CN117878529A - Low-moisture high-heat-resistance ceramic coating diaphragm and preparation method thereof - Google Patents
Low-moisture high-heat-resistance ceramic coating diaphragm and preparation method thereof Download PDFInfo
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- CN117878529A CN117878529A CN202410283599.8A CN202410283599A CN117878529A CN 117878529 A CN117878529 A CN 117878529A CN 202410283599 A CN202410283599 A CN 202410283599A CN 117878529 A CN117878529 A CN 117878529A
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- boehmite
- ceramic coating
- silane
- binder
- diaphragm
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- 238000005524 ceramic coating Methods 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 21
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 61
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011230 binding agent Substances 0.000 claims abstract description 54
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 53
- -1 silane modified boehmite Chemical class 0.000 claims abstract description 48
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 41
- 229910000077 silane Inorganic materials 0.000 claims abstract description 35
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 32
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 30
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 30
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 27
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 11
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- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- AXNJHBYHBDPTQF-UHFFFAOYSA-N trimethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OC)(OC)OC AXNJHBYHBDPTQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
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- 238000010521 absorption reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- Cell Separators (AREA)
Abstract
The invention discloses a low-moisture high-heat-resistance ceramic coating diaphragm and a preparation method thereof, wherein the coating diaphragm comprises a diaphragm base film and a coating coated on the base film, and the coating is formed by drying after being coated by ceramic coating slurry; the ceramic coating slurry comprises the following components: the modified boehmite comprises silane modified boehmite, a binder A, a binder B, a thickener, a dispersing agent and a wetting agent; the content of each component is calculated by mass parts, and the silane modified boehmite: binder a: binder B: and (3) a thickening agent: dispersant = 100: (3-8): (0.3 to 0.8): (0.2-1): (0.5-2), wherein the content of the wetting agent is 0.1-0.5% of the total mass of the ceramic coating slurry. According to the invention, long-chain silane coupling agent and short-chain double bond-containing silane coupling agent are adopted in ceramic coating slurry to blend and modify boehmite and alkyl modified hydrophobic sodium carboxymethyl cellulose, and the hydrophobic effect of the boehmite and sodium carboxymethyl cellulose is enhanced by utilizing the hydrophobic effect of alkyl, so that the water content of the ceramic coating diaphragm is reduced, and the heat resistance of the ceramic coating diaphragm is improved.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a low-moisture high-heat-resistance ceramic coating diaphragm and a preparation method thereof.
Background
With the development of new energy industry, lithium batteries, which are the main stream sites in the fields of energy storage and power batteries, are also becoming more and more widely used. Meanwhile, the requirements for the safety performance of lithium batteries are continuously increasing.
The diaphragm is used as an important component of the lithium battery, plays an important role in isolating the anode and the cathode, and has a great influence on the safety performance of the lithium battery. The single polyolefin film has the defects of low melting point, large thermal shrinkage and the like due to the inherent characteristics of the material, and is easy to cause short circuit after being heated, so that the safety performance of the battery is affected. Therefore, it is an effective technical path to coat the surface of the polyolefin separator with a layer of ceramic particles. However, porous ceramic coatings increase the moisture content of the separator and may cause problems with gas expansion, reduced cycle life, etc. when applied to a cell. Therefore, it is important to find a ceramic coating having both low heat shrinkage and low moisture content properties.
Disclosure of Invention
The invention provides a low-moisture high-heat-resistance ceramic coated diaphragm and a preparation method thereof, which are used for solving the problem of gas expansion caused by high moisture and the problem of battery short circuit caused by high heat shrinkage in a battery and ensuring the safety performance of the battery.
The invention is realized by the following technical scheme.
In one aspect, a low moisture, high heat resistant ceramic coated separator comprises: a separator base film and a coating applied to the base film.
The moisture content of the ceramic coating diaphragm is less than 500ppm, and the heat shrinkage rate after baking for 1h at 150 ℃ is less than 2%.
The separator base film includes, but is not limited to, polypropylene (PP) separator, polyethylene (PE) separator, and polypropylene/polyethylene (PP/PE) composite separator.
The thickness of the diaphragm base film is 7-25 mu m.
The thickness of the ceramic coating is 2-4 mu m.
