Description

MICROPQROUS MEMBRANES AND METHODS FOR MAKING AND USING SUCH MEMBRANES

FIELD OF THE INVENTION

[0001] The invention relates to a microporous membrane having suitable permeability, mechanical strength, electrolytic solution absorption characteristics, compression resistance, and heat shrinkage resistance; and methods for producing and using such a microporous polyolefin membrane. It also relates to battery separators comprising such a microporous polyolefin membrane, and to batteries utilizing such battery separators.

BACKGROUND OF THE INVENTION [0002] Microporous membranes are useful as separators for primary batteries and secondary batteries such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary ^, batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, etc. When the microporous polyolefin membrane is used as a battery separator, particularly for lithium ion batteries, the membrane's performance significantly affects the battery's properties, productivity, and safety. Accordingly, the microporous polyolefin membrane should have appropriate permeability, mechanical properties, heat resistance, dimensional stability, shutdown properties, meltdown properties, electrolytic solution absorption, etc. It is desirable for such batteries to have a relatively low shutdown temperature and a relatively high meltdown temperature for improved battery safety properties, particularly for batteries exposed to high temperatures under operating conditions. High separator permeability is desirable for high capacity batteries. A separator with high mechanical strength is desirable for commercially acceptable battery assembly and fabrication. [0003] The optimization of material compositions, stretching conditions, heat treatment conditions, etc., has been proposed to improve the properties of microporous polyolefin membranes used as battery separators. For example, JP6-240036A discloses a microporous polyolefin membrane having improved pore diameter and a sharp pore diameter distribution. The membrane is made from a polyethylene resin containing 1% or more by mass of ultra-high molecular weight polyethylene having a weight-average

molecular weight ("Mw") of 7 x 10 ⁵ or more, the polyethylene resin having a molecular weight distribution (weight-average molecular weight/number-average molecular weight) of 10 to 300, and the microporous polyolefin membrane having a porosity of 35 to 95%, an average penetrating pore diameter of 0.05 to 0.2 μm, a rupture strength (15 mm width) of 0.2 kg or more, and a pore diameter distribution (maximum pore diameter/average penetrating pore diameter) of 1.5 or less. This microporous membrane is produced by extruding a melt-blend of the above polyethylene resin and a membrane-forming solvent through a die, stretching the gel-like sheet obtained by cooling at a temperature from the crystal dispersion temperature ("Ted") of the above polyethylene resin to the melting point +10°C, removing the membrane-forming solvent from the gel-like sheet, re-stretching the resultant membrane to 1.5 to 3 fold as an area magnification at a temperature of the melting point of the above polyethylene resin -10°C or less, and heat-setting it at a temperature from the crystal dispersion temperature of the above polyethylene resin to the melting point. [0004] WO 1999/48959 discloses a microporous polyolefin membrane having suitable strength and permeability, as well as a uniformly porous surface without local permeability variations. The membrane is made of a polyolefin resin, for instance, high density polyethylene, having an Mw of 50,000 or more and less than 5,000,000, and a molecular weight distribution of 1 or more to less than 30, which has a network structure with fine gaps formed by uniformly dispersed micro-fibrils, having an average micro-fibril size of 20 to 100 nm and an average micro-fibril distance of 40 to 400 nm. This microporous membrane is produced by extruding a melt-blend of the above polyolefin resin and a membrane-forming solvent through a die, stretching a gel-like sheet obtained by cooling at a temperature of the melting point of the above polyolefin resin -50°C or higher and lower than the melting point, removing the membrane-forming solvent from the gel-like sheet, re-stretching it to 1.1-5 fold at a temperature of the melting point of the above polyolefin resin -50°C or higher and lower than the melting point, and heat-setting it at a temperature from the crystal dispersion temperature of the above polyolefin resin to the melting point. [0005] WO 2000/20492 discloses a microporous polyolefin membrane of improved permeability which is characterized by fine polyethylene fibrils having an Mw of 5 x 10 ⁵ or more, the composition comprising polyethylene. The microporous polyolefin membrane has an average pore diameter of 0.05 to 5 μm, and the percentage of lamellas at

angles θ of 80 to 100° relative to the membrane surface is 40% or more in longitudinal and transverse cross sections. This polyethylene composition comprises 1 to 69% by weight of ultra-high molecular weight polyethylene having a weight-average molecular weight of 7 x 10 ⁵ or more, 1 to 98% by weight of high density polyethylene and 1 to 30% by weight of low density polyethylene. This microporous membrane is produced by extruding a melt-blend of the above polyethylene composition and a membrane-forming solvent through a die, stretching a gel-like sheet obtained by cooling, heat-setting it at a temperature from the crystal dispersion temperature of the above polyethylene or its composition to the melting point +30°C, and removing the membrane-forming solvent. [0006] WO 2002/072248 discloses a microporous membrane having improved permeability, particle-blocking properties and strength. The membrane is made using a polyethylene resin having an Mw of less than 380,000. The membrane has a porosity of 50 to 95% and an average pore diameter of 0.01 to 1 μm. This microporous membrane has a three-dimensional network skeleton formed by micro-fibrils having an average diameter of 0.2 to 1 μm connected to each other throughout the overall microporous membrane, and openings defined by the skeleton to have an average diameter of 0.1 μm or more and less than 3 μm. This microporous membrane is produced by extruding a melt-blend of the above polyethylene resin and a membrane-forming solvent through a die, removing the membrane-forming solvent from the gel-like sheet obtained by cooling, stretching it to 2 to 4 fold at a temperature of 20 to 140°C, and heat-treating the stretched membrane at a temperature of 80 to 140°C.

[0007] WO 2005/113657 discloses a microporous polyolefϊn membrane having suitable shutdown properties, meltdown properties, dimensional stability, and high-temperature strength. The membrane is made using a polyolefin composition comprising (a) polyethylene resin containing 8 to 60% by mass of a component having a molecular weight of 10,000 or less, and an Mw/Mn ratio of 11 to 100, wherein "Mn" is the number-average molecular weight of the polyethylene resin, and a viscosity-average molecular weight ("Mv") of 100,000 to 1,000,000, and (b) polypropylene. The membrane has a porosity of 20 to 95%, and a heat shrinkage ratio of 10% or less at 100 ⁰ C. This microporous polyolefϊn membrane is produced by extruding a melt-blend of the above polyolefin and a membrane-forming solvent through a die, stretching the gel-like sheet obtained by cooling, removing the membrane-forming solvent, and annealing the sheet.

[0008] With respect to the properties of separators, not only permeability, mechanical strength, dimensional stability, shutdown properties and meltdown properties, but also properties related to battery productivity such as electrolytic solution absorption, and battery cyclability, such as electrolytic solution retention properties, have recently been given importance. In particular, electrodes for lithium ion batteries expand and shrink according to the intrusion and departure of lithium, and an increase in battery capacity leads to larger expansion ratios. Because separators are compressed when the electrodes expand, it is desired that the separators when compressed suffer as little a decrease as possible in electrolytic solution retention. [0009] Moreover, even though improved microporous membranes are disclosed in JP6-240036A, WO 1999/48959, WO 2000/20492, WO 2002/072248, and WO 2005/113657, further improvements are still needed, particularly in membrane permeability, mechanical strength, heat shrinkage resistance, compression resistance, and electrolytic solution absorption properties. It is thus desired to form battery separators from microporous membranes having improved permeability, mechanical strength, heat shrinkage resistance, compression resistance, and electrolytic solution absorption.

SUMMARY OF THE INVENTION

[0010] The invention relates to the discovery of a microporous polymeric membrane, and a method for manufacturing same, having a good balance of permeability, mechanical strength, and electrolytic solution absorption, compression resistance, and heat shrinkage resistance properties. An embodiment of the invention relates to a microporous membrane comprising pores characterized by a pore size (or pore diameter when the pores are approximately cylindrical) distribution curve obtained by mercury intrusion porosimetry having at least two peaks. It has been discovered that such a membrane has improved permeability, mechanical strength, heat shrinkage resistance, compression resistance, and electrolytic solution absorption characteristics. The microporous polyolefin membrane can be produced by a method comprising (1) combining a polyolefin composition and at least one diluent (e.g., membrane-forming solvent) to form e.g., a polyolefin solution, the polyolefin composition comprising from about 73 wt. % to about 97 wt. % of a first polyethylene resin having a weight average molecular weight of less than 7 x 10 ⁵ , e.g., in the range of from about 2.5 x 10 ⁵ to 6 x 10 ⁵ , and a molecular weight distribution of from about 5 to about 100, from about 3 wt. % to about 20 wt. %

polypropylene resin having a weight average molecular weight of from about 3 x 10 to about 1.5 x 10 ⁶ , a heat of fusion of 80 J/g or higher, and a molecular weight distribution of from about 1.0 to about 100, and from about 0 wt. % to about 7 wt. % of a second polyethylene resin having a weight average molecular weight that is greater than that of the first polyethylene, e.g., in the range of 7 x 10 ⁵ or higher, percentages based on the weight of the polyolefin composition, (2) extruding the polyolefin solution through a die to form an extrudate, (3) cooling the extrudate to form a cooled extrudate, (4) optionally stretching the extrudate or cooled extrudate, (5) removing at least a portion of the diluent from the extrudate or cooled extrudate to form the membrane. Optionally, the method can further comprise (6) stretching the membrane in at least one direction, and (7) heat-setting the stretched microporous membrane.

