CN117977103A - High-strength low-moisture high-temperature-resistant battery diaphragm and preparation method thereof - Google Patents
High-strength low-moisture high-temperature-resistant battery diaphragm and preparation method thereof Download PDFInfo
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- CN117977103A CN117977103A CN202410300666.2A CN202410300666A CN117977103A CN 117977103 A CN117977103 A CN 117977103A CN 202410300666 A CN202410300666 A CN 202410300666A CN 117977103 A CN117977103 A CN 117977103A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007822 coupling agent Substances 0.000 claims abstract description 43
- 239000003365 glass fiber Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- 238000009210 therapy by ultrasound Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Abstract
The invention discloses a high-strength low-moisture high-temperature-resistant battery diaphragm and a preparation method thereof, wherein the high-strength low-moisture high-temperature-resistant battery diaphragm comprises: the coating is formed by coating high-strength low-moisture high-temperature-resistant slurry, wherein the high-strength low-moisture high-temperature-resistant slurry comprises the following components: glass fiber, alumina and titanate coupling agent. The invention realizes the purposes of improving the needling strength and the binding power of the diaphragm and reducing the thermal shrinkage of the diaphragm and the water content of the diaphragm through the cooperation of glass fiber, alumina and titanate coupling agent.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a high-strength low-moisture high-temperature-resistant battery diaphragm and a preparation method thereof.
Background
Along with the increasing severity of environmental problems, more and more new energy projects are paid attention to in society, wherein electric automobiles are favored, the safety, the service life and the like of lithium ion batteries serving as power sources of the electric automobiles are important points of scientific research, and lithium battery diaphragms play important roles in the lithium ion batteries.
Based on the above, the safety and service life of lithium ion batteries are more focused, and conventional lithium battery separators are PP or PE separators, which have the disadvantage of low heat resistance, and the heat resistance is improved by coating the separator with common inorganic ceramics (alumina, boehmite, silica, etc.), but the water content is also greatly increased, which can lead to decomposition of electrolyte lithium salt in the battery, and cause significant deterioration of chemical characteristics (such as capacity, internal resistance, products, etc.) of the lithium battery, and also have an influence on the safety performance of the battery. In addition, the conventional battery separator has a problem of poor adhesion. How to improve the binding force, reduce the internal resistance of a lithium battery and improve the battery capacity and the safety of the lithium battery while ensuring the heat resistance of the battery diaphragm is a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide high-strength low-moisture high-temperature-resistant slurry.
Another object of the present invention is to provide a method for preparing the slurry with high strength, low moisture and high temperature resistance.
Another object of the present invention is to provide a high strength, low moisture, high temperature resistant battery separator.
Another object of the present invention is to provide a method for preparing the above-mentioned high-strength low-moisture high-temperature-resistant battery separator.
The aim of the invention is achieved by the following technical scheme.
A high strength, low moisture, high temperature resistant slurry comprising: the glass fiber, the alumina and the titanate coupling agent are mixed according to the mass parts, wherein the ratio of the glass fiber to the alumina to the titanate coupling agent is (2-3): (5-9): (3-6).
In the above technical scheme, the titanate coupling agent is monoalkoxy, monoalkoxy pyrophosphate, integral or ligand.
In the above technical solution, further includes: the aluminum oxide-water composite material comprises a dispersing agent and water, wherein the weight portion of the aluminum oxide, the dispersing agent and the water is (5-9): (0.1-0.5): (81.5 to 89.9).
In the technical scheme, the dispersing agent is ammonium polyacrylate, polyvinyl alcohol or polyethylene glycol.
In the above technical scheme, the particle size of the high-strength low-moisture high-temperature-resistant slurry is D50: 0.3-0.7 micrometers; d90:1.0 to 1.5 micrometers.
A preparation method of high-strength low-moisture high-temperature-resistant slurry comprises the following steps: mixing glass fiber, alumina, water, titanate coupling agent and dispersing agent uniformly to obtain high-strength low-moisture high-temperature-resistant slurry, wherein the ratio of the glass fiber to the alumina to the water to the titanate coupling agent to the dispersing agent is (2-3): (5-9): (81.5 to 89.9): (3-6): (0.1-0.5).
In the technical scheme, the preparation method comprises the following steps of:
Step 1, mixing a dispersing agent, water, glass fibers and alumina, stirring and then carrying out ultrasonic treatment until the mixture is uniform to obtain a first solution;
in step 1, the stirring and then ultrasonic treatment until uniform comprises the following steps: stirring at rotation speed of 1500-3100 r/min and revolution speed of 20-50 r/min for 10-20 min, and then ultrasonic-treating at ultrasonic frequency of 10-50 kHz for 10-20 min.
