WO2023056825A1 - 一种隔离膜、含有其的二次电池和用电装置 - Google Patents

一种隔离膜、含有其的二次电池和用电装置 Download PDF

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WO2023056825A1
WO2023056825A1 PCT/CN2022/118084 CN2022118084W WO2023056825A1 WO 2023056825 A1 WO2023056825 A1 WO 2023056825A1 CN 2022118084 W CN2022118084 W CN 2022118084W WO 2023056825 A1 WO2023056825 A1 WO 2023056825A1
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formula
coating
layered silicate
separator
organic
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PCT/CN2022/118084
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English (en)
French (fr)
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代志鹏
任苗苗
朱田广
谭显明
吴子睿
严观福生
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宁德时代新能源科技股份有限公司
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Publication of WO2023056825A1 publication Critical patent/WO2023056825A1/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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of battery technology, and in particular to a separator, a secondary battery containing the same and an electrical device.
  • the first aspect of the present application provides a separator, including: a substrate; a coating, the coating includes an organic-inorganic hybrid layered silicate;
  • the organic part includes one or more of alkylammonium, quaternary ammonium salt, octadecylamine and organosilicon;
  • the inorganic part in the layered silicate includes the compound shown in formula 1, M 2 (Al 2 -x Mg x )[Si 4 O 10 ](OH) 2 Formula 1, in Formula 1, M includes one or more of Na, Li, K, Ca, and the subscript x takes a value of 0-2.
  • the present application adds a layered silicate with a specific structure to the coating slurry of the isolation film, which is swollen and dispersed in a solvent to form a colloid.
  • the layered silicate can be attached to the surface of the isolation film after drying, thereby playing Enhance the mechanical strength of the separator.
  • the organic part in the layered silicate includes one or more of the compounds shown in formula 2A or formula 2B;
  • R 11 -R 14 are independently selected from C 1 -C 25 alkyl groups
  • R 21 is selected from C 1 -C 25 alkyl groups
  • X is each independently a halogen, preferably Cl or Br.
  • At least one of R 11 -R 14 is selected from C 10 -C 25 alkyl groups; and/or, R 21 is selected from C 10 -C 25 alkyl groups.
  • the mass proportion of layered silicate in the coating is 50%-80%, optionally 60%-70%.
  • the thickness of the coating is less than or equal to 3 ⁇ m; it may be 0.5 ⁇ m-3 ⁇ m.
  • the longitudinal tensile strength of the separator is 3000 kgf/cm 2 to 3500 kgf/cm 2 .
  • the longitudinal heat shrinkage rate of the separator at 150° C. is 3.5%-5%.
  • the second aspect of the present application also provides a method for preparing a separator, which includes the following steps:
  • Step S1 providing a substrate
  • Step S2 providing a slurry, the slurry includes an organic-inorganic hybrid layered silicate; the organic part in the layered silicate includes one of alkyl ammonium, quaternary ammonium salt, octadecylamine and organic silicon or several; the inorganic part in the layered silicate includes the compound shown in formula 1, M 2 (Al 2-x Mg x )[Si 4 O 10 ](OH) 2 formula 1, in formula 1, M Including one or more of Na, Li, K, Ca, the value of subscript x is 0-2;
  • Step S3 coating the slurry on at least one surface of the substrate to form a coating.
  • the phyllosilicate is composed of an organic part and an inorganic part.
  • the organic part is intercalated or exfoliated between layers of the inorganic part.
  • layered silicate is added to the coating slurry to disperse and thicken.
  • the layered silicate can adhere to the surface of the isolation film after drying. , to enhance the mechanical strength of the separator.
  • the third aspect of the present application provides a secondary battery, comprising the separator of the first aspect of the present application or the separator prepared according to the method of the second aspect of the present application.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • the sixth aspect of the present application provides an electric device, including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application. kind.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 4 .
  • FIG. 6 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 (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) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • 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).
  • Secondary batteries also known as rechargeable batteries or accumulators, refer to batteries that can be activated by charging the active materials and continue to be used after the battery is discharged.
  • a secondary battery includes a positive pole piece, a negative pole piece, a separator, and an electrolyte.
  • active ions such as lithium ions
  • the separator is arranged between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows active ions to pass through.
  • the electrolyte is between the positive pole piece and the negative pole piece, and mainly plays the role of conducting active ions.
  • a separator comprising: a substrate; a coating, the coating includes an organic-inorganic hybrid layered silicate; the organic part in the layered silicate includes an alkane One or more of base ammonium, quaternary ammonium salt, octadecylamine and organic silicon; the inorganic part in the layered silicate includes the compound shown in formula 1, M 2 (Al 2-x Mg x ) [Si 4 O 10 ](OH) 2 Formula 1.
  • M includes one or more of Na, Li, K, and Ca, and the subscript x takes a value of 0-2.
