CN108467503B - Preparation method of heat-resistant lithium battery diaphragm - Google Patents
Preparation method of heat-resistant lithium battery diaphragm Download PDFInfo
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Abstract
The invention discloses a preparation method of a heat-resistant lithium battery diaphragm, which comprises the steps of adding an inorganic material and a dispersing agent into deionized water, grinding to obtain a uniform solution, adding a suspension stabilizer, a defoaming agent, a wetting agent, a surfactant, a first binder and a second binder, dispersing at a low speed to obtain water-based ceramic slurry, coating the water-based ceramic slurry on a base film, and drying to obtain the heat-resistant lithium battery diaphragm. The diaphragm has better liquid absorption rate, peeling strength and thermal stability.
Description
Technical Field
The invention relates to the technical field of coating diaphragms, in particular to a preparation method of a heat-resistant lithium battery diaphragm.
Background
The polyolefin diaphragm has low price and wide application in lithium ion batteries, but because the heat resistance of the diaphragm material is poor and the affinity with the organic solvent of the electrolyte is poor, the retention capacity of the electrolyte is poor, and certain influence is caused on the service performance of the battery.
The slurry used in the coating process is prepared from ceramic particles, a binder, a solvent, a surfactant and the like according to a certain formula. Through coating ceramic slurry on one side or both sides of polyolefin, can promote the thermal stability of diaphragm, improve its mechanical strength, prevent that the diaphragm from contracting and the positive negative pole that leads to contacts by a large scale, can improve its resistant piercing ability moreover, prevent that battery long-term circulation lithium dendrite from piercing the short circuit that the diaphragm caused, the porosity of ceramic coating is greater than the porosity of diaphragm in addition, is favorable to strengthening the liquid retention and the infiltration nature of diaphragm to extension battery cycle life.
The ceramic layer and the base film of the ceramic composite diaphragm prepared at present are weak in binding force, the ceramic layer is easy to fall off, and particularly the heat resistance at the temperature of more than 140 ℃ is poor.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the binding force between the ceramic layer and the base film of the diaphragm prepared at present is weak, the ceramic layer is easy to fall off, and the heat resistance is poor particularly at the temperature of more than 140 ℃.
The invention provides a preparation method of a heat-resistant lithium battery diaphragm, wherein an inorganic material with the average particle size of 300-600 nm is used, the mass proportion of inorganic particles smaller than 100nm in the inorganic material is 5-30%, the prepared water-based ceramic slurry has better heat resistance, the glass transition temperature of a first binder is lower, the binding power and flexibility of a ceramic coating are provided, the falling-off of ceramic particles is effectively avoided, the glass transition temperature of a second binder is higher, a specific rigid framework is formed, and the diaphragm can be effectively prevented from shrinking and melting under the thermal runaway condition by virtue of extremely high thermal stability.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a preparation method of a heat-resistant lithium battery diaphragm is characterized by comprising the following specific steps of:
step 1: preparation of aqueous ceramic slurry
Adding 40-60 parts of inorganic material and 0.02-1 part of dispersing agent into 50-80 parts of deionized water, grinding for 0.5-3 h to obtain a uniform solution, adding 0.1-1 part of suspension stabilizer, 0.1-1 part of defoaming agent, 0.1-1 part of wetting agent, 0.1-1 part of surfactant, 1-3 parts of first binder and 1-3 parts of second binder, and dispersing at low speed for 10-60 min to obtain aqueous ceramic slurry;
step 2: coating of
Coating the water-based ceramic slurry prepared in the step (1) on one side or two sides of a base film with the thickness of 6-20 microns in a coating mode to obtain a water-based ceramic slurry coating, and then baking for 1-4 min at the temperature of 40-80 ℃ to obtain a heat-resistant lithium battery diaphragm; wherein:
the coating mode is one of gravure roll coating, narrow-slit coating, anilox roll coating, Slot-die coating and spraying;
the base film is one of a polyethylene single-layer film, a polypropylene single-layer film and a polyethylene and polypropylene multi-layer composite film.
The inorganic material is alumina or boehmite with the average particle size of 300-600 nm, wherein the mass ratio of inorganic particles with the particle size of less than 100nm to the inorganic material is 5-30%.
The dispersing agent is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, ammonium polyacrylate salt, octyl phenol polyoxyethylene and polyethylene glycol.
The suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 30-60% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 30-60% of the total mass of the monomers, and the acrylic acid accounts for 5-20% of the total mass of the monomers.
The defoaming agent is at least one of emulsified silicone oil, a high-alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether and polyoxypropylene glycerol ether.
The wetting agent is at least one of fluorinated alkyl ethoxy alcohol ether, polyoxyethylene alkyl amide and fatty alcohol-polyoxyethylene ether.
The surfactant is at least one of allyloxy hydroxypropyl sodium sulfonate, methacrylic acid hydroxypropyl sodium sulfonate, hydroxymethyl sodium sulfonate, hydroxyethyl sodium sulfonate and 4-hydroxyethyl piperazine ethyl sodium sulfonate.
The first binder is a quaternary copolymerization emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 5-40% of the total mass of the monomers, the isooctyl acrylate accounts for 50-90% of the total mass of the monomers, the methacrylic acid accounts for 0.5-6% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 0.5-6% of the total mass of the monomers.
The second binder is quaternary copolymerization emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 60-90% of the total mass of the monomers, the butyl acrylate accounts for 5-30% of the total mass of the monomers, the methacrylic acid accounts for 0.5-6% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 0.5-6% of the total mass of the monomers.
Compared with the prior art, the invention has the following beneficial effects:
the ceramic layer has good adhesive force on the surface of the base film, and the ceramic coating is not easy to fall off;
the ceramic coating has strong electrolyte absorption and retention capacity and good electrolyte resistance;
the heat resistance of the ceramic-coated separator is greatly improved compared with that of an uncoated separator, and particularly, the thermal shrinkage of the ceramic-coated separator is small at the temperature of more than 140 ℃.
Drawings
Fig. 1 is a scanning electron microscope image of a heat-resistant lithium battery separator prepared in example 1 of the present invention;
fig. 2 is a graph showing the effect of 4 μ L of electrolyte on the wetting ability of the ceramic-coated separator in the same time period when 4 μ L of electrolyte was dropped on each of the separators of example 1, comparative example 1 and comparative example 2.
Detailed Description
Example 1
a. Preparing water-based ceramic slurry: adding 40 parts of aluminum oxide and 0.1 part of sodium dodecyl sulfate into 50 parts of deionized water, grinding for 1 hour to obtain a uniform solution, then adding 0.1 part of suspension stabilizer, 0.1 part of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.1 part of polyoxyethylene alkylamide, 0.1 part of sodium hydroxypropyl methacrylate sulfonate, 1 part of first binder and 1 part of second binder, and dispersing at a low speed for 30min to obtain a water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polyethylene single-layer film in a gravure roll coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 70 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 4 microns in thickness.
Wherein the average grain diameter of the alumina is 300nm, and the alumina with the grain diameter less than 100nm accounts for 10 percent of the total alumina by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 30% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 50% of the total mass of the monomers, and the acrylic acid accounts for 20% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 40% of the total mass of the monomers, the isooctyl acrylate accounts for 50% of the total mass of the monomers, the methacrylic acid accounts for 5% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 5% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 60% of the total mass of the monomers, the butyl acrylate accounts for 30% of the total mass of the monomers, the methacrylic acid accounts for 5% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 5% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Example 2
a. Preparing water-based ceramic slurry: adding 45 parts of aluminum oxide and 0.2 part of lauryl sodium sulfate into 60 parts of deionized water, grinding for 1 hour to obtain a uniform solution, then adding 0.2 part of a suspension stabilizer, 0.3 part of polyoxyethylene polyoxypropylene ether, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.2 part of sodium hydroxypropyl methacrylate, 2 parts of a first binder and 2 parts of a second binder, and dispersing at a low speed for 20 minutes to obtain a water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polyethylene single-layer film in a reticulate pattern roller coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 60 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 4 microns in thickness.
