IP Library Granted Patent US 10,680,224
Granted Patent B2
US 10,680,224 · App. 15/318,323 · Granted Jun 9, 2020

Polyolefin multilayer microporous film, method for producing same, and cell separator

Inventors: Kosuke Harumoto (Tochigi, JP); Yukiko Miura (Tochigi, JP); Hideto Mitsuoka (Tochigi, JP)
Assignee: TORAY INDUSTRIES, INC.
H01M2/1686B32B5/18B32B5/32B32B27/08B32B27/20B32B27/24B32B27/32C08J9/00C08J9/28H01M2/16H01M2/1653B32B2264/025B32B2264/0235B32B2264/0257B32B2264/10B32B2264/102B32B2264/104B32B2266/025B32B2266/102B32B2270/00B32B2307/20B32B2307/306B32B2307/50B32B2307/514B32B2307/581B32B2307/724B32B2307/732B32B2457/10
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Quick Facts
Patent No.
US 10,680,224
App. No.
15/318,323
Granted
Jun 9, 2020
Kind
B2
Abstract

A polyolefin multilayer microporous membrane is disclosed. The polyolefin multilayer microporous membrane has a low air permeability value, maintains high porosity and mechanical strength even when formed into a thin film. The polyolefin multilayer microporous membrane also has excellent impedance characteristics. The polyolefin multilayer microporous membrane has excellent battery characteristics when used as a battery separator.

Claims (36)

1. A polyolefin multilayer microporous membrane comprising:

a first microporous layer comprising a first polyolefin resin containing a polypropylene; and

a second microporous layer comprising a second polyolefin resin containing an ultrahigh molecular weight polyethylene,

wherein a thickness of the multilayer microporous membrane is not greater than 25 μm,

wherein an air permeability of the multilayer microporous membrane in terms of a membrane thickness of 16 μm is not less than 100 sec/100 cm 3 /16 μm and not greater than 300 sec/100 cm 3 /16 μm,

wherein an impedance of the multilayer microporous membrane is less than 7.5 Q·cm 2 , wherein a weight average molecular weight (Mw) of the polypropylene is not less than 1×10 6 and not greater than 4×10 6 ,

wherein the content of the polypropylene in the first microporous layer having a Mw of 5×10 4 is not greater than 5 mass %, and

wherein the thickness in urn and a porosity in % of the multilayer microporous membrane satisfy the relationship: porosity/thickness >3.5.

2. The polyolefin multilayer microporous membrane according to claim 1 , wherein a content of the polypropylene in the polyolefin multilayer microporous membrane is not less than 2.0 mass % of the total of the first and second polyolefin resins.

3. The polyolefin multilayer microporous membrane according to claim 1 , wherein the first polyolefin resin contains a polypropylene in an amount of not less than 10 mass % and not greater than 55 mass % and a high-density polyethylene in an amount of not less than 45 mass % and not greater than 90 mass %, wherein the second polyolefin resin contains an ultrahigh molecular weight polyethylene in an amount of not less than 10 mass % and not greater than 60 mass % and a high-density polyethylene in an amount of not less than 40 mass % and not greater than 90 mass %.

4. The polyolefin multilayer microporous membrane according to claim 1 , wherein a maximum pore size as measured with a perm porometer is not less than 5 nm and not greater than 55 nm.

5. The polyolefin multilayer microporous membrane according to claim 1 , wherein a mean flow pore size as measured with a perm porometer is not less than 20 nm.

6. The polyolefin multilayer microporous membrane according to claim 1 , wherein a pin puncture strength in terms of a membrane thickness of 16 μm is not less than 250 gf/16 μm.

7. The polyolefin multilayer microporous membrane according to claim 1 , wherein a meltdown temperature according to a falling ball test method is not lower than 150° C. and not higher than 190° C.

8. The polyolefin multilayer microporous membrane according to claim 1 , further comprising an inorganic filler and/or a heat-resistant resin on at least one surface of the polyolefin multilayer microporous membrane.

9. The polyolefin multilayer microporous membrane according to claim 1 , wherein the thickness of the multilayer microporous membrane is not greater than 16 μm.

10. A battery separator comprising a polyolefin multilayer microporous membrane, wherein the polyolefin multilayer microporous membrane comprises:

a first microporous layer comprising a first polyolefin resin containing a polypropylene; and

a second microporous layer comprising a second polyolefin resin containing an ultrahigh molecular weight polyethylene,

wherein a thickness of the multilayer microporous membrane is not greater than 25 μm,

wherein an air permeability of the multilayer microporous membrane in terms of a membrane thickness is not less than 100 sec/100 cm 3 /16 pm and not greater than 300 sec/100 cm 3 /16 pm,

wherein an impedance of the multilayer microporous membrane is less than Q·cm 2 ,

wherein a weight average molecular weight (Mw) of the polypropylene is not less than 1×10 6 and not greater than 4×10 6 , and

wherein the content of the polypropylene in the first microporous layer having a Mw of 5×10 4 is not greater than 5 mass %, and

wherein the thickness in urn and a porosity in % of the multilayer microporous membrane satisfy the relationship: porosity/thickness >3.5.

11. The battery separator of claim 10 , wherein the polyolefin multilayer microporous membrane further comprises an inorganic filler and/or a heat-resistant resin on at least one surface of the polyolefin multilayer microporous membrane.

12. A method of manufacturing the polyolefin multilayer microporous membrane of claim 1 , the method comprising:

(1) preparing a first polyolefin solution by melt-kneading the first polyolefin resin containing the polypropylene and a solvent;

(2) preparing a second polyolefin solution by melt-kneading the second polyolefin resin containing the ultrahigh molecular weight polyethylene and the solvent;

(3) coextruding the first and second polyolefin solutions to form a multilayer sheet and subsequently cooling the multilayer sheet to form a gel-like multilayer sheet;

(4) performing a first stretching step of stretching the gel-like multilayer sheet at a temperature not less than 112° C. and not greater than 117° C. to form a stretched multilayer sheet;

(5) removing the solvent from the stretched multilayer sheet after performing the first stretching step;

(6) drying the stretched multilayer sheet after removing the solvent; and

(7) performing a second stretching step of stretching the stretched multilayer sheet after the drying.

13. The method according to claim 12 , wherein a stretching magnification (B) in the first stretching step and a stretching magnification (C) in the second stretching step satisfy the relationship 0.01≤A/(B×C)≤0.35,

wherein A is a content of polypropylene in the polyolefin multilayer microporous membrane with respect to a total of 100 mass % of the first and second polyolefin resins in the polyolefin multilayer microporous membrane.

Assignments (2)
MERGER AND CHANGE OF NAME Recorded Oct 10, 2017
From: TORAY BATTERY SEPARATOR FILM CO., LTD.; TORAY INDUSTRIES, INC.
To: TORAY INDUSTRIES, INC.
Reel/Frame 044821/0223 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: HARUMOTO, KOSUKE; MIURA, YUKIKO; MITSUOKA, HIDETO
To: TORAY BATTERY SEPARATOR FILM CO., LTD.
Reel/Frame 041093/0625 →
Priority Claims (1)
JP 2014-126831 · Jun 20, 2014 · national
Continuity (1)
Related Publication 20170125766A1 · May 4, 2017