4是本申请一实施方式的卷绕型电极组件的示意图。
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；10隔膜；100多孔基材；101第一区域；102第二区域；001负极；002正极；200拐角
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隔膜、二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下 面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，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)。
具有卷绕型电极组件的二次电池以其快速、高效的生产效率得到广泛应用。然而，在卷绕型电极组件中，特别是在卷绕型电极组件最内圈的拐角部位，正极极片和负极极片之间的间距过大，影响锂离子在充放电过程中的传输，表现为电池容量衰减等问题。
经过大量实验，本申请发明人发现，当隔膜的涂层含有第一区域和第二区域，在电解液中，所述第二区域在卷绕型电极组件最内圈的拐角处形成凸起，使得正负极片可以紧密接触，促进锂离子在充放电过程中的正常传输，从而改善二次电池的循环性能和安全性能。
[隔膜]
本申请的一个实施方式中，本申请提出了一种隔膜，包括
多孔基材，和
在所述多孔基材的至少一个表面上的涂层，所述涂层包括第一区域和第二区域，所述第一区域包含无机陶瓷颗粒和第一聚合物，所述第二区域包含第二聚合物，所述第一区域与所述第二区域具有相同的厚度，其中，所述第二聚合物在所述第二区域中的重量含量为20％-100％，可选地为50％-100％，基于所述第二区域的总重量计。
虽然机理尚不清楚，本申请发明人推测是由于以下原因：本申请的隔膜的涂层包括第一区域和第二区域，第一区域包含无机陶瓷颗粒和第一聚合物，第二区域包含第二聚合物，并且第二聚合物在第二区域中的重量含量20％-100％，可选地为50％-100％，当组装成二次电池时，在电解液中，第二区域的溶胀厚度大于第一区域的溶胀厚度，即第二区域相对于第一区域形成凸起。当将第二区域设置在卷绕型电极组件最内圈的拐角处时，凸起可以使此处的正负极片紧密接触，促进锂离子在充放电过程中的正常传输，从而改善二次电池的循环性能和安全性能。
此外，在组装到二次电池中之前，第一区域与第二区域具有相同的厚度，可以确保生产效率和组装效率。
如图1和2所示，隔膜包括多孔基材100和涂层，涂层包括第一区域101和第二区域102，第一区域101和第二区域102具有相同的厚度。
如图3所示，在电解液中溶胀之后，第二区域102的溶胀厚度大于第一区域101的溶胀厚度，即第二区域102相对于第一区域101形成凸起。
在一些实施方式中，所述第二聚合物在所述第二区域中的重量含量为50％-99％，基于所述第二区域的总重量计。
在一些实施方式中，所述第二聚合物选自聚偏二氟乙烯、聚乙烯醇、聚丙烯醇、氯化橡胶、乙烯-醋酸乙烯共聚物、聚醋酸乙烯酯、聚丁酸乙烯酯、聚氯乙烯、聚丁二烯、环化橡胶、丙烯腈-丙烯酸甲酯共聚物与羧甲基纤维素钠中的至少一种。
在一些实施方式中，所述第二聚合物与所述第一聚合物相同。
在一些实施方式中，所述第二聚合物与所述第一聚合物不同。
在一些实施方式中，所述第二区域还包含所述第一聚合物。
在一些实施方式中，所述第二聚合物为颗粒。
在本申请中，所述第二聚合物的粒径范围为1μm-20μm，可选地为0.1μm-10μm，进一步可选地为1μm-10μm，可以采用本领域已知的设备和方法进行测试，例如，使用电子扫描显微镜进行直接观察。
在一些实施方式中，所述无机陶瓷颗粒在所述第一区域中的重量含量为50％-99％，基于所述第一区域的总重量计。当无机陶瓷颗粒在第一区域中的重量含量在所给范围内时，可以确保隔膜具有良好耐热性，从而进一步提高二次电池的循环性能和安全性能。
在一些实施方式中，所述第一聚合物在所述第一区域中的重量含量为1％-50％，基于所述第一区域的总重量计。当第一聚合物在第一区域中的重量含量在所给范围内时，可以改善隔膜和极片之间的界面稳定性，从而进一步改善二次电池的循环性能和安全性能。
在一些实施方式中，所述无机陶瓷颗粒选自勃姆石、氧化铝、氧化硅、氢氧化镁、二氧化钛、二氧化锆、二氧化锡、氧化镁和氧化锌中的至少一种。
在一些实施方式中，所述无机陶瓷颗粒的粒径分布为0.05μm-5μm。当无机陶瓷颗粒的粒径分布在所给范围内时，可以确保二次电池在具有较好的循环性能和安全性能的前提下，进一步提高二次电池的体积能量密度。
根据一些实施例，无机陶瓷颗粒的粒径分布为本领域公知的含义， 可采用本领域已知的仪器及方法进行测定。例如可以参照GB/T19077-2016粒度分布激光衍射法，采用激光粒度分析仪(例如Master Size 3000)测定。
