CN114940720A - High-nickel anode lithium ion battery binder, preparation method thereof and lithium ion battery anode - Google Patents

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

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CN114940720A
CN114940720A CN202210606163.9A CN202210606163A CN114940720A CN 114940720 A CN114940720 A CN 114940720A CN 202210606163 A CN202210606163 A CN 202210606163A CN 114940720 A CN114940720 A CN 114940720A
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lithium ion
ion battery
binder
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acrylate
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CN114940720B (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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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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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 buffering agent, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution; adding the monomer into the emulsifier, and stirring to obtain a second solution; providing an initiator, adding a part of the initiator and a part of the second solution into the first solution, and carrying out pre-reaction to obtain a third solution; adding the rest of initiator and the rest of second solution into the third solution, and reacting for 1-24 h at constant temperature to obtain polymer emulsion; adding sulfate into the polymer emulsion, and stirring and demulsifying to obtain a solid; and sequentially purifying, crushing and sieving the solid to prepare the high-nickel anode lithium ion battery binder. Compared with the existing binder, the binder prepared by the invention can improve the gelation of the positive slurry in the using process and is beneficial to improving the overall conductivity of the battery.

Description

High-nickel anode lithium ion battery binder, preparation method thereof and lithium ion battery anode
Technical Field
The invention relates to the field of high-nickel anode lithium ion batteries, in particular to a high-nickel anode lithium ion battery binder, a preparation method thereof and a lithium ion battery anode.
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 a longer cycle life, the lithium ion battery with a ternary cathode material is continuously developed towards high nickel, wherein the high nickel means that the content of nickel in the used ternary material is continuously increased, and the nickel-cobalt-manganese material can be further divided into NCM111, NCM523, NCM622, NCM811 and the like according to the proportion of nickel. The energy density of the currently and generally used NCM523 in China can reach 200Wh/kg, a few enterprises can produce batteries of the NCM622 model, the energy density can reach 230Wh/kg, and the energy density of the NCM811 can reach 280 Wh/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 Reacting to form LiOH and Li on the surface of the material 2 CO 3 Thereby increasing the basicity thereof. Polyvinylidene fluoride (PVDF) is the most commonly used binder in China, the alkali resistance of the PVDF is poor, and Hydrogen Fluoride (HF) elimination reaction can occur after molecular chains are influenced by alkali substances to generate double bonds, so that cross-linking reaction occurs among PVDF molecular chains to cause slurry gelation, the coating process is influenced finally, 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 cathode lithium ion battery, which can improve the gelation of the cathode slurry during the use process, contribute to the improvement of the overall conductivity of the battery, and improve the cycle performance and safety performance of the high-nickel ternary material battery due to the increase of the nickel content.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a high-nickel cathode lithium ion battery binder, a preparation method thereof and a lithium ion battery cathode, and aims to solve the problem that the cycle performance and the safety performance of the battery are affected because the cathode slurry is easy to be gelatinized in the using process of the existing PVDF binder.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a high-nickel anode lithium ion battery binder comprises the following steps:
mixing a solvent and a buffering agent, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
adding the monomer into the emulsifier, and stirring to obtain a second solution;
providing an initiator, adding a part of the initiator and a part of the second solution into the first solution, and carrying out pre-reaction to obtain a third solution;
adding the rest of initiator and the rest of second solution into the third solution, and reacting for 1-24 h at constant temperature to obtain polymer emulsion;
adding sulfate into the polymer emulsion, and stirring and demulsifying to obtain a solid;
and purifying, crushing and sieving the solid in sequence to obtain the high-nickel anode lithium ion battery binder.
The preparation method of the high-nickel anode lithium ion battery binder comprises the following steps of mixing a solvent and a buffer, and then adding the solvent into the mixture to prepare the high-nickel anode lithium ion battery binder.
The preparation method of the high-nickel anode lithium ion battery binder comprises the following steps of: 40-60% of styrene unit, 30-50% of acrylate unit and 1-10% of acrylamide unit.
The preparation method of the high-nickel anode lithium ion battery binder comprises the following steps of preparing an acrylate unit, wherein the acrylate unit is one of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isoamyl 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, isoamyl methacrylate, n-hexyl methacrylate and isooctyl methacrylate; the acrylamide unit is one of acrylamide, N-methacrylamide, N-ethylacrylamide, N-butylacrylamide and 2-methacrylamide.
