WO2020238246A1 - 一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途 - Google Patents

一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途 Download PDF

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WO2020238246A1
WO2020238246A1 PCT/CN2020/071414 CN2020071414W WO2020238246A1 WO 2020238246 A1 WO2020238246 A1 WO 2020238246A1 CN 2020071414 W CN2020071414 W CN 2020071414W WO 2020238246 A1 WO2020238246 A1 WO 2020238246A1
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vinylidene fluoride
monomer
add
molecular weight
lithium ion
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PCT/CN2020/071414
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French (fr)
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陈炜
苗国祥
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浙江孚诺林化工新材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/20—Vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/28—Hexyfluoropropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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 fluorine chemical polymer materials, and is specifically a vinylidene fluoride polymer used as a binder for lithium ion power batteries, and a preparation method and application thereof.
  • lithium-ion batteries can be used as power batteries to store clean electric energy in electric vehicles and new energy technologies such as solar and wind energy on a large scale, and they have received extensive attention and research.
  • the battery pole piece is a key factor that affects the performance of the battery.
  • the key technology of the battery pole piece is the adhesive used on the pole piece.
  • the properties of the binder such as adhesion, flexibility, alkali resistance, etc., directly affect the performance of the battery. Adding a smaller amount of binder to obtain larger capacity, longer cycle life and lower internal resistance has a promoting effect on improving battery cycle performance, rapid charging and discharging capabilities, and reducing battery internal resistance.
  • the requirements for energy density are increasing year by year, and the amount of binder is required to be controlled below 1.5%.
  • PVDF Polyvinylidene fluoride
  • the first stage low molecular weight homopolymer, the molecular weight is between 300,000 and 400,000, and the dosage accounts for 6-10% of the positive electrode formula
  • the second stage the high molecular weight homopolymer, the molecular weight is between 600,000 and 700,000
  • high molecular weight homopolymer the molecular weight is about 1 million, and the dosage accounts for 3-5% of the positive electrode formula
  • the fourth stage medium molecular weight
  • the modified polymer has a molecular weight of about 600,000-700,000, and the amount of modified monomer is less than 1%, which accounts for 2.5-3.0% of the positive electrode formula.
  • the PVDF with high molecular weight in the prior art is a homopolymer with a relatively high crystallinity, generally around 50%.
  • the crystallinity of PVDF makes it difficult for the electrolyte molecules to circulate and wet, and the charge and discharge load increases; the crystallinity of PVDF makes the polymer less flexible, which will cause the brittleness of the pole piece when making the pole piece, which will cause the roll Problems such as peeling and fragmentation occur during pressing, cutting and winding, which affect the production and performance of the battery; the crystallinity of PVDF leads to a large difference between the shrinkage rate and the shrinkage rate of the current collector.
  • the modified PVDF in the prior art has a relatively low molecular weight and has a large swelling of the electrolyte, especially at high temperatures, which will cause rapid deterioration of battery capacity and cycle.
  • Patent CN 103755851 A discloses a soap-free emulsion polymerization method of polyvinylidene fluoride for lithium battery electrode binder.
  • the method adopts an emulsion polymerization process, the molecular weight is less than one million, the viscosity is not more than 12000cp (10% NMP solution), and there is no modified monomer to participate in the polymerization, so it is impossible to reduce the dosage to meet the requirements of power batteries.
  • Patent CN 103387633 A discloses a method for preparing ultra-high molecular weight polyvinylidene fluoride materials. This method copolymerizes vinylidene fluoride and acrylate monomers by emulsion polymerization. The polymerization temperature is above 90°C. It is impossible to prepare products with a molecular weight of more than one million, and it is inevitable that incomplete reaction will occur during the reaction. Molecular compound; a large amount of surfactant needs to be added in the polymerization process, so the product cannot meet the requirements of lithium battery binder.
  • Patent CN 104530276 A discloses a method for preparing polyvinylidene fluoride special for lithium battery binders. The method uses an emulsion polymerization process and the selection of persulfate to prepare PVDF homopolymers with low crystallinity. The molecular weight is not high, the reaction efficiency is slow, and the adhesion is low.
  • Patent CN 106299378 A discloses a binder and a lithium ion battery. This patent only describes the structure and composition of PVDF copolymer ideally, and does not describe any product realization.
  • the vinylidene fluoride homopolymer of emulsion polymerization has low molecular weight and insufficient adhesion performance.
