CN114940720B - High-nickel positive electrode lithium ion battery binder, preparation method thereof and lithium ion battery positive electrode - Google Patents

High-nickel positive electrode lithium ion battery binder, preparation method thereof and lithium ion battery positive electrode Download PDF

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CN114940720B
CN114940720B CN202210606163.9A CN202210606163A CN114940720B CN 114940720 B CN114940720 B CN 114940720B CN 202210606163 A CN202210606163 A CN 202210606163A CN 114940720 B CN114940720 B CN 114940720B
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lithium ion
positive electrode
ion battery
solution
binder
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CN114940720A (en
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何传新
余子辉
杨恒攀
胡琪
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Shenzhen University
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Shenzhen University
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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
    • 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
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • 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
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a high-nickel anode lithium ion battery binder, a preparation method thereof and a lithium ion battery anode, wherein the method comprises the following steps: mixing a solvent and a buffer, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution; adding a monomer into an emulsifier, and stirring to obtain a second solution; providing an initiator, adding part of the initiator and part of the second solution into the first solution, and performing a pre-reaction to obtain a third solution; adding the rest initiator and the rest second solution into the third solution, and reacting for 1-24 hours at constant temperature to obtain polymer emulsion; adding sulfate into the polymer emulsion, stirring and demulsifying to obtain solid; and (3) sequentially purifying, crushing and sieving the solid to obtain the high-nickel positive electrode lithium ion battery binder. Compared with the existing adhesive, the adhesive prepared by the invention can improve the gelation of the positive electrode slurry in the use process, and is beneficial to improving the overall conductivity of the battery.

Description

High-nickel positive electrode lithium ion battery binder, preparation method thereof and lithium ion battery positive electrode
Technical Field
The invention relates to the field of high-nickel positive electrode lithium ion batteries, in particular to a high-nickel positive electrode lithium ion battery binder, a preparation method thereof and a lithium ion battery positive electrode.
Background
With the development of electric vehicles, the energy density requirement for lithium ion batteries is also increasing. In order to ensure that the battery has longer cycle life, the ternary positive electrode material lithium ion battery is also continuously developed towards the high nickel, wherein the high nickel refers to the fact that the content of nickel in the ternary material is continuously increased, and according to the proportion of nickel, the nickel-cobalt-manganese material can be divided into NCM111, NCM523, NCM622, NCM811 and the like. Currently, NCM523 is commonly used in China, the energy density of the NCM523 can reach 200Wh/kg, few enterprises can produce NCM622 type batteries, the energy density of the NCM523 can reach 230Wh/kg, and the energy density of NCM811 can reach 280Wh/kg.
In the actual production process of the high-nickel cathode material lithium ion battery, a plurality of problems occur. The higher the nickel content of the ternary material, the easier it is to react with H in air 2 O and CO 2 Reaction to form LiOH and Li on the surface of the material 2 CO 3 Thereby increasing its basicity. Polyvinylidene fluoride (PVDF) is the most commonly used adhesive in China, has poor alkali resistance, and after a molecular chain is influenced by an alkaline substance, hydrogen Fluoride (HF) elimination reaction can be generated to generate double bonds, so that crosslinking reaction between PVDF molecular chains occurs, slurry gelation is caused, the coating process is finally influenced, and the cycle efficiency of a lithium ion battery is reduced.
