Organic/inorganic composite coating porous separator and secondary battery element using same
There is provided an organic/inorganic complex coating porous separator including a porous substrate, and an organic/inorganic complex coating layer formed in a single layer or multiple layers on a single surface or both surfaces of the porous substrate or at least a part of a pore portion of the porous substrate using a coating solution comprising a binder dispersed or suspended in a certain size and selectively comprising inorganic particles, and a secondary battery including the same. According to the present invention, since the coating solution comprising the binder dispersed in a certain size or less in a solvent is coated/dried on the porous substrate, a organic/inorganic complex coating porous separator having excellent air permeability and adhesive strength and a secondary battery including the organic/inorganic complex coating porous separator are provided.
1. A method for preparing a coating porous separator comprising:
(a) a step of dispersing inorganic particles by adding and mixing the inorganic particles with a solvent;
(b) a step of preparing a coating solution by adding and mixing a binder in the form of particles and a second organic binder which is dissolved in the solvent with the mixed solution obtained in the step (a); and
(c) a step of coating and drying the coating solution obtained in the step (b) on one or more regions selected from the group consisting of a one surface, both surfaces of a porous substrate, and at least a part of a pore portion of the substrate in a single layer or multiple layers;
wherein a mean particle diameter of the binder in the form of particles in the solvent is less than one and a half times a mean pore diameter of the porous substrate,
wherein the binder in the form of particles which is dispersed or suspended in the solvent is one or two or more selected from latex or emulsions or suspensions formed by dispersing polymer compounds selected from the group consisting of polystyrene-based, styrene butadiene-based, nitrile-based, polyvinyl chloride-based, polyolefin-based, acryl-based, acetate-based, polyvinylidene fluoride-based, ethylene-vinyl acetate-based, polyvinyl butyral-based, polytetrafluoro ethylene-based, polyimide-based, polyethylene oxide-based, cellulose-based, polyvinyl alcohol-based, and starch-based polymers and copolymers, in an organic solvent or a water-based solvent, and
wherein the second organic binder which is dissolved in the solvent is a modified polyacryl polyether copolymer, and
wherein a weight ratio of the inorganic particles:the binder in the form of particles is 20:1 to 140:1.
2. The method of claim 1 , wherein the mean particle diameter of the binder in the form of particles is a half or less of a mean diameter of the inorganic particles.
3. The method of claim 1 , wherein the inorganic particles include one or two or more selected from the group consisting of SnO 2 , BaTiO 2 , Al 2 O 3 , CeO 2 , SiO 2 , TiO 2 , Li 3 PO 4 , NiO, ZnO, MgO, Mg(OH) 2 , CaO, ZrO 2 , and Y 2 O 3 , and have a sphere shape, a plate shape, or an irregular shape having a mean particle diameter of 0.1 to 5 μm.
4. The method of claim 3 , wherein the inorganic particles are Al 2 O 3 .
5. The method of claim 4 , wherein the Al 2 O 3 inorganic particles have a mean particle diameter of between 0.5 and 1.0 μm.
6. The method of claim 1 , wherein the coating solution further comprises one or more additives selected from the group consisting of a polymer dispersion agent, a wetting agent, an antifoaming and defoaming agent, a leveling agent, a thickener, a rheology additive, an adhesion promoter, an additive for surface, and a UV absorber.
7. The method of claim 1 , wherein the porous substrate has a thickness of 1 to 100 μm and a porosity of 5 to 90%.
8. The method of claim 7 , wherein the substrate has a thickness between 1 and 30 μm and a porosity between 20 and 80%.
9. The method of claim 1 , wherein the substrate has a mean pore diameter between 80 and 400 nm.
10. The method of claim 9 , wherein the substrate has a thickness between 1 and 30 μm and a porosity between 20 and 80%.
11. The method of claim 9 , wherein the inorganic particles include one or two or more selected from the group consisting of SnO 2 , BaTiO 2 , Al 2 O 3 , CeO 2 , SiO 2 , TiO 2 , Li 3 PO 4 , NiO, ZnO, MgO, Mg(OH) 2 , CaO, ZrO 2 , and Y 2 O 3 , and have a sphere shape, a plate shape, or an irregular shape having a mean particle diameter of 0.1 to 5 μm.
12. The method of claim 11 , wherein the inorganic particles are Al 2 O 3 .
13. The method of claim 12 , wherein the Al 2 O 3 inorganic particles have a mean particle diameter of between 0.5 and 1.0 μm.
14. The method of claim 1 , wherein the inorganic particles have a sphere shape, plate shape, or irregular shape with a mean particle diameter of 0.1-5 μm; and, wherein the porous substrate has a thickness of 1 to 100 μm and a porosity of 5-90%.
15. The method of claim 1 , wherein the porous separator further undergoes corona treatment.
16. The method of claim 15 , wherein the binder has a mean particle diameter d 50 of between 50 and 180 nm.
17. The method of claim 1 , wherein the porous substrate is polypropylene or polyethylene and the binder is selected from the group consisting of styrene butadiene, acryl emulsion, polyvinylidene fluoride, carboxyl methyl cellulose, and combinations thereof.