Wherein the average grain diameter of the alumina is 400nm, and the alumina with the grain diameter less than 100nm accounts for 15 percent of the total alumina by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 40% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 40% of the total mass of the monomers, and the acrylic acid accounts for 20% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 20% of the total mass of the monomers, the isooctyl acrylate accounts for 75% of the total mass of the monomers, the methacrylic acid accounts for 2.5% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 2.5% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 80% of the total mass of the monomers, the butyl acrylate accounts for 15% of the total mass of the monomers, the methacrylic acid accounts for 1% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 4% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Example 3
a. Preparing water-based ceramic slurry: adding 55 parts of boehmite and 0.2 part of ammonium polyacrylate salt into 75 parts of deionized water, grinding for 1 hour to obtain a uniform solution, adding 0.2 part of a suspension stabilizer, 0.1 part of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.3 part of polyoxyethylene alkylamide, 0.5 part of sodium hydroxyethyl sulfonate, 3 parts of a first binder and 2 parts of a second binder, and dispersing at a low speed for 40min to obtain a water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polyethylene single-layer film in a reticulate pattern roller coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 60 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 4 microns in thickness.
Wherein the boehmite with the average particle size of 450nm and the boehmite with the particle size of less than 100nm accounts for 25 percent of the total boehmite by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 60% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 30% of the total mass of the monomers, and the acrylic acid accounts for 10% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 5% of the total mass of the monomers, the isooctyl acrylate accounts for 90% of the total mass of the monomers, the methacrylic acid accounts for 3% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 2% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 90% of the total mass of the monomers, the butyl acrylate accounts for 5% of the total mass of the monomers, the methacrylic acid accounts for 3% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 2% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Example 4
a. Preparing water-based ceramic slurry: adding 60 parts of aluminum oxide and 0.5 part of sodium dodecyl sulfate into 50 parts of deionized water, grinding for 2 hours to obtain a uniform solution, then adding 0.1 part of a suspension stabilizer, 0.5 part of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.4 part of fluoroalkyl ethoxy alcohol ether, 0.8 part of allyloxy hydroxypropyl sodium sulfonate, 2 parts of a first binder and 3 parts of a second binder, and dispersing at a low speed for 30 minutes to obtain a water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polypropylene single-layer film in a narrow-slit coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 60 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 5 microns thick.
Wherein the average grain diameter of the alumina is 500nm, and the alumina with the grain diameter less than 100nm accounts for 15 percent of the total alumina by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 40% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 50% of the total mass of the monomers, and the acrylic acid accounts for 10% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 10% of the total mass of the monomers, the isooctyl acrylate accounts for 88% of the total mass of the monomers, the methacrylic acid accounts for 1% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 1% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 70% of the total mass of the monomers, the butyl acrylate accounts for 25% of the total mass of the monomers, the methacrylic acid accounts for 1% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 4% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Example 5
a. Preparing water-based ceramic slurry: adding 50 parts of alumina and 0.5 part of sodium dodecyl sulfate into 80 parts of deionized water, grinding for 1 hour to obtain a uniform solution, then adding 0.8 part of suspension stabilizer, 0.2 part of polyoxypropylene glycerol ether, 0.6 part of fatty alcohol-polyoxyethylene ether, 0.2 part of sodium hydroxymethyl sulfonate, 1 part of first binder, 3 parts of second binder, and dispersing at a low speed for 30 minutes to obtain aqueous ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polypropylene single-layer film in a narrow-slit coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 60 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 5 microns thick.
Wherein the average grain diameter of the alumina is 600nm, and the alumina with the grain diameter less than 100nm accounts for 10 percent of the total alumina by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 45% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 45% of the total mass of the monomers, and the acrylic acid accounts for 10% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 15% of the total mass of the monomers, the isooctyl acrylate accounts for 88% of the total mass of the monomers, the methacrylic acid accounts for 3% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 4% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 85% of the total mass of the monomers, the butyl acrylate accounts for 12% of the total mass of the monomers, the methacrylic acid accounts for 0.5% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 2.5% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Example 6
a. Preparing water-based ceramic slurry: adding 60 parts of boehmite and 0.4 part of polyacrylic acid into 70 parts of deionized water, grinding for 1 hour to obtain a uniform solution, then adding 0.2 part of a suspension stabilizer, 0.2 part of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.3 part of fluoroalkyl ethoxy alcohol ether, 0.3 part of sodium hydroxypropyl methacrylate sulfonate, 3 parts of a first binder and 3 parts of a second binder, and dispersing at a low speed for 40min to obtain a water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polypropylene single-layer film in a spraying mode to obtain a water-based ceramic slurry coating, and then baking for 3min at the temperature of 70 ℃ to obtain the heat-resistant lithium battery diaphragm, wherein the ceramic coating is 6 microns thick.
