CN115340636A - Additive for battery and preparation method and application thereof - Google Patents

Additive for battery and preparation method and application thereof Download PDF

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Publication number
CN115340636A
CN115340636A CN202211122984.1A CN202211122984A CN115340636A CN 115340636 A CN115340636 A CN 115340636A CN 202211122984 A CN202211122984 A CN 202211122984A CN 115340636 A CN115340636 A CN 115340636A
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emulsion
battery
additive
monomer
pole piece
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岳敏
王伟华
刘俊
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Xuancheng Research And Development Amperex Technology Ltd
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Xuancheng Research And Development Amperex Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • 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
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides an additive for a battery, a preparation method and application thereof. The additive for the battery is used for the battery pole piece, so that the wettability and the liquid absorption performance of the pole piece can be effectively improved, the duration of a battery liquid injection procedure is shortened, and the productivity is improved; meanwhile, the additive for the battery has a large amount of gap storage electrolyte, so that the liquid retention capacity of the pole piece is obviously improved, the lithium ion conduction is enhanced, and the cycle performance of the battery is improved.

Description

Additive for battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to an additive for a battery, and a preparation method and application thereof.
Background
In order to meet the demand of future electromotion, especially the further development of mobile electronic products such as mobile phones, the electric automobile industry and other circulating energy systems, the performance improvement of lithium ion batteries also faces a huge challenge. At present, the market not only has an increasing demand for lithium ion batteries, but also gradually increases the performance requirements of the lithium ion batteries, including the increase of battery capacity, the increase of energy density, the increase of battery cycle life, the reduction of charging time, and the like.
The lithium ion battery is generally assembled by a positive plate, a negative plate, a diaphragm and electrolyte, and the quality of the plate directly influences the performance of the lithium ion battery. The pole piece of the commercial lithium ion battery is mostly prepared by coating slurry on the surface of a current collector, wherein the slurry contains active substances, conductive additives, binders and the like, and the binders are divided into water-based binders and oil-based binders according to different solubilities of the binders. In order to obtain a lithium ion battery with better performance, people improve the performance of a pole piece, for example, CN110061222A discloses a preparation method and application of a lithium battery slurry, wherein a conductive agent is respectively added into a glue solution and an active material in batches to obtain a conductive slurry and a premix, the conductive slurry is added into the premix for kneading and vacuum defoaming to obtain a battery slurry; the battery slurry is used for preparing pole pieces, especially thick pole pieces, and has long service life and high multiplying power charge-discharge performance. In addition to the preparation of thick pole pieces, methods commonly used in the industry also include increasing the proportion of active materials in the slurry, increasing the compactness of the pole pieces, and the like, thereby increasing the capacity and energy density of the lithium ion battery. However, the pole piece with high energy density usually has the problem of poor wettability, which causes difficulty in electrolyte impregnation, hinders ion transmission, generates a lithium metal precipitation phenomenon after use, and seriously reduces the cycle performance, rate capability and safety of the battery.
In order to improve the wettability and the liquid retention performance of the pole piece, researchers propose a method for adding a liquid retention agent into slurry, for example, CN113611823A discloses a positive pole piece, and the preparation method of the positive pole slurry comprises the following steps: dry-mixing the positive active material, the carbon black conductive agent, the binder and the liquid retention agent, adding the dispersant and the solvent, and uniformly mixing and stirring to prepare positive slurry; wherein the liquid retention agent is one of polyacrylate, polymethyl methacrylate, polyacrylonitrile, polyacrylamide and polystyrene. Compared with the common thick pole piece, the wettability and the liquid retention can be improved to a certain extent by adding the liquid retention agent, but the effect is limited, and the problem of the cycle performance of the pole piece and the battery cannot be well solved.
The effect of the battery pole piece on the battery performance is also reflected in the process. In the production process of the lithium ion battery, one process is to inject electrolyte into the battery. The electrolyte injection process is an important process in the production of the lithium ion battery, and the consistency and the production efficiency of the lithium ion battery are directly determined by the precision of the electrolyte injection amount and the electrolyte injection efficiency. At present, the wettability of a pole piece is poor, and due to factors such as winding, lamination, extrusion and the like, the liquid absorption efficiency is low, liquid injection needs a long time, the situation of uneven liquid absorption is easy to occur, and the production efficiency and the yield of a battery are seriously influenced. Meanwhile, the battery has poor cycle performance due to poor wettability of the pole piece and limited liquid retention capacity and high consumption speed of electrolyte in the battery cycle process.