And step 2, mixing the first solution with a titanate coupling agent, and simultaneously stirring and carrying out ultrasonic treatment in a vacuum environment to obtain high-strength low-moisture high-temperature-resistant slurry.
In the step 2, the time of stirring and ultrasonic treatment in a vacuum environment is 10-20 min.
In the step 2, the rotation speed of stirring is 1000-3800 r/min, and the revolution speed is 20-40 r/min.
In the step 2, the ultrasonic frequency of the ultrasonic wave is 5-8 kHz.
In the step2, the vacuum degree of the vacuum environment is 0.06-0.08 kPa.
A high strength, low moisture, high temperature resistant battery separator comprising: the coating is formed by coating high-strength low-moisture high-temperature-resistant slurry.
In the technical scheme, the thickness of the coating is 2-3 mu m.
The method for preparing the high-strength low-moisture high-temperature-resistant battery separator comprises the following steps: and coating the high-strength low-moisture high-temperature-resistant slurry on a base film, and drying to obtain the high-strength low-moisture high-temperature-resistant battery diaphragm.
In the technical scheme, the drying time is 1-3 min, and the drying temperature is 50-70 ℃.
In the technical scheme, the coating speed is 30-50 m/min.
In the above technical solution, the base film is a PE film.
A high strength, low moisture, high temperature resistant battery separator comprising: a base film and a coating applied to the base film, the coating comprising: the glass fiber, the alumina and the titanate coupling agent are mixed according to the mass parts, wherein the ratio of the glass fiber to the alumina to the titanate coupling agent is (2-3): (5-9): (3-6).
Use of glass fiber, alumina and titanate coupling agent in combination with a separator to improve the needling strength and/or adhesion of the separator.
Use of glass fiber, alumina and titanate coupling agent together in a separator to reduce heat shrinkage and/or water content of the separator.
The invention adopts the titanate coupling agent, the glass fiber and the alumina for synergistic modification, and compared with the prior art, the invention has the following beneficial effects:
1. The titanate coupling agent adopted by the invention can be bent and entangled with an organic polymer (such as PE) in the base film, so that the compatibility of the organic polymer and an inorganic substance (the inorganic substance is alumina and glass fiber) is improved, a stronger intermolecular acting force can be formed on the surfaces of organic molecules and inorganic powder, the impact strength of the diaphragm is improved, the cohesiveness between a coating and the diaphragm is improved, and the diaphragm cohesiveness is improved;
The titanate coupling agent belongs to a substance with an amphoteric structure, the structural general formula of the titanate coupling agent is (RO) m Ti(OX-R-Y)n, one part of groups in the molecule can react with chemical groups on the inorganic surface to form chemical bonding, and the other part of groups have the property of being organophilic and can chemically react with organic molecules or generate stronger intermolecular action, so that two materials with distinct properties are firmly combined together to enable the two materials to be tightly bonded together; the phosphorous oxo group in the titanate coupling agent can provide antioxidant, flame resistance and the like, and the titanate can have coupling and cohesiveness through the selection of OX-; the long carbon bond alkane in the titanate coupling agent is softer, and can be bent and intertwined with the organic polymer, so that the compatibility of the organic matters and the inorganic matters is improved, and the impact strength of the material is improved.
2. The aluminum oxide and the glass fiber are mixed and then adhered together, which is equivalent to that a part of the surface of the aluminum oxide is covered by the glass fiber, the specific surface area of the aluminum oxide is reduced, the water absorption of the glass fiber is smaller than that of the aluminum oxide, the specific surface area of the aluminum oxide contacted with air is indirectly reduced, the water absorption of a coating diaphragm can be reduced, and the titanate coupling agent is coated on the surfaces of the aluminum oxide and the glass fiber after being mixed with the aluminum oxide and the glass fiber.
3. The glass fiber has the advantages of high temperature resistance, incombustibility, heat insulation and small water absorption, can increase the compactness of the diaphragm coating by mixing with alumina, and simultaneously, the titanate coupling agent can tightly bond the coating and the base film together, thereby enhancing the supporting effect of the coating on the diaphragm and further enhancing the heat resistance of the diaphragm.
