WO2018032665A1 - 丙烯腈共聚物粘合剂及其在锂离子电池中的应用 - Google Patents

丙烯腈共聚物粘合剂及其在锂离子电池中的应用 Download PDF

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WO2018032665A1
WO2018032665A1 PCT/CN2016/109197 CN2016109197W WO2018032665A1 WO 2018032665 A1 WO2018032665 A1 WO 2018032665A1 CN 2016109197 W CN2016109197 W CN 2016109197W WO 2018032665 A1 WO2018032665 A1 WO 2018032665A1
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acrylate
binder
monomer
acrylonitrile
acrylamide
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PCT/CN2016/109197
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English (en)
French (fr)
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潘中来
张晓正
吕川
杜鸿昌
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四川茵地乐科技有限公司
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Application filed by 四川茵地乐科技有限公司 filed Critical 四川茵地乐科技有限公司
Priority to EP16913417.8A priority Critical patent/EP3502151B1/en
Priority to JP2019530528A priority patent/JP6758505B2/ja
Priority to US16/326,597 priority patent/US11603423B2/en
Priority to KR1020197007036A priority patent/KR102235389B1/ko
Publication of WO2018032665A1 publication Critical patent/WO2018032665A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
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    • C08F220/48—Acrylonitrile with nitrogen-containing monomers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C09D133/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/622—Binders being 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M50/42—Acrylic resins
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    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
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    • 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
    • H01M50/44—Fibrous material
    • 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
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 field of lithium ion batteries, and more particularly to an acrylonitrile copolymer binder and its use in a lithium ion battery.
  • Lithium-ion batteries have high energy density and long cycle life, and are widely used in portable electronic devices, electric vehicles, and energy storage.
  • Lithium-ion batteries are mainly composed of a positive electrode, a negative electrode, a separator, an electrolyte, and an outer casing.
  • the working principle is to store and release electric energy by a redox reaction in which lithium ions are reversibly embedded/deintercalated in an electrode active material.
  • the preparation method of the positive electrode and the negative electrode of the lithium ion battery is to mix the positive electrode active material or the carbon negative electrode material with the electrode binder, the conductive agent, the dispersion medium, etc. into a slurry, apply to the corresponding current collector foil, and bake. Dry, rolling, cutting and other processing techniques are produced.
  • Electrode adhesives as a link between the various material particles and current collectors in the electrode, must have the ability to remain perfectly resistant to this change, which requires the electrode adhesive to remain elastic in the working electrolyte environment without slack. Otherwise, this change is likely to cause the peeling of the electrode coating or the increase in the interface resistance of the various material particles in the coating, thereby significantly affecting the capacity, rate, internal resistance, safety, cycle life and the like of the battery. influences. Therefore, the electrode binder must ensure good adhesion between the electrode material particles and between the material particles and the current collector.
  • Electrode binder Although the amount of electrode binder is small, it is an indispensable component in the production of lithium ion batteries. Due to the good stability of carbon anode materials and copper current collectors to water, most of the anode binder market has been occupied by water-based binders that have great advantages in environmental protection, process, performance and cost.
  • the positive electrode binder is highly alkaline in the aqueous slurry due to various positive electrode active materials, and the aluminum foil as the positive electrode current collector is a lively amphoteric metal material, which is neither acid nor alkali resistant, so the water system is The coating of the alkaline slurry on the aluminum foil will cause the collector to be severely corroded and lose its function as a positive electrode, resulting in the positive electrode binder still being dominated by the conventional PVDF/NMP solvent-based adhesive.
  • the PVDF binder is a fluorine-containing material, which has a high price and a weak cohesive force, and the pyrolysis has a risk of releasing HF.
  • Those skilled in the art have designed a new solvent-based adhesive system of PAN/NMP type by using various modified polyacrylonitrile (PAN) as a binder main resin and NMP solvent.
  • PAN is a highly polar polymer with good affinity and electrochemical stability.
  • the use of PAN instead of polyvinylidene fluoride (PVDF) can increase the polarity and bond strength of electrode active materials and reduce material cost.
  • the PAN homopolymer has a high glass transition temperature (Tg ⁇ 85 ° C) and insufficient flexibility at room temperature, which cannot fully meet the process requirements for preparing high-performance cells.
  • the technician uses an acrylate monomer and an acrylonitrile (AN) copolymerization method to improve the flexibility at room temperature to meet the requirements of the cell preparation process.
  • AN acrylonitrile
  • the polarity and solubility parameters of the acrylate monomer and the carbonate solvent in the electrolyte are close to each other, resulting in a large degree of swelling of the PAN copolymer binder in the electrolyte, and deterioration of the core performance.
  • the present invention provides an acrylonitrile copolymer solvent-based adhesive which is suitable for preparation of a modified coating of a lithium ion battery electrode sheet and a polyolefin separator; it has better flexibility to satisfy the preparation of the battery core.
  • the process requirements, at the same time, the degree of swelling in the electrolyte is kept within a specific range to adapt to the periodic variation of the volume of lithium ion embedded/extracted during the charging and discharging process of the electrode active material, thereby increasing the energy density of the battery and Cycle performance.
  • a first technical problem to be solved by the present invention is to provide an acrylonitrile copolymer binder comprising the following structural units by weight: 78 to 95% of acrylonitrile units, acrylates The unit is 1 to 10%, and the acrylamide unit is 2 to 15%.
  • the acrylonitrile unit is introduced from acrylonitrile
  • the acrylate unit can be introduced from the acrylate monomer
  • the acrylamide unit can be introduced from the acrylamide monomer.
  • the acrylonitrile copolymer binder of the present invention may be copolymerized by the following weight percentage of monomers: acrylonitrile 78 to 95%, acrylate monomer 1 to 10%, and acrylamide monomer 2 to 15%.
  • the acrylate monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and acrylic acid.
  • Amyl ester isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate And at least one of isooctyl methacrylate.
  • the acrylamide monomer is preferably at least one selected from the group consisting of acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-butyl acrylamide, and 2-methyl acrylamide. .
  • the acrylate monomer is preferably at least one selected from the group consisting of lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate.
  • the acrylonitrile copolymer binder of the present invention has good flexibility at room temperature and has a suitable degree of swelling at normal temperature (25 ° C) and high temperature (60 ° C). At 25 ° C, the degree of swelling in the electrolyte is maintained in the range of 10 to 20%; at 60 ° C, the degree of swelling in the electrolyte is maintained in the range of 40 to 68%.
  • a second technical problem to be solved by the present invention is to provide a method for preparing the above acrylonitrile copolymer binder, which is carried out by polymerizing the above monomers under the action of an initiator.
  • the initiator is a water-soluble initiator or an oil-soluble initiator, and the water-soluble initiator includes ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyl hydrazine or the above water-soluble initiator and NaHSO 3 , FeSO 4
  • the redox initiation system is composed; the oil-soluble initiator includes an organic peroxide and an azo compound, and the initiator is used in an amount of 0.2 to 2.0% by weight based on the total weight of the monomers.
  • an auxiliary agent may also be added.