在一些实施方式中，所述第一聚合物选自聚偏二氟乙烯、瓜儿豆胶、海藻酸钠、羧甲基纤维素、***胶、黄原胶、明胶、淀粉、环糊精、壳聚糖和角叉莱胶中的至少一种。
在一些实施方式中，所述第二区域的宽度为100μm-10mm。
在一些实施方式中，所述涂层包括三个所述第二区域。
根据一些实施例，所述涂层中还可以包括其他有机化合物，例如，可以包括改善耐热性的聚合物、分散剂、润湿剂等。本申请对上述其他有机化合物的种类没有特别的限制，可以选用任意公知的具有良好改善性能的材料。
在一些实施方式中，本申请对多孔基材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基材。
在一些实施方式中，所述多孔基材选自聚乙烯和聚丙烯中的至少一种。
在一些实施方式中，所述多孔基材的厚度5μm-20μm；例如，所述多孔基材的厚度可以为5μm-10μm。当所述多孔基材的厚度控制在所给范围内时，可以在确保二次电池的倍率性能和安全性能的前提下，进一步提高二次电池的能量密度。
[二次电池]
本申请的一个实施方式中，提供一种二次电池，包括卷绕型电极组件，所述卷绕型电极组件包含本申请第一方面的隔膜，并且所述第二区域设置在所述卷绕型电极组件最内圈的拐角处。
在一些实施方式中，所述第二区域设置在所述卷绕型电极组件的最内圈的三个拐角处。
如图4所示，在卷绕型电极组件中，隔膜的第二区域设置在最内圈的拐角处。
另外，以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
通常情况下，二次电池包括正极极片、负极极片、电解质和隔膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔膜设置在正极极片和负极极片之间，主要起到防止正负极片短路的作用，同时可以使离子通过。
[正极极片]
正极极片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，所述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，所述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 1/3Mn 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，所述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，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
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。
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，所述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(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。所述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。所述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。所述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。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。
[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。
在一些实施方式中，所述电解质采用电解液。所述电解液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，所述电解液还可选地包括添加剂。例如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。
在一些实施方式中，正极极片、负极极片和隔膜可通过卷绕工艺制成电极组件。
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***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。
作为另一个示例的用电装置可以是手机、平板电脑、笔记本电脑等。该用电装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
