WO2020000164A1 - 一种复合锂电池隔膜及其制备方法 - Google Patents

一种复合锂电池隔膜及其制备方法 Download PDF

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Publication number
WO2020000164A1
WO2020000164A1 PCT/CN2018/092725 CN2018092725W WO2020000164A1 WO 2020000164 A1 WO2020000164 A1 WO 2020000164A1 CN 2018092725 W CN2018092725 W CN 2018092725W WO 2020000164 A1 WO2020000164 A1 WO 2020000164A1
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Prior art keywords
lithium battery
battery separator
composite lithium
coating
inorganic particles
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PCT/CN2018/092725
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English (en)
French (fr)
Inventor
姚勇强
平翔
张柳浩
叶斌
陈秀峰
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Shenzhen Senior Technology Material Co Ltd
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Shenzhen Senior Technology Material Co Ltd
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Priority to EP18924083.1A priority Critical patent/EP3817092A4/en
Priority to CN202211639467.1A priority patent/CN116130885A/zh
Priority to JP2020570121A priority patent/JP7217297B2/ja
Priority to US17/254,870 priority patent/US12040507B2/en
Priority to CN201880000766.6A priority patent/CN110859053B/zh
Priority to KR1020217002501A priority patent/KR102543254B1/ko
Priority to PCT/CN2018/092725 priority patent/WO2020000164A1/zh
Publication of WO2020000164A1 publication Critical patent/WO2020000164A1/zh
Anticipated expiration legal-status Critical
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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Definitions

  • the present disclosure relates to the field of lithium ion batteries, and in particular, to a composite lithium battery separator and a method for preparing the same.
  • the separator plays the role of electronic insulation between the positive electrode material and the negative electrode material to ensure the mechanical isolation of the positive electrode and the negative electrode.
  • the diaphragm has a certain pore size and porosity, ensuring low resistance and high ionic conductivity, and good permeability to lithium ions. The characteristics and quality of the separator seriously affect the safety performance, rate performance, cycle life and basic electrical performance of the battery.
  • the static electricity of the separator is too large, which causes the poor fit of the pole pieces in the assembled battery or the separator under high temperature conditions.
  • the positive and negative electrodes of the battery will cause internal short circuit of the battery; the hardness and mechanical properties of the thin battery cells will be poor, which will cause the performance of lithium battery products to decline.
  • the liquid may leak due to the poor liquid absorption capacity of the separator in the liquid battery.
  • the present disclosure provides a composite lithium battery separator with high ionic conductivity, good liquid absorption / retention ability, strong peel resistance, and high adhesion to positive and negative electrode sheets.
  • the present disclosure also provides a method for preparing a composite lithium battery separator, which is suitable for large-scale production.
  • At least one of the objects of the present disclosure can be achieved by the following technical measures.
  • a composite lithium battery separator includes a base film or a ceramic film, and a coating layer covering one or both sides of the base film or the ceramic film.
  • the coating layer is formed by slurry coating. Including coating polymer 5% -45% and organic solvent 55% -95%, coating polymer includes fluorine-based or acrylic resin polymer 10-10 parts by weight parts, high molecular adhesive 0.5-10 Parts and inorganic nanoparticles 0-90 parts.
  • the thickness of the base film is 5-30 ⁇ m, preferably 10-20 ⁇ m; the porosity is 30% -60%, preferably 40% -50%; the thickness of the coating layer is 0.5-10 ⁇ m, preferably 3 -8 ⁇ m.
  • the base film is selected from a polyethylene-based film, a polypropylene-based film, a polypropylene / polyethylene / polypropylene composite-based film, a polyimide-based film, a polyvinylidene fluoride-based film, and a polyethylene nonwoven.
  • a polyethylene-based film a polypropylene-based film, a polypropylene / polyethylene / polypropylene composite-based film, a polyimide-based film, a polyvinylidene fluoride-based film, and a polyethylene nonwoven.
  • the organic solvent comprises a combination selected from the group consisting of acetone, dimethylacetamide, dimethylformamide, chloroform, dichloromethane, dichloroethane, dimethylsulfoxide, and N-methylpyrrolidone. At least one of.
  • the fluorine-based or acrylic resin polymer comprises a polymer selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride and hexafluoropropylene copolymer, polyvinylidene fluoride and dichloroethylene copolymer, polystyrene, poly In a combination of n-butyl acrylate, polymethyl methacrylate, polyethyl methacrylate, poly-t-butyl acrylate, polyvinyl acetate, polyacrylonitrile, polyvinyl acetate, acrylamide, and polymethyl acrylate
  • the molecular weight of the fluorine-based or acrylic resin polymer is 50,000-500000, preferably 200,000-300,000.
  • the polymer adhesive comprises a composition selected from the group consisting of styrene-butadiene latex, styrene-acrylic latex, polyvinyl acetate, polyvinyl alcohol, polyethyl acrylate, polybutyl methacrylate, ethylene-vinyl acetate copolymer, and polyurethane. At least one of a combination.
  • the inorganic nano particles are mainly a mixture of conventional inorganic particles and inorganic particles having lithium ion conductivity, and the weight ratio of the conventional inorganic particles to the inorganic particles having lithium ion conductivity is 80-95: 20- 5.
  • the conventional inorganic particles include at least one selected from the group consisting of alumina, silica, barium titanate, magnesium oxide, boehmite, titanium oxide, calcium carbonate, and zirconium dioxide.
  • the particle size range of conventional inorganic particles is 0.01-10um; the conventional inorganic particles are composed of low-sized inorganic particles and high-sized inorganic particles in a weight ratio of 80-90: 20-10.
  • the particle size range of the particles is 0.01-0.2um, and the particle size range of the high-particle size inorganic particles is 0.2-10um.
  • the inorganic particles having lithium ion conductivity include at least one selected from the group consisting of lithium phosphate, lithium titanate phosphate, lithium aluminum titanate phosphate, lithium nitrogen compounds, and lithium lanthanum titanate.
  • the coating polymer further comprises 0.5 to 10 parts by weight of a dispersant, and the dispersant includes a fluorocarbon dispersant selected from the group consisting of carboxylate-based fluorine dispersant, triethyl phosphate, sulfonate-based fluorine dispersant, At least one of a combination consisting of sodium polyacrylate, potassium polyacrylate, and polyethylene glycol.
  • a dispersant includes a fluorocarbon dispersant selected from the group consisting of carboxylate-based fluorine dispersant, triethyl phosphate, sulfonate-based fluorine dispersant, At least one of a combination consisting of sodium polyacrylate, potassium polyacrylate, and polyethylene glycol.
  • the coating polymer further comprises 0.1 to 8 parts by weight of a wetting agent, the wetting agent comprising a member selected from the group consisting of polycarbonate, sodium dodecyl sulfate, and sodium dodecylbenzenesulfonate.
  • a wetting agent comprising a member selected from the group consisting of polycarbonate, sodium dodecyl sulfate, and sodium dodecylbenzenesulfonate.
  • the coating polymer further comprises 0.1-10 parts of a pore-forming agent, and the pore-forming agent is deionized water.
  • the coating polymer further comprises 0.1-5 parts by weight of an antistatic agent
  • the antistatic agent comprises a member selected from octadecyldimethyl quaternary ammonium nitrate, trimethyloctadecyl At least one selected from the group consisting of ammonium acetate, N-hexadecylpyridine nitrate, N-alkyl amino acid salt, betaine type and imidazoline salt derivatives.
  • a method for preparing the above-mentioned composite lithium battery separator includes the following steps:
  • the slurry is coated on one or both sides of the base film or ceramic film, and after solidification, washing, drying, and shaping, a composite lithium battery separator is obtained.
  • the stirring speed in step S1 is 40-80R and the stirring time is 15-40min; the stirring speed in step S3 is 20-60R, the dispersion speed is 300-800R, the stirring time is 15-30min, and the slurry is The viscosity of the material is 50-1000cp.