The ceramic coating consists of ceramic coating slurry;
the ceramic coating slurry comprises the following components: the modified boehmite comprises silane modified boehmite, a binder A, a binder B, a thickener, a dispersing agent and a wetting agent. The usage amount of each component is calculated according to mass parts, and the silane modified boehmite: binder a: binder B: and (3) a thickening agent: dispersant = 100: (3-8): (0.3 to 0.8): (0.2-1): (0.5-2);
preferably, the silane modified boehmite is as follows: binder a: binder B: and (3) a thickening agent: dispersant=100, (4-6): 0.4-0.6): 0.3-0.6): 0.8-1.2;
further, the content of the wetting agent is 0.1-0.5%, preferably 0.2-0.4% of the total mass of the ceramic coating slurry.
The silane modified boehmite is obtained by blending and modifying a long-chain silane coupling agent and a short-chain double bond-containing silane coupling agent.
The long-chain silane coupling agent is one or more of dodecyl trimethoxy silane, n-octyl triethoxy silane, tetradecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl trimethoxy silane;
the short-chain double-bond-containing silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane and vinyl tri (beta-methoxyethoxy) silane.
The ratio of the long-chain silane coupling agent to the short-chain double bond-containing silane coupling agent is 1:1.
The particle size of the silane modified boehmite is 0.5-2 mu m.
The adhesive A is a polyacrylate emulsion adhesive with higher molecular weight, and is mainly formed by copolymerizing two or more monomers of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile and the like, wherein the molecular weight is 500000-800000, the solid content is 40-50%, the viscosity is 1000-3000 cps, and T is the same as that of the adhesive A g Is 5-20 ℃.
The binder B is a water-soluble binder with smaller molecular weight, the main component of the binder B is one of polyacrylic acid, polyvinyl alcohol, amino resin and phenolic resin, the molecular weight of the binder B is 1000-5000,the solid content is 40-50%, the viscosity is 200-1000 cps, T g Is at the temperature of minus 30 to minus 10 ℃.
The thickener refers to alkyl hydrophobically modified sodium carboxymethyl cellulose.
The alkyl hydrophobically modified sodium carboxymethyl cellulose has a side chain alkyl group with 10-20 carbon atoms, preferably 12-15 carbon atoms, because the hydrophobic effect is not obvious when the number of carbon atoms on the side chain alkyl group is too low, and the solubility and the stability in solution of sodium carboxymethyl cellulose are affected when the number of carbon atoms is too high.
The hydrophobically modified sodium carboxymethyl cellulose has a molecular weight of 50000-200000,2% and an aqueous solution viscosity of 7000-10000 cps because when the molecular weight and viscosity are too small, the content of sodium carboxymethyl cellulose required to perform the same function increases, which is disadvantageous in lowering the water content; when the molecular weight and viscosity are too large, the stabilizing effect of sodium carboxymethyl cellulose on the ceramic coating paste is weakened, thereby causing agglomeration and sedimentation phenomena to occur.
The dispersing agent is one or two of ammonium polycarboxylate, ammonium polyacrylate, sodium dodecyl sulfate and polystyrene-b-polyacrylic acid, and is preferably styrene-b-polyacrylic acid.
The wetting agent is a polyhydric alcohol type small molecule organic matter, specifically one or two of ethanol, n-butanol, glycerol, methanol, propanol and isopropanol, and preferably ethanol.
The polyol small molecular organic matters play a role in wetting, and can be mutually dissolved with water so as to reduce the boiling point of water, so that the water is more easily volatilized from the coating, and the water content of the coating is reduced.
In another aspect, a method for preparing a low moisture, high heat resistant ceramic coated separator comprises the steps of:
step one: preparation of silane-modified boehmite
The method comprises the steps of blending and dissolving a long-chain silane coupling agent and a short-chain double bond-containing silane coupling agent in ethanol, adding boehmite, and stirring at a rotating speed of 400-600 rpm for 10-20 min until the boehmite is uniformly dispersed, wherein the dosage ratio of the boehmite, the long-chain silane coupling agent and the short-chain double bond-containing silane coupling agent is 100: (0.5-2): (0.5-2); then, placing the uniformly dispersed boehmite slurry in a condition of 60-80 ℃ for heat preservation for 20-50 min, then heating to 130-160 ℃ for heat preservation for 10-30 min, filtering and drying to obtain silane modified boehmite;
step two: preparation of alkyl hydrophobically modified sodium carboxymethyl cellulose
Firstly, adding sodium carboxymethyl cellulose into n-heptane, stirring for 20-40 min to uniformly disperse the sodium carboxymethyl cellulose in the n-heptane, and then adding acyl chloride containing 10-18 alkyl groups, wherein the mass ratio of the sodium carboxymethyl cellulose to the acyl chloride is 1: (0.2 to 0.6); then, reacting for 4-8 hours at the temperature of 40-80 ℃, and finally filtering and drying the obtained product to obtain the alkyl modified sodium carboxymethyl cellulose;
step three: preparation of ceramic coating slurries
Firstly, mixing silane modified boehmite obtained in the first step with a thickener (alkyl hydrophobic modified sodium carboxymethyl cellulose) obtained in the second step, a dispersing agent and water, stirring at a rotation speed of 400-600 rpm for 5-10 min, then sequentially adding a binder A, a binder B and a wetting agent, dispersing at a rotation speed of 800-1200 rpm for 20-40 min, and finally stirring at a rotation speed of 100-200 rpm for 10-20 min to obtain uniform foam-free ceramic coating slurry;
wherein the content of the silane modified boehmite, the binder A, the binder B, the thickener and the dispersant is 100 mass percent: (3-8): (0.3 to 0.8): (0.2-1): (0.5-2), preferably 100, (4-6): (0.4-0.6): (0.3-0.6): (0.8-1.2), the content of wetting agent being 0.1-0.5%, preferably 0.2-0.4% of the total mass of the ceramic coating slurry;
the solid content of the obtained ceramic coating slurry is 30-40%, and the viscosity is 30-80 cps;
step four: preparation of ceramic coated separator
And (3) uniformly coating the ceramic coating slurry obtained in the step (III) on the surface of the diaphragm, and baking for 2-5 min at the temperature of 70-120 ℃ to obtain the ceramic coating diaphragm.