  • the auxiliary agent is a chain transfer agent, an emulsifier or a dispersing agent, and the auxiliary agent is used in an amount of 0.1 to 10% by weight based on the total weight of the monomers;
  • the above ternary copolymer binder is prepared by first adding a dispersion medium (water, an organic solvent or a mixed solvent) to the reactor, introducing an inert gas, and then adding acrylonitrile and acrylate under stirring.
  • a dispersion medium water, an organic solvent or a mixed solvent
  • the monomer and acrylamide monomer are heated to 40-80 ° C under an inert atmosphere.
  • the initiator is added to carry out polymerization for 2-24 hours to obtain a polymer dispersion, and finally, by precipitation, filtration, washing, drying,
  • the acrylonitrile copolymer binder is obtained by pulverization and sieving.
  • the above quaternary copolymer binder is prepared by first adding an acrylate monomer to a dispersion medium, stirring and dissolving, and then adding acrylonitrile, an acrylate monomer, an acrylamide monomer, and a desired auxiliary agent. (Also without adding auxiliary agent), the temperature is raised to 40-80 ° C under an inert atmosphere. After the temperature is constant, the initiator is added for polymerization for 2-24 hours to obtain a polymer dispersion, and finally, by precipitation, filtration, washing, drying and pulverization. The acrylonitrile copolymer binder is obtained by sieving.
  • the auxiliary agent includes a chain transfer agent, an emulsifier, a dispersing agent and the like which may be used as needed, and examples thereof include a chain transfer agent such as ethanol, methanol, ethyl mercaptan or dodecyl mercaptan, and sodium dodecylbenzenesulfonate.
  • a chain transfer agent such as ethanol, methanol, ethyl mercaptan or dodecyl mercaptan, and sodium dodecylbenzenesulfonate.
  • octyl dodecyl phenyl ether sulfonate sodium lauryl sulfate, sodium lauryl sulfate, sodium laurate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene sorbitan lauryl ester and other emulsifiers
  • a water-soluble polymer dispersant such as gelatin, polyvinylpyrrolidone, sodium polyacrylate, polyvinyl alcohol or sodium carboxymethylcellulose.
  • a third technical problem to be solved by the present invention is the use of the above acrylonitrile copolymer binder in a positive electrode sheet of a lithium ion battery and a coated separator.
  • a fourth technical problem to be solved by the present invention is to provide a positive electrode sheet for a lithium ion battery, comprising a positive electrode material and a binder, the binder being the above acrylonitrile copolymer binder, and the amount of the binder used It is 0.5 to 5 wt%, preferably 1 to 3 wt%, based on the total solid content.
  • a fifth technical problem to be solved by the present invention is to provide a coated separator for a lithium ion battery, comprising a base film, a filler and a binder, the binder being the above acrylonitrile copolymer binder, and a binder
  • the amount used is from 1 to 40% by weight, preferably from 5 to 20% by weight based on the total solids.
  • the binder of the present invention mainly comprises an acrylonitrile monomer, and an acrylate monomer, a strongly polar acrylamide or a derivative monomer thereof, and an acrylate monomer are copolymerized in acrylonitrile, thereby Maintaining the strong adhesion or intermolecular force of the acrylonitrile polymer molecule, while imparting flexibility to the polymer film, electrolyte affinity, and proper swelling in the electrolyte, thereby improving the lithium ion battery. Energy density and cycle performance.
  • the coated separator prepared using the acrylonitrile copolymer binder of the present invention has excellent battery properties.
  • Fig. 1 is a cycle capacity retention ratio of a battery made of different binders in Example 9 of the present invention.
  • Example 9 is a cyclic thickness expansion ratio of a battery made of different binders in Example 9 of the present invention.
  • the first technical problem to be solved by the present invention is to provide an acrylonitrile copolymer binder which uses acrylonitrile as a main polymerization monomer and can reduce acrylonitrile by introducing an acrylate monomer into an acrylonitrile monomer.
  • Polymer glass The temperature is increased, the flexibility of the polymer is increased, and the monomer of acrylamide or its derivative is introduced to control the degree of swelling of the binder in the electrolyte in the range of 10 to 68%.
  • the acrylonitrile copolymer binder of the present invention is an acrylonitrile copolymer having a degree of swelling in the electrolyte within the above range.
  • the acrylonitrile copolymer binder of the present invention has a degree of swelling in the electrolyte of from 10 to 68%.
  • the degree of swelling of the binder in the electrolyte is greater than 68%, the spacing between the active material particles in the electrode sheet is excessively large, increasing the resistance of electronic transition between the particles, increasing the internal resistance of the battery and reducing the capacity, and at the same time, the electrode sheet Expansion, the thickness of the cell increases, and the electrode active material is easily separated from the current collector during the charge and discharge cycle, and the cycle performance is deteriorated;
  • the degree of swelling of the binder in the electrolyte is less than 10%, during charging and discharging It is unable to effectively buffer the periodic change of the volume of the electrode active material, and the coating of the electrode active material is broken, which increases the internal resistance of the battery and reduces the cycle life of the battery; when the viscosity of the adhesive in the electrolyte is 10 to 68 In the range of %, it can effectively buffer the change of
  • the degree of swelling of the binder of the present invention is the degree of swelling when the solvent is immersed in the electrolyte, and is specifically a value obtained by the following test method.
  • the NMP solution of the binder is poured into a specific container, and the NMP solvent is volatilized to obtain a binder polymer film.
  • the thickness of the film is controlled to 100 ⁇ m, and the film is cut into a film of 50 mm ⁇ 50 mm in width. .
  • the film was vacuum dried for 24 hours, and then weighed, and then the completely dried film was immersed in an electrolyte solution at room temperature (25 ° C) for 72 hours or 60 ° C in an electrolyte solvent for 24 hours, and then removed and wiped off.
  • the increase rate (%) of the weight of the film before and after immersion in the electrolyte solvent at a normal temperature (25 ° C) or a high temperature of 60 ° C is the swelling degree of the binder at room temperature (25 ° C) or 60 ° C at a high temperature.
  • the acrylonitrile copolymer binder is designed to comprise the following structural units by weight: 78 to 95% of the acrylonitrile unit, 1 to 10% of the acrylate unit, and 2 to 15% of the acrylamide unit.
  • the acrylonitrile unit is introduced from acrylonitrile
  • the acrylate unit may be introduced from an acrylate monomer
  • the acrylamide unit may be introduced from an acrylamide monomer
  • other units such as an acrylate unit may be contained.
  • the following weight percentage of monomers may be copolymerized: 78 to 95% of acrylonitrile, 1 to 10% of acrylate monomers, and 2 to 15% of acrylamide monomers.
  • the following percentage by weight of monomers may be copolymerized: 78 to 95% of acrylonitrile, 1 to 10% of acrylate monomers, 2 to 15% of acrylamide monomers, and acrylic acid. Salt monomer 2 ⁇ 8%.
  • the addition of an acrylate monomer can control the high temperature swelling degree to a lower level.
  • the acrylate monomer is preferably selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and acrylic acid.