  • step S2 0.5-10 parts of the dispersant is first added and stirred according to parts by weight, the stirring speed is 40-90R, the stirring time is 10-20min, and then an organic solvent is added.
  • the method for adding organic solvents is: firstly add gradually according to 4% -5% of the total amount of organic solvents, and stop adding when the powder is just kneaded and agglomerated, and the stirring speed after the powder is kneaded is 80- 120R, stirring time is 30-90min, and then add organic solvents according to the gradient of solid content change to reduce the solid content of the slurry from high until it meets the specified solid content.
  • the stirring speed when the solid content is higher than the specified solid content, the stirring speed is 40-100R, the dispersion speed is 2000-4000R, and the stirring time is 15-45min; when the solid content meets the specified solid content, the stirring speed is 40-80R The dispersion speed is 3000-4500R, and the stirring time is 30-90min.
  • the coating method includes one of a dip coating method, a micro gravure coating method, a spray coating method, a slope coating method, or a slit coating method, and the drying temperature is 40-80 ° C.
  • the advantages and beneficial effects of the present disclosure include at least:
  • the composite lithium battery separator of the present disclosure has both a pore structure existing on a base film or a ceramic film, and an oil coating on the base film or the ceramic film in a coating layer formed of inorganic nanoparticles and a binder.
  • the porous structure, so the composite lithium battery separator has a high coating porosity, which can increase the volume of the space in which the liquid electrolyte penetrates, greatly improving the lithium ion conductivity and the liquid absorption and retention of the separator, forming a gel-like electrolyte, reducing Risk of battery leakage; strong peel resistance and high adhesion to positive and negative electrode sheets.
  • the slurry prepared according to the preparation method of the present disclosure has high stability, can be used normally after being sealed for more than 60 days, and there is no obvious delamination and precipitation, which is conducive to the continuous and large-scale production of the coating layer in the composite lithium battery separator. Therefore, the preparation method of the present disclosure is suitable for large-scale production.
  • the inorganic particles having lithium ion conductivity in the inorganic nanoparticles of the present disclosure can have a synergistic effect with conventional inorganic particles, can improve lithium ion conductivity, and improve battery performance.
  • the present disclosure uses both high-diameter inorganic particles and low-diameter inorganic particles at the same time, which will cause the inorganic particles in the coating layer to form a densely packed state, improve the high temperature resistance of the coating layer, and reduce the thermal shrinkage of the separator. Sex.
  • Example 1 is an electron microscope picture of a composite lithium battery separator according to Example 1 of the present disclosure
  • FIG. 2 is a data chart of a cycle test of a soft-pack battery prepared in Example 1 and Comparative Example 2 of the present disclosure.
  • the present disclosure provides a composite lithium battery separator including a base film or a ceramic film, and a coating layer covering one or both sides of the base film or the ceramic film.
  • the coating layer is formed by slurry coating. Includes 5% -45% of coating polymer and 55% -95% of organic solvent in weight percent.
  • Coating polymer includes 10-100 parts of fluorine-based or acrylic resin polymer, polymer adhesive in terms of parts by weight. 0.5-10 parts and inorganic nanoparticles 0-90 parts.
  • the thickness of the base film is 5-30 ⁇ m, preferably 10-20 ⁇ m; the porosity is 30% -60%, preferably 40% -50%; the thickness of the coating layer is 0.5-10 ⁇ m, preferably 3-8 ⁇ m .
  • the composite lithium battery separator of the present disclosure has both a pore structure existing on the base film or the ceramic film, and an oil coating on the base film or the ceramic film in a coating layer formed of inorganic nanoparticles and a binder.
  • the porous structure so the composite lithium battery separator has a high coating porosity, which can increase the volume of the space in which the liquid electrolyte penetrates, greatly improving the lithium ion conductivity and the liquid absorption and retention of the separator, forming a gel-like electrolyte, reducing Risk of battery leakage.
  • the van der Waals force between the polar functional groups on the molecular chains of the first and second binders and the electrode material will make the separator and the pole piece stick together well, reducing the probability of battery short-circuits and increasing Battery hardness and physical retention.
  • the base film in the composite lithium battery separator of the present disclosure may be specifically selected from a polyethylene-based film, a polypropylene-based film, a polypropylene / polyethylene / polypropylene composite-based film, a polyimide-based film, and a polyvinylidene fluoride-based film.
  • a polyethylene non-woven base film a polypropylene non-woven base film and a polyimide non-woven base film.
  • the organic solvent used in the composite lithium battery separator of the present disclosure may specifically include a material selected from the group consisting of acetone, dimethylacetamide (DMAC), dimethylformamide (DMF), chloroform, dichloromethane, dichloroethane, and dimethyl. At least one of a combination consisting of sulfoxide and N-methylpyrrolidone (NMP).
  • DMAC dimethylacetamide
  • DMF dimethylformamide
  • NMP N-methylpyrrolidone
  • the fluorine- or acrylic-based resin polymer used in the composite lithium battery separator of the present disclosure may specifically be selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride and hexafluoropropylene copolymers, polyvinylidene fluoride and dichloroethylene copolymers, Polystyrene, poly-n-butyl acrylate, polymethyl methacrylate, polyethyl methacrylate, poly-t-butyl acrylate, polyvinyl acetate, polyacrylonitrile, polyvinyl acetate, acrylamide, and polymethacrylate At least one of a combination of esters; the molecular weight of the fluorine-based or acrylic resin polymer is 50,000-500000, preferably 200,000-300,000.
  • the polymer adhesive used in the composite lithium battery separator of the present disclosure may specifically include a material selected from the group consisting of styrene-butadiene latex, styrene-acrylic latex, polyvinyl acetate (PVAC), polyvinyl alcohol (PVA), polyethylene acrylate (PEA), and polymethylmethacrylate. At least one selected from the group consisting of butyl acrylate (PBMA), ethylene-vinyl acetate copolymer (EVA), and polyurethane (PU).
  • PVAC polyvinyl acetate
  • PVA polyvinyl alcohol
  • PEA polyethylene acrylate
  • PU polyurethane
  • the inorganic nanoparticles used in the composite lithium battery separator of the present disclosure are mainly a mixture of conventional inorganic particles and inorganic particles having lithium ion conductivity, and the weight ratio of the conventional inorganic particles to the inorganic particles having lithium ion conductivity is 80- 95: 20-5.
  • the inorganic nanoparticles lithium ion-conducting inorganic particles and conventional inorganic particles (having piezoelectricity) can produce a synergistic effect, can improve lithium ion conductivity, and improve battery performance.
  • the conventional inorganic particles include at least one selected from the group consisting of alumina, silica, barium titanate, magnesium oxide, boehmite, titanium oxide, calcium carbonate, and zirconium dioxide.
  • the particle size range of conventional inorganic particles is 0.01-10um; the conventional inorganic particles are composed of low particle size inorganic particles and high particle size inorganic particles in a weight ratio of 80-90: 20-10, and the particle size range of low particle size inorganic particles is 0.01-0.2um, the particle size range of high-particle size inorganic particles is 0.2-10um.
  • the present disclosure uses both high-particle size inorganic particles and low-size particle inorganic particles at the same time, which will cause the inorganic particles in the coating layer to form a densely packed state, improve the high temperature resistance of the coating layer, and reduce the heat shrinkability of the separator.
  • the inorganic particles having lithium ion conductivity include at least one selected from the group consisting of lithium phosphate, lithium titanium phosphate, lithium aluminum titanate, lithium nitrogen compounds, and lithium lanthanum titanate.