  • suspension polymerization can achieve the level of million-level molecular weight, it still cannot meet the defect of ensuring adhesion under the condition of reducing the dosage;
  • the copolymerization of vinyl fluoride and modified monomers can greatly improve the bonding performance, but due to the large gap in reactivity between vinylidene fluoride and modified monomers, the production process is complicated and the realization is very difficult.
  • Patent CN 108172836 A introduces a preparation method of polyvinylidene fluoride modified composite conductive adhesive.
  • the method uses fluorine-containing monomer graft copolymerization to modify polyvinylidene fluoride, reduces the crystallinity of PVDF, and improves the adhesion and flexibility of polyvinylidene fluoride.
  • This method also uses an emulsion polymerization process, and inevitably has the defects of low product molecular weight, low viscosity, and poor adhesion, and it is impossible to reduce the dosage to meet the needs of power batteries.
  • the second stage the vinylidene fluoride monomer, the second monomer, and the third monomer are copolymerized to obtain a high molecular weight vinylidene fluoride copolymer resin;
  • the vinylidene fluoride polymer used as a binder for lithium ion power batteries is characterized in that the ultra-high molecular weight vinylidene fluoride homopolymer resin described in the first stage has a molecular weight of 1.6 to 2 million.
  • the viscosity of the 7.4% (wt%) N-methylpyrrolidone solution is 8000-16000cp; the molecular weight of the high molecular weight vinylidene fluoride copolymer resin described in the second stage is 1 million to 1.3 million, which is at 8% (wt%) )
  • the viscosity of the N-methylpyrrolidone solution is 5000-8000cp.
  • the method for preparing vinylidene fluoride polymer for lithium ion power battery binder is characterized in that in step 1) and step 2): the dispersant is methyl cellulose, ethyl cellulose, One or two of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and hydroxyethyl methyl ethyl cellulose; the initiator is benzoyl peroxide, One of methyl ethyl ketone peroxide, tert-butyl benzoyl peroxide, tert-butyl peroxypivalate, diethyl peroxide dicarbonate, diisopropyl peroxide dicarbonate, di-n-propyl peroxide dicarbonate Species; the chain transfer agent is ethyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, diethyl malonate, acetone,
  • the method for preparing a vinylidene fluoride polymer used as a binder for lithium ion power batteries is characterized by steps 1) and 2): the amount of deionized water is 300-400 of the vinylidene fluoride mass %, preferably 340-370%; the amount of the dispersant is 0.08-0.60% of the vinylidene fluoride mass, preferably 0.1-0.5%, more preferably 0.2-0.4%; the amount of the initiator in the reactor A is 0.05-0.2% of the mass of vinylidene fluoride, preferably 0.08-0.15%, more preferably 0.1-0.12%; in the reactor B, it is 0.42-1.18% of the mass of vinylidene fluoride, preferably 0.5-1.15%, more preferably 0.65-1.0 %; the amount of the chain transfer agent in the reactor A is 0.75-1.85% of the vinylidene fluoride mass, preferably 0.8-1.7%, more preferably 1-1.5%; in the reactor B, it is vinylidene fluoride
  • the chain transfer agent is added 3-4 times in the reactor A, 45-65% of the total weight of the chain transfer agent is added before the reaction starts, and 15-20% of the total weight of the chain transfer agent is added every 60 minutes after the reaction starts; Add 2-4 times in reactor B. Add 10-25% of the total weight of the chain transfer agent before the reaction starts. Add 30-60% of the total weight of the chain transfer agent every 90 minutes after the start of the reaction. The last time will follow the last time. Add the initiator at the same time;
  • the second monomer is added at once before the reaction; the third monomer is added for the first time after 30 minutes of reaction, the added amount accounts for 40-60% of the total weight, and the same amount is added later along with the additional initiator .
  • the method for preparing vinylidene fluoride polymer for lithium ion power battery binder is characterized in that in steps 1) and 2): the polymerization temperature is 50-80°C, preferably 55-75°C, more preferably 60-70°C; polymerization pressure is 8.0-13.0MPa, preferably 9.0-12.0MPa, more preferably 10.0-11.0MPa;
  • the stirring speed of step 1) is 100-400rpm, preferably 150-350rpm, more preferably 200-300rpm;
  • the stirring speed of step 2) is 300-800rpm; preferably 400-700rpm, more preferably 500-600rpm.