The preparation method of the high-nickel anode lithium ion battery binder comprises the step of preparing a high-nickel anode lithium ion battery binder, 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 sodium lauryl ether sulfate.
The preparation method of the high-nickel anode lithium ion battery binder comprises the following steps of (1) preparing a high-nickel anode lithium ion battery binder, wherein the initiator is a water-soluble initiator or an oil-soluble initiator, and 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 anode lithium ion battery binder comprises the step of preparing a high-nickel anode lithium ion battery binder, wherein sulfate is one of lithium sulfate, sodium sulfate and aluminum sulfate.
The high-nickel anode lithium ion battery binder is prepared by the preparation method of the scheme.
A lithium ion battery anode 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 the high nickel positive electrode lithium ion battery binder and PVDF.
The lithium ion battery anode is characterized in that the weight ratio of the high-nickel anode lithium ion battery binder to PVDF is 3: 7-5: 5.
has the beneficial effects that: compared with the existing binder, the mixed binder prepared by the preparation method can improve the gelation of the anode slurry in the using 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 the nickel content, is beneficial to improving the market application prospect of the product of a battery generator, 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 retention of the cycling capacity of the batteries made with different binders in examples 1-3 of the present invention and comparative example 1.
Detailed Description
The invention provides a high-nickel anode lithium ion battery binder, a preparation method thereof and a lithium ion battery anode, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
With the development of electric vehicles, the energy density requirement on lithium ion batteries is also increasing. In order to ensure longer cycle life of the battery, the ternary anode material lithium ion battery is continuously developed to the direction of high nickel, and the high nickel anode material lithium ionIn the actual production process of the 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 Reacting to form LiOH and Li on the surface of the material 2 CO 3 Thereby increasing the basicity thereof. Polyvinylidene fluoride (PVDF) is the most commonly used binder in China, the alkali resistance of the PVDF is poor, and Hydrogen Fluoride (HF) elimination reaction can occur after molecular chains are influenced by alkali substances to generate double bonds, so that cross-linking reaction occurs among PVDF molecular chains, the anode slurry is gelatinized, the coating process is influenced finally, and the cycle efficiency of the lithium ion battery is reduced.
Based on the above, the invention provides a preparation method of a high-nickel anode lithium ion battery binder, which comprises the following steps of:
s10, mixing the solvent and the buffering agent, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
s20, adding the monomer into the emulsifier, and stirring to obtain a second solution;
s30, providing an initiator, adding a part of the initiator and a part of the second solution into the first solution, and carrying out pre-reaction to obtain a third solution;
s40, adding the rest of initiator and the rest of second solution into the third solution, and reacting for 1-24 h at constant temperature to obtain polymer emulsion;
s50, adding sulfate into the polymer emulsion, and stirring and demulsifying to obtain a solid;
and S60, sequentially purifying, crushing and sieving the solid to obtain the high-nickel anode lithium ion battery binder.
Compared with the existing binder, the acrylic acid oil-soluble binder prepared by the preparation method disclosed by the invention can reduce the usage amount of PVDF (polyvinylidene fluoride), so that the gelation of anode slurry in the stirring process is improved, the defects can be mutually compensated when the acrylic acid oil-soluble binder is mixed with PVDF for use, the binding effect on the surface of an electrode is improved, the overall conductivity of a battery is favorably improved, the problems of the cycle performance and the safety performance of a high-nickel ternary material battery caused by the increase of the nickel content can be solved, the market application prospect of products of battery manufacturers is favorably improved, and the preparation method has great practical significance.
In this embodiment, the solvent is at least one of water and an organic solvent, the amount of the solvent added is 40% to 70% of the total amount of all raw materials added, the buffer is sodium bicarbonate, and the inert gas is nitrogen.
Specifically, the organic solvent may be selected from aromatic hydrocarbon organic solvents such as benzene, toluene, 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 organic solvents such as diethyl ether, propylene oxide; ester 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 may also be used; the solvent may also be a mixed solvent of an organic solvent and an organic solvent.
In step S10, the buffer is used to maintain the solution pH value stable; the purpose of introducing the inert gas is to remove air from the liquid and avoid influence on the subsequent reaction, and the inert gas is preferably nitrogen in the embodiment.
In this embodiment, the monomers include, in weight percent: 40-60% of styrene unit, 30-50% of acrylate unit and 1-10% of acrylamide unit.
Specifically, the acrylate unit comprises a general formula of CH 2 ＝CR 1 -COOR 2 Wherein R is 1 is-H or-CH 3 ，R 2 Is alkyl or cycloalkyl.