  • the present application has no particular limitation on the type of substrate, and any known porous substrate with good chemical stability and mechanical stability can be selected.
  • the substrate may be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • a layered inorganic substance of a specific composition is added to the coating slurry of the isolation film, wherein the chain-like organic substance is intercalated or peeled off between the inorganic substance sheets to achieve compounding.
  • the obtained separator coating can not only strengthen the mechanical properties of the separator, but also has good dispersion and is easy to coat.
  • the secondary battery comprising the coating separator has the characteristics of high safety, high capacity and long life.
  • the organic part in the organic-inorganic hybrid material includes one or more of the compounds shown in formula 2A or formula 2B,
  • R 11 -R 14 are independently selected from C 1 -C 25 alkyl groups
  • R 21 is selected from C 1 -C 25 alkyl groups
  • X is each independently a halogen, preferably Cl or Br.
  • Organic-inorganic hybridization is well known in the art, and is usually a composite material in which inorganic materials and organic materials are bonded at the nanometer scale through intermolecular forces, hydrogen bonds or covalent bonds. Each material learns from each other in terms of performance to produce synergistic effects, and macroscopically composes materials with new properties. Common methods include sol-gel method and so on.
  • the inorganic part of the present application (such as Na 0.5 (Al 1.5 Mg 0.5 )[Si 4 O 10 ](OH) 2 ) can be modified on the surface of the organic part (such as organic ammonium salt), and the In the dispersion medium of the agent, after stirring at a high speed at a certain temperature, the medium is removed by distillation and then dried and pulverized.
  • the organic part such as organic ammonium salt
  • At least one of R 11 -R 14 is selected from C 10 -C 25 alkyl groups; and/or, the R 21 is selected from C 10 -C 25 alkyl groups.
  • the longer molecular chain of the organic part is conducive to the exfoliation of the layered silicate on the microscopic scale, and it is easy to compound and prepare the silicate when modifying the silicate, and the formed layered silicate structure is highly stable; Higher affinity, at the same time, the organic compound itself acts as a surfactant, and the organically modified silicate formed after compounding with the silicate can have a better dispersion effect in the coating slurry preparation process.
  • the mass proportion of layered silicate in the coating is 50%-80%, optionally 60%-70%.
  • the mass proportion of layered silicate will affect the physical properties of the isolation film and the bonding stability of the coating. The membrane strength is higher, and the effect of enhancing the safety performance of the secondary battery is better.
  • the thickness of the coating is less than or equal to 3 ⁇ m; optionally 0.5 ⁇ m-3 ⁇ m.
  • the thickness of the separator coating satisfies this range, the safety performance of the separator is significantly improved, and at the same time, the increase in the internal resistance of the cell is small, which has little impact on the first effect.
  • the longitudinal tensile strength is 3000kgf/cm 2 -3500kgf/cm 2 .
  • the heat shrinkage rate in the machine direction is 3.5%-5% at 150°C.
  • One embodiment of the present application provides a method for preparing a separator, which includes the following steps:
  • Step S1 providing a substrate
  • Step S2 providing a slurry, the slurry includes layered silicate, and the layered silicate includes an organic-inorganic hybrid material mainly composed of layered silicate;
  • the organic matter is one or more of alkyl ammonium, quaternary ammonium salt, octadecylamine and organic silicon;
  • M includes one or more of Na, Li, and K, and the subscript x takes a value of 0-2;
  • Step S3 coating the slurry on at least one surface of the substrate to prepare an isolation film.
  • the phyllosilicate is composed of an organic part and an inorganic part.
  • the organic matter is intercalated or exfoliated between the phyllosilicate sheets.
  • the coating slurry has the characteristics of simple composition, good dispersibility, and high leveling property. At the same time, the slurry is easy to coat while reducing the types of materials used as much as possible, and can adapt to various types of current coatings. cloth method. This type of material is easily soluble in hydrocarbon solvents. Adding a small amount of polar solvents such as methanol, ethanol, acetone, etc. can make the quaternary ammonium hydrocarbon chains between the layered silicate layers bridged by hydrogen bonds to obtain effective solvation. In this way, the layers are expanded and dispersed, and a thixotropic gel with a card-layer house structure is formed to prevent the precipitation of inorganic fillers.
  • the main purpose of using the coating slurry is to obtain a stable and easy-to-coat slurry, and at the same time realize the film formation of silicate on the isolation film and enhance the mechanical strength of the isolation film.
  • S2 in the preparation method also includes the following steps:
  • the organic-inorganic hybrid material and the binder are mixed and stirred to obtain mixed solid phase particles; alcohol solvent is added to the mixed solid phase particles.
  • the binder includes one or more of polyvinylidene fluoride, polyacrylic acid, and polyacrylate.
