WO2024016587A1 - 一种水性粘结剂及其制备方法和应用 - Google Patents

一种水性粘结剂及其制备方法和应用 Download PDF

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WO2024016587A1
WO2024016587A1 PCT/CN2022/140684 CN2022140684W WO2024016587A1 WO 2024016587 A1 WO2024016587 A1 WO 2024016587A1 CN 2022140684 W CN2022140684 W CN 2022140684W WO 2024016587 A1 WO2024016587 A1 WO 2024016587A1
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metal salt
polymer
water
acrylate
lithium
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PCT/CN2022/140684
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English (en)
French (fr)
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岳敏
刘俊
王伟华
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深圳市研一新材料有限责任公司
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Publication of WO2024016587A1 publication Critical patent/WO2024016587A1/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
    • 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
    • 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
    • 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 embodiments of this application relate to the technical field of lithium-ion battery materials, such as a water-based binder and its preparation method and application.
  • Binder is one of the main components of the battery pole piece. It is used to connect the active material, conductive agent and electrode current collector to ensure overall connectivity between them. During the charge and discharge process, the binder effectively maintains the structural integrity of the electrode, ensuring that the electrode material can reproducibly insert and remove lithium, and also plays an important role in maintaining cycle performance. Binders have an important impact on the electrical properties of pole pieces and batteries. High-performance lithium-ion batteries require matching high-performance binders.
  • PVDF Polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • water-based binders to replace oil-based binders such as PVDF to make the lithium battery production process meet environmental requirements is one of the current development trends of battery pole pieces.
  • Existing water-based binders include polyacrylic acid (PAA), sodium carboxymethylcellulose/styrene-butadiene rubber (CMC/SBR), sodium alginate, chitosan, etc.
  • PAA polyacrylic acid
  • CMC/SBR sodium carboxymethylcellulose/styrene-butadiene rubber
  • SBR-type binders are It is widely used in negative electrode systems because of its small amount of addition and strong bonding force with active materials and current collectors; however, the components in SBR binders have low polarity and are not compatible with highly polar electrolytes.
  • CN109802139A discloses a water-based adhesive and a battery.
  • the water-based adhesive includes a binding component and a thickening component.
  • the binding component includes any one of styrene-butadiene latex and polyacrylic acid.
  • the embodiments of the present application provide a water-based binder and its preparation method and application.
  • the water-based binder has excellent bonding properties, lithium ions, etc. With its conductivity and appropriate swelling characteristics, it can be used in battery pole pieces and lithium-ion batteries, which can significantly improve the cycle performance and rate performance of the battery.
  • a water-based adhesive which is a copolymer formed of a polymer metal salt and a polymerizable monomer;
  • the polymerizable monomer includes an acrylic ester monomer and A combination of olefin monomers;
  • the polymer metal salt is selected from any of phosphate metal salt polymers, carboxyl metal salt polymers, sulfonate metal salt polymers or disulfonimide metal salt polymers One or a combination of at least two.
  • the water-based adhesive provided by this application is a copolymer formed by the reaction of a polymer metal salt and a polymerizable monomer.
  • the polymerizable monomer includes acrylate monomers and olefin monomers with different solubility parameters.
  • the formed copolymer segments contain specific repeating structural units, thereby obtaining products with different solubility parameters, making the water-based viscosity
  • the binder has appropriate swelling characteristics; at the same time, the structural fragments of the polymer metal salt can enhance the strength and metal salt content of the binder, so that the water-based binder has excellent bonding properties and lithium ion conductivity .
  • the water-based binder provided by this application achieves a good balance between bonding performance, lithium ion conductivity and swelling characteristics through the design of structural units in the copolymer, and has excellent bonding strength, bonding stability and Electrochemical properties, thereby significantly improving the cycle performance and rate performance of battery pole pieces and lithium-ion batteries containing it.
  • the polymer metal salt includes any one or a combination of at least two of polymer lithium salts, polymer sodium salts, polymer potassium salts or polymer magnesium salts.
  • the phosphate metal salt polymer is selected from the group consisting of polyphosphate metal salt, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate metal salt-based polymer, bis(2-(methacryloyloxy) Any one or a combination of at least two of the ethyl)phosphate metal salt-based polymers, 2-methacryloyloxyethyl phosphate metal salt-based polymers or vinyl phosphate metal salt-based polymers, further Preferred are lithium polyphosphate, 2-methyl-2-acrylic acid-2-hydroxyethyl ester lithium phosphate polymer, bis(2-(methacryloyloxy)ethyl)lithium phosphate polymer, 2-methyl Any one or a combination of at least two of acryloyloxyethyl lithium phosphate-based polymers or vinyl lithium phosphate-based polymers.
  • the carboxyl metal salt polymer is selected from the group consisting of methacrylic acid metal salt-based polymers, acrylic acid metal salt-based polymers, maleic acid metal salt-based polymers, itaconic acid metal salt-based polymers, and citrate trisulfate-based polymers.
  • lithium-based polymers lithium maleate-based polymers, lithium itaconate-based polymers, lithium triallyl citrate-based polymers, lithium carboxymethyl cellulose-based polymers or lithium alginate-based polymers Any one or a combination of at least two.
  • the sulfonate metal salt polymer is selected from the group consisting of styrene sulfonate metal salt based polymer, vinyl sulfonate metal salt based polymer, propylene sulfonate metal salt based polymer, methacrylic sulfonic acid Metal salt-based polymer, 4-vinylbenzenesulfinic acid metal salt-based polymer, allyl vinyl sulfonate metal salt-based polymer, 3-sulfonate propyl methacrylic acid metal salt-based polymer, methacrylic acid 2-ethanesulfonate metal salt-based polymer, 2-acrylamido-2-methyl-1-propanesulfonic acid metal salt-based polymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid metal salt Any one or a combination of at least two of 3-allyloxy-2-hydroxy-1-propanesulfonate metal salt-based polymer, more preferably lithium styrene s
  • the disulfonimide metal salt polymer is selected from the group consisting of vinyl disulfonimide metal salt-based polymers and/or styryl disulfonimide metal salt-based polymers, and vinyl disulfonimide metal salt-based polymers are further preferred. Lithium disulfonimide polymer and/or lithium styryl disulfonimide polymer.
  • the "polymer” in the polymer metal salt includes homopolymers and/or copolymers.
  • the polymer can be a methacrylic acid metal salt.
  • the homopolymer can also be a copolymer of a metal salt of methacrylate and other monomers, as long as the polymer contains structural units formed by a metal salt of methacrylate.
  • Other polymers have the same meaning and will not be described again for the sake of simplicity.
  • the weight average molecular weight of the polymer metal salt is 1000-10000000, for example, it can be 2000, 5000, 8000, 10000, 30000, 50000, 80000, 100000, 300000, 500000, 800000, 1000000, 3000000, 5000000, 70 00000 Or 9000000, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, this application will not exhaustively list the specific point values included in the range.
  • the polymer metal salt can be purchased from the market, or can be obtained by subjecting the acidic polymer to metal salt formation by methods known in the prior art.
  • the mass of the polymer metal salt is 1-90%, for example, it can be 2%, 5%, 8%, 10% %, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, and the points above
  • the specific point values between the values are limited by space and for the sake of simplicity. This application will not exhaustively list the specific point values included in the range, and 10-50% is further preferred.