Therefore, there is an urgent need to develop a binder for a high-nickel positive lithium ion battery, which can improve gelation of a positive electrode slurry during use, contribute to improvement of conductivity of the whole battery, and can improve the problems of cycle performance and safety performance of a high-nickel ternary material battery due to an increase of nickel content.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a high-nickel positive electrode lithium ion battery binder, a preparation method thereof and a lithium ion battery positive electrode, and aims to solve the problem that the conventional PVDF binder is easy to cause gelation of positive electrode slurry in the use process, so that the cycle performance and the safety performance of the battery are affected.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the high-nickel positive electrode lithium ion battery binder comprises the following steps:
mixing a solvent and a buffer, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
adding a monomer into an emulsifier, and stirring to obtain a second solution;
providing an initiator, adding part of the initiator and part of the second solution into the first solution, and performing a pre-reaction to obtain a third solution;
adding the rest initiator and the rest second solution into the third solution, and reacting for 1-24 hours at constant temperature to obtain polymer emulsion;
adding sulfate into the polymer emulsion, stirring and demulsifying to obtain solid;
and (3) sequentially purifying, crushing and sieving the solid to obtain the high-nickel positive electrode lithium ion battery binder.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the steps of preparing a high-nickel positive electrode lithium ion battery binder, wherein the solvent is at least one of water and an organic solvent, and the buffer is at least one of sodium bicarbonate and sodium dihydrogen phosphate.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the following steps of: 40 to 60 percent of styrene units, 30 to 50 percent of acrylic ester units and 1 to 10 percent of acrylamide units.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the steps of preparing an acrylic ester unit from one of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate and isooctyl methacrylate; the acrylamide unit is one of acrylamide, N-methylacrylamide, N-ethylacrylamide, N-butylacrylamide and 2-methylacrylamide.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the step of preparing an emulsifier, wherein the emulsifier is one of sodium dodecyl benzene sulfonate, sodium dodecyl phenyl ether sulfonate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium laurate and polyoxyethylene lauryl ether sodium sulfate.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the steps that the initiator is a water-soluble initiator or an oil-soluble initiator, wherein the water-soluble initiator comprises at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the oil-soluble initiator includes at least one of an organic peroxide and an azo compound.
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the step of preparing a high-nickel positive electrode lithium ion battery binder, wherein sulfate is one of lithium sulfate, sodium sulfate and aluminum sulfate.
A high nickel positive electrode lithium ion battery binder is prepared by the preparation method according to the scheme.
A lithium ion battery positive electrode, comprising, in weight percent: 96% -98% of ternary high-nickel positive electrode material, 0.5% -2% of binder and 0.5% -2% of conductive agent, wherein the binder comprises the high-nickel positive electrode lithium ion battery binder and PVDF.
The lithium ion battery anode comprises a high nickel anode lithium ion battery binder and PVDF, wherein the weight ratio of the high nickel anode lithium ion battery binder to PVDF is 3: 7-5: 5.
the beneficial effects are that: compared with the existing binder, the mixed binder prepared by the preparation method can improve gelation of positive electrode slurry in the use process, is beneficial to improving the overall conductivity of the battery, can solve the problems of cycle performance and safety performance of the high-nickel ternary material battery caused by the increase of nickel content, is beneficial to improving the market application prospect of battery manufacturer products, and has great practical significance.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a method for preparing a high nickel positive electrode lithium ion battery binder according to the present invention.
Fig. 2 shows the cycle capacity retention rates of the batteries made of the different binders of examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The invention provides a high-nickel positive electrode lithium ion battery binder, a preparation method thereof and a lithium ion battery positive electrode, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
With the development of electric vehicles, the energy density requirement for lithium ion batteries is also increasing. In order to ensure that the battery has longer cycle life, the ternary positive electrode material lithium ion battery is also continuously developed towards the high nickel direction, and a plurality of problems occur in the actual production process of the high nickel positive electrode material lithium ion battery. The higher the nickel content of the ternary material, the easier it is to react with H in air 2 O and CO 2 Reaction to form LiOH and Li on the surface of the material 2 CO 3 Thereby increasing its basicity. Polyvinylidene fluoride (PVDF) is the most commonly used binder in China, has poor alkali resistance, and after a molecular chain is influenced by an alkaline substance, hydrogen Fluoride (HF) elimination reaction can be generated to generate double bonds, so that crosslinking reaction between PVDF molecular chains occurs, gelation of positive electrode slurry is caused, and finally, the coating process is influenced and the cycle efficiency of a lithium ion battery is reduced.
