WO2018145666A1 - 耐高温多种涂层的锂离子电池隔膜及其制备方法 - Google Patents

耐高温多种涂层的锂离子电池隔膜及其制备方法 Download PDF

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WO2018145666A1
WO2018145666A1 PCT/CN2018/076683 CN2018076683W WO2018145666A1 WO 2018145666 A1 WO2018145666 A1 WO 2018145666A1 CN 2018076683 W CN2018076683 W CN 2018076683W WO 2018145666 A1 WO2018145666 A1 WO 2018145666A1
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coating
slurry
battery separator
lithium ion
ion battery
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PCT/CN2018/076683
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English (en)
French (fr)
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徐锋
袁海朝
邓云飞
马文献
田海龙
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河北金力新能源科技股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • 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 invention belongs to the technical field of battery separators, and relates to a composite lithium ion battery separator, in particular to a lithium ion battery separator with high temperature resistant multiple coatings and a preparation method thereof.
  • Lithium battery has the advantages of high specific energy, small volume, light weight, less self-discharge, long cycle life, no pollution, etc. It has been widely used, and the market extends to mobile phones, laptops, digital cameras, power tools, Electric bicycles, electric motorcycles, electric vehicles, energy storage, aerospace, military vehicles, weapons, and many other fields are important components of the new energy industry.
  • the lithium ion battery is composed of a positive and negative electrode material, an electrolyte, a separator, and a battery case.
  • the diaphragm acts as the "third pole" of the battery and is one of the key inner components in lithium-ion batteries.
  • the basic function of the battery separator in the lithium battery is to separate the positive and negative electrodes, and the adsorption of the electrolyte allows lithium ions to pass.
  • 3C products including computer, communication and consumer electronics, are the main areas of lithium battery applications.
  • PP separators and PE separators can be used to better meet their performance.
  • the performance of lithium batteries must be further improved to meet the requirements of electric vehicles.
  • Lithium batteries have more stringent requirements.
  • lithium ion battery separators are microporous membranes made of polyolefin materials, especially those used in consumer lithium ion batteries. Due to the urgent demand for high-power, high-speed charge-discharge lithium-ion batteries in various industries, people have gradually realized that the separator has the following defects: promoting the precipitation of dendrites is easy to pierce the diaphragm and causing short-circuit; the wettability of the electrolyte Low, resulting in low lithium ion conductivity; poor temperature resistance, the high temperature often generated during excessive charge and discharge causes the diaphragm to shrink or even melt, causing the electrode to directly contact the short circuit, causing fire and even explosion and causing personal injury.
  • the power lithium-ion battery puts forward higher requirements on the porosity, electrolyte wettability, temperature resistance and mechanical properties of the separator.
  • the single-layer polyolefin separator can not meet the needs of lithium battery use and safety, and restricts lithium. The development of ion batteries and related industries.
  • the main research direction is the diaphragm coating treatment, that is, coating a ceramic material on the surface of the diaphragm.
  • the ceramic coated diaphragm is the most effective way to improve the safety of the lithium battery. After coating the ceramic, the heat shrinkage, safety and thermal stability of the separator can be effectively improved and the mechanical strength of the separator can be improved, thereby prolonging the service life of the separator.
  • the conventional coating film coating is in direct contact with the positive and negative electrodes, and it is difficult to avoid some side reactions.
  • the preparation method of the new lithium battery separator such as the preparation of the multilayer diaphragm composite lithium ion battery separator, has received more and more attention.
  • the composite membrane the composite material obtained by chemically blending the three membrane substrates is called a three-layer composite membrane, and its essence is not a multi-layer structure in the true sense, but a new composite material.
  • Diaphragm has great progress for lithium-ion batteries and related industries, but chemical blending to obtain composite materials is too complicated, inconvenient to operate, and easily cause environmental pollution and safety problems.
  • the composite membrane will lead to an increase in the impedance of the battery, which restricts the further development of the lithium ion battery and related industries; the other is to apply a coating slurry on one or both sides of the battery separator to form a composite.
  • the layer is used to meet the demand for the separator, but the coating coating of this type will increase the impedance of the battery regardless of the thickness, which restricts the further development of the lithium ion battery and related industries.
  • the present invention provides a lithium ion battery separator with high temperature resistance and a coating method thereof, and the lithium ion battery separator has good heat shrinkage resistance and safety.
  • the utility model has the advantages of high heat resistance, good thermal stability and long service life of the separator; and the preparation method of the invention is simple and easy to operate, and the prepared composite lithium ion battery separator has good mechanical properties.
  • a lithium ion battery separator having a high temperature resistant multiple coating comprising a coating film composed of a battery separator coated with a coating slurry on one or both sides, wherein Applying an additional layer of slurry on one or both sides of the coating film, the additional layer of the slurry comprising at least one coating layer composed of a coating slurry, the coating slurry being in mass percentage, Including a slurry consisting of a coating slurry of weight ratio (10-30): (60-80) and N-methylpyrrolidone, sodium polyacrylate, sodium polymetaphosphate, 0.5-5% by weight of the slurry, One or more mixtures of sodium orthophosphate, sodium silicate, sodium lauryl sulfate, and ammonia, the static eliminator of 0.3-0.5% by weight of the slurry, and 0.5-10% by weight of the slurry.
  • the PVDF glue accounts for 0.3-0.5% by weight of the slurry of sodium carboxymethylcellulose
  • the NMP solvent accounts for ⁇ 0% of the slurry weight.
  • the coating slurry is an Al 2 O 3 ceramic slurry, a PVDF slurry, a PTFE slurry, a ZrO 2 ceramic slurry or a SiO 2 slurry.
  • the coating slurry used for any one of the coatings of the lithium ion battery separator is the same or different kinds of coating slurry as the coating slurry used for the other layers.
  • the substrate of the lithium ion battery separator is polypropylene, polyethylene, non-woven fabric, PMIA or fiber membrane.
  • a method for preparing a high temperature resistant multi-coating lithium ion battery separator according to the first aspect of the present invention comprising the steps of:
  • A. Preparation of coating slurry Raw materials are prepared in proportion to prepare Al 2 O 3 ceramic coating slurry, PVDF coating slurry, PTFE coating slurry, ZrO 2 ceramic coating slurry or SiO 2 coating. Slurry, spare;
  • Pretreatment of the battery separator pretreat the membrane for 5-120 s with ozone with a flow rate of 0.5-5 L/min, and reserve;
  • the pretreated membrane is coated on one side or both sides to control the coating speed of 5-20 m/min, and the coating thickness after coating is controlled to be 1-5 ⁇ m, and dried to obtain a coating film. And then performing the above coating and drying operations on one or both sides of the coating film until the desired number of coatings is reached, and the standby is performed;
  • multi-layer composite coating may be carried out by means of dip coating, dicavity coating, dipping, and micro-concave combined coating.
  • Different types of coating slurry are coated on both sides, and when coating, it may be only dip coating, only dicavity coating or first dip coating, second time dip coating, or Dip coating is used once and dip coating is used for the second time.
  • the drying temperature is 50-70 ° C, and the drying time is 0.6-1.8 min.
  • the preparation of the coating slurry comprises the following steps:
  • the alumina, the zirconia, the silica, the PVDF, and the PTFE powder each have a particle diameter of 0.05 to 1.0 ⁇ m.
  • the speed at which high speed agitation is controlled is greater than 1000 r/min.
  • the invention forms a plurality of coatings on the separator by using the same or different kinds of coating slurry to obtain the lithium ion battery separator, which has the high safety of the coated membrane to the battery, and can High temperature resistance, reduce the shrinkage rate of the separator under high temperature conditions, increase the overall life of the battery, and improve the affinity of the separator and the electrolyte to ensure that the diaphragm is fully swelled by the electrolyte to help extend the cycle life of the battery.
  • the preparation method of the invention provides a mature and efficient process for the preparation of the lithium ion battery separator, wherein the operation is simple, the cost is low, the automation degree is high during operation, the production efficiency of the diaphragm is obviously improved, and the battery processing can be stably continued.
  • the diaphragm raw materials, and finally processing a variety of coated diaphragm products with high quality and stable performance, especially in lithium-ion batteries used in electric vehicles the diaphragm can withstand higher temperatures during the operation of electric vehicles
  • the diaphragm shrinkage rate is significantly lower than that of the existing ceramic coated diaphragm, so that the overall life of the battery is significantly prolonged, the safety is greatly improved, and the convenience, safety and stability of the electric vehicle are also improved.
  • the high-temperature resistant multi-coated lithium ion battery separator prepared by the preparation method of the invention has the same coating thickness, uniform micropores, and uniform micropores to make the current density uniform, so that the voltage of the battery is uniform, so that the performance of the battery is more it is good.
  • the high temperature resistant multi-coating lithium ion battery separator of the present invention may have an areal density of 10 to 50 g/m 2 , preferably 10 to 20 g/m 2 , a thickness of 10 to 30 ⁇ m, and a pore diameter of 0.02 to 0.1 ⁇ m.
  • the porosity can be 40-70%.
  • the lithium ion battery separator of the invention has high porosity and good consistency, ensures unimpeded passage of ions, has uniform current density, and has good electrode activity.
  • the invention provides a coating material of a plurality of coatings such as aluminum oxide, zirconium dioxide and silicon dioxide, and has a plurality of coatings, and has the advantages of small pore diameter, high strength and good temperature resistance.
  • the battery separator of the present invention can be used as a lithium ion battery separator and a filter material in addition to a lithium ion battery separator.
  • a lithium ion battery separator having a high temperature resistant multiple coating comprising a coating film composed of a battery separator coated with a coating slurry on one or both sides, wherein Applying an additional layer of slurry on one or both sides of the coating film, the additional layer of the slurry comprising at least one coating layer composed of a coating slurry, the coating slurry being in mass percentage, Including a slurry consisting of a coating slurry of weight ratio (10-30): (60-80) and N-methylpyrrolidone, sodium polyacrylate, sodium polymetaphosphate, 0.5-5% by weight of the slurry, At least one of sodium orthophosphate, sodium silicate, sodium lauryl sulfate and aqueous ammonia, the static eliminator of 0.3-0.5% by weight of the slurry, 0.5-10% by weight of the slurry of alcohol, propylene carbonate, At least one of glycerin, dimethyl
  • the coating slurry is preferably an Al 2 O 3 coating slurry, a PVDF coating slurry, a PTFE coating slurry, a ZrO 2 coating slurry or a SiO 2 coating slurry. That is, the coating slurry (i.e., the solid component in the slurry) in the slurry is Al 2 O 3 ceramic, PVDF, PTFE, ZrO 2 ceramic or SiO 2 .
  • the mass ratio of the control coating slurry to the solvent is controlled at (10-30): (60-80) and the amount of other components to control the solid content of the coating slurry, and the solid content is largely high. Influence the thickness of the coating.
  • the Al 2 O 3 coating slurry has a solid content of 10 to 50%.
  • the PVDF coating has a solids content of 10-30%.
  • the PTFE coating slurry has a solids content of 20-40%.
  • the ZrO 2 coating slurry has a solids content of 25-35%.
  • the SiO 2 coating slurry has a solid content of 15 to 40%.
  • NMP N-methylpyrrolidone
  • NMP is an abbreviation for N-methylpyrrolidone, which is described separately in the present invention, but for the sake of clearer expression, the former focuses on the slurry.
  • the solvent in the latter which focuses on the additional solvent (i.e., used to adjust the solids content) to make the entire coating slurry meet the desired solids content.
  • the PVDF glue acts as an adhesive to provide a coating force to the coating slurry, so that the coating slurry can be firmly bonded to the surface of the separator.
  • the PVDF glue liquid content is 5-10% by weight of the slurry.
  • the sodium polyacrylate, sodium polymetaphosphate, sodium orthophosphate, sodium silicate, sodium lauryl sulfate and aqueous ammonia are used as dispersing agents to make the material dispersion more uniform and stable.