The invention has the beneficial effects that:
(1) The ceramic coating diaphragm prepared based on the silane modified boehmite slurry has lower water content, the water content is less than 500ppm and is far lower than the conventional 1000 ppm on the market, the requirement of low water content required by a lithium battery can be well met, and the problems of expansion and the like caused by the excessively high water content of the battery are effectively prevented; in addition, the ceramic coated diaphragm has lower heat shrinkage rate, the heat shrinkage rate is lower than 2% under the condition of 150 ℃/1/h, and the problem of short circuit of the battery caused by shrinkage of the high-temperature diaphragm can be effectively avoided.
(2) As a component of the coating layer in an amount exceeding 90%, the water absorption capacity of boehmite plays an important role in the water content of the whole ceramic-coated separator; according to the invention, the long-chain silane coupling agent and the short-chain double bond-containing silane coupling agent are grafted to the boehmite, so that the hydroxyl groups on the surface of part of the boehmite can be consumed, and the alkyl grafted to the surface of the boehmite has a hydrophobic effect, so that the hydrophobic effect of the boehmite is enhanced, the water absorption capacity of the boehmite is weakened, and the water content of the ceramic coating diaphragm is reduced. In addition, the presence of long-chain alkyl can improve the dispersing capability of boehmite, the presence of double bonds can enhance the combining capability of boehmite, a thickener and a binder, and the two can jointly act to obtain more uniform silane modified boehmite slurry, so that the uniformity and heat resistance of the ceramic coating diaphragm coating are improved.
(3) The conventional sodium carboxymethyl cellulose has a strong water absorption capacity, and when used as a thickener for ceramic coating slurry, remains in the coating layer to absorb water, resulting in a diaphragm having a large water content. According to the invention, alkyl modified hydrophobic sodium carboxymethyl cellulose is used as a thickener instead of traditional sodium carboxymethyl cellulose, so that the viscosity of ceramic slurry is regulated, a ceramic slurry dispersion system is stabilized, and the water absorption capacity of sodium carboxymethyl cellulose is weakened, thereby reducing the water content of the ceramic coated diaphragm.
(4) The invention adopts the bi-component adhesive, which can improve the adhesive force and the heat shrinkage performance of the ceramic coating diaphragm while keeping the water content not to increase. In the invention, the binder A is a polyacrylate emulsion type binder and plays a role of a framework of serial boehmite particlesActs on, and bonds the boehmite to, the membrane base film. In addition, binder A has a relatively high molecular weight and T g The temperature can maintain the stability of the ceramic coating diaphragm coating and the adhesive force with the diaphragm base film at a higher temperature, so that the ceramic coating diaphragm coating has better heat resistance. The adhesive B is a water-soluble adhesive, can penetrate into all corners of the ceramic coating diaphragm coating, is combined with unreacted double bonds on silane modified boehmite, alkyl hydrophobic modified sodium carboxymethyl cellulose and polyacrylate emulsion adhesive to generate firmer chemical bonds, and enhances the bonding force between each component of the coating and between the coating and the diaphragm substrate, thereby obviously enhancing the heat shrinkage performance of the ceramic coating diaphragm.