  • the method for preparing vinylidene fluoride polymer for lithium ion power battery binder is characterized in that in step 2): the second monomer in the vinylidene fluoride copolymer resin in the second stage
  • the mass percentage content is 1-3%, preferably 1.5-2%
  • the mass percentage content of the third monomer is 0.5-1.5%, preferably 1-1.2%
  • the second monomer is ethylene, vinyl fluoride, or trifluoroethylene , At least one of chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether
  • the third monomer is acrylic acid, acrylonitrile, methyl acrylate, acrylic acid At least one of ethyl ester, butyl acrylate, methyl methacrylate, hydroxyethyl acrylate, and acetamide.
  • the method for preparing vinylidene fluoride polymer for lithium ion power battery binder is characterized in that in step 3): ultra-high molecular weight vinylidene fluoride homopolymer resin and high molecular weight vinylidene fluoride copolymer resin The weight ratio is 0.3:0.7 ⁇ 0.7:0.3.
  • the prepared product can further reduce its consumption in lithium-ion batteries and maintain excellent adhesion performance and resistance to electrolyte With low swelling, it can better meet the needs of high energy density of power batteries, and has broad development prospects.
  • test methods and conditions in the following implementation and comparative examples are as follows:
  • the viscosity is obtained by dissolving the vinylidene fluoride polymer in N-methylpyrrolidone (NMP) at 8:92 (w%) and measuring it with a digital viscometer # 3 rotor at 25°C.
  • NMP N-methylpyrrolidone
  • Mw weight average molecular weight
  • test conditions use 0.1% lithium bromide in dimethylformamide (DMF) as eluent, differential refractive index RI as detector , Polystyrene calibration reagent as standard sample, test temperature 40°C, flow rate 1.0mL/min.
  • DMF dimethylformamide
  • Melting point and melting enthalpy are measured by differential scanning calorimeter (DSC) according to GB/T 19466.
  • the heating program is as follows: at a heating rate of 10°C/min from 80°C to 200°C, holding at 200°C for 5 minutes, cooling at a cooling rate of 20°C/min to 80°C, holding at 80°C for 5 minutes, at 10°C/min
  • the heating rate in min is increased from 80°C to 200°C. Record the DSC spectrum of the second melting.
  • the bonding performance of the adhesive is characterized by the peel strength, which is specifically measured by the intelligent electronic tensile testing machine according to the standard of GB/T 2792.
  • the reaction was completed after 2.8 hours.
  • the polymer slurry is devolatilized in a degassing tank to recover unreacted monomers; the polymer slurry is washed with deionized water until the conductivity of the washing solution drops below 1 ⁇ s/cm, and then the 35% concentration slurry is heated to 105 Spray drying at °C to obtain finished products.
  • the tested product has a molecular weight of 1.82 million and a viscosity of 14,500 mpas.
  • Methyl ester the reaction is over after 6.2h.
  • the polymer slurry is devolatilized in a degassing tank to recover unreacted monomers; the polymer slurry is washed with deionized water until the conductivity of the washing solution drops below 1 ⁇ s/cm, and then the 35% concentration slurry is heated to 105 Spray drying at °C to obtain finished products.
  • the tested product has a molecular weight of 1.1 million and a viscosity of 5800 mpas.
  • the test results show that the vinylidene fluoride polymer prepared by the method of the present invention has extremely high viscosity and molecular weight, and low melting enthalpy; when the polymer is used to prepare lithium-ion batteries, its proportion in the formulation can be greatly reduced And to ensure the solution viscosity, the excellent copolymer technology can give the material a certain degree of flexibility, effectively improve the force between the active material and the metal pole piece, and improve the bonding performance; the lithium ion power battery made of the polymer has high peel strength , The outstanding advantage of high circulation capacity retention rate.