  • the static eliminator can reduce the electrostatic content of the coating film.
  • Alcohol polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyvinyl alcohol, and the like can improve the bubble content of the coating slurry (hereinafter also referred to as "antifoaming agent" for convenience of description).
  • the coating slurry formulation of the invention has better comprehensive performance than the existing coating slurry, and can specifically improve the heat resistance, strength, toughness, gas permeability, water content and stability of the coating film.
  • the invention can achieve different performance requirements by controlling the proportion of the coating slurry formulation, that is, the formulation ratio of different coating coating slurry is different.
  • the dispersant affects the stability of the product, and the difference in the active ingredient and the difference in the solid content differs from the amount of the dispersant required.
  • the difference in coating thickness and type of coating slurry has a great influence on the heat resistance and strength of the separator product, and the battery safety performance such as heat resistance and lithium dendrite penetration resistance are improved.
  • At least one layer of a coating film formed of the coating slurry is included on one side of the lithium ion battery separator.
  • the coating slurry used for any one of the lithium ion battery separators may be the same as or different from the coating slurry used for the other layers.
  • the types of coating slurries used in the adjacent two coating layers may be the same or different, preferably different.
  • the substrate of the lithium ion battery separator is polypropylene, polyethylene, nonwoven fabric, PMIA (meta-aramid) or a fiber membrane.
  • the lithium ion battery separator of the plurality of coating layers may specifically have the following structure:
  • the present invention provides a method for preparing a high temperature resistant multiple coating lithium ion battery separator, comprising the steps of:
  • A. Preparation of coating slurry Raw materials are prepared in proportion to prepare Al 2 O 3 ceramic coating slurry, PVDF coating slurry, PTFE coating slurry, ZrO 2 ceramic coating slurry or SiO 2 coating. Slurry, spare;
  • Pretreatment of the battery separator pretreat the membrane for 5-120 s with ozone with a flow rate of 0.5-5 L/min, and reserve;
  • the pretreated membrane is coated on one side or both sides to control the coating speed of 5-20 m/min, and the coating thickness after coating is controlled to be 1-5 ⁇ m, and dried to obtain a coating film. And then performing the above coating and drying operations on one or both sides of the coating film until the desired number of coatings is reached, and the standby is performed;
  • the pretreatment time is 5-120 s, wherein the pretreatment time is too short, which affects the adhesion of the membrane surface and the appearance quality of the coating.
  • the excessive pretreatment time will affect the strength and performance of the membrane itself.
  • multi-layer composite coating can be carried out by means of dip coating, dicavity coating, dipping and dicavity combined coating. For example, coating a coating slurry on one or both sides of the separator, and then applying another type of coating slurry on one or both sides of the coating film, or coating different types on both sides of the separator. Coating the slurry, when coating, it can be dip coating only, dimple coating or first dip coating, second dip coating, or first dip coating The second time, dip coating is used.
  • the drying temperature is 50-70 ° C, and the drying time is 0.6-1.8 min.
  • the segmented drying is adopted, and the segmented drying can be implemented by a multi-stage oven, and the multi-stage oven can conveniently adjust the temperature and the frequency of entering and leaving the air to make the drying effect better.
  • the dried coating film is subjected to gas flushing with nitrogen for 1-2 s before the next coating, and then coating is performed.
  • the inventors of the present invention have found through intensive research that nitrogen flushing can reduce the shrinkage rate during the application of the separator, and the shrinkage rate is reduced by more than 10% compared with the separator which has not undergone the special treatment, thereby increasing the liquid absorption rate of the separator, and simultaneously Nitrogen flushing improves its high-temperature melt integrity, and the high-temperature melt integrity is improved by more than 15% compared to the separator that has not been subjected to this special treatment. The reason is that it improves the diaphragm structure and makes the overall performance of the separator better.
  • step D the main purpose of the corona treatment is to improve the hydrophilicity of the membrane surface and improve the liquid absorption performance of the membrane surface to the coating slurry. If the hydrophilicity is poor, the adsorption capacity of the separator on the coating slurry is poor, and the adhesive performance and appearance quality of the coating are poor. Excessive corona time can affect the strength and performance of the diaphragm.
  • the corona treatment uses a high-frequency alternating voltage of 5000-15000 V/m 2 , and the principle is to use a high frequency and a high voltage to corona discharge on the surface of the treated plastic (high-frequency AC voltage is as high as 5000-15000 V/m 2 ) ), a low temperature plasma is generated to cause a radical reaction on the surface of the separator to crosslink the polymer.
  • the surface becomes rough and increases its wettability to polar solvents - these ions destroy the molecular structure by electric shock and penetration into the surface of the substrate, which in turn oxidizes and polarizes the surface molecules being treated, and ion shocks erode the surface. So as to increase the adhesion of the substrate surface.
  • the membrane of the present invention is disposed on a take-up reel, which is released by the take-up reel and moves in the direction of the take-up reel, during which the membrane passes through the coating, drying, Corona treatment, and finally the reel is wound up to get the final product.
  • the tension of the coated diaphragm is kept at 7-15N during the drying process.
  • the tension is too large, the coating film is easily deformed and curled; if the tension is too small, the process tends to be deviated and unstable.
  • the winding tension is 4-12N. If the winding tension is too large, it is easy to warp and bulge, and the stress in the coating film is too large to cause deformation. If the winding tension is too small, the winding end face is uneven and the product is not smooth. Loose.
  • the following examples control the tension of the diaphragm in accordance with this method.
  • the preparation of the coating slurry includes the following steps,
  • N-methylpyrrolidone and aluminum oxide (Al 2 O 3 ), zirconium dioxide (ZrO 2 ), silicon dioxide (SiO 2 ), PVDF to a vacuum, high-speed, planetary agitation device with ultrasonic oscillation function
  • the weight ratio of the powder to N-methylpyrrolidone is (10-30): (60-80), and the mixture is ultrasonically shaken at a high speed for 0.5-2 h to obtain a slurry;
  • the solid content is determined to determine whether or not the NMP solvent is added, while the high-speed stirring is simultaneously performed by ultrasonic vibration for 0.5-2 h;
  • the rotational speed of the high speed agitation is controlled to be greater than 1000 r/min.
  • the particle diameters of the alumina, the zirconia, the silica, the PVDF, and the PTFE powder are each 0.05 to 1.0 ⁇ m.
  • the Al 2 O 3 coating slip can be obtained by the following method:
  • N-methylpyrrolidone and alumina powder are added to a vacuum, high-speed planetary agitating device with ultrasonic oscillation function.
  • the weight ratio of the powder to N-methylpyrrolidone is 10:60, and the ultrasonic vibration is 0.5 while stirring at a high speed. h, obtaining a slurry;
  • the preparation of the SiO 2 coating slurry :
  • N-methylpyrrolidone and silica powder were added to a vacuum, high-speed, planetary stirring device having ultrasonic wave oscillating function.
  • the weight ratio of the powder to N-methylpyrrolidone was 20:70, and the mixture was ultrasonically shaken for 1 hour while stirring at a high speed. Obtaining slurry;
  • the preparation of the ZrO 2 coating slip :
  • N-methylpyrrolidone and zirconium dioxide powder are added to a vacuum, high-speed planetary stirring device having ultrasonic wave oscillating function, and the weight ratio of the powder to N-methylpyrrolidone is 30:80, and ultrasonic stirring is performed for 2 hours while stirring at high speed. Obtaining a slurry;
  • the preparation of the PVDF coating slurry :
  • N-methylpyrrolidone and PVDF powder were added to a vacuum, high-speed, planetary agitation device with ultrasonic oscillation function.
  • the weight ratio of the powder to N-methylpyrrolidone was 15:75, and the mixture was ultrasonically shaken for 1.5 h under high-speed stirring.
  • the preparation of the PTFE coating slurry :
  • N-methylpyrrolidone and PTFE powder were added to a vacuum, high-speed planetary stirring device having ultrasonic wave oscillating function.
  • the weight ratio of the powder to N-methylpyrrolidone was 25:68, and the mixture was ultrasonically shaken for 1.3 h at high speed.
  • the coating of the invention adopts different kinds of coatings to improve the comprehensive performance of the coating film in comparison with the coating of one coating, and combines the advantages of different coatings to have a synergistic effect, the battery separator Better performance.
  • a 16 ⁇ m wet PE separator Take a 16 ⁇ m wet PE separator, and use a micro-concave roller to select one side of the wet PE separator to coat a 2 ⁇ m thick Al 2 O 3 coating slurry (added dispersant, defoamer are sodium polyacrylate, glycerin, the same below) a coating film is formed, and then a 1 ⁇ m SiO 2 coating slurry is applied to both sides of the coating film by using a dip coating device (the dispersing agent and the antifoaming agent are sodium lauryl sulfate and alcohol, respectively).
  • the dispersing agent and the antifoaming agent are sodium lauryl sulfate and alcohol, respectively.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry and SiO 2 coating slurry, standby;
  • the membrane is pretreated with ozone with a flow rate of 0.5 L/min for 120 s, and used;
  • the drying adopts the segmented drying process, which is followed by drying at 56°C, drying at 64°C, drying at 56°C, and controlling the total drying time of 1.2 min.
  • the interval between coating and drying is 0.5. s, obtaining a coating film;
  • the SiO 2 coating slurry was coated on both sides of the coating film to control the coating speed of 10 m/min, followed by drying at 56 ° C, drying at 64 ° C, drying at 56 ° C, and controlling the total drying. Use 1.2min, spare;
  • a 10 ⁇ m wet PP separator was taken, and a 2 ⁇ m thick SiO 2 coating slurry was applied to both sides of the wet PP separator by using a dip coating apparatus to form a coating film, and then a dip coating device was used on both sides of the coating film.
  • the coating slurry of 1 ⁇ m Al 2 O 3 was further coated to obtain two coating slurry-coated composite lithium ion battery separators of SiO 2 and Al 2 O 3 having a thickness of 16 ⁇ m, and the structure thereof was Al 2 O 3 coating-SiO. 2 coating - PP separator - SiO 2 coating - Al 2 O 3 coating.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry and SiO 2 coating slurry, standby;
  • Pretreatment of the battery separator pretreating the membrane for 100 s with ozone with a flow rate of 1 L/min, and standby;
  • coating the double-sided dip coating of the pretreated separator is coated with SiO 2 coating slurry, the coating speed is controlled to be 10 m / min, and the coating thickness after coating is controlled to be 2 ⁇ m, and dried;
  • the drying adopts the segmented drying process, which is followed by drying at 55 °C, drying at 65 °C, drying at 55 °C, and controlling the total drying time by 1 min, and the time interval between coating and drying is 3 s.
  • the Al 2 O 3 coating slurry was coated on both sides of the coating film to control the coating speed of 10 m/min, and the thickness of the coating after the coating was controlled to be 1 ⁇ m, followed by drying at 55 ° C and 65 ° C. Drying, drying at 55 °C, control drying for 1 min, standby;
  • a 9 ⁇ m PMIA separator was used, and a 2 ⁇ m thick Al 2 O 3 coating slurry was coated on one side of the PMIA separator using a dimple roll, and a 1 ⁇ m thick PTFE coating slurry (added dispersant,
  • the defoaming agent is sodium silicate, alcohol, the same as below, forming a coating film, and then coating a 1 ⁇ m thick PTFE coating slurry on the side of the coating film coated with the Al 2 O 3 coating slurry using a micro concave roller.
  • a 2 ⁇ m thick Al 2 O 3 coating slurry was coated on the other side of the coating film coated with the PTFE coating slurry to obtain a coating slurry composite lithium of PTFE and Al 2 O 3 having a thickness of 15 ⁇ m.
  • Pretreatment of the battery separator pretreating the membrane for 80 s with ozone with a flow rate of 2 L/min, standby;
  • one side of the pretreated separator was coated with an Al 2 O 3 coating slurry, and the other side was coated with a dried PTFE coating slurry to control a coating speed of 15 m/min to control the coated Al.
