CN114243022B - Three-dimensional network water system binder for lithium ion battery, preparation and application thereof - Google Patents
Three-dimensional network water system binder for lithium ion battery, preparation and application thereof Download PDFInfo
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- CN114243022B CN114243022B CN202210170913.2A CN202210170913A CN114243022B CN 114243022 B CN114243022 B CN 114243022B CN 202210170913 A CN202210170913 A CN 202210170913A CN 114243022 B CN114243022 B CN 114243022B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
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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
- H01M2004/027—Negative electrodes
Abstract
The invention relates to a three-dimensional network water system binder for a lithium ion battery, and preparation and application thereof, wherein the binder comprises the following raw materials: the polyacrylic acid derivative is prepared by polymerizing an acrylic monomer, an acrylamide organic acid monomer and a hydroxyl-containing fluorinated acrylate monomer. The invention takes the polyacrylic acid derivative as a main component of the binder, takes the polyvinyl alcohol and the amine-terminated dendritic macromolecule as auxiliary components to prepare the water-based binder, the binder has good flexibility and mechanical strength, the volume change of the silicon cathode can be inhibited, and the battery manufactured by the binder has good cycling stability and higher capacity. Meanwhile, unexpected discovery is also found that the amine-terminated dendritic macromolecule and the polyacrylic acid derivative have the function of improving the low-temperature performance of the adhesive by cooperating with the polyvinyl alcohol.
Description
Technical Field
The invention belongs to the technical field of battery binders, and particularly relates to a three-dimensional network water system binder for a lithium ion battery, and preparation and application thereof.
Background
The lithium ion battery has the advantages of high energy density and power density, high voltage, long cycle life and the like, and is widely applied to the fields of portable electronic equipment, new energy automobiles, large-scale energy storage and the like. The traditional lithium ion battery mainly adopts graphite as a negative electrode, the theoretical specific capacity of the graphite is 372mAh/g, and the current battery technology can enable the utilization rate of the graphite negative electrode in the lithium ion battery to be very close to the theoretical value of the graphite negative electrode, which means that the energy density of the lithium ion battery is gradually close to the theoretical upper limit of the graphite negative electrode, so that the space is not increased any more, and the graphite negative electrode can not meet the requirements of human beings in the face of the increasing electric quantity requirements of people.
Compared with the graphite negative electrode material, the theoretical specific capacity of the silicon material with higher content in the earth crust is the highest in the negative electrode materials researched at present, and can reach 4200 mAh/g when lithium is completely embedded. And it has a low intercalation/deintercalation lithium potential (-0.4V vs. Li/Li)+) And the lithium ion battery has good safety performance and is one of the most promising cathode materials in the field of high-specific energy lithium ion batteries. However, when lithium ions are inserted and extracted back and forth in the silicon particles, the silicon volume is greatly expanded up to 300-400%, stress is generated inside the electrode, the breakage and loss of electrical contact of the silicon particles occur, and the constant rupture and recombination of a solid electrolyte interface film (SEI) occur, so that the rapid decay of the electrode capacity and the cycle stability are difficult to maintain, and therefore, the selection of a suitable binder is required to improve the stability of the silicon negative electrode. For example, patent CN202010727516.1 discloses a lithium ion battery negative electrode binder, slurry and a negative electrode material thereof, which are prepared by mixing the following components: 10-50 parts of a conventional binder, 0.01-2.0 parts of an additive and 50-90 parts of deionized water, wherein the particle size of the conventional binder is less than or equal to 80nm and is selected from one or more of styrene butadiene rubber, polyacrylic acid, polyacrylonitrile and polyvinyl alcohol; the additive is prepared from 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and graphene-based nano powder according to a mass ratio of 1: 0.2-0.3, the coating agent is obtained by ultrasonic oscillation for 30-40 minutes, the problems of slurry agglomeration, sedimentation and the like caused by small particle size of the binder can be effectively avoided, and the coating performance of the slurry is well improved. Patent CN202010004798.2 discloses a three-dimensional network aqueous composite binder and its application in lithium ion batteries, comprising aqueous polymer emulsion, water-soluble polymer and cross-linking agent, wherein the aqueous polymer emulsion accounts for 5-50 wt%, the water-soluble polymer accounts for 94.5-50 wt%, and the cross-linking agent accounts for 0.5-10 wt%. The three-dimensional network water-based composite binder is formed by crosslinking an aqueous polymer emulsion with a crosslinking agentThe liquid and the water-soluble polymer are crosslinked to form a three-dimensional network type molecular structure. The three-dimensional molecular network structure of the binder enhances the toughness, can buffer the damage of the volume change of active substances to the electrode plate structure in the charging and discharging process of the battery, and keeps the cycle stability of the lithium ion battery, but the cross-linked ionic bond of the binder with the structure is difficult to self-heal at low temperature and difficult to repair without external stimulation, so that the binder causes permanent damage, has poor fatigue resistance and is reflected in poor low-temperature electrochemical performance of the battery.