  • the coating polymer in the present disclosure may further include 0.5 to 10 parts by weight of a dispersant, the dispersant comprising a fluorocarbon dispersant selected from carboxylates, triethyl phosphate (TEP ), At least one of a sulfonate-based fluorine dispersant, sodium polyacrylate (PAA-Na), potassium polyacrylate (PAA-K), and polyethylene glycol.
  • a dispersant comprising a fluorocarbon dispersant selected from carboxylates, triethyl phosphate (TEP ), At least one of a sulfonate-based fluorine dispersant, sodium polyacrylate (PAA-Na), potassium polyacrylate (PAA-K), and polyethylene glycol.
  • the coating polymer in the present disclosure may further include 0.1-8 parts of a wetting agent based on parts by weight.
  • the wetting agent contains a member selected from the group consisting of polycarbonate, sodium lauryl sulfate, ten Sodium dialkylbenzenesulfonate, sodium polyacrylate, polyvinyl alcohol, fluoroalkyl methoxy ether alcohol, fluoro alkyl ethoxy ether alcohol, alkyl phenol polyoxyethylene ether (APEO), fatty alcohol poly At least one of a combination of oxyethylene ether (AEO), fatty acid polyoxyethylene ether (FMEE), and polyoxyethylene alkylamide.
  • AEO oxyethylene ether
  • FMEE fatty acid polyoxyethylene ether
  • the coating polymer in the present disclosure may further include 0.1-10 parts of a pore-forming agent, and the pore-forming agent is deionized water.
  • the composite lithium battery separator of the present disclosure has both a pore structure existing on a base film or a ceramic film, and a porous structure in a coating layer.
  • the pore-forming agent can greatly increase the number of pores in the coating layer, thereby further improving Performance of composite lithium battery separators.
  • the pore-forming agent is preferably deionized water, which is inexpensive, and the formed coating layer does not release excessive impurities in the coagulation tank and the water washing tank during the coagulation and water washing processes, which reduces the difficulty of wastewater recovery in the coagulation tank and the water washing tank. .
  • the coating polymer in the present disclosure may further include 0.1-5 parts by weight of an antistatic agent, and the antistatic agent contains an octadecyldimethyl quaternary ammonium nitrate (SN), at least one selected from the group consisting of trimethyloctadecylammonium acetate, N-hexadecylpyridine nitrate, N-alkyl amino acid salt, betaine type and imidazoline salt derivatives.
  • SN octadecyldimethyl quaternary ammonium nitrate
  • the disclosure uses an antistatic agent, and the surface of the formed separator has less static electricity, which reduces the problem of uneven bonding between the separator and the pole pieces during assembly, and facilitates battery assembly; the anti-peeling ability of the separator and the adhesive force with the positive and negative pole pieces High, battery hardness is improved, greatly reducing the risk of internal short circuit of the battery.
  • the present disclosure also provides a method for preparing the above-mentioned composite lithium battery separator, including the following steps:
  • the dispersant first add the dispersant to the small-capacity mixing tank, stir, and gradually add the organic solvent.
  • the stirring speed of the dispersant is 40-90R, and the stirring time is 10-20min. According to 4% of the total organic solvent, -5% is added gradually.
  • the stirring speed of the powder is 80-120R, and the stirring time is 30-90min. Transfer the slurry in the small-capacity mixing tank to the large-capacity. In a mixing tank;
  • the stirring speed is 40-100R
  • the dispersion speed is 2000-4000R
  • the stirring time is 15-45min
  • the stirring speed is 40-80R
  • the dispersion speed is 3000-4500R
  • the stirring time is 30-90min.
  • the slurry is coated on one or both sides of the base film or ceramic film, and after solidification, washing, drying, and shaping, a composite lithium battery separator is obtained.
  • the coating method includes one of a dip coating method, a micro gravure coating method, a spray coating method, a slope coating method, or a slit coating method, and the drying temperature is 40-80 ° C.
  • This embodiment provides a composite lithium battery separator, which is prepared according to the following steps:
  • the slurry was applied to both sides of a polypropylene-based film with a thickness of 16 ⁇ m and a porosity of 47% by using a microgravure coating method, and a composite lithium battery separator and a composite lithium battery were obtained after solidification, washing, drying, and shaping.
  • the thickness of the separator was 23 ⁇ m, and the thickness of each side coating layer was 3.5 ⁇ m.
  • This embodiment provides a composite lithium battery separator, which is prepared according to the following steps:
  • Example 2 According to 2-4 of Example 1, a slurry having a solid content of 20% and a viscosity of 230 cp was obtained.
  • the slurry was applied to both sides of a polypropylene-based film with a thickness of 12 ⁇ m and a porosity of 42% by using a microgravure coating method, and a composite lithium battery separator and a composite lithium battery were obtained after solidification, washing, drying, and shaping
  • the thickness of the separator was 18 ⁇ m, and the thickness of each side coating layer was 3 ⁇ m.
  • This embodiment provides a composite lithium battery separator, which is prepared according to the following steps:
  • the high-adhesive slurry was applied to both sides of a polyethylene-based film with a thickness of 12 ⁇ m and a porosity of 40% by spraying, and a composite lithium battery separator was obtained after solidification, washing, drying, and shaping.
  • the thickness of the lithium battery separator was 16 ⁇ m, and the thickness of each side coating layer was 2 ⁇ m.
  • This embodiment provides a composite lithium battery separator, which is prepared according to the following steps:
  • the dip coating method was used to coat the high-adhesive slurry on both sides of a PP / PE / PP composite base film with a thickness of 16 ⁇ m and a porosity of 45%, and the composite was obtained after solidification, washing, drying, and shaping.
  • the thickness of a lithium battery separator and a composite lithium battery separator is 20 ⁇ m, and the thickness of each side coating layer is 2 ⁇ m.
  • This embodiment provides a composite lithium battery separator, which is prepared according to the following steps:
  • the micro gravure coating method was used to apply the slurry to both sides of a single-sided ceramic film with a thickness of 16 ⁇ m, and the composite lithium battery separator was prepared after solidification, washing, drying, and shaping.
  • the thickness of the composite lithium battery separator was 18 ⁇ m.
  • the thickness of each side coating layer was 1 ⁇ m.
  • This comparative example provides a lithium battery separator, which is a polypropylene-based film with a thickness of 16 ⁇ m and a porosity of 47%, without any coating treatment.
  • This comparative example provides a traditional ceramic slurry-coated lithium-ion battery separator.
  • the thickness of the separator is 22 ⁇ m
  • the base film is a polypropylene-based film with a thickness of 16 ⁇ m and a porosity of 47%.
  • the side coating forms a coating, and the thickness of each side coating is 3 ⁇ m.
  • FIG. 1 is an electron microscope picture.
  • the composite lithium battery separator has a porous structure and has a very high porosity. Therefore, the composite lithium battery separator prepared according to the preparation method of the present disclosure has high ionic conductivity and good absorption / liquid holding capacity.
  • the composite lithium battery separator prepared according to the preparation method of the present disclosure has good heat shrinkage performance, high adhesion to the pole pieces, and large bending strength of the battery cells, which is significantly better than the uncoated ones in the comparative example.
  • Comparative Example 1 and Comparative Example 2 are polyolefin separators and ceramic separators.
  • Polyolefin separators can provide sufficient mechanical strength and chemical stability at room temperature, but they may exhibit large thermal shrinkage at high temperatures, making positive The negative electrode contacts and quickly accumulates a large amount of heat, causing high pressure inside the battery, which causes the battery to burn or explode.
  • diaphragm thickness reduction With the development of the trend of diaphragm thickness reduction, smaller film thicknesses will face a relatively high risk of puncture and low thermal stability. For this reason, diaphragm companies apply ceramic coating on the surface of the diaphragm or water-based coating on the surface of the ceramic film. The polymer strengthens the separator, but it does not improve the adhesion between the separator and the pole piece, and the ability of the separator to absorb the electrolyte, so that the safety performance of the battery cannot be well guaranteed.