[0011] In an embodiment, the microporous polyolefin membrane has dense domains corresponding to a main peak in a range of 0.01 to 0.08 μm in the pore size (or pore diameter when the pores are approximately cylindrical) distribution curve, and coarse domains corresponding to at least one sub-peak in a range of more than 0.08 μm to 1.5 μm in the pore size (or pore diameter when the pores are approximately cylindrical) distribution curve. In an embodiment, the pore volume ratio of the dense domains to the coarse domains is 0.5 to 49. In a further embodiment, the microporous polyolefin membrane has surface roughness of 3 x 10 ² nm or more as the maximum height difference between any two points on the surface of the membrane. In a further embodiment, the upper limit on the surface roughness of the microporous polyolefin membrane is 3 x 10 ³ nm. With surface roughness within this range, the microporous membrane has a large contact area with an electrolytic solution when used as a battery separator, exhibiting desirable electrolytic solution absorption characteristics. [0012] In an embodiment, the polyolefin composition of the microporous membrane is produced or obtained from a mixture comprising from about 73 wt. % to about 97 wt. % high density polyethylene resin having a weight average molecular weight of from about 2.5 x 10 ⁵ to about 4 x 10 ⁵ and a molecular weight distribution of from about 5 to about 50, from about 3 wt. % to about 20 wt. % polypropylene resin having a weight average molecular weight of from about 3 x 10 ⁵ to about 1.5 x 10 ⁶ , a heat of fusion of 80 J/g or higher, and a molecular weight distribution of from about 1.0 to about 100, and from about 0 wt. % to about 7 wt. % ultra-high molecular weight polyethylene resin having a weight

average molecular weight of that is greater than that of the high density polyethylene, e.g., 7 x 10 ⁵ or higher. The high density polyethylene may, for example, have a weight average molecular weight of from about 2.5 x 10 ⁵ to about 4 x 10 ⁵ and a molecular weight distribution of from about 5 to about 30. The microporous polyolefϊn membrane comprises 3 wt. % to 20 wt. % of polypropylene obtained from polypropylene resin and 80 wt. % to 97 wt. % of polyethylene obtained from polyethylene resins, based on the weight of the microporous polyolefin membrane.

[0013] In an embodiment, the microporous membrane is manufactured by a method comprising the steps of (1) combining a polyolefin composition and a membrane-forming solvent to form a polyolefϊn solution, the polyolefin composition comprising from about 73 wt. % to about 97 wt. % of a first polyethylene resin having a weight average molecular weight of from about 2.5 x 10 ⁵ to about 6 x 10 ⁵ and a molecular weight distribution of from about 5 to about 100, from about 3 wt. % to about 20 wt. % polypropylene resin having a weight average molecular weight of from about 3 x 10 ⁵ to about 1.5 x 10 ⁶ , a heat of fusion of 80 J/g or higher, and a molecular weight distribution of from about 1.0 to about 100, and from about 0 wt. % to about 7 wt. % of a second polyethylene resin having a weight average molecular weight that is greater than that of the first polyethylene resin, e.g., in the range of from 7 x 10 ⁵ to about 5 x 10 ⁶ , percentages based on the weight of the polyolefin composition, with the polyolefin solution preferably having a solvent concentration of from about 25 wt. % to about 50 wt. % based on the weight of the polyolefin solution, (2) extruding the polyolefin solution through a die to form an extrudate, (3) cooling the extrudate to form a gel-like sheet having a high resin content, (4) stretching the gel-like sheet to a magnification of from about 9 to about 400 fold, for example from about 16 to about 49 fold, in at least one direction at a high stretching temperature of from about Ted to about Ted + 30 °C, for example from about Ted + 15 to about Ted + 25 °C, to form a stretched gel-like sheet, (5) removing the membrane-forming solvent from the stretched gel-like sheet to form a membrane, (6) stretching the membrane to a high magnification of from about 1.1 to about 1.8 fold, for example from about 1.2 to about 1.6 fold, in at least one direction to form a stretched membrane, and (7) heat-setting the stretched microporous membrane to form the microporous membrane.

[0014] In the above method, the stretching of the microporous membrane in step (6) may be called "re-stretching," because it is conducted after the stretching of the gel-like

sheet in step (4).

[0015] In yet another embodiment, the invention relates to a microporous membrane comprising polyethylene and polypropylene and having an electrolytic solution absorption speed > 4.3.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The inventions relate to a microporous membrane (or film) having enhanced properties, especially electrolyte injection, compression and heat resistance, e.g. melt down, properties. As an initial step in the method for making such a film, certain specific polyethylene resin or resins and certain specific polypropylene resin are combined, e.g. by melt-blending, to form a polyolefin composition. These starting materials will now be described in more detail.

[1] Materials used to produce the microporous membranes (1) Polyolefin Composition [0017] The polyolefin composition is produced by combining (a) from about 73 wt. % to about 97 wt. % at a first polyethylene resin having a weight average molecular weight of from about 2.5 x 10 ⁵ to about 6 x 10 ⁵ and a molecular weight distribution of from about 5 to about 100, (b) from about 3 wt. % to about 20 wt. % polypropylene resin having a weight average molecular weight of from about 3 x 10 ⁵ to about 1.5 x 10 ⁶ , a heat of fusion of 80 J/g or higher, and a molecular weight distribution of from about 1.0 to about 100, and (c) from about 0 wt. % to about 7 wt. % of a second polyethylene resin having a weight average molecular weight greater than that of the first polyethylene resin, e.g., in the range of from about 7 x 10 ⁵ to about 5 x 10 ⁶ , and an MWD of 5-100, with the weight percents based on the weight of the polyolefin composition. In another embodiment, the amount the first polyethylene resin is in the range of 80 wt% to 90 wt%, the amount of polypropylene resin is in the range of about 5 wt% to about 15 wt%, and the amount of the second polyethylene resin is in the range of 1 wt% to 5 wt%, based on the weight of the polyolefin composition. (a) Polyethylene resins (i) Composition

[0018] The first polyethylene resin has a weight average molecular weight ("Mw") < 7 x 10 ⁵ , e.g., of from about 2.5 x 10 ⁵ to about 6 x 10 ⁵ and a molecular weight distribution ("MWD") of from about 5 to about 100. A non-limiting example of the first polyethylene

resin for use herein is one that has a Mw of from about 2.5 x 10 ⁵ to about 4 x 10 ⁵ and an MWD of from about 5 to about 50. Another non-limiting example of the first polyethylene resin is one having an Mw of about 3 x 10 ⁵ to 6 x 10 ⁵ and an MWD of from about 5 to about 30. The first polyethylene resin can be a high density polyethylene such as an ethylene homopolymer, or an ethylene/α-olefϊn copolymer, such as, for example, one containing a small amount, e.g. about 5 mole %, of a third α-olefin. The third α-olefin, which is not ethylene, is preferably propylene, ctane-1, pentene-1, ctane-1, 4-methylpentene-l, ctane-1, vinyl acetate, methyl methacrylate, or styrene or combinations thereof. Optionally, such a copolymer can be produced using a single-site catalyst.

[0019] The second polyethylene resin has an Mw greater than that of the first polyethylene resin, e.g., an Mw > 7 x 10 ⁵ , and an MWD of from about 5 to about 100. A non-limiting example of the second polyethylene resin for use herein is one that has an Mw of from about 5 x 10 ⁵ to about 5 x 10 ⁶ and an MWD of from about 5 to about 50. Another non-limiting example of the second polyethylene resin is one having an Mw in the range of 1 x 10 ⁶ to 2 x 10 ⁶ and an MWD from about 4 to about 8. The second polyethylene can be an ultra-high molecular weight polyethylene such as an ethylene homopolymer, or an ethylene/α-olefin copolymer, such as, for example, one containing a small amount, e.g. about 5 mole %, of a third α-olefin. The third α-olefin, which is not ethylene, is preferably propylene, ctane-1, pentene-1, ctane-1, 4-methylpentene-l, ctane-1, vinyl acetate, methyl methacrylate, or styrene or combinations thereof. Such copolymer is preferably produced using a single-site catalyst. (U) Mw and MWD Determination [0020] MWD is equal to the ratio of Mw to the number-average molecular weight ("Mn"). The MWD of the polymers used to produce the microporous membrane can be controlled e.g., by a multi-stage polymerization. The MWD of the polyethylene composition can be controlled by the molecular weights and mixing ratios of the polyethylene components. [0021] Mw and Mn of the poly ethylenes are determined using a High Temperature Size Exclusion Chromatograph, or "SEC", (GPC PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three PLgel Mixed-B columns (available from Polymer Laboratories) are used. The nominal flow rate is 0.5 cm ³ /min,

and the nominal injection volume was 300 μL. Transfer lines, columns, and the DRI detector were contained in an oven maintained at 145°C. The measurement is made in accordance with the procedure disclosed in "Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001)". [0022] The GPC solvent used is filtered Aldrich reagent grade 1 ,2,4-Trichlorobenzene (TCB) containing approximately 1000 ppm of butylated hydroxy toluene (BHT). The TCB was degassed with an online degasser prior to introduction into the SEC. Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of above TCB solvent, then heating the mixture at 160°C with continuous agitation for about 2 hours. The concentration of UHMWPE solution was 0.25 to 0.75mg/ml. Sample solution will be filtered off-line before injecting to GPC with 2μm filter using a model SP260 Sample Prep Station (available from Polymer Laboratories). [0023] The separation efficiency of the column set is calibrated with a calibration curve generated using a seventeen individual polystyrene standards ranging in Mp from about 580 to about 10,000,000, which is used to generate the calibration curve. The polystyrene standards are obtained from Polymer Laboratories (Amherst, MA). A calibration curve (logMp vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd-order polynomial. Samples are analyzed using IGOR Pro, available from Wave Metrics, Inc.

