Composite membrane and preparation method thereof and battery comprising composite membrane
A technology of composite diaphragm and porous membrane, which is applied in the direction of secondary batteries, battery pack parts, chemical instruments and methods, etc., can solve the problem of uneven pore size of polyimide porous membrane, achieve uniform pore diameter distribution, high Effects of mechanical strength and high thermal stability
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[0020] According to the preparation method provided by the present invention, according to the above-mentioned first pore-forming principle, the pore-forming substance is selected from one of hydroxides of alkaline earth metal elements, aluminum hydroxide, phosphates of alkali metals and sodium tripolyphosphate Or several, and the average particle size is 0.01-2 microns. Wherein, the hydroxide of the alkaline earth metal element is magnesium hydroxide and / or calcium hydroxide; the phosphate of the alkali metal is trisodium phosphate and tripotassium phosphate. The coagulation solution is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. Experiments have shown that one or more of hydrochloric acid, sulfuric acid and phosphoric acid is selected from the hydroxides of alkaline earth metal elements, aluminum hydroxide, alkali metal phosphates and sodium tripolyphosphate as pore-forming substances. Or the solubility of several kinds at 25°C is not more than 1% (...
Embodiment approach
[0048] According to a kind of preferred embodiment of the present invention, the preparation method of polyimide porous membrane of the present invention comprises the steps:
[0049] (1) Tetraacid dianhydride and organic diamine are added to the solvent according to the molar ratio of 0.8-1.2:1, the amount of solvent used is such that the concentration of the obtained polyamic acid is 5-40% by weight, at 20-70°C After stirring and reacting for 3-15 hours, add pore-forming substances, the weight ratio of pore-forming substances to the obtained polyamic acid is 0.01-0.3:1; vacuum degassing at the same temperature for 1-12 hours to obtain a polyamic acid solution;
[0050] (2) At a temperature of 10-40°C and a relative humidity of 20-80%, the above polyamic acid solution is coated on a stainless steel or glass support, dried at 20-200°C, and the solvent is removed to obtain 5 - 50 micron polyamic acid film;
[0051] (3) immersing the support body of the above-mentioned polyamic a...
Embodiment 1
[0071] This embodiment illustrates the preparation of the composite membrane provided by the invention
[0072] (1) 4,4'-diaminodiphenyl ether and pyromellitic dianhydride are added to 300 milliliters of N,N-dimethylacetamide at a molar ratio of 1:1, wherein the solid content (solid content It means that the weight of the polyamic acid generated in the system accounts for the mass percentage of the total weight of the mixture) is 10% by weight. Stir the reaction at 25°C for 8 hours, then add 3 grams of propylene glycol methyl ether acetate, and vacuum degassing at this temperature for 1 hour to obtain a viscous mixture with an intrinsic viscosity η int =150 ml / g (measurement conditions: Ubbelohde viscometer, constant temperature 30°C, the mixture is diluted to a solid content of 0.005 g / ml);
[0073] (2) At a temperature of 10°C and a relative humidity of 50%, the above mixture is coated on a stainless steel plate, dried at 100°C for 20 minutes, and then the solvent is remove...
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