Wherein the boehmite with the average particle size of 500nm and the boehmite with the particle size of less than 100nm accounts for 20 percent of the total boehmite by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 55% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 40% of the total mass of the monomers, and the acrylic acid accounts for 5% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The first binder is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 22% of the total mass of the monomers, the isooctyl acrylate accounts for 68% of the total mass of the monomers, the methacrylic acid accounts for 4% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 6% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
The second binder is quaternary copolymer emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 65% of the total mass of the monomers, the butyl acrylate accounts for 30% of the total mass of the monomers, the methacrylic acid accounts for 3% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 2% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Comparative example 1: 12 μm polyethylene monolayer film, no ceramic coating.
Comparative example 2:
a. preparing water-based ceramic slurry: adding 40 parts of aluminum oxide and 0.1 part of sodium dodecyl sulfate into 50 parts of deionized water, grinding for 1 hour to obtain a uniform solution, then adding 0.1 part of suspension stabilizer, 0.1 part of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.1 part of polyoxyethylene alkylamide, 0.1 part of sodium hydroxypropyl methacrylate and 2 parts of binder, and dispersing at a low speed for 30min to obtain water-based ceramic slurry;
b. coating: and (b) coating the water-based ceramic slurry prepared in the step (a) on one side of a 12-micron polyethylene single-layer film in a gravure roll coating mode to obtain a water-based ceramic slurry coating, and then baking for 1min at the temperature of 70 ℃ to obtain the lithium battery diaphragm, wherein the ceramic coating is 4 microns in thickness.
Wherein the average grain diameter of the alumina is 300nm, and the alumina with the grain diameter less than 100nm accounts for 10 percent of the total alumina by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 30% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 50% of the total mass of the monomers, and the acrylic acid accounts for 20% of the total mass of the monomers; the suspension stabilizer is prepared according to the preparation method disclosed in Chinese patent 201511026680.5. The adhesive is quaternary copolymer emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 40% of the total mass of the monomers, the isooctyl acrylate accounts for 50% of the total mass of the monomers, the methacrylic acid accounts for 5% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 5% of the total mass of the monomers; the acrylic ester emulsion is prepared according to the preparation method disclosed in Chinese patent 201110450289.3.
Performance test experiment
1. Scanning and analyzing by an electron microscope: fig. 1 is a scanning electron microscope image of the ceramic coated separator prepared by the method of example 1, and the ceramic powder in the surface bonding functional layer of the prepared ceramic coated separator is uniformly dispersed.
2. Electrolyte absorption capacity, fig. 2 shows the wetting capacity of the electrolyte to the ceramic-coated separator in the same time period when 4 μ L of the electrolyte was dropped on the separator of example 1, comparative example 1 and comparative example 2, respectively. The surfaces of the example 1 and the comparative example 2 are both provided with the ceramic coatings, so that the electrolyte absorption capacity is better, and the comparative example 1 is not provided with the ceramic coatings, so that the electrolyte is difficult to wet the diaphragm.
3. Peel Strength and Heat resistance test
Table 1 membrane performance testing
The performance test results in table 1 show that the ceramic slurry coating membrane prepared by the invention has better adhesion of the coating to the base material, and the thermal shrinkage of the membrane at 140 ℃ is obviously smaller than that of comparative example 1 and comparative example 2.