(b) Polypropylene resin

[0024] The polypropylene for use herein has an Mw of from about 3 x 10 ⁵ to about 1.5 x 10 ⁶ , for example from about 6 x 10 ⁵ to about 1.5 x 10 ⁶ , a heat of fusion ("δHm") of 80 J/g or higher, for non-limiting example from about 80 to about 200 J/g, and an MWD of from about 1.0 to about 100, for example from about 1.1 to about 50, and can be a propylene homopolymer or a copolymer of propylene and another, i.e. a fourth, olefin, though the homopolymer is preferable. The copolymer may be a random or block copolymer. The fourth olefin, which is an olefin other than propylene, includes α-olefins such as ethylene, ctane-1, pentene-1, ctane-1, 4-methylpentene-l, ctane-1, vinyl acetate, methyl methacrylate, styrene, etc., and diolefins such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1 ,9-decadiene, etc. The percentage of the fourth olefin in the propylene copolymer is preferably in a range not deteriorating the properties of the microporous

polyolefin membrane such as heat resistance, compression resistance, heat shrinkage resistance, etc., and is preferably less than about 10 mole %, e.g. from about 0 to less than about 10 mole %.

[0025] In an embodiment, the MWD of polypropylene is from about 1.0 to about 100, for example from about 2 to about 50, or about 2.5 to 6.

[0026] The amount of polypropylene in the polyolefin composition can be from about 3 wt. % to about 20 wt. % based on the weight of the polyolefin composition. When the percentage of polypropylene is more than 20 wt. %, the resultant microporous membrane has relatively lower strength and is difficult to form into a bimodal structure. The percentage of polypropylene may be, for example, from about 5 wt. % to about 15 wt. %, and for further example from about 7 wt. % to about 13 wt. %, based on the weight of the polyolefin composition. In an embodiment, the propylene has a δHm in the range of about 110 J/g to 120 J/g. [0027] The Mw, MWD and the δHm of the polypropylene are measured in accordance with the procedures described in patent publication US 2008/0057389, which is incorporated by reference herein in its entirety. (T) Other components

[0028] In addition to the above components, the polyolefin composition can contain (a) additional polyolefin and/or (b) heat-resistant polymer resins having melting points or glass transition temperatures ("Tg") of about 170 ⁰ C or higher, in amounts not deteriorating the properties of the microporous membrane, for example 10 wt. % based on the weight of the polyolefin composition.

(a) Additional Polvolefins

[0029] The additional polyolefin can be at least one of (a) polybutene-1, polypentene-1, poly-4-methylpentene-l, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene and an ethylene/α-olefϊn copolymer, each of which may have an Mw of from 1 x 10 ⁴ to 4 x 10 ⁶ , and (b) a polyethylene wax having an Mw of from 1 x 10 ³ to 1 x 10 ⁴ . Polybutene-1, polypentene-1, poly-4-methylpentene-l, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate and polystyrene are not restricted to homopolymers, but may be copolymers containing still other α-olefins.

(b) Heat-resistant resins

[0030] The heat-resistant resins are preferably (i) amorphous resins having melting

points of about 170°C or higher, which may be partially crystalline, and (ii) completely amorphous resins having a Tg of about 170°C or higher and mixtures thereof. The melting point and Tg are determined by differential scanning calorimetry (DSC) according to method JIS K7121. Specific examples of the heat-resistant resins include polyesters such as polybutylene terephthalate (melting point: about 160-230°C), polyethylene terephthalate (melting point: about 250-270°C), etc., fluororesins, polyamides (melting point: 215-265°C), polyarylene sulfide, polyimides (Tg: 280°C or higher), polyamideimides (Tg: 280°C), polyether sulfone (Tg: 223 ⁰ C), polyetheretherketone (melting point: 334°C), polycarbonates (melting point: 220-240 ⁰ C), cellulose acetate (melting point: 220 ⁰ C), cellulose triacetate (melting point: 300°C), polysulfone (Tg: 190°C), polyetherimide (melting point: 216°C), etc. (c) Content

[0031] The total amount of the additional polyolefin and the heat-resistant resin is preferably 20% or less, for example from about 0 wt. % to about 20 wt. %, based on the weight of the polyolefin composition.

[21 Method for producing the microporous polyolefin membrane [0032] The invention relates to a method for producing the microporous membrane having desirable electrolytic solution absorption, compression and heat resistance, e.g. melt down, properties, comprising the steps of (1) combining a certain specific polyolefin composition and at least one diluent, (2) extruding the combined diluent and polyolefin composition through a die to form an extrudate, (3) cooling the extrudate to form a cooler extrudate sheet, (4) stretching the extrudate to form a stretched extrudate, (5) removing at least a portion of the diluent from the stretched extrudate to form a solvent-removed membrane, (6) stretching the solvent-removed membrane at a certain specific temperature and to a certain specific high magnification to form a stretched membrane, and (7) heat-setting the stretched membrane to form the finished microporous membrane. A heat-setting treatment step (4i), a heat roll treatment step (4ii), and/or a hot solvent treatment step (4iii) may be conducted between the steps (4) and (5), if desired. A heat-setting treatment step (5i) may be conducted between the steps (5) and (6). A step (5ii) of cross-linking with ionizing radiations following step (5i) prior to step (6), and a hydrophilizing treatment step (7i) and a surface-coating treatment step (7ii) may be conducted after the step (7), if desired.

(1) Combining the polymer and diluent

[0033] The polyolefin composition comprising polyethylene and polypropylene is blended with at least one diluent to form a mixture. The mixture may contain various additives such as anti-oxidants, fine silicate powder (pore-forming material), etc., in ranges not deteriorating the effects of the present invention, if desired.

[0034] To better enable stretching at relatively higher magnifications, the diluent can be preferably liquid at room temperature. When the diluent is a solvent for one or more of the polymers in the mixture, it can be called a "solvent" or "membrane-forming solvent". When the diluent is a solvent (or membrane-forming solvent), the mixture can be called a "polyolefin solution". The diluent can be, for example, aliphatic, alicyclic or aromatic hydrocarbons such as nonane, decane, decalin, p-xylene, undecane, dodecane, liquid paraffin, mineral oil distillates having boiling points comparable to those of the above hydrocarbons, and phthalates liquid at room temperature such as dibutyl phthalate, dioctyl phthalate, etc. To most effectively obtain an extrudate in the form of a gel-like sheet having a stable solvent content, it is preferable to use a non- volatile liquid solvent such as liquid paraffin. In an embodiment, one or more solid solvents which are miscible with the polyolefin composition during melt-blending but solid at room temperature may be added to the liquid solvent. Such solid solvents are preferably stearyl alcohol, ceryl alcohol, paraffin waxes, etc. In another embodiment, solid solvent can be used without liquid solvent. However, when only the solid solvent is used, uneven stretching, etc., can occur.

[0035] The viscosity of the liquid solvent is preferably from about 30 to about 500 cSt, more preferably from about 30 to about 200 cSt, when measured at a temperature of 25°C. When the viscosity at 25°C is less than 30 cSt, the polyolefin solution may foam, resulting in difficulty in blending. On the other hand, when the viscosity is more than 500 cSt, the removal of the liquid solvent can be difficult.

[0036] Though not particularly critical, the polyolefin solution is preferably melt-blended in a double-screw extruder to prepare a high resin concentration polyolefin solution. The membrane-forming solvent may be added before starting melt-blending, or supplied to the double-screw extruder in an intermediate portion during blending, though the latter is preferable. [0037] The melt-blending temperature of the polyolefin solution is preferably in a

range of the melting point ("Tm") of the polyethylene resin +10°C to Tm +12O ⁰ C. The melting point can be measured by differential scanning calorimetry (DSC) according to JIS K7121. In an embodiment, the melt-blending temperature is from about 140 to about 25O ⁰ C, preferably from about 170 to about 240 ⁰ C, particularly where the polyethylene resin has a melting point of about 130 to about 140 ⁰ C.

[0038] To obtain a hybrid structure, the concentration of the polyolefin composition in the polyolefin solution is preferably from about 25 wt. % to about 50 wt. %, for example from about 25 wt. % to about 45 wt. %, based on the weight of the polyolefin solution. [0039] The ratio L/D of the screw length L to the screw diameter D in the double-screw extruder is preferably in a range of from about 20 to about 100, more preferably in a range of from about 35 to about 70. When L/D is less than 20, melt-blending can be inefficient. When L/D is more than 100, the residence time of the polyolefin solution in the double-screw extruder can be too long. In this latter case, the membrane's Mw deteriorates as a result of excessive shearing and heating, which is undesirable. The cylinder of the double-screw extruder preferably has an inner diameter of from about 40 to about 100 mm.

