CN116003694A - Preparation method of aqueous adhesive for lithium ion battery and aqueous adhesive for lithium ion battery - Google Patents
Preparation method of aqueous adhesive for lithium ion battery and aqueous adhesive for lithium ion battery Download PDFInfo
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- CN116003694A CN116003694A CN202211592003.XA CN202211592003A CN116003694A CN 116003694 A CN116003694 A CN 116003694A CN 202211592003 A CN202211592003 A CN 202211592003A CN 116003694 A CN116003694 A CN 116003694A
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Abstract
The application relates to the technical field of aqueous adhesives, and particularly provides a preparation method of a lithium ion battery aqueous adhesive and the lithium ion battery aqueous adhesive, wherein a VAE polymer and an acrylic acid monomer in a VAE emulsion are prepared according to a weight ratio of 1:4-4:1; adding the VAE emulsion and water into a container, uniformly mixing, adding part of the acrylic acid monomer by weight, heating to a certain temperature, dropwise adding a first initiator solution, dropwise adding the rest acrylic acid monomer, dropwise adding a second initiator solution, and cooling to obtain the water-based adhesive; or adding the VAE emulsion and water into a container, uniformly mixing, adding the acrylic acid monomer, heating to a certain temperature, dripping a third initiator solution, continuously reacting for 0-6 hours, and cooling to obtain the water-based adhesive. The aqueous adhesive can provide good stripping force and softness for the positive electrode material of the lithium ion battery.
Description
Technical Field
The application relates to the technical field of aqueous adhesives, in particular to a preparation method of an aqueous adhesive for a lithium ion battery and the aqueous adhesive for the lithium ion battery.
Background
The aqueous adhesive for the lithium ion battery anode material is usually polyacrylic acid (PAA) aqueous adhesive, but the PAA aqueous adhesive is difficult to balance the stripping force between the pole piece and the aluminum foil and the softness of the pole piece, the pole piece can fall off due to the excessively low stripping force, the pole piece is too fragile due to the excessively low softness, and the problem of cracking easily occurs after rolling. Therefore, there is an urgent need to improve the softness of PAA-based aqueous adhesives while ensuring sufficient peel force.
Disclosure of Invention
In order to solve the technical problems that the PAA aqueous adhesive in the prior art is difficult to obtain good peeling force and softness at the same time, the application provides a preparation method of the lithium ion battery aqueous adhesive and the lithium ion battery aqueous adhesive.
The application adopts the following technical scheme:
the preparation method of the aqueous binder for the lithium ion battery comprises the following steps:
preparing a VAE polymer and an acrylic acid monomer in a weight ratio of 1:4-4:1 in the VAE emulsion;
adding the VAE emulsion and water into a container, uniformly mixing, adding part of the acrylic acid monomer by weight, heating to a certain temperature, dropwise adding a first initiator solution, dropwise adding the rest acrylic acid monomer, dropwise adding a second initiator solution, and cooling to obtain the water-based adhesive;
or adding the VAE emulsion and water into a container, uniformly mixing, adding the acrylic acid monomer, heating to a certain temperature, dripping a third initiator solution, continuously reacting for 0-6 hours, and cooling to obtain the water-based adhesive.
Preferably, the weight ratio of VAE polymer to acrylic monomer in the VAE emulsion is 1:2-2:1.
Preferably, the acrylic monomer is composed of a hydrophilic monomer and a hydrophobic monomer, and the hydrophilic monomer accounts for 40-90% of the weight of the acrylic monomer.
More preferably, the hydrophilic monomer has the chemical formula CH 2 ＝CR 1 R 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) a H and-COO (CH) 2 ) b PO 3 H, and/or contains-COOH, -COOM, - (C) 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, a=1-40, b=1-12, M is selected from Li + 、Na + And K + One or more of them.
More preferably, the hydrophobic monomer has the chemical formula CH 2 ＝CR 3 R 4 Wherein R is 3 Selected from H or C1-C4 alkyl, R 4 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-40, m=0-6.
Preferably, the fraction is 10-90% by weight.
Preferably, the dripping time of the first initiator solution, the dripping time of the second initiator solution and the dripping time of the third initiator solution are respectively 30 minutes to 6 hours.