Therefore, the problem to be solved in the field is to improve the wettability of the pole piece and the liquid retention capacity of the pole piece.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the additive for the battery, the preparation method and the application thereof, the additive for the battery has a porous structure and good swelling performance, is used for a battery pole piece, and can remarkably improve the liquid absorption performance and the liquid retention capacity of the pole piece, so as to improve the performance of a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an additive for a battery comprising porous latex particles.
The additive for the battery provided by the invention contains porous latex particles, has a porous structure and a larger specific surface area, and has good swelling performance. The additive for the battery is used for the battery pole piece, so that on one hand, the liquid absorption performance of the pole piece can be improved, the time of a battery liquid injection procedure is shortened, and the productivity is improved; on the other hand, the soakage property of the pole piece is improved, and the consistency of the pole piece soaking electrolyte is improved. Moreover, the porous latex particles have a large amount of gaps for storing electrolyte due to high swelling performance, so that the liquid retention capacity of the pole piece can be improved, the lithium ion conduction is enhanced, and the cycle performance of the battery is improved.
Preferably, the particle size of the porous latex particles is 0.1-10.0 μm, and may be, for example, 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm, 6.5 μm, 7.0 μm, 7.5 μm, 8.0 μm, 8.5 μm, 9.0 μm or 9.5 μm, and specific points therebetween are not to be considered as limiting in the figures and for the sake of brevity, and the invention is not intended to list the specific points included within the range.
Preferably, the specific surface area of the porous latex particles is more than or equal to 10m 2 A value of,/g, for example, 15m 2 /g、20m 2 /g、25m 2 /g、30m 2 /g、50m 2 /g、80m 2 /g、100m 2 /g、200m 2 /g、300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g、500m 2 /g、550m 2 /g、600m 2 /g、650m 2 /g、700m 2 /g、750m 2 /g、800m 2 /g、850m 2 /g、900m 2 In g or 950m 2 And/g, etc.
Preferably, the swelling ratio of the porous latex particles is 40% to 10000%, for example, it may be 50%, 80%, 100%, 120%, 150%, 180%, 200%, 300%, 500%, 700%, 900%, 1000%, 2000%, 3000%, 4000%, 5000%, 6000%, 7000%, 8000% or 9000%, and specific points therebetween, which are not exhaustive, and for brevity, the present invention does not list the specific points included in the range, and further preferably 100% to 10000%.
Illustratively, the swelling ratio is the mass change rate of the porous latex particles after soaking in the electrolyte at 85 ℃ for 24h.
Preferably, the porous latex particles are obtained by reacting seed emulsion, acidic monomers and other monomers and then forming pores by using alkaline substances.
As a preferred technical scheme of the present invention, the porous latex particles are obtained by reacting a seed emulsion, an acidic monomer and other monomers, and then forming pores with an alkaline substance, wherein the acidic monomer and other monomers are compounded and polymerized with the seed emulsion to form polymer particles (latex particles), and under the action of the alkaline substance, a linear polymer polymerized from the acidic monomer in the polymer particles is dissolved, so that abundant pores are generated, and the porous latex particles are obtained.
Preferably, the seed emulsion may be a conventional polymer emulsion, commercially available.
Preferably, the seed emulsion comprises any one of pure acrylic emulsion, styrene-acrylic emulsion, vinyl acetate-acrylic emulsion, silicone-acrylic emulsion, styrene-butadiene emulsion, nitrile-butadiene emulsion, polyvinylidene fluoride emulsion or polytetrafluoroethylene emulsion or a combination of at least two of the pure acrylic emulsion, the styrene-acrylic emulsion, the vinyl acetate-acrylic emulsion, the silicone-acrylic emulsion, the styrene-butadiene emulsion, the nitrile-butadiene emulsion, the polyvinylidene fluoride emulsion or the polytetrafluoroethylene emulsion.
Preferably, the latex particles in the seed emulsion have a particle size of 50-500nm, such as 60nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm or 480nm, and the specific values therebetween are not exhaustive for reasons of brevity and conciseness.
Preferably, the acidic monomer is a polymerizable monomer containing at least one (e.g., 1, 2, or 3) of a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
Preferably, the acidic monomer comprises any one of Acrylic Acid (AA), methacrylic acid (MAA), a vinyl phosphate ester or a vinyl sulfonic acid or a combination of at least two thereof.
Preferably, the other monomer is a polymerizable monomer having no acidic group (having no carboxyl group, sulfonic acid group, or phosphoric acid group).
Preferably, the other monomer is a water-insoluble monomer.
