Multi-layer, microporous membrane, battery separator and battery
View Patent ↗The invention relates to a multi-layer, microporous polyolefin membrane having appropriate permeability, pin puncture strength, shutdown temperature, shutdown speed, meltdown temperature, and thickness uniformity. The invention also relates to a battery separator formed by such multi-layer, microporous membrane, and a battery comprising such a separator. Another aspect of the invention relates to a method for making the multi-layer, microporous polyolefin membrane, a method for making a battery using such a membrane as a separator, and a method for using such a battery.
1. A three-layer microporous membrane, comprising:
a first microporous layer containing a first layer material, a third microporous layer containing the first layer material, and a second microporous layer containing a second layer material, the second microporous layer being located between the first and third microporous layers,
wherein the first layer material comprises a first polyethylene and a first polypropylene and the second layer material comprises a second polyethylene and a second polypropylene, the second polypropylene having (1) a weight-average molecular weight of 6×10 5 or more, (2) a heat of fusion of 90 J/g or more, and (3) a fraction having a molecular weight of 5×10 4 or less with the fraction being 5% or less by mass of the second polypropylene, and
the first polyethylene is present in the first layer material in a first polyethylene amount in the range of from about 50 wt. % to about 99 wt. % based on the weight of the first layer material,
the first polypropylene is present in the first layer material in a first polypropylene amount in the range of from about 1 wt. % to about 50 wt. % based on the weight of the first layer material,
the second polyethylene is present in the second layer material in a second polyethylene amount in the range of from about 5 wt. % to about 95 wt. % based on the weight of the second layer material, and
the second polypropylene is present in the second layer material in a second polypropylene amount in the range of from about 5 wt. % to about 95 wt. % based on the weight of the second layer material.
2. The three-layer microporous membrane of claim 1 , wherein the multi-layer microporous membrane comprises a first microporous layer containing the first microporous layer material and a second microporous layer containing the second microporous layer material.
3. The three-layer microporous membrane of claim 1 , comprising:
a first microporous layer containing the second layer material, a third microporous layer containing the second layer material, and a second microporous layer containing the first layer material, the second microporous layer being located between the first and third microporous layers.
4. The three-layer microporous membrane of claim 1 wherein
(a) the first and/or second polyethylene comprises a polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 , a polyethylene having an Mw of at least about 1×10 6 , or both a polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 and a polyethylene having an Mw of at least about 1×10 6 , wherein
(1) the first and/or second polyethylene has an Mw in the range of about 1×10 4 to about 1×10 7 ;
(2) the first and/or second polyethylene has an Mw ranging from about 1×10 4 to about 5×10 5 ;
(3) the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 is one or more of a high-density polyethylene, a medium-density polyethylene, a branched low-density polyethylene, or a linear low-density polyethylene;
(4) the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 is at least one of (i) an ethylene homopolymer or (ii) a copolymer of ethylene and a third α-olefin selected from the group of propylene, butene-1, hexene-1;
(5) the polyethylene having an Mw of at least 1×10 6 has an Mw of at least about 1×10 6 ;
(6) the polyethylene having an Mw of at least 1×10 6 is at least one of (i) an ethylene homopolymer or (ii) a copolymer of ethylene and a fourth α-olefin selected from the group of propylene, butene-1, hexene-1;
(7) the amount of the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 in the first microporous layer material is in the range of from about 70 wt. % to about 90 wt. %, based on the weight of the first microporous layer material;
(8) the amount of the polyethylene having an Mw of at least about 1×10 6 in the first microporous layer material is in the range of from about 0 wt. % to about 10 wt. %, based on the weight of the first microporous layer material;
(9) the amount of the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 in the second microporous layer material is in the range of from about 40 wt. % to about 60 wt. %, based on the weight of the second microporous layer material;
(10) the amount of the polyethylene having an Mw of at least about 1×10 6 in the second microporous layer material is in the range of from about 0 wt. % to about 10 wt. %, based on the weight of the second microporous layer material;
(11) the first and/or second polyethylene has a molecular weight distribution (“Mw/Mn”) of about 5 to about 300;
(b) the first polypropylene has at least one characteristic selected from:
(1) the first polypropylene is one or more of (i) a propylene homopolymer or (ii) a copolymer of propylene and a fifth olefins selected from one or more of α-olefins such as ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, styrene, butadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene;
(2) the first polypropylene has an Mw ranging from about 1×10 4 to about 4×10 6 ;
(3) the first polypropylene has an Mw/Mn ranging from about 1.01 to about 100;
(4) the first polypropylene is isotactic;
(5) the first polypropylene has a heat of fusion of at least about 90 Joules/gram;
(6) The first polypropylene has a melting peak (second melt) of at least about 160° C.; and
(c) the second polypropylene has at least one characteristic selected from:
(1) an Mw/Mn of 2.5 or less;
(2) a weight-average molecular weight of 6.5×10 5 or more;
(3) a heat of fusion of 95 J/g or more, and
(4) the fraction of the second polypropylene having a molecular weight of 5×10 4 or less being 4.5% or less by mass of the second polypropylene.
5. The three-layer microporous membrane of claim 1 , wherein the first and/or second polyethylene has an Mw in the range of about 2×10 5 to about 3×10 6 .
6. The three-layer microporous membrane of claim 1 , wherein the first and/or second polyethylene has a weight-average molecular weight in the range of 1×10 4 to 5×10 5 .
7. The three-layer microporous membrane of claim 4 , wherein the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 is high-density polyethylene and the polyethylene having an Mw of at least about 1×10 6 is ultra-high molecular weight polyethylene.
8. The three-layer microporous membrane of claim 4 , wherein the first and/or second polyethylene comprises 10 wt. % or less of the polyethylene having an Mw of at least about 1×10 6 and 90 wt. % or more of the polyethylene having an Mw ranging from about 1×10 4 to about 5×10 5 .
9. A battery comprising an anode, a cathode, an electrolyte, and the multi-layer microporous membrane of claim 1 , wherein the multi-layer microporous membrane of claim 1 separates at least the anode from the cathode.
10. The battery of claim 9 , wherein the electrolyte contains lithium ions and the battery is a secondary battery.
11. The battery of claim 9 , wherein the multi-layer membrane has a porosity of 25 to 80%, an air permeability of 20 to 700 seconds/100 cc (converted to the value at 20-μm thickness), a pin puncture strength of 2,000 mN/20 μm or more, a shut down temperature of 120 to 140° C., a meltdown temperature of 170° C. or higher, and a battery capacity recovery ratio of 70% or higher.
12. The battery of claim 9 used as a source or sink of electric charge.