  • the line a in FIG. 2 represents the tendency of the capacity retention rate of the soft-battery battery corresponding to Example 1 as the number of cycles is accumulated, and the line b represents the change in the capacity retention rate of the soft-battery battery corresponding to Comparative Example 2 as the number of cycles is accumulated.
  • the capacity retention rate of Example 1 is stable. This is because the polymer resin used in the present disclosure has a lower specific gravity than the ceramic particles used in Comparative Example 2, which is beneficial for improving the lithium ion battery's performance. Energy density, and compared with traditional ceramic slurry, the hardness of polymer resin is smaller than that of alumina, and the loss of equipment in the production process is small.
  • the composite lithium battery separator of the present disclosure has high ionic conductivity, good liquid absorption / retention capacity, strong peel resistance, and high adhesion to positive and negative electrode sheets.
  • the method for preparing the composite lithium battery separator is suitable for large-scale production , Thereby improving its practicability and economy.

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Abstract

本公开是一种复合锂电池隔膜及其制备工艺，属于锂离子电池技术领域，复合锂电池隔膜包括基膜或者陶瓷膜，以及覆盖于基膜或者陶瓷膜的单侧或双侧的涂覆层，涂覆层是采用浆料涂布形成，浆料按照重量百分比计包括涂层聚合物5％-45％和有机溶剂55％-95％，涂层聚合物按照重量份数计包括氟类或丙烯酸类的树脂聚合物10-100份、高分子胶粘剂0.5-10份、无机纳米粒子0-90份。本公开的复合锂电池隔膜引入高涂层孔隙率和具有锂离子传导能力的无机粒子，极大提高了隔膜的离子传导率和对电解液的吸/保液率，同时本公开的隔膜表面静电少，易于电池组装，隔膜的抗剥离能力和与正负极片的粘结力高，电池硬度得到提高，极大降低电池内部短路的风险。

Description

一种复合锂电池隔膜及其制备方法 技术领域
本公开涉及锂离子电池领域，具体而言，涉及一种复合锂电池隔膜及其制备方法。
背景技术
近年来，随着3C市场和电动汽车市场的蓬勃发展，市场对锂离子电池的需求量越来越大，对锂离子电池也提出了一些新的要求。隔膜作为锂离子电池的重要组成部件之一，在正极材料与负极材料之间起电子绝缘的作用，保证正负极的机械隔离。隔膜有一定的孔径与孔隙率，保证低电阻和高离子电导率，对锂离子的透过性好。隔膜的特性和品质严重影响着电池的安全性能、倍率性能、循环寿命和基本电性能的发挥。如在传统的消费电子产品上，为了追求高的电池能量密度，需要在狭小的体积中容纳更多的电极材料，因此隔膜的厚度越来越薄；电动汽车续航里程的提升，也会对电池能量密度的要求越来越高，导致隔膜的厚度越来越薄。
但是锂离子电池在隔膜越来越薄的趋势下，此同时也带来了一些性能方面的问题：隔膜静电太大，导致在组装电池中与极片贴合不好或在高温条件下隔膜发生了熔缩，从而导致电池正负极接触产生电池内部短路；薄电芯的硬度、机械性能较差，导致锂电池产品的性能下降。另外，从锂电池结构上看，由于液态电池中隔膜吸液能力差，液体有可能泄漏。
因此，如何提高隔膜吸液能力、减少电池短路成为目前锂电池急需解决的问题。
公开内容
为克服上述缺点中的至少一个，本公开提供了一种复合锂电池隔膜，其离子电导率高，吸/保液能力好，抗剥离力强，且与正负极片粘结力高。
本公开还提供了一种复合锂电池隔膜的制备方法，适合大规模生产。
本公开的目的中的至少一个目的可以通过以下技术措施实现。
一种复合锂电池隔膜，其包括基膜或者陶瓷膜，以及覆盖于基膜或者陶瓷膜的单侧或双侧的涂覆层，涂覆层是采用浆料涂布形成，浆料按照重量百分比计包括涂层聚合物5％-45％和有机溶剂55％-95％，涂层聚合物按照重量份数计包括氟类或丙烯酸类的树脂聚合物10-100份、高分子胶粘剂0.5-10份和无机纳米粒子0-90份。
作为一种优选方式，基膜厚度为5-30μm，优选为10-20μm；孔隙率为30％-60％，优选为40％-50％；涂覆层的厚度为0.5-10μm，优选为3-8μm。
作为一种优选方式，基膜选自聚乙烯基膜、聚丙烯基膜、聚丙烯/聚乙烯/聚丙烯复合基膜、聚酰亚胺基膜、聚偏氟乙烯基膜、聚乙烯无纺布基膜、聚丙烯无纺布基膜和聚酰亚胺无纺布基膜组成的组合中的一种。
作为一种优选方式，有机溶剂包含选自由丙酮、二甲基乙酰胺、二甲基甲酰胺、氯仿、二氯甲烷、二氯乙烷、二甲基亚砜和N-甲基吡咯烷酮组成的组合中的至少一种。
作为一种优选方式，氟类或丙烯酸类的树脂聚合物包含选自由聚偏氟乙烯、聚偏氟乙烯和六氟丙烯共聚物、聚偏氟乙烯和二氯乙烯共聚物、聚苯乙烯、聚丙烯酸正丁酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚丙烯酸叔丁酯、聚醋酸乙烯酯、聚丙烯腈、聚乙酸乙烯酯、丙烯酰胺和聚丙烯酸甲酯组成的组合中的至少一种；氟类或丙烯酸类的树脂聚合物的分子量为50000-500000，优选为200000-300000。
作为一种优选方式，高分子胶粘剂包含选自丁苯乳胶、苯丙乳胶、聚醋酸乙烯酯、聚乙烯醇、聚丙烯酸乙酯、聚甲基丙烯酸丁酯、乙烯-醋酸乙烯共聚物和聚氨酯组成的组合中的至少一种。
作为一种优选方式，无机纳米粒子主要为是由常规无机粒子与具有锂离子传导能力的无机粒子的混合物，常规无机粒子与具有锂离子传导能力的无机粒子的重量比为80-95：20-5。
作为一种优选方式，常规无机粒子包含选自三氧化二铝、二氧化硅、钛酸钡、氧化镁、勃姆石、氧化钛、碳酸钙和二氧化锆组成的组合中的至少一种。