  • the mass proportion of the polymer metal salt is 1-90%, and more preferably 10-50%, so that the copolymer formed by the reaction contains an appropriate proportion of polymer metal salt structural fragments,
  • the water-based binder has excellent bonding performance and lithium ion conductivity and at the same time shows appropriate swelling characteristics, so that the lithium-ion battery containing the water-based binder has better cycle performance and rate performance. If the mass proportion of the polymer metal salt is too low, the strength of the water-based binder will be reduced, and the swelling rate in the electrolyte will be increased.
  • the acrylate monomer is alkyl acrylate and/or alkyl methacrylate.
  • the "alkyl groups" in the alkyl acrylate and alkyl methacrylate are each independently a C1-C10 linear or branched alkyl group, such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 linear or branched alkyl group; for example, when the alkyl group is C1, it represents methyl acrylate and methyl methacrylate; and so on, for the sake of simplicity, no further details will be given.
  • the acrylate monomer includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. , any one or a combination of at least two of amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, isooctyl acrylate or octyl methacrylate.
  • the olefinic monomer includes any one of styrene, C5-C10 (such as C5, C6, C7, C8, C9 or C10) linear or branched olefins, or a combination of at least two.
  • the C5-C10 (such as C5, C6, C7, C8, C9 or C10) linear or branched olefins, examples include but are not limited to: pentene, hexene, heptene, octene, nonane Alkenes, decenes, etc., as well as the isomers of the aforementioned alkenes.
  • the mass ratio of the acrylate monomer to the olefin monomer is (0.5-2):1, for example, it can be 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1 or 1.9:1, etc., further preferably (0.8-1.5):1.
  • the mass ratio of the acrylate monomer to the olefin monomer is (0.5-2):1, more preferably (0.8-1.5):1, so that the copolymer formed by the reaction contains
  • the specific proportion of polyacrylate structural fragments and polyolefin structural fragments enables the water-based binder to have suitable swelling characteristics, excellent bonding performance and lithium ion conductivity; by controlling the proportion of two types of polymerizable monomers with different solubility parameters , to obtain products with different solubility parameters, so that the swelling performance of the aqueous binder in the electrolyte can be adjusted, and the adhesive force will not be lost due to too high swelling, nor will the lithium ion conductivity be lost due to too low swelling. .
  • the amount of acrylate monomer is too much, the swelling of the water-based binder in the electrolyte will be high, and the adhesive force will weaken after long-term use, resulting in poor cycle performance of the battery; if the amount of olefin monomer is If it is too much, the swelling of the water-based binder will be low, and the lithium ion conductive performance will not be fully exerted, which will affect the rate performance of the battery pole piece and lithium ion battery.
  • the polymerizable monomers also include functional monomers.
  • the functional monomer includes acrylic acid and/or methacrylic acid.
  • the mass percentage of functional monomers in the polymerizable monomer is ⁇ 10%, for example, it can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5% etc.
  • the polymerizable monomers also include functional monomers, which help to improve the emulsion stability of the aqueous binder.
  • embodiments of the present application provide a method for preparing an aqueous binder as described in the first aspect.
  • the preparation method includes: mixing a polymer metal salt, a polymerizable monomer, an initiator and a solvent. react to obtain the aqueous binder.
  • the initiator includes persulfate, more preferably ammonium persulfate.
  • the mass of the initiator is 0.05-5%, for example, it can be 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, this application will not exhaustively enumerate the range. Specific point values included.
  • the solvent includes water.
  • the temperature of the reaction is 60-80°C, for example, it can be 61°C, 63°C, 65°C, 68°C, 70°C, 71°C, 73°C, 75°C, 77°C or 79°C, and the above points Regarding the specific point values between the values, due to space limitations and for the sake of simplicity, this application will not exhaustively list the specific point values included in the stated range.
  • the reaction time is 1-12h, for example, it can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, as well as specific points between the above points, limited by space and time.
  • this application does not exhaustively list the specific point values included in the stated range.
  • the reaction further includes a neutralization step after completion.
  • the neutralizing reagent is lithium hydroxide solution.
  • embodiments of the present application provide an application of the aqueous binder described in the first aspect in battery materials.
  • the battery material is a lithium ion battery material.
  • embodiments of the present application provide a battery pole piece, which includes the aqueous adhesive as described in the first aspect.
  • the battery pole piece includes a current collector and a coating disposed on the current collector, and the material of the coating includes the aqueous binder as described in the first aspect.
  • the coating material includes an active substance, a conductive agent and an aqueous binder as described in the first aspect.
  • the battery pole piece is a negative pole piece.
  • embodiments of the present application provide a lithium-ion battery, which includes at least one of the aqueous binder as described in the first aspect and the battery pole piece as described in the fourth aspect.
  • the formed copolymer segment contains specific repeating structural units, so that the formed copolymer segment contains specific repeating structural units, so that the The water-based binder has suitable swelling characteristics, excellent bonding performance and lithium ion conductivity. Its swelling rate in the electrolyte (85°C, 24h) is adjustable in the range of 10-100%, and the peeling stress is 15-100%. 30N/m, which combines excellent bonding strength, bonding stability and electrochemical performance, significantly improving the cycle performance and rate performance of lithium-ion batteries containing it.
  • the water-based binder is used in the negative electrode sheet, so that the capacity retention rate of the lithium-ion battery after 100 cycles at room temperature is ⁇ 98%, the 3C capacity retention rate is ⁇ 94%, the cycle performance and rate performance are excellent, and it can meet the needs of high-performance lithium ion batteries. Battery application requirements.
  • compositions, step, method, article, or device containing listed elements need not be limited to those elements and may also include other elements not expressly listed or inherent to such composition, step, method, article, or device .
  • the water-based binder is a copolymer formed by the reaction of lithium polyacrylate (weight average molecular weight is 10,000, purchased from McLean) and polymerizable monomers. Lithium polyacrylate and polymerizable The mass ratio of monomers is 1:2; the polymerizable monomer is a mixed monomer of styrene (St), butyl acrylate (BA) and acrylic acid (AA), including 50% styrene in terms of mass percentage. , butyl acrylate 48%, acrylic acid 2%.
  • the preparation method of the water-based binder is as follows: add 50 parts by mass of lithium polyacrylate to 550 parts by mass of deionized water, raise the temperature to 70°C with stirring, and add 100 parts by mass of polymerizable monomer (as described above) mixed monomer), and add 0.25 parts by mass of ammonium persulfate, and react for 6 hours. After the reaction is completed, adjust the pH value to 7.0 with 10% lithium hydroxide solution to obtain the aqueous adhesive.
  • Example 1 A kind of water-based binder and its preparation method, the only difference between it and Example 1 is that lithium polyacrylate is replaced by equal mass of poly-2-methyl-2-acrylic acid-2-hydroxyethyl phosphate potassium (heavy The average molecular weight is 10,000, purchased from McLean), and other components, proportions and preparation methods are the same as in Example 1.
  • Example 1 A kind of water-based binder and its preparation method, the only difference between it and Example 1 is that lithium polyacrylate is replaced by equal mass of sodium polystyrene sulfonate (weight average molecular weight is 10000, purchased from McLean), Other components, proportions and preparation methods are the same as in Example 1.
  • Example 1 A kind of water-based binder and its preparation method, the only difference between it and Example 1 is that lithium polyacrylate is replaced by equal mass of lithium polyvinyl disulfonimide (weight average molecular weight is 10000, purchased from McLean ), other components, proportions and preparation methods are the same as in Example 1.
  • a kind of water-based binder and its preparation method the only difference between it and Example 1 is that the mass ratio of lithium polyacrylate and polymerizable monomer is 1:49; other components, proportions and preparation methods are the same as those in Example 1 1 is the same.