Therefore, the development of the three-dimensional network binder which has good long-term cycle performance, high-rate charge and discharge performance, good self-healing capability and good electrochemical performance at low temperature has important significance for the popularization of the application of the three-dimensional network structure binder in the silicon negative electrode lithium battery.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a three-dimensional network water system binder for a lithium ion battery, and preparation and application thereof, wherein an acrylic acid derivative copolymer polymerized by acrylic monomers, acrylamide organic acid monomers and fluoroacrylate monomers is used as a main binder component, and polyvinyl alcohol and amine-terminated dendritic macromolecules are used as auxiliary components to prepare a water-based binder; the terminal amino dendritic macromolecules are used as connecting nodes, the polyacrylic acid derivatives and the polyvinyl alcohol are used as bridging bodies, the two substances are mutually interacted to form a binder with a three-dimensional network flexible framework structure in a self-assembly mode, the binder with the structure has good flexibility and mechanical strength, the volume change of a silicon cathode can be inhibited, and a battery manufactured by the binder has good long-cycle stability and good high-rate charge and discharge performance.
In order to realize the purpose, the following specific technical scheme is adopted:
a three-dimensional network water system binder for a lithium ion battery comprises the following raw materials: the polyacrylic acid derivative is prepared by polymerizing an acrylic monomer, an acrylamide organic acid monomer and a hydroxyl-containing fluorinated acrylate monomer.
Further, the binder comprises the following raw materials in parts by weight: 100 parts of polyacrylic acid derivative emulsion, 5-10 parts of polyvinyl alcohol and 3-8 parts of amine-terminated dendritic macromolecules, wherein the solid content of the polyacrylic acid derivative emulsion is 20-30%.
Furthermore, in the polyacrylic acid derivative, the weight ratio of the acrylic monomer, the acrylamide organic acid monomer and the hydroxyl-containing fluoroacrylate monomer is 4-5:0.5-1: 1-2.
The structural formula of the hydroxyl-containing fluoroacrylate monomer is shown as follows:
wherein R is1Is a linear or branched alkyl group of C1-C5, R2Is a linear or branched alkylene group of C1-C3, R3Is C4-C10 fluoroalkyl.
Preferably, the unsaturated fluoroacrylate monomer is selected from the group consisting of 3- (perfluorobutyl) -2-hydroxymethylacrylate, 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 3- (perfluorobutyl) -2-hydroxypropyl methacrylate, 3-perfluorooctyl 2-hydroxypropyl acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, and mixtures thereof, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 4,5,5,6,6,7,7, 7-nonafluoro-2-hydroxyheptyl acrylate, 4,5,5,6,6,7,7,8,8,9,9, 9-tridecafluoro-2-hydroxynonyl acrylate, and 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl methacrylate.
The acrylic acid monomer comprises acrylic acid and lithium acrylate, and the acrylamide organic acid monomer comprises acrylamide organic acid and lithium acrylamide organic acid. The lithium acrylate is prepared by the neutralization reaction of acrylic acid and lithium hydroxide, and accounts for 60-80% of the acrylic monomer; the lithium acrylamido organic acid is prepared by neutralizing reaction between acrylamido organic acid and lithium hydroxide, wherein the lithium acrylamido organic acid accounts for 60-80% of the acrylamido organic acid monomer.