[0040] In the double-screw extruder, the ratio Q/Ns of the amount Q (kg/h) of the polyolefin solution charged to the number of revolution Ns (rpm) of a screw is preferably from about 0.1 to about 0.55 kg/h/rpm. When Q/Ns is less than 0.1 kg/h/rpm, the polyolefin can be damaged by shearing, resulting in decrease in strength and meltdown temperature. When Q/Ns is more than 0.55 kg/h/rpm, uniform blending cannot be achieved. Q/Ns is more preferably from about 0.2 to about 0.5 kg/h/rpm. The number of revolutions Ns of the screw is preferably 180 rpm or more. Though not particularly critical, the upper limit of the number of revolutions Ns of the screw is preferably about 500 rpm.

(2) Extrusion

[0041] The polyolefin solution can be melt-blended in the extruder and extruded from a die. In another embodiment, the polyolefin can be extruded and then pelletized. In this latter embodiment, the pellets can be melt-blended and extruded in a second extrusion to make the gel-like molding or sheet. In either embodiment, the die may be a sheet-forming die having a rectangular orifice, a double-cylindrical, hollow die, an inflation die, etc. In the case of the sheet-forming die, the die gap is preferably from

about 0.1 to about 5 mm. The extrusion temperature is preferably from about 140 to about 250 ⁰ C, and the extruding speed is preferably from about 0.2 to about 15 m/minute. The direction of extrusion (i.e., the direction of extrudate travel during extrusion and steps downstream of extrusion) is called the machine direction or "MD". The direction perpendicular to both the thickness of the membrane and MD is called the transverse direction or "TD". (3) Cooling the extrudate

[0042] The extrudate produced from the die is cooled to form a cooled extrudate, e.g., a high resin content gel-like molding or sheet. Cooling can be conducted by exposing the extrudate to a temperature < the extrudate's gelation temperature at a cooling rate of about 50°C/minute or more. Cooling can be preferably conducted to about 25°C or lower. Such cooling sets the micro-phase of the polyolefϊn separated by the membrane-forming solvent. Generally, the slower cooling rate provides the gel-like sheet with larger pseudo-cell units, resulting in a coarser higher-order structure. On the other hand, a higher cooling rate results in denser cell units. A cooling rate of less than 50°C/minute can lead to increased crystallinity, making it more difficult to provide the gel-like sheet with suitable stretchability. Usable cooling methods include bringing the extrudate into contact with a cooling medium such as cooling air, cooling water, etc.; bringing the extrudate into contact with cooling rollers; etc. (4) Stretching the cooled extrudate

[0043] The cooled extrudate can be stretched in at least one direction. While not wishing to be bound by any theory or model, it is believed that the cooled extrudate (e.g., a gel-liked sheet) can be uniformly stretched because the sheet contains the membrane-forming solvent. The gel-like sheet is preferably stretched to a predetermined magnification after heating by, for example, a tenter method, a roll method, an inflation method or a combination thereof. The stretching may be conducted monoaxially or biaxially, though biaxial stretching is preferable. In the case of biaxial stretching, any of simultaneous biaxial stretching, sequential stretching or multi-stage stretching (for instance, a combination of the simultaneous biaxial stretching and the sequential stretching) may be used, though simultaneous biaxial stretching is preferable. When biaxial stretching is used, the amount of stretching in each direction need not be the same. [0044] The stretching magnification of this first stretching step is preferably 2 fold or

more, more preferably 3 to 30 fold in the case of monoaxial stretching. In the case of biaxial stretching, the stretching magnification is preferably 3 fold or more in any direction, namely 9 fold or more, more preferably 16 fold or more, most preferably 25 fold or more, in area magnification. In an embodiment, the cooled extrudate is simultaneously stretched 3 to 7 fold (e.g., 5 fold) in MD and 3 to 7 fold (e.g., 5 fold) in TD. An example for this first stretching step would include stretching from about 9 fold to about 400 fold. A further example would be stretching from about 16 to about 49 fold. With the area magnification of 9 fold or more, the pin puncture strength of the microporous membrane is improved. When the area magnification is more than 400 fold, stretching apparatuses, stretching operations, etc., involve large-sized stretching apparatuses, which can be difficult to operate.

[0045] During stretching, the extrudate can be exposed to a temperature in the range of from about the crystal dispersion temperature ("Ted") of the polyethylene used to produce the extrudate to about Ted + 30 °C, e.g. in a range of Ted of the combined polyethylene content of the cooled extrudate to Ted + 25°C, more preferably in a range of Ted + 10°C to Ted + 25°C, most preferably in a range of Ted + 15°C to Ted + 25°C. When the stretching temperature of the cooled extrudate is lower than Ted, it is believed that the polyethylene resin is so insufficiently softened that the gel-like sheet is easily broken by stretching, failing to achieve high-magnification stretching. [0046] The crystal dispersion temperature is determined by measuring the temperature characteristics of dynamic viscoelasticity according to ASTM D 4065. Because the polyethylene resin has a crystal dispersion temperature of about 90 to 100°C, the stretching temperature is from about 90 to 125°C; preferably form about 100 to 125°C, more preferably from 105 to 125°C. [0047] The above stretching causes cleavage between polyethylene lamellas, making the polyethylene phases finer and forming large numbers of fibrils. The fibrils form a three-dimensional network structure. The stretching is believed to improve the mechanical strength of the final microporous membrane and expands its pores, making the microporous membrane suitable for use as a battery separator. [0048] Depending on the desired properties, stretching may be conducted with a temperature distribution in a thickness direction, to provide the final microporous membrane with further improved mechanical strength. The detailed description of this

method is given by Japanese Patent 3347854. (5) Diluent Removal

[0049] Any convenient method can be used for removing at least a portion of the diluent from the cooled extrudate. For example, the diluent can be removed (e.g., washed, displaced, or dissolved) using a washing solvent. Because the polyolefin composition phase is phase-separated from a membrane-forming solvent phase, the removal of the diluent provides a microporous membrane. The removal of the liquid solvent can be conducted by using one or more suitable washing solvents, i.e., one capable of displacing the liquid solvent from the membrane. Examples of the washing solvents include volatile solvents, e.g., saturated hydrocarbons such as pentane, hexane, heptane, etc., chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, etc., ethers such as diethyl ether, dioxane, etc., ketones such as methyl ethyl ketone, etc., linear fluorocarbons such as trifluoroethane, C ₆ F _]4 , etc., cyclic hydrofluorocarbons such as C ₅ H ₃ F ₇ , etc., hydrofluoroethers such as C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ Hs, etc., perfluoroethers such as C ₄ F ₉ OCF ₃ , C ₄ F ₉ OC ₂ F ₅ , etc., and mixtures thereof.

[0050] The washing of the stretched membrane can be conducted by immersion in the washing solvent and/or showering with the washing solvent. The washing solvent used is preferably from about 300 to about 30,000 parts by mass per 100 parts by mass of the stretched membrane. The washing temperature is usually from about 15 to about 30°C, and if desired, heating may be conducted during washing. The heating temperature during washing is preferably about 80°C or lower. Washing is preferably conducted until the amount of the remaining liquid solvent becomes less than 1 wt. % of the amount of liquid solvent that was present in polyolefin solution prior to extrusion. [0051] The microporous membrane deprived of the membrane-forming solvent can be dried by a heat-drying method, a wind-drying (e.g., air drying using moving air) method, etc. Any drying method capable of removing a significant amount of the washing solvent can be used. Preferably, substantially all of the washing solvent is removed during drying. During drying, the membrane can be exposed to a temperature that is preferably equal to or lower than Ted, more preferably 5°C or more lower than Ted. Drying is conducted until the remaining washing solvent becomes preferably 5 wt. % or less, more preferably 3 wt. %, based on the weight (on a dry basis) of the microporous membrane. Insufficient drying can be recognized because it results in an undesirable decrease in the porosity of the

microporous membrane.

(6) Stretching the dried microporous membrane

[0052] The dried microporous membrane is stretched in a second stretching step (re-stretched) at least monoaxially at high magnification. The re-stretching of the microporous membrane can be conducted, for example, while heating, by a tenter method, etc., as in the first stretching step. The re-stretching may be monoaxial or biaxial. In the case of biaxial stretching, any one of simultaneous biaxial stretching or sequential stretching may be used, though simultaneous biaxial stretching is preferable. Because re-stretching is usually conducted on the microporous membrane in a long sheet form, which is obtained from the stretched gel-like sheet, the directions of MD and TD during the re-stretching is usually the same as those in the stretching of the cooled extrudate. The high stretching magnification in this step is from about 1.1 to about 1.8 fold in at least one direction, for example from about 1.2 to about 1.6 fold. The amount of stretching need not be the same in each stretching direction. [0053] The second stretching is conducted while exposing the membrane at a second temperature preferably equal to Tm or lower, more preferably in a range of Ted to Tm, (the "second stretching temperature"). When the second stretching temperature is higher than Tm, it is believed that the melt viscosity is generally too low to conduct good stretching, resulting in low permeability. When the second stretching temperature is lower than Ted, it is believed that the polyolefin is insufficiently softened so that the membrane might be broken by stretching, i.e., a failure to achieve uniform stretching. In an embodiment, the second stretching temperature is usually from about 90 to about 135°C, for example from about 95 to about 130°C. [0054] The monoaxial second stretching magnification of the microporous membrane in this step, as mentioned above, is preferably from about 1.1 to about 1.8 fold. A magnification of 1.1 to 1.8 fold generally provides the microporous membrane of the present invention with a hybrid structure having a large average pore size. In the case of monoaxial second stretching, the magnification can be form 1.1 to 1.8 fold in a longitudinal or transverse direction. In the case of biaxial second stretching, the microporous membrane may be stretched at the same or different magnifications, though preferably the same, as long as the stretching magnifications in both directions are form 1.1 to 1.8 fold.

