CN115340625A - Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof - Google Patents

Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof Download PDF

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CN115340625A
CN115340625A CN202211197716.6A CN202211197716A CN115340625A CN 115340625 A CN115340625 A CN 115340625A CN 202211197716 A CN202211197716 A CN 202211197716A CN 115340625 A CN115340625 A CN 115340625A
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adhesive
reaction
lithium ion
ion battery
kettle
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魏仁兴
王金娥
蔡业茂
王建
魏世昊
顾思聪
谈巧
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Huizhou Sailida Chemical Co ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to the technical field of lithium ion battery adhesives, in particular to a water-based polymer adhesive for replacing an oily PVDF adhesive for a lithium ion battery anode and a preparation method thereof, wherein the preparation method comprises the following steps: the components are as follows: unsaturated monomer, emulsifier, initiator and water, wherein the unsaturated monomer, the emulsifier and the initiator are subjected to high-molecular polymerization reaction at the temperature of 80 ℃ by using the water as a medium and a carrier through a process sequence to obtain the sexual polymerization adhesive. The invention uses a simple and environment-friendly method to obtain the aqueous polymer adhesive which is more environment-friendly, better in performance, better in quality and lower in price than PVDF oily adhesive, so as to replace the PVDF adhesive which is widely used in the existing lithium ion battery, expensive in price, inconvenient to use, not environment-friendly and harmful to human body.

