WO2022016630A1 - 水性高分子功能浆料及其制备方法和应用 - Google Patents

水性高分子功能浆料及其制备方法和应用 Download PDF

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WO2022016630A1
WO2022016630A1 PCT/CN2020/108564 CN2020108564W WO2022016630A1 WO 2022016630 A1 WO2022016630 A1 WO 2022016630A1 CN 2020108564 W CN2020108564 W CN 2020108564W WO 2022016630 A1 WO2022016630 A1 WO 2022016630A1
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slurry
water
grinding
polymer functional
preparation
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PCT/CN2020/108564
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English (en)
French (fr)
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张海明
林妙云
邱钧锋
李越旺
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佛山市金辉高科光电材料股份有限公司
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Publication of WO2022016630A1 publication Critical patent/WO2022016630A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention is in the technical field of polymer materials, in particular to a water-based polymer functional slurry and its preparation method and application.
  • lithium-ion batteries are mainly composed of four key components: positive electrode, negative electrode, separator and electrolyte.
  • the main function of the separator is to prevent the short circuit caused by the contact between the positive and negative electrodes inside the battery, and to provide a transmission channel for lithium ions between the positive and negative electrodes.
  • the separator is not the active component of the lithium-ion battery, its quality directly affects the internal resistance, capacity, cycle life and safety of the entire lithium-ion battery.
  • Polyolefin is the most widely used material in the field of lithium battery separators, but polyolefin separators also have shortcomings such as low thermal stability and poor wettability to electrolytes, which in turn affect the capacity, cycle life, rate charge-discharge and safety performance of lithium batteries. .
  • the development research on improving the performance of the polyolefin lithium battery separator is mainly to improve its surface properties, and the main research direction to improve the surface properties of the separator is to coat the separator.
  • the design and preparation of the functional slurry for separator coating is the key factor to determine the quality of the coated separator.
  • the coated separator coated with the functional slurry with good performance can effectively improve the comprehensive performance of lithium batteries.
  • the thermal shrinkage resistance of the separator can be effectively improved, thereby improving the safety and thermal stability of the battery.
  • the liquid-holding performance and the pole piece bonding performance of the separator can be significantly improved.
  • Mastering the preparation technology and coating technology of lithium-ion battery separator functional coating slurry plays an important role in enhancing the overall competitiveness of self-developed lithium-ion battery separators and improving the structure of the industrial chain.
  • the inorganic functional components are ceramic powders such as alumina, boehmite, and magnesium oxide, whose main function is to improve the thermal stability of the polyolefin separator;
  • the organic functional components are PMMA (polymethyl methacrylate), PVDF ( Polyvinylidene fluoride), PVDH-HPF (polyvinylidene fluoride-hexafluoropropylene copolymer), aramid and other high molecular polymers, different functional components can be selected to make different functional slurries, and then different functional pastes can be obtained after coating.
  • Functional lithium battery separator The organic functional polymer-coated separator has good wettability and liquid retention to the electrolyte, which can effectively bond the separator and the pole piece, increase the cycle performance of the battery, and significantly improve the safety of the battery.
  • the existing organic functional polymer-coated separators of lithium ion batteries are generally coated with oily functional slurry. Although the oily functional slurry is coated with good adhesion, it is prone to blocking pores and poor ventilation. N-methylpyrrolidone, dimethylacetamide, acetone, etc. are used as organic solvents, which are expensive, pollute the environment, and harm the health of operators, and become unsafe factors in the production and use of slurry.
  • water-based organic polymer functional slurries have become the focus of research. Compared with oil-based functional slurries, water-based slurries use water as a solvent, which has the advantages of low production cost and less environmental pollution.
  • the water-based polymer functional slurry obtained by the process has problems such as poor storage performance and short shelf life of the slurry system; and the water-based polymer functional slurry uses a lot of wetting and dispersing agents, and the adhesion performance is weakened. There are problems such as softness and poor thermocompression bonding with the pole piece. Therefore, it is necessary to study and optimize the formulation design and preparation process of water-based polymer functional slurry to improve the stability of the slurry and improve the adhesion.
  • the purpose of the present invention is to provide a preparation method of water-based polymer functional slurry with simple process and high production efficiency, which has excellent storage stability, excellent quality stability, and has good wettability and preservation of electrolyte.
  • the water-based polymer functional slurry with liquid, strong adhesion to the pole piece and greatly improved safety can be used to coat lithium battery separators.
  • a preparation method of water-based polymer functional slurry comprising the following steps:
  • the mass percentages of the polymer material, the deflocculating water-based dispersant and the water I in the dispersing slurry are respectively 30%-60%, 1%-5% and 35%-70%;
  • the mass percentages of the dispersing slurry, the volume-hindered aqueous dispersant and the grinding medium in the grinding slurry are: 39.9%-78.5%, 0.1%-1.5% and 20%-60% respectively;
  • the mass percentages of the abrasive slurry, wetting agent, binder and water II in the aqueous polymer functional slurry are respectively: 30%-80%, 0.1%-0.5%, 0.5%-2.5% and 17% -69.4%;
  • the deflocculating water-based dispersant is selected from one or more of polyacrylate and phosphoric acid ester;
  • the volume sterically hindered aqueous dispersant is selected from one or more of block copolymers of polyurethane and copolymers of polyacrylates.
  • the polyacrylate copolymer is a polyacrylate terpolymer.
  • the polyacrylate copolymer is a hydrophobically modified polyacrylate copolymer.
  • the mass percentages of the polymer material, the deflocculating aqueous dispersant and the water I in the dispersing slurry are 40%-45%, 1%-5% and 50%-55%, respectively. %.
  • the mass percentages of the dispersing slurry, the volume-hindered aqueous dispersant and the grinding medium in the grinding slurry are: 40%-50%, 0.8%-1.0% and 49%-59.2%, respectively. .
  • the mass percentages of the abrasive slurry, wetting agent, binder and water II in the aqueous polymer functional slurry are respectively: 40%-50%, 0.2%-0.3%, 0.8% %-1.2% and 48.5%-59%.
  • the polymer material is selected from polytetrafluoroethylene, polyvinylidene fluoride homopolymer, polyvinylidene fluoride copolymer, polymethyl methacrylate homopolymer, polymethyl methacrylate One or more of ester copolymer, water-based polyimide, aramid, polyethylene oxide.
  • the polymer material is selected from one or both of polyvinylidene fluoride homopolymer and polyvinylidene fluoride copolymer synthesized by emulsion polymerization.
  • the deflocculating aqueous dispersant is selected from one or more of polyacrylates and phosphates.
  • the water I is ultrapure water; at 25° C., the water I has a resistivity of 5M ⁇ cm-15M ⁇ cm, and a pH value of 6.0-8.0.
  • the dispersion slurry is prepared under stirring, and the process parameters are as follows:
  • the rotating speed is 1000r/min-2500r/min, the time is 20min-40min, and the temperature is 20°C-60°C.
  • the process parameters for preparing the dispersion slurry are as follows:
  • the rotating speed is 1800r/min-2000r/min, the time is 25min-30min, and the temperature is 25°C-30°C.
  • a specific feeding sequence is selected, and the feeding sequence is part of water I, deflocculating water-based dispersant, macromolecular material, and the balance of water I. .
  • the volume sterically hindered aqueous dispersant is selected from one or two of bentonite and hydrophobically modified polyacrylic acid copolymer.
  • the grinding medium is selected from one or more of glass beads, alumina grinding balls, zirconia beads, yttrium-stabilized zirconia beads, and cerium zirconia beads.
  • the particle size of the grinding medium is 0.5mm-10mm.
  • the grinding medium is selected from one of zirconia beads and cerium-stabilized zirconia beads, and the particle size is 0.5mm-10mm.
  • the grinding slurry is prepared under stirring, and the process parameters are as follows:
  • the rotating speed is 800r/min-2000r/min, the time is 30min-240min, and the temperature is 10°C-40°C.
  • the process parameters for preparing the grinding slurry are as follows:
  • the speed is 1200r/min-1500r/min, the time is 60min-120min, and the temperature is 15°C-20°C.
  • a specific feeding sequence is adopted, and the feeding sequence is the grinding medium, the above-mentioned dispersing slurry, and the volume sterically hindered aqueous dispersant.
  • the wetting agent is selected from the group consisting of alkyl sulfate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, and polyether modified polydimethylsiloxane. or more.
  • the adhesive is selected from one or more of waterborne polyurethane, waterborne epoxy resin, and waterborne polymethyl acrylate adhesive.
  • the water II is ultrapure water; at 25° C., the resistivity of the water II is >10 M ⁇ cm, and the pH value is 6.5-7.0.
  • the aqueous polymer functional slurry is prepared under stirring, and the process parameters are as follows:
  • the rotating speed is 200r/min-500r/min, the time is 10min-40min, and the temperature is 20°C-30°C.
  • the process parameters for preparing the aqueous polymer functional slurry are as follows:
  • the speed is 300r/min-350r/min, the time is 20min-30min, and the temperature is 20°C-30°C.
  • a specific feeding sequence is adopted, and the feeding sequence is grinding slurry, wetting agent, binder and water II in sequence.
