CN114335903A - Heat-resistant diaphragm and preparation method and application thereof - Google Patents
Heat-resistant diaphragm and preparation method and application thereof Download PDFInfo
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- CN114335903A CN114335903A CN202111601278.0A CN202111601278A CN114335903A CN 114335903 A CN114335903 A CN 114335903A CN 202111601278 A CN202111601278 A CN 202111601278A CN 114335903 A CN114335903 A CN 114335903A
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 29
- 239000011268 mixed slurry Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920000131 polyvinylidene Polymers 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 7
- 239000011247 coating layer Substances 0.000 claims 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 239000004816 latex Substances 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 210000003141 lower extremity Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Abstract
The invention provides a heat-resistant diaphragm and a preparation method and application thereof, wherein the heat-resistant diaphragm comprises a polyolefin-based diaphragm, a heat-resistant layer and a composite coating, the heat-resistant layer is positioned between the polyolefin-based diaphragm and the composite coating, the heat-resistant layer comprises ceramic and an adhesive, the composite coating comprises ceramic and a polymer, the ceramic in the heat-resistant layer and the ceramic in the composite coating can be the same or different, the heat-resistant diaphragm simultaneously meets the requirements of thermal safety and hardness of a battery, the polymer proportion is low, and the risk of diaphragm pore blocking is low.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a heat-resistant diaphragm and a preparation method and application thereof.
Background
The diaphragm is used as a key safety component of the lithium ion battery, has rich pore channel structures, and has the function of blocking the contact of active substances of the anode and the cathode and transmitting lithium ions of the lithium ion battery. Polyethylene (PE) and polypropylene (PP) separators generally have a melting point of less than 200 ℃, are poor in heat resistance, and have no adhesive property, so that a separator currently commercialized is coated with a ceramic or polymer on a PE or PP separator to enhance the heat resistance and adhesive property of the separator. After the diaphragm is coated with a layer of polymer, although the bonding strength with the pole piece is improved, the air permeability value is increased, the ionic resistance is increased, and therefore the internal resistance of the lithium ion battery is increased, and the performance of the battery is reduced.
CN106328867B discloses a heat-shrinkage-resistant lithium ion battery separator, which comprises a first outer layer, a second outer layer and an inner layer sandwiched therebetween, wherein the first outer layer, the second outer layer and the inner layer have different microporous structures. The pore size of each layer of the diaphragm is different, so that the hardness of the diaphragm is lower.
CN110556495A discloses a lithium ion battery diaphragm and contain lithium ion battery of this diaphragm, and lithium ion battery diaphragm includes heat-resisting composite substrate layer, the one side of heat-resisting composite substrate layer is provided with first organic glue coating, heat-resisting composite substrate layer include the base film and set up in the ceramic layer on base film surface, the base film has a plurality of holes, and is a plurality of adhere to in the hole and have modified polyolefin coating, first organic glue coating includes first complete coating district, check intermittent type coating district and the complete coating district of second from the top edge to the lower limb of base film in proper order, its diaphragm polymer accounts for than too big, has the risk of diaphragm shutoff hole.
The above-mentioned solutions have problems in that the separator has poor hardness or the proportion of the polymer is too large to cause clogging of the separator, and therefore it is necessary to develop a heat-resistant separator having good hardness and a small proportion of the polymer.
Disclosure of Invention
The invention aims to provide a heat-resistant diaphragm, a preparation method and application thereof, wherein the heat-resistant diaphragm simultaneously meets the requirements of thermal safety and hardness of a battery, and has low polymer proportion and low risk of diaphragm hole plugging.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a heat-resistant separator including a polyolefin-based separator, a heat-resistant layer between the polyolefin-based separator and the composite coating, the heat-resistant layer including a ceramic and a binder, and a composite coating including a ceramic and a polymer.
The ceramic in the heat-resistant layer and the ceramic in the composite coating can be the same or different.
According to the invention, one side or two sides of the polyolefin-based diaphragm are coated with the heat-resistant layer, and then the heat-resistant layer is coated with the lithium ion battery composite diaphragm of the ceramic and polymer mixture, so that the heat-resistant layer can improve the heat-resistant performance of the material, and simultaneously, the proportion of the polymer in the diaphragm is reduced, and further, the risk of the diaphragm blocking holes is reduced.
Preferably, the polyolefin-based separator includes any one of a polyethylene separator, a polypropylene separator, or a polyethylene-polypropylene composite separator, or a combination of at least two thereof.
Preferably, the polyolefin-based separator has a thickness of 5 to 20 μm, for example: 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, or the like.