The structural formula of the acrylamido organic acid derivative is shown below:
wherein R is4Is a linear or branched alkylene group of C2-C10, an arylene group of C2-C10, M1Is one of sulfonic acid group, carboxylic acid group, lithium sulfonate and lithium carboxylate.
Preferably, the acrylamido organic acid derivative is at least one selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, 3-acrylamido-3-methylbutyric acid, 4- (acrylamido) benzoic acid, lithium 2-acrylamido-2-methylpropanesulfonate, lithium 3-acrylamido-3-methylbutyrate, and lithium 4- (acrylamido) benzoate.
The emulsion particle size of the polyacrylic acid derivative emulsion is 100-150 nm.
The branching generation number of the dendritic macromolecule is 2.0-5.0 generations, and the terminal group is an amino group.
Preferably, the dendrimer is selected from at least one of a polyamidoamine dendrimer and a polypropyleneimine dendrimer.
The dendritic macromolecule consists of a central core, an inner layer repeating unit and an outer layer end group, has high symmetry in structure, has an approximately spherical structure in three-dimensional space, and is a typical nano material. The terminal group of the outer layer of the terminal amino group dendritic macromolecule has a large amount of amino groups, and can form three-dimensional stable hydrogen bond connection with polyacrylic acid derivatives and polyvinyl alcohol, thereby being beneficial to improving the bonding strength of the adhesive.
The molecular weight of the polyvinyl alcohol is 10-15 ten thousand, and the alcoholysis degree is 78-89%.
The invention also provides a preparation method of the three-dimensional network water system binder for the lithium ion battery, which comprises the following steps:
1) under the inert atmosphere, mixing an emulsifier and water, adding the mixture into a reaction kettle, dropwise adding an acrylic monomer dissolved with an initiator, an acrylamide organic acid monomer and a hydroxyl-containing fluoroacrylate monomer into the reaction kettle, uniformly stirring, performing ultrasonic dispersion at a low temperature to form a miniemulsion, and heating to perform a constant-temperature reaction to obtain an emulsion for later use;
2) adding polyvinyl alcohol and amine-terminated dendritic macromolecules into water, heating, keeping stirring until the polyvinyl alcohol and the amine-terminated dendritic macromolecules are completely dissolved, cooling, keeping the temperature constant, adding the mixture into the emulsion obtained in the step 1), stirring until the mixture is uniformly dispersed, cooling to room temperature, and sieving to obtain the emulsion-shaped binder.
Step 1) the emulsifier comprises octadecyl trimethyl ammonium bromide (C)18TAB) and NP-40, wherein the amount of the emulsifier is 0.1-0.3wt% of the total amount of water and monomers, the initiator comprises but is not limited to at least one of AIBN, potassium persulfate and ammonium persulfate, the amount of the initiator is 1-3wt% of the total amount of the monomers, the low temperature is-5-5 ℃, the temperature is increased to 50-80 ℃, and the reaction time is 3-8 hours;
and 2) raising the temperature to 70-100 ℃, cooling to 50-70 ℃, and sieving with a sieve of 100 meshes and 400 meshes.
The application of the three-dimensional network water system binder for the lithium ion battery is to prepare an electrode by using the binder, a negative electrode active material and a conductive agent.
The proportion of the binder in the electrode is 0.3% -20%, and preferably the proportion of the binder is 1% -10%.
The electrode is prepared by a preparation method comprising the following steps of: diluting the binder by deionized water, adding a negative electrode active substance and a conductive agent into the binder diluent, heating and keeping stirring, cooling to room temperature, coating the mixture on a current collector, drying and rolling, and then drying in vacuum.
The temperature is raised to 60-100 ℃, the stirring time is 1-3h, the vacuum drying temperature is 80-100 ℃, and the vacuum drying time is 10-20 h.
The negative electrode active material is at least one selected from silicon, micron silicon, porous silicon, amorphous silicon, silicon oxide (SiOx), silicon compound and silicon-carbon composite material.
The conductive agent is selected from at least one of superconducting carbon black, Super-P, VGCF or carbon nano-tubes.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes polyacrylic acid derivative polymerized by acrylic acid monomer, acrylamide organic acid monomer and fluorinated acrylate monomer containing hydroxyl as main binder component, and polyvinyl alcohol and amine-terminated dendritic macromolecule as auxiliary components to prepare the water-based binder, the binder has good flexibility and mechanical strength, can inhibit the volume change of silicon cathode, and the battery made of the binder has good cycling stability.