  • Amyl ester isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate And at least one of isooctyl methacrylate.
  • the acrylamide monomer is preferably at least one of the following compounds: acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-butyl acrylamide, 2-methyl acrylamide.
  • acrylamide N-methyl acrylamide
  • N-ethyl acrylamide N-butyl acrylamide
  • 2-methyl acrylamide 2-methyl acrylamide.
  • the acrylate monomer is preferably at least one selected from the group consisting of lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate.
  • a method of polymerizing the above selected monomer composition to prepare a binder is not particularly limited, and any one of a solution polymerization method, a suspension polymerization method, a bulk polymerization method, an emulsion polymerization method, and the like can be employed.
  • the polymerization reaction is preferably carried out under an aqueous medium, and at the same time, an auxiliary agent such as a chain transfer agent, an emulsifier or a dispersant may be added to the system depending on the needs of the polymerization reaction.
  • the preparation method of the above acrylonitrile copolymer binder is specifically: adding the above preferred monomer composition and an auxiliary agent added as needed to the dispersion medium, and then adding an initiator capable of initiating polymerization reaction to the system.
  • the above composition is caused to undergo polymerization under a certain temperature condition.
  • the auxiliary agent for the polymerization mainly refers to a chain transfer agent, an emulsifier or a dispersant, and includes a chain transfer agent of an alcohol commonly used in emulsion polymerization, an ionic and nonionic emulsifier, and a polymer dispersant, and an optional column.
  • chain transfer agents such as ethanol, methanol, ethanethiol, and dodecyl mercaptan, and sodium dodecylbenzenesulfonate, sodium dodecylphenyl ether sulfate, sodium lauryl sulfate, and dodecyl sulfate.
  • the amount of the auxiliary agent added is 0.1 to 10% based on the total weight of the monomer composition.
  • the initiator may be selected from a water-soluble initiator or an oil-soluble initiator, and the water-soluble initiator includes ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyl hydrazine or the above water-soluble initiator and NaHSO 3 , FeSO. 4 is a redox initiation system; the oil-soluble initiator includes an organic peroxide, an azo compound, and the like. The amount of the initiator is from 0.2 to 2.0% by weight based on the total weight of the monomers.
  • the preparation method of the acrylonitrile copolymer binder of the present invention is:
  • the terpolymer is prepared by first introducing an inert gas into the dispersion medium to drive oxygen, and then adding acrylonitrile, a second monomer acrylate monomer, a third monomer acrylamide monomer, and, if necessary, stirring.
  • the auxiliaries which may be used are heated to 40-80 ° C under an inert atmosphere. After the temperature is constant, the initiator is added for polymerization for 2 to 24 hours to obtain a polymer dispersion, which is finally precipitated, filtered, washed, dried, pulverized and passed. The sieve gives an acrylonitrile copolymer binder.
  • the quaternary copolymer binder is prepared by first adding an acrylate monomer to a dispersion medium, stirring and dissolving, and then adding acrylonitrile, a second monomer acrylate monomer to the stirred dispersion medium, The third monomer acrylamide monomer and the auxiliary agent which may be used as needed are heated to 40 to 80 ° C in an inert atmosphere, and after the temperature is constant, the initiator is added to carry out polymerization for 2 to 24 hours to obtain a polymer dispersion, and finally The acrylonitrile copolymer binder is obtained by precipitation, filtration, washing, drying, pulverization, and sieving.
  • the above acrylonitrile copolymer binder is used in a positive electrode sheet of a lithium ion battery and a coated separator.
  • a positive electrode sheet for a lithium ion battery which comprises the above acrylonitrile copolymer binder, and the binder is used in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight based on the total solids.
  • the positive electrode material is at least one of LiFePO 4 , LiCoO 2 , LiNiO 2 , Li(Ni x Co y Mn z )O 2 or LiMn 2 O 4 .
  • a coated separator for a lithium ion battery which comprises the above acrylonitrile copolymer binder, and the binder is used in an amount of 1 to 40% by weight, preferably 5 to 20% by weight based on the total solids.
  • the base film of the separator is a polyolefin microporous membrane, a polymer woven membrane or a polymer non-woven membrane, and the filler is at least one of nano-scale inorganic ceramic particles or polymer powder materials.
  • the acrylonitrile copolymer adhesive of the invention is prepared by coating the diaphragm preparation route and the lithium ion battery production process according to the common coating preparation route and the lithium ion battery production process in the industry, assembling the aluminum plastic film flexible packaging battery and performing the battery property. Can test and investigate.
  • 900 parts of distilled water was added to the reaction vessel, stirring was started, and oxygen was removed by high-purity nitrogen gas for 1 hour, and then 4 parts of methyl acrylate, 12 parts of acrylamide, and 84 parts of acrylonitrile were added, and heated to 60 ° C under an inert atmosphere and kept at a constant temperature; Then, 5 parts of a 20% ammonium persulfate initiator solution was added to initiate the reaction, and the reaction was completed after 4 hours.
  • the binder is obtained by filtration, drying, pulverization, and sieving.
  • Example 2 Basically the same as in Example 1, only methyl acrylate was changed to an equal part by weight of butyl acrylate.
  • Example 4 Basically the same as in Example 4, only methyl acrylate was changed to an equal part by weight of butyl acrylate.
  • the flexibility of each of the examples and the comparative samples was measured by referring to "GB/T 1731-93 Paint Film Flexibility Test".
  • the sample powder was placed in a 5% NMP solution, and baked on a polytetrafluoroethylene plate to obtain a cast film having a thickness of 100 ⁇ 20 ⁇ m, and the flexibility of the sample was measured using a QTX type paint film elastic tester.
  • the film is pressed into the shaft 1 to the shaft 7 in sequence, bent 180 degrees around the shaft, 90 degrees left and right, bent for 2-3 seconds, and the film is observed with a four-fold magnifying glass without occurrence of texture, cracks and breaks.
  • the minimum diameter passed is the index of flexibility of the adhesive film.
  • Each group of samples was measured three times and averaged.
  • the test results are shown in Table 1.
  • the radius of the rod in which the adhesive obtained by the present invention is cracked is from 1 to 1.5 mm, indicating that the adhesive prepared by the present invention has good flexibility and can be used for a lithium ion battery.
  • the low temperature swellability was tested by holding at 25 ° C for 72 hours, and the high temperature swellability was tested by holding at 60 ° C for 24 hours. Five parallel experiments were set for each adhesive and the results were averaged.
  • the dry film swelling test data of the adhesives prepared in the above Comparative Examples and Examples are shown in Table 1.
  • the low temperature swelling degree of the adhesive prepared by the present invention is 7.5 to 18.1%, and the high temperature swelling degree is 41.1 to 67.8%; and the low temperature swelling degree of the obtained binder in the comparative example is 41.7 to 208%.
  • the high temperature swelling degree is 76.4 to 256%; it can be found that the direct addition of the acrylate monomer such as MA or BA for copolymerization causes the adhesive film to excessively swell or even dissolve in the electrolyte solvent.