Based on the above, the invention provides a preparation method of a high nickel positive electrode lithium ion battery binder, referring to fig. 1, comprising the following steps:
s10, mixing a solvent with a buffering agent, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
s20, adding a monomer into the emulsifier, and stirring to obtain a second solution;
s30, providing an initiator, adding part of the initiator and part of the second solution into the first solution, and performing a pre-reaction to obtain a third solution;
s40, adding the rest initiator and the rest second solution into the third solution, and reacting for 1-24 hours at constant temperature to obtain polymer emulsion;
s50, adding sulfate into the polymer emulsion, and stirring and demulsifiing to obtain a solid;
and S60, sequentially purifying, crushing and sieving the solid to obtain the high-nickel positive electrode lithium ion battery binder.
Compared with the existing adhesive, the acrylic acid oil-soluble adhesive prepared by the preparation method can reduce the use amount of PVDF, thereby improving the gelation of the positive electrode slurry in the stirring process, compensating the defects mutually when the adhesive is mixed with PVDF for use, improving the bonding effect on the surface of an electrode, being beneficial to improving the overall conductivity of the battery, solving the problems of the cycle performance and the safety performance of the high-nickel ternary material battery caused by the increase of the nickel content, and being beneficial to improving the market application prospect of the products of battery manufacturers, and having great practical significance.
In this embodiment, the solvent is at least one of water and an organic solvent, the addition amount of the solvent accounts for 40% -70% of the total addition amount of all raw materials, the buffer is sodium bicarbonate, and the inert gas is nitrogen.
Specifically, the organic solvent can be selected from aromatic hydrocarbon organic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon organic solvents such as pentane, hexane, octane; alicyclic hydrocarbon organic solvents such as cyclohexane, cyclohexanone, toluene cyclohexanone; halogenated hydrocarbon organic solvents such as chlorobenzene, dichlorobenzene, dichloromethane; alcohol organic solvents such as methanol, ethanol, isopropanol, etc.; ether-type organic solvents such as diethyl ether and propylene oxide; esters organic solvents such as methyl acetate, ethyl acetate, propyl acetate; ketone organic solvents such as acetone, methyl butanone, methyl isobutyl ketone; glycol derivative organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; other organic solvents such as acetonitrile, pyridine, phenol; other organic solvents commonly used in the art are also possible; the solvent may be a mixed solvent of an organic solvent and an organic solvent.
In the step S10, the buffer is used to maintain the solution pH stable; the purpose of the inert gas is to expel air from the liquid and avoid the influence on the subsequent reaction, which in this embodiment is preferably nitrogen.
In this embodiment, the monomers include, in weight percent: 40 to 60 percent of styrene units, 30 to 50 percent of acrylic ester units and 1 to 10 percent of acrylamide units.
Specifically, the acrylic ester unit comprises a general formula CH 2 ＝CR 1 -COOR 2 Wherein R is 1 is-H or-CH 3 ，R 2 Is alkyl or cycloalkyl.
Further, the acrylic acid ester unit may be one of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate.
Specifically, the acrylamide unit comprises a general formula CH 2 ＝CR 3 CONHR 4 Wherein R is 3 is-H or-CH 3 ，R 4 Is one of-H, alkyl, cycloalkyl or aryl.
Further, the acrylamide unit may be one of acrylamide, N-methacrylamide, N-ethylacrylamide, N-butylacrylamide, 2-methylacrylamide.
In this embodiment, the emulsifier is one of sodium dodecyl benzene sulfonate, sodium dodecyl phenyl ether sulfonate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium laurate, and sodium polyoxyethylene lauryl ether sulfate.
The emulsifying agent is a substance which can lead mixed liquid of two or more mutually insoluble components to form stable emulsion, and the action principle is that in the emulsification process, a disperse phase is dispersed in a continuous phase in the form of microdroplets (micron-sized), the emulsifying agent reduces the interfacial tension of each component in the mixed system, a firm film is formed on the surface of the microdroplets or an electric double layer is formed on the surface of the microdroplets due to charges given by the emulsifying agent, the microdroplets are prevented from being aggregated, and the uniform emulsion is maintained, and the emulsifying agent selected in the embodiment is an anionic emulsifying agent which can be ionized in water to generate hydrophilic groups with anions.
In some embodiments, the step S30 specifically includes: and adding part of the initiator into the first solution, stirring for 10min, adding part of the second solution, and stirring for 20min to perform pre-reaction to obtain a third solution.