作为一种优选方式，常规无机粒子的粒径范围为0.01-10um；常规无机粒子是由低粒径无机粒子和高粒径无机粒子按重量比80-90：20-10组成，低粒径无机粒子的粒径范围为0.01-0.2um，高粒径无机粒子的粒径范围为0.2-10um。
作为一种优选方式，具有锂离子传导能力的无机粒子包含选自磷酸锂、锂钛磷酸盐、锂铝钛磷酸盐、锂氮化合物和锂镧钛酸盐组成的组合中的至少一种。
作为一种优选方式，涂层聚合物按照重量份数计还包括分散剂0.5-10份，分散剂包含选自羧酸盐类氟分散剂、磷酸三乙酯、磺酸盐类氟分散剂、聚丙烯酸钠、聚丙烯酸钾和聚乙二醇组成的组合中的至少一种。
作为一种优选方式，涂层聚合物按照重量份数计还包括润湿剂0.1-8份，润湿剂包含选自聚碳酸酯、十二烷基硫酸钠、十二烷基苯磺酸钠、聚丙烯酸钠、聚乙烯醇、氟代烷基甲氧基醚醇、氟代烷基乙氧基醚醇、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚和聚氧乙烯烷基酰胺组成的组合中的至少一种。
作为一种优选方式，涂层聚合物按照重量份数计还包括成孔剂0.1-10份，成孔剂为去离子水。
作为一种优选方式，涂层聚合物按照重量份数计还包括抗静电剂0.1-5份，抗静电剂包含选自十八烷基二甲基季铵硝酸盐、三甲基十八烷基乙酸铵、N-十六烷基吡啶硝酸盐、N-烷基氨基酸盐、甜菜碱型和咪唑啉盐类衍生物组成的组合中的至少一种。
一种上述的复合锂电池隔膜的制备方法，包括下述步骤：
S1、把称量好的氟类或丙烯酸类的树脂聚合物、无机纳米粒子搅拌均匀；
S2、按固含量变化梯度加入有机溶剂，并搅拌均匀；
S3、加入高分子胶粘剂，搅拌均匀后，过滤得到浆料；
S4、将浆料涂布于基膜或陶瓷膜的单侧或两侧，经凝固、水洗、烘干、定型，即得复合锂电池隔膜。
作为一种优选方式，步骤S1中的搅拌速度为40-80R，搅拌时间为15-40min；步骤S3中的搅拌速度为20-60R，分散速度为300-800R，搅拌时间为15-30min，浆料粘度为50-1000cp。
作为一种优选方式，步骤S2中，先按照重量份数计加入分散剂0.5-10份并搅拌，搅拌速度为40-90R，搅拌时间为10-20min，再加入有机溶剂。
作为一种优选方式，有机溶剂的加入方法是：先按照有机溶剂总量的4％-5％逐步加入，待粉体刚好捏合凝聚成团则停止加入，粉体捏合后的搅拌速度为80-120R，搅拌时间为30-90min，再按照固含量变化梯度加入有机溶剂，使浆料固含量从高降低，直至符合规定固含量。
作为一种优选方式，固含量高于规定固含量时，搅拌速度为40-100R，分散速度为2000-4000R，搅拌时间为15-45min；固含量符合规定固含量时，搅拌速度为40-80R，分散速度为3000-4500R，搅拌时间为30-90min。
作为一种优选方式，步骤S4中，涂布方法包括浸涂法、微凹版涂法、喷涂法、坡流涂法或条缝涂法中的一种，烘干温度为40-80℃。
与现有的技术相比，本公开的优点和有益效果至少包括：
1、本公开的复合锂电池隔膜既有存在于基膜或者陶瓷膜上的孔结构，又有油涂在基膜或者陶瓷膜上由无机纳米粒子和粘合剂所形成的涂覆层中的多孔结构，因此复合锂电池隔膜具有高涂层孔隙率，能增加液体电解液渗入的空间体积，极大地提高了锂离子传导率和隔膜的吸保液率，形成凝胶态的电解质，减少了电池的漏液风险；抗剥离力强，且与正负极片粘结力高。
2、按照本公开的制备方法制备的浆料稳定性高，密封放置60days以上还能正常使用，未出现明显分层、沉淀，有利于复合锂电池隔膜中涂覆层的连续、大规模生产，因此本公开的制备方法适合大规模生产。
3、本公开的无机纳米粒子中的具有锂离子传导能力的无机粒子与常规无机粒子能产生协同作用，能提高锂离子传导率，改进电池性能。
4、本公开同时使用高粒径无机粒子和低粒径无机粒子，会使涂覆层中的无机粒子形成较为密集的堆积形态，提高了涂覆层的耐高温性，降低了隔膜的热收缩性。
附图说明
为了更清楚地说明本公开具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本公开的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本公开实施例1的复合锂电池隔膜的电镜图片；
图2是本公开实施例1和对比例2制备的软包电池做循环测试的数据图。
具体实施方式
下面将结合附图和具体实施方式对本公开的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本公开一部分实施例，而不是全部的实施例，仅用于说明本公开，而不应视为限制本公开的范围。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本公开提供一种复合锂电池隔膜，其包括基膜或者陶瓷膜，以及覆盖于基膜或者陶瓷膜的单侧或双侧的涂覆层，涂覆层是采用浆料涂布形成，浆料按照重量百分比计包括涂层聚合物5％-45％和有机溶剂55％-95％，涂层聚合物按照重量份数计包括氟类或丙烯酸类的树脂聚合物10-100份、高分子胶粘剂0.5-10份和无机纳米粒子0-90份。可选地，基膜厚度为5-30μm，优选为10-20μm；孔隙率为30％-60％，优选为40％-50％；涂覆层的厚度为0.5-10μm，优选为3-8μm。
其中，氟类或丙烯酸类的树脂聚合物作为第一粘合剂，高分子胶粘剂作为第二粘合剂，这些油性的聚合物和无机纳米粒子复合形成涂覆层。因此，本公开的复合锂电池隔膜既有存在于基膜或者陶瓷膜上的孔结构，又有油涂在基膜或者陶瓷膜上由无机纳米粒子和粘合剂所形成的涂覆层中的多孔结构，因此复合锂电池隔膜具有高涂层孔隙率，能增加液体电解液渗入的空间体积，极大地提高了锂离子传导率和隔膜的吸保液率，形成凝胶态的电解质，减少了电池的漏液风险。而且第一粘合剂和第二粘合剂分子链上的极性官能团与电极 材料的之间的范德华力会让隔膜与极片很好地粘结在一起，降低电池短路的发生几率，提高电池的硬度和形体保持能力。
本公开的复合锂电池隔膜中的基膜具体可选自聚乙烯基膜、聚丙烯基膜、聚丙烯/聚乙烯/聚丙烯复合基膜、聚酰亚胺基膜、聚偏氟乙烯基膜、聚乙烯无纺布基膜、聚丙烯无纺布基膜和聚酰亚胺无纺布基膜组成的组合中的一种。
本公开的复合锂电池隔膜采用的有机溶剂具体可包含选自由丙酮、二甲基乙酰胺(DMAC)、二甲基甲酰胺(DMF)、氯仿、二氯甲烷、二氯乙烷、二甲基亚砜和N-甲基吡咯烷酮(NMP)组成的组合中的至少一种。
本公开的复合锂电池隔膜采用的氟类或丙烯酸类的树脂聚合物具体可包含选自由聚偏氟乙烯、聚偏氟乙烯和六氟丙烯共聚物、聚偏氟乙烯和二氯乙烯共聚物、聚苯乙烯、聚丙烯酸正丁酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚丙烯酸叔丁酯、聚醋酸乙烯酯、聚丙烯腈、聚乙酸乙烯酯、丙烯酰胺和聚丙烯酸甲酯组成的组合中的至少一种；氟类或丙烯酸类的树脂聚合物的分子量为50000-500000，优选为200000-300000。
本公开的复合锂电池隔膜采用的高分子胶粘剂具体可包含选自丁苯乳胶、苯丙乳胶、聚醋酸乙烯酯(PVAC)、聚乙烯醇(PVA)、聚丙烯酸乙酯(PEA)、聚甲基丙烯酸丁酯(PBMA)、乙烯-醋酸乙烯共聚物(EVA)和聚氨酯(PU)组成的组合中的至少一种。