[0055] When the second stretching magnification of the microporous membrane is less than 1.1 fold, it can be more difficult to produce a membrane having a hybrid structure, and having good permeability, electrolytic solution absorption capability, and compression resistance in the finished membrane. When the second stretching magnification is more than 1.8 fold, it can be more difficult to maintain a fibrous structure, and it is believed that the heat shrinkage resistance and the electrolytic solution absorption characteristics of the membrane are reduced. This second stretching magnification can be, e.g., from 1.2 to 1.6 fold. [0056] The stretching rate is preferably 3%/second or more in the stretching direction. In the case of monoaxial stretching, stretching rate is 3%/second or more in a MD or TD. In the case of biaxial stretching, stretching rate is 3%/second or more in both MD and TD. A stretching rate of less than 3%/second can make it more difficult to produce a membrane having good permeability without undue permeability variation across TD. The stretching rate is preferably 5%/second or more, more preferably 10%/second or more. Though not particularly critical, the upper limit of the stretching rate is e.g., 50%/second to avoid membrane rupture during stretching. (7) Heat treatment

[0057] The dried microporous membrane can be thermally treated (heat-set) to stabilize crystals and make uniform lamellas in the membrane. The heat-setting can be conducted by a tenter method or a roll method. The heat-setting temperature can be conducted while exposing the membrane to a temperature in a range of the second stretching temperature ±5°C, more preferably in a range of the second stretching temperature ±3°C. It is believed that too low a heat-setting temperature makes it more difficult to produce a membrane having the desired pin puncture strength, tensile rupture strength, tensile rupture elongation and heat shrinkage resistance, while too high a heat-setting temperature can adversely affect membrane permeability. [0058] An annealing treatment can be conducted after the heat-setting step. The annealing is a heat treatment with no load applied to the microporous membrane, and may be conducted by using, for example, a heating chamber with a belt conveyer or an air-floating-type heating chamber. The annealing may also be conducted continuously after the heat-setting with the tenter slackened. The annealing can be conducted while exposing the membrane to a temperature of Tm or lower, more preferably in a range from

about 60 ⁰ C to about Tm -5°C. Annealing is believed to provide the microporous membrane with improved permeability and strength. Optionally, the membrane can be annealed without prior heat-setting.

(8) Heat-setting treatment of stretched gel-like sheet [0059] The stretched extrudate between the steps (4) and (5) may be heat-set, if desired. The heat-setting method may be conducted the same way as described above for step (7).

(9) Heat roller treatment

[0060] Following step (4), at least one surface of the stretched extrudate step (4) may be brought into contact with one or more heat rollers following any of steps (4) to (7). The roller temperature is preferably in a range of from Ted +10°C to Tm. The contact time of the heat roll with the stretched extrudate is preferably from about 0.5 second to about 1 minute. The heat roll may have a flat or rough surface. The heat roll may have a suction functionality to remove the solvent. Though not particularly critical, one example of a roller-heating system may comprise holding heated oil in contact with a roller surface.

(10) Hot solvent treatment

[0061] The stretched extrudate may be contacted with a hot solvent between steps (4) and (5). A hot solvent treatment turns fibrils formed by stretching to a leaf vein form with relatively thick fiber trunks, providing the microporous membrane with large pore size and suitable strength and permeability. The term "leaf vein form" means that the fibrils have thick fiber trunks, and thin fibers extending in a complicated network structure from the trunks. The details of the hot solvent treatment method are described in WO 2000/20493.

(11) Heat-setting of microporous membrane containing washing solvent

[0062] The microporous membrane containing at least a portion of the washing solvent can be heat set between the steps (5) and (6) if desired. The heat-setting procedure can be the same as described above in step (7).

(12) Cross-linking

[0063] The heat-set microporous membrane can be cross-linked by ionizing radiation rays such as α-rays, β-rays, γ-rays, electron beams, etc. In the case of irradiating electron beams, the amount of electron beams is preferably from about 0.1 to about 100 Mrad, and the accelerating voltage is preferably form about 100 to about 300 kV. The cross-linking treatment is believed to elevate the meltdown temperature of the microporous membrane.

(13) Hvdrophilizing treatment

[0064] The heat-set microporous membrane may be subjected to a hydrophilizing treatment (a treatment that makes the membrane more hydrophilic). The hydrophilizing treatment may be a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc. Optionally, the monomer-grafting treatment is conducted after the cross-linking treatment.

[0065] In the case of surfactant treatment hydrophilizing the heat-set microporous membrane, any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants may be used, and the nonionic surfactants are preferred. The microporous membrane can be dipped in a solution of the surfactant in water or a lower alcohol such as methanol, ethanol, isopropyl alcohol, etc., or coated with the solution by a doctor blade method.

(14) Surface-coating treatment

[0066] Optionally, the heat-set microporous membrane resulting from step (7) can be coated with porous polypropylene, porous fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene, porous polyimides, porous polyphenylene sulfide, etc., to improve meltdown properties when the membrane is used as a battery separator. The polypropylene used for the coating preferably has Mw of form about 5,000 to about 500,000, and a solubility of about 0.5 grams or more in 100 grams of toluene at 25°C. Such polypropylene more preferably has a racemic diade fraction of from about 0.12 to about 0.88, the racemic diade being a structural unit in which two adjacent monomer units are mirror-image isomers to each other. The surface-coating layer may be applied, for instance, by applying a solution of the above coating resin in a good solvent to the microporous membrane, removing part of the solvent to increase a resin concentration, thereby forming a structure in which a resin phase and a solvent phase are separated, and removing the remainder of the solvent. Examples of the good solvents for this purpose include aromatic compounds, such as toluene, xylene. f3] Structure, properties, and composition of microporous polyolefin membrane (1) Structure [0067] The microporous polyolefin membrane of this invention has a hybrid structure derived from the polyethylene, in which its pore size distribution represented as a differential pore volume obtained by mercury intrusion porosimetry has at least two peaks

(main peak and at least one sub-peak). As used herein, the term "pore size" is analogous to the pore diameter in the case where the pores are approximately cylindrical. The main peak and sub-peak respectively correspond to the dense domains and coarse domains of the polyethylene phase. [0068] The microporous membrane produced by the above-described method has a relatively wide pore size distribution when plotted as a differential pore volume curve. Pore size distribution can be measured, e.g., by conventional methods such as mercury porosimetry.

[0069] When mercury porosimetry is used to measure the distribution of pore sizes and pore volume in the membrane, it is conventional to measure pore diameter, pore volume, and the specific surface area of the membrane. The measurements can be used to

determine a differential pore volume expressed as K-^- where Vp is the pore volume, dLog{r) and r is the pore radius, assuming cylindrical pores. The differential pore volume when plotted on the y axis with pore diameter on the x axis is conventionally referred to as the "pore size distribution." For membranes exhibiting a hybrid structure, at least about 25%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, of the differential pore volume is associated with pores that are about 100 nanometers in size

(diameter) or larger. In other words, for the curve of K-^ vs. pore diameter, the dLogyr) fraction of the area under the curve from a pore diameter of about 100 nanometers to about 1,000 nanometers is at least about 25%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60% of the total area under that curve for pore sizes (or diameters assuming cylindrical pores) of from about 10 nanometers to about 1,000 nanometers. In an embodiment, the area under the curve for pore diameters of from about 100 nanometers to about 1,000 nanometers is in the range of about 25% to about 60%, or about 30% to about 55%, or about 35% to about 50% of the total area under the curve for pore diameters of from about 10 nanometers to about 1,000 nanometers. [0070] Though not critical, dense domains (relatively small pores) and coarse domains (relatively large pores) are irregularly entangled to form a hybrid structure in any cross sections of the microporous polyolefϊn membrane viewed in longitudinal and transverse

directions. The hybrid structure can be observed by a transmission electron microscope (TEM), etc.

[0071] Because the microporous membrane of the present invention has relatively large internal space and openings due to coarse domains, it has suitable permeability and electrolytic solution absorption, with little air permeability variation when compressed. This microporous membrane also has relatively small internal space and openings which influence safety properties of the membrane when used as a battery separator, such as shutdown temperature and shutdown speed. Accordingly, lithium ion batteries such as lithium ion secondary batteries comprising separators formed by such microporous membrane have suitable productivity and cyclability while retaining their high safety performance.

[0072] The mercury intrusion porosimetry method used to determine the microporous membrane structure involves use of a Pore Sizer 9320 (Micromeritics Company, Ltd.), a pressure range of from 3.6 kPa to 207 MPa, and a cell volume of 15 cm ³ . For the measurements, a contact angle of mercury of 141.3 and a surface tension of mercury of 484 dynes/cm was employed. The parameters obtained by this included pore volume, surface area ratio, peak top of pore size, average pore size and porosity. References teaching this method include Raymond P. Mayer and Robert A. Stowe, J. Phys. Chem.70,12(1966); L. C. Drake, Ind.Eng.Chem., 41,780(1949); H. L. Ritter and L. C. Drake, Ind.Eng.Chem.AnaL, 17,782(1945) and E. W. Washburn,

Proc.Nat.Acad.Sci.,7, 115(1921 ).