  • the present invention also provides the water-based polymer functional slurry prepared by the above-mentioned preparation method of the water-based polymer functional slurry.
  • the present invention also provides the application of the above-mentioned aqueous polymer functional slurry in preparing the modified lithium battery separator.
  • the present invention has the following beneficial effects:
  • the preparation method of the aqueous polymer functional slurry provided by the present invention includes: mixing a specific amount of polymer material, a deflocculating type aqueous dispersant and water I to prepare a dispersion slurry; The aqueous dispersant and the grinding medium are mixed to prepare a grinding slurry; and the grinding slurry is mixed with a wetting agent, a binder, and water II to prepare an aqueous polymer functional slurry.
  • water is used as a dispersing medium, and through the action of a deflocculating water-based dispersant, the repulsion between the polymer material particles is greater than the attractive force, and it is in a deflocculated state, which is better dispersed in water to obtain a uniform dispersion slurry, which is convenient for subsequent operate.
  • aqueous dispersants provide a framework/steric hindrance structure to separate the dispersed slurry particles, resulting in a uniform, stable and high solids slurry.
  • the grinding slurry is mixed with wetting agent, binder and water, and water is used as dispersing medium and thinner. Dilute the grinding slurry to make the water-based polymer functional slurry have good wettability, liquid retention, storage stability and quality stability; Excellent adhesion, not easy to fall off after bonding with the pole piece, to ensure the performance of the battery.
  • the water-based polymer functional slurry with excellent storage stability, quality stability and strong bonding ability can be prepared only by using less water-based additives.
  • it When it is coated on the separator of lithium ion battery, it has strong bonding ability, high hardness of the cell, and excellent thermocompression bonding performance with the pole piece, which can significantly improve the comprehensive performance of the lithium ion battery.
  • the preparation method provided by the present invention has simple technological process, low cost, continuous production, and is suitable for large-scale production.
  • Fig. 1 shows the 1st, 7th, 14th and 28th days of the water-based polymer functional pastes of Comparative Example 1, Comparative Example 2, Examples 1, 2, 3, and 4 stored in 100 mL plastic bottles Effect;
  • FIG. 2 shows the effects of the aqueous polymer functional slurries of Examples 5-6 and Comparative Examples 3-6 after the first day of storage in a 100 mL plastic bottle.
  • the existing water-based polymer functional slurry has problems such as poor storage performance and short shelf life of the slurry system; and the water-based polymer functional slurry uses a lot of wetting and dispersing agents, and the adhesion performance is weakened.
  • the battery core has problems such as softness and poor thermocompression bonding with the pole piece.
  • the present invention provides a preparation method of an aqueous polymer functional slurry with simple process and high production efficiency, which can obtain excellent storage stability, excellent quality stability, and good wettability and liquid retention for electrolyte.
  • the water-based polymer functional slurry with strong adhesion to the pole piece and greatly improved safety can be used to coat lithium battery separators.
  • a preparation method of water-based polymer functional slurry comprising the following steps:
  • the mass percentages of the polymer material, the deflocculating water-based dispersant and the water I in the dispersed slurry are 30%-60%, 1%-5% and 35%-70%, respectively;
  • the mass percentages of the dispersing slurry, the volume-hindered aqueous dispersant and the grinding medium in the grinding slurry are: 39.9%-78.5%, 0.1%-1.5% and 20%-60% respectively;
  • the mass percentages of the abrasive slurry, wetting agent, binder and water II in the aqueous polymer functional slurry are respectively: 30%-80%, 0.1%-0.5%, 0.5%-2.5% and 17% -69.4%;
  • the deflocculating water-based dispersant is selected from one or more of polyacrylate and phosphoric acid ester;
  • the volume sterically hindered aqueous dispersant is selected from one or more of block copolymers of polyurethane and polyacrylate copolymers.
  • Water is used as a dispersion medium, and through the action of a deflocculating water-based dispersant, the repulsion between the polymer particles is greater than the attractive force, and it is in a deflocculated state.
  • aqueous dispersants provide a framework/steric hindrance structure to separate the dispersed slurry particles, resulting in a uniform, stable and high solids slurry.
  • the grinding slurry is mixed with wetting agent, binder and water, and water is used as dispersing medium and thinner. Dilute the grinding slurry to make the water-based polymer functional slurry have good wettability, liquid retention, storage stability and quality stability; Excellent adhesion, not easy to fall off after bonding with the pole piece, to ensure the performance of the battery.
  • the aqueous dispersant of macromolecular material, deflocculation type and water I are mixed, and the step of preparing dispersion slurry is:
  • the mass percentages of the polymer material, the deflocculating aqueous dispersant and the water I in the dispersing slurry are 40%-45%, 1%-5% and 50%, respectively. %-55%.
  • the polymer material is selected from polytetrafluoroethylene, polyvinylidene fluoride homopolymer, polyvinylidene fluoride copolymer, polymethyl methacrylate homopolymer, polymethyl methacrylate One or more of ester copolymer, water-based polyimide, aramid, polyethylene oxide.
  • the polymer material is selected from one or both of polyvinylidene fluoride homopolymer and polyvinylidene fluoride copolymer synthesized by emulsion polymerization.
  • the melting point of the polyvinylidene fluoride homopolymer is 150°C-170°C
  • the primary particle size is 90 nm-120 nm
  • the secondary particle size is 10 ⁇ m-20 ⁇ m.
  • the polyvinylidene fluoride copolymer has a melting point of 90° C.-160° C., a primary particle size of 100 nm-200 nm, and a secondary particle size of 10 ⁇ m-20 ⁇ m.
  • the deflocculating type aqueous dispersant is selected from one or more of polyacrylates and phosphates.
  • the polyacrylate includes one or more of polymethyl methacrylate, polyethyl methacrylate, and polypropyl methacrylate.
  • Phosphate esters include one or more of triethyl phosphate, styryl polyether phosphate, fatty alcohol ether phosphate, and nonylphenol polyether phosphate.
  • the water I is ultrapure water; at 25° C., the water I has a resistivity of 5M ⁇ cm-15M ⁇ cm, and a pH value of 6.0-8.0.
  • the resistivity of the water I is >10 M ⁇ cm, and the pH value is 6.5-7.0.
  • the preparation of the dispersion slurry is carried out under stirring, and the process parameters are as follows:
  • the rotating speed is 1000r/min-2500r/min, the time is 20min-40min, and the temperature is 20°C-60°C.
  • the process parameters for preparing the dispersion slurry are as follows:
  • the rotating speed is 1800r/min-2000r/min, the time is 25min-30min, and the temperature is 25°C-30°C.
  • a specific feeding sequence is selected, and the feeding sequence is part of water I, deflocculating water-based dispersant, polymer material, balance water I.
  • the part of water I is 50%-70% of water I
  • the balance of water I is 30%-50% of water I.
  • the dispersion slurry is prepared by dispersion.
  • the agitator is a high-speed disperser
  • the dispersing disc is a toothed dispersing disc
  • the rotating speed is 1000r/min-2500r/min
  • the time is 20min-40min
  • the temperature is 20°C-60°C.
  • the above-mentioned dispersing slurry 39.9%-78.5%, grinding medium 20%-60% and volume steric hindrance aqueous dispersant 0.1%-1.5% are added to a sand mill, ground and filtered to prepare a grinding slurry.
  • the mass percentages of the dispersing slurry, the volume-hindered aqueous dispersant and the grinding medium in the grinding slurry are: 40%-50%, 0.8%-1.0% and 49%, respectively. -59.2%.
  • the volume sterically hindered aqueous dispersant is selected from one or more of polyurethane block copolymers and polyacrylate copolymers.
  • the polyacrylate copolymer is a polyacrylate terpolymer.
  • the polyacrylate copolymer is a hydrophobically modified polyacrylate copolymer.
  • the terpolymer of polyacrylate refers to the polymerization of other monomers in addition to the propylene-based monomer, and the ternary refers to the copolymerization of three monomer units such as acrylic acid-ethylene-styrene.
  • Hydrophobic modification refers to the introduction of hydrophobic -R (such as alkane, phenyl, etc.) segments by the carboxyl group-COOH in acrylic acid through esterification and other reactions (such as condensation polymerization with aliphatic alcohol R-OH).
  • the volume-hindered aqueous dispersant is selected from hydrophobically modified polyacrylic acid copolymers.
  • the grinding medium is selected from one or more of glass beads, alumina grinding balls, zirconia beads, yttrium-stabilized zirconia beads, and cerium zirconia beads.
  • the particle size of the grinding medium is 0.5mm-10mm.
  • the grinding medium is selected from one of zirconia beads and cerium-stabilized zirconia beads, and the particle size is 0.5mm-10mm.
  • the preparation of the grinding slurry is carried out under stirring, and the process parameters are as follows:
  • the rotating speed is 800r/min-2000r/min, the time is 30min-240min, and the temperature is 10°C-40°C.
  • the process parameters for preparing the grinding slurry are as follows:
  • the speed is 1200r/min-1500r/min, the time is 60min-120min, and the temperature is 15°C-20°C.