  • 2 O 3 coating thickness is 2 ⁇ m
  • PTFE coating thickness is 12 ⁇ m, drying;
  • the segmented drying process is adopted, which is followed by drying at 50°C, drying at 60°C, drying at 50°C, and controlling the total drying time of 1.8 minutes, and the time interval between coating and drying is 0.5 s.
  • the coating film is coated with a PTFE coating on one side of the Al 2 O 3 coating layer, and the Al 2 O 3 coating is slightly concavely coated on the PTFE coated side, and sequentially dried at 50 ° C. Drying at 60 °C, drying at 50 °C, and controlling the total drying time of 1.8 min, standby;
  • the embodiment also prepares another lithium ion battery separator according to the above method, except that
  • the dried coating film was gas-washed with nitrogen gas for 2 s before the next coating, and then coated.
  • the other side of the slurry was coated with a 2 ⁇ m thick SiO 2 coating slurry to obtain a coating slurry-coated composite lithium ion battery separator of SiO 2 and Al 2 O 3 having a thickness of 14 ⁇ m, and the structure thereof was Al 2 O 3 coated.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry and SiO 2 coating slurry;
  • Pretreatment of the battery separator pretreating the membrane for 70 s with ozone with a flow rate of 3 L/min, and standby;
  • the pretreated membrane was coated with Al 2 O 3 coating slurry on one side, and the other surface was coated with SiO 2 coating slurry to control the coating speed of 20 m/min to control the coating of Al 2 O 3 .
  • the coating thickness is 2 ⁇ m, the thickness of the SiO 2 coating is 1 ⁇ m, and drying;
  • the drying adopts the segmented drying process, which is followed by drying at 53 °C, drying at 62 °C, drying at 53 °C, and controlling the total drying time of 0.8 min.
  • the time interval between coating and drying is 0.4. s, obtaining a coating film;
  • the coating film coated on the other surface is coated with a coating slip SiO SiO 2 2 coating the slurry, controlling the coating speed of 20m / min, controlling the thickness of the Al 2 O 3 coating after coating is 1 ⁇ m, the thickness of the SiO 2 coating is 2 ⁇ m, drying, wherein the drying is performed by sectional drying. It is sequentially dried in 53°C section, dried in 62°C section, and dried in 53°C section. The total drying time is 0.8min, and the time interval between coating and drying is 0.4s.
  • the battery separator obtained by directly coating 3 ⁇ m Al 2 O 3 coating and SiO 2 coating on both sides of the non-woven membrane separator, the battery separator coating and the separator which have been directly coated.
  • the bonding ability between the two is worse than the bonding ability of the embodiment.
  • the method of the present invention improves the adhesiveness between the thickness coating and the separator, and the outer coating is applied again on the surface of the inner coating layer. The bonding performance is good, which can reduce the influence of the adhesive on the gas permeability and other properties of the coating film.
  • a 10 ⁇ m wet PE separator was applied, and a 2 ⁇ m thick Al 2 O 3 coating slurry was coated on one side of the wet PE separator using a dimple roll, and a 2 ⁇ m thick SiO 2 coating slurry was coated on the other side of the wet PE separator.
  • A. Preparation of coating slurry preparation of Al 2 O 3 coating slurry, SiO 2 coating slurry, PVDF coating slurry and ZrO 2 coating slurry
  • Pretreatment of the battery separator pretreating the membrane for 30 s with ozone with a flow rate of 4 L/min, and standby;
  • one side of the pretreated separator was coated with an Al 2 O 3 coating slurry, and the other side was coated with a SiO 2 coating slurry to control a coating speed of 18 m/min to control the coating after coating.
  • the thickness is 2 ⁇ m, drying; wherein, the drying adopts the segmented drying process, followed by drying at 57°C, drying at 68°C, drying at 57°C, and controlling the total drying time by 0.6 min.
  • the drying time is 0.5 s to obtain a coating film;
  • the PVDF coating slurry was coated on one side of the coating film coated with the Al 2 O 3 coating slurry using a dimple roller, and the ZrO 2 coating was applied on the other side of the coating film coated with the SiO 2 coating slurry.
  • Slurry, control coating speed 18m / min, control coating thickness after coating is 2 ⁇ m, followed by drying at 57 ° C section, drying at 68 ° C section, drying at 57 ° C section, controlling total drying time 0.6min ,spare;
  • the embodiment also prepares another lithium ion battery separator according to the above method, except that
  • the dried coating film was gas-washed with nitrogen gas for 1.5 s before the next coating, and then coated.
  • a 10 ⁇ m wet PE separator was taken, and a 2 ⁇ m thick ZrO 2 coating slurry was coated on one side of the wet PE separator using a dimple roll to form a coating film, and the coating film was coated with a ZrO 2 coating slurry using a micro concave roller.
  • One side of the material was coated with a 2 ⁇ m thick PTFE coating slurry to obtain a ZrO 2 and PTFE coated slurry coating composite lithium ion battery separator having a thickness of 14 ⁇ m, and the structure was a PTFE coating-ZrO 2 coating-PE separator. .
  • A, preparation of coating slurry preparing PTFE coating slurry and ZrO 2 coating slurry;
  • Pretreatment of battery separator pretreating the membrane with ozone with a flow rate of 5L/min for 5s, standby; too short pretreatment time will affect the adhesion of the membrane surface and the appearance quality of the coating. The long pretreatment time will affect the membrane. Self strength and performance;
  • one side of the pretreated separator is coated with ZrO 2 coating slurry, the coating speed is controlled at 13 m / min, the coating thickness after coating is controlled to be 2 ⁇ m, and dried;
  • the drying adopts the segmented drying process, followed by the drying at 58 °C, the drying at 62 °C, and the drying at 58 °C.
  • the total drying time is 1.4 min, and the time interval between coating and drying is 0.2. s, obtaining a coating film;
  • the PTFE coating slurry was coated on one side of the coating film coated with the ZrO 2 coating slurry, and the coating speed was controlled to 10 m/min, followed by drying at 58 ° C, drying at 62 ° C, and drying at 58 ° C. , the total drying time is 1.4min, and the time interval between coating and drying is 0.2s, standby;
  • a 12 ⁇ m wet PE separator was used, and a 2 ⁇ m thick ZrO 2 coating slurry was coated on one side of the wet PE separator using a dimple roller, and a 1 ⁇ m thick Al 2 O 3 coating slurry was coated on the other side of the wet PE separator.
  • Forming a coating film coating a 2 ⁇ m-thick SiO 2 coating slurry on one side of the coating film coated with the ZrO 2 coating slurry using a dimple roll to obtain ZrO 2 , Al 2 O 3 , SiO 2 having a thickness of 17 ⁇ m.
  • Three coated slurry coated composite lithium ion battery separators having a structure of SiO 2 coating-ZrO 2 coating-PE separator-Al 2 O 3 coating.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry, SiO 2 coating slurry and ZrO 2 coating slurry;
  • the membrane is pretreated with ozone with a flow rate of 4.5 L/min for 20 s, and used;
  • the pretreated membrane was coated with ZrO 2 coating slurry on one side, and the Al 2 O 3 coating slurry was coated on the other side to control the coating speed of 8 m/min, and the coated ZrO 2 coating was controlled.
  • the layer thickness is 2 ⁇ m, the thickness of the Al 2 O 3 coating is 1 ⁇ m, and drying;
  • the drying adopts the segmented drying process, followed by drying at 60°C, drying at 70°C, drying at 60°C, and controlling the total drying time of 1.1 min.
  • the time interval between coating and drying is 0.3. s, obtaining a coating film;
  • the coating film coated with the ZrO 2 coating was coated with a SiO 2 coating slurry to control the coating speed of 8 m/min, and the thickness of the coated SiO 2 coating was controlled to be 2 ⁇ m, followed by drying at 60 ° C. Drying at 70°C, drying at 60°C, controlling the total drying time of 1.1min, and the time interval between coating and drying is 0.3s, standby;
  • a 12 ⁇ m wet PE separator was taken, and a 2 ⁇ m thick ZrO 2 coating slurry was dip coated on both sides of the wet PE separator by an impregnation apparatus to form a coating film, and then a coating thickness of 2 ⁇ m was applied on either side of the coating film using a dimpled roller.
  • the PVDF coating slurry obtained two coating slurry coated lithium ion battery separators of ZrO 2 and PVDF having a thickness of 18 ⁇ m, and the structure thereof was a PVDF coating-ZrO 2 coating-PE separator-ZrO 2 coating.
  • A, preparation of coating slurry preparing PVDF coating slurry and ZrO 2 coating slurry;
  • Pretreatment of battery separator Pretreatment of the membrane with ozone at a flow rate of 3.5L/min for 80s, standby; too short pretreatment time will affect the adhesion of the membrane surface and the appearance quality of the coating. The strength and performance of the diaphragm itself;
  • the pretreated separator is coated on both sides with a ZrO 2 coating slurry, the coating speed is controlled to be 16 m/min, and the coating thickness after the coating is controlled to be 2 ⁇ m, and dried;
  • the drying adopts the segmented drying process, followed by the drying at 51 °C, the drying at 69 °C, and the drying at 51 °C.
  • the total drying time is 0.9 min, and the time interval between coating and drying is 0.4. s, obtaining a coating film;
  • the PVDF coating slurry is coated on either side of the coating film, the coating speed is controlled to be 16 m/min, the coating thickness after the coating is controlled to be 2 ⁇ m, and drying is performed, wherein the drying is performed by the segmented drying process. After drying at 51 °C, drying at 69 °C, drying at 51 °C, the total drying time is 0.9 min, and the time between coating and drying is 0.4 s.
  • a 10 ⁇ m wet PE separator was taken, and a 2 ⁇ m thick SiO 2 coating slurry was coated on one side of the wet PE separator using a dimple roll to form a coating film, and then a 1 ⁇ m thick Al was coated on both sides of the coating film by an dipping device.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry, SiO 2 coating slurry, ZrO 2 coating slurry, PVDF coating slurry;
  • Pretreatment of battery separator pretreating the membrane for 90s with ozone with a flow rate of 2.5L/min, standby;
  • one side of the pretreated separator is coated with SiO 2 coating slurry, the coating speed is controlled 14m / min, the coating thickness after coating is controlled to 2 ⁇ m, drying;
  • the drying adopts the segmented drying process, followed by the drying at 57 °C, the drying at 66 °C, and the drying at 57 °C.
  • the total drying time is 1.4 min, and the time interval between coating and drying is 0.3. s, obtaining a coating film;
  • the Al 2 O 3 coating slurry is coated on both sides of the coating film, and the thickness of the coating after coating is controlled to be 1 ⁇ m, followed by drying at 57 ° C, drying at 66 ° C, and drying at 57 ° C. , the total drying time is 1.4 min, and the coating to drying time interval is 0.3 s to obtain a coating film;
  • the PVDF coating slurry and the ZrO 2 coating slurry were respectively coated on both sides of the coating film by using a dimple roller, and the coating thickness after coating was controlled to be 2 ⁇ m, followed by drying at 57 ° C, 66 ° C. Section drying, drying at 57 °C, controlling the total drying time of 1.4 min, standby;
  • a 16 ⁇ m wet PE separator was taken, and a 2 ⁇ m thick Al 2 O 3 coating slurry was coated on one side of the wet PE separator using a dimple roll to form a coating film, and the coating film was coated with Al 2 O using a dimpled roller.
  • 2 ⁇ m thickness coated on one side PVDF coating slip slurry coating 3 having a thickness of 20 ⁇ m of Al 2 O 3 PVDF two types of coating slurry was coated composite lithium ion battery separator, the structure of a PVDF coating -Al 2 O 3 coating - PE separator, the microscopic morphology of the membrane is shown in Figures 1 to 6.
