Multilayer porous film, separator for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
View Patent ↗Provided is a multilayer porous film that has extremely high powder fall-off resistance and superior electrolyte solution adsorptivity and heat resistance and exhibits superior properties when used as a battery separator without decreasing the high air permeability of a porous film. The multilayer porous film includes a polyolefin-based resin porous film and a coating layer containing a filler and a resin binder on at least one surface of the polyolefin-based resin porous film. The amount of particles with particle sizes of less than 0.2 μm (D 0.2 ) in the filler is 1% or more, and the specific surface area of the filler is 5 m 2 /g or more and less than 10 m 2 /g. The multilayer porous film satisfies a particular condition.
1. A multilayer porous film, comprising:
a polyolefin-based resin porous film, and
a coating layer comprising a filler and a resin binder on at least one surface of the polyolefin-based resin porous film,
wherein the filler has an average particle size from 0.2-1.5 μm and comprises particles with particles sizes of less than 0.2 μm and particles with particles sizes of 1.0 μm or more,
wherein the particles with particle sizes of less than 0.2 μm (D 0.2 ) in the filler are present and present in an amount of 5% or more, and the particles with particles sizes of 1.0 μm or more (D 1.0 ) in the filler are present and present in an amount of 20% or less,
wherein a specific surface area of the filler is 5 m 2 /g or more and less than 10 m 2 /g, and
wherein the multilayer porous film satisfies a condition (1):
condition (1): after the multilayer porous film is cut to a size of 50 mm ×50 mm and is stuck on paper in a state where the coating layer faces upward, a column-shaped weight having a diameter of 40 mm and a weight of 700 g and covered with a cotton cloth on an entire bottom surface thereof is placed on the coating layer, and the weight is rotated at a rotational speed of 50 rpm for 10 minutes to rub the surface of the coating layer, observation of the surface of the coating layer shows that the coating layer has a missing portion with an area of less than 10% of a contact area of the weight.
2. The multilayer porous film of claim 1 , wherein the filler comprises a metal oxide.
3. The multilayer porous film of claim 2 , wherein the resin binder is at least one selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, and a polyacrylic acid derivative.
4. The multilayer porous film of claim 3 , wherein a content of the filler to a total amount of filler and resin binder in the coating layer is from 80% to 99.9% by mass.
5. The multilayer porous film of claim 2 , wherein a content of the filler to a total amount of filler and resin binder in the coating layer is from 80% to 99.9% by mass.
6. The multilayer porous film of claim 2 , wherein the polyolefin-based resin porous film comprises a polypropylene-based resin.
7. The multilayer porous film of claim 1 , wherein the resin binder is at least one selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, and a polyacrylic acid derivative.
8. The multilayer porous film of claim 7 , wherein a content of the filler to a total amount of filler and resin binder in the coating layer is from 80% to 99.9% by mass.
9. The multilayer porous film of claim 7 , wherein the polyolefin-based resin porous film comprises a polypropylene-based resin.
10. The multilayer porous film of claim 1 , wherein a content of the filler to a total amount of filler and resin binder in the coating layer is from 80% to 99.9% by mass.
11. The multilayer porous film of claim 10 , wherein the polyolefin-based resin porous film comprises a polypropylene-based resin.
12. The multilayer porous film of claim 1 , wherein the polyolefin-based resin porous film comprises a polypropylene-based resin.
13. The multilayer porous film of claim 1 , wherein the polyolefin-based resin porous film has β-crystal activity.
14. The multilayer porous film of claim 1 , wherein the coating layer is formed on the polyolefin-based resin porous film by a method comprising applying a dispersion to the polyolefin-based resin porous film.
15. The multilayer porous film of claim 14 , wherein a dispersion medium in the dispersion comprises water as a major component.
16. The multilayer porous film of claim 1 , wherein the amount of particles with particles sizes of less than 0.2 μm (D 0.2 ) in the filler is 10% or more and the amount of particles with particles sizes of 1.0 μm or more (D 1.0 ) in the filler is 15% or less.
17. A separator comprising the multilayer porous film of claim 1 .
18. A nonaqueous electrolyte secondary battery comprising the separator of claim 17 .