  • a specific feeding sequence is adopted, and the feeding sequence is the grinding medium, the above-mentioned dispersing slurry, and the volume sterically hindered aqueous dispersant.
  • the dispersing slurry is mixed with volume steric hindrance-type aqueous dispersant and grinding medium, and ground, and the steps of preparing the grinding slurry are:
  • the grinding medium is pre-weighed and added to the grinding machine, and then the above-mentioned dispersing slurry is pumped into the grinding machine through the diaphragm pump. After grinding for a certain period of time, the volumetric hindered water-based dispersant is added, and the grinding process is carried out under a certain grinding process. , filtered to prepare a grinding slurry.
  • the sand mill is a horizontal sand mill with a cooling water jacket, the grinding speed is 1200r/min-1500r/min, the time is 60min-120min, and the temperature is 15°C-20°C.
  • the mass percentages of the abrasive slurry, wetting agent, binder and water II in the aqueous polymer functional slurry are respectively: 40%-50%, 0.2%-0.3% %, 0.8%-1.2% and 48.5%-59%.
  • the wetting agent is selected from one of alkyl sulfates, polyoxyethylene alkyl phenol ethers, polyoxyethylene fatty alcohol ethers, and polyether-modified polydimethylsiloxanes or more.
  • the adhesive is selected from one or more of waterborne polyurethane, waterborne epoxy resin, and waterborne polyacrylate adhesive.
  • Waterborne polyurethane adhesives include polyurethane emulsion, vinyl polyurethane emulsion, polyisocyanate emulsion, closed polyurethane emulsion;
  • waterborne epoxy resin adhesives include CYWD series waterborne epoxy resin CYDW-100, CYDW of Sinopec Baling Petrochemical Branch -100P, CTDW-120;
  • water-based polyacrylate adhesives include ⁇ -methyl cyanoacrylate and ⁇ -isopropyl cyanoacrylate.
  • the adhesive is selected from methyl ⁇ -cyanoacrylate and/or isopropyl ⁇ -cyanoacrylate.
  • the water II is ultrapure water; at 25° C., the resistivity of the water II is >10 M ⁇ cm, and the pH value is 6.5-7.0.
  • the preparation of the aqueous polymer functional slurry is carried out under stirring, and the process parameters are as follows:
  • the rotating speed is 200r/min-500r/min, the time is 10min-40min, and the temperature is 20°C-30°C.
  • the process parameters for preparing the aqueous polymer functional slurry are as follows:
  • the speed is 300r/min-350r/min, the time is 20min-30min, and the temperature is 20°C-30°C.
  • a specific feeding sequence is adopted, and the feeding sequence is grinding slurry, wetting agent, binder and water II in sequence.
  • the grinding slurry is mixed with a wetting agent, a binder, and water II, and the steps of preparing an aqueous polymer functional slurry are:
  • the grinding slurry, the wetting agent, the binder and the water II are added in sequence under the stirring of the mixer, and the finished slurry of the aqueous functional slurry is prepared by stirring evenly.
  • the agitator is a disperser with a propeller-type or butterfly-type stirring blade, and the settings of the mixer are: 200r/min-500r/min, time is 10min-40min, and temperature is 20°C-30°C.
  • the present invention also provides the water-based polymer functional slurry prepared by the above-mentioned preparation method of the water-based polymer functional slurry.
  • the present invention also provides the application of the above-mentioned aqueous polymer functional slurry in preparing the modified lithium battery separator.
  • the deflocculating and coagulating acrylate aqueous dispersing agent in the following Examples 1-5 and Comparative Examples 3, 5, and 6 refers to polymethyl methacrylate, and the deflocculating and coagulating acrylate aqueous dispersing agent in Example 6 refers to polymethyl methacrylate. Ethyl acrylate.
  • the polyacrylate terpolymer in the following examples and comparative examples refers to a terpolymer composed of polyacrylic acid-polyethylene-polystyrene.
  • Hydrophobically modified polyacrylate copolymer refers to a copolymer composed of polyacrylic acid-polybutadiene, and hydrophobic modification refers to the esterification reaction of carboxyl groups in acrylic acid with butanol.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application.
  • step (3) Preparation of finished slurry: 25kg of the grinding slurry obtained in step (2), 0.15kg of polyether-modified polydimethylsiloxane wetting agent, 0.6kg of polyacrylate adhesive, and 24.25kg of ultrapure water It is added into the supporting production tank of the mixer in turn, the speed of the mixer is 350r/min, the stirring is 20min, and the temperature is controlled at 20-30°C to prepare the finished water-based polymer functional slurry 1.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of polyacrylate adhesive, and 29.5kg of ultrapure water It is added into the supporting production tank of the mixer in turn, the speed of the mixer is 350r/min, the stirring is for 20min, and the temperature is controlled at 20-30°C to prepare the finished water-based polymer functional slurry 2.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application.
  • dispersion slurry 31kg of ultrapure water, 45kg of polyvinylidene fluoride homopolymer powder, 4kg of deflocculated agglomerated acrylate aqueous dispersant, and 20kg of ultrapure water were added to the dispersant production tank in turn, and the dispersion speed was set to 2000r/min, dispersion time 25min, temperature controlled at 20-30°C, to obtain dispersion slurry.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of water-based epoxy resin adhesive, 29.5kg of ultra Pure water is added to the production tank of the mixer in turn, the mixer rotates at 350 r/min, stirs for 20 minutes, and controls the temperature at 20-30 °C to obtain the finished water-based polymer functional slurry 3.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of polyurethane adhesive, and 29.5kg of ultrapure water are sequentially Put it into the supporting production tank of the mixer, the speed of the mixer is 350r/min, the stirring is 20min, and the temperature is controlled at 20-30°C to prepare the finished water-based polymer functional slurry 4.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application. It is basically the same as Example 3, except that in this example, a hydrophobically modified polyacrylate copolymer is selected as the volume-hindered water-based dispersant.
  • dispersion slurry 31kg of ultrapure water, 45kg of polyvinylidene fluoride homopolymer powder, 4kg of deflocculated agglomerated acrylate aqueous dispersant, and 20kg of ultrapure water were added to the dispersant production tank in turn, and the dispersion speed was set to 2000r/min, dispersion time 25min, temperature controlled at 20-30°C, to obtain dispersion slurry.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of water-based epoxy resin adhesive, 29.5kg of ultra Pure water is added to the production tank of the mixer in turn, the mixer rotates at 350r/min, stirs for 20min, and controls the temperature at 20-30°C to obtain the finished water-based polymer functional slurry 5.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This embodiment provides a preparation method of water-based polymer functional slurry and its preparation method and application.
  • dispersion slurry 32kg of ultrapure water, 34kg of polyvinylidene fluoride copolymer powder, 1kg of deflocculated fatty acid polyethylene glycol ester aqueous dispersant, and 33kg of ultrapure water were added to the dispersant production tank in turn, and the dispersion rate was The setting is 1200r/min, the dispersion time is 20min, and the temperature is controlled at 40-50°C to obtain a dispersion slurry.
  • Step (2) Preparation of grinding slurry: put 20kg glass beads (particle size 0.8-1.2mm) into the grinding machine cavity, and pump 40kg with a diaphragm pump to prepare disperse slurry and 0.4kg aqueous carboxymethyl cellulose in step (1). Dispersant, grinding machine speed 1000r/min, temperature controlled at 15-20°C, grinding time 120min, to obtain grinding slurry.
  • step (3) Preparation of finished slurry: Add 20kg of the grinding slurry obtained in step (2), 0.1kg of alkyl sulfate, 0.4kg of polyurethane adhesive, and 29.5kg of ultrapure water into the supporting production tank of the mixer in turn, and the mixer rotates at 350r /min, stirring for 20 min, and controlling the temperature at 20-30° C., to prepare a finished water-based polymer functional slurry 6.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • the water-based polymer functional slurry used in this comparative example is a commercially available water-based polyvinylidene fluoride functional slurry J04-001 for coating a commercial lithium-ion battery separator.
  • Coating Separator Coating 2 ⁇ m water-based polyvinylidene fluoride coating on 9+3 ⁇ m ceramic coating separator by gravure roll coating, and obtaining water-based functional coating separator after oven baking.
  • Steps First add ultrapure water, add dispersant and anti-settling agent under stirring, disperse at 1500rpm for 30min, then add polyvinylidene fluoride powder, adjust the speed to 800-1000rpm, add defoamer and wetting agent, and disperse for 30min to obtain slurry.
  • This comparative example provides a preparation method of water-based polymer functional slurry and its preparation method and application. It is basically the same as Example 5, except that in this comparative example, a volumetric hindered aqueous dispersant is added in the first step, and a deflocculation type aqueous dispersant is added in the second step.