Preferably, the other monomer includes any one of styrene (St), (meth) acrylate, acrylonitrile (AN), or vinyl acetate (VAc), or a combination of at least two thereof.
Preferably, the (meth) acrylate includes any one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, or pentyl (meth) acrylate, or a combination of at least two thereof.
Preferably, the mass ratio of the acidic monomer to other monomers is (0.1-10.0): 1.0, and for example, may be 0.2.
In a preferred embodiment of the present invention, the mass ratio of the acidic monomer to the other monomer is (0.1 to 10.0): 1.0, more preferably (1.0 to 8.0): 1.0; the two types of monomers and the seed emulsion are polymerized to form latex particles, and the pores are formed under the action of alkaline substances to form porous latex particles with good pore-size structures. If the proportion of the acidic monomer to other monomers exceeds the range and the dosage of the acidic monomer is too small, porous latex particles with rich pore channel structures cannot be formed, and the liquid absorption and retention performances of the pole piece are further influenced; when the amount of the acidic monomer is too large and the amount of other monomers is too small, the acidic monomer cannot effectively enter the latex of the seed emulsion, and cannot be well polymerized into latex particles with larger particle size, so that porous latex particles with excellent performance cannot be obtained.
Preferably, the mass ratio of the sum of the mass of the acidic monomer and the other monomer to the seed emulsion is 1.0 (0.1-10.0), and for example, the ratio can be 1.0.
As a preferred technical scheme of the invention, the mass ratio of the total mass of the two types of monomers to the seed emulsion is 1.0 (0.1-10.0), more preferably 1.0 (2.0-8.0), the two types of monomers can fully enter the latex of the seed emulsion and be polymerized to form latex particles with larger particle size, and then, the pores are formed under the action of alkaline substances to form porous latex particles with rich pore size structures. If the mass ratio of the monomer to the seed emulsion exceeds the preferred range and the dosage of the seed emulsion is too much, the content of the polymer based on the acidic monomer in the latex particles obtained by polymerization is too small, so that porous latex particles with rich pore-size structures cannot be formed, and the liquid absorption and retention performances of the pole piece are influenced; if the amount of the seed emulsion is too small, an excessive amount of the monomer may cause the latex particles in the seed emulsion to be broken, and thus, the latex particles having a large particle size cannot be polymerized, and thus, desired porous latex particles cannot be obtained.
In the present invention, the mass of the seed emulsion and the mass ratio of the seed emulsion to the monomer are calculated by the solid content thereof, and the solvent/dispersant and the like are not included therein.
In a second aspect, the present invention provides a method for preparing the additive for a battery according to the first aspect, the method comprising: reacting the seed emulsion, the acidic monomer and other monomers in the presence of an initiator to obtain a polymer emulsion; and mixing the polymer emulsion with an alkaline substance to perform pore-forming, thereby obtaining the additive for the battery.
Preferably, the seed emulsion, the acidic monomer and the other monomer are mixed, and then an initiator is added thereto to perform a reaction.
Preferably, the mixing time is 0.1-2.0h, for example, 0.2h, 0.5h, 0.8h, 1.0h, 1.2h, 1.5h or 1.8h, and the specific values therebetween are not exhaustive for the invention and are included for brevity.
As a preferred technical scheme of the invention, in the preparation method, the seed emulsion, the acidic monomer and other monomers are mixed firstly, so that the seed emulsion swells and adsorbs enough monomers (the acidic monomer and other monomers), and then the initiator is added into the seed emulsion for polymerization reaction to form the latex particles with larger particle size.
Preferably, the initiator comprises a water-soluble azo initiator and/or a persulfate, and further preferably ammonium persulfate.
Preferably, the mass of the initiator is 0.05 to 5.00%, for example 0.08%, 0.10%, 0.30%, 0.50%, 0.80%, 1.00%, 1.50%, 2.00%, 2.50%, 3.00%, 3.50%, 4.00% or 4.50%, based on 100% of the sum of the mass of the acidic monomer and the other monomers, and the specific values between the above values are limited to space and for the sake of brevity and are not exhaustive.
Preferably, the reaction temperature is 60-80 ℃, for example, 61 ℃, 63 ℃, 65 ℃, 68 ℃,70 ℃, 71 ℃, 73 ℃, 75 ℃, 77 ℃ or 79 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the reaction time is 1 to 12 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or 11 hours, and specific values therebetween, for reasons of space and brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the polymer emulsion is mixed with the alkaline substance such that the pH of the system is 7.0-9.0, for example, the pH of the system is 7.1, 7.3, 7.5, 7.7, 7.9, 8.0, 8.1, 8.3, 8.5, 8.7 or 8.9, and the specific values therebetween, are not exhaustive and for the sake of brevity, the invention is not intended to include the specific values included within the recited ranges.