  • the selection of the binder will affect the bonding effect of the coating on the surface of the separator, and the dispersion effect of polyvinylidene fluoride in the organic slurry is better.
  • the alcohol solvent includes one or more of methanol, ethanol, ethylene glycol, and propanol. Alcohol solvents play a role in strengthening the dispersion effect of the slurry in the slurry, and ethanol is easier to disperse.
  • the mass fraction ⁇ 1 of layered silicate in the mixed solid phase particles is 50%-80%
  • the mass fraction ⁇ 2 of the binder in the mixed solid phase particles is 20%-50%
  • ⁇ 1 / ⁇ 2 satisfies 1 ⁇ 1 / ⁇ 2 ⁇ 4.
  • the alcohol solvent accounts for 5%-20% by mass of the total solvent.
  • the slurry includes a lithium supplementing agent, optionally including one or more of lithium powder or lithium oxide.
  • the slurry coating method includes any one or a combination of at least two of transfer coating, spray coating, extrusion coating, gravure coating, or knife coating.
  • the positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current 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.
  • a metal foil or a composite current collector can be used as the positive electrode current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material 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 LiNi
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also may be abbreviated as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon At least one of a composite material, lithium manganese iron phosphate, and a composite material of lithium manganese iron phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also may be abbreviated as LFP)
  • composite materials of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium 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 meta-copolymer, 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.
  • a metal foil or a composite current collector can be used as the negative electrode current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a base layer of polymer material and a metal layer formed on at least one surface of the base material of polymer material.
  • 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 can be selected from at least one of simple tin, tin oxide and tin alloy.
  • 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 may be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), At least one of polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may also optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • the negative electrode sheet can be prepared 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
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is liquid and 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 also optionally includes additives.
  • the additives may include negative film-forming additives, positive 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 the battery, 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 or a lamination 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 bag can be plastic, and examples of plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG. 1 shows a square-shaped secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and 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. 3 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 use requirements.
  • FIG. 6 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 positive electrode active material NCM523, the conductive agent acetylene black, and the binder polyvinylidene fluoride (PVDF) are dissolved in the solvent N-methylpyrrolidone (NMP) in a weight ratio of 96.5:1.5:2, and fully stirred and mixed to obtain Positive electrode slurry: Afterwards, the positive electrode slurry is evenly coated on the positive electrode current collector, and then dried, cold pressed, and cut to obtain the positive electrode sheet.
  • NMP N-methylpyrrolidone
  • the negative electrode slurry is prepared by uniformly mixing with the solvent deionized water; then the negative electrode slurry is evenly coated on the copper foil of the negative electrode current collector, and the negative electrode diaphragm is obtained after drying, and then the negative electrode sheet is obtained by cold pressing and cutting.
  • Slurry preparation layered silicate and viscose compounded by Na 0.5 (Al 1.5 Mg 0.5 )[Si 4 O 10 ](OH) 2 and octadecyltrimethylammonium bromide by sol-gel method
  • the binder polyvinylidene fluoride is dry mixed at a ratio of 40:60 to obtain mixed solid phase particles; add the above mixed solid phase particles into N-methylpyrrolidone, and add 8% ethanol as a solvent, and fully stir in a stirring tank; Adjust the atmosphere of the mixing tank to be a nitrogen atmosphere, and continue to stir to obtain the slurry;
  • Isolation film preparation using PE substrate, using gravure coating, the above slurry is coated on both sides of the substrate to form a coating, and the thickness of the coating on one side is 2 ⁇ m.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1:1, and then LiPF 6 was uniformly dissolved in the above solution to obtain an electrolyte.
  • the concentration of LiPF 6 is 1 mol/L.
  • Examples 2-12 and Comparative Examples 1-4 are similar to the preparation method of the secondary battery in Example 1, but the composition and product parameters of the layered silicate are adjusted, and the different preparation parameters are shown in Table 1 for details.
  • the materials used in the coating can be distinguished through simple physical property characterization, including conventional material analysis methods such as XRD crystal form confirmation, ICP elemental analysis and infrared organic functional group confirmation.
  • Test equipment high-speed rail servo control desktop tensile testing machine (AI-3000); test environment: normal temperature, relative humidity 45%-55%.
  • Test equipment high-speed rail servo control desktop tensile testing machine (AI-3000); test environment: normal temperature, relative humidity 45%-55%.
  • Test equipment high temperature oven; test environment: relative humidity 45%-55%.
  • the test was carried out at room temperature of 25°C.
  • Comparative Examples 1-3 the strength and puncture strength of the separator are poor and the thermal shrinkage rate is high, and the overall performance of the separator is poor; in terms of battery performance, the DC resistance is high, the thermal failure temperature is low, and the safety performance is relatively low. Difference.