Drawings
FIG. 1 is an SEM of a high strength, low moisture, high temperature resistant battery separator prepared according to example 4;
FIG. 2 is an SEM of a battery separator prepared according to comparative example 6;
FIG. 3 is an SEM of a battery separator prepared according to comparative example 7;
Fig. 4 is an SEM of the battery separator prepared in comparative example 8;
FIG. 5 is an SEM of a battery separator prepared according to comparative example 9;
Fig. 6 is an SEM of the battery separator prepared in comparative example 10.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The drug purchase sources involved in the following examples are as follows:
titanate coupling agent: isopropyl tri (dioctyl pyrophosphoryloxy) titanate;
Glass fiber: the length of the glass fiber is 0.5-1.8 mu m, and the width is 0.12-0.4 mu m;
Acrylic ester copolymer: butyl acrylate;
aluminum silicate fibers: the length of the aluminum silicate fiber is 0.5-1.8 mu m, and the width is 0.12-0.4 mu m;
silane coupling agent: aminopropyl trimethoxysilane;
Ammonium polyacrylate salt: and (3) polyacrylamide.
The water in the following examples is pure water.
In the following examples, the base film was a PE film having a thickness of 9. Mu.m.
Peel strength (peel strength was used to characterize adhesion): selecting a smooth high-strength low-moisture high-temperature-resistant battery diaphragm/battery diaphragm, cutting the battery diaphragm/battery diaphragm into a sample with the width of 30mm and the length of 200mm, flatly attaching a special adhesive tape with the length of 200mm on a coating surface of the sample, uniformly pressing the sample for 3 times by using a standard roller, tearing one end, and using a stretcher for peeling test to obtain the peeling strength.
Example 1
A preparation method of high-strength low-moisture high-temperature-resistant slurry comprises the following steps:
Step 1, mixing a dispersing agent, water, glass fibers and aluminum oxide in a stirrer, stirring for 10min at a rotation speed of 3100r/min and a revolution speed of 20r/min, and then carrying out ultrasonic treatment at an ultrasonic frequency of 50kHz for 15min until the mixture is uniform to obtain a first solution, wherein the ratio of the glass fibers to the aluminum oxide to the water to the dispersing agent is 2 in parts by weight: 8:84.8:0.2, the dispersing agent is polyacrylate ammonium salt, and the particle size of the alumina is D50:0.588 microns; d90:1.256 microns;
Step 2, mixing the first solution and the titanate coupling agent, stirring and ultrasonic treatment for 15min (high-speed dispersion) in a vacuum environment with an ultrasonic oscillation function (the vacuum degree is 0.07 kPa) to obtain high-strength low-moisture high-temperature-resistant slurry, wherein the rotation speed of stirring is 1000r/min, the revolution speed is 40r/min, the ultrasonic frequency of ultrasonic treatment is 5kHz, and the ratio of the titanate coupling agent to the alumina in the first solution is 5:8.
Example 2
A preparation method of high-strength low-moisture high-temperature-resistant slurry comprises the following steps:
Step 1, mixing a dispersing agent, water, glass fibers and aluminum oxide in a stirrer, stirring for 15min at a rotation speed of 2000r/min and a revolution speed of 30r/min, and then carrying out ultrasonic treatment at an ultrasonic frequency of 30kHz for 15min until the mixture is uniform to obtain a first solution, wherein the ratio of the glass fibers to the aluminum oxide to the water to the dispersing agent is 2.5 in parts by weight: 7.5:84.8:0.2, the dispersing agent is polyacrylate ammonium salt, and the particle size of the alumina is D50:0.543 microns; d90:1.208 microns;
Step 2, mixing the first solution and the titanate coupling agent, stirring and ultrasonic treatment for 15min (high-speed dispersion) in a vacuum environment with an ultrasonic oscillation function (the vacuum degree is 0.07 kPa) to obtain high-strength low-moisture high-temperature-resistant slurry, wherein the stirring rotation speed is 2800r/min, the revolution speed is 30r/min, the ultrasonic frequency of ultrasonic treatment is 6kHz, and the ratio of the titanate coupling agent to the alumina in the first solution is 5 in parts by weight: 7.5.
Example 3
A preparation method of high-strength low-moisture high-temperature-resistant slurry comprises the following steps:
Step1, mixing a dispersing agent, water, glass fibers and aluminum oxide in a stirrer, stirring for 20min at a rotation speed of 1500r/min and a revolution speed of 50r/min, and then carrying out ultrasonic treatment at an ultrasonic frequency of 50kHz for 15min until the mixture is uniform to obtain a first solution, wherein the ratio of the glass fibers to the aluminum oxide to the water to the dispersing agent is 3 in parts by weight: 7:84.8:0.2, the dispersing agent is polyacrylate ammonium salt, and the particle size of the alumina is D50:0.523 micrometers; d90:1.298 microns;
Step 2, mixing the first solution and the titanate coupling agent, stirring and ultrasonic treatment for 15min (high-speed dispersion) in a vacuum environment with an ultrasonic oscillation function (the vacuum degree is 0.07 kPa) to obtain high-strength low-moisture high-temperature-resistant slurry, wherein the stirring rotation speed is 3800r/min, the revolution speed is 20r/min, the ultrasonic frequency of ultrasonic treatment is 8kHz, and the ratio of the titanate coupling agent to the alumina in the first solution is 5 in parts by weight: 7.