本公开的复合锂电池隔膜采用的无机纳米粒子具体主要为是由常规无机粒子与具有锂离子传导能力的无机粒子的混合物，常规无机粒子与具有锂离子传导能力的无机粒子的重量比为80-95：20-5。无机纳米粒子中的具有锂离子传导能力的无机粒子与常规无机粒子(具有压电性)能产生协同作用，能提高锂离子传导率，改进电池性能。
可选的，常规无机粒子包含选自三氧化二铝、二氧化硅、钛酸钡、氧化镁、勃姆石、氧化钛、碳酸钙和二氧化锆组成的组合中的至少一种。常规无机粒子的粒径范围为0.01-10um；常规无机粒子是由低粒径无机粒子和高粒径无机粒子按重量比80-90：20-10组成，低粒径无机粒子的粒径范围为0.01-0.2um，高粒径无机粒子的粒径范围为0.2-10um。本公开同时使用高粒径无机粒子和低粒径无机粒子，会使涂覆层中的无机粒子形成较为密集的堆积形态，提高了涂覆层的耐高温性，降低了隔膜的热收缩性。
可选的，具有锂离子传导能力的无机粒子包含选自磷酸锂、锂钛磷酸盐、锂铝钛磷酸盐、锂氮化合物和锂镧钛酸盐组成的组合中的至少一种。
在上述技术方案的基础上，本公开中的涂层聚合物按照重量份数计还可以包括分散剂0.5-10份，分散剂包含选自羧酸盐类氟分散剂、磷酸三乙酯(TEP)、磺酸盐类氟分散剂、聚丙烯酸钠(PAA-Na)、聚丙烯酸钾(PAA-K)和聚乙二醇组成的组合中的至少一种。
在上述技术方案的基础上，本公开中的涂层聚合物按照重量份数计还可以包括润湿剂0.1-8份，润湿剂包含选自聚碳酸酯、十二烷基硫酸钠、十二烷基苯磺酸钠、聚丙烯酸钠、聚乙烯醇、氟代烷基甲氧基醚醇、氟代烷基乙氧基醚醇、烷基酚聚氧乙烯醚(APEO)、脂肪醇聚氧乙烯醚(AEO)、脂肪酸聚氧乙烯醚(FMEE)和聚氧乙烯烷基酰胺组成的组合中的至少一种。
在上述技术方案的基础上，本公开中的涂层聚合物按照重量份数计还可以包括成孔剂0.1-10份，成孔剂为去离子水。本公开的复合锂电池隔膜既有存在于基膜或陶瓷膜上的孔结构，又有涂覆层中的多孔结构，同时成孔剂能够使涂覆层的成孔数量大大提升，从而进一步提升复合锂电池隔膜的性能。成孔剂优选为去离子水，价格低廉，且形成的涂覆层在凝固、水洗过程中不会在凝固槽和水洗槽中释放过多的杂质，降低了凝固槽和水洗槽的废水回收难度。
在上述技术方案的基础上，本公开中的涂层聚合物按照重量份数计还可以包括抗静电剂0.1-5份，抗静电剂包含选自十八烷基二甲基季铵硝酸盐(SN)、三甲基十八烷基乙酸铵、N-十六烷基吡啶硝酸盐、N-烷基氨基酸盐、甜菜碱型和咪唑啉盐类衍生物组成的组合中的至少一种。本公开使用抗静电剂，形成的隔膜表面静电少，降低了隔膜与极片在组装过程中贴合不平整的问题，易于电池组装；隔膜的抗剥离能力和与正负极片的粘结力高，电池硬度得到提高，极大降低电池内部短路的风险。
本公开还提供一种上述的复合锂电池隔膜的制备方法，包括下述步骤：
S1、把称量好的氟类或丙烯酸类的树脂聚合物、无机纳米粒子(具体包括高粒径无机粒子、低粒径无机粒子和具有锂离子传导能力的无机粒子)搅拌均匀，可选的，将上述原料放在小容量搅拌罐中搅拌均匀，搅拌速度为40-80R，搅拌时间为15-40min。
S2、按固含量变化梯度加入有机溶剂，并搅拌均匀。
可选的，先往小容量搅拌罐中加入分散剂、搅拌，并逐渐加入有机溶剂，加入分散剂的搅拌速度为40-90R，搅拌时间为10-20min；先按照有机溶剂总量的4％-5％逐步加入，待粉体刚好捏合凝聚成团则停止加入，粉体捏合后的搅拌速度为80-120R，搅拌时间为30-90min，把小容量搅拌罐中的浆料转移到大容量搅拌罐中；
再往大容量搅拌罐中按固含量变化梯度加入有机溶剂，使浆料固含量从高降低，直至符合规定固含量(高→中→符合的固含量)，并搅拌均匀。在此过程中，当固含量高于规定固含量时，搅拌速度为40-100R，分散速度为2000-4000R，搅拌时间为15-45min；固含量符合规定固含量时，搅拌速度为40-80R，分散速度为3000-4500R，搅拌时间为30-90min。
S3、加入高分子胶粘剂，搅拌均匀后，过滤得到浆料，可选的，往大容量搅拌罐中加 入高分子胶粘剂、润湿剂、成孔剂和抗静电剂搅拌均匀，搅拌速度为20-60R，分散速度为300-800R，搅拌时间为15-30min，浆料粘度为50-1000cp；可选的，用200目尼龙筛网进行过滤。按照上述方法制备的浆料稳定性高，密封放置60days以上还能正常使用，未出现明显分层、沉淀，有利于复合锂电池隔膜中涂覆层的连续、大规模生产。
S4、将浆料涂布于基膜或陶瓷膜的单侧或两侧，经凝固、水洗、烘干、定型，即得复合锂电池隔膜。涂布方法包括浸涂法、微凹版涂法、喷涂法、坡流涂法或条缝涂法中的一种，烘干温度为40-80℃。
下面结合具体实施例和对比例对上述方案作进一步说明。
实施例1
本实施例提供一种复合锂电池隔膜，按照下述步骤制备而成：
①把3kg聚偏氟乙烯和六氟丙烯共聚物、2.42kg高粒径三氧化二铝粉体、430g低粒径三氧化二铝粉体和150g锂钛磷酸盐放在小容量搅拌罐中以70R转速搅拌25min。
②往小容量搅拌罐中加入120g聚乙二醇，并逐渐加入NMP 1.5kg，搅拌粉体捏合凝聚成团，并在此状态下以110R转速持续搅拌50min；待搅拌好后把小容量搅拌罐中的浆料往大容量搅拌罐中转移。
③往大容量搅拌罐中加入NMP 3kg，使浆料固含量为58％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入10kg，使浆料固含量为30％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入11.15kg，使浆料固含量为19.3％，并以80R搅拌速度和3500R分散速度搅拌50min。
④往大容量搅拌罐中分别加入180g聚乙烯醇、60g十二烷基硫酸钠、30g去离子水和60g十八烷基二甲基季铵硝酸盐，以30R搅拌速度和600R分散速度搅拌浆料30min，待浆料搅拌均匀后，用200目尼龙筛网进行过滤，即可得到固含量为20％、粘度为210cp的浆料。
⑤采用微凹版涂法将浆料涂布于厚度为16μm、孔隙率为47％的聚丙烯基膜的双侧，经凝固、水洗、烘干、定型后制得复合锂电池隔膜，复合锂电池隔膜的厚度为23μm，各侧面涂覆层的厚度为3.5μm。
实施例2
本实施例提供一种复合锂电池隔膜，按照下述步骤制备而成：
①把3kg聚偏氟乙烯和二氯乙烯共聚物、2.42kg高粒径勃姆石粉体、430g低粒径勃姆石和150g磷酸锂放在小容量搅拌罐中以70R转速搅拌25min。
②按照实施例1的②-④，可得到固含量为20％、粘度为230cp的浆料。
③采用微凹版涂法将浆料涂布于厚度为12μm、孔隙率为42％的聚丙烯基膜的双侧，经凝固、水洗、烘干、定型后制得复合锂电池隔膜，复合锂电池隔膜的厚度为18μm，各侧面涂覆层的厚度为3μm。
实施例3
本实施例提供一种复合锂电池隔膜，按照下述步骤制备而成：
①把3kg第一粘合剂(聚甲基丙烯酸甲酯：聚偏氟乙烯＝20:80)、3.6kg高粒径勃姆石粉体、700g低粒径勃姆石粉体和200g锂铝钛磷酸盐放在小容量搅拌罐中以60R转速搅拌30min。
②往小容量搅拌罐中加入172.5g聚丙烯酸钠，并逐渐加入丙酮2kg，搅拌粉体捏合凝聚成团，并在此状态下以110R转速持续搅拌50min；待搅拌好后把小容量搅拌罐中的浆料往大容量搅拌罐中转移。