Preferably, the first initiator, the second initiator and the third initiator are independently selected from one or more of a water-soluble azo initiator, a water-soluble peroxide initiator, a water-soluble persulfate initiator and a water-soluble redox initiator.
Preferably, the dropping time of the acrylic acid monomer remaining in the dropping is 1 to 8 hours.
The aqueous binder for lithium ion batteries is prepared by the preparation method of the aqueous binder for lithium ion batteries in any embodiment.
In summary, the present application has the following beneficial effects:
1. the aqueous adhesive for the lithium ion battery is formed by reacting vinyl acetate-ethylene copolymer (VAE) and acrylic acid monomer, takes the VAE as a core (soft core) and grafts acrylic acid Polymer (PAA) on the surface, and the VAE and the PAA cooperate to provide good adhesiveness to aluminum foil of a current collector, so that the VAE has good flexibility and the hydrogen bonding effect between ester bonds of the VAE and the PAA improves the flexibility of the pole piece. Thus, the aqueous adhesive of the present application can achieve both good peel force and softness.
2. The inventors have found that the hydrogen bonding between the protective colloid, polyvinyl alcohol (PVA), and PAA in the VAE emulsion also helps to improve the flexibility of the pole piece.
3. According to the application, the VAE is used as a soft core, hydrogen abstraction reaction is easier to occur with free radicals, new free radicals are generated on a VAE polymer molecular chain, and acrylic monomers are initiated to undergo polymerization reaction, so that a structure of grafting PAA polymer chains on the surface of the VAE soft core is formed, and the hydrophilic PAA polymer chains can provide good stability for the water-based adhesive.
4. The inventor further discovers that the combination of the hydrophilic and hydrophobic structures of the VAE and the PAA polymer chain synergistically plays a role, so that the whole aqueous adhesive has a good hydrophilic and hydrophobic structure, plays a good dispersing role on active particles of the positive electrode material, and has high stripping force.
Drawings
FIG. 1 is a schematic representation of the interaction of VAE, PVA and PAA in the aqueous adhesive of the present application.
1-VAE soft core, 2-PAA,3-PVA.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
In one aspect, the application provides a preparation method of a lithium ion battery water-based adhesive, which comprises the following steps: preparing a VAE polymer and an acrylic acid monomer in a weight ratio of 1:4-4:1 in the VAE emulsion;
adding VAE emulsion and water into a container, uniformly mixing, adding part of acrylic acid monomer by weight, heating to a certain temperature, dropwise adding a first initiator solution, dropwise adding the rest acrylic acid monomer, dropwise adding a second initiator solution, and cooling to obtain a water-based adhesive;
or adding the VAE emulsion and water into a container, uniformly mixing, adding the acrylic acid monomer, heating to a certain temperature, dripping a third initiator solution, continuously reacting for 0-6 hours, and cooling to obtain the water-based adhesive.
The solids content of the VAE emulsion is typically 40-70wt%, the weight of VAE polymer in the VAE emulsion described above being calculated as the solids content in the VAE emulsion, the weight of VAE polymer = weight of VAE emulsion x solids content.
VAE emulsions are obtained by free radical emulsion polymerization of vinyl acetate with ethylene in water in the presence of a surfactant (or also polyvinyl alcohol). Other monomers such as methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, acrylamide, N-methacrylamide, methyl methacrylate, butyl methacrylate, isooctyl methacrylate, etc. may be added in addition to vinyl acetate and ethylene as main monomers, and the addition amount of the other monomers may be 0 to 10% by weight of the total monomers. The weight ratio of the vinyl acetate to the ethylene is 9:1-6:4, further selected from 9:1-7:3, and still further selected from 85:15-75:25.
In this application, VAE emulsions are further selected which contain polyvinyl alcohol as protective colloid, the polyvinyl alcohol being used as protective colloid in an amount generally between 1 and 6% by weight of the VAE emulsion. In this application, the degree of hydrolysis of the polyvinyl alcohol is selected to be between 70 and 99%, and further, the degree of hydrolysis of the polyvinyl alcohol is selected to be between 80 and 90%. The inventors have unexpectedly found that the inclusion of polyvinyl alcohol in the VAE emulsion can further improve the flexibility of the aqueous adhesive after film formation on the pole piece.
In this application, further, the weight ratio of VAE polymer to acrylic monomer in the VAE emulsion is from 1:2 to 2:1.