Further, the acrylate unit may be 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, isooctyl methacrylate.
Specifically, the acrylamide unit is represented by the 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, and 2-methacrylamide.
In this embodiment, the emulsifier is one of sodium dodecylbenzene sulfonate, sodium dodecylphenyl ether sulfonate, sodium lauryl sulfate, sodium laurate, and sodium polyoxyethylene lauryl ether sulfate.
The emulsifier is a substance which can form stable emulsion from a mixed solution of two or more immiscible components, and the action principle is that in the emulsification process, a dispersed phase is dispersed in a continuous phase in the form of micro-droplets (micron-sized), the emulsifier reduces the interfacial tension of each component in the mixed system, forms a firmer film on the surface of the micro-droplets or forms an electric double layer on the surface of the micro-droplets due to the charge given by the emulsifier, prevents the micro-droplets from aggregating with each other, and maintains uniform emulsion.
In some embodiments, the step S30 is specifically: and adding part of initiator into the first solution, stirring for 10min, adding part of the second solution, and stirring for 20min for pre-reaction to obtain a third solution.
The step S40 specifically includes: and adding the rest initiator into the rest 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 the embodiment, 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 comprises at least one of organic peroxide and azo compounds, 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 t-butyl peroxide, methyl ethyl ketone peroxide, or the like; the azo compound includes compounds of the general formula R-N-R', and specifically 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 the preparation of the polymer emulsion is an anionic emulsifier, the demulsifier selected in this embodiment is also an anionic demulsifier, and a hydrophilic group generated after dissolving in water is an ionic group having a negative charge.
In some embodiments, the step of purifying comprises: filtering, washing and drying.
The invention also provides a high-nickel anode lithium ion battery binder which is prepared by the preparation method of 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 anode material, 0.5-2% of binder and 0.5-2% of conductive agent, wherein the binder comprises PVDF and the binder of the high nickel anode lithium ion battery in the scheme.
Specifically, the binder is prepared by mixing the high-nickel anode lithium ion battery binder and the PVDF binder in a weight ratio of (3: 7) - (5): 5, and when the lithium ion battery is used, the lithium ion battery is dissolved in a solvent and then added into a 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 the positive plate for the lithium ion battery is prepared, firstly, a nickel positive lithium ion battery binder and a PVDF binder are mixed according to a proportion, and are dissolved in N-methyl pyrrolidone to prepare a binder solution with the mass percentage concentration of 10%, the binder solution, a conductive agent and a high-nickel ternary positive material are sequentially added in a stirrer according to the proportion, a certain amount of N-methyl pyrrolidone is added, stirring is carried out for three hours for pulping, and the positive plate for the lithium ion battery is obtained after coating, drying, slicing and tabletting.
The technical solution 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 is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. 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.
The embodiment of the invention assembles the button cell according to the universal coating technology and the button cell assembly technology in the industry to carry out the cycle performance test.
Example 1
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, the air in the liquid is discharged, the temperature is set to be 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 min. 30g of the solution in the beaker was added to the reaction apparatus and stirred for 20 min. And then adding 0.05g of sodium persulfate into the beaker, dropwise adding the liquid in the beaker into a reaction device within 3h, and reacting at constant temperature for 4h to obtain the polymer emulsion. Adding lithium sulfate into the polymer emulsion and stirring to break the emulsion to obtain 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 and PVDF in a proportion of 1: 1 is dissolved in N-methyl pyrrolidone to prepare a solution with the mass percentage concentration of 10%. 10g of mixed solution of the high-nickel anode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of high-nickel ternary anode material and 12.42g of NMP are added into a stirrer, and stirred for three hours to prepare pulp. And coating, drying, slicing and tabletting to obtain the positive plate, assembling the positive plate into the button cell, and 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, the air in the liquid is discharged, the temperature is set to be 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 min. 30g of the solution in the beaker was added to the reaction apparatus and stirred for 20 min. And adding 0.05g of sodium persulfate into the beaker, dropwise adding the liquid in the beaker into a reaction device within 3h, and reacting at constant temperature for 4h to obtain the polymer emulsion. Lithium sulfate is added to the polymer emulsion and stirred to break the emulsion, resulting in 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 and PVDF in a proportion of 1: 1 is dissolved in N-methyl pyrrolidone to prepare a solution with the mass percentage concentration of 10%. 10g of mixed solution of the high-nickel anode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of high-nickel ternary anode material and 12.42g of NMP are added into a stirrer, and stirred for three hours to prepare pulp. And coating, drying, slicing and tabletting to obtain the positive plate, assembling the positive plate into the button cell, and testing.