[0073] The mercury intrusion porosimetry method can be briefly summarized as follows. Pressurized mercury is applied to a planar surface of the microporous membrane at a pressure P. This pressure does work Wl on the mercury, which causes the mercury to intrude into the pores of the microporous membrane until equilibrium is reached. In equilibrium, the force Fl on the surface of the mercury applied by pressure P is balanced by a Force F2 equal in magnitude to Fl but acting in the opposite direction. According to the conventional Washbum model, the amount of work needed to move the surface of the mercury in to the pore W\ = 2πrLχcosθ is balanced by the work done by the opposing force, which can be expressed as Wl = Pw ¹ L . In these equations, L is the depth and r is the radius of the pores, assuming the pores are cylindrical. The contact angle of the mercury is expressed as θ. The surface tension of mercury is expressed as γ, which is

generally recognized as 0.48Nm ^"1 . Consequently, according to the Washbum model, pore radius r can be expressed as a function of the pressure P according to the equation

r = — . The measurement of differential pore volume can then proceed as

follows. First, the volume V of mercury intruded into the pores is measure as a function of pressure P. The measured value of P is used to calculate pore radius r, as described above. P is increased incrementally, and the volume of mercury is determined at each value of P. In this way, a table can be constructed showing the pore volume associated with pores of a particular r, tabulated over the range of r as determined by the range of P selected for the measurement. The tabulated values of r can be conveniently converted to Log (r). Pore volume Vp is generally expressed as cm ³ per gram of the microporous

membrane. Differential pore volume expressed as γ-τ can be calculated from the dLog[r) tabulated values of Vp and r, where dVp is approximated by the difference between adjacent tabulated values of Vp, and where dLog(r) is approximated by the difference between adjacent tabulated values of Log( r). [0074] Because the microporous polyolefin membrane has relatively large internal space and openings due to coarse domains, it has suitable permeability and electrolytic solution absorption, with little air permeability variation when compressed. Accordingly, lithium ion batteries such as lithium ion secondary batteries comprising separators formed by such microporous polyolefin membrane have suitable productivity and cyclability. [0075] In an embodiment, the microporous polyolefin membrane is a single-layer membrane, where the has a hybrid structure, e.g., the microporous layer material is characterized by a differential pore volume curve having an area under the curve over the range of pore diameters of from about 100 run to about 1,000 nm that is about 25% or more of a total area under the curve over the range of pore diameters of from about 10 nm to about 1,000 nm

[0076] A hybrid structure is more difficult to produce when the percentage of the first polyethylene in the membrane is more than 97 wt. % based on the total weight of polyolefin in the membrane. A hybrid structure is also more difficult to produce when the percentage of polypropylene in the membrane is more than 20 wt. %based on the total weight of polyolefin in the membrane. A hybrid structure is more difficult to produce when the percentage of the second polyethylene in the membrane is more than 7 wt. %,

based on the total weight of polyolefin in the membrane. Membranes having a hybrid structure generally have better electrolytic solution absorption characteristics than membranes that do not have a hybrid structure.

[0077] In an embodiment of the microporous membrane, the main peak is in a pore size range of 0.01 to 0.08 μm, and at least one sub-peak is in a pore size ranging from more than 0.08 μm to 1.5 μm. In other words, at least one sub-peak has a pore size of greater than 0.08 μm to 1.5 μm or less. More preferably, the main peak is a first peak in a pore size range of about 0.04 to 0.07 μm, and the sub-peaks comprise a second peak in a pore size range of about 0.1 to 0.11 μm, a third peak at a pore size of about 0.7 μm, and a fourth peak in a pore size range of about 1 to 1.1 μm. However, the sub-peaks need not have the third and fourth peaks. For example, the pore size distribution curve may have first to fourth peaks at about 0.06 μm, about 0.1 μm, about 0.7 μm, and about 1.1 μm, respectively. When distinct peaks are not observed in the raw porosimitry data, the approximate positions can be obtained using, e.g., conventional peak deconvolution analysis. For example, the first derivative of the curve representing the number of pores on the y axis and the pore size on the x axis can be used to more clearly identify a change in slope (e.g., an inflection) on the curve.

[0078] The pore volume ratio of the dense domains to the coarse domains of the microporous polyolefin membrane of the present invention is determined by standard methods using a transmission electron microscope (TEM), mercury porosimetry, etc, as described in PCT Patent Application No. WO2008/016174, which is incorporated by reference herein in its entirety. As shown in the PCT reference, a hatched area Si (as shown in the PCT publication) on the smaller diameter side and a vertical line Li passing the first peak corresponds to the pore volume of the dense domains, and a hatched area S ₂ on the larger diameter side and a vertical line L ₂ passing the second peak corresponds to the pore volume of the coarse domains. The pore volume ratio Si /S ₂ of the dense domains to the coarse domains is preferably from about 0.5 to about 49, more preferably from about 0.6 to about 10, most preferably from 0.7 to 2. [0079] Though not critical, dense domains and coarse domains are irregularly entangled to form a hybrid structure in any cross sections of the microporous polyolefin membrane viewed in longitudinal and transverse directions. (2) Properties

[0080] The thickness of the final membrane is generally in the range of 3 μm to 200 μm. For example, the membrane can have a thickness in the range of from about 5 μm to about 50 μm, e.g., from about 15 μm to about 30 μm. The thickness of the microporous membrane can be measured, e.g., by a contact thickness meter at 1 cm longitudinal intervals over the width of 10 cm, and then averaged to yield the membrane thickness. Thickness meters such as the Litematic available from Mitsutoyo Corporation are suitable. Non-contact thickness measurement methods are also suitable, e.g. optical thickness measurement methods.

(a) Air permeability of 500 seconds/ 100cm ² or less (converted to the value at 20 μm thickness)

[0081] The membrane's air permeability is measured according to JIS P8117. In an embodiment, the membrane's air permeability is in the range of from 20 to 400 seconds/ 100 cm ³ . If desired, air permeability Pi measured on a microporous membrane having a thickness Ti according to JIS P8117 can be converted to air permeability P ₂ at a thickness of 20 μm by the equation of P ₂ = (Pi x 20)/T).

(b) Porosity of from about 25 to about 80%

[0082] The membrane's porosity is measured conventionally by comparing the membrane's actual weight to the weight of an equivalent non-porous membrane of 100% polyethylene (equivalent in the sense of having the same length, width, and thickness). Porosity is then determined using the formula: Porosity % = 100 x (w2-wl)/w2, wherein "wl" is the actual weight of the microporous membrane and "w2" is the weight of an equivalent non-porous membrane of 100% polyethylene having the same size and thickness.

(c) Pin puncture strength of 2,000 niN or more (converted to the equivalent value for a membrane having a 20 μm thickness)

[0083] The membrane's pin puncture strength (converted to the value at membrane thickness of 20 μm) is represented by the maximum load measured when the microporous membrane is pricked with a needle of 1 mm in diameter with a spherical end surface (radius R of curvature: 0.5 mm) at a speed of 2 mm/second. When the pin puncture strength is less than 2,000 mN/20 μm, short-circuiting might occur in batteries with separators formed by the microporous membrane. In an embodiment, the membrane's pin puncture strength (converted to 20 μm) is in the range of 4,000 to 5,000 mN.

[0084] The maximum load is measured when each microporous membrane having a thickness of Ti is pricked with a needle of 1 mm in diameter with a spherical end surface (radius R of curvature: 0.5 mm) at a speed of 2 mm/second. The measured maximum load Li is converted to the maximum load L ₂ at a thickness of 20 μm by the equation of L ₂ = (Li x 20)/T], and defined as pin puncture strength.

(d) Tensile strength of 49,000 kPa or more

[0085] A tensile strength of 49,000 kPa or more in both longitudinal and transverse directions (measured using a 10mm wide test piece according to ASTM D-882), is characteristic of suitable durable microporous membranes, particularly when used as battery separators. The tensile rupture strength is preferably about 80,000 kPa or more.

(e) Tensile elongation of 100% or more

[0086] A tensile elongation of 100% or more in both longitudinal and transverse directions (measured according to ASTM D-882), is characteristic of suitably durable microporous membranes, particularly when used as battery separators. (f) Heat shrinkage ratio of 12% or less in MD and TD

[0087] The heat shrinkage ratio of the microporous membrane orthogonal planar directions (e.g., machine direction or transverse direction) at 105°C is measured as follows: (i) Measure the size of a test piece of microporous membrane at ambient temperature in both the machine direction and transverse direction, (ii) equilibrate the test piece of the microporous membrane at a temperature of 105 ⁰ C for 8 hours with no applied load, and then (iii) measure the size of the membrane in both the machine and transverse directions. The heat (or "thermal") shrinkage ratio in either the machine or transverse directions can be obtained by dividing the result of measurement (i) by the result of measurement (ii) and expressing the resulting quotient as a percent. [0088] In an embodiment, the microporous membrane has a TD heat shrinkage ratio at 105°C in the range of 3% to 10%, e.g., 3.5% to 5%; and an MD heat shrinkage ratio at 105 ⁰ C in the range of 1% to 8%, e.g., 1.5% to 3%.

