CN112290161B - Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof - Google Patents
Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 7
- 238000005524 ceramic coating Methods 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 238000007385 chemical modification Methods 0.000 claims abstract description 5
- 150000003254 radicals Chemical class 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 claims description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 claims description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001482 poly(N-isopropylacrylamide) copolymer Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000153 supplemental effect Effects 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012528 membrane Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses an ultralow-moisture ceramic coated lithium ion battery diaphragm and a preparation method thereof, wherein at least one surface of a base film is provided with a modified nano inorganic ceramic coating layer, and the coating layer comprises a chemical modified coated nano inorganic ceramic particle dispersion liquid, self-crosslinking aqueous polymer glue, an auxiliary agent, a film forming auxiliary agent and a solvent; the chemical modification coating nano inorganic ceramic particle dispersion liquid comprises inorganic ceramic particles, an organosilane coupling agent containing double bonds, a free radical polymerizable hydrophobic monomer containing double bonds and an initiator. The battery diaphragm has the characteristics of non-hydrophilic water retention, low water content, non-moisture regain, strong coating cohesiveness and excellent heat resistance. The modification method of the ultralow-moisture ceramic coated lithium ion battery diaphragm is reliable, the coating mode is simple, and the diaphragm is convenient for large-scale continuous production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an ultralow-moisture ceramic-coated lithium ion battery diaphragm and a preparation method thereof.
Background
The safety of lithium battery systems is the most important issue for electric car power systems, while the separator is one of the short plates that support the "barrel effect" of the overall battery system. Therefore, from the viewpoint of safety and adapting to the high energy density power battery, the coated separator is gradually the first choice for the separator for the power battery at the present stage. The current coating materials are mainly organic materials and inorganic materials. The inorganic material is usually alumina, silica-based ceramics, boehmite, barium sulfate, mica powder, or the like. The organic materials are mostly of polyvinylidene fluoride (PVDF) type, and among them, aqueous PVDF and oily PVDF type coated separators are also classified, and Polyimide (PI), polyethylene terephthalate (PET) and the like are also known.
With the rising of the membrane coating industry at home and abroad, the ceramic coating membrane has wide application in recent years and has an increasing duty ratio year by year, and the ceramic coating membrane has excellent heat resistance and can meet the heat resistance requirement of the battery at 130 ℃. However, ceramic coating diaphragms generally have the problems of high moisture content, difficult water removal, gas expansion when applied to a battery core, low initial capacity of the battery and shortened cycle life, and need improvement; particularly, with the improvement of the energy density of the battery, the positive electrode adopts a high-nickel ternary material which is very sensitive to moisture, and a ceramic diaphragm with high water content cannot be matched with the high-nickel ternary material, so that the high-nickel ternary material becomes a road blocking stone which hinders the application of the high-capacity ternary positive electrode material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an ultralow-moisture ceramic coated lithium ion battery diaphragm and a preparation method thereof. The modification method is reliable, the coating mode is simple, and the large-scale continuous production is convenient.
The invention adopts the following technical scheme:
an ultralow-moisture ceramic coated lithium ion battery diaphragm, wherein at least one surface of a base film is provided with a modified nano inorganic ceramic coating layer, and the coating layer comprises chemical modified coated nano inorganic ceramic particle dispersion liquid, self-crosslinkable aqueous polymer glue, an auxiliary agent, a film forming auxiliary agent and a solvent; wherein, the chemical modification coating nano inorganic ceramic particle dispersion liquid accounts for 5 to 60 percent of the weight of the solvent; the self-crosslinking aqueous polymer glue accounts for 1-20% of the weight of the solvent.