  • a kind of water-based binder and its preparation method the only difference between it and Example 1 is that the mass ratio of lithium polyacrylate and polymerizable monomer is 4:1; other components, proportions and preparation methods are the same as those in Example 1 1 is the same.
  • Example 1 A water-based binder and its preparation method, the only difference from Example 1 is that the molecular weight of lithium polyacrylate is 100,000; other components, proportions and preparation methods are the same as Example 1.
  • Example 1 A water-based binder and its preparation method, the only difference from Example 1 is that the molecular weight of lithium polyacrylate is 1,000,000; other components, proportions and preparation methods are the same as Example 1.
  • a kind of water-based binder and its preparation method the difference between it and Example 1 is that the mass ratio of lithium polyacrylate and polymerizable monomer is 1:1; the polymerizable monomer is styrene, butyl acrylate and
  • the mixed monomers of acrylic acid include, in terms of mass percentage, 40% styrene, 52% butyl acrylate, and 8% acrylic acid; other components, proportions, and preparation methods are the same as in Example 1.
  • a kind of water-based binder and its preparation method the difference between it and Example 1 is that the mass ratio of lithium polyacrylate and polymerizable monomer is 1:9; the polymerizable monomer is styrene, butyl acrylate and
  • the mixed monomers of acrylic acid include, in terms of mass percentage, 52% styrene, 43% butyl acrylate, and 5% acrylic acid; other components, proportions, and preparation methods are the same as in Example 1.
  • a water-based adhesive and its preparation method which differs from Example 1 in that the polymerizable monomers include 35% styrene, 60% butyl acrylate, and 5% acrylic acid in terms of mass percentage; other groups
  • the ingredients, proportions and preparation methods are the same as those in Example 1.
  • a water-based adhesive and its preparation method which differs from Example 1 in that the polymerizable monomers include 60% styrene, 35% butyl acrylate, and 5% acrylic acid in terms of mass percentage; other groups
  • the ingredients, proportions and preparation methods are the same as those in Example 1.
  • the water-based binder is a copolymer of polymerizable monomers (styrene, butyl acrylate and acrylic acid).
  • the polymerizable monomers include benzene in terms of mass percentage. Ethylene 50%, butyl acrylate 48%, acrylic acid 2%.
  • the preparation method of the water-based binder is as follows: add 50 parts by mass of polymerizable monomer to 200 parts by mass of deionized water, and add 0.25 parts by mass of ammonium persulfate, react at 70°C for 6 hours, and end the reaction with 10%
  • the pH value of the lithium hydroxide solution was adjusted to 7.0 to obtain the aqueous adhesive.
  • Example 1 A water-based adhesive and its preparation method, the only difference from Example 1 is that the polymerizable monomer is a mixed monomer of styrene and acrylic acid, including 98% styrene and 2% acrylic acid in terms of mass percentage. ; Other components, proportions and preparation methods are the same as in Example 1.
  • Example 1 A water-based adhesive and its preparation method, the only difference from Example 1 is that the polymerizable monomer is a mixed monomer of butyl acrylate and acrylic acid, including 98% butyl acrylate and 98% acrylic acid in terms of mass percentage. 2%; other components, proportions and preparation methods are the same as Example 1.
  • a water-based binder and a preparation method thereof is a copolymer formed by the reaction of lithium acrylate (LiAA) and polymerizable monomers.
  • the mass ratio of lithium acrylate and polymerizable monomers is 1:2; so
  • the polymerizable monomer is a mixed monomer of styrene, butyl acrylate and acrylic acid, including 50% styrene, 48% butyl acrylate and 2% acrylic acid in terms of mass percentage.
  • the preparation method of the water-based binder is as follows: in 550 parts by mass of deionized water, add 50 parts by mass of lithium acrylate and 100 parts by mass of polymerizable monomers, and add 0.75 parts by mass of ammonium persulfate, and react at 70°C After 6 hours, the reaction was completed and the pH value was adjusted to 7.0 with 10% lithium hydroxide solution to obtain the aqueous adhesive.
  • a water-based binder and a preparation method thereof is a mixture of lithium polyacrylate and a terpolymer of styrene-butyl acrylate-acrylic acid.
  • the mass ratio of lithium polyacrylate to the terpolymer is 1:2; the polymerized monomers of the terpolymer include 50% styrene, 48% butyl acrylate, and 2% acrylic acid in terms of mass percentage.
  • the preparation method of the water-based binder is as follows: add 100 parts by mass of the polymerized monomer of the terpolymer to 500 parts by mass of deionized water, and add 0.25 parts by mass of ammonium persulfate, and react at 70°C for 6 hours. Finally, adjust the pH value to 7.0 with 10% lithium hydroxide solution; then add 50 parts by mass of lithium polyacrylate to the system, stir and mix evenly at room temperature, and obtain the water-based adhesive.
  • a water-based adhesive a commercially available SBR adhesive.
  • a water-based adhesive is commercially available LA132 adhesive.
  • a battery pole piece which is a negative pole piece, including a current collector (Cu foil) and a coating disposed on the current collector.
  • the material of the coating includes a negative active material (silica material SiO-450, Beterui New Energy Materials Co., Ltd., silicon content 10%), conductive agent (carbon black SP), binder and thickener (sodium carboxymethylcellulose CMC), the binders are Examples 1-12 respectively , the water-based adhesive provided in Comparative Examples 1-7.
  • the preparation method of the negative electrode sheet is as follows: mix the negative active material, conductive agent, binder and thickener according to the mass ratio of 96.5:1.0:1.0:1.5, and add them in such a proportion that the solid content of the system is 40wt%. Stir and mix thoroughly in ionized water to make a uniform negative electrode slurry. After passing through a 100-mesh screen, apply it on the negative electrode current collector Cu foil, then dry it, and use a roller with a unit length load of 10 ⁇ 10 4 N/m. Roll and press to obtain the negative electrode piece.
  • a lithium-ion battery includes a positive electrode plate, a negative electrode plate, a separator and an electrolyte.
  • the negative electrode plate is the aforementioned negative electrode plate.
  • the preparation method is as follows:
  • Preparation of positive electrode sheet Mix the positive active material (lithium iron phosphate material), conductive carbon black, and binder (PVDF) in a mass ratio of 96.5:2.0:2.5 based on solid content, and follow the system Add N-methylpyrrolidone (NMP) with a solid content of 50wt% and mix thoroughly to make a uniform positive electrode slurry. After passing through a 100-mesh screen, apply it on the positive electrode current collector Al foil, and then dry it. Use a roller to roll with a unit length load of 10 ⁇ 10 4 N/m to obtain the positive electrode piece;
  • NMP N-methylpyrrolidone
  • the coating layer is peeled off in the 180° direction at a speed, and the peeling stress is measured. The peeling stress is used as the basis for judging the bonding performance. The greater the peeling stress, the better the bonding strength.
  • the lithium-ion battery prepared above was charged to 4.2V at a constant current of 0.33C, then charged to a cut-off current of 0.02C at a constant voltage, discharged to 2.5V at a rate of 0.33C; left aside for 5 minutes, charged to 4.2V at a constant current of 0.33C, and then charged at a constant voltage of 0.33C to a cut-off current of 0.02C.
  • the initial adjustment was carried out by charging to a cut-off current of 0.02C and discharging to 2.5V at 0.33C;
  • Capacity retention rate (%) after 100 cycles 100% ⁇ 100th cycle discharge capacity/first cycle discharge capacity.