Detailed Description
The invention will be further illustrated with reference to specific examples.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
Step one: preparation of silane-modified boehmite
Mixing and dissolving dodecyl trimethoxy silane and vinyl trimethoxy silane in ethanol, then adding boehmite, and stirring at a rotating speed of 500 rpm for 15 min until the boehmite is uniformly dispersed, wherein the mass ratio of the boehmite to the dodecyl trimethoxy silane to the vinyl trimethoxy silane is 100:0.5:0.5. and (3) placing the uniformly dispersed boehmite slurry into a reaction kettle for heat preservation at 70 ℃ for 40 min, then heating to 140 ℃ for heat preservation for 20 min, filtering and drying to obtain the silane modified boehmite.
Step two: preparation of alkyl hydrophobically modified sodium carboxymethyl cellulose
Adding sodium carboxymethyl cellulose into n-heptane, stirring for 30 min to uniformly disperse the sodium carboxymethyl cellulose in the n-heptane, and then adding tetradecyl chloride, wherein the mass ratio of the sodium carboxymethyl cellulose to the acyl chloride is 1:0.4. then, reacting at 60 ℃ for 6 h, and finally filtering and drying the obtained product to obtain the alkyl modified sodium carboxymethyl cellulose.
Step three: preparation of ceramic coating slurries
Mixing the silane modified boehmite obtained in the first step, the styrene-B-polyacrylic acid and the alkyl hydrophobic modified sodium carboxymethyl cellulose obtained in the second step with water, stirring for 8 min at a rotation speed of 500 rpm, sequentially adding a binder A (ethyl acrylate-methyl methacrylate copolymer emulsion type binder), a binder B (polyacrylic acid water-soluble binder) and a wetting agent (ethanol), dispersing at a high speed of 1000 rpm for 30 min, and stirring for 15 min at a rotation speed of 150 rpm to obtain the uniform foam-free ceramic coating slurry. Wherein the content of the silane modified boehmite, the ethyl acrylate-methyl methacrylate copolymer emulsion binder, the polyacrylic acid water-soluble binder, the alkyl hydrophobically modified sodium carboxymethyl cellulose and the styrene-b-polyacrylic acid is 100:3:0.3:0.2:0.5, the content of ethanol is 0.3% of the total mass of the ceramic coating slurry, and the solid content of the obtained ceramic coating slurry is 30%.
Step four: preparation of ceramic coated separator
And (3) uniformly coating the ceramic coating slurry obtained in the step (III) on the surface of a Polyethylene (PE) diaphragm, and baking for 2 min at 70 ℃ to obtain the ceramic coating diaphragm. The thickness of the membrane base film was 9 μm and the thickness of the ceramic coating was 3 μm.
Example 2
The following changes were made in step one on the basis of example 1:
the dosage ratio of boehmite, dodecyl trimethoxy silane and vinyl trimethoxy silane is adjusted to be 100 according to the parts by weight: 1.0:1.0; the remaining steps remain unchanged.
Example 3
The following changes were made in step one on the basis of example 1:
the dosage ratio of boehmite, dodecyl trimethoxy silane and vinyl trimethoxy silane is adjusted to be 100 in parts by mass: 2.0:2.0; the remaining steps remain unchanged.
Example 4
The following changes were made in step three on the basis of example 2:
the dosage proportion of the silane modified boehmite, the ethyl acrylate-methyl methacrylate copolymer emulsion type binder, the polyacrylic acid water-soluble binder, the alkyl hydrophobically modified sodium carboxymethyl cellulose and the styrene-b-polyacrylic acid is adjusted to be 100 according to the mass parts: 5:0.5:0.5:1.0, wherein the content of ethanol is 0.3% of the total mass of the ceramic coating slurry, and the solid content of the obtained ceramic coating slurry is 35%; the remaining steps remain unchanged.
Example 5
The following changes were made in step three on the basis of example 2:
the dosage proportion of the silane modified boehmite, the ethyl acrylate-methyl methacrylate copolymer emulsion type binder, the polyacrylic acid water-soluble binder, the alkyl hydrophobically modified sodium carboxymethyl cellulose and the styrene-b-polyacrylic acid is adjusted to be 100 according to the mass parts: 8:0.8:1:2, the content of ethanol is 0.3% of the total mass of the ceramic coating slurry, and the solid content of the obtained ceramic coating slurry is 40%; the remaining steps remain unchanged.
Example 6
The following changes were made in step four on the basis of example 4:
adjusting the thickness of the ceramic coating to be 4 mu m; the baking temperature is 120 ℃, the baking time is 5min, and the rest steps are kept unchanged.