Preferably, the alkaline substance is a metal hydroxide, further preferably any one of sodium hydroxide, lithium hydroxide or potassium hydroxide or a combination of at least two thereof.
Preferably, the basic substance is mixed with the polymer emulsion in the form of an aqueous solution thereof.
Preferably, the pore-forming time is 0.5-5.0h, for example, 0.8h, 1.0h, 1.2h, 1.5h, 1.8h, 2.0h, 2.2h, 2.5h, 2.8h, 3.0h, 3.2h, 3.5h, 3.8h, 4.0h, 4.2h, 4.5h or 4.8h, and the specific values therebetween are not intended to be exhaustive, and for the sake of brevity, the invention is not intended to include specific values within the indicated ranges.
Preferably, the preparation method comprises the following steps: mixing the seed emulsion, the acidic monomer and other monomers for 0.1-2.0h, adding an initiator, and reacting at 60-80 ℃ for 1-12h to obtain polymer emulsion; and adding an alkaline substance into the polymer emulsion to enable the pH value of the system to be 7.0-9.0, and forming porous latex particles through pore forming to obtain the battery additive.
In a third aspect, the present invention provides an electrode material composition comprising the additive for batteries according to the first aspect.
Preferably, the electrode material composition includes a combination of an electrode active material, a conductive agent, a binder, and the battery additive.
Preferably, the battery additive is 0.01 to 1.00 parts by mass, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.10 parts, 0.20 parts, 0.30 parts, 0.40 parts, 0.50 parts, 0.60 parts, 0.70 parts, 0.80 parts, or 0.90 parts by mass based on 100 parts by mass of the electrode active material, and specific point values between the above point values are limited to space and are not exhaustive, and the specific point values included in the range are not enumerated in the present invention for the sake of brevity.
Preferably, the electrode active material is a positive electrode active material or a negative electrode active material.
Preferably, the positive active material includes an active material that can intercalate and deintercalate lithium, and exemplary includes, but is not limited to: any one of lithium iron phosphate and lithium transition metal composite oxide (such as nickel-cobalt-manganese ternary material) or a combination of at least two of the above materials.
Preferably, the negative electrode active material includes any one of a carbon material, a silicon oxygen material, or a combination of at least two thereof.
Preferably, the carbon material comprises any one of graphite, carbon black, carbon nanotubes, carbon fibers, mesocarbon microbeads or petroleum coke, or a combination of at least two of them.
Preferably, the conductive agent comprises any one of carbon black, graphite, carbon nanotubes or carbon fibers or a combination of at least two thereof.
Preferably, the conductive agent is 0.1 to 5.0 parts by mass, for example, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1.0 part, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4.0 parts, 4.2 parts, 4.5 parts, or 4.8 parts by mass based on 100 parts by mass of the electrode active material.
Preferably, the binder comprises polyvinylidene fluoride (PVDF) or Styrene Butadiene Rubber (SBR).
Preferably, the binder is 0.01 to 5.00 parts by mass, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.10 parts, 0.30 parts, 0.50 parts, 0.70 parts, 0.90 parts, 1.00 parts, 1.20 parts, 1.50 parts, 1.80 parts, 2.00 parts, 2.20 parts, 2.50 parts, 2.80 parts, 3.00 parts, 3.20 parts, 3.50 parts, 3.80 parts, 4.00 parts, 4.20 parts, 4.50 parts, or 4.80 parts by mass based on 100 parts by mass of the electrode active material.
Preferably, a thickening agent is further included in the electrode material composition; the thickener is preferably sodium carboxymethylcellulose (CMC).
Preferably, the electrode material composition is a negative electrode material composition including a negative electrode active material, a conductive agent, a binder, and the battery additive.
In a fourth aspect, the present invention provides a battery pole piece comprising a current collector and a coating disposed on the current collector, the material of the coating comprising the electrode material composition according to the third aspect.
Preferably, the battery pole piece is a negative pole piece.