  • Rate performance At 25°C, charge the initially adjusted lithium-ion battery to 4.2V at a constant current of 0.5C, then charge at a constant voltage to a cut-off current of 0.02C, leave it aside for 5 minutes, then discharge it at a constant current of 1C to 2.5V, and leave it aside 5min, measure the 1C discharge capacity. Then charge to 4.2V with a constant current of 0.5C, then charge with a constant voltage to a cut-off current of 0.02C, leave it for 5 minutes, then discharge it with a constant current of 3C to 2.5V, leave it for 5 minutes, and measure the discharge capacity at 3C rate.
  • 3C capacity retention rate (%) 100% ⁇ 3C discharge capacity/1C discharge capacity.
  • Comparative example 6 10 95 85.9 Comparative example 7 12 96 87.8
  • the performance adjustment and optimization of water-based adhesives can be achieved by adjusting the ratio of polymer metal salts to polymerizable monomers and designing the ratio of acrylate monomers and olefin monomers in the polymerizable monomers.
  • the water-based binder provided by this application is a copolymer formed by the reaction of a polymer metal salt and a polymerizable monomer.
  • the polymerizable monomer includes an acrylate monomer and an olefin monomer.
  • the water-based binder does not contain the structural unit of the polymer metal salt (Comparative Example 1), its swelling rate in the electrolyte will be too high, and its bonding force and lithium ion conductivity will be insufficient, which will affect the cycle performance and rate of the battery. The performance drops seriously; if the polymerizable monomer does not contain acrylate monomer (Comparative Example 2), the water-based binder has poor bonding performance, and the battery has poor cycle and rate performance; if the polymerizable monomer does not contain If it contains olefin monomer (Comparative Example 3), the performance of the water-based binder will be reduced, resulting in a decrease in the capacity retention rate of the lithium-ion battery and poor cycleability.

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Abstract

本文公布一种水性粘结剂及其制备方法和应用，所述水性粘结剂为聚合物金属盐与可聚合单体反应形成的共聚物；所述可聚合单体包括丙烯酸酯类单体和烯烃类单体的组合，所述聚合物金属盐选自磷酸金属盐类聚合物、羧基金属盐类聚合物、磺酸金属盐类聚合物或双磺酰亚胺金属盐类聚合物中的任意一种或至少两种的组合。本申请通过聚合物金属盐、可聚合单体等结构单元的设计及其相互协同，使形成的共聚物链段中包含特定的重复结构单元，使所述水性粘结剂具有适宜的溶胀特性、优异的粘结性能和锂离子传导能力，兼具优异的粘结强度、粘结稳定性和电化学性能，显著提高了包含其的锂离子电池的循环性能和倍率性能。

Description

一种水性粘结剂及其制备方法和应用 技术领域
本申请实施例涉及锂离子电池材料技术领域，例如一种水性粘结剂及其制备方法和应用。
背景技术
近年来，为了适应电动化仪器设备的需求，特别是手机和电动汽车行业的进一步发展，锂离子电池的性能提升也面临巨大的挑战。目前，市场不仅对锂离子电池的能量密度提出了更高的要求，而且对快速充电的功能需求也愈发重要。粘结剂是电池极片的主要组分之一，用于连接活性物质、导电剂和电极集流体，使它们之间具有整体的连接性。在充放电过程中，粘结剂有效维持电极的结构完整，确保电极材料能够可重复地嵌脱锂，对保持循环性能也有着重要的作用。粘结剂对极片及电池的电性能具有重要的影响，高性能的锂离子电池需要与之匹配的高性能粘结剂。
聚偏氟乙烯(PVDF)是目前锂离子电池中最常用的油性粘结剂，其具有较好的氧化还原能力和稳定性，但其需要以N-甲基吡咯烷酮(NMP)作为溶剂才能实现良好分散，NMP的挥发温度高，价格贵，而且不利于人体健康，存在环境污染风险；此外，PVDF易发生水解，因此在极片制备过程中需要严格控制环境湿度，增加了电池的制作成本，且PVDF在电解液中会发生溶胀，从而影响电池的使用可靠性和安全性。
采用水性粘结剂替换PVDF等油性粘结剂，使锂电池生产工艺符合环保要求，是目前电池极片的发展趋势之一。目前已有的水性粘结剂包括聚丙烯酸(PAA)、羧甲基纤维素钠/丁苯橡胶(CMC/SBR)、海藻酸钠、壳聚糖等，其中，SBR型粘结剂因在体系中的添加量少、与活性物质和集流体之间的粘结力强而被广泛应用在负极体系中；但是，SBR粘结剂中组分的极性低，与强极性电解液的亲和性较差，其作为粘结剂的锂离子电池的动力学性能较差，无法实现满意的快速充电性能；而且，SBR通常搭配增稠剂CMC共同使用，CMC的粘结性能一般，脆性大，充放电时极片易龟裂。CN109802139A公开了一种水性粘结剂及电池，所述水性粘结剂包括粘结成分和增稠成分，所述粘结成分包括 丁苯乳胶、聚丙烯酸中的任意一种，所述增稠成分包括环糊精、壳聚糖中的一种；该水性粘结剂能够有效减少中间产物的穿梭效应，降低脱落风险，增加电池的电化学性能；但聚丙烯酸的玻璃化转变温度较高，在常温下较硬，易导致极片硬脆，因此，PAA水性粘结剂在涂布过程中易发生开裂，冷压后出现条纹等缺陷，卷绕过程中极片弯折处掉粉的现象，从而制约了其在电池中的广泛应用。此外，海藻酸钠、壳聚糖等天然高分子材料作为粘结剂，在环保和水溶性等方面表现良好，但其在电化学性能、机械性能、粘结性能等方面存在很多不足之处，难以满足电池的应用要求。