The chemical modification coating nano inorganic ceramic particle dispersion liquid comprises inorganic ceramic particles, an organosilane coupling agent containing double bonds, a hydrophobic monomer containing double bonds and capable of free radical polymerization and an initiator;
the preparation method of the chemical modified coated nano inorganic ceramic particle dispersion liquid comprises the following steps:
mixing the inorganic ceramic particles A with an organosilane coupling agent containing double bonds, wherein the concentration of the organosilane coupling agent is 0.5-5%, uniformly dispersing the mixture by using a grinding process, adjusting the pH value to 3-5, maintaining the temperature to 30-80 ℃, and preserving the heat for 0.5-2 hours, grafting active double bonds on the surfaces of the inorganic ceramic particles, and consuming hydrophilic hydroxyl groups to obtain grafted and modified inorganic ceramic particles;
and B, adding a hydrophobic monomer containing double bonds and capable of free radical polymerization and an initiator, stirring and heating to 30-100 ℃, and performing polymerization reaction on the grafted and modified inorganic ceramic particles to form a hydrophobic shell, thereby obtaining the chemically modified coated nano inorganic ceramic particle dispersion liquid with a core-shell structure.
Specifically, a seed emulsion polymerization method is adopted to prepare core-shell emulsion (chemical modification coating nano inorganic ceramic particle dispersion liquid), seed emulsion (inorganic ceramic particles after grafting modification), shell monomer (hydrophobic monomer containing double bonds and capable of free radical polymerization) and initiator are added into a reactor, and then the temperature is raised to 30-100 ℃ for polymerization.
Wherein the dosage of the hydrophobic monomer is 0.5-5% of the solvent mass, and the dosage of the initiator is 0.01-1% of the solvent mass.
Further, the inorganic ceramic particles are one or more of aluminum oxide, silicon dioxide, magnesium hydroxide, zirconium dioxide, magnesium oxide and boehmite.
Still further, the self-crosslinkable aqueous polymer glue is one or more of carboxylated modified polyacrylate copolymer, polyacrylic acid-acrylonitrile-glycollic acid copolymer, carboxylated modified polyacrylamide, polyvinyl alcohol grafted poly-N-isopropyl acrylamide copolymer, citric acid grafted modified polyvinyl alcohol and the like; wherein the dosage of the self-crosslinkable aqueous polymer glue is 1-20% of the weight of the solvent.
Further, the film forming auxiliary agent is one or more of PVPK-17, PVPK-30, CMC-Na, PVA-1799 and EC cellulose; wherein the film forming additive is used in an amount of 0.5 to 5% by weight of the solvent.
Still further, the organic silane coupling agent containing double bonds is one or more of silane coupling agent A-150, silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172 and silane coupling agent KH-570.
Further, the double bond-containing free radical polymerizable hydrophobic monomer is one or more of butadiene, styrene, acrylonitrile, octadecyl acrylate, methyl methacrylate and 2-methyl propylene.
Still further, the initiator is one or more of BPO, BIBP, DTBP, TBPB and TBHP.
Further, the solvent is one or more of ethanol, isopropanol, dimethyl carbonate and deionized water.
Still further, the auxiliary agent is one or more of formic acid, acetic acid, oxalic acid, glycollic acid and citric acid. Wherein, the pH value in the step A can be regulated by using the auxiliary agents of the types.
The preparation method of the ultralow-moisture ceramic coated lithium ion battery diaphragm comprises the following steps:
1) Mixing the chemical modified coated nano inorganic ceramic particle dispersion liquid, self-crosslinking aqueous polymer glue, an auxiliary agent, a film forming auxiliary agent and a solvent, and stirring fully to obtain modified nano ceramic particle slurry;
2) And coating the modified nano ceramic particle slurry on one side or two sides of the base film, and drying, rolling and packaging to obtain the ultra-low-moisture ceramic coated lithium ion battery diaphragm.
Specifically, the base membrane selected by the ultra-low moisture ceramic coated lithium ion battery diaphragm is a PE-based lithium ion battery diaphragm produced by a wet process, the thickness is 5-16 mu m, and the porosity is 35-50%. The coating mode can be dip coating, roller coating or extrusion coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts inorganic ceramic particle dispersion liquid with core-shell structure and self-crosslinking aqueous polymer glue which are modified by 'seed polymerization' and hydrophobic property as main raw materials to prepare the battery diaphragm, and the lithium ion battery diaphragm has the characteristics of low moisture, non-hydrophilic water retention, non-moisture regain and good adhesive property, is suitable for high-capacity ternary positive electrode materials, and solves the problems of low initial capacity and short cycle life of the battery; and the heat resistance is excellent, and the heat resistance requirement of the lithium ion battery at 130 ℃ can be met.