  • the adhesive will be difficult to ensure its proper bonding ability; on the other hand, while adding MA or BA, a higher polarity AM and acrylate monomer are added for copolymerization, and the adhesive film is The degree of swelling in the electrolyte solvent is effectively controlled, and the adhesive is weakened by the dissolution of the electrolyte, which can better maintain the bonding ability and the bonding effect.
  • the binder prepared in Example 6 was dissolved in NMP, and then conductive carbon and lithium cobaltate were added, and the mixture was stirred at a high speed for 12 hours to obtain a mixed slurry.
  • the mixed slurry was applied to an aluminum foil by a battery coater and dried at a temperature of 110 °C. Will The dried pole piece was rolled, and the original 170 ⁇ m thick pole piece was compacted to 107 ⁇ m.
  • Experiment 1 used PVDF adhesive for production
  • Experiment 2 used the adhesive of Example 6, the positive electrode materials used for the two pole pieces were the same, and the preparation process was the same.
  • Experiments 1 and 2 were designed with 5 sets of parallel experiments.
  • the peel strength is averaged.
  • the slurry ratio and the peel strength (90° peel strength) of the obtained pole piece are shown in Table 2. It can be seen from the table that compared with the amount of binder of PVDF, the binder obtained by the invention can achieve the same pole piece peeling strength by only 60%; the ratio of the binder is lowered, and the active material lithium cobaltate The increase in the proportion has a positive effect on increasing the battery capacity and reducing the influence of the binder on the electrical performance of the lithium ion battery.
  • the lithium cobaltate/PVDF electrode and the lithium cobaltate/PAN electrode prepared in Example 8 were used as the positive electrode, and the same carbon electrode was prepared as the negative electrode with the same aqueous binder, and assembled into a battery for performance comparison test.
  • the production process was as follows:
  • the positive electrode sheet, the negative electrode sheet and the separator are wound and shaped to obtain a bare cell. After the bare cell is placed in an aluminum molded case, the battery is vacuum-baked, poured into an electrolyte, and vacuum sealed to form a square cell, and then in a battery. The tester performs performance tests such as formation, charge and discharge, and cycle life. In this example, 30 batteries were prepared for each of Experiments 1 and 2, PVDF adhesive was used for Experiment 1, and the adhesive of Example 6 was used for Experiment 2.
  • the positive electrode sheets prepared by the different binders have the same negative electrode sheets, separators, electrolytes and amounts used in assembling the batteries.
  • the basic parameters of the battery are shown in Table 3.
  • the data in each group in Table 3 are the average of 10 batteries.
  • the rate performance of the battery is shown in Table 4.
  • the data in each group in Table 4 is the average of 10 batteries.