Description

Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery adhesives, in particular to a water-based polymer adhesive for replacing an oily PVDF adhesive for a lithium ion battery anode and a preparation method thereof.
Background
At present, both domestically and abroad can verify that all the positive binders used for manufacturing lithium ion batteries are PVDF (polyvinylidene fluoride) which is a Chinese name and is one of fluorocarbon plastics, and the positive binders are prepared by carrying out harsh-condition chemical reaction on raw materials of R142b, chinese name 1,1-difluoro-chloroethane (difluorochloroethane, molecular formula C2H3ClF2 for short), the difluorochloroethane belongs to a fluorine chemical product, a second-generation Freon refrigerant has serious destructive influence on ozone in the earth atmosphere, international environmental protection organization has signed contract and reduced and limited use in various countries, quota of upstream raw materials is reduced and limited, downstream products PVDF are naturally in shortage and price rise, PVDF is a fluorine resin high-molecular product, and the production process of the PVDF is that R142b can be prepared into vinylidene fluoride (VDF) by cracking, HCl removal, dehydration, rectification and other processes, and the like, and the polyvinylidene fluoride (VDF) can be obtained by polymerization, the process is complex, the condition is harsh, uneconomic, the environmental pressure is huge, and more importantly, when PVDF is used as the dispersing adhesive and matched with the anode slurry, NMP (N-methyl pyrrolidone) solvent accounting for 40 percent of the mass of the slurry is used for dissolving PVDF and the dispersing main body anode material (lithium iron phosphate or ternary lithium and conductive agent), the solvent is used as the surplus substance during coating and drying, drying and evaporating are carried out, the solvent is collected and recovered, but 15 to 25 percent of the loss is always generated during evaporation, in addition, the cost of the recovered solvent is 2000 to 3000 yuan/ton for transportation and purification treatment with relatively complex high energy consumption and then is recycled, the process is a process with high cost and large VOC discharge amount and is not environment-friendly, lithium batteries made of PVDF are used as the dispersing adhesive, and a method of high-temperature calcination is generally used when expensive lithium salt and useful aluminum metal are scrapped and extracted, PVDF contains fluorine, the decomposition product of high-temperature calcination and combustion is toxic fluorine-containing gas, the environment is not friendly, and the PVDF has the following defects: a. the raw materials are limited substances, the expansion production is strictly controlled by policies, the process is complex, the high temperature, the high pressure and the high toxicity risk coefficient are high, a large amount of three wastes are generated in the production, a solvent is used in the use, the drying energy consumption is high, the environment protection is difficult to realize in the recovery treatment of waste batteries, the price of the d-phase is high, and the supply is tense.
Therefore, an aqueous polymer binder for a positive electrode of a lithium ion battery instead of an oily PVDF binder and a method for preparing the same are proposed to solve the above problems.
Disclosure of Invention
The invention achieves the aim through the following technical scheme, and the aqueous polymerization adhesive for replacing an oily PVDF adhesive for the positive electrode of the lithium ion battery comprises the following components: the components are as follows: unsaturated monomer, emulsifier, initiator and water, wherein the unsaturated monomer, the emulsifier and the initiator are subjected to high-molecular polymerization reaction at the temperature of 80 ℃ by using the water as a medium and a carrier through a process sequence to obtain the reactive polymeric binder, and the reaction equation is as follows:
Figure DEST_PATH_IMAGE001
。
preferably, the unsaturated monomers include acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, and N-methyl acrylamide.
A process for preparing the aqueous polymer adhesive used as the anode of Li-ion battery to replace the oily PVDF adhesive includes such steps as preparing raw materials, heating for dissolving, synthesizing reaction, cooling, regulating, detecting, filtering and packing.
Preferably, the production process is controlled within 8-10 h.
Preferably, the specific process comprises the following steps:
A. preparing materials: the liquid raw materials are automatically weighed and fed, and the solid raw materials are manually fed. The method comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, the process water and the like into a polymerization kettle, and uniformly stirring;
B. heating and dissolving: heating the polymerization kettle to 80-86 ℃, keeping the temperature for 10-30 minutes, and stirring and mixing uniformly;
C. and (3) synthesis reaction: dripping a small amount of pre-emulsion from a pre-emulsion kettle into a polymerization kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out priming reaction. After the bottoming reaction is finished, starting to dropwise add the pre-emulsion to carry out synthesis reaction, controlling the temperature to be 80-86 ℃, wherein the time is about 4-6 h, and adding cooling water into a reaction kettle jacket to control the reaction temperature to be 80-86 ℃ along with the reaction;
D. and (3) cooling: after the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and the cooling, and post-treatment agents and the like are added for adjustment;
E. packaging and discharging: after the adjustment, the product is qualified by inspection, filtered, packaged and discharged.
The invention uses a simple and environment-friendly method to obtain a water-based polymer adhesive which is more environment-friendly, better in performance, better in quality and lower in price than a PVDF oily adhesive to replace the PVDF adhesive which is widely used by the existing lithium ion battery, is expensive, inconvenient to use, not environment-friendly and harmful to human body, and the positive pole water-based adhesive which has excellent performance and can well meet the manufacturing and use requirements of the lithium ion battery is synthesized by an emulsion polymerization method to replace the PVDF used at present, and simultaneously water is used to replace an expensive NMP solvent.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aqueous polymerization adhesive for a lithium ion battery anode is used for replacing an oily PVDF adhesive, and is obtained by a special emulsion polymerization method, wherein the special emulsion polymerization method comprises the following steps: various unsaturated monomers (including but not limited to acrylic acid, methacrylic acid, methyl methacrylate, styrene, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, acrylamide, N-methacrylamide and the like), an emulsifier, an initiator and water are used as a medium and a carrier according to a certain process sequence, and a high molecular polymerization reaction is carried out at about 80 ℃ to obtain the aqueous high molecular polymerization adhesive, the special emulsion polymerization is mainly embodied in the special formula and process, and a very pure component which hardly contains small molecules or useless high molecules can be obtained through the emulsion polymerization adhesive, wherein all substances are completely used for various aspects such as positive electrode adhesion and the like, the polymerization reaction condition is mild, the temperature is only 80 ℃, all the substances are liquid and water-soluble substances at the temperature, and the oily adhesive can not be obtained through complex process, harsh conditions, huge safety, environment and occupational hazards of PVDF. The emulsion polymerization reaction is carried out under normal pressure, the added materials are subjected to reaction and post-treatment, and are reserved in the product to become useful components, the useful components are directly used for the lithium ion battery, useless impurities cannot be left in the product, the product is particularly pure, the influence of the output of useless byproducts on the environment is avoided, and the used medium is water, so that the method is safe, low-carbon, environment-friendly and economical.
The emulsion polymerization is the polymerization of various monomers and water in an emulsion prepared under the action of an emulsifier, the system mainly comprises four main components of monomers (various unsaturated monomers (including but not limited to acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, N-methacrylamide and the like), water, the emulsifier (a plurality of composite emulsifiers) and a water-soluble initiator, and a specific reaction equation is as follows (the four unsaturated monomers only indicate that the four unsaturated monomers actually comprise a plurality of components):
Figure 967478DEST_PATH_IMAGE001
。
as shown in fig. 1, the preparation method of the aqueous polymeric binder for the lithium ion battery anode to replace the oily PVDF binder is a semi-continuous process, and the process comprises the steps of material preparation, heating and dissolution, synthesis reaction, cooling, adjustment, detection, filtration, packaging and the like. The production process needs 8-10h, and the equipment needed in the production process is as follows: the pre-emulsifying process comprises the following specific process operation steps:
A. preparing materials: the liquid raw materials are automatically weighed and fed, and the solid raw materials are manually fed. Comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, the process water and the like into a polymerization kettle, and uniformly stirring;
B. heating for dissolving: heating the polymerization kettle to 80-86 ℃, preserving the heat for 10-30 minutes, and stirring and mixing uniformly;
C. and (3) synthesis reaction: dripping a small amount of pre-emulsion from a pre-emulsion kettle into a polymerization kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out priming reaction. After the bottoming reaction is finished, starting to dropwise add the pre-emulsion to carry out synthesis reaction, controlling the temperature to be 80-86 ℃, wherein the time is about 4-6 h, and adding cooling water into a reaction kettle jacket to control the reaction temperature to be 80-86 ℃ along with the reaction;
D. and (3) cooling: after the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and the cooling, and post-treatment agents and the like are added for adjustment;
E. packaging and discharging: after the adjustment, the product is qualified by inspection, filtered, packaged and discharged.
And (3) analysis: the original PVDF has chemical inertness, acid resistance, alkali resistance, aging resistance, high-energy impact resistance, electrolyte resistance, good strength and toughness, and simultaneously is analyzed to have non-conductivity, need a special solvent to dissolve and the like. The invention relates to a cathode binder, which mainly aims at lithium iron phosphate cathode materials, and a ternary cathode material is not involved temporarily. The main chain structure and the bonding performance of the binder are designed by comprehensively considering the surface of aluminum, the particle size (about 1 mu m) and the surface performance of lithium iron phosphate particles, and the particle size and the surface performance of conductive agent particles at the interfaces of three cathode materials needing to be bonded. The formula is elaborately designed according to the requirements of three aspects, namely the stability of the battery using process in consideration of penetration and transmission of conductive particles, the liquid absorption rate of electrolyte, appropriately required expansion and contraction, charge and discharge energy storage resistance, high and low temperature resistance, aging resistance and the like, the stability of the battery using process in storage stability and no floating and sinking of slurry for a certain time, the viscosity and rheological property of the slurry, the uniformity of a coating layer, the moisture content of the slurry, the coating speed, the baking time, the winding and coiling of the slurry, the processability of procedures such as heating, dehumidifying and curing and the like, and the aqueous positive electrode dispersion adhesive which is used for replacing PVDF and meets the comprehensive performance requirements is obtained through verification and optimization of thousands of experimental tests.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (5)