因此，开发一种兼具优异的粘结性能、倍率性能和循环性能的水性粘结材料，以满足高性能的电池极片及锂离子电池的应用要求，是本领域亟待解决的问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种水性粘结剂及其制备方法和应用，通过聚合物金属盐、可聚合单体等结构单元的设计，使所述水性粘结剂具有优异的粘结性能、锂离子传导能力和适宜的溶胀特性，其用于电池极片和锂离子电池中，能够显著提升电池的循环性能和倍率性能。
第一方面，本申请实施例提供一种水性粘结剂，所述水性粘结剂为聚合物金属盐与可聚合单体形成的共聚物；所述可聚合单体包括丙烯酸酯类单体和烯烃类单体的组合；所述聚合物金属盐选自磷酸金属盐类聚合物、羧基金属盐类聚合物、磺酸金属盐类聚合物或双磺酰亚胺金属盐类聚合物中的任意一种或至少两种的组合。
本申请提供的水性粘结剂是一种由聚合物金属盐与可聚合单体反应形成的共聚物，所述可聚合单体包括具有不同溶解度参数的丙烯酸酯类单体和烯烃类单体的组合，通过特定种类的聚合物金属盐、可聚合单体等结构单元的设计，使形成的共聚物链段中包含特定的重复结构单元，从而得到具有不同溶解度参数的产品，使所述水性粘结剂具有适宜的溶胀特性；同时，所述聚合物金属盐的结构片段能够增强粘结剂的强度和金属盐含量，从而使所述水性粘结剂具有 优异的粘结性能和锂离子传导能力。本申请提供的水性粘结剂通过共聚物中结构单元的设计，在粘结性能、锂离子传导能力和溶胀特性之间取得良好的平衡效果，兼具优异的粘结强度、粘结稳定性和电化学性能，从而显著提高了包含其的电池极片和锂离子电池的循环性能和倍率性能。
优选地，所述聚合物金属盐包括聚合物锂盐、聚合物钠盐、聚合物钾盐或聚合物镁盐中的任意一种或至少两种的组合。
优选地，所述磷酸金属盐类聚合物选自聚磷酸金属盐、2-甲基-2-丙烯酸-2-羟乙基酯磷酸金属盐基聚合物、二(2-(甲基丙烯酰氧基)乙基)磷酸金属盐基聚合物、2-甲基丙烯酰氧基乙基磷酸金属盐基聚合物或乙烯基磷酸金属盐基聚合物中的任意一种或至少两种的组合，进一步优选聚磷酸锂、2-甲基-2-丙烯酸-2-羟乙基酯磷酸锂基聚合物、二(2-(甲基丙烯酰氧基)乙基)磷酸锂基聚合物、2-甲基丙烯酰氧基乙基磷酸锂基聚合物或乙烯基磷酸锂基聚合物中的任意一种或至少两种的组合。
优选地，所述羧基金属盐类聚合物选自甲基丙烯酸金属盐基聚合物、丙烯酸金属盐基聚合物、马来酸金属盐基聚合物、衣康酸金属盐基聚合物、柠檬酸三烯丙酯金属盐基聚合物、羧甲基纤维素金属盐基聚合物或海藻酸金属盐基聚合物中的任意一种或至少两种的组合，进一步优选甲基丙烯酸锂基聚合物、丙烯酸锂基聚合物、马来酸锂基聚合物、衣康酸锂基聚合物、柠檬酸三烯丙酯锂基聚合物、羧甲基纤维素锂基聚合物或海藻酸锂基聚合物中的任意一种或至少两种的组合。
优选地，所述磺酸金属盐类聚合物选自苯乙烯基磺酸金属盐基聚合物、乙烯基磺酸金属盐基聚合物、丙烯基磺酸金属盐基聚合物、甲基丙烯磺酸金属盐基聚合物、4-乙烯苯亚磺酸金属盐基聚合物、烯丙基乙烯基磺酸金属盐基聚合物、3-磺酸丙基甲基丙烯酸金属盐基聚合物、甲基丙烯酸2-乙磺酸酯金属盐基聚合物、2-丙烯酰氨基-2-甲基-1-丙烷磺酸金属盐基聚合物、丙烯酸-2-丙烯酰胺-2-甲基丙磺酸金属盐基聚合物、3-烯丙氧基-2-羟基-1-丙烷磺酸金属盐基聚合物中的任意一种或至少两种的组合，进一步优选苯乙烯基磺酸锂基聚合物、苯乙烯基磺酸钠基聚合物、苯乙烯基磺酸钾基聚合物、乙烯基磺酸锂基聚合物、丙烯基磺酸锂基聚合物、甲基丙烯磺酸锂基聚合物、4-乙烯苯亚磺酸锂基聚合物、烯丙基乙烯基磺酸锂基聚合物、3-磺酸丙基甲基丙烯酸锂基聚合物、甲基丙烯酸2- 乙磺酸酯锂基聚合物、2-丙烯酰氨基-2-甲基-1-丙烷磺酸锂基聚合物、丙烯酸-2-丙烯酰胺-2-甲基丙磺酸锂基聚合物、3-烯丙氧基-2-羟基-1-丙烷磺酸锂基聚合物中的任意一种或至少两种的组合。
优选地，所述双磺酰亚胺金属盐类聚合物选自乙烯基双磺酰亚胺金属盐基聚合物和/或苯乙烯基双磺酰亚胺金属盐基聚合物，进一步优选乙烯基双磺酰亚胺锂基聚合物和/或苯乙烯基双磺酰亚胺锂基聚合物。
本申请中，所述聚合物金属盐中的“聚合物”包括均聚物和/或共聚物，以“甲基丙烯酸金属盐基聚合物”为例，该聚合物可以为甲基丙烯酸金属盐的均聚物，也可以为甲基丙烯酸金属盐与其他单体的共聚物，只要聚合物中包含了由甲基丙烯酸金属盐形成的结构单元即可。其他聚合物具有相同的含义，简明起见，不再赘述。
优选地，所述聚合物金属盐的重均分子量为1000-10000000，例如可以为2000、5000、8000、10000、30000、50000、80000、100000、300000、500000、800000、1000000、3000000、5000000、7000000或9000000，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
本申请中，所述聚合物金属盐可以通过市场途径购买获得，或可通过现有技术中已知的方法对酸性聚合物进行金属成盐化处理而成。
优选地，以所述聚合物金属盐与可聚合单体的总质量为100％计，所述聚合物金属盐的质量为1-90％，例如可以为2％、5％、8％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％或85％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选10-50％。
作为本申请的优选技术方案，所述聚合物金属盐的质量占比为1-90％，进一步优选10-50％，从而使反应形成的共聚物中含有适宜比例的聚合物金属盐结构片段，使水性粘结剂在具有优异的粘结性能和锂离子传导能力的同时，表现出适宜的溶胀特性，从而使包含所述水性粘结剂的锂离子电池具有更好循环性能和倍率性能。如果聚合物金属盐的质量占比过低，则会使水性粘结剂强度降低，同时在电解液中的溶胀率升高，长期使用后粘结力衰减严重，电池的循环性能欠佳；若聚合物金属盐的质量占比过高，则会使水性粘结剂柔软性不足，影响 极片加工性能。
优选地，所述丙烯酸酯类单体为丙烯酸烷基酯和/或甲基丙烯酸烷基酯。
优选地，所述丙烯酸烷基酯、甲基丙烯酸烷基酯中的“烷基”各自独立地为C1-C10直链或支链烷基，例如C1、C2、C3、C4、C5、C6、C7、C8、C9或C10的直链或支链烷基；例如当烷基为C1时，即代表丙烯酸甲酯、甲基丙烯酸甲酯；依次类推，简明起见，不再赘述。
优选地，所述丙烯酸酯类单体包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸戊酯、甲基丙烯酸戊酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸辛酯、丙烯酸异辛酯或甲基丙烯酸辛酯中的任意一种或至少两种的组合。
优选地，所述烯烃类单体包括苯乙烯、C5-C10(例如C5、C6、C7、C8、C9或C10)直链或支链烯烃中的任意一种或至少两种的组合。
优选地，所述C5-C10(例如C5、C6、C7、C8、C9或C10)直链或支链烯烃，示例性地包括但不限于：戊烯、己烯、庚烯、辛烯、壬烯、癸烯等，以及前述烯烃的各异构体。