Abstract

一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途，属于氟化工高分子材料技术领域。具体包括三个阶段：第一阶段：偏氟乙烯单体经均聚得到超高分子量偏氟乙烯均聚物树脂；第二阶段：偏氟乙烯单体和第二单体、第三单体经共聚得到高分子量偏氟乙烯共聚物树脂；第三阶段：偏氟乙烯均聚物树脂和共聚物树脂共混得到所述偏氟乙烯聚合物。上述一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途，制得的偏氟乙烯聚合物树脂不但具有很高的分子量和溶液粘度，而且具有优异的黏结性能和柔韧性，可用于动力电池黏结剂。

Description

一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途 技术领域
本发明属于氟化工高分子材料技术领域，具体为一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途。
背景技术
锂离子电池的正极电位很高，负极电位很低，两极之间能组成电压很高的电池单体。由于能量是电压和容量的乘积，所以锂离子电池的能量密度非常高；此外，锂离子电池的重量小，使得电池的比能量很高。因此，锂离子电池可作为动力电池大规模应用于电动汽车和太阳能、风能等新能源技术清洁电能的储存，受到了人们的广泛关注和研究。
电池极片是影响电池性能的关键因素，电池极片的关键技术是极片上使用的黏结剂。黏结剂的性能，如黏结力、柔韧性、耐碱性等，直接影响着电池的性能。加入更少量的黏结剂，获得较大的容量、较长的循环寿命和较低的内阻，这对提高电池的循环性能、快速充放能力以及降低电池的内阻等具有促进作用。特别是电动汽车上用的动力电池，对能量密度的要求逐年提高，对黏结剂的用量要求控制在1.5％以下。
聚偏氟乙烯(PVDF)是锂离子电池最常用的黏结剂，其在锂离子电池中的应用经历了四个发展阶段。第一阶段：低分子量的均聚物，分子量在30-40万之间，用量在正极配方中占比6-10％；第二阶段，中高分子量的均聚物，分子量在60-70万之间，用量在正极配方中占比5-6％；第三阶段，高分子量均聚物，分子量在100万左右，用量在正极配方中占比3-5％；第四阶段，中等分子子量的改性聚合物，分子量在60-70万左右，改性单体用量在1％以下，用量在正极配方中占比2.5-3.0％。
现有技术中高分子量的PVDF为均聚物，结晶度比较高，一般在50％左右。PVDF 的结晶性使电解液的分子很难流通和润湿，充放电负荷增大；PVDF的结晶性使聚合物的柔韧性较低，在制作极片时会引起极片的脆性大，导致辊压、裁片及卷绕过程中发生起皮、断片等问题，影响电池的制作和性能；PVDF的结晶性导致收缩率与集电体的收缩率差异比较大，随着时间的迁移，电极的内部应力使电极合剂层从集电体上部分或全部剥离，引起容量和循环劣化。现有技术中改性的PVDF分子量较低，对电解液的溶胀大，特别是在在高温下会引起电池容量和循坏的急剧恶化。
专利CN 103755851 A公布了一种锂电池电极粘结剂用聚偏氟乙烯的无皂乳液聚合方法。该方法采用乳液聚合的工艺，分子量达不到百万级以上，黏度不超过12000cp(10％的NMP溶液)，也没有改性单体参与聚合，故不可能降低用量来满足动力电池的要求。
专利CN 103387633 A公布了一种超高分子量聚偏氟乙烯材料的制备方法。该方法通过乳液聚合的方式将偏氟乙烯，丙烯酸酯类单体共聚，聚合温度在90℃以上，不可能制备百万级以上分子量的产品，而且在反应过程中难免会出现反应未完全的低分子化合物；在聚合过程中需要加入大量的表面活性剂，故产物达不到锂电池黏结剂的要求。
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发明内容
针对现有技术中存在的上述问题，本发明的目的在于设计提供一种超高分子量、低结晶度、含有改性官能团的用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途的技术方案，制备的产品可以进一步地减少其在锂离子电池中的用量，出色地保持黏结性能和对电解液的低溶胀，更能够适应动力电池高能量密度的需要，具有广泛的发展前景。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物，其特征在于包括以下三个阶段：
第一阶段：偏氟乙烯单体经均聚得到超高分子量偏氟乙烯均聚物树脂；
第二阶段：偏氟乙烯单体和第二单体、第三单体经共聚得到高分子量偏氟乙烯共聚物树脂；
第三阶段：第一阶段的产物超高分子量偏氟乙烯均聚物树脂和第二阶段的产物高分子量偏氟乙烯共聚物树脂共混，得到偏氟乙烯聚合物。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物，其特征在于：第一阶段中所述的超高分子量偏氟乙烯均聚物树脂的分子量为160-200万，在7.4％(wt％)的N-甲基吡咯烷酮溶液中的黏度为8000-16000cp；第二阶段中所述的高分子量偏氟乙烯共聚物树脂的分子量为100-130万,在8％(wt％)的N-甲基吡咯烷 酮溶液中的黏度为5000-8000cp。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于包括以下步骤：