The step S40 specifically includes: and adding the residual initiator into the residual second solution to obtain a mixed solution, dropwise adding the mixed solution into the third solution within 3h, and reacting at constant temperature for 1-24 h to obtain the polymer emulsion.
In this embodiment, the initiator is a water-soluble initiator or an oil-soluble initiator, wherein the water-soluble initiator includes at least one of ammonium persulfate, potassium persulfate, and sodium persulfate; the oil-soluble initiator comprises at least one of an organic peroxide and an azo compound, and the addition amount of the initiator is 0.01-0.1%, preferably 0.03-0.08% of the addition amount of the monomer.
Specifically, the organic peroxide may be benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, or the like; the azo compound is a compound comprising a general formula of R-N=N-R', and specifically can be azobisisobutyronitrile AIBN and the like.
In this embodiment, the sulfate is one of lithium sulfate, sodium sulfate, and aluminum sulfate.
Specifically, the sulfate is used as a demulsifier, and since the emulsifier used in preparing the polymer emulsion is an anionic emulsifier, the demulsifier selected in this embodiment is also an anionic demulsifier, and the hydrophilic group generated after the demulsifier is dissolved in water is an ionic group with negative charge.
In some embodiments, the step of purifying comprises: filtering, washing and drying.
The invention also provides a high-nickel positive electrode lithium ion battery binder which is prepared by adopting the preparation method according to the scheme.
The invention also provides a lithium ion battery anode, which comprises the following components in percentage by weight: 96% -98% of ternary high-nickel positive electrode material, 0.5% -2% of binder and 0.5% -2% of conductive agent, wherein the binder comprises PVDF and the high-nickel positive electrode lithium ion battery binder according to the scheme.
Specifically, the binder is prepared from the high-nickel positive electrode lithium ion battery binder and the PVDF binder in a weight ratio of 3:7-5: 5, and the positive electrode material is required to be dissolved in a solvent and then added to the positive electrode material for use.
In some embodiments, the solvent is NMP, i.e., N-methylpyrrolidone, and the ternary high nickel positive electrode material is NCM811, i.e., liNi 0.8 Co 0.1 Mn 0.1 O 2 The conductive agent is one of conductive carbon black, conductive graphite and graphene.
Specifically, when preparing the positive plate for the lithium ion battery, firstly mixing a nickel positive electrode lithium ion battery binder and a PVDF binder according to a proportion, dissolving the mixture in N-methylpyrrolidone to prepare a binder solution with the mass percentage concentration of 10%, sequentially adding the binder solution, a conductive agent and a high nickel ternary positive electrode material according to a proportion in a stirrer, adding a certain amount of N-methylpyrrolidone, stirring for three hours, pulping, and coating, drying, slicing and tabletting to obtain the positive plate for the lithium ion battery.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention, and are merely illustrative of the invention and in no way limiting of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to the embodiment of the invention, the button cell is assembled according to the industrial general coating technology and button cell assembling technology for testing the cycle performance.
Example 1
154g of distilled water, 0.83g of sodium bicarbonate and nitrogen are added into a reaction device, the gas needs to enter below the liquid level, air in the liquid is discharged, the temperature is set at 78 ℃, stirring is started, 59.26g of distilled water and 2.37g of sodium dodecyl benzene sulfonate are added into a beaker, stirring is carried out for 5min, 80g of styrene, 72g of isooctyl acrylate and 8g of acrylamide are added into the beaker, and stirring is continued. 0.077g of sodium persulfate was added to the reaction apparatus and stirred for 10 minutes. 30g of the solution in the beaker was taken and added to the reaction apparatus, followed by stirring for 20 minutes. Then 0.05g of sodium persulfate is added into a beaker, the liquid in the beaker is dripped into a reaction device within 3h, and the reaction is completed after the constant temperature reaction for 4h, thus obtaining the polymer emulsion. Lithium sulfate was added to the polymer emulsion and stirred to break the emulsion to give a solid. And filtering, washing, drying, crushing and sieving to obtain the high-nickel anode lithium ion battery binder. Mixing the high-nickel positive electrode lithium ion battery binder with PVDF according to the ratio of 1:1 in the weight ratio of N-methyl pyrrolidone to prepare a solution with the mass percent concentration of 10 percent. 10g of a mixed solution of a high-nickel positive electrode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of a high-nickel ternary positive electrode material and 12.42g of NMP are added into a stirrer, and the mixture is stirred for three hours to prepare slurry. The positive plate is obtained after coating, drying, slicing and tabletting, and then the positive plate is assembled into a button cell for testing.