  • the battery of Experiment 2 is slightly better than the battery of Experiment 1 in terms of capacity, internal resistance, thickness and rate performance, and is superior to the battery of Experiment 1 in high-temperature storage performance.

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Abstract

本发明涉及一种丙烯腈共聚物粘合剂及其在锂离子电池中的应用，属于锂离子电池领域。本发明解决的技术问题是提供一种丙烯腈共聚物粘合剂，所述丙烯腈共聚物粘合剂包含以下重量百分比的结构单元：丙烯腈单元78～95％，丙烯酸酯类单元1～10％，丙烯酰胺类单元2～15％。本发明的粘合剂，以丙烯腈单体为主体，在丙烯腈中加入丙烯酸酯类单体、强极性的丙烯酰胺类单体或丙烯酸盐类单体进行共聚，从而在保持丙烯腈聚合物分子强大的粘附力或分子间作用力的同时，赋予聚合物胶膜以柔韧性、电解液亲和性以及在电解液中适当的溶胀度，以适应电极活性材料在充放电过程中随着锂离子的嵌入\脱出的体积周期性变化，从而提高了锂离子电池的能量密度和循环性能。

Description

丙烯腈共聚物粘合剂及其在锂离子电池中的应用 技术领域
本发明属于锂离子电池领域，更具体地讲，涉及一种丙烯腈共聚物粘合剂及其在锂离子电池中的应用。
背景技术
锂离子电池能量密度大、循环寿命长，在便携式电子设备、电动汽车、储能等领域广泛应用。锂离子电池主要由正极、负极、隔膜、电解液、外壳组成，其工作原理是通过锂离子在电极活性材料中可逆嵌入/脱嵌的氧化还原反应储存和释放电能。锂离子电池正极和负极的制备方法，是将正极活性材料或碳负极材料与电极粘合剂、导电剂、分散介质等一起调配成浆料，涂覆至相应的集流体箔材上，经烘干，辊压，裁切等加工工艺制得。
电池充放电过程中，锂离子深入活性材料粒子内部的嵌入/脱出电化学反应，通常会引起活性材料粒子体积的变化。电极粘合剂作为连接电极中各种材料粒子和集流体的纽带，必须具备保持完美抵抗这种变化的能力，这就要求电极粘合剂必须在工作电解液环境中保持不会松弛的弹性，否则，这种变化容易造成电极涂层的剥离或者涂层内各种材料颗粒间相互接触的界面电阻的增加，从而对电池的容量、倍率、内阻、安全性、循环寿命等性能产生显著的影响。因此，电极粘合剂必须确保电极材料粒子相互之间以及材料粒子与集流体之间的良好粘结，这种良好粘结应持续贯穿于电极制作的工艺过程和锂离子电池寿命周期内的工作过程。在电解液存在下，要使电极粘合剂抵抗材料粒子反复膨胀收缩的体积变化、保持良好粘结力，必须通过粘合剂的结构设计，严格控制电极粘合剂对电解液的吸收，电解液的适度吸收一方面可以增塑粘合剂，使其产生弹性，另一方面可控制溶胀程度，以保证电极粘合剂不因过度增塑而消耗电解液、失去弹性。
电极粘合剂用量虽少，却是锂离子电池生产不可或缺的成分。由于碳负极材料及铜集流体对水的稳定性佳，负极粘合剂市场大部分已由在环保、工艺、性能、成本等多方面有巨大优势的水性粘合剂占据。正极粘合剂则由于多种性能优良的正极活性材料在水性浆料中呈较强碱性，而作为正极集流体的铝箔为活泼的两性金属材质，既不耐酸、也不耐碱，所以水系碱性浆料在铝箔上的涂覆将使集电体受到严重腐蚀而失去正极应有功能，从而导致正极粘合剂仍以传统的PVDF/NMP溶剂型粘合剂为主。
PVDF粘合剂为含氟材料，价格较高，粘结力偏弱，高温分解有放出HF的风险。本领域工作技术人员设计以各种改性聚丙烯腈(PAN)为粘合剂主体树脂，配合NMP溶剂，发展PAN/NMP类新型溶剂型粘合剂体系。PAN为强极性聚合物，与电解液亲和性以及电化学稳定性好，使用PAN替代聚偏氟乙烯(PVDF)可以提高电极活性材料的极性和粘结强度，降低材料成本。但PAN均聚物玻璃化转变温度(Tg≈85℃)高，常温下柔性不足，无法完全满足制备高性能电芯的工艺要求。为了增加PAN的柔韧性，技术人员采用丙烯酸酯类单体与丙烯腈(AN)共聚方法，改善其常温下的柔性以使其满足电芯制备工艺的要求。但丙烯酸酯类单体与电解液中碳酸酯类溶剂的极性和溶解度参数接近，造成PAN共聚物粘合剂在电解液中溶胀度偏大，并致电芯性能劣化。
发明内容
针对前述问题，本发明提供一种丙烯腈共聚物溶剂型粘合剂，其适用于锂离子电池电极片以及聚烯烃隔膜的改性涂覆的制备；其具有较好的柔性满足电芯制备的工艺要求，同时，其在电解液中的溶胀度保持在特定范围内，以适应电极活性材料在充放电过程中随着锂离子的嵌入\脱出的体积周期性变化，从而提高电池的能量密度和循环性能。
本发明的技术方案：
本发明要解决的第一个技术问题是提供一种丙烯腈共聚物粘合剂，所述丙烯腈共聚物粘合剂包含以下重量百分比的结构单元：丙烯腈单元78～95％，丙烯酸酯类单元1～10％，丙烯酰胺类单元2～15％。
其中，丙烯腈单元由丙烯腈引入，丙烯酸酯类单元可以由丙烯酸酯类单体引入，丙烯酰胺类单元可以由丙烯酰胺类单体引入。
进一步，本发明丙烯腈共聚物粘合剂可采用以下重量百分比的单体共聚而成：丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％。
也可采用以下重量百分比的单体共聚而成：丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％，丙烯酸盐类单体2～8％。加入了第四单体丙烯酸盐类单体，能够将高温溶胀度控制得更低。
进一步，所述丙烯酸酯类单体包括通式为CH2＝CR1-COOR2所示的化合物单体，其中，R1＝-H或-CH3，R2表示烷基或环烷基。
更进一步，所述丙烯酸酯类单体选自下述化合物：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正 戊酯、丙烯酸异戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸异辛酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸正戊酯、甲基丙烯酸异戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸异辛酯中的至少一种。
所述丙烯酰胺类单体包含通式为CH2＝CR3CONHR4所示的化合物单体，其中R3＝-H或-CH3，R4表示-H、烷基、环烷基或芳香基中的一种。
更进一步，所述丙烯酰胺类单体优选自下述化合物：丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丁基丙烯酰胺、2-甲基丙烯酰胺的至少一种。
所述丙烯酸盐类单体包含通式为CH2＝CR5-COOM所示的化合物单体，其中R5＝-H或-CH3，M＝Li+、Na+或K+。
进一步，所述丙烯酸盐类单体优选自下述化合物：丙烯酸锂、丙烯酸钠、甲基丙烯酸锂、甲基丙烯酸钠中的至少一种。通常，采用直接加入等当量的丙烯酸类单体和相应的氢氧化物、碳酸盐或碳酸氢盐进行中和，也是可行的方法。