As a preferred technical scheme of the invention, the negative pole piece containing the additive for the battery has good wettability to the electrolyte, the consistency of the pole piece in the electrolyte wetting process is good, the liquid absorption time of the negative pole piece is less than or equal to 10s through the component design and optimization of the additive for the battery, and compared with the common pole piece, the liquid absorption time is shortened by more than 70 percent, so that the time of the battery liquid injection process is obviously shortened. The negative pole piece containing the additive for the battery has excellent liquid absorption and retention performances, reduces the consumption of electrolyte in the battery circulation process, enhances the lithium ion conduction, enables the capacity retention rate of the lithium ion battery circulating for 100 weeks at normal temperature to be not less than 99.0%, and has excellent circulation performance.
In a fifth aspect, the present invention provides an electrochemical energy storage device comprising at least one of the battery additive of the first aspect, the electrode material composition of the second aspect, and the battery pole piece of the third aspect.
Preferably, the electrochemical energy storage device comprises any one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
Compared with the prior art, the invention has the following beneficial effects:
the battery additive provided by the invention comprises porous latex particles, has a rich pore channel structure and a large specific surface area, and the specific surface area can reach 414.7-572m 2 The swelling agent has good swelling performance, and the swelling rate can reach 400-9300%. The additive for the battery is used for the battery pole piece, so that the wettability and the liquid absorption performance of the pole piece can be effectively improved, the time of a battery liquid injection procedure is shortened, and the productivity is improved; meanwhile, a large amount of gap storage electrolyte is provided, the liquid retention capacity of the pole piece is obviously improved, the lithium ion conduction is enhanced, and the cycle performance of the battery is improved.
Drawings
FIG. 1 is a scanning electron micrograph of the porous latex particles described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optionally" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are used without limitation to the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplary," "specific examples" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Seed emulsions according to the following embodiments of the present invention are commercially available, for example, styrene-acrylic, styrene-butadiene, acrylic, nitrile-butadiene, vinyl acetate, and polyvinylidene fluoride (PVDF) emulsions are available from Michelin.
Example 1
An additive for a battery and a preparation method thereof, wherein the additive for the battery comprises porous latex particles, and is obtained by reacting seed emulsion (styrene-acrylic emulsion), acidic monomer (acrylic acid, AA) and other monomer (styrene, st) and then performing pore-forming on alkaline substances; the mass ratio of the seed emulsion, the acidic monomer and other monomers is 16; the preparation method comprises the following steps:
adding 15 parts of acidic monomer AA and 5 parts of other monomer St into 80 parts of seed emulsion (styrene-acrylic emulsion, the average particle size of latex particles is 150nm, and the mass parts are calculated by solid content), mixing for 2 hours to enable the seed emulsion to absorb enough monomers, then adding 0.1 part of initiator ammonium persulfate, and carrying out polymerization reaction for 6 hours at 70 ℃ to obtain polymer emulsion; and adding a sodium hydroxide solution into the polymer emulsion to enable the pH value of the system to be 8.0, and forming pores after pore forming for 1 hour to form porous latex particles to obtain the battery additive.
Examples 2 to 10
An additive for a battery and a preparation method thereof are different from those of example 1 in that the components of porous latex particles are different, specifically as shown in table 1; the "mass ratio" in table 1 is the mass ratio of the seed emulsion, the acidic monomer and the other monomer; the mass of the seed emulsion is based on the solid content.
TABLE 1
Seed emulsion Acidic monomer Other monomers Mass ratio of
Example 1 Styrene-acrylic emulsion Acrylic acid Styrene (meth) acrylic acid ester 16:3:1
Example 2 Butylbenzene emulsion Acrylic Acid (AA) Styrene (meth) acrylic acid ester 15:4:1
Example 3 Pure acrylic emulsion Methacrylic acid Acrylic acid butyl ester 17:2:1
Example 4 Butyronitrile emulsion Vinyl sulfonic acid Acrylonitrile 14:5:1
Example 5 Vinyl acetate acrylic emulsion Vinyl phosphate ester Vinyl acetate ester 16:1:1
Example 6 PVDF emulsion Acrylic Acid (AA) Styrene (meth) acrylic acid ester 14:6:1
Example 7 Styrene-acrylic emulsion Acrylic Acid (AA) Styrene (meth) acrylic acid ester 16:1:3
Example 8 Styrene-acrylic emulsion Acrylic acid Styrene (meth) acrylic acid ester 16:3.8:0.2
Example 9 Styrene-acrylic emulsion Acrylic Acid (AA) Styrene (meth) acrylic acid ester 1:3:1
Example 10 Styrene-acrylic emulsion Acrylic Acid (AA) Styrene (meth) acrylic acid ester 40:1:3
Comparative example 1
One battery additive was the conventional styrene-acrylic latex particles, i.e., the latex particles of the seed emulsion in example 1.