  • dispersion slurry 31kg of ultrapure water, 45kg of polyvinylidene fluoride homopolymer powder, 4kg of volume sterically hindered hydrophobically modified polyacrylate copolymer aqueous dispersant, and 20kg of ultrapure water were sequentially added to the dispersant for supporting production
  • the dispersion speed is set to 2000r/min
  • the dispersion time is 25min
  • the temperature is controlled at 20-30°C to prepare a dispersion slurry.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of water-based epoxy resin adhesive, 29.5kg of ultra Pure water is added to the production tank of the mixer in turn, the mixer rotates at 350r/min, stirs for 20min, and controls the temperature at 20-30°C to prepare the finished water-based polymer functional slurry 7.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This comparative example provides a preparation method of water-based polymer functional slurry and its preparation method and application. Basically the same as Example 5, the difference is that the fatty acid polyethylene glycol ester aqueous dispersant is selected as the deflocculation type aqueous dispersant in this comparative example.
  • dispersion slurry 31kg of ultrapure water, 45kg of polyvinylidene fluoride homopolymer powder, 4kg of deflocculated fatty acid polyethylene glycol ester aqueous dispersant, and 20kg of ultrapure water were added to the dispersant production tank in turn, and dispersed.
  • the speed is set to 2000r/min, the dispersion time is 25min, and the temperature is controlled at 20-30°C to obtain a dispersion slurry.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of water-based epoxy resin adhesive, 29.5kg of ultra Pure water is added to the production tank of the mixer in turn, the mixer rotates at 350r/min, stirs for 20min, and controls the temperature at 20-30°C to obtain the finished water-based polymer functional slurry 8.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • This comparative example provides a preparation method of water-based polymer functional slurry and its preparation method and application. It is basically the same as Example 5, the difference is that the carboxymethyl cellulose aqueous dispersant is selected as the volume-hindered aqueous dispersant in this comparative example.
  • step (3) Preparation of finished slurry: 20kg of the grinding slurry obtained in step (2), 0.1kg of polyether-modified polydimethylsiloxane wetting agent, 0.4kg of polyurethane adhesive, and 29.5kg of ultrapure water are sequentially Put it into the production tank of the mixer, the speed of the mixer is 350r/min, the stirring is 20min, and the temperature is controlled at 20-30°C to prepare the finished water-based polymer functional slurry 9.
  • Finished slurry-coated separator Coat 2 ⁇ m water-based PVDF coating on 9+3 ⁇ m ceramic separator by gravure roll coating, and obtain water-based functional coating separator after oven baking.
  • the formula components are as follows: 33.58kg ultrapure water, 3.6kg polyvinylidene fluoride copolymer powder, 0.32kg deflocculation and coagulation acrylate water-based dispersion agent, 11.84kg of cerium-stabilized zirconia beads, 0.16kg of hydrophobically modified polyacrylate copolymer aqueous dispersant, 0.1kg of polyether-modified polydimethylsiloxane wetting agent, and 0.4kg of polyurethane adhesive.
  • Preparation method firstly add cerium-stabilized zirconia beads to the dispersion basket of the basket disperser, then add ultrapure water, add deflocculating agglomeration acrylate water-based dispersant and anti-settling agent under stirring, disperse at 1500rpm for 10min, and then add polymer Vinylidene fluoride powder, hydrophobically modified polyacrylate copolymer, polyether modified polydimethylsiloxane wetting agent, polyurethane adhesive, adjust the speed to 800-1000rpm, and disperse for 30min to obtain a slurry.
  • Slurry storage stability Store the finished slurry in a 100ml plastic bottle at 25 degrees Celsius, and watch the slurry stratification and precipitation. The results are shown in Figure 1-2. Among them, for the sake of convenience, numbers 1-6 represent the products of Examples 1-6, the abbreviation J04-001 represents the products of Comparative Example 1, BYK represents the products of Comparative Example 2, and numbers 7-10 represent the products of Comparative Example 3- 6 products.
  • Figures 1(a)-1(d) are the first water-based polymer functional pastes (from left to right) of Comparative Example 1, Comparative Example 2, and Examples 1, 2, 3, and 4 stored in a 100 mL plastic bottle. day, day 7, day 14 and day 28. After the first day of storage, there is no obvious layering and precipitation in the plastic bottles of Comparative Examples 1, 2 and Examples 1-4. After 7 days of storage, the comparative example 1 has obvious layered precipitation phenomenon, and the slurry stability of the comparative example 2 and examples 1-4 is good, and there is no obvious layered sedimentation phenomenon.