In the present application, further, the acrylic monomer is composed of a hydrophilic monomer and a hydrophobic monomer, and the hydrophilic monomer accounts for 40-90% of the weight of the acrylic monomer. Further, the hydrophilic monomer accounts for 50-90% of the weight of the acrylic monomer. Still further, the hydrophilic monomer accounts for 70-85% of the weight of the acrylic monomer. The ratio of the hydrophilic monomer to the hydrophobic monomer is adjusted, so that the aqueous adhesive with different hydrophilic and hydrophobic properties can be obtained.
Hydrophilic monomers refer to compounds having at least one carbon-carbon unsaturated double bond in the molecule that can undergo free radical polymerization, and having at least one hydrophilic group in the molecular structure, such as hydroxyl, carboxyl, carboxylate, phosphate, sulfonate, amino, substituted amino, amide, substituted amide, etc., or polyethylene glycol groups containing at least two ethylene glycol units. The hydrophobic monomer refers to a compound having at least one carbon-carbon unsaturated double bond in a molecule capable of undergoing free radical polymerization, and the compound does not have a hydrophilic group in a molecular structure.
In the present application, further, the hydrophilic monomer has a chemical formula of CH 2 ＝CR 1 R 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) a H and-COO (CH) 2 ) b PO 3 H, and/or contains-COOH, -COOM, - (C) 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, a=1-40, b=1-12, M is selected from Li + 、Na + And K + One or more of them. By way of example, the hydrophilic monomer may be acrylic acid, methacrylic acid, acrylamide, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, acrylamide, N-dimethylacrylamide, and the like.
In this application, further, the hydrophobic monomer has the chemical formula CH 2 ＝CR 3 R 4 Wherein R is 3 Selected from H or C1-C4 alkyl, R 4 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-40, m=0-6. By way of example, the hydrophobic monomer may be methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearic methacrylate, acrylonitrile, and the like.
In this application, further, the partial weight is 10 to 90% by weight. The acrylic acid monomer is added into the reaction system step by step to carry out free radical polymerization, so that the reaction process can be better controlled, and the copolymerization conditions of monomers with different polymerization reaction rates can be adjusted. Of course, the acrylic acid monomer can be added into the reaction system all at once, and the performance difference between the obtained aqueous adhesive and the aqueous adhesive obtained by adding the acrylic acid monomer step by step is small.
In the present application, further, the dropping time of dropping the first initiator solution, the second initiator solution, and the third initiator solution is 30 minutes to 6 hours, respectively. Further, the first initiator solution is added dropwise for 30 minutes to 2 hours; further, the second initiator solution is added dropwise for 30 minutes to 4 hours, and still further, the second initiator solution is added dropwise for 30 minutes to 2 hours; further, the third initiator solution is added dropwise for 30 minutes to 4 hours.
In the present application, the first initiator solution is 0.2 to 0.8% by weight of the first initiator based on the weight of the acrylic monomer. The second initiator solution is 0.2 to 0.8% by weight of the second initiator based on the weight of the acrylic monomer. The third initiator solution is 0.3-1.5% by weight of the third initiator based on the weight of the acrylic monomer. The first initiator solution, the second initiator solution, and the third initiator solution may have a concentration of 1 to 20wt%.
In the present application, further, the first initiator, the second initiator and the third initiator are independently selected from one or more of a water-soluble azo initiator, a water-soluble peroxide initiator, a water-soluble persulfate initiator and a water-soluble redox initiator. The water-soluble azo initiator is not particularly limited, and may be azobisisobutyrimidine hydrochloride (AIBA), azobisiso Ding Mi-inhydrochloride (AIBI), or the like; the water-soluble peroxide initiator is not particularly limited, and may be hydrogen peroxide, sodium peroxide, ammonium peroxide, or the like; the water-soluble persulfate initiator is not particularly limited, and may be ammonium persulfate, potassium persulfate, sodium persulfate, or the like; the water-soluble redox initiator is not particularly limited, and may be ammonium persulfate/sodium hydrogen sulfite, potassium persulfate/sodium hydrogen sulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium hydrogen sulfite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, or the like. Different water-soluble initiators have different corresponding reaction temperatures, for example, when the water-soluble initiator is AIBA, a certain temperature can be 50-60 ℃, when the water-soluble initiator is ammonium persulfate, a certain temperature can be 60-80 ℃, and when the water-soluble initiator is ammonium persulfate/sodium bisulphite, a certain temperature can be 40-45 ℃.