③往大容量搅拌罐中加入丙酮4kg，使浆料固含量为52％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入10kg，使浆料固含量为32％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入7.9kg，使浆料固含量为24.3％，并以80R搅拌速度和3500R分散速度搅拌50min。
④往大容量搅拌罐中分别加入180g苯丙乳胶、60g十二烷基苯磺酸钠、30g去离子水和60g三甲基十八烷基乙酸铵，以30R搅拌速度和600R分散速度搅拌浆料30min，待浆料搅拌均匀后，用200目尼龙筛网进行过滤，即可得到固含量为25％、粘度为160cp的浆料。
⑤采用喷涂法将高粘结性浆料涂布于厚度为12μm、孔隙率为40％的聚乙烯基膜的双侧，经凝固、水洗、烘干、定型后制得复合锂电池隔膜，复合锂电池隔膜的厚度为16μm，各侧面涂覆层的厚度为2μm。
实施例4
本实施例提供一种复合锂电池隔膜，按照下述步骤制备而成：
①把3.5kg第一粘合剂(聚偏氟乙烯和六氟丙烯共聚物：聚甲基丙烯酸甲酯＝90:10)、4.4kg高粒径二氧化钛粉体、800g低粒径二氧化钛粉体和300g锂氮化合物放在小容量搅拌罐中以50R转速搅拌30min。
②往小容量搅拌罐中加入180g磷酸三乙酯，并逐渐加入DMAC 2.5kg，搅拌粉体捏合凝聚成团，并在此状态下以110R转速持续搅拌50min；待搅拌好后把小容量搅拌罐中的浆料往大容量搅拌罐中转移。
③往大容量搅拌罐中加入DMAC 5kg，使浆料固含量为55％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入8kg，使浆料固含量为37％，并以75R搅拌速度和3000R分 散速度搅拌20min；继续加入6.9kg，使浆料固含量为29.1％，并以80R搅拌速度和3500R分散速度搅拌50min。
④往大容量搅拌罐中分别加入270g聚甲基丙烯酸丁酯、60g聚碳酸酯、45g去离子水和90g N-十六烷基吡啶硝酸盐，以30R搅拌速度和600R分散速度搅拌浆料30min，待浆料搅拌均匀后，用200目尼龙筛网进行过滤，即可得到固含量为30％、粘度为400cp的浆料。
⑤采用浸涂法将高粘结性浆料涂布于厚度为16μm、孔隙率为45％的PP/PE/PP复合基膜的双侧，经凝固、水洗、烘干、定型后制得复合锂电池隔膜，复合锂电池隔膜的厚度为20μm，各侧面涂覆层的厚度为2μm。
实施例5
本实施例提供一种复合锂电池隔膜，按照下述步骤制备而成：
①把4.8kg聚偏氟乙烯和六氟丙烯共聚物、969g高粒径三氧化二铝粉体、171g低粒径三氧化二铝粉体和60g锂镧钛酸盐放在小容量搅拌罐中以70R转速搅拌30min。
②往小容量搅拌罐中加入120g磺酸盐类氟分散剂，并逐渐加入NMP 1.5kg，搅拌粉体捏合凝聚成团，并在此状态下以110R转速持续搅拌50min；待搅拌好后把小容量搅拌罐中的浆料往大容量搅拌罐中转移。
③往大容量搅拌罐中加入NMP 3kg，使浆料固含量为58％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入15kg，使浆料固含量为24％，并以75R搅拌速度和3000R分散速度搅拌20min；继续加入17kg，使浆料固含量为14.4％，并以80R搅拌速度和3500R分散速度搅拌50min。
④往大容量搅拌罐中分别加入180g乙烯-醋酸乙烯共聚物、80g氟代烷基甲氧基醚醇、30g去离子水和60g N-烷基氨基酸盐，以30R搅拌速度和600R分散速度搅拌浆料30min，待浆料搅拌均匀后，用200目尼龙筛网进行过滤，即可得到固含量为15％、粘度为280cp的浆料。
⑤采用微凹版涂法将浆料涂布于厚度为16μm的单面陶瓷膜的双侧，经凝固、水洗、烘干、定型后制得复合锂电池隔膜，复合锂电池隔膜的厚度为18μm，各侧面涂覆层的厚度为1μm。
对比例1
本对比例提供一种锂电池隔膜，其是厚度为16μm，孔隙率为47％的聚丙烯基膜，并且不进行任何涂层处理。
对比例2
本对比例提供了一种传统陶瓷浆料涂布的锂离子电池隔膜，隔膜厚度为22μm，其中基 膜是厚度为16μm、孔隙率为47％的聚丙烯基膜；采用传统陶瓷浆料在双侧涂布形成涂层，各侧面涂层厚度为3μm。
以下通过试验对实施例和对比例的产品进行检测。
一、对实施例1的复合锂电池隔膜进行电镜扫描，图1为电镜图片。
由图1可以看出，该复合锂电池隔膜呈多孔结构，且孔隙率非常高，因此，按照本公开的制备方法制得的复合锂电池隔膜的离子电导率高，吸/保液能力好。
二、对实施例1-5的复合锂电池隔膜和对比例1的锂电池隔膜、对比例2的锂离子电池隔膜的涂层孔隙率、热收缩数据、涂层与极片之间的界面粘结力和电芯的抗弯曲强度进行检测，其中界面粘结力的测试条件：温度90℃，压力8Mpa，时长1min，极片为钴酸锂极片，各检测数据结果如下表1所示。
表1产品的检测数据结果
Figure PCTCN2018092725-appb-000001
由上表可以看出，按照本公开的制备方法制得的复合锂电池隔膜的热收缩性能好，与极片的粘结力高，电芯抗弯强度大，明显优于对比例中未涂布涂层的隔膜和涂布陶瓷浆料的隔膜。
对比例1和对比例2为聚烯烃隔膜和陶瓷隔膜，聚烯烃隔膜在常温下可以提供足够的机械强度和化学稳定性，但在高温条件下则可能会表现出较大的热收缩，使正、负极接触并迅速积聚大量的热，导致电池内部产生高气压，从而引起电池燃烧或爆炸。随着隔膜降厚趋势的发展，而较小的膜厚会面临着相对高的穿刺风险和较低的热稳定性，为此隔膜企业在隔膜表面进行陶涂布或者在陶瓷膜表面涂布水性聚合物来强化隔膜，但并不能很好地改善隔膜与极片的粘合能力、隔膜对电解液的吸液能力，以致电池的安全性能不能得到很好地保障。
三、对实施例1的复合锂电池隔膜、对比例2的锂离子电池隔膜在相同工艺及条件下制备软包电池，并在1C的倍率充放电下做循环测试，图2为循环测试的数据图。
图2中a线表示实施例1对应的软包电池的容量保持率随循环次数累积的变化趋势，b线表示对比例2对应的软包电池的容量保持率随循环次数累积的变化趋势，由图2可以看出：与对比例2相比，实施例1的容量保持率稳定，这是因为本公开使用的聚合物树脂比重比对比例2使用的陶瓷颗粒低，有利于提高锂离子电池的能量密度，而且与传统陶瓷浆料相比，聚合物树脂的硬度比氧化铝的小，在生产过程中对设备的损耗小。
尽管已用具体实施例来说明和描述了本公开，然而应意识到，以上各实施例仅用以说明本公开的技术方案，而非对其限制；本领域的普通技术人员应当理解：在不背离本公开的精神和范围的情况下，可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围；因此，这意味着在所附权利要求中包括属于本公开范围内的所有这些替换和修改。
工业实用性
本公开的复合锂电池隔膜的离子电导率高，吸/保液能力好，抗剥离力强，且与正负极片粘结力高，本公开的复合锂电池隔膜的制备方法适合大规模生产，进而提高了其实用性和经济性。

Claims (20)

  1. 一种复合锂电池隔膜，其特征在于：其包括基膜或者陶瓷膜，以及覆盖于所述基膜或者所述陶瓷膜的单侧或双侧的涂覆层，所述涂覆层是采用浆料涂布形成，所述浆料按照重量百分比计包括涂层聚合物5％-45％和有机溶剂55％-95％，所述涂层聚合物按照重量份数计包括氟类或丙烯酸类的树脂聚合物10-100份、高分子胶粘剂0.5-10份和无机纳米粒子0-90份。