  • Comparative Example 1 After 14 days of storage, the layered precipitation of Comparative Example 1 was intensified, and the upper layer liquid was clarified; the bottom layered sedimentation phenomenon began to appear in Comparative Example 2, and the slurry stability of Examples 1-4 was good without obvious layered sedimentation phenomenon. After 28 days of storage, Comparative Example 1 was completely divided into two layers, an obvious precipitation layer also appeared at the bottom of Comparative Example 2, and a slightly clear liquid layer began to appear in the upper layer of Examples 1-4, and the overall stability of the slurry was good. It can be clearly seen from FIG. 1 that, compared with Comparative Examples 1-2, the aqueous polymer functional pastes prepared in Examples 1-4 of the present invention have excellent storage stability.
  • FIG. 2 shows the situation after the first day of storage of the aqueous polymer functional slurries of Examples 5-6 and Comparative Examples 3-6 (from left to right) in a 100 mL plastic bottle.
  • the water-based polymer functional slurry of Examples 5-6 of the present invention has excellent storage stability, and the water-based polymer functional slurry of Comparative Example 3 has hard precipitation on the bottom layer and turbid upper layer liquid;
  • the water-based polymer functional slurry of Comparative Example 4 has a layering phenomenon, the upper layer is clear and the lower layer is turbid;
  • the water-based polymer functional slurry of Comparative Example 5 has serious sedimentation;
  • the water-based polymer functional slurry of Comparative Example 6 has hard precipitation at the bottom, and the upper layer is turbid. .
  • the basic performance data such as thickness, air permeability, areal density, thermal shrinkage, peel strength, etc. of the water-based functional slurry coated diaphragm are tested with reference to the national standard GBT36363-2018 or the enterprise standard test method.
  • Dry pressing refers to winding the positive electrode sheet, the water-based functional coated separator, and the negative electrode sheet, placing it in an aluminum-plastic film, encapsulating it, and pressing it for 30 minutes at 65 degrees Celsius and 1MPa pressure. After cooling, the hardness of the cell was measured. and pole piece adhesion test.
  • the cell hardness test is to use a round needle with a diameter of 1mm, apply a force of 1kg to press the cell, and measure the indentation depth value. The larger the value, the softer the cell, and the smaller the value, the harder the cell.
  • Example 1-6 and Comparative Example 1-2 were coated with water-based functional slurry and made into 506090 soft-packed cells, the test results are shown in Table 3:

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Abstract

本发明涉及一种水性高分子功能浆料的制备方法及其制备方法和应用。该制备方法，包括以下步骤：将高分子材料30％-60％、特定种类的解絮凝型的水性分散剂1％-5％和水I35％-70％混合，制备分散浆；将分散浆39.9％-78.5％和特定种类的体积位阻型水性分散剂0.1％-1.5％、研磨介质20％-60％混合，研磨，制备研磨浆；将研磨浆30％-80％和润湿剂0.1％-0.5％、粘结剂0.5％-2.5％、水II17％-69.4％混合，制备得到存储稳定性好，粘结力强，润湿性和保液性良好的水性高分子功能浆料，可涂覆于锂离子电池的隔膜上。该制备方法工艺流程简单，成本低廉，可连续化生产，适于大规模生产。

Description

水性高分子功能浆料及其制备方法和应用 技术领域
本发明高分子材料技术领域，特别是涉及一种水性高分子功能浆料及其制备方法和应用。
背景技术
随着能源危机和环境污染日益严重，大力发展绿色环保的新能源产业已成为世界主流共识。我国是汽车消费大国，发展新能源汽车是我国新能源产业发展的最重要方向，也是由汽车大国转为汽车强国的必由之路。目前限制新能源汽车发展的重要因素车载的动力锂电池。
一般来说，锂离子电池主要由正极、负极、隔膜和电解液四大关键组分构成。其中的隔膜主要作用是防止电池内部的正、负极接触造成短路，同时提供锂离子在正、负极之间的传输通道。隔膜虽然不是锂离子电池的活性组分，但其质量的优劣直接影响整个锂离子电池的内阻、容量、循环寿命和安全等性能。聚烯烃是锂电池隔膜领域应用最广泛的材料，但聚烯烃隔膜也存在耐热稳定性低、对电解液润湿性差等不足，进而影响锂电池的容量、循环寿命、倍率充放电和安全性能。
目前，在提高聚烯烃锂电池隔膜性能方面的发展研究主要是改善其表面性质，而改善隔膜表面性质主要的研究方向是对隔膜进行涂覆处理。其中隔膜涂覆用的功能浆料的设计与制备是决定涂覆隔膜优劣的关键要素，性能良好的功能浆料涂覆出来的涂覆隔膜能有效提高锂电池综合性能。应用隔膜涂覆陶瓷功能浆料后可有效地提高隔膜耐热收缩性，进而提高电池的安全性、热稳定性。 涂覆凝胶功能浆料后隔膜的保液性能和极片粘接性能可得到明显提升。掌握锂电隔膜功能涂层浆料的制备技术、涂覆技术对于提升自主研发锂离子电池隔膜的整体竞争力、对完善产业链结构具有重要的作用。
现今，应用在锂电隔膜涂覆上的功能浆料主要有两大类：一类是以无机材料为功能组分的涂覆浆料，形式以水性浆料居多；另外一类是以有机高分子为功能组分的涂覆浆料，类型以油性浆料居多。其中，无机功能组分为氧化铝、勃姆石、氧化镁等陶瓷粉末，其主要功能为提高聚烯烃隔膜的热稳定性；有机功能组分有PMMA(聚甲基丙烯酸甲酯)、PVDF(聚偏氟乙烯)、PVDH-HPF(聚偏氟乙烯-六氟丙烯共聚物)、芳纶等高分子聚合物，选择不同的功能组分可制得不同功能浆料，涂覆后进而获得不同功能的锂电隔膜。有机功能高分子涂覆隔膜对电解液有良好的的润湿性和保液性，可有效粘接隔膜和极片，增加电池的循环性能，显著提高电池的安全性。
现有锂离子电池有机功能高分子涂覆隔膜普遍采用油性功能浆料涂覆，虽然油性功能浆料涂覆粘结性较好，但容易发生堵孔及透气不良现象，而且浆料中多采用N-甲基吡咯烷酮、二甲基乙酰胺、丙酮等作有机溶剂，成本高，对环境污染大，对操作人员身体健康也有伤害，成为浆料生产及使用过程中的不安全因素。
近年来，水性有机高分子功能浆料成为研究重点，与油性功能浆料相比，水性浆料采用水作为溶剂，具有生产成本低、对环境污染小等的优点；但采用常规配方设计和制备工艺得到的水性高分子功能浆料，存在的浆料体系储存性能差、保质期短等问题；而且水性高分子功能浆料由于使用较多的润湿分散剂，粘接性能减弱，涂覆隔膜制作的电芯存在发软及与极片热压粘结性差等问题。因此，需要研究优化水性高分子功能浆料的配方设计及制备工艺，提升浆料稳 定性，提高粘结力。
发明内容
基于此，本发明的目的在于提供一种工艺简单、生产效率高的水性高分子功能浆料的制备方法，制备得到存储稳定性优异，质量稳定性优异，对电解液有良好润湿性和保液性，与极片粘接力强，安全性大大提高的水性高分子功能浆料，可用于涂覆锂电池隔膜。
技术方案如下：
一种水性高分子功能浆料的制备方法，包括以下步骤：
将高分子材料、解絮凝型的水性分散剂和水I混合，制备分散浆；
将所述分散浆、体积位阻型水性分散剂和研磨介质混合，研磨，制备研磨浆；
将所述研磨、浆润湿剂、粘结剂和水II混合，制备水性高分子功能浆料；
所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为30％-60％、1％-5％和35％-70％；
所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：39.9％-78.5％、0.1％-1.5％和20％-60％；
所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：30％-80％、0.1％-0.5％、0.5％-2.5％和17％-69.4％；
所述解絮凝型的水性分散剂选自聚丙烯酸酯、磷酸酯中的一种或多种；
所述体积位阻型水性分散剂选自聚氨酯的嵌段共聚物、聚丙烯酸酯的共聚物中的一种或多种。
在其中一个实施例中，所述聚丙烯酸酯的共聚物为聚丙烯酸酯的三元共聚 物。
在其中一个实施例中，所述聚丙烯酸酯的共聚物为疏水改性的聚丙烯酸酯共聚物。
在其中一个实施例中，所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为40％-45％、1％-5％和50％-55％。
在其中一个实施例中，所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：40％-50％、0.8％-1.0％和49％-59.2％。
在其中一个实施例中，所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：40％-50％、0.2％-0.3％、0.8％-1.2％和48.5％-59％。