1)在密闭聚合反应釜A中吹扫氮气除氧，加入去离子水、分散剂、偏氟乙烯，开启搅拌，升温升压，在引发剂的作用下通过补加偏氟乙烯单体和链转移剂制得偏氟乙烯均聚物树脂浆料；
2)在密闭聚合反应釜B中吹扫氮气除氧，加入去离子水、分散剂、偏氟乙烯、第二单体，开启搅拌，升温升压，在引发剂的作用下通过补加偏氟乙烯单体、第三单体和链转移剂制得偏氟乙烯共聚物树脂浆料；
3)将步骤1)和步骤2)得到的树脂经洗涤、闪蒸干燥后混合均匀，即得偏氟乙烯聚合物树脂。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)和步骤2)中：所述分散剂为甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羟乙基甲基乙基纤维素中的一种或两种；所述引发剂为过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯、过氧化新戊酸叔丁酯、过氧化二碳酸二乙酯、过氧化二碳酸二异丙酯、过氧化二碳酸二正丙酯中的一种；所述链转移剂为乙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、丙二酸二乙酯、丙酮、丙酸甲酯、丙酸乙酯、丁二酸二乙酯中的一种。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)和步骤2)：所述去离子水的用量为偏氟乙烯质量的300-400％，优选340-370％；所述分散剂的用量为偏氟乙烯质量的0.08-0.60％，优选0.1-0.5％，更优选0.2-0.4％；所述引发剂的用量在反应釜A中为偏氟乙烯质量的0.05-0.2％，优选0.08-0.15％，更优选0.1-0.12％；在反应釜B中为偏氟乙烯质量的0.42-1.18％，优选0.5-1.15％，更优选0.65-1.0％；所述链转移剂的用量在反应釜A中为偏氟乙 烯质量的0.75-1.85％，优选0.8-1.7％，更优选1-1.5％；在反应釜B中为偏氟乙烯质量的的0.12-0.47％，优选0.2-0.4％，更优选0.25-0.35％。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)和步骤2)：所述分散剂在反应釜A、B中均在反应前一次性加入；所述引发剂在反应釜A中分2-5次加入，反应开始前加入引发剂总重量的30-50％，反应开始后每隔45min等量加入剩余部分；在反应釜B中分4-8次加入，反应开始前加入引发剂总重量的15-45％，反应开始后每隔30min加入引发剂总重量的10-15％；
所述链转移剂在反应釜A中分3-4次加入，反应开始前加入链转移剂总重量的45-65％，反应开始后每隔60min加入链转移剂总重量的15-20％；在反应釜B中分2-4次加入，反应开始前加入链转移剂总重量的10-25％，反应开始后每隔90min加入链转移剂总重量的30-60％，最后一次随最末次的引发剂同时加入；
在反应釜B中，第二单体在反应前一次性加入；第三单体在反应30min后首次加入，加入量占总重量的40-60％，以后随补加的引发剂一起等量加入。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)、2)中：聚合温度为50-80℃，优选55—75℃，更优选60—70℃；聚合压力为8.0～13.0MPa，优选9.0～12.0MPa，更优选10.0—11.0MPa；
步骤1)的搅拌速度为100-400rpm,优选150-350rpm，更优选200-300rpm；
步骤2)的搅拌速度为300-800rpm；优选400-700rpm，更优选500-600rpm。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤2)中：第二阶段中所述的偏氟乙烯共聚物树脂中第二单体的质量百分比含量为1-3％，优选1.5-2％；第三单体的质量百分比含量为0.5-1.5％，优选1-1.2％；所述第二单体为乙烯、氟乙烯、三氟乙烯、三氟氯乙烯、四氟乙烯、六氟丙烯、全氟甲基乙烯基醚、全氟丙基乙烯基醚中的至少一种；第三单体为丙烯酸、丙烯腈、 丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸羟乙酯、乙酰胺中的的至少一种。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤3)中：超高分子量偏氟乙烯均聚物树脂和高分子量偏氟乙烯共聚物树脂的重量比为0.3:0.7～0.7:0.3。
所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物在制备锂离子电池黏结剂中的应用。