1. The aqueous polymer adhesive for replacing an oily PVDF adhesive for the positive electrode of the lithium ion battery is characterized by comprising the following components: unsaturated monomer, emulsifier, initiator and water, wherein the unsaturated monomer, the emulsifier and the initiator are subjected to high-molecular polymerization reaction at the temperature of 80 ℃ by using the water as a medium and a carrier through a process sequence to obtain the reactive polymeric binder, and the reaction equation is as follows:
Figure 218513DEST_PATH_IMAGE001
。
2. the aqueous polymeric binder for the positive electrode of the lithium ion battery, which replaces the oily PVDF binder, according to claim 1, is characterized in that: the unsaturated monomer comprises acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide and N-methyl acrylamide.
3. The method for preparing the aqueous polymeric binder used for replacing the oily PVDF binder for the positive electrode of the lithium ion battery as claimed in any one of claims 1-2, wherein the process comprises the steps of material preparation, heating dissolution, synthesis reaction, cooling, adjustment, detection, filtration and packaging.
4. The preparation method of the aqueous polymeric binder for the lithium ion battery anode to replace the oily PVDF binder is characterized in that the production process is controlled within 8-10 h.
5. The preparation method of the aqueous polymerization adhesive for replacing the oily PVDF adhesive for the lithium ion battery anode according to claim 3 is characterized by comprising the following specific processes:
A. preparing materials: automatically weighing and feeding liquid raw materials, and manually feeding solid raw materials;
comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, the process water and the like into a polymerization kettle, and uniformly stirring;
B. heating for dissolving: heating the polymerization kettle to 80-86 ℃, keeping the temperature for 10-30 minutes, and stirring and mixing uniformly;
C. and (3) synthesis reaction: dropwise adding a small amount of pre-emulsion into a polymerization kettle from a pre-emulsion kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out a priming reaction;
after the bottoming reaction is finished, starting to dropwise add the pre-emulsion to carry out synthesis reaction, controlling the temperature to be 80-86 ℃, wherein the time is about 4-6 h, and adding cooling water into a reaction kettle jacket to control the reaction temperature to be 80-86 ℃ along with the reaction;
D. and (3) cooling: after the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and the cooling, and post-treatment agents and the like are added for adjustment;
E. packaging and discharging: after the adjustment, the product is qualified by inspection, filtered, packaged and discharged.
CN202211197716.6A 2022-09-29 2022-09-29 Aqueous polymerization adhesive for replacing oily PVDF adhesive for lithium ion battery anode and preparation method thereof Pending CN115340625A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109777328A (en) * 2019-01-18 2019-05-21 广州天赐高新材料股份有限公司 A kind of negative electrode of lithium ion battery aqueous binders and preparation method thereof, negative electrode material
CN112029448A (en) * 2019-06-03 2020-12-04 3M创新有限公司 Aqueous acrylate adhesive composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109777328A (en) * 2019-01-18 2019-05-21 广州天赐高新材料股份有限公司 A kind of negative electrode of lithium ion battery aqueous binders and preparation method thereof, negative electrode material
CN112029448A (en) * 2019-06-03 2020-12-04 3M创新有限公司 Aqueous acrylate adhesive composition
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Application publication date: 20221115