Example 7
The following changes were made in step four on the basis of example 6:
the diaphragm base material is regulated to be polypropylene (PP); the remaining steps remain unchanged.
Example 8
The following changes were made in step three on the basis of example 4:
the adhesive A (ethyl acrylate-methyl methacrylate copolymer emulsion adhesive) is adjusted to be methyl acrylate-isooctyl acrylate copolymer emulsion adhesive, and the adhesive B (polyacrylic acid water-soluble adhesive) is adjusted to be amino resin water-soluble adhesive; the remaining steps remain unchanged.
Example 9
Step one: preparation of silane-modified boehmite
Mixing and dissolving dodecyl trimethoxy silane and vinyl trimethoxy silane in ethanol, then adding boehmite, and stirring at 400 rpm for 20 min until the boehmite is uniformly dispersed, wherein the mass ratio of the boehmite to the dodecyl trimethoxy silane to the vinyl trimethoxy silane is 100:1.0:1.0. and (3) placing the uniformly dispersed boehmite slurry into a heat-preserving reaction at 60 ℃ for 50 min, then heating to 130 ℃ for heat-preserving reaction for 30 min, filtering and drying to obtain the silane modified boehmite.
Step two: preparation of alkyl hydrophobically modified sodium carboxymethyl cellulose
Adding sodium carboxymethyl cellulose into n-heptane, stirring for 20 min to uniformly disperse the sodium carboxymethyl cellulose in the n-heptane, and then adding tetradecyl chloride, wherein the mass ratio of the sodium carboxymethyl cellulose to the acyl chloride is 1:0.2. then, reacting at 40 ℃ for 4 h, and finally filtering and drying the obtained product to obtain the alkyl modified sodium carboxymethyl cellulose.
Step three: preparation of ceramic coating slurries
Mixing the silane modified boehmite obtained in the first step, the styrene-B-polyacrylic acid and the alkyl hydrophobic modified sodium carboxymethyl cellulose obtained in the second step with water, stirring for 10 min at a rotation speed of 400 rpm, sequentially adding a binder A (ethyl acrylate-methyl methacrylate copolymer emulsion type binder), a binder B (polyacrylic acid water-soluble binder) and a wetting agent (ethanol), dispersing at a high speed of 800 rpm for 40 min, and stirring for 20 min at a rotation speed of 100 rpm to obtain the uniform foam-free ceramic coating slurry. Wherein the content of the silane modified boehmite, the ethyl acrylate-methyl methacrylate copolymer emulsion binder, the polyacrylic acid water-soluble binder, the alkyl hydrophobically modified sodium carboxymethyl cellulose and the styrene-b-polyacrylic acid is 100:5:0.5:0.5:1.0, the ethanol content is 0.1% of the total mass of the ceramic coating slurry, and the solid content of the obtained ceramic coating slurry is 36%.
Step four: preparation of ceramic coated separator
And (3) uniformly coating the ceramic coating slurry obtained in the step (III) on the surface of a Polyethylene (PE) diaphragm, and baking for 2 min at 70 ℃ to obtain the ceramic coating diaphragm. The thickness of the membrane base film was 9 μm and the thickness of the ceramic coating was 2 μm.
Example 10
Step one: preparation of silane-modified boehmite
Mixing and dissolving dodecyl trimethoxy silane and vinyl trimethoxy silane in ethanol, then adding boehmite, and stirring at 600 rpm for 10 min until the boehmite is uniformly dispersed, wherein the mass ratio of the boehmite to the dodecyl trimethoxy silane to the vinyl trimethoxy silane is 100:1.0:1.0. and (3) placing the uniformly dispersed boehmite slurry into a heat-preserving reaction at 80 ℃ for 20 min, then heating to 160 ℃ for heat-preserving reaction for 10 min, filtering and drying to obtain the silane modified boehmite.
Step two: preparation of alkyl hydrophobically modified sodium carboxymethyl cellulose
Adding sodium carboxymethyl cellulose into n-heptane, stirring for 40 min to uniformly disperse the sodium carboxymethyl cellulose in the n-heptane, and then adding tetradecyl chloride, wherein the mass ratio of the sodium carboxymethyl cellulose to the acyl chloride is 1:0.6. then, reacting 8h at 80 ℃, and finally filtering and drying the obtained product to obtain the alkyl modified sodium carboxymethyl cellulose.
