Polyolefin microporous membrane and separator for nonaqueous electrolyte battery
The present invention provides a polyolefin microporous membrane made of a polyolefin resin and an inorganic particle, and the puncture strength of the microporous membrane is 3 N/20 μm or more and the membrane thickness retention ratio in penetration creep is 16% or more, thereby being excellent in safety and long-term reliability, and a separator for a nonaqueous electrolyte battery, and the like can be provided.
1. A lithium ion secondary battery comprising a separator comprising a polyolefin microporous membrane comprising a polyolefin resin and inorganic particles, wherein the polyolefin resin comprises a composition containing polypropylene is contained in an amount of 20% by weight or more and 40% by weight or less in 100% by weight of polyolefin resin, wherein the microporous membrane has a puncture strength of 3 N/20 μm or more, a membrane thickness retention ratio in penetration creep of 23% or more and 48% or less and a shutdown temperature of more than 160° C. wherein the inorganic particle content is 20% by mass or more and less than 60% by mass, and wherein particle diameter of the inorganic particle is 1 nm or more and less than 100 nm, and at least a part of the inorganic particles are fused with polyolefin.
2. The lithium ion secondary battery according to claim 1 , wherein the microporous membrane has a membrane thickness reduction rate in penetration creep of 10% or less.
3. The lithium on secondary battery according to claim 1 or 2 , wherein the inorganic particles comprise one, or two or more kinds selected from oxides and nitrides of silicon, aluminum and titanium, and carbonates and sulfates of calcium and barium.
4. The lithium on secondary battery according claim 1 wherein inorganic particles having a hydrophilic group and inorganic particles subjected to a hydrophobic treatment are used in combination as the inorganic particles.
5. The lithium on secondary battery according to claim 4 , wherein the inorganic particles having a hydrophilic group in a proportion of 1% by weight or more and less than 50% by weight of all inorganic particles and the inorganic particles subjected to a hydrophobic treatment in a proportion of 50% by weight or more and less than 99% by weight of all inorganic particles are used in combination.
6. The lithium on secondary battery according to claim 1 , wherein a viscosity average molecular weight of the microporous membrane is 50,000 or more and 500,000 or less.
7. The lithium on secondary battery according to claim 1 , wherein a viscosity average molecular weight of the microporous membrane is more than 500,000 and less than 2,000,000.
8. A method for producing a polyolefin microporous membrane for the lithium secondary battery according to claim 1 , comprising the steps of:
(1) melt-kneading a polyolefin resin, inorganic particles and a plasticizer to obtain a molten substance;
(2) transferring the molten substance and molding into a sheet form, thereafter solidifying by cooling to obtain a sheet;
(3) stretching the sheet at least in a uniaxial direction by a surface stretching ratio of 20 times or more and less than 200 times; and
(4) extracting the plasticizer after the stretching step (3),
wherein a temperature from transferring the molten substance until molding into a sheet form in (2) is set at higher than a preset temperature in the melt-kneading step.
9. The method for producing a polyolefin microporous membrane according to claim 8 , comprising stretching in a biaxial direction in the stretching step (3).