优选地，所述丙烯酸酯类单体与烯烃类单体的质量比为(0.5-2):1，例如可以为0.6:1、0.7:1、0.8:1、0.9:1、1:1、1.1:1、1.2:1、1.3:1、1.4:1、1.5:1、1.6:1、1.7:1、1.8:1或1.9:1等，进一步优选(0.8-1.5):1。
作为本申请的优选技术方案，所述丙烯酸酯类单体与烯烃类单体的质量比为(0.5-2):1，进一步优选(0.8-1.5):1，使反应形成的共聚物中含有特定比例的聚丙烯酸酯结构片段和聚烯烃结构片段，使水性粘结剂具有适宜的溶胀特性、优异的粘结性能和锂离子传导能力；通过控制两类溶解度参数不同的可聚合单体的比例，得到不同溶解度参数的产品，使所述水性粘结剂在电解液中的溶胀性能可调，不会因为溶胀过高而失去粘结力，也不会因为溶胀过低而失去锂离子传导能力。如果丙烯酸酯类单体的用量过多，则会使水性粘结剂在电解液中的溶胀偏高，长期使用后粘结力衰减，导致电池的循环性能欠佳；如果烯烃类单体的用量过多，则会使水性粘结剂的溶胀偏低，无法很好地发挥锂离子传导性能，影响电池极片和锂离子电池的倍率性能。
优选地，所述可聚合单体中还包括功能性单体。
优选地，所述功能性单体包括丙烯酸和/或甲基丙烯酸。
优选地，所述可聚合单体中功能性单体的质量百分含量≤10％，例如可以为0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％或9.5％等。
作为本申请的优选技术方案，所述可聚合单体中还包括功能性单体，有助于提高水性粘结剂的乳液稳定性。
第二方面，本申请实施例提供一种如第一方面所述的水性粘结剂的制备方法，所述制备方法包括：将聚合物金属盐、可聚合单体、引发剂和溶剂混合后进行反应，得到所述水性粘结剂。
优选地，所述引发剂包括过硫酸盐，进一步优选过硫酸铵。
优选地，以所述可聚合单体的质量为100％计，所述引发剂的质量为0.05-5％，例如可以为0.08％、0.1％、0.3％、0.5％、0.8％、1％、1.5％、2％、2.5％、3％、3.5％、4％或4.5％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述溶剂包括水。
优选地，所述反应的温度为60-80℃，例如可以为61℃、63℃、65℃、68℃、70℃、71℃、73℃、75℃、77℃或79℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述反应的时间为1-12h，例如可以为2h、3h、4h、5h、6h、7h、8h、9h、10h或11h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述反应完成后还包括中和的步骤。
优选地，所述中和的试剂为氢氧化锂溶液。
第三方面，本申请实施例提供一种如第一方面所述的水性粘结剂在电池材料中的应用。
优选地，所述电池材料为锂离子电池材料。
第四方面，本申请实施例提供一种电池极片，所述电池极片包括如第一方面所述的水性粘结剂。
优选地，所述电池极片包括集流体和设置于所述集流体上的涂层，所述涂层的材料包括如第一方面所述的水性粘结剂。
优选地，所述涂层的材料包括活性物质、导电剂和如第一方面所述的水性 粘结剂。
优选地，所述电池极片为负极极片。
第五方面，本申请实施例提供一种锂离子电池，所述锂离子电池包括如第一方面所述的水性粘结剂、如第四方面所述的电池极片中的至少一种。
相对于相关技术，本申请实施例具有以下有益效果：
本申请实施例提供的水性粘结剂中，通过聚合物金属盐、可聚合单体等结构单元的设计及其相互协同，使形成的共聚物链段中包含特定的重复结构单元，使所述水性粘结剂具有适宜的溶胀特性、优异的粘结性能和锂离子传导能力，其在电解液中的溶胀率(85℃，24h)在10-100％范围内可调，剥离应力为15-30N/m，兼具优异的粘结强度、粘结稳定性和电化学性能，显著提高了包含其的锂离子电池的循环性能和倍率性能。所述水性粘结剂用于负极极片中，使锂离子电池常温循环100周的容量保持率≥98％，3C容量保持率≥94％，循环性能和倍率性能优良，能够满足高性能锂离子电池的应用要求。
在阅读并理解了附图和详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本文所用术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，还可包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。
本申请要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显只指单数形式。
本申请所描述的术语“一个实施例”、“一些实施例”、“示例性地”、“具体示例”或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结 构、材料或者特点包含于本申请的至少一个实施例或示例中。在本文中，对上述术语的示意性表述不是必须针对相同的实施例或示例。
而且，本申请各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
一种水性粘结剂及其制备方法，所述水性粘结剂为聚丙烯酸锂(重均分子量为10000，购自麦克林)与可聚合单体反应形成的共聚物，聚丙烯酸锂与可聚合单体的质量比为1:2；所述可聚合单体为苯乙烯(St)、丙烯酸丁酯(BA)和丙烯酸(AA)的混合单体，以质量百分含量计包括苯乙烯50％，丙烯酸丁酯48％，丙烯酸2％。
所述水性粘结剂的制备方法如下：于550质量份的去离子水中，加入50质量份的聚丙烯酸锂，升温至70℃搅拌下，加入100质量份的可聚合单体(如前所述的混合单体)，并加入0.25质量份的过硫酸铵，反应6h，反应结束用10％的氢氧化锂溶液调节pH值为7.0，得到所述水性粘合剂。
实施例2
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，将聚丙烯酸锂替换为等质量的聚2-甲基-2-丙烯酸-2-羟乙基酯磷酸钾(重均分子量为10000，购自麦克林)，其他组分、配比以及制备方法均与实施例1相同。
实施例3
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，将聚丙烯酸锂替换为等质量的聚苯乙烯基磺酸钠(重均分子量为10000，购自麦克林)，其他组分、配比以及制备方法均与实施例1相同。
实施例4
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，将聚丙烯酸锂替换为等质量的聚乙烯基双磺酰亚胺锂(重均分子量为10000，购自麦克林)，其他组分、配比以及制备方法均与实施例1相同。
实施例5
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，聚丙烯酸锂与可聚合单体的质量比为1:49；其他组分、配比以及制备方法均与实施例1相同。
实施例6
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，聚丙烯酸锂与可聚合单体的质量比为4:1；其他组分、配比以及制备方法均与实施例1相同。
实施例7
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，聚丙烯酸锂的分子量为100000；其他组分、配比以及制备方法均与实施例1相同。
实施例8
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，聚丙烯酸锂的分子量为1000000；其他组分、配比以及制备方法均与实施例1相同。
实施例9