  • 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 solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects 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

本申请提供了一种隔离膜，包括基材；涂层，所述涂层包括有机-无机杂化的层状硅酸盐；所述层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种；所述层状硅酸盐中的无机部分包括式1所示的化合物，M2(Al2-xMgx)[Si4O10](OH)2式1，在式1中，M包括Na、Li、K、Ca中的一种或几种，x取值为0-2。

Description

一种隔离膜、含有其的二次电池和用电装置
本申请要求2021年10月9日提交的202111179556.8的优先权。
技术领域
本申请涉及电池技术领域，尤其涉及一种隔离膜、含有其的二次电池和用电装置。
背景技术
近年来，二次电池的应用范围越来越广泛，其被广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。
二次电池的安全性能一直被行业内高度重视，因此，如何提高电池的安全性能仍然是亟待解决的问题。
发明内容
为了达到上述目的，本申请的第一方面提供一种隔离膜，包括：基材；涂层，所述涂层包括有机-无机杂化的层状硅酸盐；所述层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种；所述层状硅酸盐中的无机部分包括式1所示的化合物，M 2(Al 2-xMg x)[Si 4O 10](OH) 2式1，在式1中，M包括Na、Li、K、Ca中的一种或几种，下标x取值为0-2。
由此，本申请通过在隔离膜涂层浆料中加入特定结构的层状硅酸盐，在溶剂中溶胀分散成胶体，同时，干燥后层状硅酸盐能依附在隔离膜表面，起到增强隔离膜机械强度的作用。
在任意实施方式中，层状硅酸盐中的有机部分包括式2A或式2B所示的化合物中的一种或几种；
Figure PCTCN2022118084-appb-000001
在式2A中，R 11-R 14中至少有三个各自独立地选自C 1-C 25的烷基；
在式2B中，R 21选自C 1-C 25的烷基；
式2A和式2B中，X各自独立为卤素，优选Cl、Br。
在任意实施方式中，R 11-R 14中至少一个选自C 10-C 25的烷基；和/或，R 21选自C 10-C 25的烷基。
在任意实施方式中，层状硅酸盐在涂层中的质量占比为50％-80％，可选为60％-70％。
在任意实施方式中，涂层的厚度小于等于3μm；可选为0.5μm-3μm。
在任意实施方式中，隔离膜的纵向拉伸强度为3000kgf/cm 2-3500kgf/cm 2。
在任意实施方式中，隔离膜在150℃下的纵向热收缩率为3.5％-5％。
本申请的第二方面还提供一种隔离膜的制备方法，其中，包括如下步骤：
步骤S1：提供基材；
步骤S2：提供浆料，浆料包括有机-无机杂化的层状硅酸盐；层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种；层状硅酸盐中的无机部分包括式1所示的化合物，M 2(Al 2-xMg x)[Si 4O 10](OH) 2式1，在式1中，M包括Na、Li、K、Ca中的一种或几种，下标x取值为0-2；
步骤S3：将浆料涂覆在基材的至少一个表面上形成涂层。
层状硅酸盐由有机部分与无机部分复合而成，可选地，所述有机部分在无机部分层间插层或剥离。
由此，采用本申请的方法制备的隔离膜，在涂层浆料中加入层状硅酸盐，起到分散和增稠的作用，同时，干燥后层状硅酸盐能依附在隔离膜表面，起到增强隔离膜机械强度的作用。
本申请的第三方面提供一种二次电池，包括本申请第一方面的隔离膜或根据本申请第二方面的方法制备的隔离膜。
本申请的第四方面提供一种电池模块，包括本申请的第三方面的二次电池。
本申请的第五方面提供一种电池包，包括本申请的第四方面的电池模块。
本申请的第六方面提供一种用电装置，包括选自本申请的第三方面的二次电池、本申请的第四方面的电池模块或本申请的第五方面的电池包中的至少一种。
附图说明
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的隔离膜、正极极片、负极极片、电解液、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，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
[二次电池]
二次电池又称为充电电池或蓄电池，是指在电池放电后可通过充电的方式使活性材料激活而继续使用的电池。通常情况下，二次电池包括正极极片、负极极片、隔离膜及电解液。在电池充放电过程中，活性离子(例如锂离子)在正极极片和负极极片之间往返嵌入和脱出。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使活性离子通过。电解质在 正极极片和负极极片之间，主要起到传导活性离子的作用。
[隔离膜]
