Separator having silane-modified polyolefin and polyethylene, and method for producing the same
There is provided a method for producing a separator for an electricity storage device that includes a step of contacting a porous body formed from a silane-modified polyolefin-containing molded sheet with a base solution or acid solution, and a separator for an electricity storage device comprising a microporous film with a melted film rupture temperature of 180° C. to 220° C. as measured by thermomechanical analysis (TMA).
1. A method for producing a separator for an electricity storage device, comprising the following steps:
(1) a sheet-forming step in which a silane graft-modified polyolefin, polyethylene and a plasticizer are extruded into a sheet using an extruder, cooled to solidification and shaped into a molded sheet, wherein the silane graft-modified polyolefin is not a master batch resin containing a dehydrating condensation catalyst that crosslinks the silane graft-modified polyolefin before the sheet-forming step;
(2) a stretching step in which the molded sheet is subjected to biaxial stretching to a 20-fold to 250-fold area increase to form a stretched sheet;
(3) a porous body-forming step in which the plasticizer is extracted from the stretched sheet to form a porous body;
(4) a heat treatment step in which the porous body is subjected to heat treatment and subjected to stretching and relaxation in a transverse direction, which is perpendicular to a machine direction of the porous body, to obtain a heat-treated porous body;
(5) an affinity treatment step in which the heat-treated porous body is immersed in an organic solvent that is amphiphilic for water and organic materials, and the liquid affinity of the heat-treated porous body is increased to obtain an affinity-treated porous body impregnated with the organic solvent;
(6) a crosslinking step in which the affinity-treated porous body is immersed in a base solution containing alkali metal hydroxides or alkaline earth metal hydroxides, and conducting a silane dehydration condensation reaction of the affinity-treated porous body to form oligosiloxane bonds, obtaining a crosslinked porous body; and
(7) a washing and drying step in which the crosslinked porous body is washed with water and dried.
2. The method for producing a separator for an electricity storage device according to claim 1 , wherein the separator for an electricity storage device comprises a microporous membrane having a melted membrane rupture temperature of 180° C. to 220° C. as measured by thermomechanical analysis (TMA) in fixed-length mode.
3. The method for producing a separator for an electricity storage device according to claim 1 , wherein content of scandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin, titanium, iron, nickel or lead in the separator for an electricity storage device is 0.10 ppm to 200 ppm as the total in terms of atoms.
4. The method for producing a separator for an electricity storage device according to claim 1 , wherein the weight ratio of the silane graft-modified polyolefin and the polyethylene (silane graft-modified polyolefin weight/polyethylene weight) is 0.05/0.95 to 0.40/0.60.
5. The method for producing a separator for an electricity storage device according to claim 1 , wherein in the washing and drying step, the crosslinked porous body is washed with water at a temperature of 20 to 100° C. and a pH of 6 to 8 and dried.
6. The method for producing a separator for an electricity storage device according to claim 1 , wherein in the crosslinking step, the affinity-treated porous body is immersed in the base solution.
7. The method for producing a separator for an electricity storage device according to claim 6 , wherein the temperature of the base solution is 20° C. to 100° C. and the pH thereof is 8 to 14.
8. A method for producing an electricity storage device, comprising the following steps:
a step of laminating and/or winding a positive electrode, a separator for an electricity storage device obtained by the method for producing a separator for an electricity storage device according to claim 1 , and a negative electrode, to obtain a laminated stack or wound body;
a step of inserting the laminated stack or wound body into an exterior body;
a step of pouring an electrolyte solution into the exterior body; and
a step of connecting lead terminals to the positive electrode and negative electrode.
9. The method for producing an electricity storage device according to claim 8 , wherein the electrolyte solution includes a LiPF 6 -containing electrolyte or another fluorine (F)-containing lithium salt electrolyte.