一种水性粘结剂及其制备方法，其与实施例1的区别在于，聚丙烯酸锂与可聚合单体的质量比为1:1；所述可聚合单体为苯乙烯、丙烯酸丁酯和丙烯酸的混合单体，以质量百分含量计包括苯乙烯40％，丙烯酸丁酯52％，丙烯酸8％；其他组分、配比以及制备方法均与实施例1相同。
实施例10
一种水性粘结剂及其制备方法，其与实施例1的区别在于，聚丙烯酸锂与可聚合单体的质量比为1:9；所述可聚合单体为苯乙烯、丙烯酸丁酯和丙烯酸的混合单体，以质量百分含量计包括苯乙烯52％，丙烯酸丁酯43％，丙烯酸5％；其他组分、配比以及制备方法均与实施例1相同。
实施例11
一种水性粘结剂及其制备方法，其与实施例1的区别在于，所述可聚合单体以质量百分含量计包括苯乙烯35％，丙烯酸丁酯60％，丙烯酸5％；其他组分、配比以及制备方法均与实施例1相同。
实施例12
一种水性粘结剂及其制备方法，其与实施例1的区别在于，所述可聚合单体以质量百分含量计包括苯乙烯60％，丙烯酸丁酯35％，丙烯酸5％；其他组分、配比以及制备方法均与实施例1相同。
对比例1
一种水性粘结剂及其制备方法，所述水性粘结剂为可聚合单体(苯乙烯、丙烯酸丁酯和丙烯酸)的共聚物，所述可聚合单体以质量百分含量计包括苯乙 烯50％，丙烯酸丁酯48％，丙烯酸2％。
所述水性粘结剂的制备方法如下：于200质量份的去离子水中，加入50质量份的可聚合单体，并加入0.25质量份的过硫酸铵，70℃反应6h，反应结束用10％的氢氧化锂溶液调节pH值为7.0，得到所述水性粘合剂。
对比例2
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，可聚合单体为苯乙烯与丙烯酸的混合单体，以质量百分含量计包括苯乙烯98％，丙烯酸2％；其他组分、配比以及制备方法均与实施例1相同。
对比例3
一种水性粘结剂及其制备方法，其与实施例1的区别仅在于，可聚合单体为丙烯酸丁酯与丙烯酸的混合单体，以质量百分含量计包括丙烯酸丁酯98％，丙烯酸2％；其他组分、配比以及制备方法均与实施例1相同。
对比例4
一种水性粘结剂及其制备方法，所述水性粘结剂为丙烯酸锂(LiAA)与可聚合单体反应形成的共聚物，丙烯酸锂与可聚合单体的质量比为1:2；所述可聚合单体为苯乙烯、丙烯酸丁酯和丙烯酸的混合单体，以质量百分含量计包括苯乙烯50％，丙烯酸丁酯48％，丙烯酸2％。
所述水性粘结剂的制备方法如下：于550质量份的去离子水中，加入50质量份的丙烯酸锂和100质量份的可聚合单体，并加入0.75质量份的过硫酸铵，70℃反应6h，反应结束用10％的氢氧化锂溶液调节pH值为7.0，得到所述水性粘合剂。
对比例5
一种水性粘结剂及其制备方法，所述水性粘结剂为聚丙烯酸锂与苯乙烯-丙烯酸丁酯-丙烯酸的三元共聚物的混合物，聚丙烯酸锂与三元共聚物的质量比为1:2；三元共聚物的聚合单体以质量百分含量计包括苯乙烯50％，丙烯酸丁酯48％，丙烯酸2％。
所述水性粘结剂的制备方法如下：于500质量份的去离子水中，加入100质量份的三元共聚物的聚合单体，并加入0.25质量份的过硫酸铵，70℃反应6h，反应结束用10％的氢氧化锂溶液调节pH值为7.0；然后向体系中加入50质量份的聚丙烯酸锂，室温下搅拌混合均匀，得到所述水性粘合剂。
对比例6
一种水性粘结剂，为市售的SBR粘结剂。
对比例7
一种水性粘结剂，为市售的LA132粘结剂。
应用例
一种电池极片，其为负极极片，包括集流体(Cu箔)和设置于所述集流体上的涂层，涂层的材料包括负极活性物质(硅氧材料SiO-450，贝特瑞新能源材料股份有限公司，硅含量10％)、导电剂(碳黑SP)、粘结剂和增稠剂(羧甲基纤维素钠CMC)，所述粘结剂分别为实施例1-12、对比例1-7提供的水性粘结剂。
所述负极极片的制备方法如下：将负极活性物质、导电剂、粘结剂和增稠剂按照质量份比96.5:1.0:1.0:1.5进行混合，按照体系固含量为40wt％的比例加入去离子水中充分搅拌混合，制成均匀的负极浆料，过100目筛网后，涂覆于负极集流体Cu箔上，再烘干，利用辊子以10×10 4N/m的单位长度载荷进行辊压，得到负极极片。
一种锂离子电池，包括正极极片、负极极片、隔膜和电解液，所述负极极片为前述负极极片，制备方法如下：
(1)正极极片的制备：将作为正极活性物质(磷酸铁锂材料)、导电炭黑、粘结剂(PVDF)分别按固含量计按照质量份比96.5:2.0:2.5进行混合，按照体系固含量为50wt％的比例加入N-甲基吡咯烷酮(NMP)中充分搅拌混合，制成均匀的正极浆料，过100目筛网后，涂覆于正极集流体Al箔上，再烘干，利用辊子以10×10 4N/m的单位长度载荷进行辊压，得到正极极片；
(2)负极极片：如前文所述；
(3)隔膜：采用PE多孔聚合物薄膜(深圳市星源材质科技股份有限公司)作为隔膜；
(4)锂离子电池的组装：将正极极片、隔离膜、负极极片按顺序卷绕，得到电芯；电芯用铝塑膜封装，烘烤除水后注入电解液，经过真空封装、搁置、化成、二封、整形等工序，得到所述锂离子电池。
性能测试：
(1)溶胀性能
将待测的水性粘结剂滴加到干净的模具中，保证固体含量为4g±0.1g，再 放入烘箱70℃干燥12h，取出裁片1cm×1cm，然后120℃干燥2h备用；将备好的膜片称重，记录质量M 1；称量5g左右电解液，加入装有前述膜片的玻璃瓶中，确保电解液完全浸没膜片，并将瓶子密封好，在85℃水浴中放置24h。把膜片从玻璃瓶中取出，用干净无尘纸将膜片上的电解液擦干，称量溶胀后膜片的质量，记为M 2。
溶胀率＝100％×(M 2-M 1)/M 1。
(2)粘结性能
将负极极片的切成20cm×2.5cm的长条状，在集流体侧用双面胶粘接于厚1mm的钢板，在涂布层侧粘贴透明胶带，用拉伸试验机以100mm/min的速度将涂布层朝180°方向剥离，并测定剥离应力，以剥离应力作为粘结性能的判断依据，剥离应力越大，代表粘结强度越好。
(3)电池的循环性能和倍率性能
将上述制备的锂离子电池以0.33C恒流充电至4.2V，再恒压充电至截止电流0.02C，以0.33C放电至2.5V；搁置5min，以0.33C恒流充电至4.2V，再恒压充电至截止电流0.02C，以0.33C放电至2.5V，从而进行了初期调整；
在25℃下，将初期调整后的锂离子电池以0.5C恒流充电至4.2V，再恒压充电至截止电流0.02C，搁置5min，然后以1C恒流放电至2.5V，搁置5min，测定首次循环放电容量。依此循环，充电/放电100次循环后，测定第100次循环放电容量，利用以下的公式计算第100周次循环容量保持率：
循环100周的容量保持率(％)＝100％×第100次循环放电容量/首次循环放电容量。
倍率性能：在25℃下，将初期调整后的锂离子电池以0.5C恒流充电至4.2V，再恒压充电至截止电流0.02C，搁置5min，然后以1C恒流放电至2.5V，搁置5min，测定1C放电容量。然后以0.5C恒流充电至4.2V，再恒压充电至截止电流0.02C，搁置5min，然后以3C恒流放电至2.5V，搁置5min，测定3C倍率下的放电容量。
3C容量保持率(％)＝100％×3C放电容量/1C放电容量。
性能测试结果如表1和表2所示。
表1
Figure PCTCN2022140684-appb-000001
Figure PCTCN2022140684-appb-000002
Figure PCTCN2022140684-appb-000003
表1中，“--”代表不含该组分、该数据不存在。
表2
水性粘结剂 粘结性能(N/m) 循环性能(％) 倍率性能(％)
实施例1 20 98.1 95.4
实施例2 22 98.2 95.5
实施例3 23 98.3 95.4
实施例4 25 98.4 95.4
实施例5 15 97.5 94.0