  • A, preparation of coating slurry preparation of Al 2 O 3 coating slurry and PVDF coating slurry;
  • Pretreatment of the battery separator pretreating the membrane with ozone with a flow rate of 5 L/min for 5 s, standby;
  • one side of the pretreated separator is coated with Al 2 O 3 coating slurry, the coating speed is controlled to 10 m / min, the coating thickness after coating is controlled to 2 ⁇ m, and dried;
  • the drying adopts the segmented drying process, which is followed by drying at 55 °C, drying at 60 °C, drying at 58 °C, and controlling the total drying time of 1.2 min.
  • the time interval between coating and drying is 0.4. s, obtaining a coating film;
  • the PVDF coating slurry is coated on one side of the coating film coated with the Al 2 O 3 coating slurry, and the coating speed is controlled to be 10 m/min, followed by drying at 55 ° C, drying at 60 ° C, and 55 ° C. Drying, control drying for a total time of 1.4min, coating to drying time interval of 0.2s, standby;
  • the coated battery separator is corona treated, and the processing time is 8s winding, and the lithium ion with high temperature resistant coating of PVDF coating-Al 2 O 3 coating-PE membrane is obtained. Battery separator.
  • a battery separator was prepared in accordance with the method of Example 6, except that in step C, only one side of the pretreated separator was coated with a ZrO 2 coating slurry and dried; thereby obtaining a structure of ZrO 2 coating-PE. Diaphragm lithium ion battery separator.
  • the air permeability of the battery separator prepared in the above examples and comparative examples was tested according to ISO 5636 using a Gurley 4340 gas permeability meter; the heat shrinkage rate was tested according to ISO 14616; the tensile properties were tested according to GB/T 1040.3; the diaphragm ion conductivity was passed through electricity. ChemStation test.
  • the base film refers to a bare cell separator without a coating slurry.
  • Example 5 the longitudinal values of the shrinkage ratio (90 ° C * 2 h) were 0.6%, 0.61%, and 0.7%, respectively, and the lateral values were 0.15.
  • the longitudinal values of %, 0.13%, 0.14%, shrinkage (130 °C*1h) were 1.7%, 1.6%, and 1.68%, respectively, and the lateral values were 1.5%, 1.4%, and 1.57%, respectively.
  • the TMA method was at 250 °C.
  • the high temperature melt integrity is 49%, 45%, 44%, respectively; compared with the corresponding data in Tables 1 and 2, nitrogen flushing can reduce the shrinkage rate during the application of the diaphragm, and the shrinkage rate is compared with the case without the special treatment.
  • the diaphragm, the shrinkage rate is reduced by more than 10%, the liquid absorption rate of the diaphragm is increased, and the nitrogen flushing improves the high-temperature melt integrity, and the high-temperature melt integrity is improved by more than 15% compared with the separator which has not been subjected to the special treatment. Analysis of the improved diaphragm structure makes the overall performance of the diaphragm better.
  • the various coated lithium ion battery separators of Example 6, the battery separators of Comparative Example 1 and Comparative Example 2 were assembled into a half-cell with LiCoO 2 and metallic lithium, respectively, to examine the electrical properties.
  • the results show that the initial discharge capacity of the battery at 13C is 137.2mAh ⁇ g -1 and 142.7mAh ⁇ g -1 respectively .
  • the battery capacity is attenuated to 133.1mAh ⁇ g -1 and 127.9mAh ⁇ g. -1
  • the capacity retention rates were 97.01% and 89.6%, respectively
  • the average attenuation amounts were 0.082 mAh ⁇ g -1 and 0.296 mAh ⁇ g -1 , respectively. It can be seen that the lithium ion battery separator with multiple coatings of the present invention is assembled. Battery performance is stable.
  • the lithium ion battery separator provided by the present invention has both safety in use and high temperature resistance, and the coating slurry can not only exert the safety function of the ceramic coating but also adhere to the electric field. In the battery of the vehicle field, the safety and life of the battery can be improved.
  • the preparation method provided by the invention provides a relatively mature and stable production process for producing a high-temperature resistant multi-coated lithium ion battery separator, and the production process is arranged for each process of the high temperature resistant multi-coated lithium ion battery mechanism. The interval between the cloth process and the drying process enables the final product to be of high quality and stable.
  • the conventional coated separator is severely deformed at 130 ° C, and the composite lithium ion battery separator of the present invention can maintain a good shape at 200 ° C, and the heat resistance is better, and the battery separator is maintained at 130 ° C for 1 h.
  • the shrinkage rate is MD ⁇ 2.5, TD ⁇ 2.4, and the thermal performance is obviously better than that of the ordinary coated separator;
  • the common double-sided coating membrane with a thickness of about 22 ⁇ m generally has a gas permeability value of about 300-380 s/100 mL, and the composite lithium ion of the present invention.
  • the battery diaphragm permeability value is less than 280s/100mL.
  • the value of this value is the time required for a certain area of the diaphragm to pass a certain amount of gas under a certain pressure.
  • the discharge speed is faster, which is obviously superior to the common coated diaphragm; and the lithium ion battery of the battery separator with multiple coatings also has higher ionic conductivity and better charge and discharge performance of the battery.