本发明的丙烯腈共聚物粘合剂，在室温下具有较好的柔性，同时在常温(25℃)和高温(60℃)条件下，具有合适的溶胀度。在25℃时，在电解液中的溶胀度保持在10～20％范围内；在60℃时，在电解液中的溶胀度保持在40～68％范围内。
本发明所要解决的第二个技术问题是提供上述丙烯腈共聚物粘合剂的制备方法，将上述各单体在引发剂的作用下进行聚合反应即可。
所述引发剂为水溶性引发剂或者油溶性引发剂，水溶性引发剂包括过硫酸铵、过硫酸钾、过氧化氢、偶氮二异丁脒或者上述水溶性引发剂与NaHSO3、FeSO4构成的氧化还原引发体系；油溶性引发剂包括有机过氧化物和偶氮化合物，引发剂用量占单体总重量的0.2～2.0％。
进一步，上述方法中，还可加入助剂。
所述助剂为链转移剂、乳化剂或分散剂，助剂用量占单体总重量的0.1～10％；
进一步，上述三元共聚物粘合剂的制备方法为：首先向反应器中加入分散介质(水、有机溶剂或混合溶剂)，通入惰性气体，然后在搅拌状态下加入丙烯腈、丙烯酸酯类单体、丙烯酰胺类单体，在惰性气氛下升温至40～80℃，待温度恒定后加入引发剂进行聚合反应2～24h，得到聚合物分散液，最后通过沉淀、过滤、洗涤、干燥、粉碎、过筛即得丙烯腈共聚物粘合剂。
上述四元共聚合物粘合剂的制备方法为：首先向分散介质中加入丙烯酸盐单体，搅拌溶解，然后再加入丙烯腈、丙烯酸酯类单体、丙烯酰胺类单体以及所需助剂(也可不加入助剂)，在惰性气氛下升温至40～80℃，待温度恒定后加入引发剂进行聚合反应2～24h，得到聚合物分散液，最后通过沉淀、过滤、洗涤、干燥、粉碎、过筛即得丙烯腈共聚物粘合剂。
所述助剂包括根据需要可能使用到的链转移剂、乳化剂、分散剂等，可以列举出乙醇、甲醇、乙硫醇、十二硫醇等链转移剂以及十二烷基苯磺酸钠、十二烷基苯基醚磺酸钠、月桂基硫酸钠、十二烷基硫酸钠、月桂酸钠、聚氧乙烯月桂基醚硫酸钠盐、聚氧乙烯山梨糖醇酐月桂酯等乳化剂以及明胶、聚乙烯吡咯烷酮、聚丙烯酸钠、聚乙烯醇、羧甲基纤维素钠等水溶性高分子分散剂。
本发明要解决的第三个技术问题是上述丙烯腈共聚物粘合剂在锂离子电池正极片及涂覆隔膜中的应用。
本发明要解决的第四个技术问题是提供一种锂离子电池用正极片，包括正极材料和粘合剂，所述粘合剂为上述丙烯腈共聚物粘合剂，粘合剂的使用量占总固量的0.5～5wt％，优选为1～3wt％。
本发明要解决的第五个技术问题是提供一种锂离子电池用涂覆隔膜，包括基膜、填料和粘合剂，所述粘合剂为上述丙烯腈共聚物粘合剂，粘合剂的使用量占总固量的1～40wt％，优选为5～20wt％。
本发明的有益效果：
本发明的粘合剂，以丙烯腈单体为主体，在丙烯腈中加入丙烯酸酯类单体、强极性的丙烯酰胺或其衍生物类单体、丙烯酸盐类单体进行共聚，从而在保持丙烯腈聚合物分子强大的粘附力或分子间作用力的同时，赋予聚合物胶膜以柔韧性、电解液亲和性以及在电解液中适当的溶胀度，从而提高了锂离子电池的能量密度和循环性能。使用本发明的丙烯腈共聚物粘合剂制备的涂覆隔膜具有优异的电池性能。
附图说明
图1为本发明实施例9中不同粘合剂制成的电池的循环容量保持率。
图2为本发明实施例9中不同粘合剂制成的电池的循环厚度膨胀率。
具体实施方式
本发明要解决的第一个技术问题是提供一种丙烯腈共聚物粘合剂，其以丙烯腈为主要聚合单体，通过在丙烯腈单体中引入丙烯酸酯类单体，可降低丙烯腈聚合物玻璃 化温度、提高聚合物柔韧性，同时引入丙烯酰胺或其衍生物单体控制粘合剂在电解液中的溶胀度在10～68％范围内。优选的，本发明所述的丙烯腈共聚物粘合剂为在电解液中的溶胀度在上述范围内的丙烯腈共聚物。
本发明所述的丙烯腈共聚物粘合剂在电解液中的溶胀度在10～68％范围内。当粘合剂在电解液中的溶胀度大于68％时，电极片中活性材料粒子之间的间距过大，增加粒子之间电子跃迁的阻力，电池内阻增大和容量降低，同时，电极片膨胀，电芯厚度增加，且在充放电循环过程中电极活性材料容易从集流体上分离，循环性能变差；当粘合剂在电解液中的溶胀度小于10％时，在充放电过程中无法有效缓冲电极活性材料体积周期性的变化，电极活性材料涂层发生破裂，增大了电池的内阻并且降低了电池的循环寿命；当粘合剂在电解液中的溶胀度在10～68％范围内时，能有效缓冲电极活性材料体积的变化，减少电极活性材料涂层的破裂，并且抑制了电极的过度溶胀，改善了电池的容量和循环寿命。
本发明所述粘合剂的溶胀度为其浸渍电解液溶剂时的溶胀度，具体为通过如下测试方法求得的值。首先，将粘合剂的NMP溶液倒入特定的容器内，烘烤使NMP溶剂挥发而制得粘合剂聚合物薄膜，薄膜的厚度控制在100μm，将其剪裁成长50mm×宽50mm的膜片。其次，将该膜片抽真空干燥24h后称重，然后将完全干燥的膜片分别浸渍在常温(25℃)的电解液溶剂中72h或60℃的电解液溶剂中24h后取出，擦去附着在薄膜表面上的电解液溶剂后称取膜片吸收电解液溶剂的重量。该膜片常温(25℃)或高温下60℃的浸渍于电解液溶剂前后的重量的增加率(％)即为该粘合剂常温(25℃)或高温下60℃的溶胀度。
具体地在本发明中，设计丙烯腈共聚物粘合剂包含以下重量百分比的结构单元：丙烯腈单元78～95％，丙烯酸酯类单元1～10％，丙烯酰胺类单元2～15％。
丙烯腈单元由丙烯腈引入，丙烯酸酯类单元可以由丙烯酸酯类单体引入，丙烯酰胺类单元可以由丙烯酰胺类单体引入，此外，还可含有其他单元，比如丙烯酸盐类单元。
作为本发明的一个实施方式，可采用以下重量百分比的单体共聚而成：丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％。
作为本发明的另一个实施方式，也可采用以下重量百分比的单体共聚而成：丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％，丙烯酸盐类单体2～ 8％。加入了丙烯酸盐类单体，能够将高温溶胀度控制得更低。
进一步，所述丙烯酸酯类单体包括通式为CH2＝CR1-COOR2所示的化合物单体，其中，R1＝-H或-CH3，R2表示烷基或环烷基。
更进一步，所述丙烯酸酯类单体优选自下述化合物：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正戊酯、丙烯酸异戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸异辛酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸正戊酯、甲基丙烯酸异戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸异辛酯中的至少一种。
所述丙烯酰胺类单体包含通式为CH2＝CR3CONHR4所示的化合物单体，其中R3＝-H或-CH3，R4表示-H、烷基、环烷基或芳香基中的一种。
更进一步，所述丙烯酰胺类单体优选自下述化合物：丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丁基丙烯酰胺、2-甲基丙烯酰胺中的至少一种。
所述丙烯酸盐类单体包含通式为CH2＝CR5-COOM所示的化合物单体，其中R5＝-H或-CH3，M＝Li+、Na+或K+。
进一步，所述丙烯酸盐类单体优选自下述化合物：丙烯酸锂、丙烯酸钠、甲基丙烯酸锂、甲基丙烯酸钠中的至少一种。通常，采用直接加入等当量的丙烯酸类单体和相应的氢氧化物、碳酸盐、碳酸氢盐进行中和，也是可行的方法。