  2. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述基膜厚度为5-30μm，优选为10-20μm；孔隙率为30％-60％，优选为40％-50％；所述涂覆层的厚度为0.5-10μm，优选为3-8μm。
  3. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述基膜选自聚乙烯基膜、聚丙烯基膜、聚丙烯/聚乙烯/聚丙烯复合基膜、聚酰亚胺基膜、聚偏氟乙烯基膜、聚乙烯无纺布基膜、聚丙烯无纺布基膜和聚酰亚胺无纺布基膜组成的组合中的一种。
  4. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述有机溶剂包含选自由丙酮、二甲基乙酰胺、二甲基甲酰胺、氯仿、二氯甲烷、二氯乙烷、二甲基亚砜和N-甲基吡咯烷酮组成的组合中的至少一种。
  5. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述氟类或丙烯酸类的树脂聚合物包含选自由聚偏氟乙烯、聚偏氟乙烯和六氟丙烯共聚物、聚偏氟乙烯和二氯乙烯共聚物、聚苯乙烯、聚丙烯酸正丁酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚丙烯酸叔丁酯、聚醋酸乙烯酯、聚丙烯腈、聚乙酸乙烯酯、丙烯酰胺和聚丙烯酸甲酯组成的组合中的至少一种；所述氟类或丙烯酸类的树脂聚合物的分子量为50000-500000，优选为200000-300000。
  6. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述高分子胶粘剂包含选自丁苯乳胶、苯丙乳胶、聚醋酸乙烯酯、聚乙烯醇、聚丙烯酸乙酯、聚甲基丙烯酸丁酯、乙烯-醋酸乙烯共聚物和聚氨酯组成的组合中的至少一种。
  7. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述无机纳米粒子主要为是由常规无机粒子与具有锂离子传导能力的无机粒子的混合物，所述常规无机粒子与所述具有锂离子传导能力的无机粒子的重量比为80-95：20-5。
  8. 根据权利要求7所述的复合锂电池隔膜，其特征在于：所述常规无机粒子包含选自三氧化二铝、二氧化硅、钛酸钡、氧化镁、勃姆石、氧化钛、碳酸钙和二氧化锆组成的组合中的至少一种。
  9. 根据权利要求7或8所述的复合锂电池隔膜，其特征在于：所述常规无机粒子 的粒径范围为0.01-10um；所述常规无机粒子是由低粒径无机粒子和高粒径无机粒子按重量比80-90：20-10组成，所述低粒径无机粒子的粒径范围为0.01-0.2um，所述高粒径无机粒子的粒径范围为0.2-10um。
  10. 根据权利要求7所述的复合锂电池隔膜，其特征在于：所述具有锂离子传导能力的无机粒子包含选自磷酸锂、锂钛磷酸盐、锂铝钛磷酸盐、锂氮化合物和锂镧钛酸盐组成的组合中的至少一种。
  11. 根据权利要求1所述的复合锂电池隔膜，其特征在于：所述涂层聚合物按照重量份数计还包括分散剂0.5-10份，所述分散剂包含选自羧酸盐类氟分散剂、磷酸三乙酯、磺酸盐类氟分散剂、聚丙烯酸钠、聚丙烯酸钾和聚乙二醇组成的组合中的至少一种。
  12. 根据权利要求1至11中任一项所述的复合锂电池隔膜，其特征在于：所述涂层聚合物按照重量份数计还包括润湿剂0.1-8份，所述润湿剂包含选自聚碳酸酯、十二烷基硫酸钠、十二烷基苯磺酸钠、聚丙烯酸钠、聚乙烯醇、氟代烷基甲氧基醚醇、氟代烷基乙氧基醚醇、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚和聚氧乙烯烷基酰胺组成的组合中的至少一种。
  13. 根据权利要求1至12中任一项所述的复合锂电池隔膜，其特征在于：所述涂层聚合物按照重量份数计还包括成孔剂0.1-10份，所述成孔剂为去离子水。
  14. 根据权利要求1至13中任一项所述的复合锂电池隔膜，其特征在于：所述涂层聚合物按照重量份数计还包括抗静电剂0.1-5份，所述抗静电剂包含选自十八烷基二甲基季铵硝酸盐、三甲基十八烷基乙酸铵、N-十六烷基吡啶硝酸盐、N-烷基氨基酸盐、甜菜碱型和咪唑啉盐类衍生物组成的组合中的至少一种。
  15. 一种如权利要求1-14中任一项所述的复合锂电池隔膜的制备方法，其特征在于，包括下述步骤：
    S1、把称量好的氟类或丙烯酸类的树脂聚合物、无机纳米粒子搅拌均匀；
    S2、按固含量变化梯度加入有机溶剂，并搅拌均匀；
    S3、加入高分子胶粘剂，搅拌均匀后，过滤得到浆料；
    S4、将所述浆料涂布于基膜或陶瓷膜的单侧或两侧，经凝固、水洗、烘干、定型，即得复合锂电池隔膜。
  16. 根据权利要求15所述的复合锂电池隔膜的制备方法，其特征在于：所述步骤S1中的搅拌速度为40-80R，搅拌时间为15-40min；所述步骤S3中的搅拌速度为20-60R，分散速度为300-800R，搅拌时间为15-30min，浆料粘度为50-1000cp。
  17. 根据权利要求15所述的复合锂电池隔膜的制备方法，其特征在于：所述步骤 S2中，先按照重量份数计加入分散剂0.5-10份并搅拌，搅拌速度为40-90R，搅拌时间为10-20min，再加入有机溶剂。
  18. 根据权利要求15或17所述的复合锂电池隔膜的制备方法，其特征在于：有机溶剂的加入方法是：先按照有机溶剂总量的4％-5％逐步加入，待粉体刚好捏合凝聚成团则停止加入，粉体捏合后的搅拌速度为80-120R，搅拌时间为30-90min，再按照固含量变化梯度加入有机溶剂，使浆料固含量从高降低，直至符合预定固含量。
  19. 根据权利要求18所述的复合锂电池隔膜的制备方法，其特征在于：固含量高于规定固含量时，搅拌速度为40-100R，分散速度为2000-4000R，搅拌时间为15-45min；固含量符合规定固含量时，搅拌速度为40-80R，分散速度为3000-4500R，搅拌时间为30-90min。
  20. 根据权利要求15所述的制备方法，其特征在于：所述步骤S4中，涂布方法包括浸涂法、微凹版涂法、喷涂法、坡流涂法或条缝涂法中的一种，烘干温度为40-80℃。
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WO2023179550A1 (zh) * 2022-03-21 2023-09-28 惠州锂威电子科技有限公司 一种复合油基隔膜及其制备方法和二次电池
CN115312963A (zh) * 2022-08-19 2022-11-08 和人新材料科技(苏州)有限公司 一种电池隔膜及其制备方法及电池
CN116259925A (zh) * 2023-02-20 2023-06-13 上海兰钧新能源科技有限公司 一种锂电池隔离膜及其制备方法
CN118017155A (zh) * 2024-04-02 2024-05-10 沧州明珠隔膜科技有限公司 一种高安全性隔膜及其制备方法和应用
CN118017155B (zh) * 2024-04-02 2024-07-30 沧州明珠隔膜科技有限公司 一种高安全性隔膜及其制备方法和应用

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