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Abstract

本发明属于电池隔膜的技术领域，公开了一种耐高温多种涂层的锂离子电池隔膜及其制备方法。电池隔膜包括由单面或双面涂布有涂布浆料的电池隔膜构成的涂层膜，在涂层膜的单面或双面涂布有浆料附加层，其包括至少一层由涂布浆料构成的涂层，涂布浆料包括由重量比为(10-30)：(60-80)的涂层浆料和N-甲基吡咯烷酮组成的料浆，占料浆重量0.5-5％的聚丙烯酸钠、多偏磷酸钠和正磷酸钠等中的至少一种，占料浆0.3-0.5％的静电消除剂，占料浆0.5-10％的酒精、丙烯碳酸酯和甘油等中的至少一种等。本发明的电池隔膜既具备较高的安全性，同时又能够耐高温，能保证隔膜被电解液充分溶胀有助于延长电池的循环寿命。

Description

耐高温多种涂层的锂离子电池隔膜及其制备方法 技术领域
本发明属于电池隔膜的技术领域，涉及复合锂离子电池隔膜，具体涉及一种耐高温多种涂层的锂离子电池隔膜及其制备方法。
背景技术
锂电池具有比能量高、体积小、重量轻、自放电少、长循环寿命、无污染等优点，得到了越来越广泛的应用，市场延伸到移动手机、手提电脑、数码摄像、电动工具、电动自行车、电动摩托车、电动汽车、储能、航空航天、军车舰船、武器等诸多领域，是新能源产业的重要组成部分。
锂离子电池由正、负极材料、电解液、隔膜以及电池外壳组成。隔膜作为电池的“第三极”，是锂离子电池中的关键内层组件之一。电池隔膜在锂电池中的基本作用为隔开正负极，并且吸附电解液允许锂离子通过。3C产品包括计算机、通信和消费类电子产品，是锂电池应用的主要领域，对于3C产品的锂电池，仅使用PP隔膜和PE隔膜，其性能就能得到较好的满足。但是随着电动汽车的不断发展，锂电池的性能必须进一步提升才能满足电动汽车的要求，比如在安全性、充放电性能、循环性能及倍率性等方面，电动汽车用锂电池就比3C产品用锂电池有更加严格的要求。
目前，大多数锂离子电池隔膜为采用聚烯烃材料制造的微孔膜，尤其是消费类锂离子电池所用隔膜。由于各行各业对大功率、高速充放电锂离子电池的迫切需求，在使用过程中，人们逐渐认识到该隔膜存在如下缺陷：促进枝状晶体析出容易刺破隔膜造成短路；电解液的润湿度低从而造成锂离子导电率低；耐温性能差，在过度充放电时往往产生的高温使隔膜大量收缩甚至融化，造成电极直接接触短路，从而引发火灾甚至爆炸造成人员伤害。尤其是动力锂离子电池，对隔膜的孔隙率、电解液润湿度、耐温性能、力学性能提出了更高的要求，单层聚烯烃隔膜已经不能满足锂电池使用和安全的需要，制约了锂离子电池及相关行业的发展。
另外，锂电池中的金属Li电极也存在很多问题，主要是循环寿命短和安全问题，Li +在金属Li的表面析出时，由于局部极化的存在，很容易形成Li枝晶，即便是在目前广泛采用的石墨负极上，在大电流充电、过充和低温充电等恶劣情况下，仍然会出现Li枝晶的析出问题。严重的Li枝晶会刺穿隔膜，导致正负极短路，引发安全问题。即使Li枝晶不引发安全问题也会造成电池容量的损失，当Li枝晶生长到一定的长度，就会发生断裂，形成死Li，造成不可逆的容量损失。
目前，在提高锂电池隔膜性能方面的发展研究是以改善隔膜表面性质和调整隔膜基体材料为主。在改善隔膜表面性质方面，主要的研究方向是隔膜涂布处理，即在隔膜表面涂覆一层陶瓷材料，就目前情况来看，陶瓷涂布隔膜是提高锂电池安全性最有效的方式，隔膜涂布陶瓷后可有效提高隔膜的耐热收缩性、安全性、热稳定性并改善隔膜的机械强度，从而延长隔膜的使用寿命。但是传统涂层膜涂层与正负极直接接触，难以避免会有一些副反应的发生。为了进一步使电池隔膜的性能满足动力锂电池的要求，新型锂电池隔膜的制备方法，如制备多层隔膜复合锂离子电池隔膜得到越来越多的关注。
就目前来说，传统涂布隔膜的抗锂枝晶穿透能力、耐高温性以及耐热收缩率在一定温度条件下不能够满足要求，因而，越来越多的关注放在了复合隔膜领域，然而现有的复合隔膜，无论是两层还是三层或更多层结构，主要有两种形成方式：第一种是采用共混的方式，也就是采用化学的方式，将两种或两种以上的隔膜基材融合、共混或聚合成一种复合材料，将这样的复合材料称之为复合隔膜，实际就是，两种隔膜基材化学共混后得到的复合材料被称之为两层的复合隔膜，三种隔膜基材化学共混后得到的复合材料被称之为三层的复合隔膜，其本质不是真正意义上的多层结构，而是一种新的复合材料，这种复合隔膜对锂离子电池及相关行业具有很大的进步意义，但是采用化学 共混得到复合材料过于复杂、操作不便，同时易造成环境污染、存在安全性问题；同时，该种复合隔膜会导致电池的阻抗增加，制约了锂离子电池及相关行业的进一步发展；另一种是在电池隔膜的单面或双面涂布一层涂布浆料来构成复合层，用以满足对隔膜的需求，但是该种方式的涂料涂层无论薄厚也均会导致电池的阻抗增加，制约了锂离子电池及相关行业的进一步发展。
发明内容
为了解决现有锂离子电池隔膜存在的上述问题，本发明提供了一种耐高温多种涂层的锂离子电池隔膜及其制备方法，所述锂离子电池隔膜具有耐热收缩性好、安全性高、热稳定性好，隔膜使用寿命长的特点；且本发明的制备方法简单、易操作，制备的复合锂离子电池隔膜机械性能好。
根据本发明的第一方面，本发明提供了一种耐高温多种涂层的锂离子电池隔膜，包括由单面或双面涂布有涂布浆料的电池隔膜构成的涂层膜，其中，在涂层膜的单面或双面涂布有浆料附加层，所述浆料附加层包括至少一层由涂布浆料构成的涂层，所述涂布浆料按质量百分比计，包括由重量比为(10-30)：(60-80)的涂层浆料和N-甲基吡咯烷酮组成的料浆，占料浆重量0.5-5％的聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠、氨水中的一种或一种以上的混合物，占料浆重量0.3-0.5％的静电消除剂，占料浆重量0.5-10％的酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚、聚乙烯醇中的一种或一种以上的混合物，占料浆重量5-10％的PVDF胶液，占料浆重量0.3-0.5％的羧甲基纤维素钠，占料浆重量≥0％的NMP溶剂。
优选地，所述涂层浆料为Al 2O 3陶瓷浆料、PVDF浆料、PTFE浆料、ZrO 2陶瓷浆料或SiO 2浆料。
本发明中，所述锂离子电池隔膜的任意一涂层所用涂布浆料与其它层所用的涂布浆料为相同或不同种类的涂布浆料。
优选地，所述锂离子电池隔膜的基材为聚丙烯、聚乙烯、无纺布、PMIA或纤维膜。
根据本发明的第二方面，本发明提供了本发明第一方面所述的耐高温多种涂层的锂离子电池隔膜的制备方法，包括以下步骤：
A、涂布浆料的制备：按比例准备原料，配制成Al 2O 3陶瓷涂布浆料、PVDF涂布浆料、PTFE涂布浆料、ZrO 2陶瓷涂布浆料或SiO 2涂布浆料，备用；
B、电池隔膜的预处理：采用流量为0.5-5L/min的臭氧对隔膜进行预处理5-120s，备用；
C、涂布：将预处理后的隔膜进行单面或双面涂布，控制涂布速度5-20m/min，控制涂布后的涂层厚度为1-5μm，烘干，得到涂层膜，然后对涂层膜的单面或双面进行上述涂布、烘干操作，至达到所需涂层数，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为5-10s收卷，得到耐高温多种涂层的锂离子电池隔膜。
在本发明中，涂布时，可以选用浸渍涂布、微凹涂布、浸渍和微凹组合式涂布的方式进行多层复合涂布。例如，在隔膜的单面或者双面涂布一种所述的涂布浆料，然后在涂层膜的单面或者双面再次涂布其它种类的所述的涂布浆料，或者在隔膜两面分别涂布不同种类的涂布浆料，在涂布的时候，可以是只浸渍涂布、只微凹涂布或者第一次选用浸渍涂布、第二次选用微凹涂布，或者第一次选用微凹涂布、第二次选用浸渍涂布。
优选地，所述烘干的温度为50-70℃，烘干时间为0.6-1.8min。
优选地，所述涂布浆料的制备包括以下步骤：
在同时具有超声波振荡功能的真空、高速、行星搅拌设备中加入N-甲基吡咯烷酮和三氧化二铝、二氧化锆、二氧化硅、PVDF、PTFE中的至少一种粉末，该粉末与N-甲基吡咯烷酮的重量比为(10-30)：(60-80)，高速搅拌同时超声波振荡0.5-2h，得到料浆；
向所述料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的0.5-5％；加入静电消除剂，加入量为料浆的0.3-0.5％，高速搅拌同时超 声波振荡0.5-2h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的0.5-10％；高速搅拌同时超声波振荡0.5-2h；
加入料浆量5-10％的PVDF胶液，加入料浆量0.3-0.5％的羧甲基纤维素钠，高速搅拌同时超声波振荡0.5-2h；
检测浆料固含量，加入浆料量≥0％的NMP溶剂，高速搅拌同时超声波振荡0.5-2h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.5-1h，然后关闭真空平衡大气压后放出料浆过筛，备用。
优选地，所述三氧化二铝、二氧化锆、二氧化硅、PVDF、PTFE粉末的粒径分别为0.05-1.0μm。
控制高速搅拌的转速大于1000r/min。
本发明的有益效果是：
本发明借助相同或不同种类的涂布浆料在隔膜上形成多种涂层，得到所述锂离子电池隔膜，该电池隔膜既具备涂层隔膜对电池带来的较高安全性，同时又能够耐高温，减小高温条件下隔膜的收缩率，增加电池的整体寿命，且能提高隔膜与电解液的亲和性，保证隔膜被电解液充分溶胀有助于延长电池的循环寿命。
本发明的制备方法为所述锂离子电池隔膜的制备提供了成熟高效的工艺，其中的操作简单、成本较低，操作时自动化程度较高，隔膜的生产效率明显提高，能够为电池加工稳定持续地提供隔膜原材料，最后加工得到的多种涂层隔膜成品的品质较高且性能较为稳定，尤其是应用在电动汽车所用锂离子电池中，在电动汽车工作过程中，隔膜能够耐受较高温度，隔膜收缩率较现有的陶瓷涂覆隔膜有显著降低，使得电池整体寿命显著延长，安全性大大提高，电动车的使用便利性、安全性和稳定性也随之提高。
本发明的制备方法制备的所述耐高温多种涂层的锂离子电池隔膜的涂层厚度一致、微孔均匀，微孔均匀使电流密度均匀，从而使电池的电压一致，使得电池的性能更好。
本发明的耐高温多种涂层的锂离子电池隔膜，其面密度可以为10-50g/m 2，优选为10-20g/m 2，厚度可以为10-30μm，孔径可以为0.02-0.1μm，孔隙率可以为40-70％。本发明的锂离子电池隔膜孔隙率高且一致性好，保证离子的通过不受阻碍，电流密度一致，电极活性好。而本领域公知，孔隙率高对电池隔膜是一项非常好的性能，但是孔隙率高，会导致孔在受热时不能有效关闭，影响孔的关闭功能，存在孔隙率高与孔关闭功能相矛盾的问题，面对该问题，现有技术没有有效的解决方案，发明人通过对浆料的改进，以及对锂离子电池隔膜的结构改进，使得本发明的电池隔膜在孔受热时，孔依然可以有效闭合，不影响孔的关闭功能，解决了目前没有解决的孔隙率高与孔关闭功能相矛盾的问题。
本发明提供了三氧化二铝、二氧化锆、二氧化硅等多种涂布浆料，多种涂层的锂离子电池隔膜材料，具有孔径小、强度高、耐温性好等优点。另外，本发明所述的电池隔膜除了可以用做锂离子电池隔膜外，还可以用做镍氢电池隔膜和过滤材料等。
附图说明
图1是实施例10制备的锂离子电池隔膜在Mag＝2.00kx、WD＝2.4mm的SEM图。
图2是实施例10制备的锂离子电池隔膜在Mag＝1.00kx、WD＝2.4mm的SEM图。
图3是实施例10制备的锂离子电池隔膜在Mag＝5.00kx、WD＝2.4mm的SEM图。
图4是实施例10制备的锂离子电池隔膜在Mag＝10.00kx、WD＝2.4mm的SEM图。
图5是实施例10制备的锂离子电池隔膜在Mag＝20.00kx、WD＝2.4mm的SEM图。
图6是实施例10制备的锂离子电池隔膜在Mag＝500x、WD＝2.4mm的SEM图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
根据本发明的第一方面，本发明提供了一种耐高温多种涂层的锂离子电池隔膜，包括由单面或双面涂布有涂布浆料的电池隔膜构成的涂层膜，其中，在涂层膜的单面或双面涂布有浆料附加层，所述浆料附加层包括至少一层由涂布浆料构成的涂层，所述涂布浆料按质量百分比计，包括由重量比为(10-30)：(60-80)的涂层浆料和N-甲基吡咯烷酮组成的料浆，占料浆重量0.5-5％的聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，占料浆重量0.3-0.5％的静电消除剂，占料浆重量0.5-10％的酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，占料浆重量5-10％的PVDF胶液，占料浆重量0.3-0.5％的羧甲基纤维素钠，占料浆重量≥0％的NMP溶剂。
在本发明中，所述涂布浆料优选为Al 2O 3涂布浆料、PVDF涂布浆料、PTFE涂布浆料、ZrO 2涂布浆料或SiO 2涂布浆料。即，所述料浆中的涂层浆料(即料浆中的固体组分)为Al 2O 3陶瓷、PVDF、PTFE、ZrO 2陶瓷或SiO 2。
本发明中，控制涂层浆料与溶剂的质量比在(10-30)：(60-80)以及其它组分的加入量来控制涂布浆料的固含量，固含量的高低很大程度上影响涂层厚度。
优选情况下，所述Al 2O 3涂布浆料的固含量为10-50％。
优选情况下，所述PVDF涂布的固含量为10-30％。