在本发明中，聚合上述所选单体组合物来制备粘合剂的方法没有特别限定，可采用溶液聚合法、悬浮聚合法、本体聚合法、乳液聚合法等方法中的任何一种。聚合反应优选在水相介质下进行，同时，可根据聚合反应的需要向体系中加入链转移剂、乳化剂、分散剂等助剂。
进一步的，上述丙烯腈共聚物粘合剂的制备方法具体为：向分散介质中加入上述优选的单体组合物以及根据需要添加的助剂，然后向该体系加入可引发聚合反应发生的引发剂，在一定温度条件下引发上述组合物进行聚合。
所述聚合反应的助剂主要指链转移剂、乳化剂或分散剂，包括乳液聚合中常用的醇类的链转移剂、离子型和非离子型乳化剂以及聚合物分散剂，可选择的列出如下：乙醇、甲醇、乙硫醇、十二硫醇等链转移剂以及十二烷基苯磺酸钠、十二烷基苯基醚磺酸钠、月桂基硫酸钠、十二烷基硫酸钠、月桂酸钠、聚氧乙烯月桂基醚硫酸钠盐、 聚氧乙烯山梨糖醇酐月桂酯等乳化剂以及明胶、聚乙烯吡咯烷酮、聚丙烯酸钠、聚乙烯醇、羧甲基纤维素钠等水溶性高分子分散剂，这些助剂可以单独使用也可以组合两种以上使用。助剂的加入量相对于单体组合物总重量的0.1～10％。
所述引发剂可选择水溶性引发剂或者油溶性引发剂，水溶性引发剂包括过硫酸铵、过硫酸钾、过氧化氢、偶氮二异丁脒或者上述水溶性引发剂与NaHSO3、FeSO4构成的氧化还原引发体系；油溶性引发剂包括有机过氧化物和偶氮化合物等。引发剂用量则占单体总重量的0.2～2.0％。
更进一步的，本发明的丙烯腈共聚物粘合剂的制备方法是：
三元共聚物的制备方法为：首先向分散介质中通入惰性气体驱氧，然后搅拌下加入丙烯腈、第二单体丙烯酸酯类单体、第三单体丙烯酰胺类单体以及根据需要可能使用的助剂，在惰性气氛下升温至40～80℃，待温度恒定后加入引发剂进行聚合反应2～24h，得到聚合物分散液，最后通过沉淀、过滤、洗涤、干燥、粉碎、过筛即得丙烯腈共聚物粘合剂。
四元共聚合物粘合剂的制备方法为：首先向分散介质中加入丙烯酸盐类单体，搅拌溶解，之后向搅拌着的分散介质中加入丙烯腈、第二单体丙烯酸酯类单体、第三单体丙烯酰胺类单体以及根据需要可能使用的助剂，在惰性气氛下升温至40～80℃，待温度恒定后加入引发剂进行聚合反应2～24h，得到聚合物分散液，最后通过沉淀、过滤、洗涤、干燥、粉碎、过筛即得丙烯腈共聚物粘合剂。
上述丙烯腈共聚物粘合剂在锂离子电池正极片及涂覆隔膜中的应用。
一种锂离子电池用正极片，采用上述丙烯腈共聚物粘合剂，粘合剂的使用量为占总固量的0.5～5wt％，优选为1～3wt％。
作为一种实施方式，所述正极材料为LiFePO4、LiCoO2、LiNiO2、Li(NixCoyMnz)O2或LiMn2O4中的至少一种。
一种锂离子电池用涂覆隔膜，采用上述丙烯腈共聚物粘合剂，粘合剂的使用量占总固量的1～40wt％，优选为5～20wt％。
作为一种实施方式，所述隔膜的基膜为聚烯烃微孔膜、聚合物织造隔膜或聚合物非织造隔膜，填料为纳米级无机陶瓷颗粒或聚合物粉体材料中的至少一种。
本发明的丙烯腈共聚物粘合剂，按本行业通用的涂覆隔膜制备路线和锂离子电池生产工艺制作涂覆隔膜和锂离子电池电极片，组装成铝塑膜软包装电池并进行电池性 能测试考察。
实施例1本发明新型粘合剂的制备
在反应容器中加入蒸馏水900份，启动搅拌，通入高纯氮气除氧1小时，然后加入丙烯酸甲酯4份、丙烯酰胺12份、丙烯腈84份，惰性气氛下加热至60℃并恒温；然后加入20％的过硫酸铵引发剂溶液5份引发反应，至反应4小时后结束。经过滤、烘干、粉碎、过筛后获得粘合剂。
实施例2本发明新型粘合剂的制备
与实施例1基本相同，仅将丙烯酰胺的用量降低至5份，即丙烯酸甲酯、丙烯酰胺、丙烯腈的用量分别调整为4份、5份、91份。
实施例3本发明新型粘合剂的制备
在反应容器中加入蒸馏水900份，启动搅拌，加入甲基丙烯酸锂4份，并调节pH至7～9，然后通入高纯氮气除氧1小时，然后加入丙烯酸甲酯4份、丙烯酰胺8份、丙烯腈84份，加热至60℃并恒温。然后加入20％的过硫酸铵引发剂溶液5份引发反应，至反应4小时后结束。经过滤、烘干、粉碎、过筛后获得粘合剂。
实施例4本发明新型粘合剂的制备
与实施例3基本相同，仅将丙烯酰胺和甲基丙烯酸的用量分别调整为6份和6份。
实施例5本发明新型粘合剂的制备
与实施例1基本相同，仅将丙烯酸甲酯换为等重量份的丙烯酸丁酯。
实施例6本发明新型粘合剂的制备
与实施例4基本相同，仅将丙烯酸甲酯换为等重量份的丙烯酸丁酯。
实施例7本发明新型粘合剂的制备
在反应容器中加入蒸馏水890份，启动搅拌，通入高纯氮气除氧1小时，然后加入丙烯酸甲酯4份、丙烯酰胺5份、丙烯腈91份、无水乙醇10份，惰性气氛下加热至60℃并恒温；然后加入20％的过硫酸铵引发剂溶液5份引发反应，至反应4小时后结束。经过滤、烘干、粉碎、过筛后获得粘合剂。
对比例1粘合剂的制备
在反应容器中加入蒸馏水400份，启动搅拌，通入高纯氮气除氧1小时，然后加入聚乙烯醇PVA溶解，再加入丙烯酸甲酯10份、丙烯腈80份，加热至50℃并恒温；将0.7份偶氮二异丁腈引发剂溶于10份丙烯腈配成溶液加入到反应容器中开始反应， 反应6小时后结束。经过滤、烘干、粉碎、过筛后获得粘合剂。
对比例2粘合剂的制备
与对比例1基本相同，仅将丙烯酸甲酯换为等重量份丙烯酸丁酯。
对比例3粘合剂的制备
在反应容器中加入蒸馏水900份，启动搅拌，通入高纯氮气除氧1小时，然后加入丙烯酸甲酯5份、丙烯腈95份，惰性气氛下加热至60℃并恒温；然后加入20％的过硫酸铵引发剂溶液5份引发反应，至反应4小时后结束。经过滤、烘干、粉碎、过筛后获得粘合剂。
对比例4粘合剂的制备
与对比例2基本相同，仅将丙烯酸丁酯和丙烯腈的用量分别调整为5份和85份。
对比例5粘合剂的制备
与对比例1基本相同，仅将丙烯酸甲酯和丙烯腈的用量分别调整为20份和70份。
试验例1粘合剂性能测试
1.1粘合剂柔韧性测定
参考《GB/T 1731-93漆膜柔韧性测定法》测定各实施例和对比例样品的柔韧性。将样品粉末配置成5％的NMP溶液，于聚四氟乙烯板上烘烤制得100±20μm厚度的流延膜，用QTX型漆膜弹性试验器的使用方法，测定样品的柔韧性。将胶膜按顺序紧压于轴棒1至轴棒7，绕轴棒弯曲180度，左右各90度，弯曲2-3秒钟，用四倍放大镜观察胶膜不发生网纹、裂纹和断裂现象时，所通过最小直径即为粘合剂胶膜的柔韧性指标。其中轴棒1至轴棒7的半径或曲率半径为R1＝7.5mm，R2＝5mm，R3＝2.5mm，R4＝2mm，R5＝1.5mm，R6＝1mm，R7＝0.5mm。每组样品测量三次，取平均值，测试结果如表1所示。由表1可知，本发明所得粘合剂产生裂纹的轴棒半径为1～1.5mm，表明本发明制得的粘合剂柔韧性好，能够用于锂离子电池。
1.2粘合剂溶胀性能测试
将各实施例和对比例粘合剂在400转/分搅拌、60℃条件下溶解于NMP中，配制为5％的溶液，溶解完后经100目筛网过滤，于聚四氟乙烯板上烘烤制得100±20μm厚度的流延膜。