(g~) Thickness variation ratio of 21% or less after heat compression (expressed as an absolute value) [0089] The thickness variation ratio after heat compression at 90°C under pressure of 2.2 MPa for 5 minutes is generally 20% or less per 100% of the thickness before compression. Batteries comprising microporous membrane separators with a thickness

variation ratio of 20% or less have suitably large capacity and good cyclability. In an embodiment, the membrane's thickness variation ratio is in the range of 10% to 20%. [0090] To measure the thickness variation ratio after heat compression, a microporous membrane sample is situated between a pair of highly flat plates, and heat-compressed by a press machine under a pressure of 2.2 MPa (22 kgf/cm ² ) at 90 ⁰ C for 5 minutes, to determine an average thickness in the same manner as above. A thickness variation ratio is calculated by the formula of (average thickness after compression - average thickness before compression) / (average thickness before compression) x 100. (h) Air permeability after heat compression of 700 sec/ 100 cm ³ or less [0091] The microporous polyolefin membrane when heat-compressed under the above conditions generally has air permeability (Gurley value) of 700 sec/ 100 cm ³ or less. Batteries using such membranes have suitably large capacity and cyclability. The air permeability is preferably 650 sec/100 cm ³ or less, e.g., in the range of 400 sec/100cm ³ to 500 sec/cm ³ . [0092] Air permeability after heat compression is measured according to JIS P8117. (i) Surface roughness of 3 x 10 ² nm or more

[0093] The surface roughness of the membrane measured by an atomic force microscope (AFM) in a dynamic force mode is generally 3 x 10 ² nm or more (measured as the average maximum height difference across the membrane). The membrane's surface roughness is preferably 3.5 x 10 ² nm or more, e.g., in the range of 400 nm to 700 nm. (j) Melt-down temperature of 160 ⁰ C or more

[0094] Melt down temperature is measured by the following procedure: A rectangular sample of 3 mm x 50 mm is cut out of the microporous membrane such that the long axis of the sample is aligned with the transverse direction of the microporous membrane as it is produced in the process and the short axis is aligned with the machine direction. The sample is set in a thermomechanical analyzer (TMA/SS6000 available from Seiko Instruments, Inc.) at a chuck distance of 10 mm, i.e., the distance from the upper chuck to the lower chuck is 10mm. The lower chuck is fixed and a load of 19.6mN applied to the sample at the upper chuck. The chucks and sample are enclosed in a tube which can be heated. Starting at 30 ⁰ C, the temperature inside the tube is elevated at a rate of 5°C/minute, and sample length change under the 19.6mN load is measured at intervals of 0.5 second and recorded as temperature is increased. The temperature is increased to 200 ⁰ C. The melt

down temperature of the sample is defined as the temperature at which the sample breaks, generally at a temperature in the range of about 145°C to about 200°C. [0095] In an embodiment, the meltdown temperature is in the range of from 160 ⁰ C to 20O ⁰ C ₅ e.g., in the range of 17O ⁰ C to 18O ⁰ C. (k) Electrolytic solution absorption speed of 4.3 or greater

[0096] Using a dynamic surface tension measuring apparatus (DCAT21 with high-precision electronic balance, available from Eko Instruments Co., ltd.), a microporous membrane sample is immersed in an electrolytic solution for 600 seconds (electrolyte: 1 mol/L of LiPF ₆ , solvent: ethylene carbonate/dimethyl carbonate at a volume ratio of 3/7) kept at 18°C, to determine an electrolytic solution absorption speed by the formula of [weight (in grams) of microporous membrane after immersion / weight (in grams) of microporous membrane before immersion]. The electrolytic solution absorption speed is expressed by a relative value, assuming that the electrolytic solution absorption rate in the microporous membrane of Comparative Example 6 is 1. In an embodiment, the membrane's electrolytic solution absorption speed is in the range of 4.3 to 6. (1) Pore size distribution

[0097] The pore size distribution of the microporous membrane is determined by mercury intrusion porosimetry. At least about 25% of the differential pore volume is associated with pores larger than 100 nanometers (nm). (m) Surface roughness

[0098] The maximum height difference of a surface measured by AFM in a dynamic force mode (DFM) is used as surface roughness.

(3) Microporous polvolefϊn membrane composition

[0099] An embodiment, the microporous membrane has good electrolytic solution absorption, compression and heat resistance properties and comprises (a) from about 73 wt. % to about 97 wt. % of a first polyethylene having an Mw of from about 2.5 x 10 ⁵ to about 6 x 10 ⁵ and an MWD of from about 5 to about 100, for example, an Mw of from about 2.5 x 10 ⁵ to about 4 x 10 ⁵ and an MWD of from about 5 to about 50; and (b) from about 3 wt. % to about 20 wt. % of polypropylene resin having an Mw of from about 3 x 10 ⁵ to about 1.5 x 10 ⁶ , a heat of fusion of 80 J/g or higher, and an MWD of from about 1 to about 100, for example, an Mw of from about 3 x 10 ⁵ to about 5 x 10 ⁵ and an MWD of from about 1.1 to about 50; and (c) from about 0 wt. % to about 7 wt. % of a second

polyethylene having a weight average molecular weight of 5 x 10 ⁵ or higher, for example, an Mw of from about 5 x 10 ⁵ to about 5 x 10 ⁶ ; the weight percents being based on the combined weight of the polyethylene and the polypropylene in the membrane. [00100] The microporous membrane generally comprises the same polymers used to produce the polymeric composition, in generally the same relative amounts. Washing solvent and/or process solvent (diluent) can also be present, generally in amounts less than 1 wt% based on the weight of the microporous membrane. A small amount of polymer molecular weight degradation might occur during processing, but this is acceptable. In an embodiment where the polymer is polyolefϊn and the membrane is produced in a wet process, molecular weight degradation during processing, if any, causes the MWD value of the polymers in the membrane to differ from the Mw/Mn of the polymers used to produce the membrane by no more than about 5%, or no more than about 1%, or no more than about 0.1%. [41 Battery separator [00101] In an embodiment of the present invention, the battery separator formed from any of the above microporous polyolefϊn membranes of the present invention has a thickness of from about 3 to about 200 μm, or from about 5 to about 50 μm, or from about 7 to about 35 μm, though the most suitable thickness is properly selected depending on the type of battery to be manufactured. f51 Battery

[00102] Though not particularly critical, the microporous polyolefin membranes of the present invention may be used as separators for primary and secondary batteries, particularly such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, particularly for lithium ion secondary batteries.

[00103] The lithium ion secondary battery comprises a cathode and an anode laminated via a separator, and the separator contains an electrolyte, usually in the form of an electrolytic solution ("electrolyte"). The electrode structure is not critical and conventional structures are suitable. The electrode structure may be, for instance, a coin type in which a disc-shaped positive and anodes are opposing, a laminate type in which planar positive and anodes are alternately laminated, a toroidal type in which

ribbon-shaped positive and anodes are wound, etc.

[00104] The cathode usually comprises a current collector, and a cathodic active material layer capable of absorbing and discharging lithium ions which is formed on the current collector. The cathodic active materials may be inorganic compounds such as transition metal oxides, composite oxides of lithium and transition metals (lithium composite oxides), transition metal sulfides, etc. The transition metals may be V, Mn, Fe, Co, Ni, etc. Preferred examples of the lithium composite oxides are lithium nickelate, lithium cobaltate, lithium manganate, laminar lithium composite oxides based on Ci-NaFeO ₂ , etc. The anode comprises a current collector, and a negative-electrode active material layer formed on the current collector. The negative-electrode active materials may be carbonaceous materials such as natural graphite, artificial graphite, coke, carbon black, etc.

[00105] The electrolytic solution can be a solution obtained by dissolving a lithium salt in an organic solvent. The lithium salt may be LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiC(CF ₃ SO ₂ ) ₃ , Li ₂ Bi ₀ CIi ₀ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₃ (C ₂ Fs) ₃ , lower aliphatic carboxylates of lithium, LiAlCl ₄ , etc. These lithium salts may be used alone or in combination. The organic solvent may be an organic solvent having a high boiling point and high dielectric constant such as ethylene carbonate, propylene carbonate, ethylmethyl carbonate, γ-butyrolactone, etc.; and/or organic solvents having low boiling points and low viscosity such as tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dioxolane, dimethyl carbonate, dimethyl carbonate, etc. These organic solvents may be used alone or in combination. Because the organic solvents having high dielectric constants generally have high viscosity, while those having low viscosity generally have low dielectric constants, their mixtures are preferably used.

[00106] When the battery is assembled, the separator is impregnated with the electrolytic solution, so that the separator (microporous polyolefin membrane) is provided with ion permeability. The impregnation treatment is usually conducted by immersing the microporous membrane in the electrolytic solution at room temperature. When a cylindrical battery is assembled, for instance, a cathode sheet, a microporous membrane separator and an anode sheet are laminated in this order, and the resultant laminate is wound to a toroidal-type electrode assembly. The resultant electrode assembly is

charged/formed into a battery can and then impregnated with the above electrolytic solution, and the battery lid acting as a cathode terminal provided with a safety valve is caulked to the battery can via a gasket to produce a battery.

[00107] The present invention will be explained in more detail referring to examples below without intention of restricting the scope of the present invention. Example 1

[00108] Dry-blended are 100 parts by mass of polyolefin composition comprising (i) a polyethylene (PE) composition comprising (a) 2% by mass of ultra-high molecular weight polyethylene (UHMWPE) having a weight average molecular weight (Mw) of 2 x 10 and a molecular weight distribution (Mw/Mn) of 8, and (b) 88% by mass of high density polyethylene (HDPE) having an Mw of 3.0 x 10 ⁵ and Mw/Mn of 8.6, and (ii) a polypropylene (PP) composition comprising 10% by mass of polypropylene having an Mw of 6.6 x 10 ⁵ and a heat of fusion (δHm) of 83.3 J/g, and 0.2 parts by mass of tetrakis[methylene-3-(3,5-ditertiary-butyl-4-hydroxyphenyl)- propionate] methane as an antioxidant. The polyethylene in the mixture has a melting point of 135°C and a crystal dispersion temperature of 100°C.