本申请的一个实施方式提供一种隔离膜，包括：基材；涂层，所述涂层包括有机-无机杂化的层状硅酸盐；所述层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种；所述层状硅酸盐中的无机部分包括式1所示的化合物，M 2(Al 2-xMg x)[Si 4O 10](OH) 2式1，在式1中，M包括Na、Li、K、Ca中的一种或几种，下标x取值为0-2。
本申请对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结构基材。
在一些实施方式中，基材可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。
本申请通过在隔离膜涂层浆料中加入特定组成的层状无机物，其中，链状有机物在无机物片层间插层或剥离实现复合。所得隔离膜涂层不仅能加强隔离膜机械性能，还分散性好，易于涂布。包含该涂层隔离膜的二次电池具有高安全、高容量、长寿命的特点。
在一些实施方式中，有机-无机杂化材料中的有机部分包括式2A或式2B所示的化合物中的一种或几种，
Figure PCTCN2022118084-appb-000002
在式2A中，R 11-R 14中至少有三个各自独立地选自C 1-C 25的烷基；
在式2B中，R 21选自C 1-C 25的烷基；
式2A和式2B中，X各自独立为卤素，优选Cl、Br。
有机-无机杂化是本领域公知的，通常是无机材料和有机材料在纳米尺度通过分子间作用力、氢键或共价键结合的复合材料。各材料在性能上相互取长补短，产生协同效应，宏观上组成具有新性能的材料，常用方法有溶胶凝胶法等。例如，本申请的无机部分(例如Na 0.5(Al 1.5Mg 0.5)[Si 4O 10](OH) 2)可在有机部分(例 如有机铵盐)表面进行修饰处理，在包含引发剂、抗氧剂的分散介质中，以一定温度高速搅拌后，采用蒸馏去除介质后干燥粉碎制成。
在一些实施方式中，R 11-R 14中至少一个选自C 10-C 25的烷基；和/或，所述R 21选自C 10-C 25的烷基。
有机部分较长的分子链有利于层状硅酸盐微观尺度上的剥离，在对硅酸盐改性时易于复合制备，形成的层状硅酸盐结构稳定高；并且其对有机溶剂体系具有较高的亲和性，同时该有机物本身作为表面活性剂，与硅酸盐复合后形成的有机改性硅酸盐能在涂层浆料制备过程中具有更好的分散效果。
在一些实施方式中，层状硅酸盐在涂层中的质量占比为50％-80％，可选为60％-70％。层状硅酸盐的质量占比会影响到隔离膜的物理特性和涂层的粘结稳定性，含量控制在该范围下时，既可保证粘结力较大，涂覆效果好，同时隔离膜强度较高，对二次电池的安全性能增强效果较好。
在一些实施方式中，涂层的厚度小于等于3μm；可选为0.5μm-3μm。隔离膜涂层的厚度满足该范围时，隔离膜安全性能的加强效果较明显，同时电芯内阻增加量少，对首效影响较小。
在一些实施方式中，纵向拉伸强度为3000kgf/cm 2-3500kgf/cm 2。
在一些实施方式中，纵向在150℃下热收缩率为3.5％-5％。
[隔离膜制备方法]
本申请的一个实施方式提供一种隔离膜的制备方法，其中，包括如下步骤：
步骤S1：提供基材；
步骤S2：提供浆料，浆料包括层状硅酸盐，层状硅酸盐包括以层状硅酸盐为主体的有机-无机杂化材料；
其中，有机物为烷基铵、季铵盐、十八胺和有机硅中的一种或几种；
层状硅酸盐通式由式1所示，
M x(Al 2-xMg x)[Si 4O 10](OH) 2  式1，
在式1中，M包括Na、Li、K中的一种或几种，下标x取值为0-2；
步骤S3：将浆料涂覆在所述基材的至少一个表面上，制得隔离膜。
层状硅酸盐由有机部分和无机部分复合而成，可选地，有机物在所述层状硅酸盐片层间插层或剥离。
该涂层浆料具有成分简单、分散性好、流平性高的特点，同时，该浆料在保证尽可能减少用料种类的同时，制备的浆料易于涂布，能适应当前各类型涂布方法。该类该料易溶于烃类溶剂，加少量极性溶剂如甲醇、乙醇、丙酮等，能使层状硅酸盐层间的季铵碳氢链通过氢键桥接，获得有效的溶剂化，从而使层间膨胀、分散，并形成卡层屋结构的触变性凝胶体，防止无机填料沉淀。涂层浆料中使用的主要目的在于获得稳定易涂布浆料，同时实现硅酸盐在隔离膜上成膜，增强隔离膜机械强度。
在一些实施方式中，制备方法中S2还包括以下步骤：
将有机-无机杂化材料与粘结剂混合搅拌获得混合固相颗粒；在混合固相颗粒中加入醇类溶剂。
在一些实施方式中，粘结剂包括聚偏氟乙烯、聚丙烯酸、聚丙烯酸酯中的一种或几种。粘结剂的选取会影响涂层在隔离膜表面的粘结效果，其中聚偏氟乙烯在有机浆料中分散效果更佳。
在一些实施方式中，醇类溶剂包括甲醇、乙醇、乙二醇、丙醇中的一种或几种。醇类溶剂在浆料中起到加强浆料分散效果的作用，其中乙醇较易分散。
在一些实施方式中，层状硅酸盐在混合固相颗粒中的质量分数ω 1为50％-80％，粘结剂在混合固相颗粒中的质量分数ω 2为20％-50％，可选地，ω 1/ω 2满足1≤ω 1/ω 2≤4。
在一些实施方式中，醇类溶剂占总溶剂质量比5％-20％。
在一些实施方式中，浆料包括补锂剂，可选地，包括锂粉或氧化锂中的一种或几种。
在一些实施方式中，浆料涂覆的方法包括转移式涂布、喷涂、挤压式涂布、凹版涂布或刮涂中的任意一种或至少两种的组合。
[正极极片]