In the present application, further, the dropping time of dropping the remaining acrylic monomer is 1 to 8 hours. In a further step, the remaining acrylic acid monomer is added dropwise for 2 to 6 hours.
In the present application, the aqueous binder has a solids content of 5 to 60wt%, further 10 to 40wt%, and a viscosity (25 ℃) of 500 to 20000mpa.s.
The application provides a lithium ion battery water-based adhesive, which is prepared by the preparation method of the lithium ion battery water-based adhesive in any embodiment. The application of the aqueous adhesive to the positive electrode material of the lithium ion battery to prepare the positive electrode slurry can be carried out according to a conventional method.
The technical scheme of the present application will be described in detail with reference to examples, comparative examples and experimental data.
Preparation example 1
2 parts of sodium dodecyl benzene sulfonate, 0.7 part of Triton X-100 and 37.3g of sodium dodecyl benzene sulfonate, 28 parts of vinyl acetate are added into a reaction kettle, the temperature is raised to 67 ℃, ethylene gas is introduced into the reaction kettle, the pressure of the reaction kettle reaches 4MPa, 0.2 part of ammonium persulfate aqueous solution (the concentration is 10 wt%) is dropwise added, the polymerization temperature is controlled to 75+/-2 ℃, the ethylene gas introducing pressure is regulated to 5.7MPa, and 20 parts of vinyl acetate are dropwise added. And (3) after the dropwise adding of vinyl acetate, stopping introducing ethylene gas, continuing to react for 6 hours, cooling, exhausting, defoaming, discharging to obtain the VAE emulsion, wherein the solid content is 59.8%.
Preparation example 2
In preparation example 1, 2 parts of sodium dodecylbenzenesulfonate, 0.7 part of Triton X-100 were replaced with 2.7 parts of polyvinyl alcohol 17-88 (17 means that the polymerization degree of polyvinyl alcohol was 1700 and 88 means that the alcoholysis degree was 88%), and the remaining steps were kept unchanged to obtain a VAE emulsion, and the solid content was 59.5%.
Preparation example 3
In preparation example 1, 2 parts of sodium dodecylbenzenesulfonate, 0.7 part of Triton X-100 were replaced with 5 parts of polyvinyl alcohol 17-88, and the remaining steps were kept unchanged to obtain a VAE emulsion, the solid content was found to be 60.3%.
Preparation example 4
In preparation example 1, 2 parts of sodium dodecylbenzenesulfonate, 0.7 part of Triton X-100 was replaced with 2.7 parts of hydroxypropyl methylcellulose, and the remaining steps were kept unchanged to obtain a VAE emulsion, the solid content was 59.4%.
Preparation example 5
In preparation example 1, 2 parts of sodium dodecylbenzenesulfonate, 0.7 part of Triton X-100 were replaced with 5 parts of hydroxypropyl methylcellulose, and the remaining steps were kept unchanged to obtain a VAE emulsion, the solid content was 59.7%.
Example 1
The acrylic monomer consists of methacrylic acid, hydroxyethyl methacrylate and methacrylonitrile in a weight ratio of 4:4:2.
16.7 parts of the VAE emulsion of preparation example 1 and 65 parts of water are added into a reactor, uniformly mixed, 7 parts of the acrylic acid monomer and 0.05 part of sodium bisulphite are added, the temperature is raised to 45 ℃, 0.5 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 2 hours, 3 parts of the acrylic acid monomer is dropwise added within 4 hours, then 0.3 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 1.5 hours, the temperature is lowered to below 30 ℃, the pH is regulated to 7.5-8, and the solid content is regulated to 19.9wt% by adding water, so that the aqueous adhesive is obtained.
Example 2
In example 1, the VAE emulsion of preparation 1 was replaced with an equal weight of the VAE emulsion of preparation 2, the remaining steps remaining unchanged.
Example 3
In example 1, the VAE emulsion of preparation 1 was replaced with an equal weight of the VAE emulsion of preparation 3, the remaining steps remaining unchanged.