The inventor unexpectedly discovers that the polyvinyl alcohol, the amine-terminated dendritic macromolecule and the polyacrylic acid derivative have the function of synergistically improving the low-temperature performance of the adhesive.
Drawings
FIG. 1 is a scanning electron micrograph of an electrode according to example 1.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are all parts by weight. All reagents used are commercially available in the art.
Polyvinyl alcohol was purchased from national institutes and had a weight average molecular weight of 12 ten thousand.
Polyamidoamine dendrimers were purchased from Sigma-Aldrich, generation 4.0, amine terminated, ethylenediamine cored.
Preparation of the Binder
Preparation example 1
1) Under nitrogen atmosphere, 0.005 part of C18TAB, 0.0025 part NP-40, and 50 parts water were mixed and added to a reaction vessel, and 1.72 parts acrylic acid, 6.88 parts lithium acrylate, 0.44 part 2-acrylamido-2-methylpropanesulfonic acid, 1.76 parts lithium 2-acrylamido-2-methylpropanesulfonate, and 4.2 parts 3- (perfluorobutyl) -2-Dropwise adding hydroxyl methacrylate into a reaction kettle, stirring uniformly, performing ultrasonic dispersion at 0 ℃ to form miniemulsion, heating to 70 ℃, reacting for 6 hours, and keeping constant temperature for later use;
2) adding 10 parts of polyvinyl alcohol and 8 parts of polyamide-amine dendritic macromolecule into water, heating to 100 ℃, keeping stirring until the polyvinyl alcohol and the polyamide-amine dendritic macromolecule are completely dissolved, cooling to 70 ℃, keeping the temperature, adding the mixture into the emulsion obtained in the step 1), stirring until the mixture is uniformly dispersed, cooling to room temperature, and sieving with a 400-mesh sieve to obtain the emulsion-shaped binder.
Preparation example 2
The procedure was repeated as in preparation example 1 except that acrylic acid, lithium acrylate, 2-acrylamido-2-methylpropanesulfonic acid, lithium 2-acrylamido-2-methylpropanesulfonic acid, and 3- (perfluorobutyl) -2-hydroxymethylacrylate were used in amounts of 2 parts, 8 parts, 0.5 part, 2 parts, and 2.5 parts, respectively.
Preparation example 3
The procedure was repeated as in preparation example 1, except that acrylic acid, lithium acrylate, 2-acrylamido-2-methylpropanesulfonic acid, lithium 2-acrylamido-2-methylpropanesulfonic acid, and 3- (perfluorobutyl) -2-hydroxymethylacrylate were used in amounts of 1.8 parts, 7.4 parts, 0.9 part, 0.3 part, and 4.6 parts, respectively.
Preparation example 4
The procedure was repeated as in preparation example 1, except that acrylic acid, lithium acrylate, 2-acrylamido-2-methylpropanesulfonic acid, lithium 2-acrylamido-2-methylpropanesulfonic acid, and 3- (perfluorobutyl) -2-hydroxymethylacrylate were used in amounts of 1.9 parts, 7.5 parts, 1.5 parts, 0.4 part, and 3.7 parts, respectively.
Preparation example 5
The procedure was repeated as in preparation example 1, except that acrylic acid, lithium acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and lithium 2-acrylamido-2-methylpropanesulfonate were used in amounts of 1.4 parts, 5.3 parts, 1.3 parts, 0.3 part, and 6.7 parts, respectively.
Comparative preparation example 1
The procedure was repeated as in preparation example 1, except that acrylic acid, lithium acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and lithium 2-acrylamido-2-methylpropanesulfonate were used in amounts of 2.4 parts, 9.6 parts, 2.4 parts, and 0.6 part, respectively.