正极极片通常包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，正极膜层包括正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，正极集流体可采用金属箔片或复合集流体。例如，作 为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 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，粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于 溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
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，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。作为示例，粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。作为示例，导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧 甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，电解质为液态的，且包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，电解液还可选地包括添加剂。作为示例，添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是 塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。 所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
[实施例]
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
正极极片的制备
将正极活性材料NCM523、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按重量比为96.5:1.5:2溶于溶剂N-甲基吡咯烷酮(NMP)中，充分搅拌混合均匀后得到正极浆料；之后将正极浆料均匀涂覆于正极集流体上，之后经过烘干、冷压、分切，得到正极极片。
负极极片的制备
将活性物质人造石墨、导电剂乙炔黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC)按照重量比为95:2:2:1溶于溶剂去离子水中与溶剂去离子水均匀混合后制备成负极浆料；然后将负极浆料均匀涂覆在负极集流体铜箔上，烘干后得到负极膜片，再经过冷压、分切得到负极极片。
隔离膜
浆料制备：将Na 0.5(Al 1.5Mg 0.5)[Si 4O 10](OH) 2与十八烷基三甲基溴化铵使用溶胶凝胶法复合而成的层状硅酸盐和粘结剂聚偏氟乙烯按40：60比例进行干混获 得混合固相颗粒；将上述混合固相颗粒加入N-甲基吡咯烷酮中，并加入8％的乙醇作为溶剂，在搅拌罐中充分搅拌；调整搅拌罐气氛为氮气气氛，继续搅拌后获得浆料；
隔离膜制备：采用PE基材，使用凹版涂布，将上述浆料涂覆在基材两侧形成涂层，单面涂层的厚度为2μm。
电解液的制备
将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按体积比1:1:1混合，然后将LiPF 6均匀溶解在上述溶液中，得到电解液。该电解液中，LiPF 6的浓度为1mol/L。
二次电池的制备
将上述正极极片、隔离膜、负极极片按顺序堆叠并卷绕，得到电极组件；将电极组件放入外包装中，加入上述制备的电解液，经封装、静置、化成、老化等工序后，得到二次电池。
实施例2-12和对比例1-4与实施例1的二次电池制备方法相似，但是调整了层状硅酸盐的组成和产品参数，不同的制备参数详见表1。
表1：实施例1-12与对比例1-3的制备参数
Figure PCTCN2022118084-appb-000003
隔离膜测试
(1)涂层材料测试
涂层中使用的材料可通过简单的物性表征分辨，包括XRD晶型确认、ICP元素分析和红外有机官能团确认等常规材料分析手段。
(2)穿刺强度测试
1)测试设备：高铁伺服控制桌上型拉力试验机(AI-3000)；测试环境：常温，相对湿度45％-55％。
2)确保样品隔离膜表面无瑕疵，用剪刀将隔离膜裁成条状，其中条状隔离膜的宽度大于100mm。
3)将宽度为100mm的试片安装在样膜固定夹环上，然后用直径为1.0mm、直径顶端半径为0.5mm的钢针以(50±5)mm/min的速度去顶刺，读取钢针穿透试片的最大负荷，作为样品隔离膜的穿刺强度。
(3)拉伸强度测试
1)测试设备：高铁伺服控制桌上型拉力试验机(AI-3000)；测试环境：常温，相对湿度45％-55％。
2)确保样品隔离膜表面无瑕疵，用剪刀将隔离膜裁成100mm×15mm的条状。
3)使用拉力机固定隔离膜，沿样品隔离膜长度方向拉伸，直至拉断，记录最大载荷即为隔离膜拉伸强度。
(4)热收缩率测试
1)测试设备：高温烘箱；测试环境：相对湿度45％-55％。
2)确保样品隔离膜表面无瑕疵，用剪刀将隔离膜裁成10cm×10cm的方片，并用两片玻璃板夹住放入烘箱。
3)以5℃/min的升温速度将烘箱温度加热至150℃，保温1小时。
4)取出隔离膜，待冷却后测量隔离膜长宽收缩量，长度收缩量和加热前比值即为热收缩率。