Preferably, the polyolefin-based separator has a pore size of 10 to 400nm, for example: 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, etc.
Preferably, the ceramic comprises any one of boehmite, alumina, magnesium hydroxide, magnesium oxide, barium titanate, zinc oxide or barium sulfate or a combination of at least two thereof.
Preferably, the mass ratio of the ceramic is 85-95% based on 100% of the mass of the heat-resistant layer, for example: 85%, 88%, 90%, 92%, 95%, etc.
Preferably, the mass ratio of the ceramic is 70-90% based on 100% of the mass of the composite coating, for example: 70%, 75%, 80%, 85%, 90%, etc.
Preferably, the polymer comprises any one of polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-octafluoroisobutylene copolymer, polyvinylidene fluoride-tetrafluoroethylene copolymer, polymethyl methacrylate or polystyrene acid ester or a combination of at least two of the same.
In a second aspect, the present invention provides a method for preparing the heat-resistant separator according to the first aspect, the method comprising the steps of:
(1) mixing ceramic powder with a binder solution to obtain ceramic slurry, coating part of the ceramic slurry on the surface of a polyolefin-based diaphragm, drying to obtain the polyolefin-based diaphragm coated with a heat-resistant layer, and mixing a polymer with the other part of the ceramic slurry to obtain mixed slurry;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
Preferably, the binder solution of step (1) comprises a binder, an auxiliary agent, a dispersant and an aqueous solvent.
In a third aspect, the present invention provides a lithium ion battery comprising the heat resistant separator according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the heat-resistant diaphragm provided by the invention can meet the requirements of thermal safety and hardness of a battery, and has low polymer proportion and low risk of diaphragm hole plugging.
(1) The heat-resistant diaphragm has the advantages that the heat shrinkage rate can reach below 2%, the liquid absorption rate can reach above 13.5%, the deformation amount can reach below 2%, the wettability of the diaphragm is good, the bonding performance is good, and the thermal safety performance of the battery is excellent.
Drawings
FIG. 1 is a schematic view showing the structure of a heat-resistant separator according to an example, 1-ceramic particles, 2-heat-resistant layer, 3-base film, 4-polymer colloidal particles.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the examples of the present application, the parts are all parts by mass.
Example 1
This example provides a heat resistant separator made by the following method:
(1) mixing 9 parts of alumina powder and 1 part of a polyvinyl alcohol binder solution to obtain ceramic slurry, wherein the mass ratio of the ceramic in the ceramic slurry is 90%, coating part of the ceramic slurry on the surface of a polyethylene diaphragm, drying to obtain a polyolefin-based diaphragm coated with a heat-resistant layer, and mixing 0.5 part of polystyrene acrylate with the other part of the ceramic slurry to obtain mixed slurry, wherein the mass ratio of the ceramic in the solid material of the mixed slurry is 80%;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
The structural schematic diagram of the heat-resistant diaphragm is shown in fig. 1, a heat-resistant layer 2 is positioned on the surface of a base film 3, and a composite coating is positioned on the surface of the heat-resistant layer 2, wherein the composite coating contains ceramic particles 1 and polymer colloidal particles 4.
Example 2
This example provides a heat resistant separator made by the following method:
(1) mixing 9 parts of boehmite powder and 1 part of polyacrylate binder solution to obtain ceramic slurry, wherein the mass ratio of ceramics in the ceramic slurry is 90%, coating part of the ceramic slurry on the surface of a polyethylene diaphragm, drying to obtain a polyolefin-based diaphragm coated with a heat-resistant layer, and mixing 0.5 part of polystyrene acrylate with the other part of the ceramic slurry to obtain mixed slurry, wherein the mass ratio of the ceramics in a solid material of the mixed slurry is 80%;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
Example 3
This example provides a heat resistant separator made by the following method:
(1) mixing 9 parts of alumina powder and 1 part of a polyvinyl alcohol binder solution to obtain ceramic slurry, wherein the mass percentage of ceramics in the ceramic slurry is 80%, coating part of the ceramic slurry on the surface of a polyethylene diaphragm, drying to obtain a polyolefin-based diaphragm coated with a heat-resistant layer, and mixing 0.5 part of polystyrene acrylate with the other part of the ceramic slurry to obtain mixed slurry, wherein the mass percentage of the ceramics in the solid material of the mixed slurry is 80%;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
Example 4
This example provides a heat resistant separator made by the following method:
(1) mixing 9 parts of alumina powder and 1 part of a polyvinyl alcohol binder solution to obtain ceramic slurry, wherein the mass ratio of ceramics in the ceramic slurry is 90%, coating part of the ceramic slurry on the surface of a polyethylene diaphragm, drying to obtain a polyolefin-based diaphragm coated with a heat-resistant layer, and mixing 1 part of polystyrene acrylate and the other part of the ceramic slurry to obtain mixed slurry, wherein the mass ratio of the ceramics in a solid material of the mixed slurry is 60%;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
Example 5
This example provides a heat resistant separator made by the following method:
(1) mixing 9 parts of alumina powder and 1 part of a polyvinyl alcohol binder solution to obtain ceramic slurry, wherein the mass ratio of the ceramic in the ceramic slurry is 90%, coating part of the ceramic slurry on the surface of a polyethylene diaphragm, drying to obtain a polyolefin-based diaphragm coated with a heat-resistant layer, and mixing 0.25 part of polystyrene acrylate with the other part of the ceramic slurry to obtain mixed slurry, wherein the mass ratio of the ceramic in the solid material of the mixed slurry is 95%;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
Comparative example 1
This comparative example is different from example 1 only in that a heat-resistant layer was not provided, and other conditions and parameters were exactly the same as those of example 1.