Preparation of the Battery
Examples 1 to 5, comparative example 1
And (3) manufacturing an electrode:
diluting the binder prepared in the preparation examples 1-5 and the comparative preparation example 1 with deionized water to reach a solid content of 10%, weighing 100 parts, adding 10 parts of conductive agent (Super-P) and 80 parts of silica material, heating to 85 ℃, stirring for 1.5h, naturally cooling to room temperature, coating on a copper foil current collector, naturally drying at room temperature to remove most of water, further drying at 60 ℃ for 12 hours under a vacuum condition, cutting into a circular pole piece with a diameter of 10 mm, wherein the active material loading capacity is 1.5 mg/cm2。
Assembling the battery:
a metallic lithium sheet is adopted as a counter electrode, and 1mol/L LiPF6(the solvent is a mixed solution of ethylene carbonate and diethyl carbonate with the volume ratio of 1:1, 5% by volume of fluoroethylene carbonate is added) is used as an electrolyte, a polypropylene microporous diaphragm is assembled into a 2032 type button cell in a glove box in an argon atmosphere, 50 mu L of electrolyte is added into each cell, and the cell is kept stand for 24h and then subjected to the following performance test.
Example 6
The procedure of example 1 was repeated, except that 5 parts of polyvinyl alcohol was used.
Example 7
The rest is the same as in example 1, except that the amount of the polyamidoamine dendrimer is 3 parts.
Example 8
The rest is the same as in example 1, except that the amount of the polyamidoamine dendrimer is 2 parts.
Example 9
The rest is the same as in example 1, except that the amount of the polyamidoamine dendrimer is 10 parts.
Example 10
And (3) manufacturing an electrode:
the corresponding binders prepared in preparation examples 1 to 5 and comparative preparation example 1 were mixed with deionized waterDiluting to solid content of 10%, weighing 100 parts, adding 10 parts of conductive agent (Super-P) and 80 parts of silica material, mixing to obtain uniform slurry, coating on copper foil current collector, naturally drying at room temperature to remove most of water, further drying at 60 deg.C under vacuum condition for 12 hr, cutting into circular pole piece with diameter of 10 mm and active material loading of 1.5 mg/cm2。
Assembling the battery:
a metallic lithium sheet is adopted as a counter electrode, and 1mol/L LiPF6(the solvent is a mixed solution of ethylene carbonate and diethyl carbonate with the volume ratio of 1:1, 5% by volume of fluoroethylene carbonate is added) is used as an electrolyte, a polypropylene microporous diaphragm is assembled into a 2032 type button cell in a glove box in an argon atmosphere, 50 mu L of electrolyte is added into each cell, and the cell is kept stand for 24h and then subjected to the following performance test.
Comparative example 2
The procedure is as in example 1, except that the polyamidoamine dendrimer is not used and the polyvinyl alcohol is used in an amount of 18 parts.
Comparative example 3
The remainder was the same as in example 1, except that polyvinyl alcohol was not used and the amount of the polyamidoamine dendrimer was 18 parts.
The cells prepared in the above examples and comparative examples were subjected to the following electrochemical performance tests:
and (3) charge and discharge test: the blue tester was used for charge and discharge tests with a charge and discharge cutoff voltage of 1.5V and 0.005V, respectively, and a charge and discharge current of 0.1C, 1C =1000mA/g, and then the charge and discharge tests were performed.
Cycle performance:
the battery was subjected to a charge-discharge test at 0.5C, and the number of cycles was 100.
Low temperature performance:
and charging and discharging the battery at normal temperature and low temperature by adopting 0.5C current, and carrying out low-temperature test in a high-low temperature test box. Firstly, the battery is subjected to a charge-discharge test under a normal temperature environment to test the discharge capacity at the normal temperature, and then the battery is subjected to a charge-discharge test under a low temperature condition to test the discharge capacity at a low temperature of-5 ℃ and-10 ℃. The battery is placed in a low-temperature box for 5 to 8 hours before low-temperature test, so that the internal environment of the battery reaches the temperature required by low temperature, and the experimental result is more effective. The test procedure is constant current charging, constant voltage charging, constant current discharge placement, constant current charging, and stopping after 5 cycles.