(2) The battery diaphragm disclosed by the invention is simple in coating mode and convenient for large-scale continuous production.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
Example 1
The preparation method of the ultralow-moisture ceramic coated lithium ion battery diaphragm comprises the following steps:
1) Modifying an inorganic ceramic particle coupling agent: adding 50g of alumina powder into 100g of an alcohol-water mixed solution (mass ratio: ethanol/water=50/50) of a silane coupling agent KH-570 with the concentration of 0.5%, mixing, uniformly dispersing by using a grinder, adding formic acid to adjust the pH value of the solution to 4.0, stirring for 1.5 hours at 70 ℃, and completing the reaction to obtain grafted modified inorganic ceramic particles;
2) Hydrophobic modification of the grafted and modified inorganic ceramic particles: adding 2g of styrene monomer and 0.1g of BPO into the step 1), continuing to stir at 70 ℃ for 1.0h under heat preservation, and obtaining a hydrophobic grafting modified alumina dispersion liquid after the reaction is completed;
3) Adding 10g of carboxylated modified polyacrylamide glue and 3g of film forming auxiliary PVPK-30 into the step 2), supplementing 0.5g of auxiliary formic acid, and uniformly stirring to obtain modified nano ceramic particle slurry;
4) And (3) coating the slurry obtained in the step (3) on one side or two sides of a base film, and then performing processes such as drying, rolling and packaging to obtain the ultralow-moisture ceramic coated lithium ion battery diaphragm.
Example 2
The preparation method of the ultralow-moisture ceramic coated lithium ion battery diaphragm comprises the following steps:
1) Modifying an inorganic ceramic particle coupling agent: adding 40g of boehmite powder into 100g of an alcohol-water mixed solution (mass ratio: ethanol/water=40/60) of a silane coupling agent A-151 with the concentration of 1.0%, mixing, uniformly dispersing by using a grinder, adding acetic acid to adjust the pH value of the solution to 4.5, stirring at 80 ℃ for 2.0h, and completing the reaction to obtain grafted and modified inorganic ceramic particles;
2) Obtaining the hydrophobic modification of the inorganic ceramic particles after grafting modification: adding 3g of octadecyl acrylate monomer and 0.15g of DTBP into the step 1), continuing to stir at 80 ℃ for 1.5 hours, and obtaining a hydrophobic grafting modified alumina dispersion after the reaction is completed;
3) Adding 8g of citric acid grafted modified polyvinyl alcohol glue and 2g of film forming additive PVA-1799 in the step 2), supplementing 0.5g of additive acetic acid, and uniformly stirring to obtain modified nano ceramic particle slurry;
4) And (3) coating the slurry obtained in the step (3) on one side or two sides of a base film, and then performing processes such as drying, rolling and packaging to obtain the ultralow-moisture ceramic coated lithium ion battery diaphragm.
Comparative example 1
Comparative example 1 the same amount of unmodified alumina was used as in example 1, and the other steps and components were the same as in example 1.
Comparative example 2
Comparative example 2 the same amount of ordinary glue SBR as used in example 1 was used, and the other steps and components were the same as in example 1.
Comparative example 3
Comparative example 3 was prepared using the same amount of unmodified alumina as in example 1 and the same amount of ordinary glue SBR as in example 1, the remaining steps and components being the same as in example 1.