在其中一个实施例中，所述的高分子材料选自聚四氟乙烯、聚偏氟乙烯均聚物、聚偏氟乙烯共聚物、聚甲基丙烯酸甲酯均聚物、聚甲基丙烯酸甲酯共聚物、水性聚酰亚胺、芳纶、聚氧化乙烯中的一种或多种。
在其中一个实施例中，所述的高分子材料选自由乳液聚合合成的聚偏氟乙烯均聚物、聚偏氟乙烯共聚物的一种或两种。
在其中一个实施例中，所述解絮凝型的水性分散剂选自聚丙烯酸盐、磷酸酯中的一种或多种。
在其中一个实施例中，所述水I为超纯水；在25℃条件下，所述水I的电阻率为5MΩ·cm-15MΩ·cm，pH值为6.0-8.0。
在其中一个实施例中，所述分散浆是在搅拌状态下制备的，工艺参数如下：
转速为1000r/min-2500r/min，时间为20min-40min，温度为20℃-60℃。
在其中一个实施例中，所述制备分散浆的工艺参数如下：
转速为1800r/min-2000r/min，时间为25min-30min，温度为25℃-30℃。
在其中一个实施例中，在所述制备分散浆的步骤中，选用了特定的加料顺序，加料顺序依次为部分的水I、解絮凝型的水性分散剂、高分子材料、余量的水I。
在其中一个实施例中，所述体积位阻型水性分散剂选自膨润土、疏水改性的聚丙烯酸共聚物中的一种或两种。
在其中一个实施例中，所述的研磨介质选自玻璃珠、氧化铝研磨球、氧化锆珠、钇稳定氧化锆珠、铈氧化锆珠中的一种或多种。
在其中一个实施例中，所述的研磨介质的粒径为0.5mm-10mm。
在其中一个实施例中，所述的研磨介质选自氧化锆珠、铈稳定氧化锆珠中的一种，粒径为0.5mm-10mm。
在其中一个实施例中，所述研磨浆是在搅拌状态下制备的，工艺参数如下：
转速为800r/min-2000r/min，时间为30min-240min，温度为10℃-40℃。
在其中一个实施例中，所述制备研磨浆的工艺参数如下：
转速为1200r/min-1500r/min，时间为60min-120min，温度为15℃-20℃。
在其中一个实施例中，在所述制备研磨浆的步骤中，采用了特定的加料顺序，加料顺序依次为研磨介质、上述的分散浆、体积位阻型水性分散剂。
在其中一个实施例中，所述的润湿剂选自烷基硫酸盐、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚、聚醚改性聚二甲基硅氧烷中的一种或多种。
在其中一个实施例中，所述的粘接剂选自水性聚氨酯类、水性环氧树脂类、水性聚丙烯酸甲酯类粘结剂中的一种或多种。
在其中一个实施例中，所述水II为超纯水；在25℃条件下，所述水II的电阻率＞10MΩ·cm，pH值为6.5-7.0。
在其中一个实施例中，所述水性高分子功能浆料是在搅拌状态下制备的， 工艺参数如下：
转速为200r/min-500r/min，时间为10min-40min，温度为20℃-30℃。
在其中一个实施例中，所述制备水性高分子功能浆料的工艺参数如下：
转速为300r/min-350r/min，时间为20min-30min，温度为20℃-30℃。
在其中一个实施例中，在所述制备水性高分子功能浆料的步骤中，采用了特定的加料顺序，加料顺序依次为研磨浆、润湿剂、粘接剂和水II。
本发明还提供上述的水性高分子功能浆料的制备方法制备得到的水性高分子功能浆料。
本发明还提供上述的水性高分子功能浆料在制备改性锂电池隔膜上的应用。
与现有技术相比，本发明具有如下有益效果：
本发明提供的水性高分子功能浆料的制备方法，包括：将特定量的高分子材料、解絮凝型的水性分散剂和水I混合，制备分散浆；将所述分散浆和体积位阻型水性分散剂、研磨介质混合，制备研磨浆；以及将所述研磨浆和润湿剂、粘结剂、水II混合，制备水性高分子功能浆料的步骤。
其中，水作为分散介质，通过解絮凝型的水性分散剂的作用，使高分子材料微粒间的斥力大于引力，呈反絮凝态，更好地分散于水中，制得均匀的分散浆，便于后续操作。而将分散浆和两亲性的体积位阻型水性分散剂、研磨介质混合、研磨后，分散浆粒子的粒径减小，粒径减小的同时，也更易于团聚，通过体积位阻型水性分散剂提供框架/位阻结构，将分散浆粒子隔开，得到均匀、稳定、固含高的研磨浆。最后将研磨浆和润湿剂、粘结剂、水混合，水作为分散介质和调稀剂，通过润湿剂的作用，降低浆料和水的表面张力，使浆料均匀 地分散于水中，稀释研磨浆，使水性高分子功能浆料具有良好的润湿性和保液性，存储稳定性和质量稳定性；而粘结剂起增强粘结力的作用，使水性高分子功能浆料具有优异的粘结力，与极片粘结后不易脱落，保证电池的性能。
可见，本发明通过三段式的制备工艺，仅使用较少的水性助剂即能制得具有优异的存储稳定性、质量稳定性和粘接能力强的水性高分子功能浆料。将其涂覆于锂离子电池的隔膜上，粘接能力强，电芯硬度高，与极片的热压粘结性能优异，可显著提升锂离子电池的综合性能。
此外，本发明提供的制备方法工艺流程简单，成本低廉，可连续化生产，适于大规模生产。
附图说明
图1表示对比例1、对比例2、实施例1、2、3、4的水性高分子功能浆料存储在100mL塑料瓶中的第1天、第7天、第14天和第28天的效果；
图2表示实施例5-6和对比例3-6的水性高分子功能浆料存储在100mL塑料瓶中的第1天后的效果。
具体实施方式
以下结合具体实施例对本发明作进一步详细的说明。本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明公开内容理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的 术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
现有水性高分子功能浆料，存在的浆料体系储存性能差、保质期短等问题；而且水性高分子功能浆料由于使用较多的润湿分散剂，粘接性能减弱，涂覆隔膜制作的电芯存在发软及与极片热压粘结性差等问题。
针对上述问题，本发明提供了一种工艺简单、生产效率高的水性高分子功能浆料的制备方法，制备得到存储稳定性优异，质量稳定性优异，对电解液有良好润湿性和保液性，与极片粘接力强，安全性大大提高的水性高分子功能浆料，可用于涂覆锂电池隔膜。
技术方案如下：
一种水性高分子功能浆料的制备方法，包括以下步骤：
将高分子材料、解絮凝型的水性分散剂和水I混合，制备分散浆；
将所述分散浆和体积位阻型水性分散剂、研磨介质混合，研磨，制备研磨浆；
将所述研磨浆和润湿剂、粘结剂、水II混合，制备水性高分子功能浆料；
其中，所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为30％-60％、1％-5％和35％-70％；
所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：39.9％-78.5％、0.1％-1.5％和20％-60％；
所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：30％-80％、0.1％-0.5％、0.5％-2.5％和17％-69.4％；
所述解絮凝型的水性分散剂选自聚丙烯酸酯、磷酸酯中的一种或多种；
所述体积位阻型水性分散剂选自聚氨酯的嵌段共聚物、聚丙烯酸酯共聚物中的一种或多种。
水作为分散介质，通过解絮凝型的水性分散剂的作用，使高分子材料微粒间的斥力大于引力，呈反絮凝态，更好地分散于水中，制得均匀的分散浆，便于后续操作。而将分散浆和两亲性的体积位阻型水性分散剂、研磨介质混合、研磨后，分散浆粒子的粒径减小，粒径减小的同时，也更易于团聚，通过体积位阻型水性分散剂提供框架/位阻结构，将分散浆粒子隔开，得到均匀、稳定、固含高的研磨浆。最后将研磨浆和润湿剂、粘结剂、水混合，水作为分散介质和调稀剂，通过润湿剂的作用，降低浆料和水的表面张力，使浆料均匀地分散于水中，稀释研磨浆，使水性高分子功能浆料具有良好的润湿性和保液性，存储稳定性和质量稳定性；而粘结剂起增强粘结力的作用，使水性高分子功能浆料具有优异的粘结力，与极片粘结后不易脱落，保证电池的性能。
(1)优选地，将高分子材料、解絮凝型的水性分散剂和水I混合，制备分散浆的步骤为：
将高分子材料30％-60％、解絮凝型的水性分散剂1％-5％和水I 35％-70％，在高速分散机搅拌状态下，加入带冷却水夹套的移动缸中，分散制备得到分散浆。
在其中一个较为优选的实施例中，所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为40％-45％、1％-5％和50％-55％。
在其中一个实施例中，所述的高分子材料选自聚四氟乙烯、聚偏氟乙烯均聚物、聚偏氟乙烯共聚物、聚甲基丙烯酸甲酯均聚物、聚甲基丙烯酸甲酯共聚物、水性聚酰亚胺、芳纶、聚氧化乙烯中的一种或多种。
在其中一个较为优选的实施例中，所述的高分子材料选自由乳液聚合合成的聚偏氟乙烯均聚物、聚偏氟乙烯共聚物的一种或两种。
更优选地，所述的聚偏氟乙烯均聚物的熔点为150℃-170℃，一次粒径为 90nm-120nm，二次粒径为10μm-20μm。所述的聚偏氟乙烯共聚物的熔点为90℃-160℃，一次粒径为100nm-200nm，二次粒径为10μm-20μm。
所述的解絮凝型的水性分散剂选自聚丙烯酸酯、磷酸酯中的一种或多种。聚丙烯酸酯包括聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丙酯中的一种或多种。磷酸酯包括磷酸三乙酯、苯乙烯基聚醚磷酸酯、脂肪醇醚磷酸酯和壬基酚聚醚磷酸酯中的一种或多种。
在其中一个实施例中，所述水I为超纯水；在25℃条件下，所述水I的电阻率为5MΩ·cm-15MΩ·cm，pH值为6.0-8.0。
在其中一个较为优选的实施例中，在25℃条件下，所述水I的电阻率＞10MΩ·cm，pH值为6.5-7.0。
在其中一个实施例中，所述制备分散浆是在搅拌状态下进行的，工艺参数如下：
转速为1000r/min-2500r/min，时间为20min-40min，温度为20℃-60℃。
在其中一个较为优选的实施例中，所述制备分散浆的工艺参数如下：
转速为1800r/min-2000r/min，时间为25min-30min，温度为25℃-30℃。
在其中一个较为优选的实施例中，在所述制备分散浆的步骤中，选用了特定的加料顺序，加料顺序依次为部分的水I、解絮凝型的水性分散剂、高分子材料、余量的水I。优选地，所述部分的水I为50％-70％的水I，余量的水I为30％-50％的水I。
即，按照设计的原料配比，将50％-70％的水I、解絮凝型的水性分散剂、高分子材料、30％-50％的水I先后在高速分散机搅拌状态下，加入带冷却水夹套的移动缸中，分散制备得到分散浆。其中，所述搅拌机为高速分散机，分散盘为齿状分散盘，转速为1000r/min-2500r/min，时间为20min-40min，温度为 20℃-60℃。
(2)将所述分散浆和体积位阻型水性分散剂、研磨介质混合，研磨，制备研磨浆的步骤为：
将上述的分散浆39.9％-78.5％、研磨介质20％-60％和体积位阻型水性分散剂0.1％-1.5％加入到砂磨机中，研磨，过滤，制备得到研磨浆。
在其中一个较为优选的实施例中，所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：40％-50％、0.8％-1.0％和49％-59.2％。
所述的体积位阻型水性分散剂选自聚氨酯的嵌段共聚物、聚丙烯酸酯的共聚物中的一种或多种。
在其中一个实施例中，所述聚丙烯酸酯的共聚物为聚丙烯酸酯的三元共聚物。
在其中一个实施例中，所述聚丙烯酸酯的共聚物为疏水改性的聚丙烯酸酯共聚物。
聚丙烯酸酯的三元共聚物指，除了丙烯基单体外，还会引进其他单体进行聚合，三元指三个单体单元如丙烯酸-乙烯-苯乙烯共聚。疏水改性指的是丙烯酸中的羧基-COOH通过酯化等反应(如和脂肪醇R-OH缩水聚合)引进疏水的-R(如烷烃、苯基等)链段。
优选地，所述体积位阻型水性分散剂选自疏水改性的聚丙烯酸共聚物。
在其中一个实施例中，所述的研磨介质选自玻璃珠、氧化铝研磨球、氧化锆珠、钇稳定氧化锆珠、铈氧化锆珠中的一种或多种。
在其中一个实施例中，所述的研磨介质的粒径为0.5mm-10mm。
在其中一个较为优选的实施例中，所述的研磨介质选自氧化锆珠、铈稳定 氧化锆珠中的一种，粒径为0.5mm-10mm。