Comparative example 2
This comparative example differs from example 1 only in that no composite coating was provided, and the other conditions and parameters were exactly the same as those of example 1.
And (3) performance testing:
testing the thermal shrinkage rate and the liquid absorption rate of the diaphragm provided by each embodiment and the comparative example, assembling the diaphragm with a positive plate and a negative plate to form a bare cell, hot-pressing the bare cell on a frame with a fixed height, and testing the deformation amount of the cell after 24 hours, wherein the mass ratio of nickel cobalt lithium manganate, acetylene black and polyvinylidene fluoride in the positive plate is 9.5:0.2:0.3, and the mass ratio of graphite, acetylene black, sodium carboxymethylcellulose and styrene butadiene rubber in the negative plate is 9.5:0.2:0.15: 0.15.
Testing the thermal shrinkage rate of the diaphragm: 5 pieces of samples were prepared, and a square sample of 120mm × 120mm was cut in the longitudinal direction of the film roll, and the length of the sample was marked 100mm × 100 mm. The glass plates were clamped and placed in a constant temperature oven at 130 ℃ for baking for 1 hour, and the lengths in the MD and TD directions after baking were measured to calculate the shrinkage.
Size of glass plate: 220mm × 220mm × 4 mm; the glass plate is made of: and (4) tempering the glass.
And (3) testing the liquid absorption rate of the diaphragm: a coating film of 10X 10cm in size was weighed to obtain a mass of W0, immersed in a mixed solution of Ethylene Carbonate (EC) and Propylene Carbonate (PC) in a ratio of 1:1 at room temperature, allowed to stand for 2 hours, then the surface electrolyte was sucked up with a filter paper and weighed to obtain a mass of W1, and after further standing at room temperature for 10 minutes, the film was weighed again to obtain a mass of W2 and a liquid suction rate of (W2-W0)/W0.
The test results are shown in table 1:
TABLE 1
As can be seen from table 1, the heat-resistant separators according to the present invention, which were obtained in examples 1 to 5, had a heat shrinkage of 2% or less, a liquid absorption rate of 13.5% or more, and a deformation amount of 2% or less, had good wettability, good adhesion, and excellent thermal safety of batteries.
By comparing the embodiment 1 with the embodiment 3, the quality ratio of the ceramic in the ceramic slurry influences the performance of the prepared heat-resistant diaphragm, the quality ratio of the ceramic in the ceramic slurry is controlled to be 85-95%, the diaphragm with excellent performance can be prepared, and if the quality ratio of the ceramic in the ceramic slurry is too low, the heat-resistant performance of the diaphragm is reduced.
Compared with the examples 1 and 4-5, the mass ratio of the ceramic in the mixed coating affects the performance of the prepared heat-resistant diaphragm, the mass ratio of the ceramic in the mixed coating is controlled to be 70-90%, the diaphragm with excellent performance can be prepared, if the mass ratio of the ceramic in the mixed coating is too large, the bonding performance of the diaphragm is poor, and if the mass ratio of the ceramic in the mixed coating is too small, the ventilation value caused by the coating is obviously increased.