Performance testing
The membrane performance test data for examples 1-2 and comparative examples 1-3 are shown in the following table:
as can be seen from Table 1, the membrane permeation values and fluctuation of examples 1-2 are smaller than those of comparative examples 1-3, which shows that the membrane coatings of examples 1-2 are porous, have higher porosity and good pore-forming uniformity; the separator coating peel strength of examples 1-2 was good for comparative examples 1-3, demonstrating that the coating prepared from the slurries of examples 1-2 had good adhesion to the base film. The films of examples 1 to 2 are superior to comparative examples 1 to 3 in both moisture value and 130 ℃ C./1 h heat shrinkage, indicating that the films of the present invention have an ultra-low moisture content and excellent heat resistance.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. The ultra-low moisture ceramic coated lithium ion battery diaphragm is characterized in that at least one surface of a base film is provided with a modified nano inorganic ceramic coating layer, and the coating layer is prepared from a chemical modified coated nano inorganic ceramic particle dispersion liquid, self-crosslinkable aqueous polymer glue, a supplementary aid, a film forming aid and a solvent; the self-crosslinking aqueous polymer glue is one or more of carboxylated modified polyacrylate copolymer, polyacrylic acid-acrylonitrile-glycollic acid copolymer, carboxylated modified polyacrylamide, polyvinyl alcohol grafted poly-N-isopropyl acrylamide copolymer and citric acid grafted modified polyvinyl alcohol; wherein the dosage of the self-crosslinking aqueous polymer glue is 1-20% of the weight of the solvent;
the chemical modification coating nano inorganic ceramic particle dispersion liquid comprises inorganic ceramic particles, an organosilane coupling agent containing double bonds, a hydrophobic monomer containing double bonds and capable of free radical polymerization and an initiator;
the preparation method of the chemical modified coated nano inorganic ceramic particle dispersion liquid comprises the following steps:
mixing the inorganic ceramic particles with an organosilane coupling agent containing double bonds, and then adjusting the pH to 3-5 at 30-80 ℃ to obtain grafted and modified inorganic ceramic particles;
and B, adding a double bond-containing hydrophobic monomer capable of free radical polymerization and an initiator, stirring and heating to 30-100 ℃ to obtain the chemical modified coated nano inorganic ceramic particle dispersion liquid.
2. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the inorganic ceramic particles are one or more of aluminum oxide, silicon dioxide, magnesium hydroxide, zirconium dioxide, magnesium oxide, boehmite.
3. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the film forming aid is one or more of PVPK-17, PVPK-30, cmc-Na, PVA-1799 and EC cellulose; wherein the use level of the film forming auxiliary agent is 0.5-5% of the weight of the solvent.
4. The ultra-low moisture ceramic coated lithium ion battery separator according to claim 1, wherein the double bond-containing organosilane coupling agent is one or more of silane coupling agent a-150, silane coupling agent a-151, silane coupling agent a-171, silane coupling agent a-172 and silane coupling agent KH-570.
5. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the double bond containing free radical polymerizable hydrophobic monomer is one or more of butadiene, styrene, acrylonitrile, octadecyl acrylate, methyl methacrylate, and 2-methyl propylene.
6. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the initiator is one or more of BPO, BIBP, DTBP, TBPB and TBHP.
7. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the solvent is one or more of ethanol, isopropanol, dimethyl carbonate, and deionized water.
8. The ultra-low moisture ceramic coated lithium ion battery separator of claim 1, wherein the supplemental aid is one or more of formic acid, acetic acid, oxalic acid, glycolic acid, and citric acid.
9. The method for preparing the ultralow-moisture ceramic coated lithium ion battery diaphragm according to any one of claims 1-8, which is characterized by comprising the following steps:
1) Mixing the chemical modified coated nano inorganic ceramic particle dispersion liquid, self-crosslinking aqueous polymer glue, a supplementary aid, a film forming aid and a solvent, and stirring fully to obtain modified nano ceramic particle slurry;
2) And coating the modified nano ceramic particle slurry on one side or two sides of the base film, and drying, rolling and packaging to obtain the ultra-low-moisture ceramic coated lithium ion battery diaphragm.
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| CN113594632A (en) * | 2021-07-30 | 2021-11-02 | 中材锂膜有限公司 | Low-moisture solvent type PVDF coating diaphragm |
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| CN115404029A (en) * | 2022-10-19 | 2022-11-29 | 苏州德比电子材料科技有限公司 | High-temperature-resistant low-moisture-content diaphragm binder and preparation method and application thereof |
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| CN116826312B (en) * | 2023-08-30 | 2024-02-27 | 宁德卓高新材料科技有限公司 | High-adhesion heat-resistant diaphragm and preparation method and application thereof |
| CN117578028A (en) * | 2024-01-16 | 2024-02-20 | 深圳索理德新材料科技有限公司 | Ceramic coating material, ceramic coating diaphragm and preparation method of ceramic coating diaphragm |
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