在其中一个实施例中，所述制备研磨浆是在搅拌状态下进行的，工艺参数如下：
转速为800r/min-2000r/min，时间为30min-240min，温度为10℃-40℃。
在其中一个较为优选的实施例中，所述制备研磨浆的工艺参数如下：
转速为1200r/min-1500r/min，时间为60min-120min，温度为15℃-20℃。
在其中一个实施例中，在所述制备研磨浆的步骤中，采用了特定的加料顺序，加料顺序依次为研磨介质、上述的分散浆、体积位阻型水性分散剂。
优选地，将所述分散浆和体积位阻型水性分散剂、研磨介质混合，研磨，制备研磨浆的步骤为：
将研磨介质预先称量好加到研磨机中，然后将上述的分散浆通过隔膜泵抽入砂磨机中，研磨一定时间后，再加入体积位阻型水性分散剂，在一定研磨工艺下研磨，过滤，制备得到研磨浆。其中，所述砂磨机为带冷却水夹套的卧式砂磨机，研磨机转速为1200r/min-1500r/min，时间为60min-120min，温度为15℃-20℃。
(3)将所述研磨浆和润湿剂、粘结剂、水II混合，制备水性高分子功能浆料的步骤为：
依次将研磨浆30％-80％、润湿剂0.1％-0.5％、粘结剂0.5％-2.5％和水II17％-69.4％加入搅拌机中，搅拌均匀制备得到水性功能浆料的成品浆料。
在其中一个较为优选的实施例中，所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：40％-50％、0.2％-0.3％、0.8％-1.2％和48.5％-59％。
在其中一个实施例中，所述的润湿剂选自烷基硫酸盐、聚氧乙烯烷基酚醚、 聚氧乙烯脂肪醇醚、聚醚改性聚二甲基硅氧烷中的一种或多种。
在其中一个实施例中，所述的粘接剂选自水性聚氨酯类、水性环氧树脂类、水性聚丙烯酸酯类粘结剂中的一种或多种。水性聚氨酯类粘结剂包括聚氨酯乳液、乙烯基聚氨酯乳液、多异氰酸酯乳液、封闭型聚氨酯乳液；水性环氧树脂类粘结剂包括中石化巴陵石化分公司CYWD系列水性环氧树脂CYDW-100、CYDW-100P、CTDW-120；水性聚丙烯酸酯类粘结剂包括α-氰基丙烯酸甲酯和α-氰基丙烯酸异丙酯。优选地，所述的粘接剂选自α-氰基丙烯酸甲酯和/或α-氰基丙烯酸异丙酯。
在其中一个实施例中，所述水II为超纯水；在25℃条件下，所述水II的电阻率＞10MΩ·cm，pH值为6.5-7.0。
在其中一个实施例中，所述制备水性高分子功能浆料是在搅拌状态下进行的，工艺参数如下：
转速为200r/min-500r/min，时间为10min-40min，温度为20℃-30℃。
在其中一个实施例中，所述制备水性高分子功能浆料的工艺参数如下：
转速为300r/min-350r/min，时间为20min-30min，温度为20℃-30℃。
在其中一个实施例中，在所述制备水性高分子功能浆料的步骤中，采用了特定的加料顺序，加料顺序依次为研磨浆、润湿剂、粘接剂和水II。
优选地，将所述研磨浆和润湿剂、粘结剂、水II混合，制备水性高分子功能浆料的步骤为：
将研磨浆和润湿剂、粘结剂、水II在搅拌机搅拌下依次加入，搅拌均匀制备得到水性功能浆料的成品浆料。其中，所述搅拌机为带螺旋浆式或蝴蝶式搅拌叶片的分散机，搅拌机设置：200r/min-500r/min，时间为10min-40min，温度为20℃-30℃。
本发明还提供上述的水性高分子功能浆料的制备方法制备得到的水性高分子功能浆料。
本发明还提供上述的水性高分子功能浆料在制备改性锂电池隔膜上的应用。
以下为具体实施例部分。
下述实施例1-5和对比例3、5、6中的解絮凝聚丙烯酸酯水性分散剂指聚甲基丙烯酸甲酯，实施例6中的解絮凝聚丙烯酸酯水性分散剂指聚甲基丙烯酸乙酯。
下述实施例和对比例中的聚丙烯酸酯三元共聚物指由聚丙烯酸-聚乙烯-聚苯乙烯组成的三元共聚物。疏水改性聚丙烯酸酯共聚物指由聚丙烯酸-聚丁二烯组成的共聚物，疏水改性指丙烯酸中的羧基与丁醇发生酯化反应。
实施例1
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。
(1)分散浆制备：将38kg超纯水、40kg聚偏氟乙烯共聚物粉末、2kg解絮凝聚丙烯酸酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min，分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将24.5kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入25kg步骤(1)制得分散浆和0.5kg体积位阻型聚丙烯酸酯三元共聚物水性分散剂，研磨机转速1500r/min，温度控制在15-20℃，研磨时间120min，制得到研磨浆。
(3)成品浆制备：将25kg步骤(2)制得的研磨浆，0.15kg聚醚改性聚二甲基硅氧烷润湿剂，0.6kg聚丙烯酸酯粘接剂，24.25kg超纯水依次加入搅拌 机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料1。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
实施例2
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯共聚物粉末、4kg解絮凝聚丙烯酸酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min，分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将24.5kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入25kg步骤(1)制得分散浆和0.5kg体积位阻型聚丙烯酸酯三元共聚物水性分散剂，研磨机转速1500r/min，温度控制在15-20℃，研磨时间120min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg聚丙烯酸酯粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料2。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
实施例3
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯均聚物粉末、4kg解絮凝聚丙烯酸酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分 散速度设置为2000r/min,分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg体积位阻型聚丙烯酸酯三元共聚物水性分散剂，研磨机转速1200r/min，温度控制在15-20℃，研磨时间60min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg水性环氧树脂类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料3。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
实施例4
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯共聚物粉末、4kg磷酸三乙酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为1800r/min，分散时间30min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg疏水改性聚丙烯酸酯共聚物水性分散剂，研磨机转速1500r/min，温度控制在15-20℃，研磨时间120min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg聚氨酯类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成 品水性高分子功能浆料4。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
实施例5
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。与实施例3基本一致，区别在于，本实施例选用疏水改性聚丙烯酸酯共聚物作为体积位阻型的水性分散剂。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯均聚物粉末、4kg解絮凝聚丙烯酸酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min,分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg体积位阻型疏水改性聚丙烯酸酯共聚物水性分散剂，研磨机转速1200r/min，温度控制在15-20℃，研磨时间60min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg水性环氧树脂类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料5。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
实施例6
本实施例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。
(1)分散浆制备：将32kg超纯水、34kg聚偏氟乙烯共聚物粉末、1kg解 絮凝脂肪酸聚乙二醇酯水性分散剂、33kg超纯水依次加入分散剂配套生产缸中，分散速度设置为1200r/min，分散时间20min，温度控制在40-50℃，，制得到分散浆。
(2)研磨浆制备：将20kg玻璃珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入40kg步骤(1)制得分散浆和0.4kg羧甲基纤维素水性分散剂，研磨机转速1000r/min，温度控制在15-20℃，研磨时间120min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg烷基硫酸盐，0.4kg聚氨酯类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，，制得成品水性高分子功能浆料6。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
对比例1
本对比例使用的水性高分子功能浆料为市售商品化锂离子电池隔膜涂覆用水性聚偏氟乙烯功能浆料J04-001。
涂布隔膜：在9+3μm陶瓷涂覆隔膜上通过凹版辊辊涂方式涂覆2μm水性聚偏氟乙烯涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
对比例2
按行业内主流的水性聚偏氟乙烯浆料配方制备水性功能浆料，配方组份如下：66.2％超纯水，28％聚偏氟乙烯粉末，4.2％分散剂BYK-LPC22136,0.5％消泡剂BYK-1785，0.5％润湿剂BYK-LPX20990，0.6％防沉剂LAPONITE RD。
步骤：首先加入超纯水，在搅拌状态下加入分散剂和防沉剂，1500rpm下分散30min，然后加入聚偏氟乙烯粉末，转速调整至800-1000rpm加入消泡剂、润 湿剂，分散30min得到浆料。
对比例3