电池测试
(1)直流电阻测试
常温25℃下，进行测试。
1)以1/3C(标称容量)将电芯充电至标称电压后，恒压充电至电流≤0.05C，记录容量为100％SOC；搁置5min。
2)以1/3C倍率恒流放电50％SOC的电量，调节完成后测试二次电池的电压，记录为V 1。
3)以4C倍率(对应电流I)恒流持续放电10s，放电结束后测试锂离子电池的电压，记录为V 2。
4)使用公式计算即得直流电阻R：R＝(V 1-V 2)/I。
(2)二次电池热失效温度测试
1)电芯满充至标称电压后布感温线，放入加热炉中。
2)以5℃/min的升温速度加热，直至电芯起火失效。
3)记录失效时炉温作为电芯热失效温度。
表2：实施例1-12与对比例1-3的性能测试结果
Figure PCTCN2022118084-appb-000004
根据上述结果可知，实施例1-12在隔离膜涂层中添加了层状硅酸盐，其在隔离膜性能方面均取得了良好的效果，隔离膜穿刺强度和拉伸强度较高同时热收缩率较小；电池性能方面，提高了热失效温度的同时，还具有较小的直流电阻，增强了电池的安全性能。
而相对于此，对比例1-3，隔离膜强度和穿刺强度较差且热收缩率高，隔离膜性能整体较差；电池性能方面，直流电阻较高且热失效温度较低，安全性能较差。
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 (16)

  1. 一种隔离膜，包括：
    基材；
    所述基材表面的涂层，所述涂层包括有机-无机杂化的层状硅酸盐；
    所述层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种，
    所述层状硅酸盐中的无机部分包括式1所示的化合物，
    M 2(Al 2-xMg x)[Si 4O 10](OH) 2 式1，
    在式1中，M包括Na、Li、K、Ca中的一种或几种，x取值为0-2。
  2. 根据权利要求1所述的隔离膜，其中，
    所述层状硅酸盐中的有机部分包括式2A或式2B所示的化合物中的一种或几种，
    Figure PCTCN2022118084-appb-100001
    在式2A中，R 11-R 14中至少有三个各自独立地选自C 1-C 25的烷基；
    在式2B中，R 21选自C 1-C 25的烷基；
    式2A和式2B中，X各自独立为卤素，优选Cl、Br。
  3. 根据权利要求1或2所述的隔离膜，其中，
    所述R 11-R 14中至少一个选自C 10-C 25的烷基；和/或，所述R 21选自C 10-C 25的烷基。
  4. 根据权利要求1-3任一项所述的隔离膜，其中，
    所述层状硅酸盐在所述涂层中的质量占比为50％-80％，可选为60％-70％。
  5. 根据权利要求1-4任一项所述的隔离膜，其中，所述涂层的厚度小于等于3μm；可选为0.5μm-3μm。
  6. 根据权利要求1-5任一项所述的隔离膜，其中，所述隔离膜的纵向拉伸强度为3000kgf/cm 2-3500kgf/cm 2。
  7. 根据权利要求1-6任一项所述的隔离膜，其中，所述隔离膜在150℃下的纵向热收缩率为3.5％-5％。
  8. 一种隔离膜的制备方法，其中，包括如下步骤：
    步骤S1：提供基材；
    步骤S2：提供浆料，所述浆料包括有机-无机杂化的层状硅酸盐；
    所述层状硅酸盐中的有机部分包括烷基铵、季铵盐、十八胺和有机硅中的一种或几种；
    所述层状硅酸盐中的无机部分包括式1所示的化合物，
    M 2(Al 2-xMg x)[Si 4O 10](OH) 2 式1，
    在式1中，M包括Na、Li、K、Ca中的一种或几种，X取值为0-2；
    步骤S3：将所述浆料涂覆在所述基材的至少一个表面上形成涂层。
  9. 根据权利要求8所述的制备方法，其中，所述步骤S2还包括：
    将所述层状硅酸盐与粘结剂混合搅拌获得混合固相颗粒；在所述混合固相颗粒中加入溶剂。
  10. 根据权利要求9所述的制备方法，其中，所述粘结剂包括聚偏氟乙烯、聚丙烯酸、聚丙烯酸酯中的一种或几种。
  11. 根据权利要求9或10所述的制备方法，其中，所述溶剂包括醇类溶剂；可选地，所述醇类溶剂包括甲醇、乙醇、乙二醇、丙醇中的一种或几种。
  12. 根据权利要求8-11任一项所述的制备方法，其中，所述层状硅酸盐在所述涂层中的质量分数ω 1为50％-80％；可选为60％-70％。
  13. 根据权利要求9-12任一项所述的制备方法，其中，所述粘结剂在所述涂层中的质量分数ω 2为20％-50％；可选地，1≤ω 1/ω 2≤4。
  14. 根据权利要求9-13任一项所述的制备方法，其中，所述醇类溶剂在所述溶剂中的质量占比为5％-20％。
  15. 一种二次电池，包括权利要求1-7任一项所述的隔离膜或包括根据权利要求8-14任一项所述的方法制备的隔离膜。
  16. 一种用电装置，包括权利要求15所述的二次电池。
PCT/CN2022/118084 2021-10-09 2022-09-09 一种隔离膜、含有其的二次电池和用电装置 WO2023056825A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116526069A (zh) * 2023-07-04 2023-08-01 宁德时代新能源科技股份有限公司 隔离膜、电池单体、电池和用电装置