Comparative example 1
A method of preparing a lithium battery paste comprising: mixing 5 parts by weight of aluminum oxide, 89.8 parts by weight of pure water and 0.2 part by weight of dispersing agent, firstly blending for 10min at rotation speed of 3100r/min and revolution speed of 20r/min in a stirrer, then carrying out ultrasonic treatment at frequency of 50kHz for 15min to uniformity, adding 5 parts by weight of adhesive, and carrying out ultrasonic vibration (frequency of ultrasonic waves is 5 kHz) for 15min under stirring conditions (rotation speed is 1000r/min and revolution speed is 40 r/min) to obtain lithium battery slurry, wherein the adhesive is acrylic ester copolymer, the dispersing agent is ammonium polyacrylate, and particle size of aluminum oxide is D50:0.499 microns; d90:1.373 micrometers.
Comparative example 2
A method of preparing a lithium battery paste comprising: mixing 2 parts by weight of glass fiber, 8 parts by weight of alumina, 84.8 parts by weight of pure water and 0.2 part by weight of dispersing agent, blending for 10min at the rotation speed of 3100r/min and the revolution speed of 20r/min in a stirrer, then carrying out ultrasonic treatment at the frequency of 50kHz for 15min until the mixture is uniform, adding 5 parts by weight of adhesive, and carrying out ultrasonic vibration (the frequency of ultrasonic waves is 5 kHz) for 15min under the stirring condition (the rotation speed is 1000r/min and the revolution speed is 40 r/min) to obtain lithium battery slurry, wherein the adhesive is an acrylic ester copolymer, the dispersing agent is a polyacrylic acid ammonium salt, and the particle size of the alumina is D50:0.509 microns; d90:1.433 microns.
Comparative example 3
A method of preparing a lithium battery paste comprising: mixing 10 parts by weight of glass fiber, 84.8 parts by weight of pure water and 0.2 part by weight of dispersing agent, blending for 10min at rotation speed of 3100r/min and revolution speed of 20r/min in a stirrer, then carrying out ultrasonic treatment at frequency of 50kHz for 15min to uniformity, adding 5 parts by weight of titanate coupling agent, and carrying out ultrasonic vibration (frequency of ultrasonic waves is 5 kHz) for 15min under stirring conditions (rotation speed is 1000r/min and revolution speed is 40 r/min) to obtain lithium battery slurry, wherein the dispersing agent is ammonium polyacrylate salt.
Comparative example 4
A method of preparing a lithium battery paste comprising: mixing 10 parts by weight of aluminum oxide, 84.8 parts by weight of pure water and 0.2 part by weight of dispersing agent, firstly blending for 10min at rotation speed of 3100r/min and revolution speed of 20r/min in a stirrer, then carrying out ultrasonic treatment at frequency of 50kHz for 15min to uniformity, adding 5 parts by weight of titanate coupling agent, and carrying out ultrasonic vibration (frequency of ultrasonic waves is 5 kHz) for 15min under stirring conditions (rotation speed is 1000r/min, revolution speed is 40 r/min) to obtain lithium battery slurry, wherein the dispersing agent is ammonium polyacrylate, and the particle size of the aluminum oxide is D50:0.509 microns; d90:1.433 microns.
Comparative example 5
A preparation method of lithium battery slurry is basically the same as the "preparation method of high-strength low-moisture high-temperature-resistant slurry" in example 2, except that: the "glass fiber" is replaced with "aluminum silicate fiber", and the "titanate coupling agent" is replaced with "silane coupling agent".
Examples 4 to 6 and comparative examples 6 to 10
A method of making a battery separator comprising: placing a base film on a coating machine filled with slurry, wherein the particle size of the slurry is X micrometers, coating one side of the slurry on the base film at the speed of Am/min, drawing the coated slurry into a drying device through a drawing roller, drying Cmin at the temperature of B ℃ to obtain a coating with the thickness of D mu m on the base film to obtain a battery diaphragm, wherein the slurry is one of the high-strength low-moisture high-temperature-resistant slurry prepared in examples 1-3 and the lithium battery slurry prepared in comparative examples 1-5, and the battery diaphragm sequentially obtained from the high-strength low-moisture high-temperature-resistant slurry prepared in examples 1-3 is the high-strength low-moisture high-temperature-resistant battery diaphragm prepared in examples 4-6, and the battery diaphragm sequentially obtained from the lithium battery slurry prepared in comparative examples 1-5 is comparative examples 6-10. A. B, C, D and X values are shown in Table 1.
