Composite separation membrane for lithium secondary battery and manufacturing method therefor
The present invention relates to a composite separation membrane for a lithium secondary battery, having an excellent effect of improving the life time and safety of a battery and a lithium secondary battery including the membrane. The composite separation membrane includes a porous base layer; a heat-resistant layer formed on one side or both sides of the porous base layer; and a fusion layer formed on an outermost layer. The heat-resistant layer includes inorganic particles connected and fixed by binder polymers, and the fusion layer includes crystalline polymers in the form of particles having a melting temperature of 100° C. or higher.
1. A composite separation membrane for a lithium secondary battery comprising:
a porous base layer;
a heat-resistant layer including inorganic particles connected and fixed by a binder polymer, and formed on the porous base layer, and
a fusion layer including crystalline polymers in a form of particles having a melting temperature of 100° C. or higher, and formed on the heat-resistant layer, wherein the crystalline polymer comprises at least one selected from the group consisting of a crystalline polyvinylidene fluoride-based polymer and a crystalline polyacrylonitrile,
wherein the inorganic particles and the crystalline polymer satisfy Equation 1 below:
1.5 ≤D 1 /D 2 [Equation 1]
in Equation 1, D1 is an average particle diameter of the inorganic particles of the heat-resistant layer, and D2 is an average particle diameter of the crystalline polymer particles of the fusion layer,
wherein the composited separation member has a surface roughness (Ra) of 0.3 μm or less and 0.15 μm or more, and
wherein the average particle diameter of the crystalline polymer particles is 0.15 μm to 0.8 μm.
2. The composite separation membrane for a lithium secondary battery of claim 1 , further comprising:
an interfacial layer formed between the heat-resistant layer and the fusion layer and having the inorganic particles and the crystalline polymer particles mixed therein.
3. The composite separation membrane for a lithium secondary battery of claim 1 , wherein the heat-resistant layer includes one or two or more inorganic particles selected from alumina, boehmite, barium titanium oxide, titanium oxide, magnesium oxide, clay, glass powder, boron nitride, and aluminum nitride.
4. The composite separation membrane for a lithium secondary battery of claim 1 , wherein the binder polymer of the heat-resistant layer is one or two or more selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyimide, polyethylene oxide, cellulose acetate, polyvinyl alcohol, carboxymethyl cellulose, and polybutyl acrylate.
5. The composite separation membrane for a lithium secondary battery of claim 1 , wherein the heat-resistant layer has a thickness of 1 to 10 μm.
6. The composite separation membrane for a lithium secondary battery of claim 1 , wherein the crystalline polymer further comprises a crystalline polystyrene.
7. The composite separation membrane for a lithium secondary battery of claim 1 , wherein the fusion layer has a thickness of 0.1 to 2 μm.
8. A manufacturing method for the composite separation membrane for a lithium secondary battery of claim 1 , said method comprising:
applying a heat-resistant layer coating liquid including inorganic particles and a binder polymer to one side or both sides of a porous base; and
applying a fusion layer coating liquid including a crystalline polymer in a form of particles having a melting temperature of 1000 C or higher on the applied heat-resistant layer coating liquid,
wherein the crystalline polymer comprises at least one selected from the group consisting of a crystalline polyvinylidene fluoride-based polymer and a crystalline polyacrylonitrile,
wherein an average particle diameter of the inorganic particles is 1.5 times or larger than an average particle diameter of the crystalline polymer particles,
wherein the average particle diameter of the crystalline polymer particles is 0.15 μm to 0.8 μm,
resulting in the composite separation membrane of claim 1 .
9. The manufacturing method of claim 8 , wherein the heat-resistant layer coating liquid is applied, and then the fusion layer coating liquid is applied without drying the heat-resistant layer coating liquid, thereby performing simultaneous coating.