Example 4
In example 1, the VAE emulsion of preparation 1 was replaced with an equal weight of the VAE emulsion of preparation 4, the remaining steps remaining unchanged.
Example 5
In example 1, the VAE emulsion of preparation 1 was replaced with an equal weight of the VAE emulsion of preparation 5, the remaining steps remaining unchanged.
Example 6
The acrylic acid monomer consists of methacrylic acid, hydroxypropyl methacrylate, methacrylonitrile and butyl methacrylate according to the weight ratio of 4:3:2:1.
20 parts of the VAE emulsion of preparation example 2 and 65 parts of water are added into a reactor, uniformly mixed, 5 parts of the acrylic acid monomer are added, the temperature is raised to 73 ℃, 0.6 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 3 hours, then 3 parts of the acrylic acid monomer are dropwise added within 4 hours, then 0.4 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 2 hours, the temperature is lowered to below 30 ℃, the pH is regulated to 7.5-8, and water is added to regulate the solid content to 20.2wt% so as to obtain the water-based adhesive.
Example 7
The acrylic monomer consists of methacrylic acid, hydroxypropyl methacrylate and methacrylonitrile in a weight ratio of 4:3:3.
10 parts of the VAE emulsion of preparation example 3 and 60 parts of water are added into a reactor, uniformly mixed, 8 parts of the acrylic acid monomer are added, the temperature is raised to 73 ℃, 0.5 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 3 hours, then 4 parts of the acrylic acid monomer are dropwise added within 4 hours, then 0.4 part of ammonium persulfate aqueous solution with the concentration of 10wt% is dropwise added within 2.5 hours, the temperature is lowered to below 30 ℃, the pH is regulated to 7.5-8, and water is added to regulate the solid content to 20wt% so as to obtain the water-based adhesive.
Example 8
In example 2, the acrylic monomer was adjusted to consist of methacrylic acid, hydroxyethyl methacrylate and methacrylonitrile in a weight ratio of 3:2:5, the remaining steps remaining unchanged.
Comparative example 1
The VAE emulsion of preparation 2 was diluted with water to a concentration of 20wt%.
Comparative example 2
To the reaction vessel were added 75 parts of water, 12 parts of methacrylic acid, 4 parts of acrylamide, 3 parts of methacrylonitrile and 1 part of laurate, and the mixture was stirred and blended at a rotation speed of 400 rpm. Heating to 75 ℃, dropwise adding 1 part of ammonium persulfate aqueous solution with the concentration of 40wt% within 2 hours, keeping the temperature for 3 hours, cooling to below 30 ℃, adjusting the pH to 7.5-8 and the solid content to 20.1wt% to obtain the aqueous adhesive.
Comparative example 3
The VAE emulsion of preparation 2 and the aqueous binder of comparative example 2 were mixed uniformly in a weight ratio of 1:1.
Comparative example 4
The VAE emulsion of preparation 2 and the aqueous binder of comparative example 2 were mixed uniformly in a weight ratio of 1:2.
Comparative example 5
In example 2, the acrylic monomer was adjusted to consist of methacrylic acid, hydroxyethyl methacrylate and methacrylonitrile in a weight ratio of 2:1:7, the remaining steps remaining unchanged.
Performance testing
The two positive electrode materials of lithium manganate and lithium iron phosphate are adopted for testing, and the formula is as follows:
lithium manganate: aqueous adhesive: super P carbon black: lithium manganate=2.2:2.0:95.8.
Lithium iron phosphate: aqueous adhesive: super P carbon black: lithium iron phosphate=3.0:2.0:95.0.
The dispersion process is shown in table 1 below.
TABLE 1
The pole piece stripping force testing method comprises the following steps:
flat coater (MSK-AFA-SC 300, manufacturer: shenzhen City Kogyo Zhida technology Co., ltd.)
Standard tape: facestock coated with standard pressure sensitive adhesive (40 mm wide, single sided adhesive, manufacturer: 3M)
Double faced adhesive tape (50 mm wide, double faced adhesive tape, manufacturer: yiwu Yongda adhesive product factory)
Test plate (125 mm + -1 mm length, 50mm + -1 mm width, 1.5-2.0mm thickness, test plate material is OCr18Ni9 or 1Cr18Ni9Ti specified in GB/T3280-2015)
Aluminum foil (Single-sided aluminum foil, thickness 12 μm, manufacturer: xiamen Xia aluminum foil Co., ltd.)