[隔膜的制备]
(1)提供聚乙烯基材，基材的厚度为7μm，孔隙率为39％；
(2)在相对湿度小于2％的室温环境中，将勃姆石颗粒和第一聚合物聚偏二氟乙烯(PVDF)(分子量为50万)以4:1的重量比缓慢加入到N-甲基吡咯烷酮(NMP)溶液中，在25℃下以800rpm的转速搅拌2小时以上，形成均匀、稳定的固含量为20％(按重量计)的第一浆料，其中勃姆石颗粒的粒径分布为0.05μm-0.2μm；
(3)在相对湿度小于2％的室温环境中，将第二聚合物PVDF(分子量为50万)缓慢加入到NMP溶液中，在25℃下以800rpm的转速搅拌5小时以上，形成均匀、稳定的固含量为20％(按重量计)的第二浆料；
(4)通过挤压涂布的方式，将第一浆料涂敷于基材的一个表面上，在100℃下干燥10min，其中，隔膜上单面涂层的单位面积的重量为9.6g/m 2；
(5)在隔膜表面的三个位置处进行压痕，将第二浆料涂覆于压痕处，在110℃下干燥10min，滚压整形，使得隔膜表面平整光滑，分切得到包括三个第二区域的隔膜。其中第二区域的位置和宽度由待制备的卷绕型电极组件最内圈的三个拐角决定，其宽度均为：10mm。
[二次电池的制备]
1.正极极片的制备
将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2(NCM 523)、导电剂导电碳黑、粘结剂PVDF按重量比90:7:3在适量的溶剂NMP中混合均匀，得到正极浆料，将正极浆料涂覆于正极集流体铝箔上，通过烘干、冷压、分条、裁切工序，得到正极极片。正极极片的面密度为0.175mg/mm 2。
2.负极极片的制备
将负极活性材料石墨、导电剂导电炭黑、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶乳液(SBR，粘度350)按重量比96.5:1.0:1.0:1.5在适量的溶剂去离子水中混合均匀，得到负极浆料，将负极浆料涂覆于负极集流体铜箔上，通过烘干、冷压、分条、裁切工序，得到负极极片。负极极片的面密度为0.110mg/mm 2。
3.电解液的制备
电解液采用锂离子电池商用电解液，其中，有机溶剂为重量比为50:40:10的碳酸亚乙酯、碳酸二乙酯和碳酸亚丙酯的混合物，电解质盐六氟磷酸锂的浓度为1mol/L。
4.二次电池的制备
将上述正极极片、隔膜、负极极片按顺序叠好，然后卷绕得到电极组件，其中隔膜的第二区域设置在所述电极组件最内圈的三个拐角处；将电极组件置于外包装中，将上述制备好的电解液注入到干燥后的二次电池中，经过真空封装、静置、化成、整形工序，得到二次电池。
实施例2
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，将第二浆料中的部分PVDF替换为乙烯-醋酸乙烯共聚物微球(分子 量为2.4万，粒径分布为1-10μm)，使得在第二浆料中乙烯-醋酸乙烯共聚物微球与PVDF的重量比为99:1。
实施例3-5
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，将第二浆料中的部分PVDF替换为乙烯-醋酸乙烯共聚物微球(分子量为2.4万，粒径分布为1-10μm)，使得在第二浆料中乙烯-醋酸乙烯共聚物微球与PVDF的重量比分别为3:1、4:1和1:1。
实施例6
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，将第二浆料中的部分PVDF替换为丙烯腈-丙烯酸甲酯共聚物粉末(分子量为10万，粒径分布为0.1-10μm)，使得在第二浆料中丙烯腈-丙烯酸甲酯共聚物粉末与PVDF的重量比为99:1。
实施例7
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，将第二浆料中的部分PVDF替换为重量比为1:1的丙烯腈-丙烯酸甲酯共聚物(分子量为5万，粒径分布为0.1-10μm)与羧甲基纤维素钠(分子量分布为5-25万)的混合物，使得在第二浆料中丙烯腈-丙烯酸甲酯共聚物与羧甲基纤维素钠的混合物与PVDF的重量比为99:1。
实施例8
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，在隔膜基材的两个表面均制作第一和第二区域。
实施例9
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，隔膜仅包括一个第二区域，其宽度为10mm，并在二次电池的制备中，隔膜的第二区域设置在电极组件最内圈的拐角处。
对比例1
隔膜的制备和二次电池的制备整体上参照实施例1，区别在于，在隔膜的制备中，仅在基材的一个表面上涂覆第一浆料。