Example 3
154g of distilled water and 0.83g of sodium bicarbonate are added into a reaction device, nitrogen is introduced, gas needs to enter below the liquid level, air in the liquid is discharged, the temperature is set to be 78 ℃, and stirring is started. 59.26g of distilled water and 2.37g of sodium dodecylbenzenesulfonate were added to a beaker, and stirred for 5min, and 76.8g of styrene, 72g of isooctyl acrylate and 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 min. 30g of the solution in the beaker was added to the reaction apparatus and stirred for 20 min. And adding 0.05g of sodium persulfate into the beaker, dropwise adding the liquid in the beaker into a reaction device within 3h, and reacting at constant temperature for 4h to obtain the polymer emulsion. Adding lithium sulfate into the polymer emulsion and stirring to break the emulsion to obtain 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 and PVDF in a proportion of 1: 1 is dissolved in N-methyl pyrrolidone to prepare a solution with the mass percentage concentration of 10%. 10g of mixed solution of the high-nickel anode lithium ion battery binder and PVDF, 1g of conductive carbon black, 48g of high-nickel ternary anode material and 12.42g of NMP are added into a stirrer, and stirred for three hours to prepare pulp. And coating, drying, slicing and tabletting to obtain the positive plate, assembling the positive plate into the button cell, and testing.
Comparative example 1
PVDF is dissolved in N-methyl pyrrolidone to prepare a solution with the mass percentage concentration of 10%. And adding 10g of PVDF mixed solution, 1g of conductive carbon black, 48g of high-nickel ternary positive electrode material and 12.42g of NMP into a stirrer, stirring for three hours to prepare slurry, coating, drying, slicing and tabletting to obtain a positive electrode plate, assembling into a button cell, and testing.
As shown in fig. 2, in the 0.5C normal temperature cycle performance test, when the cycle number reaches 100 times, the cycle capacity retention rate of the battery in example 2 is the best, the cycle capacity retention rate of the battery in example 3 is slightly better than that in comparative example 1, and the cycle capacity retention rate of the battery in example 3 is the worst.
In summary, 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: 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 h 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 binder, the mixed binder prepared by the preparation method can improve the gelation of the anode slurry in the using 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 the nickel content, is beneficial to improving the market application prospect of the battery generator product, and has great practical significance.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a high-nickel anode lithium ion battery binder is characterized by comprising the following steps:
mixing a solvent and a buffering agent, introducing inert gas, and heating to 60-90 ℃ under stirring to obtain a first solution;
adding the monomer into the emulsifier, and stirring to obtain a second solution;
providing an initiator, adding a part of the initiator and a part of the second solution into the first solution, and carrying out pre-reaction to obtain a third solution;
adding the rest of initiator and the rest of second solution into the third solution, and reacting for 1-24 h at constant temperature to obtain polymer emulsion;
adding sulfate into the polymer emulsion, and stirring and demulsifying to obtain a solid;
and purifying, crushing and sieving the solid in sequence to obtain the high-nickel anode lithium ion battery binder.
2. The method for preparing the binder for the high-nickel positive electrode lithium ion battery 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 preparation method of the binder for the high-nickel positive electrode lithium ion battery according to claim 1, wherein the monomer comprises the following components in percentage by weight: 40-60% of styrene unit, 30-50% of acrylate unit and 1-10% of acrylamide unit.
4. The method for preparing the binder for the high-nickel positive-electrode lithium ion battery according to claim 3, wherein the acrylate unit is one of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isoamyl 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, isoamyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate; the acrylamide unit is one of acrylamide, N-methacrylamide, N-ethylacrylamide, N-butylacrylamide and 2-methacrylamide.
5. The method for preparing the binder for the high-nickel positive electrode lithium ion battery 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 and sodium polyoxyethylene lauryl ether sulfate.
6. The method for preparing the binder for the high-nickel positive electrode lithium ion battery according to 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 and sodium persulfate; the oil-soluble initiator includes at least one of an organic peroxide and an azo compound.
7. The method of claim 1, wherein the sulfate is one of lithium sulfate, sodium sulfate and aluminum sulfate.
8. The high-nickel anode lithium ion battery binder is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery positive electrode 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 as described in claim 8.
10. The lithium ion battery positive electrode of claim 9, 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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