优选情况下，所述PTFE涂布浆料的固含量为20-40％。
优选情况下，所述ZrO 2涂布浆料的固含量为25-35％。
优选情况下，所述SiO 2涂布浆料的固含量为15-40％。
关于以上提到“N-甲基吡咯烷酮”和“NMP”，本领域熟知NMP为N-甲基吡咯烷酮的简称，本发明将其分开描述，只是为了表达更清楚，前者侧重于指所述料浆中的溶剂，后者侧重于为使整个涂布浆料满足所需的固含量而额外添加的溶剂(即，为调节固含量所用)。
在本发明的涂布浆料中，所述PVDF胶液作为胶黏剂，为涂布浆料提供粘结力，使涂层浆料可以牢固的粘接在隔膜表面。所述PVDF胶液含量占料浆重量5-10％。当胶黏剂过少粘结性差，胶黏剂过多对透气影响大。
所述聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水作为分散剂，使物料分散更均匀稳定。
静电消除剂可改减小涂层膜静电含量。
酒精、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇等可改善所述涂布浆料的气泡含量(为了便于描述，下文也称为“消泡剂”)。
本发明的涂布浆料配方相较于现有的涂布浆料综合性能较好，且可针对性的对涂层膜耐热性、强度、韧性、透气、水含量、稳定性能等做改善；本发明通过对涂布浆料配方比例的控制，可达到不同的性能要求，即不同涂层涂布浆料配方配比有所不同。
所述分散剂影响产品的稳定性，而有效成份的不同以及固含量的不同对分散剂的需求量不同。涂层厚度及涂布浆料种类的不同对隔膜产品的耐热性能及强度有较大影响，对电池的安全性能如耐热性能及耐锂枝晶穿透能力有不同改善。
根据本发明，在所述锂离子电池隔膜的一面上，至少包括两层由所述涂布浆料形成的涂层膜。另外，所述锂离子电池隔膜的任意一涂层所用涂布浆料与其它层所用涂布浆料的种类可以相同或不同。例如，相邻两层涂料层所采用的涂布浆料的种类可以相同或不同，优选为不同。
本发明中，优选情况下，所述锂离子电池隔膜的基材为聚丙烯、聚乙烯、无纺布、PMIA(间位芳香族聚酰胺)或纤维膜。
按照本发明，所述多种涂层的锂离子电池隔膜具体可以具有如下的结构：
SiO 2涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层；
Al 2O 3涂层-SiO 2涂层-PP隔膜-SiO 2涂层-Al 2O 3涂层；
PTFE涂层-Al 2O 3涂层-PMIA隔膜-PTFE涂层-Al 2O 3涂层；
Al 2O 3涂层-Al 2O 3涂层-无纺布隔膜-SiO 2涂层-SiO 2涂层；
PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-ZrO 2涂层；
PTFE涂层-ZrO 2涂层-PE隔膜；
PVDF涂层-Al 2O 3涂层-PE隔膜；
SiO 2涂层-ZrO 2涂层-PE隔膜-Al 2O 3涂层；
PVDF涂层-ZrO 2涂层-PE隔膜-ZrO 2涂层；
PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-Al 2O 3涂层-ZrO 2涂层。
根据本发明的第二方面，本发明提供了所述的耐高温多种涂层的锂离子电池隔膜的制备方法，包括以下步骤：
A、涂布浆料的制备：按比例准备原料，配制成Al 2O 3陶瓷涂布浆料、PVDF涂布浆料、PTFE涂布浆料、ZrO 2陶瓷涂布浆料或SiO 2涂布浆料，备用；
B、电池隔膜的预处理：采用流量为0.5-5L/min的臭氧对隔膜进行预处理5-120s，备用；
C、涂布：将预处理后的隔膜进行单面或双面涂布，控制涂布速度5-20m/min，控制涂布后的涂层厚度为1-5μm，烘干，得到涂层膜，然后对涂层膜的单面或双面进行上述涂布、烘干操作，至达到所需涂层数，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为5-10s收卷，得到耐高温多种涂层的锂离子电池隔膜。
步骤B中，所述预处理时间为5-120s，其中，预处理时间过短会影响隔膜表面附着力以及涂层外观质量，预处理时间过长会影响隔膜自身强度和性能。
步骤C中，可以选用浸渍涂布、微凹涂布、浸渍和微凹组合式涂布的方式进行多层复合涂布。例如，在隔膜的单面或者双面涂布一种涂布浆料，然后在涂层膜的单面或者双面再次涂布其它种类的涂布浆料，或者隔膜两面分别涂布不同种类的涂布浆料，在涂布的时候，可以是只浸渍涂布、只微凹涂布或者第一次选用浸渍涂布、第二次选用微凹涂布，或者第一次选用微凹涂布、第二次选用浸渍涂布。
步骤C中，优选情况下，所述烘干的温度为50-70℃，烘干时间为0.6-1.8min。更优选采用分段式烘干，所述分段式烘干可通过多段烘箱实施，多段烘箱能方便调节温度和进排风频率，使烘干效果更好。
进一步优选地，在上一次涂布完成后，进行下一次涂布之前，对烘干后的涂层膜用氮气进行气体冲洗1-2s，然后再进行涂布。本发明的发明人通过深入研究发现，氮气冲洗可以降低隔膜应用过程中的收缩率，收缩率相较于未经过该特殊处理的隔膜，收缩率降低10％以上，提高隔膜的吸液率，同时氮气冲洗提高了其高温熔体完整性，相较于未经过该特殊处理的隔膜，高温熔体完整性提高15％以上，原因分析其改善了隔膜结构，使得隔膜的整体性能更好。
步骤D中，经过电晕处理主要目的是改善隔膜表面亲水性，提高隔膜表面对涂布浆料的吸液性能。若亲水性较差，隔膜对涂布浆料的吸附能力较差，涂层的粘剂性能及外观质量较差。电晕时间过长会对隔膜的强度及性能造成影响。
步骤D中，所述电晕处理采用高频交流电压5000-15000V/m 2，其原理是利用高频率高电压在被处理的塑料表面电晕放电(高频交流电压高达5000-15000V/m 2)，而产生低温等离子体，使隔膜表面产生游离基反应而使聚合物发生交联。表面变粗糙并增加其对极性溶剂的润湿性-这些离子体由电击和渗透进入被印体的表面破坏其分子结构，进而将被处理的表面分子氧化和极化，离子电击侵蚀 表面，以致增加承印物表面的附着能力。
在制备多种涂层的锂离子电池隔膜时，本发明的隔膜被设置在放卷轴上，由放卷轴释放隔膜，向收卷轴方向移动，在这个过程中隔膜经过所述涂布、烘干、电晕处理，最后被收卷轴收卷，得到最终产品。在这个过程中，优选控制放卷轴对隔膜的放卷张力为15-30N，放卷张力过大，涂层膜容易拉伸变形，放卷张力过小，容易造成漏涂和过程不稳定。控制烘干过程中涂层隔膜的张力保持在7-15N，张力过大，涂层膜容易变形和卷边；张力过小，过程中容易跑偏和不稳定。控制收卷时，收卷张力为4-12N，收卷张力过大容易翘边和暴筋以及造成涂层膜内应力过大造成形变，收卷张力过小容易造成收卷端面不平整和产品松卷。以下实施例按照该方法对隔膜的张力进行控制。
步骤A中，为了得到体系稳定、分散均匀、固含量适当的涂布浆料，优选对各组分的添加顺序进行控制，例如，为了避免出现团聚和分散不好现象，优选先加水再加入粉体，所述分散剂和增稠剂等的添加需要根据粉体浆料的分散情况和粘度情况进行添加。具体地，优选情况下，所述涂布浆料的制备包括以下步骤，
在同时具有超声波振荡功能的真空、高速、行星搅拌设备中加入N-甲基吡咯烷酮和三氧化二铝(Al 2O 3)、二氧化锆(ZrO 2)、二氧化硅(SiO 2)、PVDF和PTFE中的至少一种粉末，该粉末与N-甲基吡咯烷酮的重量比为(10-30)：(60-80)，高速搅拌同时超声波振荡0.5-2h，得到料浆；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的0.5-5％；加入静电消除剂，加入量为料浆的0.3-0.5％，高速搅拌同时超声波振荡0.5-2h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的0.5-10％；高速搅拌同时超声波振荡0.5-2h；
加入料浆量5-10％的PVDF胶液，加入料浆量0.3-0.5％的羧甲基纤维素钠，高速搅拌同时超声波振荡0.5-2h；
结合涂布浆料所需的固含量，在向料浆加入上述组分后，检测其固含量来确定否加入NMP溶剂，同时高速搅拌同时超声波振荡0.5-2h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.5-1h，然后关闭真空平衡大气压后放出料浆过筛，备用。
更优选地，控制所述高速搅拌的转速大于1000r/min。
步骤A中，优选情况下，三氧化二铝、二氧化锆、二氧化硅、PVDF、PTFE粉末的粒径分别为0.05-1.0μm。
按照一种具体的优选实施方式，所述Al 2O 3涂布浆料可通过以下方法制得：
在同时具有超声波振荡功能的真空、高速的行星搅拌设备中加入N-甲基吡咯烷酮和三氧化二铝粉末，该粉末与N-甲基吡咯烷酮的重量比为10：60，高速搅拌同时超声波振荡0.5h，得到料浆；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的0.5％；加入静电消除剂，加入量为料浆的0.3％，高速搅拌同时超声波振荡0.5h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的0.5％；高速搅拌同时超声波振荡0.5h；
加入料浆量5％的PVDF胶液，加入料浆量0.3％的羧甲基纤维素钠；高速搅拌同时超声波振荡0.5h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.5h，然后关闭真空平衡大气压后放出料浆过筛，备用。
按照一种具体的优选实施方式，所述SiO 2涂布浆料的制备：
在同时具有超声波振荡功能的真空、高速、行星搅拌设备中加入N-甲基吡咯烷酮和二氧化硅粉 末，该粉末与N-甲基吡咯烷酮的重量比为20：70，高速搅拌同时超声波振荡1h，得到料浆；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的1％；加入静电消除剂，加入量为料浆的0.4％，高速搅拌同时超声波振荡1h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的1％；高速搅拌同时超声波振荡1h；
加入料浆量6％的PVDF胶液，加入料浆量0.4％的羧甲基纤维素钠；高速搅拌同时超声波振荡1h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.8h，然后关闭真空平衡大气压后放出料浆过筛，备用。
按照一种具体的优选实施方式，所述ZrO 2涂布浆料的制备：
在同时具有超声波振荡功能的真空、高速的行星搅拌设备中加入N-甲基吡咯烷酮和二氧化锆粉末，该粉末与N-甲基吡咯烷酮的重量比为30：80，高速搅拌同时超声波振荡2h，得到浆料；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的5％；加入静电消除剂，加入量为料浆的0.5％，高速搅拌同时超声波振荡2h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的10％；高速搅拌同时超声波振荡2h；
加入料浆量10％的PVDF胶液，加入料浆量0.5％的羧甲基纤维素钠；高速搅拌同时超声波振荡2h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌1h，然后关闭真空平衡大气压后放出料浆过筛，备用；
按照一种具体的实施方式，所述PVDF涂布浆料的制备：
在同时具有超声波振荡功能的真空、高速、行星搅拌设备中加入N-甲基吡咯烷酮和PVDF粉末，该粉末与N-甲基吡咯烷酮的重量比为15：75，高速搅拌同时超声波振荡1.5h，得到料浆；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的3％；加入静电消除剂，加入量为料浆的0.35％，高速搅拌同时超声波振荡1.5h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的5％；高速搅拌同时超声波振荡1.5h；
加入料浆量8％的PVDF胶液，加入料浆量0.35％的羧甲基纤维素钠；高速搅拌同时超声波振荡1.5h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.7h，然后关闭真空平衡大气压后放出料浆过筛，备用。
按照一种具体的优选实施方式，所述PTFE涂布浆料的制备：
在同时具有超声波振荡功能的真空、高速的行星搅拌设备中加入N-甲基吡咯烷酮和PTFE粉末，该粉末与N-甲基吡咯烷酮的重量比为25：68，高速搅拌同时超声波振荡1.3h，得到料浆；
向料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的2％；加入静电消除剂，加入量为料浆的0.45％，高速搅拌同时超声波振荡1.3h；
加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的8％；高速搅拌同时超声波振荡1.3h；
加入料浆量9％的PVDF胶液，加入料浆量0.45％的羧甲基纤维素钠；高速搅拌同时超声波振荡0.13h；
调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.9h，然后关闭真空平衡大气压 后放出料浆过筛，备用。
本发明涂层选用不同种涂料涂层与用一种涂料涂层相比可针对性的改善涂层膜的综合性能，将不同涂层的优势进行结合，具有协同增效的作用，电池隔膜的性能更好。