Compared with the comparative example 1, the heat-resistant layer is arranged in the composite diaphragm, so that the heat resistance of the diaphragm can be effectively improved, the heat-resistant layer does not need to be additionally prepared, the manufacturing cost is saved, the preparation process is simplified, and the heat-resistant layer can prevent the base film from being blocked or oxidized after the colloidal particle position is swelled, so that the safety performance of the lithium ion battery is greatly improved.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A heat-resistant separator, characterized in that the heat-resistant separator comprises a polyolefin-based separator, a heat-resistant layer and a composite coating, the heat-resistant layer is located between the polyolefin-based separator and the composite coating, the heat-resistant layer comprises a ceramic and a binder, and the composite coating comprises a ceramic and a polymer.
2. The heat-resistant separator according to claim 1, wherein the polyolefin-based separator comprises any one of a polyethylene separator, a polypropylene separator, or a polyethylene-polypropylene composite separator, or a combination of at least two thereof.
3. The heat-resistant separator according to claim 1 or 2, wherein the polyolefin-based separator has a thickness of 5 to 20 μm;
preferably, the polyolefin-based separator has a pore size of 10 to 400 nm.
4. The heat resistant separator according to any one of claims 1 to 3, wherein the ceramic comprises any one of boehmite, alumina, magnesium hydroxide, magnesium oxide, barium titanate, zinc oxide, or barium sulfate, or a combination of at least two thereof.
5. The heat-resistant separator according to any one of claims 1 to 4, wherein the mass of the ceramic is 85 to 95% based on 100% by mass of the heat-resistant layer.
6. The heat-resistant separator according to any one of claims 1 to 5, wherein the ceramic is 70 to 90% by mass based on 100% by mass of the composite coating layer.
7. The heat-resistant separator as claimed in any one of claims 1 to 6, wherein the binder of the heat-resistant layer comprises any one or a combination of at least two of polyvinylidene fluoride, styrene-butadiene rubber, styrene-acrylic latex, polyvinyl alcohol, polyacrylic acid, and ammonium acrylate salt, preferably polyvinyl alcohol and polyacrylate.
8. The heat resistant separator according to any of claims 1 to 7, wherein the polymer of the composite coating layer comprises any one or a combination of at least two of polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-octafluoroisobutylene copolymer, polyvinylidene fluoride-tetrafluoroethylene copolymer, polymethyl methacrylate, or polystyrene acrylate, preferably polystyrene acrylate.
9. A method of making a heat resistant separator as claimed in any of claims 1 to 8, comprising the steps of:
(1) mixing ceramic powder with a binder solution to obtain ceramic slurry, coating part of the ceramic slurry on the surface of a polyolefin-based diaphragm, drying to obtain the polyolefin-based diaphragm coated with a heat-resistant layer, and mixing a polymer with the other part of the ceramic slurry to obtain mixed slurry;
(2) and (2) coating the mixed slurry obtained in the step (1) on a heat-resistant layer, and drying to obtain the heat-resistant diaphragm.
10. A lithium ion battery comprising the heat-resistant separator according to any one of claims 1 to 8.
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| CN202111601278.0A CN114335903A (en) | 2021-12-24 | 2021-12-24 | Heat-resistant diaphragm and preparation method and application thereof |
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| CN202111601278.0A CN114335903A (en) | 2021-12-24 | 2021-12-24 | Heat-resistant diaphragm and preparation method and application thereof |
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| CN114335903A true CN114335903A (en) | 2022-04-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023216376A1 (en) * | 2022-05-09 | 2023-11-16 | 上海恩捷新材料科技有限公司 | Metal compound separator, preparation method therefor and use thereof |
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| CN107275550A (en) * | 2017-06-20 | 2017-10-20 | 深圳市星源材质科技股份有限公司 | A kind of ceramics and polymer composite coated lithium-ion membrane and preparation method thereof |
| CN113178663A (en) * | 2021-04-28 | 2021-07-27 | 惠州亿纬锂能股份有限公司 | Composite diaphragm and preparation method and application thereof |
| CN113451708A (en) * | 2020-03-26 | 2021-09-28 | 广州汽车集团股份有限公司 | Functional coating diaphragm and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
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2021
- 2021-12-24 CN CN202111601278.0A patent/CN114335903A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107275550A (en) * | 2017-06-20 | 2017-10-20 | 深圳市星源材质科技股份有限公司 | A kind of ceramics and polymer composite coated lithium-ion membrane and preparation method thereof |
| CN113451708A (en) * | 2020-03-26 | 2021-09-28 | 广州汽车集团股份有限公司 | Functional coating diaphragm and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN113178663A (en) * | 2021-04-28 | 2021-07-27 | 惠州亿纬锂能股份有限公司 | Composite diaphragm and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023216376A1 (en) * | 2022-05-09 | 2023-11-16 | 上海恩捷新材料科技有限公司 | Metal compound separator, preparation method therefor and use thereof |
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