Step three: preparation of ceramic coating slurries
Mixing the silane modified boehmite obtained in the first step, the styrene-B-polyacrylic acid and the alkyl hydrophobic modified sodium carboxymethyl cellulose obtained in the second step with water, stirring for 5min at a rotation speed of 600 rpm, sequentially adding a binder A (ethyl acrylate-methyl methacrylate copolymer emulsion type binder), a binder B (polyacrylic acid water-soluble binder) and a wetting agent (ethanol), dispersing at a high speed of 1200 rpm for 20 min, and stirring for 20 min at a rotation speed of 100 rpm to obtain the uniform foam-free ceramic coating slurry. Wherein the content of the silane modified boehmite, the ethyl acrylate-methyl methacrylate copolymer emulsion binder, the polyacrylic acid water-soluble binder, the alkyl hydrophobically modified sodium carboxymethyl cellulose and the styrene-b-polyacrylic acid is 100:5:0.5:0.5:1.0, the ethanol content is 0.5% of the total mass of the ceramic coating slurry, and the solid content of the obtained ceramic coating slurry is 38%.
Step four: preparation of ceramic coated separator
And (3) uniformly coating the ceramic coating slurry obtained in the step (III) on the surface of a Polyethylene (PE) diaphragm, and baking for 5min at 120 ℃ to obtain the ceramic coating diaphragm. The thickness of the membrane base film was 9 μm and the thickness of the ceramic coating was 4 μm.
Comparative example 1
The silane-modified boehmite was converted to regular boehmite on the basis of example 4, with the other steps remaining unchanged.
Comparative example 2
The alkyl hydrophobically modified sodium carboxymethyl cellulose was changed to sodium carboxymethyl cellulose on the basis of example 4, the other steps remaining unchanged.
Comparative example 3
The silane modified boehmite was changed to regular boehmite and the alkyl hydrophobically modified sodium carboxymethyl cellulose was changed to sodium carboxymethyl cellulose on the basis of example 4, and the other steps remained unchanged.
Comparative example 4
The silane modified boehmite was changed to normal boehmite on the basis of example 4, and the alkyl hydrophobically modified sodium carboxymethyl cellulose was changed to sodium carboxymethyl cellulose, and the two-component binder composed of the ethyl acrylate-methyl methacrylate copolymer emulsion binder and the polyacrylic acid water-soluble binder was changed to the ethyl acrylate-methyl methacrylate copolymer emulsion binder, and the other steps were kept unchanged.
The properties of the ceramic coated separator obtained in examples and comparative examples were evaluated as follows:
peel force test: the test is carried out according to the method in national standard GB/T2792-2014 adhesive tape peel strength, and a universal material tester is adopted as an instrument.
Heat shrinkage test: the thermal shrinkage rate is tested according to the testing method in national standard GB/T-36363-2018 polyolefin diaphragm for lithium ion batteries, and an instrument adopts a blast oven.
And (3) water content testing: and testing by adopting a Karl Fischer moisture tester.
The results of each performance test are shown in Table 1.
Table 1 test results for examples 1 to 10 and comparative examples 1 to 4
Examples 1-3 examined the effect of the amount ratios of different boehmite, dodecyl trimethoxy silane and vinyl trimethoxy silane on the performance of the coated membrane, found that as the content of the long-chain silane coupling agent on the boehmite increases, the water content of the ceramic coated membrane gradually decreases, but the decrease degree gradually slows down, which illustrates that the presence of long-chain alkyl groups on the silane coupling agent can reduce the water absorption capacity of the boehmite, but the influence factors of the water content of the coated membrane are numerous, and the use of alkyl modified boehmite alone has a limit on the decrease of the water content of the coated membrane and should be combined with other methods.
In example 2 and example 4 and example 5, the influence of the dosage proportion of different silane modified boehmite, ethyl acrylate-methyl methacrylate copolymer emulsion type binders, polyacrylic acid water-soluble binders, alkyl hydrophobically modified sodium carboxymethyl cellulose and styrene-b-polyacrylic acid on the performance of a coating diaphragm is examined, and it is found that as the content of the alkyl hydrophobically modified sodium carboxymethyl cellulose increases, the thermal shrinkage of the ceramic coating diaphragm gradually decreases, but the water content also gradually increases, which indicates that the dosage of the alkyl hydrophobically modified sodium carboxymethyl cellulose is critical, because the sodium carboxymethyl cellulose itself has strong water absorption capacity, and remains in the coating to absorb water, so that the diaphragm water content is larger, and the alkyl hydrophobically modified sodium carboxymethyl cellulose is adopted to replace the traditional sodium carboxymethyl cellulose as a thickener, so that the water absorption capacity of the sodium carboxymethyl cellulose can be weakened while the viscosity of ceramic slurry is regulated, the dispersion system of the ceramic slurry is stabilized, and the water content of the ceramic coating diaphragm is reduced, but the dosage is still not too large.