Comparative example 2
An additive for a battery, which is styrene-acrylic emulsion particles, is obtained by polymerizing seed emulsion (styrene-acrylic emulsion), acrylic acid and styrene, wherein the mass ratio of the seed emulsion to the acrylic acid to the styrene is 16; the preparation method is different from the embodiment 1 only in that sodium hydroxide solution is not added for pore forming; the other process parameters were the same as in example 1.
Comparative example 3
An additive for battery (existing liquid retention additive), specifically a methyl methacrylate-butadiene-styrene copolymer with linear structure, has a number average molecular weight of 18 ten thousand.
Application examples 1 to 10, comparative application examples 1 to 3
A battery pole piece is a negative pole piece and comprises a current collector (Cu foil) and a coating arranged on the current collector, wherein the coating is made of an electrode material composition and comprises a negative active material (a silica material SiO-450, new energy Material GmbH, silicon content 10%), a conductive agent (carbon black SP), a binder (styrene butadiene rubber, SBR), a thickening agent (sodium carboxymethylcellulose, CMC) and the battery additive in a mass ratio of 96; the additives for batteries are the additives for batteries provided in examples 1 to 10 and comparative examples 1 to 3, respectively.
The preparation method of the negative pole piece comprises the following steps: mixing a negative electrode active material, a conductive agent, a binder, a thickening agent and the battery additive according to a mass ratio of 96Drying on Cu foil, and rolling at 10 × 10 4 And (4) rolling the N/m load per unit length to obtain the negative pole piece.
A lithium ion battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the negative pole piece is the negative pole piece; the preparation method of the lithium ion battery comprises the following steps:
(1) Preparing a positive pole piece: mixing the active material (lithium iron phosphate material) serving as a positive electrode, conductive carbon black and a binder (PVDF) according to a solid content of 95.5 in parts by mass ratio of (2) 4 Rolling the N/m load per unit length to obtain a positive pole piece;
(2) Negative pole piece: as described hereinbefore;
(3) A diaphragm: a PE porous polymer film (Shenzhen star source material science and technology Limited) is adopted as a diaphragm;
(4) Assembling the lithium ion battery: winding the positive pole piece, the isolating membrane and the negative pole piece in sequence to obtain a battery core; and packaging the battery core by using an aluminum plastic film, baking to remove water, injecting electrolyte, and performing vacuum packaging, shelving, formation, secondary sealing, shaping and other processes to obtain the lithium ion battery.
Comparative application example 4
A battery pole piece and a lithium ion battery comprising the same are disclosed, wherein the battery pole piece is a negative pole piece, and the battery pole piece is only different from an application example 1 in that a material (an electrode material composition, namely negative electrode slurry) of a coating does not contain a battery additive; other materials, proportions and preparation methods were the same as in application example 1.
And (3) performance testing:
(1) Morphology and specific surface area
The porous latex particles of the additives for batteries described in the examples were subjected to morphological tests using scanning electron microscopy (SEM, EVOMA25, ZEISS). Illustratively, the scanning electron microscope image of the porous latex particles described in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the average particle size of the porous latex particles is 0.6 μm, and the particles contain abundant pore channel structures.
The specific surface area of the porous latex particles is tested by adopting a multipoint BET method, a tester is a Michelson specific surface tester, and adsorbate is high-purity N 2 The obtained specific surface area data are shown in table 2.
(2) Swelling ratio
Dropwise adding the additive (containing the emulsion of the porous latex particles) for the battery to be detected into a clean die, ensuring that the solid content is 4g +/-0.1 g, drying the additive in an oven at 70 ℃ for 12h, taking out cut pieces of 1cm multiplied by 1cm, weighing prepared samples, and recording the mass M 1 (ii) a And weighing enough electrolyte, adding the electrolyte into a glass bottle filled with the sample to ensure that the electrolyte completely submerges the sample, sealing the bottle, and standing in a water bath at 85 ℃ for 24 hours. Taking out the sample, wiping the electrolyte on the sample with clean dust-free paper, weighing the mass of the swelled sample, and recording as M 2 。
Swelling ratio =100% × (M) 2 -M 1 )/M 1 The test results are shown in table 2.
(3) Liquid absorption performance of pole piece
And (3) dropwise adding 1mL of electrolyte DMC to the negative electrode plate to be detected, timing from the moment that the electrolyte DMC contacts the electrode plate to the moment that the electrolyte is completely absorbed by the electrode plate, and recording the liquid absorption time of the electrode plate, wherein the liquid absorption time is specifically shown in Table 2.