TABLE 1
The performance parameters of the high-strength low-moisture high-temperature-resistant battery separator prepared in example 4 are as follows:
the performance parameters of the high-strength low-moisture high-temperature-resistant battery separator prepared in example 5 are as follows:
the performance parameters of the high-strength low-moisture high-temperature-resistant battery separator prepared in example 6 are as follows:
Comparative example 6 the performance parameters of the battery separator prepared were as follows:
comparative example 7 the performance parameters of the battery separator prepared were as follows:
comparative example 8 the performance parameters of the battery separator prepared were as follows:
comparative example 9 the performance parameters of the battery separator prepared were as follows:
Comparative example 10 the performance parameters of the battery separator prepared were as follows:
The membrane coated by the slurry obtained by mixing the alumina and the glass fiber has the advantage of hydrophobicity of the glass fiber, so that the water content of the membrane can be reduced, and the skilled person knows that the high water content can cause the decomposition of electrolyte lithium salt in the battery, so that the chemical characteristics of the lithium battery such as capacity, internal resistance, product characteristics and the like can be obviously deteriorated; on the one hand, the bonding force of the diaphragm can be improved after the titanate coupling agent is added, so that the structure between the coating and the base film is firmer, and meanwhile, the titanate coupling agent is added, so that the stability between the powder (the powder after the alumina and the glass fiber are mixed) is better at a high temperature, and the impact strength of the diaphragm is improved.
Because the aluminum silicate fiber has relatively high water absorption, the titanate coupling agent has better flame retardance and improved shock resistance than the silane coupling agent. As can be seen from fig. 1 to 6, the high-strength low-moisture high-temperature-resistant battery separator (the glass fiber, the alumina and the titanate coupling agent are synergistically modified) prepared in example 4 has higher compactness and stability than those prepared in comparative examples 6 to 10.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A high strength, low moisture, high temperature resistant slurry comprising: the glass fiber, the alumina and the titanate coupling agent are mixed according to the mass parts, wherein the ratio of the glass fiber to the alumina to the titanate coupling agent is (2-3): (5-9): (3-6).
2. The high strength, low moisture, high temperature resistant slurry of claim 1, further comprising: the aluminum oxide-water composite material comprises a dispersing agent and water, wherein the weight portion of the aluminum oxide, the dispersing agent and the water is (5-9): (0.1-0.5): (81.5 to 89.9).
3. The high strength, low moisture, high temperature resistant slurry of claim 1, wherein the titanate coupling agent is monoalkoxy, monoalkoxypyrophosphate, integral, or ligand.
4. The high strength, low moisture, high temperature resistant slurry of claim 1 wherein the dispersant is a polyacrylate ammonium salt, polyvinyl alcohol, or polyethylene glycol.
5. The preparation method of the high-strength low-moisture high-temperature-resistant slurry is characterized by comprising the following steps of: mixing glass fiber, alumina, water, titanate coupling agent and dispersing agent uniformly to obtain high-strength low-moisture high-temperature-resistant slurry, wherein the ratio of the glass fiber to the alumina to the water to the titanate coupling agent to the dispersing agent is (2-3): (5-9): (81.5 to 89.9): (3-6): (0.1-0.5).
6. A high strength, low moisture, high temperature battery separator comprising: a base film and a coating layer coated on the base film, wherein the coating layer is formed by coating the slurry with high strength, low moisture and high temperature resistance according to any one of claims 1 to 4.
7. A method of making the high strength, low moisture, high temperature battery separator of claim 6, comprising: and coating the high-strength low-moisture high-temperature-resistant slurry on a base film, and drying to obtain the high-strength low-moisture high-temperature-resistant battery diaphragm.
8. A high strength, low moisture, high temperature resistant battery separator comprising: a base film and a coating applied to the base film, the coating comprising: the glass fiber, the alumina and the titanate coupling agent are mixed according to the mass parts, wherein the ratio of the glass fiber to the alumina to the titanate coupling agent is (2-3): (5-9): (3-6).
9. Use of glass fiber, alumina and titanate coupling agent in combination with a separator to improve the needling strength and/or adhesion of the separator.
10. Use of glass fiber, alumina and titanate coupling agent together in a separator to reduce heat shrinkage and/or water content of the separator.
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| CN202410300666.2A CN117977103A (en) | 2024-03-15 | 2024-03-15 | High-strength low-moisture high-temperature-resistant battery diaphragm and preparation method thereof |
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