上述一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物及其制备方法和用途，制备的产品可以进一步地减少其在锂离子电池中的用量，出色地保持黏结性能和对电解液的低溶胀，更能够适应动力电池高能量密度的需要，具有广泛的发展前景。
具体实施方式
下面结合具体实施方式对本发明作进一步说明。
在以下实施及比较例中测试方法及条件如下：
黏度是将偏氟乙烯聚合物以8:92(w％)溶解在N-甲基吡咯烷酮(NMP)中，在25℃条件下，用数字式粘度计3 #转子测量而得。
分子量用重均分子量(Mw)进行表征，具体是通过凝胶渗透色谱仪进行测试，测试条件：采用含0.1％溴化锂的二甲基甲酰胺(DMF)作为淋洗液，示差折光RI为检测器，聚苯乙烯校准试剂为标样，测试温度40℃，流速1.0mL/min。
熔点和熔融焓是通过差示扫描量热仪(DSC)按GB/T 19466的标准进行测定。升温程序为：以10℃/min的升温速度由80℃升温至200℃，在200℃保温5min，以20℃/min的降温速度降温至80℃，在80℃中保温5min，以10℃/min的升温速度由80℃升温至200℃。记录第二次熔融时的DSC谱图。
黏结剂的黏结性能以剥离强度进行表征，具体是通过智能电子拉力试验机按GB/T 2792的标准进行测定。使用的配方为：NCA：PVDF：NMP＝98.3：1.7：46(w％)
实施例1
在20L高压反应釜A中加入12Kg去离子水、12g羟丙基甲基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.5Kg偏氟乙烯，开启搅拌，转速为200r/min，升温至70℃，用计量泵加入2.52g过氧化二碳酸二异丙酯，22.4g碳酸二乙酯开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在11.5MPa，每隔60min补加碳酸二乙酯7.8g，每隔45min补加过氧化二碳酸二异丙酯1.32g，2.8h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为182万，黏度为14500mpas。
在20L高压反应釜B中加入12Kg去离子水、17g甲基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.4Kg偏氟乙烯，66g全氟甲基乙烯基醚，开启搅拌，转速为400r/min，升温至65℃，用计量泵加入10.2g过氧化新戊酸叔丁酯，1.8g乙酸乙酯开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在9.8MPa，每隔30min补加4.3g过氧化新戊酸叔丁酯，每隔90min补加5.7g乙酸乙酯，最后一次乙酸乙酯随最末次的过氧化新戊酸叔丁酯同时加入；反应开始后30min加入17g丙烯酸羟乙酯，其后随补加的过氧化新戊酸叔丁酯每次加入3.2g丙烯酸羟乙酯，5.8h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为116万，黏度为6150mpas。
将反应釜A和反应釜B中的产物按重量比0.5：0.5的比例混合均匀。测试性能，结果列于表1。
实施例2
在20L高压反应釜A中加入12Kg去离子水、4g甲基纤维素、9g羟丙基甲基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.5Kg偏氟 乙烯，开启搅拌，转速为300r/min，升温至65℃，用计量泵加入3.3g过氧化二碳酸二正丙酯，19.4g丙酮开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在12MPa，每隔60min补加丙酮6.4g，每隔45min补加过氧化二碳酸二正丙酯2.1g，2.7h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为155万，黏度为9800mpas。
在20L高压反应釜B中加入12Kg去离子水、11g羟乙基甲基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.3Kg偏氟乙烯，88g氟乙烯，开启搅拌，转速为600r/min，升温至72℃，用计量泵加入13.7g过氧化二碳酸二异丙酯，1.1g丙二酸二乙酯开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在10.6MPa，每隔30min补加5.5g过氧化二碳酸二异丙酯，每隔90min补加5.1g丙二酸二乙酯，最后一次丙二酸二乙酯随最末次的过氧化二碳酸二异丙酯同时加入；反应开始后30min加入20g甲基丙烯酸甲酯，其后随补加的过氧化二碳酸二异丙酯每次加入2.6g甲基丙烯酸甲酯，6.2h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为110万，黏度为5800mpas。
将反应釜A和反应釜B中的产物按重量比0.6：0.4的比例混合均匀。测试性能，结果列于表1。
实施例3