下面的实施例对本发明的特点做进一步的说明，但本发明的内容并不受实施例的限制。另外，上述的具体的优选实施方式分别列举了本发明的不同种类涂布浆料的制备方法，除非另有说明，以下实施例提到各种涂布浆料按照对应的以上具体的优选实施方式制备。
实施例1
取一个16μm湿法PE隔膜，使用微凹辊选择湿法PE隔膜的一面涂布2μm厚度Al 2O 3涂布浆料(添加的分散剂、消泡剂分别是聚丙烯酸钠、甘油，下同)，形成涂层膜，然后在该涂层膜两面分别使用浸渍涂布装置再涂布1μm SiO 2涂布浆料(添加的分散剂、消泡剂分别为十二烷基硫酸钠、酒精，下同)，得到厚度为20μm的Al 2O 3和SiO 2两种涂布浆料涂层复合锂离子电池隔膜，其结构为SiO 2涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料和SiO 2涂布浆料，备用；
B、电池隔膜的预处理：采用流量为0.5L/min的臭氧对隔膜进行预处理120s，备用；
C、涂布：使用微凹辊将预处理后的隔膜的单面涂布Al 2O 3涂布浆料，控制涂布速度为5m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过56℃段烘干、64℃段烘干、56℃段烘干，控制烘干总用时1.2min，涂布到烘干的时间间隔为0.5s，得到涂层膜；
然后对涂层膜的双面浸渍涂布SiO 2涂布浆料，控制涂布速度10m/min，依次经过56℃段烘干、64℃段烘干、56℃段烘干，控制烘干总用时1.2min，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为5s，收卷，得到结构为SiO 2涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层的耐高温多种涂层的锂离子电池隔膜。
实施例2
取一个10μm湿法PP隔膜，使用浸渍涂布装置在湿法PP隔膜的两面涂布2μm厚的SiO 2涂布浆料，形成涂层膜，然后在该涂层膜两面分别使用浸渍涂布装置再涂布1μm Al 2O 3涂布浆料，得到厚度为16μm的SiO 2和Al 2O 3两种涂布浆料涂层复合锂离子电池隔膜，其结构为Al 2O 3涂层-SiO 2涂层-PP隔膜-SiO 2涂层-Al 2O 3涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料和SiO 2涂布浆料，备用；
B、电池隔膜的预处理：采用流量为1L/min的臭氧对隔膜进行预处理100s，备用；
C、涂布：将预处理后的隔膜的双面浸渍涂布SiO 2涂布浆料，控制涂布速度为10m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过55℃段烘干、65℃段烘干、55℃段烘干，控制烘干总用时1min，涂布到烘干的时间间隔为3s，得到涂层膜；
然后对涂层膜的双面浸渍涂布Al 2O 3涂布浆料，控制涂布速度10m/min，控制涂布后的涂层厚度为1μm，依次经过55℃段烘干、65℃段烘干、55℃段烘干，控制烘干总用时1min，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为6s，收卷，得到结构为Al 2O 3涂层-SiO 2涂层-PP隔膜-SiO 2涂层-Al 2O 3涂层耐高温多种涂层的锂离子电池隔膜。
实施例3
取一个9μm PMIA隔膜，使用微凹辊在PMIA隔膜的一面涂布2μm厚度Al 2O 3涂布浆料，在PMIA隔膜的另一面涂布1μm厚的PTFE涂布浆料(添加的分散剂、消泡剂分别是硅酸钠、酒精，下同)，形成涂层膜，然后使用微凹辊在涂层膜涂有Al 2O 3涂布浆料的一面涂布1μm厚的PTFE涂布浆料，在涂层膜涂有PTFE涂布浆料的另一面涂布2μm厚度Al 2O 3涂布浆料，得到厚度为15μm的PTFE和Al 2O 3两种涂布浆料涂层复合锂离子电池隔膜，其结构为PTFE涂层-Al 2O 3涂层-PMIA隔膜-PTFE涂层-Al 2O 3涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料和PTFE涂布浆料
B、电池隔膜的预处理：采用流量为2L/min的臭氧对隔膜进行预处理80s，备用；
C、涂布：将预处理后的隔膜的一面涂布Al 2O 3涂布浆料，另一面涂布烘干PTFE涂布浆料，控制涂布速度15m/min，控制涂布后的Al 2O 3涂层厚度为2μm，PTFE涂层厚度为12μm，烘干；
其中，采用分段式烘干处理，依次经过50℃段烘干、60℃段烘干、50℃段烘干，控制烘干总用时1.8min，涂布到烘干的时间间隔为0.5s，得到涂层膜；
然后对涂层膜涂有Al 2O 3涂层的一面微凹涂布PTFE涂层、在涂有PTFE涂层的一面微凹涂布Al 2O 3涂层，依次经过50℃段烘干、60℃段烘干、50℃段烘干，控制烘干总用时1.8min，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为7s收卷，得到结构为PTFE涂层-Al 2O 3涂层-PMIA隔膜-PTFE涂层-Al 2O 3涂层的耐高温多种涂层的锂离子电池隔膜。
另外，实施例还按照上述方法制备另一种锂离子电池隔膜，所不同的是，
在上一次涂布完成后，进行下一次涂布之前，对烘干后的涂层膜用氮气进行气体冲洗2s，然后再进行涂布。
实施例4
取一个8μm无纺布隔膜，使用微凹辊在无纺布隔膜的一面涂布2μm厚度Al 2O 3涂布浆料，在无纺布隔膜的另一面涂布1μm厚度SiO 2涂布浆料，形成涂层膜，然后使用微凹辊在涂层膜涂有Al 2O 3涂布浆料的一面涂布1μm厚度Al 2O 3涂布浆料，在涂层膜涂有SiO 2涂布浆料的另一面涂布2μm厚度SiO 2涂布浆料，得到厚度为14μm的SiO 2和Al 2O 3两种涂布浆料涂层复合锂离子电池隔膜，其结构为Al 2O 3涂层-Al 2O 3涂层-无纺布隔膜-SiO 2涂层-SiO 2涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料和SiO 2涂布浆料；
B、电池隔膜的预处理：采用流量为3L/min的臭氧对隔膜进行预处理70s，备用；
C、涂布：将预处理后的隔膜一面涂布Al 2O 3涂布浆料，另一面涂布SiO 2涂布浆料，控制涂布速度20m/min，控制涂布后Al 2O 3涂层厚度为2μm，SiO 2涂层厚度为1μm，烘干；
其中，烘干采用分段式烘干处理，依次经过53℃段烘干、62℃段烘干、53℃段烘干，控制烘干总用时0.8min，涂布到烘干的时间间隔为0.4s，得到涂层膜；
然后使用微凹辊对涂层膜涂有Al 2O 3涂布浆料的一面涂布Al 2O 3涂布浆料，在涂层膜涂有SiO 2涂布浆料的另一面涂布SiO 2涂布浆料，控制涂布速度20m/min，控制涂布后Al 2O 3涂层厚度为1μm，SiO 2涂层厚度为2μm，烘干，其中烘干采用分段式烘干处理，依次经过53℃段烘干、62℃段烘干、53℃段烘干，控制烘干总用时0.8min，涂布到烘干的时间间隔为0.4s，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为8s，收卷，得到结构为Al 2O 3涂层-Al 2O 3涂层-无纺布隔膜-SiO 2涂层-SiO 2涂层的耐高温多种涂层的锂离子电池隔膜。
本实施例相较于现有直接在无纺布隔膜两面分别直接涂布3μm Al 2O 3涂层和SiO 2涂层得到的电池隔膜，现有直接涂布得到的电池隔膜涂层与隔膜之间的粘结能力要差于本实施例的粘结能力，本发明的方法通过改善厚度涂层与隔膜之间的粘剂性，外部涂层为在内部涂层表面再次涂布，两层之 间的粘接性能较好，可减小胶黏剂对涂层膜透气性能及其它性能的影响。
实施例5
取一个10μm湿法PE隔膜，使用微凹辊在湿法PE隔膜的一面涂布2μm厚度Al 2O 3涂布浆料，在湿法PE隔膜的另一面涂布2μm厚度SiO 2涂布浆料，形成涂层膜，然后使用微凹辊在涂层膜涂有Al 2O 3涂布浆料的一面涂布2μm厚度PVDF涂布浆料(添加的分散剂、消泡剂分别是硅酸钠、聚乙烯醇，下同)，在涂层膜涂有SiO 2涂布浆料的另一面涂布2μm厚度ZrO 2涂布浆料(添加的分散剂、消泡剂分别是硅酸钠、聚乙烯醇)，得到厚度为18μm的SiO 2、Al 2O 3、ZrO 2、PVDF四种涂布浆料涂层复合锂离子电池隔膜，其结构为PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-ZrO 2涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料、SiO 2涂布浆料、PVDF涂布浆料和ZrO 2涂布浆料
B、电池隔膜的预处理：采用流量为4L/min的臭氧对隔膜进行预处理30s，备用；
C、涂布：将预处理后的隔膜的一面涂布Al 2O 3涂布浆料，另一面涂布SiO 2涂布浆料，控制涂布速度18m/min，控制涂布后的涂层厚度均为2μm，烘干；其中，烘干采用分段式烘干处理，依次经过57℃段烘干、68℃段烘干、57℃段烘干，控制烘干总用时0.6min，涂布到烘干的时间间隔为0.5s，得到涂层膜；
然后使用微凹辊对涂层膜涂有Al 2O 3涂布浆料的一面涂布PVDF涂布浆料，在涂层膜涂有SiO 2涂布浆料的另一面涂布ZrO 2涂布浆料，控制涂布速度18m/min，控制涂布后的涂层厚度均为2μm，依次经过57℃段烘干、68℃段烘干、57℃段烘干，控制烘干总用时0.6min，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为8s，收卷，得到结构为PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-ZrO 2涂层的耐高温多种涂层的锂离子电池隔膜；该电池隔膜的性能如表3所示。
另外，实施例还按照上述方法制备另一种锂离子电池隔膜，所不同的是，
进一步的在上一次涂布完成后，进行下一次涂布之前，对烘干后的涂层膜用氮气进行气体冲洗1.5s，然后再进行涂布。
实施例6
取一个10μm湿法PE隔膜，使用微凹辊在湿法PE隔膜的一面涂布2μm厚度ZrO 2涂布浆料，形成涂层膜，使用微凹辊在涂层膜涂有ZrO 2涂布浆料的一面涂布2μm厚度PTFE涂布浆料，得到厚度为14μm的ZrO 2、PTFE两种涂布浆料涂层复合锂离子电池隔膜，其结构为PTFE涂层-ZrO 2涂层-PE隔膜。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备PTFE涂布浆料和ZrO 2涂布浆料；
B、电池隔膜的预处理：采用流量为5L/min的臭氧对隔膜进行预处理5s，备用；预处理时间过短会影响隔膜表面附着力以及涂层外观质量，预处理时间过长会影响隔膜自身强度和性能；
C、涂布：将预处理后的隔膜的一面涂布ZrO 2涂布浆料，控制涂布速度13m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过58℃段烘干、62℃段烘干、58℃段烘干，控制烘干总用时1.4min，涂布到烘干的时间间隔为0.2s，得到涂层膜；
然后对涂层膜涂有ZrO 2涂布浆料的一面涂布PTFE涂布浆料，控制涂布速度10m/min，依次经过58℃段烘干、62℃段烘干、58℃段烘干，控制烘干总用时1.4min，涂布到烘干的时间间隔为0.2s，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为8s收卷，得到结构为PTFE 涂层-ZrO 2涂层-PE隔膜的耐高温多种涂层的锂离子电池隔膜。
实施例7
取一个12μm湿法PE隔膜，使用微凹辊在湿法PE隔膜的一面涂布2μm厚度ZrO 2涂布浆料，在湿法PE隔膜的另一面涂布1μm厚度Al 2O 3涂布浆料，形成涂层膜；使用微凹辊在涂层膜涂有ZrO 2涂布浆料的一面涂布2μm厚度SiO 2涂布浆料，得到厚度为17μm的ZrO 2、Al 2O 3、SiO 2三种涂布浆料涂层复合锂离子电池隔膜，其结构为SiO 2涂层-ZrO 2涂层-PE隔膜-Al 2O 3涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料、SiO 2涂布浆料和ZrO 2涂布浆料；
B、电池隔膜的预处理：采用流量为4.5L/min的臭氧对隔膜进行预处理20s，备用；
C、涂布：将预处理后的隔膜一面涂布ZrO 2涂布浆料，另一面涂布Al 2O 3涂布浆料，控制涂布速度8m/min，控制涂布后的ZrO 2涂层厚度为2μm，Al 2O 3涂层厚度为1μm，烘干；
其中，烘干采用分段式烘干处理，依次经过60℃段烘干、70℃段烘干、60℃段烘干，控制烘干总用时1.1min，涂布到烘干的时间间隔为0.3s，得到涂层膜；
然后对涂层膜涂有ZrO 2涂层的一面涂布SiO 2涂布浆料，控制涂布速度8m/min，控制涂布后的SiO 2涂层厚度为2μm，依次经过60℃段烘干、70℃段烘干、60℃段烘干，控制烘干总用时1.1min，涂布到烘干的时间间隔为0.3s，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为9s收卷，得到结构为SiO 2涂层-ZrO 2涂层-PE隔膜-Al 2O 3涂层的耐高温多种涂层的锂离子电池隔膜。
实施例8
