Multi-layer microporous membrane, battery separator and battery
View Patent ↗The invention relates to a particular multi-layer microporous membrane having a good balance of important properties, including excellent electrochemical stability and low heat shrinkage, while maintaining high permeability and heat resistance, with good mechanical strength, compression resistance and electrolytic solution absorption. Of particular importance when used as a battery separator, the present multi-layer microporous membrane exhibits excellent heat shrinkage, melt down temperature and thermal mechanical properties, i.e. low maximum shrinkage in the molten state. The multi-layer microporous membrane of the present invention is manufactured by layering, such as for example by coextrusion, one or more microporous membrane first layers and one or more microporous membrane second layers, such as on one or both sides of a first layer. The invention further relates to battery separators comprising the multi-layer microporous membrane and batteries utilizing the battery separators.
1. A multi-layer microporous membrane comprising:
at least two first microporous membrane skin layers comprising;
(a) from about 30 to about 70% of a first polyethylene,
(b) from about 20 to about 40% of a first polypropylene, the first polypropylene having a weight average molecular weight of from about 0.8×10 6 to about 1.5×10 6 , a molecular weight distribution of from about 1 to about 100 and a heat of fusion of 80 J/g or higher and
(c) from about 10 to about 30% of a second polypropylene, the second polypropylene having a weight average molecular weight of from about 4×10 5 to about 7.5×10 5 , a molecular weight distribution of from about 5 to about 100 and a heat of fusion of 80 J/g or higher, percentages based on the weight of the first microporous membrane skin layer; and
at least one second microporous membrane layer in planar contact with the first microporous membrane comprising a high density polyethylene and an ultrahigh molecular weight polyethylene;
wherein the first and second microporous membrane layers are formed into first layer/second layer/first layer or first layer/second layer/first layer/second layer/first layer structures.
2. The membrane of claim 1 wherein
the first polyethylene has a weight average molecular weight of from about 2.5×10 5 to about 5×10 5 and a molecular weight distribution of from about 5 to about 100; and
wherein said second layer comprises (a) from about 60 to about 90% of the high density polyethylene, the high density polyethylene of the second layer having a weight average molecular weight of from about 2.5×10 5 to about 5×10 5 and a molecular weight distribution of from about 5 to about 100, and (a′) from about 10 to about 40% of the ultrahigh molecular weight polyethylene, the ultrahigh molecular weight polyethylene having a weight average molecular weight of from about 1×10 6 to about 5×10 6 and a molecular weight distribution of from about 5 to about 100, percentages based on the weight of the second microporous membrane layer; and
wherein the total first to total second microporous membrane layer thickness ratio is in the range of from about 10/90 to about 75/25.
3. The multi-layer microporous membrane of claim 2 wherein said first microporous membrane skin layer comprises (a) from about 40 to about 60% of the first polyethylene, the first polyethylene having a weight average molecular weight of from about 2.5×10 5 to about 4×10 5 and a molecular weight distribution of from about 5 to about 50, (b) from about 25 to about 40% of the first polypropylene, the first polypropylene having a weight average molecular weight of from about 0.9×10 6 to about 1.4×10 6 , a molecular weight distribution of from about 1 to about 50 and a heat of fusion of from about 80 to about 120 J/g, and (c) from about 10 to about 25% of the second polypropylene, the second polypropylene having a weight average molecular weight of from about 5×10 5 to about 7×10 5 , a molecular weight distribution of from about 5 to about 50 and a heat of fusion of from about 80 to about 120 J/g, percentages based on the weight of the first microporous membrane skin layer; and said second microporous membrane layer comprises (a) from about 70 to about 85% of the high density polyethylene, the high density polyethylene having a weight average molecular weight of from about 2.5×10 5 to about 4×10 5 and a molecular weight distribution of from about 5 to about 50, and (a′) from about 15 to about 30% of the ultrahigh molecular weight polyethylene, the ultrahigh molecular weight polyethylene having a weight average molecular weight of from about 1×10 6 to about 4×10 6 and a molecular weight distribution of from about 5 to about 50, percentages based on the weight of the second microporous membrane layer.
4. The multi-layer microporous membrane of claim 1 wherein (a) the first polyethylene is one or more of ethylene homopolymer or ethylene/α-olefin copolymer having a weight average molecular weight of from about 2.5×10 5 to about 5×10 5 and a molecular weight distribution of from about 5 to about 100, (b) the first polypropylene is one or more of propylene homopolymer or propylene/α-olefin copolymer; and (c) the second polypropylene is one or more of propylene homopolymer or propylene/α-olefin copolymer.
5. The multi-layer microporous membrane of claim 1 having a melt down temperature of 148° C. or higher and a thermal mechanical analysis maximum shrinkage in the molten state at 140° C. of 20% or less, and one or more properties of (1) an air permeability measured according to JIS P8117 ranging from about 20 to about 400 seconds/100 cm 3 , (2) a porosity ranging from about 25 to about 80%, (3) a pin puncture strength of about 3500 mN or more at a membrane thickness of 20 μm, (4) a tensile strength of about 49,000 kPa or more, (5) a tensile elongation of 100% or more, (6) a heat shrinkage ratio of 12% or less, (7) a thickness variation ratio of 20% or less after heat compression, (8) an air permeability of 700 sec/100 cm 3 or less after heat compression, and (9) a surface roughness of 3×10 2 nm or more.
6. The multi-layer microporous membrane of claim 1 wherein the second microporous membrane layer contains a greater amount of the first polyethylene than the first microporous membrane skin layer and the total amount of first polyethylene in the multilayer microporous membrane is at least 37.5 wt. % based on the weight of the multi-layer microporous membrane.