实施例6 28 98.7 96.3
实施例7 25 98.5 95.3
实施例8 30 99 95.3
实施例9 17 97.6 95.5
实施例10 28 98.7 94.5
实施例11 19 97.7 94.4
实施例12 17 97.5 94.0
对比例1 10 97 90
对比例2 9 96.8 89.1
对比例3 8 96.6 89.9
对比例4 7 96.3 90.5
对比例5 8 96.7 91.1
对比例6 10 95 85.9
对比例7 12 96 87.8
结合表1和表2的性能测试数据可知，与市售的SBR水性粘结剂(对比例6)和LA132粘结剂(对比例7)相比，本申请通过聚合物金属盐和可聚合单体的结构单元的设计及其相互协同，使所述水性粘结剂具有适宜的溶胀特性，在电解液中85℃放置24h后的溶胀率在10-100％范围内可调，并具有良好的粘结性能和锂离子传导能力，其用于负极极片的剥离应力为15-30N/m，粘结强度相对于市售的水性粘结剂有了明显提升，而且具有良好的锂离子传导能力、倍率性能和循环性能，使包含其的锂离子电池常温循环100周的容量保持率为97.5-99％，3C容量保持率为94-96.3％，循环性能和倍率性能明显提高。同时，通过聚合物金属盐与可聚合单体的比例调整以及可聚合单体中丙烯酸酯类单体和烯烃类单体的配比设计，可以实现水性粘结剂的性能调整和优化。
本申请提供的水性粘结剂是由聚合物金属盐与可聚合单体反应形成的共聚物，所述可聚合单体包括丙烯酸酯类单体和烯烃类单体，通过共聚物中结构单元的设计，使水性粘结剂在粘结性能、锂离子传导能力和溶胀特性之间取得良好的平衡效果，使粘结剂不会因为溶胀过高而失去粘结力，也不会因溶胀过低而失去锂离子传导能力，兼具优异的粘结强度、粘结稳定性和电化学性能。如果水性粘结剂中不含有聚合物金属盐的结构单元(对比例1)，则其在电解液中的溶胀率过高，粘结力和锂离子传导能力不足，使电池的循环性能和倍率性能下降严重；如果可聚合单体中不含有丙烯酸酯类单体(对比例2)，则水性粘结剂的粘结性能差，电池的循环和倍率性能不佳；如果可聚合单体中不含有烯烃类单体(对比例3)，则水性粘结剂的性能降低，使锂离子电池的容量保持率下降，循环性较差。此外，如果聚合物金属盐与苯乙烯-丙烯酸丁酯-丙烯酸三元共聚物以共混的形式存在于粘结剂中(对比例5)，或将含有双键的金属盐与其他可聚合单体进行共聚(对比例4)，则无法形成含有特定重复单元和链段结构的共聚物，导致水性粘结剂的粘结强度低，电池循环性能差。
申请人声明，本申请通过上述实施例来说明本申请的水性粘结剂及其制备方法和应用，但本申请并不局限于上述实施例，即不意味着本申请必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落 在本申请的保护范围和公开范围之内。

Claims (15)

  1. 一种水性粘结剂，其中，所述水性粘结剂为聚合物金属盐与可聚合单体形成的共聚物；所述可聚合单体包括丙烯酸酯类单体和烯烃类单体的组合；所述聚合物金属盐选自磷酸金属盐类聚合物、羧基金属盐类聚合物、磺酸金属盐类聚合物或双磺酰亚胺金属盐类聚合物中的任意一种或至少两种的组合。
  2. 根据权利要求1所述的水性粘结剂，其中，所述聚合物金属盐包括聚合物锂盐、聚合物钠盐、聚合物钾盐或聚合物镁盐中的任意一种或至少两种的组合。
  3. 根据权利要求1或2所述的水性粘结剂，其中，所述磷酸金属盐类聚合物选自聚磷酸金属盐、2-甲基-2-丙烯酸-2-羟乙基酯磷酸金属盐基聚合物、二(2-(甲基丙烯酰氧基)乙基)磷酸金属盐基聚合物、2-甲基丙烯酰氧基乙基磷酸金属盐基聚合物或乙烯基磷酸金属盐基聚合物中的任意一种或至少两种的组合。
  4. 根据权利要求1-3任一项所述的水性粘结剂，其中，所述羧基金属盐类聚合物选自甲基丙烯酸金属盐基聚合物、丙烯酸金属盐基聚合物、马来酸金属盐基聚合物、衣康酸金属盐基聚合物、柠檬酸三烯丙酯金属盐基聚合物、羧甲基纤维素金属盐基聚合物或海藻酸金属盐基聚合物中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的水性粘结剂，其中，所述磺酸金属盐类聚合物选自苯乙烯基磺酸金属盐基聚合物、乙烯基磺酸金属盐基聚合物、丙烯基磺酸金属盐基聚合物、甲基丙烯磺酸金属盐基聚合物、4-乙烯苯亚磺酸金属盐基聚合物、烯丙基乙烯基磺酸金属盐基聚合物、3-磺酸丙基甲基丙烯酸金属盐基聚合物、甲基丙烯酸2-乙磺酸酯金属盐基聚合物、2-丙烯酰氨基-2-甲基-1-丙烷磺酸金属盐基聚合物、丙烯酸-2-丙烯酰胺-2-甲基丙磺酸金属盐基聚合物、3-烯丙氧基-2-羟基-1-丙烷磺酸金属盐基聚合物中的任意一种或至少两种的组合；
    优选地，所述双磺酰亚胺金属盐类聚合物选自乙烯基双磺酰亚胺金属盐基聚合物和/或苯乙烯基双磺酰亚胺金属盐基聚合物。
  6. 根据权利要求1-5任一项所述的水性粘结剂，其中，所述聚合物金属盐的重均分子量为1000-10000000；
    优选地，以所述聚合物金属盐与可聚合单体的总质量为100％计，所述聚合物金属盐的质量为1-90％，进一步优选10-50％。
  7. 根据权利要求1-6任一项所述的水性粘结剂，其中，所述丙烯酸酯类单 体为丙烯酸烷基酯和/或甲基丙烯酸烷基酯；
    优选地，所述丙烯酸酯类单体包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸戊酯、甲基丙烯酸戊酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸辛酯、丙烯酸异辛酯或甲基丙烯酸辛酯中的任意一种或至少两种的组合；
    优选地，所述烯烃类单体包括苯乙烯、C5-C10直链或支链烯烃中的任意一种或至少两种的组合；
    优选地，所述丙烯酸酯类单体与烯烃类单体的质量比为(0.5-2):1，进一步优选(0.8-1.5):1。
  8. 根据权利要求1-7任一项所述的水性粘结剂，其中，所述可聚合单体中还包括功能性单体；
    优选地，所述功能性单体包括丙烯酸和/或甲基丙烯酸；
    优选地，所述可聚合单体中功能性单体的质量百分含量≤10％。
  9. 一种如权利要求1-8任一项所述的水性粘结剂的制备方法，其包括：将聚合物金属盐、可聚合单体、引发剂和溶剂混合后进行反应，得到所述水性粘结剂。
  10. 根据权利要求9所述的制备方法，其中，所述引发剂包括过硫酸盐，优选过硫酸铵。
  11. 根据权利要求9或10所述的制备方法，其中，以所述可聚合单体的质量为100％计，所述引发剂的质量为0.05-5％；
    优选地，所述溶剂包括水；
    优选地，所述反应的温度为60-80℃；
    优选地，所述反应的时间为1-12h；
    优选地，所述反应完成后还包括中和的步骤。
  12. 一种如权利要求1-8任一项所述的水性粘结剂在电池材料中的应用。
  13. 一种电池极片，其中，所述电池极片包括如权利要求1-8任一项所述的水性粘结剂。
  14. 根据权利要求13所述的电池极片，其中，所述电池极片包括集流体和设置于所述集流体上的涂层，所述涂层的材料包括如权利要求1-8任一项所述的水性粘结剂；
    优选地，所述电池极片为负极极片。
  15. 一种锂离子电池，其中，所述锂离子电池包括如权利要求1-8任一项所述的水性粘结剂、如权利要求13或14所述的电池极片中的至少一种。
PCT/CN2022/140684 2022-07-19 2022-12-21 一种水性粘结剂及其制备方法和应用 WO2024016587A1 (zh)

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