[00109] Forty parts by mass of the resultant mixture is charged into a strong-blending double-screw extruder having an inner diameter of 58 mm and L/D of 42, and 60 parts by mass of liquid paraffin (50 cst at 40 ⁰ C) is supplied to the double-screw extruder via a side feeder. Melt-blending is conducted at 210°C and 200 rpm to prepare a polyolefin solution. This polyolefin solution is extruded from a T-die mounted to the double-screw extruder. The extrudate is cooled while passing through cooling rolls controlled at 40 ⁰ C, to form a gel-like sheet. [00110] Using a tenter-stretching machine, the gel-like sheet is simultaneously biaxially stretched at 118.5°C to 5 fold in both longitudinal and transverse directions. The stretched gel-like sheet is fixed to an aluminum frame of 20 cm x 20 cm, immersed in a bath of methylene chloride controlled at 25 ⁰ C to remove the liquid paraffin with vibration of 100 rpm for 3 minutes, and dried by an air flow at room temperature. The dried membrane is re-stretched by a batch-stretching machine to a magnification of 1.5 fold in a transverse direction at 129°C. The re-stretched membrane, which remains fixed to the batch-stretching machine, is heat-set at 129°C for 30 seconds to produce a microporous polyethylene membrane.

Example 2

[00111] Example 1 is repeated except for the polyolefin composition comprising 90 % by mass of the HDPE resin having a weight average molecular weight of 3 x 10 ⁵ and a molecular weight distribution of 8.6; and 10 % by mass of the PP resin having a weight average molecular weight of 6.6 x 10 ⁵ and a δHm of 83.3 J/g; the re-stretching is to a magnification of 1.5 fold at 128.5 °C; and the heat setting is at 128.5 °C. Example 3

[00112] Example 1 is repeated except for the polyolefin composition comprising 2% by mass of the UHMWPE resin having a weight average molecular weight (Mw) of 2 x 10 ⁶ and a molecular weight distribution of 8; 88 % by mass of the HDPE resin having a weight average molecular weight of 3 x 10 ^D and a molecular weight distribution of 8.6; and 10 % by mass of a PP resin having a weight average molecular weight of 1.35 x 10 ⁶ and a δHm of 97.9 J/g; the re-stretching is to a magnification of 1.5 fold at 127.5 °C; and the heat setting is at 127.5 °C. Comparative Example 1

[00113] Example 1 is repeated except for the polyolefin composition comprising 5% by mass of the UHMWPE resin having a weight average molecular weight (Mw) of 2 x 10 ⁶ and a molecular weight distribution of 8; and 95 % by mass of the HDPE resin having a weight average molecular weight of 3 x 10 ⁵ and a molecular weight distribution of 8.6. No PP is included in this Comparative Example. Comparative Example 2

[00114] Example 1 is repeated except for the polyolefin composition comprising 100 % by mass of the HDPE resin having a weight average molecular weight of 3 x 10 ³ and a molecular weight distribution of 8.6; the stretching is done at 118 °C; and the re-stretching is to a magnification of 1.4 fold at 129 ⁰ C. No PP or UHMWPE are included in this Comparative Example. Comparative Example 3

[00115] Example 1 is repeated except for the polyolefin composition comprising 3% by mass of the UHMWPE resin having a weight average molecular weight of 2 x 10 ⁶ and a molecular weight distribution of 8; 92 % by mass of the HDPE resin having a weight average molecular weight of 3 x 10 ⁵ and a molecular weight distribution of 8.6; and 5 % by mass of a PP resin having a weight average molecular weight of 5.3 x 10 ⁵ and a δHm of

only 77.2 J/g; the stretching is at 116 ⁰ C; the re-stretching is to a magnification of 1.4 fold at 127 °C; and the heat setting is at 127 °C. Another exception from Example 1 for this Comparative Example 3 is that 35 parts by mass of the resultant polyolefin composition and 65 parts by mass of the liquid paraffin (50 cst at 40°C) is charged into the double-screw extruder.

[00116] The properties of the microporous membranes obtained in the Examples and Comparative Examples are shown in Table 1.

Table 1

Comparative examples

Ex-I Ex-2 Ex-3 1 2 3 4 5 6

Polyolefϊn

UHMWPE

Mw 2.0*10 ⁶ 2.0*10° 2.0*10 ⁶ - 2.0*10 ⁶ 2.0*10 ⁶ 2.0*10 ⁶ 2.0*10 ⁶

MWD 8 8 8 - 8 8 8 8

% 2 2 5 - 3 3 3 20

HDPE

Mw 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.0*10 ⁵ 3.5*10 ⁵

MWD 8.6 8.6 8.6 8.6 8.6 8.6 8.6 8.6 13.5

% 88 90 88 95 100 92 92 92 80

PP

Mw 6.6*10 ⁵ 6.6*10 ⁵ 1.35*10 ⁶ - - 5.3*10 ⁵ 2.0*10 ⁵ 1.7*10 ⁶ -

Heat of fusion 83.3 83.3 97.9 - - 77.2 69.5 88.2

% 10 10 10 - - 5 5 5

PE composition

Tm 135 135 135 135 135 135 135 135 135

Ted 100 100 100 100 100 100 100 100 100

MWD 10 8.6 10.5 10.5 10.5 14.4

Polyolefϊn concentration 40 40 40 40 40 35 35 35 30

Stretching of Gel-Like sheet

Temperature 118.5 118.5 118.5 118.5 118 116 116 116 115

Magnification MD 5 5 5 5 5 5 5 5 5

TD 5 5 5 5 5 5 5 5 5

Stretching of MPF

Temperature 129 128.5 127.5 129 129 127 127 127 -

Direction TD TD TD TD TD TD TD TD -

Magnification 1.5 1.5 1.5 1.5 1.4 1.4 1.4 1.4 -

Heat-setting

Temperature 129 128.5 127.5 129 129 127 127 127 126.8

Time 30 30 30 30 30 30 30 30 30 V

Properties of MPF thickness 21.5 20.9 19.8 19.9 20.2 20.5 19.8 20.3 20.1 air permeabilty 182 175 228 123 220 180 216 175 425 porosity 44.6 44.3 45.6 48.5 41 45.2 42.6 44.8 38 puncture strength 4460 4320 4680 4263 4998 4165 3826 4825 4900

Tensile strength MD 1 13500 107600 120250 98000 1 18090 1 13680 104530 124690 148960

TD 129650 127400 133070 133700 157780 125440 1 18700 134300 124460

Tensile elongation MD 180 185 180 165 155 190 150 200 145

TD 160 155 140 120 100 175 160 180 220 heat shrinkage MD 2.5 2.4 2 5.5 3.1 2.5 3.1 3.7 5

TD 4.4 4 3.5 5.6 3.6 2.2 2.9 4.1 4.5

Higher-order structure

1 st peak 0.07 0.07 0.07 0.06 0.07 0.06 0.06 0.06 0.04

2nd peak 0.1 1 0.1 0.1 0.1 0.1 1 0.1 0.1 0.1 -

3rd peak 0.7 0.7 - - - -

4th peak 1 1 - - - - pore vol. ratio 0.7 0.73 0.75 0.76 1.4 0.73 1.6 0.73 - surface roughness

6.4* 10 ² 6.1 * 10 ² 6.0* 10 ² 6.1 * 10 ² 6.2* 10 ² 6.4* 10 ² 7.3* 10 ² 6.0* 10 ² 2.1 * 10 ²

(nm) electrolytic solution absorption speed 4.5 4.6 4.3 4.1 4.2 4.1 2.4 3.8 1

Thickness variation after heat

18 15 20 19 10 17 16 17 20 compression (abs. val.)

Air permeability after heat

416 405 495 465 515 485 612 509 962 - compression - V

Melt-down temperature 172.6 171.4 177.6 159.6 157.2 167.8 162.4 179.5 161

[00117] As is clear from Table 1, the microporous membrane of the present invention exhibits a pore size distribution curve obtained by mercury intrusion porosimetry having a first peak at a pore size of from 0.01 to 0.08 μm, and second to fourth peaks at pore sizes of more than 0.08 μm and 1.5 μm or less, and the surface roughness as a maximum height difference was 3 x 10 ² nm or more. The microporous membrane of the present invention has suitable air permeability, pin puncture strength, tensile rupture strength, tensile rupture elongation, as well as excellent electrolytic solution absorption, compression properties and heat shrinkage resistance, with little variation of thickness and air permeability after heat compression.

[00118] On the other hand, the microporous membrane of the product of the Comparative Examples has lower electrolytic solution absorption and lower melt-down temperatures. Accordingly, the microporous membrane of the Comparative Example does not perform as well as that of the present invention. [00119] The microporous polyolefin membrane of the present invention has suitable permeability and mechanical strength, and excellent electrolytic solution absorption, compression resistance and heat shrinkage resistance. Separators formed by the microporous polyolefin membrane of the present invention provide batteries with suitable safety, heat resistance, storage properties and productivity.