(4) Cycle performance of the battery
Charging the prepared lithium ion battery to 4.2V at a constant current of 0.33C, then charging at a constant voltage to a cut-off current of 0.02C, and discharging to 2.5V at 0.33C; standing for 5min, charging to 4.2V at constant current of 0.33C, charging to cutoff current of 0.02C at constant voltage, and discharging to 2.5V at 0.33C, thereby performing initial adjustment;
and charging the lithium ion battery adjusted in the initial stage to 4.2V at a constant current of 0.5C at 25 ℃, then charging the lithium ion battery at a constant voltage to a cut-off current of 0.02C, standing for 5min, then discharging the lithium ion battery at a constant current of 1C to 2.5V, standing for 5min, and measuring the first cycle discharge capacity. After the cycle was repeated by 100 cycles of charge/discharge, the 100 th cycle discharge capacity was measured, and the 100 th cycle capacity retention ratio was calculated by the following formula:
capacity retention (%) at 100 cycles =100% × 100 th-cycle discharge capacity/first-cycle discharge capacity.
TABLE 2
Figure BDA0003847179970000151
Figure BDA0003847179970000161
In table 2, "not added" in the last row is the test data of comparative application example 4, in which the negative electrode tab does not use the battery additive, "-" represents the test data without specific surface area/swelling ratio.
As can be seen from the performance test data in Table 2, the additive for the battery provided by the invention comprises porous latex particles with rich pore channel structures and larger specific surface area, and through the design and optimization of components, the specific surface areas of examples 1 to 6 are 414.7 to 572m 2 Per g, and has good swelling performance, and the swelling ratio is 400-9300%. The negative pole piece containing the additive for the battery has excellent wettability and liquid absorption capacity through the design and optimization of components, the liquid absorption time of the negative pole piece containing the additive for the battery is less than or equal to 10s, and compared with a common negative pole piece without the additive, the liquid absorption time is shortened by over 70 percent, so that the time of a battery liquid injection process is shortened, and the productivity is improved. Meanwhile, the additive for the battery has a large amount of gap storage electrolyte, so that the liquid retention capacity of a pole piece is remarkably improved, the lithium ion conduction is enhanced, the capacity retention rate of the lithium ion battery after being cycled for 100 weeks at normal temperature is 99.0-99.5%, and the cycle performance of the battery is remarkably improved.
According to the invention, through the component and structural design of the porous latex particles, the wettability, the liquid absorption property and the liquid retention capacity of the pole piece can be obviously improved by the additive for the battery, the wettability of the pole piece cannot be effectively improved by the common latex particles (comparative example 1-2) without the porous structure defined by the invention, the liquid absorption and the liquid retention performance of the pole piece cannot be improved, and the cycle performance of the lithium ion battery is poor. The conventional liquid retention additive (comparative example 3) in the prior art can improve the liquid retention of a pole piece and the cycle performance of a battery to a certain extent, but the effect is very limited, and the liquid absorption time is not obviously improved. In addition, the structure, appearance and properties of the porous latex particles can be adjusted and optimized by setting the proportion of the acidic monomer to other monomers and the proportion of the monomer to the seed emulsion, so that the liquid absorption and liquid retention of the pole piece can be more effectively improved by the battery additive; if the ratio of the acidic monomer, other monomers and the seed emulsion is out of the preferable range (examples 7-10), the structure and properties of the porous latex particles are affected, and the improvement effect of the battery additive on the wettability of the electrode sheet is further affected.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it is not meant to be dependent on the above process steps to implement the present invention. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. An additive for a battery, characterized in that the additive for a battery comprises porous latex particles.
2. The additive for battery as defined in claim 1, wherein the porous latex particles have a particle size of 0.1 to 10.0 μm;
preferably, the specific surface area of the porous latex particles is more than or equal to 10m 2 /g；
Preferably, the swelling ratio of the porous latex particles is 40% to 10000%, and more preferably 100% to 10000%.