CN116544615A (zh) * 2023-07-03 2023-08-04 宁德时代新能源科技股份有限公司 隔离膜、锂二次电池和用电装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116581243B (zh) * 2023-07-12 2023-11-21 宁德时代新能源科技股份有限公司 电极极片、其制备方法、二次电池和用电装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256354A (ja) * 2003-02-26 2004-09-16 Fuji Photo Film Co Ltd 有機変性層状珪酸塩及びその製造方法、並びに該珪酸塩を含む組成物及び基板
CN102468465A (zh) * 2010-11-08 2012-05-23 索尼公司 抗收缩性微孔膜和电池隔膜
CN108428838A (zh) * 2018-02-26 2018-08-21 中国东方电气集团有限公司 一种电池安全隔膜的制备方法
CN109037550A (zh) * 2018-07-26 2018-12-18 中科（淮安）新能源技术开发有限公司 一种有机黏土矿物与聚偏氟乙烯共混制备锂电池涂覆隔膜的方法
CN109346655A (zh) * 2018-09-21 2019-02-15 江苏微能电子科技有限公司 超容量稳定锂电池及其制备方法
CN111224049A (zh) * 2020-01-14 2020-06-02 江苏厚生新能源科技有限公司 阻燃型锂电池涂覆隔膜及其制备方法
WO2020226310A1 (ko) * 2019-05-03 2020-11-12 주식회사 엘지화학 리튬-황 전지용 분리막 및 이를 포함하는 리튬-황 전지

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256572A (ja) * 2003-02-24 2004-09-16 Teijin Ltd 樹脂組成物およびその製造法
JP5032002B2 (ja) * 2004-06-17 2012-09-26 株式会社クラレ 電池用セパレータ及びアルカリ電池
KR20130123748A (ko) * 2012-05-03 2013-11-13 주식회사 엘지화학 세퍼레이터, 그 제조방법 및 이를 구비한 전기화학소자
CN104979516B (zh) * 2014-04-10 2018-08-03 宁德时代新能源科技股份有限公司 电化学装置及电化学装置隔离膜的制备方法
CN109411670B (zh) * 2017-08-17 2022-04-12 宁德时代新能源科技股份有限公司 一种隔离膜，其制备方法及使用该隔离膜的二次电池
KR102037061B1 (ko) * 2017-12-12 2019-10-28 한국세라믹기술원 유무기 하이브리드 필름 및 그 제조방법
CN109950451A (zh) * 2017-12-21 2019-06-28 宁德时代新能源科技股份有限公司 一种隔离膜，其制备方法及含有该隔离膜的电化学装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256354A (ja) * 2003-02-26 2004-09-16 Fuji Photo Film Co Ltd 有機変性層状珪酸塩及びその製造方法、並びに該珪酸塩を含む組成物及び基板
CN102468465A (zh) * 2010-11-08 2012-05-23 索尼公司 抗收缩性微孔膜和电池隔膜
CN108428838A (zh) * 2018-02-26 2018-08-21 中国东方电气集团有限公司 一种电池安全隔膜的制备方法
CN109037550A (zh) * 2018-07-26 2018-12-18 中科（淮安）新能源技术开发有限公司 一种有机黏土矿物与聚偏氟乙烯共混制备锂电池涂覆隔膜的方法
CN109346655A (zh) * 2018-09-21 2019-02-15 江苏微能电子科技有限公司 超容量稳定锂电池及其制备方法
WO2020226310A1 (ko) * 2019-05-03 2020-11-12 주식회사 엘지화학 리튬-황 전지용 분리막 및 이를 포함하는 리튬-황 전지
CN111224049A (zh) * 2020-01-14 2020-06-02 江苏厚生新能源科技有限公司 阻燃型锂电池涂覆隔膜及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116544615A (zh) * 2023-07-03 2023-08-04 宁德时代新能源科技股份有限公司 隔离膜、锂二次电池和用电装置
CN116526069A (zh) * 2023-07-04 2023-08-01 宁德时代新能源科技股份有限公司 隔离膜、电池单体、电池和用电装置
CN116526069B (zh) * 2023-07-04 2023-09-15 宁德时代新能源科技股份有限公司 隔离膜、电池单体、电池和用电装置

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