Example 2
154g of distilled water and 0.83g of sodium bicarbonate are added into a reaction device, nitrogen is introduced, the gas needs to enter below the liquid level, air in the liquid is discharged, the temperature is set at 78 ℃, stirring is started, 59.26g of distilled water and 2.37g of sodium dodecyl benzene sulfonate are added into a beaker, stirring is carried out for 5min, 78.4g of styrene, 72g of isooctyl acrylate and 9.6g of acrylamide are added into the beaker, and stirring is continued. 0.077g of sodium persulfate was added to the reaction apparatus and stirred for 10 minutes. 30g of the solution in the beaker was taken and added to the reaction apparatus, followed by stirring for 20 minutes. Then 0.05g of sodium persulfate is added into a beaker, the liquid in the beaker is dripped into a reaction device within 3h, and the reaction is completed after the constant temperature reaction for 4h, thus obtaining the polymer emulsion. Lithium sulfate was added to the polymer emulsion and stirred to break the emulsion to give a solid. And filtering, washing, drying, crushing and sieving to obtain the high-nickel anode lithium ion battery binder. Mixing the high-nickel positive electrode lithium ion battery binder with PVDF according to the ratio of 1:1 in the weight ratio of N-methyl pyrrolidone to prepare a solution with the mass percent concentration of 10 percent. 10g of a mixed solution of a high-nickel positive electrode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of a high-nickel ternary positive electrode material and 12.42g of NMP are added into a stirrer, and the mixture is stirred for three hours to prepare slurry. The positive plate is obtained after coating, drying, slicing and tabletting, and then the positive plate is assembled into a button cell for testing.
Example 3
154g of distilled water and 0.83g of sodium bicarbonate are added into the reaction device, nitrogen is introduced, the gas needs to enter below the liquid level, air in the liquid is discharged, the temperature is set at 78 ℃, and stirring is started. 59.26g of distilled water and 2.37g of sodium dodecyl benzene sulfonate were added to a beaker, stirred for 5min, then 76.8g of styrene, 72g of isooctyl acrylate, 11.2g of acrylamide were added to the beaker, and stirring was continued. 0.077g of sodium persulfate was added to the reaction apparatus and stirred for 10 minutes. 30g of the solution in the beaker was taken and added to the reaction apparatus, followed by stirring for 20 minutes. Then 0.05g of sodium persulfate is added into a beaker, the liquid in the beaker is dripped into a reaction device within 3h, and the reaction is completed after the constant temperature reaction for 4h, thus obtaining the polymer emulsion. Lithium sulfate was added to the polymer emulsion and stirred to break the emulsion to give a solid. And filtering, washing, drying, crushing and sieving to obtain the high-nickel anode lithium ion battery binder. Mixing the high-nickel positive electrode lithium ion battery binder with PVDF according to the ratio of 1:1 in the weight ratio of N-methyl pyrrolidone to prepare a solution with the mass percent concentration of 10 percent. 10g of a mixed solution of a high-nickel positive electrode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of a high-nickel ternary positive electrode material and 12.42g of NMP are added into a stirrer, and the mixture is stirred for three hours to prepare slurry. The positive plate is obtained after coating, drying, slicing and tabletting, and then the positive plate is assembled into a button cell for testing.
Comparative example 1
PVDF was dissolved in N-methylpyrrolidone to prepare a 10% strength by mass solution. 10g of PVDF mixed solution, 1g of conductive carbon black, 48g of high-nickel ternary positive electrode material and 12.42g of NMP are added into a stirrer, stirred for three hours to prepare slurry, coated, dried, sliced and pressed to obtain a positive plate, and then assembled into a button cell for testing.
