Ceramic membrane having support materials comprising polyaramid fibers and method for producing said membranes
View Patent ↗The present invention relates to a membrane comprising a flat, flexible substrate having a plurality of openings and having a porous inorganic coating situated on and in said substrate, the material of the substrate being selected from woven or non-woven, electrically non-conductive fibers, characterized in that the substrate comprises polyaramide fibers that are pure or connected to fibers of the further polymer or at least of one of these further polymers, wherein the fibers of at least one of said further polymers comprise a melting point that is lower than the decomposition point of the polyaramide fibers.
1. A membrane, comprising:
a sheetlike, flexible, woven or nonwoven substrate comprising electrically nonconductive fibers, which is provided with a multiplicity of openings; and
a porous inorganic coating on and inside the substrate,
wherein the electrically nonconductive fibers comprise
(i) polyaramid fibers melted to fibers of a further polymer having a melting point lower than the decomposition point of the polyaramid fibers, or
(ii) polyaramid fibers melted to one another with a polymeric binder.
2. The membrane of claim 1 , wherein the further polymer fibers are at least one selected from the group consisting of polyethylene terephthalate, a polyester, a polycarbonate, polyacrylonitrile, a polyimide, a polyamide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, polyethylene, polypropylene, and polyolefin, and
the polymeric binder is at least one selected from the group consisting of polyurethane, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-PTFE copolymer, butadiene rubber, (meth)acrylate latex, polyvinylpyrrolidone, and polyvinyl alcohol.
3. The membrane of claim 1 , wherein the polyaramid fibers are melted to further polymer polymer fibers and a mixing ratio of the polyaramid fibers to the further polymer fibers is in a range of 10:1 to 1:10.
4. The membrane of claim 1 , wherein the substrate has a porosity of 50 to 97%.
5. The membrane of claim 1 , wherein the substrate has a melting point of more than 200° C.
6. The membrane of claim 1 , having a tensile strength of more than 5 N/cm.
7. A method for producing the membrane of claim 1 , the method comprising:
(I) applying a suspension comprising an inorganic component comprising a compound comprising a metal, a semimetal, or a mixed metal and a main group element selected from the group consisting of a group 3 to group 7 element, and a sol,
to
a sheetlike, flexible substrate provided with a multiplicity of openings and comprising (i) polyaramid fibers which are joined to further polymer fibers having a melting point lower than the decomposition point of the polyaramid fibers or (ii) polyaramid fibers joined to one another with a polymeric binder; and
(II) heating the substrate to a temperature of between 200 to 350° C., to obtain a solidified suspension on the substrate, inside the substrate, or both.
8. The method of claim 7 , wherein the further polymer fibers are at least one selected from the group consisting of polyethylene terephthalate, polyacrylonitrile, polyester, polyimide, polyamide, polytetrafluoroethylene, and polyolefin,
the polymeric binder is at least one selected from the group consisting of polyurethane, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-PTFE copolymer, butadiene rubber, (meth)acrylate latex, polyvinylpyrrolidone, polyvinyl alcohol, and
the suspension comprises at least one selected from the group consisting of a sol, polyaramid particles, and at least one oxide of a metal selected from the group consisting of Al, Zr, Si, Ti, and Y.
9. The method of claim 7 , wherein the suspension comprises a sol, polyaramid particles, and at least one oxide of a metal selected from the group consisting of Al, Zr, Si, Ti, and Y.
10. The method of claim 7 , wherein the applying (I) is carried out by roll coating, printing, pressing, injecting, rolling, knifecoating, spreading, dipping, squirting, or pouring.
11. The membrane of claim 1 , wherein the membrane is suitable for use as a separator in a battery, a wall lining, or a protective and support device casing.
12. A lithium ion battery, comprising:
the membrane of claim 1 , wherein the membrane is a separator.
13. The membrane of claim 1 , wherein the polyaramid fibers have a diameter in a range of 0.5 to 50 μm.
14. The membrane of claim 1 , wherein the polyaramid fibers have a diameter in a range of 0.5 to 20 μm.
15. The membrane of claim 3 , wherein the further fibers are polyethylene terephthalate fibers.
16. The membrane of claim 15 , wherein a mixing ratio of the polyaramid fibers and the polyethylene terephthalate fibers is 1:1.
17. The membrane of claim 4 , wherein the substrate has a porosity of 75 to 90%.
18. The membrane of claim 1 , wherein the electrically nonconductive fibers comprise
(i) polyaramid fibers melted to fibers of a further polymer having a melting point lower than the decomposition point of the polyaramid fibers.
19. The membrane of claim 1 , wherein the electrically nonconductive fibers comprise
(ii) polyaramid fibers melted to one another with a polymeric binder.