Example 4 and examples 6 and 7 examined the properties of ceramic coated membranes of different coating thicknesses and different substrates, and found that as the thickness increased, the heat resistance of the coated membrane increased, but the water content also increased, mainly because the increase in coating thickness necessarily increased the binding effect of the coating on the base membrane, and also increased the water-absorbing substance content in the coating, resulting in a simultaneous increase in the heat resistance and water content of the coated membrane. Furthermore, it was found from comparative examples 6 and 7 that the adhesion of the coating to the PE separator was better than that of the PP separator, mainly due to the difference in the surface characteristics of the PE and PP separators.
Example 4 was compared with comparative examples 1 to 4, and found that the water content and heat shrinkage of the ceramic coated separator obtained in the present invention were significantly smaller, indicating that the water content and heat shrinkage of the ceramic coated separator could be reduced by using silane-modified boehmite, alkyl-hydrophobically modified sodium carboxymethyl cellulose, and using a combination of an aqueous emulsion-type binder and an aqueous solution-type binder. In particular, the water content of example 4 was significantly reduced as compared to comparative example 1, indicating that the use of boehmite modified with a long-chain silane coupling agent as a main component of the coating slurry can reduce the water content of the ceramic coated separator, since the long-chain silane coupling agent and the short-chain double bond-containing silane coupling agent are grafted to boehmite, hydroxyl groups on a part of the boehmite surface can be consumed, and alkyl groups grafted to the boehmite surface have a hydrophobic effect, thereby enhancing the hydrophobic effect of boehmite, weakening the water absorbing ability of boehmite, and thus reducing the water content of the ceramic coated separator. On the other hand, the presence of long-chain alkyl can improve the dispersing capability of boehmite, the presence of double bonds can enhance the combining capability of boehmite, a thickener and a binder, and the two can jointly act to obtain more uniform silane modified boehmite slurry, so that the uniformity and heat resistance of the ceramic coating diaphragm coating are improved. Furthermore, the lower water content of example 4 compared to comparative example 2 also demonstrates that the use of alkyl hydrophobically modified sodium carboxymethyl cellulose as a thickener can significantly reduce the water content of ceramic coated membranes. In contrast, as compared with comparative example 4, it is apparent that the addition of the solution-type binder can significantly increase the adhesion between the coating layer and the separator substrate, and reduce the thermal shrinkage of the ceramic-coated separator, thereby improving the heat resistance of the ceramic-coated separator.
Claims (10)
1. The low-moisture high-heat-resistance ceramic coating diaphragm consists of a diaphragm base film and a coating coated on the base film, and is characterized in that the base film is a PP diaphragm, a PE diaphragm or a PP/PE composite diaphragm;
the coating is formed by drying after being coated by ceramic coating slurry;
the ceramic coating slurry comprises the following components: silane modified boehmite, a binder A, a binder B, a thickener, a dispersant and a wetting agent; the content of each component is calculated by mass parts, and the silane modified boehmite: binder a: binder B: and (3) a thickening agent: dispersant = 100: (3-8): (0.3 to 0.8): (0.2-1): (0.5-2); the content of the wetting agent is 0.1-0.5% of the total mass of the ceramic coating slurry;
the thickener is alkyl hydrophobically modified sodium carboxymethyl cellulose;
the silane modified boehmite is prepared by the following method: dissolving a silane coupling agent in ethanol, adding boehmite, and stirring at a rotating speed of 400-600 rpm for 10-20 min until the boehmite is uniformly dispersed, wherein the dosage ratio of the boehmite to the silane coupling agent is 100: (1.0-4); and then, placing the uniformly dispersed boehmite slurry in a condition of 60-80 ℃ for heat preservation for 20-50 min, then heating to 130-160 ℃ for heat preservation for 10-30 min, filtering and drying to obtain the boehmite.
2. The low-moisture high-heat-resistant ceramic coated membrane according to claim 1, wherein the alkyl hydrophobically modified sodium carboxymethyl cellulose has a molecular weight of 50000-200000, a side chain alkyl group having 10-20 carbon atoms in its structure, and a 2% aqueous solution viscosity of 7000-10000 cps.
3. The low-moisture high-heat-resistant ceramic coated membrane according to claim 1, wherein the silane coupling agent is obtained by blending a long-chain silane coupling agent and a short-chain silane coupling agent containing double bonds.