Claims (5)
1. The preparation method of the heat-resistant lithium battery diaphragm is characterized by comprising the following specific steps of:
step 1: preparation of aqueous ceramic slurry
Adding 40-60 parts of inorganic material and 0.02-1 part of dispersing agent into 50-80 parts of deionized water, grinding for 0.5-3 h to obtain a uniform solution, adding 0.1-1 part of suspension stabilizer, 0.1-1 part of defoaming agent, 0.1-1 part of wetting agent, 0.1-1 part of surfactant, 1-3 parts of first binder and 1-3 parts of second binder, and dispersing at low speed for 10-60 min to obtain aqueous ceramic slurry;
step 2: coating of
Coating the water-based ceramic slurry prepared in the step (1) on one side or two sides of a base film with the thickness of 6-20 microns in a coating mode to obtain a water-based ceramic slurry coating, and then baking for 1-4 min at the temperature of 40-80 ℃ to obtain a heat-resistant lithium battery diaphragm; wherein:
the coating mode is one of gravure roll coating, narrow-slit coating, anilox roll coating, Slot-die coating and spraying;
the base film is one of a polyethylene single-layer film, a polypropylene single-layer film and a polyethylene and polypropylene multi-layer composite film;
the inorganic material is alumina or boehmite with the average particle size of 300-600 nm, wherein the inorganic particles with the particle size of less than 100nm account for 5-30% of the inorganic material by mass;
the suspension stabilizer is a terpolymer of 2-acrylamide-2-methacrylic sulfonic acid, N, N-dimethylacrylamide and acrylic acid, wherein the 2-acrylamide-2-methacrylic sulfonic acid accounts for 30-60% of the total mass of the monomers, the N, N-dimethylacrylamide accounts for 30-60% of the total mass of the monomers, and the acrylic acid accounts for 5-20% of the total mass of the monomers;
the first binder is a quaternary copolymerization emulsion of methyl methacrylate, isooctyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 5-40% of the total mass of the monomers, the isooctyl acrylate accounts for 50-90% of the total mass of the monomers, the methacrylic acid accounts for 0.5-6% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 0.5-6% of the total mass of the monomers;
the second binder is quaternary copolymerization emulsion of methyl methacrylate, butyl acrylate, methacrylic acid and vinyl triethoxysilane, wherein the methyl methacrylate accounts for 60-90% of the total mass of the monomers, the butyl acrylate accounts for 5-30% of the total mass of the monomers, the methacrylic acid accounts for 0.5-6% of the total mass of the monomers, and the vinyl triethoxysilane accounts for 0.5-6% of the total mass of the monomers.
2. The method of claim 1, wherein the dispersant is at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, ammonium polyacrylate, octylphenol polyoxyethylene, and polyethylene glycol.
3. The method for preparing a heat-resistant lithium battery separator according to claim 1, wherein the defoaming agent is at least one of silicone emulsion, a higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, and polyoxypropylene glycerol ether.
4. The method for preparing a heat-resistant lithium battery diaphragm as claimed in claim 1, wherein the wetting agent is at least one of fluorinated alkyl ethoxy alcohol ether, polyoxyethylene alkyl amide and fatty alcohol-polyoxyethylene ether.
5. The method of claim 1, wherein the surfactant is at least one of sodium allyloxy hydroxypropyl sulfonate, sodium hydroxypropyl methacrylate sulfonate, sodium hydroxymethyl sulfonate, sodium hydroxyethyl sulfonate, and sodium 4-hydroxyethyl piperazine ethanesulfonate.
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| CN109638203A (en) * | 2018-11-26 | 2019-04-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery separator |
| CN109411682B (en) * | 2018-12-11 | 2022-01-28 | 广东永邦新能源股份有限公司 | High-thermal-stability lithium battery diaphragm and preparation method thereof |
| CN111554880B (en) * | 2020-05-07 | 2023-02-28 | 珠海冠宇电池股份有限公司 | Negative plate, negative electrode slurry, preparation method of negative electrode slurry and battery |
| CN111554858B (en) * | 2020-05-15 | 2022-04-01 | 瑞固新能(上海)材料科技有限公司 | High-peel-strength ceramic slurry and ceramic coating diaphragm |
| CN113583532B (en) * | 2021-07-13 | 2022-05-27 | 珠海恩捷新材料科技有限公司 | High-temperature-resistant binder for ceramic diaphragm of lithium battery and preparation method of binder |
| CN113611984B (en) * | 2021-08-02 | 2022-11-18 | 江苏厚生新能源科技有限公司 | Coating slurry with low moisture, high temperature resistance and high peel strength and application thereof |
| CN113675532A (en) * | 2021-08-13 | 2021-11-19 | 东莞维科电池有限公司 | Diaphragm and preparation method and application thereof |
| CN113991250B (en) | 2021-10-28 | 2023-09-01 | 江苏厚生新能源科技有限公司 | High-heat-resistance high-peel strength coated diaphragm and preparation method thereof |
| CN114243208A (en) * | 2021-11-30 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Composite diaphragm, preparation method thereof and secondary battery |
| CN115000629B (en) * | 2022-06-09 | 2024-04-05 | 珠海冠宇电池股份有限公司 | Coating, separator comprising same and battery |
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