在20L高压反应釜A中加入12Kg去离子水、21g羟丙基甲基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.5Kg偏氟乙烯，开启搅拌，转速为188r/min，升温至78℃，用计量泵加入5.5g过氧化二碳酸二乙酯，30.2g丙二酸二乙酯开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在11.6MPa， 每隔60min补加丙二酸二乙酯4.7g，每隔45min补加过氧化二碳酸二乙酯2.2g，3.7h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为192万，黏度为15700mpas。
在20L高压反应釜B中加入12Kg去离子水、16.5g乙基纤维素、吹扫氮气除氧试压，使釜中氧含量低于10ppm；自初始槽内加入3.4Kg偏氟乙烯，15g三氟乙烯，100g六氟丙烯，开启搅拌，转速为570r/min，升温至66℃，用计量泵加入18.8g过氧化苯甲酰，0.8g丙二酸二乙酯开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在12.1MPa，每隔30min补加7.1g过氧化苯甲酰，每隔90min补加3.2g丙二酸二乙酯，最后一次丙二酸二乙酯随最末次的过氧化苯甲酰同时加入；反应开始后30min加入25g乙酰胺，其后随补加的过氧化苯甲酰每次加入3.3g乙酰胺，7.4h后反应结束。将聚合物浆料在脱气罐脱挥，回收未反应的单体；用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而将35％浓度的浆料在105℃喷雾干燥，制得成品。经测试产物的分子量为128万，黏度为7850mpas。
将反应釜A和反应釜B中的产物按重量比0.3：0.7的比例混合均匀。测试性能，结果列于表1。
比较例1
在20L高压反应釜中加入12Kg去离子水、1g甲基纤维素。吹扫氮气除氧试压，使釜中氧含量低于20ppm；自初始槽内加入2.2Kg偏氟乙烯，开启搅拌桨，转速为600r/min，升温至77℃，用计量泵加入10g过氧化二碳酸二异丙酯，12g丙酮开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在4.8MPa，3.8h后反应结束。用去离子水洗涤聚合物浆料至洗涤液电导率降至1μs/cm以下，进而在85℃干燥16h，制得成品。测试性能，结果列于表1。
比较例2
在20L高压反应釜中加入12Kg去离子水、20g全氟辛酸、12g石蜡。吹扫氮气除氧试压，使釜中氧含量低于20ppm；自初始槽内加入2.3Kg偏氟乙烯，开启搅拌桨，转速为500r/min，升温至85℃，用计量泵加入10g过氧化二碳酸二异丙酯，12g丙酮开始反应；用膜式泵补加偏氟乙烯单体使反应压力保持在4.2MPa，4.0h后反应结束；将聚合物浆料凝聚后用去离子水洗涤至洗涤液电导率降至1μs/cm以下，进而在85℃干燥16h，制得成品。测试性能，结果列于表1。
比较例3
市售国外样品A，测试性能，结果列于表1。
比较例4
市售国外样品B，测试性能，结果列于表1。
比较例5
市售国外样品C，测试性能，结果列于表1。
表1 偏氟乙烯聚合物性能测试
Figure PCTCN2020071414-appb-000001
试验结果表明：采用本发明方法制备的偏氟乙烯聚合物具有极高的黏度和分子量，较低的熔融焓；以该聚合物来制备锂离子电池时，可以极大地减少其在配方中的比例并保证溶液粘度，优异的共聚物技术能赋予材料一定的柔韧性，有效提升 活性物质和金属极片间的作用力，提高黏结性能；以该聚合物制得的锂离子动力电池具有剥离强度高、循环容量保持率高的突出优点。
以上技术方案和实施例对本发明作了详细的描述，但不用来限制本发明的范围。应当理解，基于本发明的启示，本领域技术人员对于本发明的的任何显而易见的变换或替代，也应当被认为是本发明的保护范围。

Claims (10)

  1. 一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物，其特征在于包括以下三个阶段：
    第一阶段：偏氟乙烯单体经均聚得到超高分子量偏氟乙烯均聚物树脂；
    第二阶段：偏氟乙烯单体和第二单体、第三单体经共聚得到高分子量偏氟乙烯共聚物树脂；
    第三阶段：第一阶段的产物超高分子量偏氟乙烯均聚物树脂和第二阶段的产物高分子量偏氟乙烯共聚物树脂共混，得到偏氟乙烯聚合物。
  2. 如权利要求1所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物，其特征在于：第一阶段中所述的超高分子量偏氟乙烯均聚物树脂的分子量为160-200万，在7.4％(wt％)的N-甲基吡咯烷酮溶液中的黏度为8000-16000cp；第二阶段中所述的高分子量偏氟乙烯共聚物树脂的分子量为100-130万,在8％(wt％)的N-甲基吡咯烷酮溶液中的黏度为5000-8000cp。
  3. 如权利要求1所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于包括以下步骤：