4. A low moisture, high heat resistant ceramic coated separator according to claim 3, wherein the long chain silane coupling agent is one or more of dodecyl trimethoxy silane, n-octyl triethoxy silane, tetradecyl trimethoxy silane, hexadecyl trimethoxy silane, and octadecyl trimethoxy silane; the short-chain double-bond-containing silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane and vinyl tri (beta-methoxyethoxy) silane.
5. The low-moisture high-heat-resistance ceramic coated membrane according to claim 3, wherein the ratio of the long-chain silane coupling agent to the short-chain double-bond-containing silane coupling agent is 1:1 by mass.
6. The low-moisture high-heat-resistant ceramic coated separator according to claim 1, wherein the binder A is a polyacrylate emulsion type binder having a molecular weight of 500000-800000, a solid content of 40-50%, a viscosity of 1000-3000 cps, and T g 5-20 ℃; is prepared by copolymerizing two or more monomers of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, styrene and acrylonitrile.
7. The low-moisture high-heat-resistant ceramic coated membrane according to claim 1, wherein the binder B is a water-soluble binder with a molecular weight of 1000-5000, and comprises one of polyacrylic acid, polyvinyl alcohol, amino resin and phenolic resin, and has a solid content of 40-50%, a viscosity of 200-1000 cps, and T g Is at the temperature of minus 30 to minus 10 ℃.
8. The low-moisture high-heat-resistant ceramic coated separator according to claim 1, wherein the dispersant is one or two of ammonium polycarboxylate, ammonium polyacrylate, sodium dodecyl sulfate and polystyrene-b-polyacrylic acid; the wetting agent is one or two of ethanol, n-butanol, glycerol, methanol, propanol and isopropanol.
9. The method for producing a low-moisture high-heat-resistant ceramic coated separator according to any one of claims 1 to 8, comprising the steps of:
(1) Step one, preparing silane modified boehmite:
the method comprises the steps of blending and dissolving a long-chain silane coupling agent and a short-chain double bond-containing silane coupling agent in ethanol, adding boehmite, and stirring at a rotating speed of 400-600 rpm for 10-20 min until the boehmite is uniformly dispersed, wherein the dosage ratio of the boehmite, the long-chain silane coupling agent and the short-chain double bond-containing silane coupling agent is 100: (0.5-2): (0.5-2); then, placing the uniformly dispersed boehmite slurry in a condition of 60-80 ℃ for heat preservation for 20-50 min, then heating to 130-160 ℃ for heat preservation for 10-30 min, filtering and drying to obtain silane modified boehmite;
(2) Step two, preparing alkyl hydrophobically modified sodium carboxymethyl cellulose:
firstly, adding sodium carboxymethyl cellulose into n-heptane, stirring for 20-40 min to uniformly disperse the sodium carboxymethyl cellulose in the n-heptane, and then adding acyl chloride containing 10-18 alkyl groups, wherein the mass ratio of the sodium carboxymethyl cellulose to the acyl chloride is 1: (0.2 to 0.6); then, reacting for 4-8 hours at the temperature of 40-80 ℃, and finally filtering and drying the obtained product to obtain the alkyl modified sodium carboxymethyl cellulose;
(3) Step three, preparing ceramic coating slurry:
according to the content of the silane modified boehmite, the binder A, the binder B, the thickener and the dispersant, the mass ratio is 100: (3-8): (0.3 to 0.8): (0.2-1): (0.5-2), firstly mixing silane modified boehmite obtained in the first step with alkyl hydrophobic modified sodium carboxymethyl cellulose obtained in the second step, a dispersing agent and water, stirring at a rotation speed of 400-600 rpm for 5-10 min, then sequentially adding a binder A, a binder B and a wetting agent, dispersing at a rotation speed of 800-1200 rpm for 20-40 min, and finally stirring at a rotation speed of 100-200 rpm for 10-20 min to obtain uniform foam-free ceramic coating slurry; the content of the wetting agent is 0.1-0.5% of the total mass of the ceramic coating slurry, the solid content of the obtained ceramic coating slurry is 30-40%, and the viscosity of the obtained ceramic coating slurry is 30-80 cps;
(4) Step four, preparing a ceramic coating diaphragm:
and (3) uniformly coating the ceramic coating slurry obtained in the step (III) on the surface of the diaphragm, and baking for 2-5 min at 70-120 ℃ to obtain the ceramic coating diaphragm.
10. The method for preparing the low-moisture high-heat-resistance ceramic coated membrane according to claim 9, wherein the thickness of the ceramic coating of the ceramic coated membrane is 2-4 μm; the water content of the ceramic coating diaphragm is less than 500ppm, and the heat shrinkage rate after baking at 150 ℃ for 1h is less than 2%.
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