As shown in fig. 2, in the test result, in the 0.5C normal temperature cycle performance test, when the cycle number reached 100 times, the battery cycle capacity retention rate of example 2 was optimal, the battery cycle capacity retention rate of example 3 was slightly better than that of comparative example 1, and the battery cycle capacity retention rate of example 3 was worst.
In summary, the invention discloses a high nickel positive electrode lithium ion battery binder, a preparation method thereof and a lithium ion battery positive electrode, wherein the method comprises the following steps: adding a solvent and a buffering agent into a reaction device, introducing inert gas, heating to 60-90 ℃, and stirring to obtain a first solution; adding a monomer into the emulsifier solution and stirring to obtain a second solution; adding an initiator into the first solution, stirring, adding the second solution, and stirring to obtain a third solution; adding an initiator into the second solution to obtain a mixed solution, adding the mixed solution into the third solution, and reacting for 1-24 hours at constant temperature to obtain a polymer emulsion; adding sulfate into the polymer emulsion, stirring and demulsifying to obtain a binder precursor; and filtering, washing, drying, crushing and sieving the binder precursor to obtain the high-nickel lithium ion battery binder. Compared with the existing adhesive, the mixed adhesive prepared by the preparation method can improve gelation of the positive electrode slurry in the use process, is beneficial to improving the overall conductivity of the battery, can solve the problems of cycle performance and safety performance of the high-nickel ternary material battery caused by the increase of nickel content, is beneficial to improving the market application prospect of the battery manufacturer products, and has great practical significance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; while the invention has been described in detail with reference to the foregoing embodiments, it will be appreciated by those skilled in the art that variations may be made in the techniques described in the foregoing embodiments, or equivalents may be substituted for elements thereof; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The high-nickel positive electrode lithium ion battery binder is characterized by being an acrylic acid oil-soluble binder, and comprises, by weight, 49% of styrene, 45% of isooctyl acrylate and 6% of acrylamide;
the ternary high-nickel positive electrode material applied to the high-nickel positive electrode lithium ion battery binder is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ；
The preparation method of the high-nickel positive electrode lithium ion battery binder comprises the following steps:
mixing a solvent and a buffer, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
adding a monomer into an emulsifier, and stirring to obtain a second solution;
providing an initiator, adding part of the initiator and part of the second solution into the first solution, and performing a pre-reaction to obtain a third solution;
adding the rest initiator and the rest second solution into the third solution, and reacting for 1-24 hours at constant temperature to obtain polymer emulsion;
adding sulfate into the polymer emulsion, stirring and demulsifying to obtain solid;
and (3) sequentially purifying, crushing and sieving the solid to obtain the high-nickel positive electrode lithium ion battery binder.
2. The high nickel positive electrode lithium ion battery binder according to claim 1, wherein the solvent is at least one of water and an organic solvent, and the buffer is at least one of sodium bicarbonate and sodium dihydrogen phosphate.
3. The high nickel positive lithium ion battery binder of claim 1, wherein the emulsifier is one of sodium dodecyl benzene sulfonate, sodium dodecyl phenyl ether sulfonate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium laurate, sodium polyoxyethylene lauryl ether sulfate.
4. The high nickel positive electrode lithium ion battery binder of claim 1, wherein the initiator is a water-soluble initiator or an oil-soluble initiator, wherein the water-soluble initiator comprises at least one of ammonium persulfate, potassium persulfate, sodium persulfate; the oil-soluble initiator includes at least one of an organic peroxide and an azo compound.
5. The high nickel positive lithium ion battery binder of claim 1, wherein the sulfate is one of lithium sulfate, sodium sulfate, aluminum sulfate.
6. The positive electrode of the lithium ion battery is characterized by comprising the following components in percentage by weight: 96% -98% of ternary high-nickel positive electrode material, 0.5% -2% of binder and 0.5% -2% of conductive agent, wherein the binder comprises the high-nickel positive electrode lithium ion battery binder and PVDF according to claim 1.
7. The positive electrode of lithium ion battery according to claim 6, wherein the weight ratio of the high nickel positive electrode lithium ion battery binder to PVDF is 3: 7-5: 5.
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