二次电池的循环测试
将电池于25℃下进行充放电，即先以1/3C的电流充电至4.2V，然后再以1/3C的电流放电至2.8V，记录下第一周的放电容量；然后使电池进行1/3C/1/3C充放电循环1000周，记录第1000周的电池放电容量，将第1000周的放电容量除以第一周的放电容量，得到第1000周的容量保持率。
按照上述过程分别测试上述实施例和对比例中得到的二次电池，具体数值参见表1。
表1
Figure PCTCN2022072330-appb-000001
由表1可以看出，所有实施例的二次电池的1000次循环容量保持率(％)均高于对比例的二次电池。换言之，通过在隔膜的涂层中设置特定的第二区域，并将第二区域设置于卷绕型电极组件最内圈的拐角处，可以明显提高二次电池的循环性能。
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 (8)

  1. 一种隔膜，包括
    多孔基材，和
    在所述多孔基材的至少一个表面上的涂层，所述涂层包括第一区域和第二区域，所述第一区域包含无机陶瓷颗粒和第一聚合物，所述第二区域包含第二聚合物，所述第一区域与所述第二区域具有相同的厚度，其中，所述第二聚合物在所述第二区域中的重量含量为20％-100％，可选地为50％-100％，基于所述第二区域的总重量计。
  2. 根据权利要求1所述的隔膜，其特征在于，所述第二聚合物选自聚偏二氟乙烯、聚乙烯醇、聚丙烯醇、氯化橡胶、乙烯-醋酸乙烯共聚物、聚醋酸乙烯酯、聚丁酸乙烯酯、聚氯乙烯、聚丁二烯、环化橡胶、丙烯腈-丙烯酸甲酯共聚物与羧甲基纤维素钠中的至少一种。
  3. 根据权利要求1或2所述的隔膜，其特征在于，所述无机陶瓷颗粒在所述第一区域中的重量含量为50％-99％，基于所述第一区域的总重量计。
  4. 根据权利要求1至3中任一项所述的隔膜，其特征在于，所述第一聚合物在所述第一区域中的重量含量为1％-50％，基于所述第一区域的总重量计。
  5. 一种二次电池，包括卷绕型电极组件，其特征在于，所述卷绕型电极组件包含权利要求1至4中任一项所述的隔膜，并且所述第二区域设置在所述卷绕型电极组件最内圈的拐角处。
  6. 一种电池模块，其特征在于，包括权利要求5所述的二次电池。
  7. 一种电池包，其特征在于，包括权利要求6所述的电池模块。
  8. 一种用电装置，其特征在于，包括选自权利要求5所述的二次电池、权利要求6所述的电池模块或权利要求7所述的电池包中的至少一种。
PCT/CN2022/072330 2022-01-17 2022-01-17 隔膜及其相关的二次电池、电池模块、电池包和用电装置 WO2023133882A1 (zh)

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JP2005093375A (ja) * 2003-09-19 2005-04-07 Hitachi Maxell Ltd 非水二次電池およびその製造方法
CN101150185A (zh) * 2006-09-19 2008-03-26 深圳市比克电池有限公司 一种卷绕式锂二次电池
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CN111211279A (zh) * 2018-11-22 2020-05-29 宁德新能源科技有限公司 隔离膜及锂离子电池
CN111954943A (zh) * 2018-02-26 2020-11-17 三星Sdi株式会社 隔板、用于制造其的方法和包括其的锂电池
WO2021189454A1 (zh) * 2020-03-27 2021-09-30 宁德新能源科技有限公司 一种电极组件及包含其的电化学装置和电子装置

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JP2005093375A (ja) * 2003-09-19 2005-04-07 Hitachi Maxell Ltd 非水二次電池およびその製造方法
CN101150185A (zh) * 2006-09-19 2008-03-26 深圳市比克电池有限公司 一种卷绕式锂二次电池
US20150010797A1 (en) * 2013-07-03 2015-01-08 Samsung Sdi Co., Ltd. Lithium pouch battery
CN111954943A (zh) * 2018-02-26 2020-11-17 三星Sdi株式会社 隔板、用于制造其的方法和包括其的锂电池
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