本对比例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。与实施例5基本一致，区别在于，本对比例在第一步中加体积位阻型水性分散剂，在第二步骤加解絮凝型水性分散剂。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯均聚物粉末、4kg体积位阻型疏水改性聚丙烯酸酯共聚物水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min,分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg解絮凝聚丙烯酸酯水性分散剂，研磨机转速1200r/min，温度控制在15-20℃，研磨时间60min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg水性环氧树脂类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料7。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
对比例4
本对比例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。与实施例5基本一致，区别在于，本对比例选用脂肪酸聚乙二醇酯水性分散剂作为解絮凝型的水性分散剂。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯均聚物粉末、4kg解絮凝脂肪酸聚乙二醇酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min,分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg疏水改性聚丙烯酸酯共聚物水性分散剂，研磨机转速1200r/min，温度控制在15-20℃，研磨时间60min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg水性环氧树脂类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料8。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
对比例5
本对比例提供一种水性高分子功能浆料的制备方法及其制备方法和应用。与实施例5基本一致，区别在于，本对比例选用羧甲基纤维素水性分散剂作为体积位阻型的水性分散剂。
(1)分散浆制备：将31kg超纯水、45kg聚偏氟乙烯共聚物粉末、4kg解絮凝聚丙烯酸酯水性分散剂、20kg超纯水依次加入分散剂配套生产缸中，分散速度设置为2000r/min,分散时间25min，温度控制在20-30℃，制得到分散浆。
(2)研磨浆制备：将29.6kg铈稳定氧化锆珠(粒径0.8-1.2mm)装入研磨机腔体中，用隔膜泵抽入20kg步骤(1)制得分散浆和0.4kg羧甲基纤维素水 性分散剂，研磨机转速1200r/min，温度控制在15-20℃，研磨时间60min，制得到研磨浆。
(3)成品浆制备：将20kg步骤(2)制得的研磨浆，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg聚氨酯类粘接剂，29.5kg超纯水依次加入搅拌机配套生产缸中，搅拌机转速350r/min，搅拌20min，温度控制在20-30℃，制得成品水性高分子功能浆料9。
成品浆涂布隔膜：在9+3μm陶瓷隔膜上通过凹版辊辊涂方式涂覆2μm水性PVDF涂层，经过烘箱烘烤后得到水性功能涂层隔膜。
对比例6
按行业内主流的水性聚偏氟乙烯浆料制备方法制备水性功能浆料，配方组份如下：33.58kg超纯水，3.6kg聚偏氟乙烯共聚物粉末，0.32kg解絮凝聚丙烯酸酯水性分散剂，11.84kg铈稳定氧化锆珠，0.16kg疏水改性聚丙烯酸酯共聚物水性分散剂，0.1kg聚醚改性聚二甲基硅氧烷润湿剂，0.4kg聚氨酯类粘接剂。
制备方法：首先在篮式分散机分散篮加入铈稳定氧化锆珠，然后加入超纯水，在搅拌状态下加入解絮凝聚丙烯酸酯水性分散剂、防沉剂，1500rpm下分散10min，然后加入聚偏氟乙烯粉末，疏水改性聚丙烯酸酯共聚物，聚醚改性聚二甲基硅氧烷润湿剂，聚氨酯类粘接剂，转速调整至800-1000rpm，分散30min分得到浆料。
试验例1
对实施例1～6和对比例1～6得到的水性高分子功能浆料进行性能测试。
(1)浆料存储稳定性：将成品浆料存储在100ml塑料瓶子，25摄氏度下存储，观看浆料分层及沉淀情况。结果见图1-2。其中，为了方便，以数字1-6表示实施例1-6的产品，以简写J04-001表示对比例1的产品，以BYK表示对比 例2的产品，以数字7-10表示对比例3-6的产品。
图1(a)-1(d)为对比例1、对比例2、实施例1、2、3、4的水性高分子功能浆料(由左到右)存储在100mL塑料瓶中的第1天、第7天、第14天和第28天的情况。存储第1天后，对比例1、2和实施例1-4在塑料瓶内无明显分层沉淀现象。存储7天后对比例1出现了明显的分层沉淀现象，对比例2和实施例1-4浆料稳定性良好，无明显分层沉淀现象。存储14天后，对比例1的分层沉淀加剧，上层液体澄清；对比例2开始出现底部分层沉淀现象，实施例1-4浆料稳定性良好无明显分层沉淀现象。存储28天后，对比例1完全分为两层，对比例2底部也出现明显的沉淀层，实施例1-4上层开始出现轻微澄清液体层，浆料整体稳定性良好。从图1中可以清楚地看出，相较于对比例1-2，本发明实施例1-4制备的水性高分子功能浆料具有优异的储存稳定性。
图2表示实施例5-6和对比例3-6的水性高分子功能浆料(由左到右)存储在100mL塑料瓶中的第1天后的情况。从图2中可以清楚地看出本发明实施例5-6的水性高分子功能浆料具有优异的储存稳定性，对比例3的水性高分子功能浆料底层出现硬沉淀，上层液体浑浊；对比例4的水性高分子功能浆料出现分层现象，上层清澈下层浑浊；对比例5的水性高分子功能浆料沉降严重；对比例6的水性高分子功能浆料底部出现硬沉淀，上层液体浑浊。
(2)表面张力测试：参照国标《GB/T 30693-2014塑料薄膜与水接触角的测量》进行测试。结果见表1：
表1
Figure PCTCN2020108564-appb-000001
试验例2
(1)水性功能浆料涂覆隔膜基本性能测试
水性功能浆料涂覆隔膜厚度、透气值、面密度、热收缩率、剥离强度等基本性能数据测试参照国标GBT36363-2018或企业行标测试方法进行测试。
实施例1-6和对比例1-2的水性高分子功能浆料涂覆隔膜检测结果如表2所示：
表2
Figure PCTCN2020108564-appb-000002
注：由于对比例3-6的水性高分子功能浆料的稳定性太差，存储1天后即发生明显沉降，不满足行业标准，生产效率低及涂覆质量稳定性差，因此，无法将其用于涂覆隔膜。
由表2可知，使用相同陶瓷膜进行涂覆时，本发明实施例1-6制备的水性功能涂层锂离子电池隔膜在厚度增加值、透气性值、电解液吸液率、剥离强度等方面均优于对比例1-2。
(2)水性功能涂层隔膜卷绕电芯后基本性能测试，方法如下：
a：干压指将正极片、水性功能涂覆隔膜、负极片通过卷绕，置于铝塑膜中，封装好，在65摄氏度和1MPa压力条件下热压30分钟，冷却后进行电芯硬度和极片粘结力测试。
b：湿压指浆正极片、水性功能涂覆隔膜、负极片卷绕后，置于铝塑膜后，先注入9g 1mol/L LiPF 6电解液(溶剂为体积比碳酸乙烯酯:碳酸二乙酯:甲基乙基碳酸酯＝1:1:1)，再封装好，在65摄氏度和1MPa压力条件下热压30分钟，冷却后进行电芯硬度和极片粘结力测试。
c：电芯硬度测试是用直径1mm的圆头针，施加1kg力压倒电芯上，测量压入深度值，值越大表示电芯越软，反之值越小电芯越硬。
实施例1-6和对比例1-2水性功能浆料涂覆隔膜制成规格为506090软包电芯后，检测结果如表3所示：
表3
Figure PCTCN2020108564-appb-000003
由表3可知，采用本发明实施例1-6制备的水性功能涂层锂离子电池隔膜制成 软包电芯后在电芯硬度、极片粘结力、内阻、容量、倍率和高温储存7天60℃保持率等方面均优于对比例1-2。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种水性高分子功能浆料的制备方法，其特征在于，包括以下步骤：
    将高分子材料、解絮凝型的水性分散剂和水I混合，制备分散浆；
    将所述分散浆、体积位阻型水性分散剂和研磨介质混合，研磨，制备研磨浆；
    将所述研磨浆、润湿剂、粘结剂和水II混合，制备水性高分子功能浆料；
    所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为30％-60％、1％-5％和35％-70％；
    所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：39.9％-78.5％、0.1％-1.5％和20％-60％；
    所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：30％-80％、0.1％-0.5％、0.5％-2.5％和17％-69.4％；
    所述的解絮凝型的水性分散剂选自聚丙烯酸酯、磷酸酯中的一种或多种；
    所述的体积位阻型水性分散剂选自聚氨酯的嵌段共聚物、聚丙烯酸酯共聚物中的一种或多种。
  2. 根据权利要求1所述的水性高分子功能浆料的制备方法，其特征在于，所述的高分子材料、解絮凝型的水性分散剂和水I占所述分散浆的质量百分比分别为40％-45％、1％-5％和50％-55％。
  3. 根据权利要求1所述的水性高分子功能浆料的制备方法，其特征在于，所述分散浆、体积位阻型水性分散剂和研磨介质占所述研磨浆的质量百分比分别为：40％-50％、0.8％-1.0％和49％-59.2％。
  4. 根据权利要求1所述的水性高分子功能浆料的制备方法，其特征在于，所述研磨浆、润湿剂、粘结剂和水II占所述水性高分子功能浆料的质量百分比分别为：40％-50％、0.2％-0.3％、0.8％-1.2％和48.5％-59％。
  5. 根据权利要求1至4任一项所述的水性高分子功能浆料的制备方法，其特征在于，所述的高分子材料选自聚四氟乙烯、聚偏氟乙烯均聚物、聚偏氟乙烯共聚物、聚甲基丙烯酸甲酯均聚物、聚甲基丙烯酸甲酯共聚物、水性聚酰亚胺、芳纶、聚氧化乙烯中的一种或多种。
  6. 根据权利要求1至4任一项所述的水性高分子功能浆料的制备方法，其特征在于，所述的研磨介质选自玻璃珠、氧化铝研磨球、氧化锆珠、钇稳定氧化锆珠、铈氧化锆珠中的一种或多种；及/或，
    所述的研磨介质的粒径为0.5mm-10mm。
  7. 根据权利要求1至4任一项所述的水性高分子功能浆料的制备方法，其特征在于，所述的润湿剂选自烷基硫酸盐、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚、聚醚改性聚二甲基硅氧烷中的一种或多种；及/或，
    所述的粘接剂选自水性聚氨酯类、水性环氧树脂类、水性聚丙烯酸酯类粘结剂中的一种或多种；及/或，
    所述水I和水II均为超纯水；在25℃条件下，所述水I的电阻率为5MΩ·cm-15MΩ·cm，pH值为6.0-8.0；所述水II的电阻率＞10MΩ·cm，pH值为6.5-7.0。
  8. 根据权利要求1至4任一项所述的水性高分子功能浆料的制备方法，其特征在于，所述分散浆是在搅拌状态下制备的，工艺参数如下：
    转速为1000r/min-2500r/min，时间为20min-40min，温度为20℃-60℃；及/或，
    所述研磨浆是在搅拌状态下制备的，工艺参数如下：
    转速为800r/min-2000r/min，时间为30min-240min，温度为10℃-40℃；及/或，
    所述水性高分子功能浆料是在搅拌状态下制备的，工艺参数如下：
    转速为200r/min-500r/min，时间为10min-40min，温度为20℃-30℃。
  9. 一种根据权利要求1至8任一项所述的水性高分子功能浆料的制备方法制备得到的水性高分子功能浆料。
  10. 权利要求9所述的水性高分子功能浆料在制备改性锂电池隔膜上的应用。
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