    1)在密闭聚合反应釜A中吹扫氮气除氧，加入去离子水、分散剂、偏氟乙烯，开启搅拌，升温升压，在引发剂的作用下通过补加偏氟乙烯单体和链转移剂制得偏氟乙烯均聚物树脂浆料；
    2)在密闭聚合反应釜B中吹扫氮气除氧，加入去离子水、分散剂、偏氟乙烯、第二单体，开启搅拌，升温升压，在引发剂的作用下通过补加偏氟乙烯单体、第三单体和链转移剂制得偏氟乙烯共聚物树脂浆料；
    3)将步骤1)和步骤2)得到的树脂经洗涤、闪蒸干燥后混合均匀，即得偏氟乙烯聚合物树脂。
  4. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的 制备方法，其特征在于步骤1)和步骤2)中：所述分散剂为甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羟乙基甲基乙基纤维素中的一种或两种；所述引发剂为过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯、过氧化新戊酸叔丁酯、过氧化二碳酸二乙酯、过氧化二碳酸二异丙酯、过氧化二碳酸二正丙酯中的一种；所述链转移剂为乙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、丙二酸二乙酯、丙酮、丙酸甲酯、丙酸乙酯、丁二酸二乙酯中的一种。
  5. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)和步骤2)：所述去离子水的用量为偏氟乙烯质量的300-400％，优选340-370％；所述分散剂的用量为偏氟乙烯质量的0.08-0.60％，优选0.1-0.5％，更优选0.2-0.4％；所述引发剂的用量在反应釜A中为偏氟乙烯质量的0.05-0.2％，优选0.08-0.15％，更优选0.1-0.12％；在反应釜B中为偏氟乙烯质量的0.42-1.18％，优选0.5-1.15％，更优选0.65-1.0％；所述链转移剂的用量在反应釜A中为偏氟乙烯质量的0.75-1.85％，优选0.8-1.7％，更优选1-1.5％；在反应釜B中为偏氟乙烯质量的的0.12-0.47％，优选0.2-0.4％，更优选0.25-0.35％。
  6. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)和步骤2)：所述分散剂在反应釜A、B中均在反应前一次性加入；所述引发剂在反应釜A中分2-5次加入，反应开始前加入引发剂总重量的30-50％，反应开始后每隔45min等量加入剩余部分；在反应釜B中分4-8次加入，反应开始前加入引发剂总重量的15-45％，反应开始后每隔30min加入引发剂总重量的10-15％；
    所述链转移剂在反应釜A中分3-4次加入，反应开始前加入链转移剂总重量的45-65％，反应开始后每隔60min加入链转移剂总重量的15-20％；在反应釜B中分2-4次加入，反应开始前加入链转移剂总重量的10-25％，反应开始后每隔90min 加入链转移剂总重量的30-60％，最后一次随最末次的引发剂同时加入；
    在反应釜B中，第二单体在反应前一次性加入；第三单体在反应30min后首次加入，加入量占总重量的40-60％，以后随补加的引发剂一起等量加入。
  7. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤1)、2)中：聚合温度为50-80℃，优选55—75℃，更优选60—70℃；聚合压力为8.0～13.0MPa，优选9.0～12.0MPa，更优选10.0—11.0MPa；
    步骤1)的搅拌速度为100-400rpm,优选150-350rpm，更优选200-300rpm；
    步骤2)的搅拌速度为300-800rpm；优选400-700rpm，更优选500-600rpm。
  8. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤2)中：第二阶段中所述的偏氟乙烯共聚物树脂中第二单体的质量百分比含量为1-3％，优选1.5-2％；第三单体的质量百分比含量为0.5-1.5％，优选1-1.2％；所述第二单体为乙烯、氟乙烯、三氟乙烯、三氟氯乙烯、四氟乙烯、六氟丙烯、全氟甲基乙烯基醚、全氟丙基乙烯基醚中的至少一种；第三单体为丙烯酸、丙烯腈、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸羟乙酯、乙酰胺中的的至少一种。
  9. 如权利要求3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物的制备方法，其特征在于步骤3)中：超高分子量偏氟乙烯均聚物树脂和高分子量偏氟乙烯共聚物树脂的重量比为0.3:0.7～0.7:0.3。
  10. 如权利要求1或3所述的一种用于锂离子动力电池黏结剂的偏氟乙烯聚合物在制备锂离子电池黏结剂中的应用。
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