TABLE 1 results of electrochemical Performance test of examples and comparative examples
The above table shows that the binder prepared by the invention has good flexibility and mechanical strength, can inhibit the volume change of the silicon cathode, and the battery prepared by the binder has good cycling stability and higher capacity. Meanwhile, the terminal amine group dendritic macromolecules and the polyacrylic acid derivatives have the effect of improving the low-temperature performance of the adhesive by cooperating with the polyvinyl alcohol, and although the mechanism is not further represented and proved, the theory can be speculated that the terminal amine group dendritic macromolecules are used as connecting nodes, the polyacrylic acid derivatives and the polyvinyl alcohol are used as a bridging body, the two substances are mutually interacted to generate self-assembly to form the adhesive with a three-dimensional network flexible framework structure, and the self-healing capacity of the adhesive with the structure at low temperature is better than that of the adhesive subjected to ionic bond crosslinking.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (7)
1. The three-dimensional network water system binder for the lithium ion battery is characterized by comprising the following raw materials in parts by weight: 100 parts of polyacrylic acid derivative emulsion, 5-10 parts of polyvinyl alcohol and 3-8 parts of amine-terminated dendritic macromolecules, wherein the polyacrylic acid derivative is obtained by polymerizing an acrylic monomer, an acrylamide organic acid monomer and a hydroxyl-containing fluoroacrylate monomer, and the solid content of the polyacrylic acid derivative emulsion is 20-30%;
the amine-terminated dendritic macromolecule is selected from at least one of polyamide-amine dendritic macromolecule and polypropylene imine dendritic macromolecule;
in the polyacrylic acid derivative, the weight ratio of an acrylic monomer, an acrylamide organic acid monomer and a hydroxyl-containing fluorinated acrylate monomer is 4-5:0.5-1: 1-2;
the acrylic monomer comprises acrylic acid and lithium acrylate, and the acrylamide organic acid monomer comprises acrylamide organic acid and lithium acrylamide organic acid; the lithium acrylate accounts for 60-80% of the acrylic monomer; the lithium acrylamide-based organic acid accounts for 60-80% of the acrylamide-based organic acid monomer.
2. The aqueous binder of claim 1 wherein the hydroxyl-containing fluoroacrylate monomer has the following formula:
wherein R is1Is a linear or branched alkyl group of C1-C5, R2Is a linear or branched alkylene group of C1-C3, R3Is C4-C10 fluoroalkyl.
3. The aqueous binder of claim 2 wherein the hydroxyl-containing fluoroacrylate monomer is selected from the group consisting of 3- (perfluorobutyl) -2-hydroxymethylacrylate, 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 3- (perfluorobutyl) -2-hydroxymethylpropyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 3-perfluorooctyl 2-hydroxypropyl acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, and mixtures thereof, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 4,5,5,6,6,7,7, 7-nonafluoro-2-heptyl hydroxyacrylate, 4,5,5,6,6,7,7,8,8,9,9, 9-tridecafluoro-2-hydroxynonyl methacrylate, and 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl methacrylate.
4. The aqueous binder as claimed in claim 1, wherein the emulsion particle size of the polyacrylic acid derivative emulsion is 100-150 nm; the branching generation number of the dendritic macromolecule is 2.0-5.0 generations; the molecular weight of the polyvinyl alcohol is 10-15 ten thousand, and the alcoholysis degree is 78-89%.
5. The method for preparing the three-dimensional network water-based binder for the lithium ion battery according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) under the inert atmosphere, mixing an emulsifier and water, adding the mixture into a reaction kettle, dropwise adding an acrylic monomer dissolved with an initiator, an acrylamide organic acid monomer and a hydroxyl-containing fluoroacrylate monomer into the reaction kettle, uniformly stirring, performing ultrasonic dispersion at a low temperature to form a miniemulsion, and heating and reacting at a constant temperature to obtain an emulsion for later use;
2) adding polyvinyl alcohol and amine-terminated dendritic macromolecules into water, heating, keeping stirring until the polyvinyl alcohol and the amine-terminated dendritic macromolecules are completely dissolved, cooling, keeping the temperature constant, adding the mixture into the emulsion obtained in the step 1), stirring until the mixture is uniformly dispersed, cooling to room temperature, and sieving to obtain the emulsion-shaped binder.
6. A negative electrode for a lithium ion battery, comprising the binder according to any one of claims 1 to 4, a negative electrode active material, and a conductive agent.
7. The lithium ion battery negative electrode of claim 6, wherein the binder is present in an amount of 1% to 10% by weight.
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