3. The additive for a battery according to claim 1 or 2, wherein the porous latex particles are obtained by reacting a seed emulsion, an acidic monomer and other monomers and then forming pores with an alkaline substance;
preferably, the seed emulsion comprises any one of pure acrylic emulsion, styrene-acrylic emulsion, vinyl acetate-acrylic emulsion, silicone-acrylic emulsion, styrene-butadiene emulsion, butyronitrile emulsion, polyvinylidene fluoride emulsion or polytetrafluoroethylene emulsion or the combination of at least two of the pure acrylic emulsion, the styrene-acrylic emulsion, the vinyl acetate-acrylic emulsion, the silicone-acrylic emulsion, the styrene-butadiene emulsion, the butyronitrile emulsion, the polyvinylidene fluoride emulsion or the polytetrafluoroethylene emulsion;
preferably, the acidic monomer is a polymerizable monomer containing at least one of a carboxyl group, a sulfonic acid group, or a phosphoric acid group;
preferably, the acidic monomer comprises any one of acrylic acid, methacrylic acid, vinyl phosphate ester or vinyl sulfonic acid or a combination of at least two of the same;
preferably, the other monomer comprises any one of styrene, (meth) acrylate, acrylonitrile or vinyl acetate or a combination of at least two thereof;
preferably, the alkaline substance is a metal hydroxide, further preferably any one of sodium hydroxide, lithium hydroxide or potassium hydroxide or a combination of at least two thereof.
4. The additive for batteries according to claim 3, wherein the mass ratio of the acidic monomer to the other monomer is (0.1-10.0): 1.0;
preferably, the mass ratio of the sum of the mass of the acidic monomer and the other monomers to the seed emulsion is 1.0 (0.1-10.0).
5. A method for preparing the additive for batteries according to any one of claims 1 to 4, characterized in that it comprises: reacting the seed emulsion, the acidic monomer and other monomers in the presence of an initiator to obtain a polymer emulsion; and mixing the polymer emulsion with an alkaline substance to perform pore-forming, thereby obtaining the additive for the battery.
6. The preparation method according to claim 5, wherein an initiator is added to the seed emulsion, the acidic monomer and the other monomer after the seed emulsion, the acidic monomer and the other monomer are mixed to perform a reaction;
preferably, the mixing time is 0.1-2.0h;
preferably, the initiator comprises a water-soluble azo initiator and/or a persulfate;
preferably, the mass of the initiator is 0.05 to 5.00 percent based on 100 percent of the sum of the mass of the acidic monomer and the mass of the other monomers;
preferably, the temperature of the reaction is 60-80 ℃;
preferably, the reaction time is 1-12h.
7. The method according to claim 5 or 6, wherein the polymer emulsion is mixed with an alkaline substance so that the pH of the system is 7.0 to 9.0;
preferably, the alkaline substance is a metal hydroxide, further preferably any one or a combination of at least two of sodium hydroxide, lithium hydroxide or potassium hydroxide;
preferably, the pore-forming time is 0.5-5.0h;
preferably, the preparation method comprises the following steps: mixing the seed emulsion, the acidic monomer and other monomers for 0.1-2.0h, adding an initiator, and reacting at 60-80 ℃ for 1-12h to obtain polymer emulsion; and adding an alkaline substance into the polymer emulsion to enable the pH value of the system to be 7.0-9.0, and forming porous latex particles through pore forming to obtain the battery additive.
8. An electrode material composition comprising the additive for batteries according to any one of claims 1 to 4;
preferably, the electrode material composition includes an electrode active material, a conductive agent, a binder, and the battery additive;
preferably, the battery additive is 0.01 to 1.00 part by mass based on 100 parts by mass of the electrode active material.
9. A battery pole piece comprising a current collector and a coating disposed on the current collector, the material of the coating comprising the electrode material composition of claim 8.
10. An electrochemical energy storage device comprising at least one of the battery additive of any one of claims 1-4, the electrode material composition of claim 8, the battery pole piece of claim 9;
preferably, the electrochemical energy storage device comprises any one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
CN202211122984.1A 2022-09-15 2022-09-15 Additive for battery and preparation method and application thereof Pending CN115340636A (en)

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CN104904050A (en) * 2012-11-19 2015-09-09 株式会社Uacj Collector, electrode structure body, and electrical storage component
CN105131872A (en) * 2015-09-07 2015-12-09 中国建筑材料科学研究总院 Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass
CN112646444A (en) * 2020-12-18 2021-04-13 汕头市广油美联新材料研究院有限公司 Preparation method of mesoporous silica water-based ceramic slurry

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280035A (en) * 2007-10-31 2008-10-08 浙江传化股份有限公司 Wet-rub resistant styrene-acrylic emulsion and preparation thereof
CN104904050A (en) * 2012-11-19 2015-09-09 株式会社Uacj Collector, electrode structure body, and electrical storage component
US20150311001A1 (en) * 2012-11-19 2015-10-29 Uacj Corporation Current collector, electrode structure, and electrical storage device
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