Microporous polyolefin multi layer film and preparing method thereof
View Patent ↗The present invention relates to a multi-layered microporous polyolefin film for a battery separator and a method for preparing the same. The microporous multi-layered film of the present invention has a characteristics to have both the low shutdown temperature conferred by the polyethylene and the high melt fracture temperature conferred by the polypropylene and heat-resistant filler. In addition, it has the high strength and stability conferred by the micropores prepared under wet process and the high permeability and high strength conferred by the macropores prepared under dry process. Therefore, this multi-layered film can be used effectively to manufacture a secondary battery with high capacity and high power.
1. A method for preparing a microporous polyolefin multilayer film which comprises steps:
(a) melting and mixing a mixture that comprises 20-50 weight % of polyethylene having a melting temperature of 125° C. or higher and 80-50 weight % of a diluent;
(b) melting and mixing a mixture, which does not contain diluent, comprising 20-60 weight % of polypropylene having a melting temperature of 160° C. or higher and 80-40 weight % of a heat-resistant filler having a melting temperature of 170° C. or higher, wherein the heat resistant filler is a heat-resistant resin, an inorganic material or a mixture thereof;
(c) forming the blended melt prepared in the (a) and (b) steps to a multi-layered sheet of 2 or 3 layers;
(d) forming a film by stretching the multi-layered sheet;
(e) extracting diluent from the film; and
(f) heat setting the film,
wherein the pores of the polyethylene layer are micropores that are fabricated by stretching and extracting after separating the phase of polyethylene and the diluent and have an average size of 0.1 μm or smaller; and pores of the polypropylene and heat-resistant filler layer are macropores that are fabricated by cracking of the interface between the polypropylene and heat-resistant filler and have an average size of 1-50 μm, and the microporous polyolefin multilayer film has a thickness of 9-30 μm, a puncture strength of 0.15 N/μm or more, a permeability of 1.5×10 −5 Darcy or more and a melt fracture temperature of 170° C. or higher.
2. The method for preparing a microporous polyolefin multilayer film according to claim 1 , wherein the polyethylene is single or combined polyethylene comprising ethylene only or ethylene and C 3 -C 8 α-olefin and having a melting temperature of 125° C. or higher; the polypropylene is single or combined polypropylene comprising propylene only or propylene, ethylene and C 4 -C 8 α-olefin having a melting temperature of 160° C. or higher; and the heat-resistant filler having a melting temperature of 170° C. or higher is a heat-resistant resin selected among polyvinylidene fluoride, polymethylpentene, polyethylene terephthalate, polycarbonate, polyester, polyvinyl alcohol, polyacrylonitrile and polymethylene oxide, and, an inorganic material that has an average particle size of 0.01-5 μm and is selected among silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), SiS 2 , SiPO 4 , MgO, ZnO, BaTiO 3 and natural or organically modified clay, or a mixture thereof.
3. The method for preparing a microporous polyolefin multilayer film according to claim 2 , wherein the polyethylene layer occupies more than 50% of the total thickness and the polypropylene and heat-resistant filler layer has a thickness of at least 1 μm.
4. The method for preparing a microporous polyolefin multilayer film according to claim 3 , wherein the polypropylene and heat-resistant filler layer is comprised of 20-50 weight % of polypropylene and 80-50 weight % of the heat-resistant filler.
5. The method for preparing a microporous polyolefin multilayer film according to claim 1 , wherein the film has a thickness of 9-30 μm, a puncture strength of 0.2 N/μm or more and a permeability of 2.5×10 −5 -10.0×10 −5 Darcy.
6. The method for preparing a microporous polyolefin multilayer film according to claim 2 , wherein the film has a thickness of 9-30 μm, a puncture strength of 0.2 N/μm or more and a permeability of 2.5×10 −5 -10.0×10 −5 Darcy.
7. The method for preparing a microporous polyolefin multilayer film according to claim 3 , wherein the film has a thickness of 9-30 μm, a puncture strength of 0.2 N/μm or more and a permeability of 2.5×10 −5 -10.0×10 −5 Darcy.
8. The method for preparing a microporous polyolefin multilayer film according to claim 4 , wherein the film has a thickness of 9-30 μm, a puncture strength of 0.2 N/μm or more and a permeability of 2.5×10 −5 -10.0×10 −5 Darcy.