The operation steps are as follows:
s1, using a coating machine to prepare a film, and then placing the film into an oven to be dried at 105 ℃ for 10min, wherein the surface density of the dried pole piece requires 280+/-5 g/square meter of lithium manganate and 200+/-5 g/square meter of lithium iron phosphate;
s2, cutting a pole piece, wherein the requirements are as follows: 50mm×125mm, number of pole pieces: 5;
s3, putting the cut pole piece into a drying oven for secondary drying, drying at 100 ℃ for 30min, and putting the pole piece into a dryer for cooling to room temperature;
s4, labeling 5 pole pieces, measuring the weight and thickness of each numbered pole piece, recording data, and then placing the pole pieces into a self-sealing bag for sealing;
s5, adhering the surface of the pole piece coated with the coating to the smooth surface of the test board by using double-sided adhesive tape;
s6, rolling the pole piece back and forth at a speed of about 300mm/min under the dead weight by using a pressing roller of an adhesive tape pressing roller machine (YGJ-02), and standing for 5min;
s7, folding the free end of the sample by 180 degrees, and continuously stripping at a descending speed of 300mm/min +/-10 mm/min;
s8, stopping peeling when the template is peeled off and remaining 25mm, and reading the peeling force by using an electronic peeling tester (BLD-200N). The 5 pole piece test results of the same aqueous adhesive were averaged.
The pole piece flexibility testing method comprises the following steps: the test was performed using an IMT-RRD01 x 1 softness tester model. The same pole piece is tested at 5 different positions on the middle line, and the average value is obtained.
The results are shown in Table 2.
TABLE 2
As can be seen from the results of table 2, the aqueous adhesive of the present application can provide a positive electrode material for lithium ion batteries excellent in the combination of peel force and softness.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. A preparation method of a lithium ion battery water-based adhesive is characterized by comprising the following steps: the method comprises the following steps:
preparing a VAE polymer and an acrylic acid monomer in a weight ratio of 1:4-4:1 in the VAE emulsion;
adding the VAE emulsion and water into a container, uniformly mixing, adding part of the acrylic acid monomer by weight, heating to a certain temperature, dropwise adding a first initiator solution, dropwise adding the rest acrylic acid monomer, dropwise adding a second initiator solution, and cooling to obtain the water-based adhesive;
or adding the VAE emulsion and water into a container, uniformly mixing, adding the acrylic acid monomer, heating to a certain temperature, dripping a third initiator solution, continuously reacting for 0-6 hours, and cooling to obtain the water-based adhesive.
2. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the weight ratio of the VAE polymer to the acrylic acid monomer in the VAE emulsion is 1:2-2:1.
3. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the acrylic acid monomer consists of a hydrophilic monomer and a hydrophobic monomer, wherein the hydrophilic monomer accounts for 40-90% of the weight of the acrylic acid monomer.
4. The method for preparing the aqueous binder for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the chemical general formula of the hydrophilic monomer is CH 2 =CR 1 R 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) a H and-COO (CH) 2 ) b PO 3 One or more of H and/or-COOH, -COOM,-(C 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, a=1-40, b=1-12, M is selected from Li + 、Na + And K + One or more of them.
5. The method for preparing the aqueous binder for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the chemical general formula of the hydrophobic monomer is CH 2 =CR 3 R 4 Wherein R is 3 Selected from H or C1-C4 alkyl, R 4 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-40, m=0-6.
6. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the weight of the portion is 10-90% by weight.
7. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the dripping time of the first initiator solution, the dripping time of the second initiator solution and the dripping time of the third initiator solution are respectively 30 minutes to 6 hours.
8. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the first initiator, the second initiator and the third initiator are independently selected from one or more of a water-soluble azo initiator, a water-soluble peroxide initiator, a water-soluble polysulfide initiator and a water-soluble redox initiator.
9. The method for preparing the aqueous binder for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the dripping time of the rest acrylic acid monomer is 1-8 hours.
10. The aqueous binder for the lithium ion battery is characterized in that: is prepared by the preparation method of the lithium ion battery water-based adhesive of any one of claims 1-9.
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