将粘合剂干膜置于电解液溶剂(碳酸乙烯酯EC∶碳酸二乙酯DEC∶碳酸二甲酯DMC＝2∶1∶1)中测试干膜在不同温度电解液溶剂中的溶胀度，溶胀度用胶膜浸泡后 的质量增加值与浸泡前的质量之比来表示。于25℃保温72小时测试低温溶胀性，于60℃保温24小时测试其高温溶胀性。每种粘合剂设置5个平行实验，其结果取平均值。上述对照例及实施例制备的粘合剂的干膜溶胀测试数据如表1所示。由表1可知，本发明制得的粘合剂的低温溶胀度为7.5～18.1％，高温溶胀度为41.1～67.8％；而对比例中所得粘合剂的低温溶胀度为41.7～208％，高温溶胀度为76.4～256％；可以发现，直接加入MA或BA等丙烯酸酯类单体进行共聚，会使粘合剂胶膜在电解液溶剂中发生过大的溶胀甚至是溶解，在这种情况下粘合剂将难以保证其应有的粘接能力；另一方面，在加入MA或BA的同时，加入极性较高的AM、丙烯酸盐单体进行共聚，其粘合剂胶膜在电解液溶剂中的溶胀度得到有效控制，粘合剂受电解液溶解的侵蚀减弱，能够更好地保持粘接能力和粘接效果。
表1 实施例和对照例所得丙烯腈共聚物粘合剂的溶胀度
Figure PCTCN2016109197-appb-000001
实施例8使用本发明粘合剂制备的极片剥离强度
首先将实施例6制得粘合剂溶于NMP中，然后加入导电碳和钴酸锂，高速搅拌12h，得混合浆料。混合浆料通过电池涂布机涂覆于铝箔上，于110℃温度下烘干。将 烘干后的极片进行辊压，将原170μm厚度的极片压实至107μm。
实验1采用生产用PVDF粘合剂，实验2采用实施例6的粘合剂，两种极片所用正极材料相同，制备过程也相同，实验1和实验2均设计5组平行实验，所得极片的剥离强度取平均值。浆料配比及所得极片的剥离强度(90°剥离强度)如表2所示。由表可知，相较于PVDF的粘合剂用量，本发明所得的粘合剂仅需60％的用量即可达到相同的极片剥离强度；粘合剂的比例的降低，活性物质钴酸锂的比例的提高，这对于提高电池容量、减少粘合剂对锂离子电池的电性能的影响有积极的作用。
表2 极片剥离强度
实验编号 正极粘合剂 粘合剂比例 钴酸锂比例 导电碳比例 极片剥离强度
实验1 PVDF 2.0％ 96.0％ 2.0％ 162N/m
实验2 实施例6 1.2％ 96.8％ 2.0％ 170N/m
实施例9使用本发明粘合剂制备的锂离子电池性能
以实施例8制得的钴酸锂/PVDF电极和钴酸锂/PAN电极作为正极，以相同水性粘合剂制得相同的碳电极作为负极，组装成电池进行性能对比测试，制作过程如下：
正极片、负极片和隔膜通过卷绕、整形制得裸电芯，将裸电芯装入铝塑壳后，通过真空烘烤、灌注电解液、真空封口，制成方形电芯，然后在电池测试仪上进行化成、充放电、循环寿命等性能测试。该实施例中，实验1和实验2各制备30只电池，实验1采用PVDF粘合剂，实验2采用实施例6的粘合剂。不同粘合剂制得的正极片在组装电池时所使用的负极片、隔膜、电解液及用量均相同。
电池的基本参数如表3所示，表3中各组数据均为10只电池的平均值。
电池的倍率性能如表4所示，表4中各组数据均为10只电池的平均值。
另外还测试了电池70℃96h高温的存储性能，结果如表5所示。表5中各组数据均为10只电池的平均值。
可见，实验2的电池在容量、内阻、厚度、倍率性能方面均略优于实验1的电池，在高温存储性能上明显优于实验1的电池。
电池循环性能测试中，每个实验选1只电池做1.0C常温循环性能，各实验的循环容量保持率随循环次数的衰减见图1。两种电池循环厚度膨胀率的比较图如图2所示。
由图1可知，在1.0C常温循环性能测试中，当循环次数达到400次以上时，实验 1的电池的容量保持率开始明显低于实验2的电池的容量保持率；由图2可知，当循环次数达到200次以上时，实验1的电池的厚度膨胀率开始明显高于实验2的电池的厚度膨胀率。容量保持率和厚度膨胀率会分别体现电池寿命和安全性能上。
表3 电池基本参数
Figure PCTCN2016109197-appb-000002
表4 电池倍率性能
Figure PCTCN2016109197-appb-000003
表5 电池70℃下96h高温存储性能
Figure PCTCN2016109197-appb-000004

Claims (15)

  1. 一种丙烯腈共聚物粘合剂，其特征在于：所述丙烯腈共聚物粘合剂包含以下重量百分比的结构单元：丙烯腈单元78～95％，丙烯酸酯类单元1～10％，丙烯酰胺类单元2～15％。
  2. 根据权利要求1所述的丙烯腈共聚物粘合剂，其特征在于：由以下重量百分比的单体共聚而成，丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％。
  3. 根据权利要求1所述的丙烯腈共聚物粘合剂，其特征在于：所述丙烯腈共聚物粘合剂包含以下重量百分比的结构单元：丙烯腈单元78～95％，丙烯酸酯类单元1～10％，丙烯酰胺类单元2～15％，丙烯酸盐类单元2～8％。
  4. 根据权利要求3所述的丙烯腈共聚物粘合剂，其特征在于：由以下重量百分比的单体共聚而成，丙烯腈78～95％，丙烯酸酯类单体1～10％，丙烯酰胺类单体2～15％，丙烯酸盐类单体2～8％。
  5. 根据权利要求2或4所述的丙烯腈共聚物粘合剂，其特征在于：
    所述丙烯酸酯类单体为CH2＝CR1-COOR2，其中，R1为-H或-CH3，R2为烷基或环烷基；
    所述丙烯酰胺类单体为CH2＝CR3CONHR4，其中，R3为-H或-CH3，R4为-H、烷基、环烷基或芳香基。
  6. 根据权利要求5所述的丙烯腈共聚物粘合剂，其特征在于：
    所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正戊酯、丙烯酸异戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸异辛酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸正戊酯、甲基丙烯酸异戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸异辛酯中的至少一种；
    所述丙烯酰胺类单体为丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丁基丙烯酰胺、2-甲基丙烯酰胺中的至少一种。
  7. 根据权利要求4所述的丙烯腈共聚物粘合剂，其特征在于：所述丙烯酸盐类单体为CH2＝CR5-COOM，其中，R5为-H或-CH3，M为Li+、Na+或K+。
  8. 根据权利要求7所述的丙烯腈共聚物粘合剂，其特征在于：所述丙烯酸盐类单体为丙烯酸锂、丙烯酸钠、甲基丙烯酸锂、甲基丙烯酸钠中的至少一种。
  9. 权利要求1～8任一项所述的丙烯腈共聚物粘合剂在锂离子电池正极片或涂覆隔膜中的应用。
  10. 一种锂离子电池用正极片，包括正极材料和粘合剂，其特征在于：所述粘合剂为权利要求1～8任一项所述的丙烯腈共聚物粘合剂。
  11. 根据权利要求10所述的锂离子电池用正极片，其特征在于：所述粘合剂的使用量占总固量的0.5～5wt％。
  12. 根据权利要求11所述的锂离子电池用正极片，其特征在于：所述粘合剂的使用量占总固量的1～3wt％。
  13. 一种锂离子电池用涂覆隔膜，包括基膜、填料和粘合剂，其特征在于：所述粘合剂为权利要求1～8任一项所述的丙烯腈共聚物粘合剂。
  14. 根据权利要求13所述的锂离子电池用涂覆隔膜，其特征在于：所述粘合剂的使用量占总固量的1～40wt％。
  15. 根据权利要求14所述的锂离子电池用涂覆隔膜，其特征在于：所述粘合剂的使用量占总固量的5～20wt％。
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