取一个12μm湿法PE隔膜，用浸渍装置在湿法PE隔膜的两面浸渍涂布2μm厚度ZrO 2涂布浆料，形成涂层膜，然后使用微凹辊在涂层膜任意一面涂布2μm厚度PVDF涂布浆料，得到厚度为18μm的ZrO 2、PVDF两种涂布浆料涂层复合锂离子电池隔膜，其结构为PVDF涂层-ZrO 2涂层-PE隔膜-ZrO 2涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备PVDF涂布浆料和ZrO 2涂布浆料；
B、电池隔膜的预处理：采用流量为3.5L/min的臭氧对隔膜进行预处理80s，备用；预处理时间过短会影响隔膜表面附着力以及涂层外观质量，预处理时间过长会影响隔膜自身强度和性能；
C、涂布：将预处理后的隔膜进行双面涂布ZrO 2涂布浆料，控制涂布速度16m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过51℃段烘干、69℃段烘干、51℃段烘干，控制烘干总用时0.9min，涂布到烘干的时间间隔为0.4s，得到涂层膜；
然后对涂层膜的任意一面涂布PVDF涂布浆料，控制涂布速度16m/min，控制涂布后的涂层厚度为2μm，烘干，其中烘干采用分段式烘干处理，依次经过51℃段烘干、69℃段烘干、51℃段烘干，控制烘干总用时0.9min，涂布到烘干的时间间隔为0.4s，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为10s收卷，得到结构为PVDF涂层-ZrO 2涂层-PE隔膜-ZrO 2涂层的耐高温多种涂层的锂离子电池隔膜。
实施例还按照上述方法制备另一种锂离子电池隔膜，所不同的是，进一步的在上一次涂布完成后，进行下一次涂布之前，对烘干后的涂层膜用氮气进行气体冲洗1.5s，然后再进行涂布。
实施例9
取一个10μm湿法PE隔膜，使用微凹辊在湿法PE隔膜的一面涂布2μm厚度SiO 2涂布浆料， 形成涂层膜，然后用浸渍装置在涂层膜的两面涂布1μm厚度Al 2O 3涂布浆料，再使用微凹辊在涂层膜涂有Al 2O 3涂布浆料的两面分别涂布2μm厚度PVDF涂布浆料和ZrO 2涂布浆料，得到厚度为18μm的SiO 2、Al 2O 3、ZrO 2、PVDF四种涂布浆料涂层复合锂离子电池隔膜，其结构为PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-Al 2O 3涂层-ZrO 2涂层。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料、SiO 2涂布浆料、ZrO 2涂布浆料、PVDF涂布浆料；
B、电池隔膜的预处理：采用流量为2.5L/min的臭氧对隔膜进行预处理90s，备用；
C、涂布：将预处理后的隔膜的一面涂布SiO 2涂布浆料，控制涂布速度14m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过57℃段烘干、66℃段烘干、57℃段烘干，控制烘干总用时1.4min，涂布到烘干的时间间隔为0.3s，得到涂层膜；
然后对涂层膜的双面浸渍涂布Al 2O 3涂布浆料，控制涂布后的涂层厚度为1μm，依次经过57℃段烘干、66℃段烘干、57℃段烘干，控制烘干总用时1.4min，涂布到烘干的时间间隔为0.3s，得到涂层膜；
再使用微凹辊在该涂层膜的双面分别涂布PVDF涂布浆料和ZrO 2涂布浆料，控制涂布后的涂层厚度为2μm，依次经过57℃段烘干、66℃段烘干、57℃段烘干，控制烘干总用时1.4min，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为8s收卷，得到结构为PVDF涂层-Al 2O 3涂层-PE隔膜-SiO 2涂层-Al 2O 3涂层-ZrO 2涂层的耐高温多种涂层的锂离子电池隔膜。
实施例10
取一个16μm湿法PE隔膜，使用微凹辊在湿法PE隔膜的一面涂布2μm厚度Al 2O 3涂布浆料，形成涂层膜，使用微凹辊在涂层膜涂有Al 2O 3涂布浆料的一面涂布2μm厚度PVDF涂布浆料，得到厚度为20μm的Al 2O 3、PVDF两种涂布浆料涂层复合锂离子电池隔膜，其结构为PVDF涂层-Al 2O 3涂层-PE隔膜，该隔膜的微观形貌如图1至图6所示。
本实施例锂离子电池隔膜的制备方法为：
A、涂布浆料的制备：制备Al 2O 3涂布浆料和PVDF涂布浆料；
B、电池隔膜的预处理：采用流量为5L/min的臭氧对隔膜进行预处理5s，备用；
C、涂布：将预处理后的隔膜的一面涂布Al 2O 3涂布浆料，控制涂布速度10m/min，控制涂布后的涂层厚度为2μm，烘干；
其中，烘干采用分段式烘干处理，依次经过55℃段烘干、60℃段烘干、58℃段烘干，控制烘干总用时1.2min，涂布到烘干的时间间隔为0.4s，得到涂层膜；
然后对涂层膜涂有Al 2O 3涂布浆料的一面涂布PVDF涂布浆料，控制涂布速度10m/min，依次经过55℃段烘干、60℃段烘干、55℃段烘干，控制烘干总用时1.4min，涂布到烘干的时间间隔为0.2s，备用；
D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为8s收卷，得到结构为PVDF涂层-Al 2O 3涂层-PE隔膜的耐高温多种涂层的锂离子电池隔膜。
对比例1
按照实施例6的方法制备电池隔膜，所不同的是，步骤C中，仅在预处理后的隔膜的一面涂布ZrO 2涂布浆料并烘干；从而得到结构为ZrO 2涂层-PE隔膜的锂离子电池隔膜。
性能测试
以上实施例和对比例制备的电池隔膜的透气度按照ISO 5636，采用Gurley4340型透气度仪测试；热收缩率按照ISO 14616测试；拉伸性能按照GB/T1040.3测试；隔膜离子电导率通过电化学工作站 测试。
表1
Figure PCTCN2018076683-appb-000001
表2
Figure PCTCN2018076683-appb-000002
表1和表2中，基膜是指没有涂布浆料的裸电池隔膜。
另外，实施例3、实施例5、实施例8经过进一步的氮气处理得到的电池隔膜，收缩率(90℃*2h)的纵向值分别为0.6％、0.61％、0.7％，横向值分别为0.15％、0.13％、0.14％，收缩率(130℃*1h)的纵向值分别为1.7％、1.6％、1.68％，横向值分别为1.5％、1.4％、1.57％，TMA法在250℃下的高温熔体完整性分别为49％、45％、44％；与表1和2相应的数据比较可知，氮气冲洗可以降低隔膜应用过程中的收缩率，收缩率相较于未经过该特殊处理的隔膜，收缩率降低10％以上，提高隔膜的吸液率，同时氮气冲洗提高了其高温熔体完整性，相较于未经过该特殊处理的隔膜，高温熔体完整性提高15％以上，原因分析其改善了隔膜结构，使得隔膜的整体性能更好。
循环性能：
将实施例6的多种涂层锂离子电池隔膜、对比例1、对比例2的电池隔膜，分别与LiCoO 2，金属锂组装成半电池来考察其电性能。考察结果为，电池在0.5C倍率下首次放电容量分别为137.2mAh·g -1、142.7mAh·g -1，经过50个循环后，电池容量衰减为133.1mAh·g -1、127.9mAh·g -1，容量保持率分别为97.01％、89.6％，平均衰减量分别为0.082mAh·g -1、0.296mAh·g -1，可见用本发明的具有多种涂层的锂离子电池隔膜组装的电池性能稳定。
综上可知，本发明提供的锂离子电池隔膜兼具使用安全性和耐高温性能，其中的涂布浆料既能够发挥陶瓷涂层的安全性功能，也能够起到粘附作用，应用于电动车领域的电池中，能够提高电池的安全性和寿命。本发明提供的制备方法为生产耐高温多种涂层锂离子电池隔膜提供了较为成熟稳定的生产工艺，该生产工艺中针对耐高温多种涂层锂离子电池的机构进行各个工序的布置，涂布工序与烘干工序之间的间隔时间能使最终产品品质较高且稳定。
另外，普通涂层隔膜在130℃下严重变形，而本发明的复合锂离子电池隔膜在200℃下仍可保持完好的形态，耐热性能更好，电池隔膜在130℃条件下保持1h后的收缩率为MD<2.5，TD<2.4，热性能明显优于普通涂布隔膜；厚度为22μm左右的普通双面涂层隔膜透气值一般在300-380s/100mL左右，而本发明的复合锂离子电池隔膜透气值小于280s/100mL，该数值的意义为一定面积的隔膜在一定压力下通过一定量气体需要的时间，透气值越大说明隔膜内阻越大，透气值小些内阻小，充放电速度更快，明显优于普通涂层隔膜；并且，具有多种涂层的电池隔膜的锂离子电池的离子电导率也较高，电池的充放电性能更好。

Claims (11)

  1. 一种耐高温多种涂层的锂离子电池隔膜，包括由单面或双面涂布有涂布浆料的电池隔膜构成的涂层膜，其特征在于，在涂层膜的单面或双面还涂布有浆料附加层，所述浆料附加层包括至少一层由涂布浆料构成的涂层，所述涂布浆料按质量百分比计，包括由重量比为(10-30)：(60-80)的涂层浆料和N-甲基吡咯烷酮组成的料浆，占料浆重量0.5-5％的聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，占料浆重量0.3-0.5％的静电消除剂，占料浆重量0.5-10％的酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，占料浆重量5-10％的PVDF胶液，占料浆重量0.3-0.5％的羧甲基纤维素钠，占料浆重量≥0％的NMP溶剂。
  2. 根据权利要求1所述的耐高温多种涂层的锂离子电池隔膜，其特征在于，所述涂层浆料为Al 2O 3陶瓷浆料、PVDF浆料、PTFE浆料、ZrO 2陶瓷浆料或SiO 2浆料。
  3. 根据权利要求2所述的耐高温多种涂层的锂离子电池隔膜，其特征在于，所述锂离子电池隔膜的任意一涂层所用涂布浆料与其它层所用的涂布浆料为相同或不同种类的涂布浆料。
  4. 根据权利要求1所述的耐高温多种涂层的锂离子电池隔膜，其特征在于，所述锂离子电池隔膜的基材为聚丙烯、聚乙烯、无纺布、PMIA或纤维膜。
  5. 一种如权利要求1所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，包括以下步骤：
    A、涂布浆料的制备：按比例准备原料，配制成Al 2O 3陶瓷涂布浆料、PVDF涂布浆料、PTFE涂布浆料、ZrO 2陶瓷涂布浆料或SiO 2涂布浆料，备用；
    B、电池隔膜的预处理：采用流量为0.5-5L/min的臭氧对隔膜进行预处理5-120s，备用；
    C、涂布：将预处理后的隔膜进行单面或双面涂布，控制涂布速度5-20m/min，控制涂布后的涂层厚度为1-5μm，烘干，得到涂层膜，然后对涂层膜的单面或双面进行上述涂布、烘干操作，至达到所需涂层数，备用；
    D、成品制备：将完成涂布的电池隔膜进行电晕处理，处理时间为5-10s收卷，得到耐高温多种涂层的锂离子电池隔膜。
  6. 根据权利要求5所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，涂布时，选用浸渍涂布、微凹涂布或浸渍与微凹组合式涂布的方式进行多层复合涂布。
  7. 根据权利要求5所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，烘干的温度为50-70℃，烘干时间为0.6-1.8min。
  8. 根据权利要求5所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，涂布浆料的制备包括以下步骤：
    在同时具有超声波振荡功能的真空、高速、行星搅拌设备中加入N-甲基吡咯烷酮和三氧化二铝、二氧化锆、二氧化硅、PVDF和PTFE中的至少一种粉末，该粉末与N-甲基吡咯烷酮的重量比为(10-30)：(60-80)，高速搅拌同时超声波振荡0.5-2h，得到料浆；
    向所述料浆中加入聚丙烯酸钠、多偏磷酸钠、正磷酸钠、硅酸钠、十二烷基硫酸钠和氨水中的至少一种，加入量为料浆的0.5-5％；加入静电消除剂，加入量为料浆的0.3-0.5％，高速搅拌同时超 声波振荡0.5-2h；
    加入酒精、丙烯碳酸酯、甘油、二甲基亚砜、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚和聚乙烯醇中的至少一种，加入量为料浆的0.5-10％；高速搅拌同时超声波振荡0.5-2h；
    加入料浆量5-10％的PVDF胶液，加入料浆量0.3-0.5％的羧甲基纤维素钠；高速搅拌同时超声波振荡0.5-2h；
    检测浆料固含量，加入浆料量≥0％的NMP溶剂，高速搅拌同时超声波振荡0.5-2h；
    调低转速至500r/min以下，关闭超声波振荡，开启真空，搅拌0.5-1h，然后关闭真空平衡大气压后放出料浆过筛，备用。
  9. 根据权利要求8所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，三氧化二铝、二氧化锆、二氧化硅、PVDF、PTFE粉末的粒径分别为0.05-1.0μm。
  10. 根据权利要求8所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，控制高速搅拌的转速大于1000r/min。
  11. 根据权利要求5-10中任意一项所述的耐高温多种涂层的锂离子电池隔膜的制备方法，其特征在于，步骤C中，在上一次涂布完成后，进行下一次涂布之前，对烘干后的涂层膜用氮气进行气体冲洗1-2s。
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