Patent Application
20100316902
The invention relates to a microporous membrane having an improved balance of important properties such as melt down temperature and thickness fluctuations. The invention also relates to a system and method for producing such a membrane, the use of such a membrane as a battery separator film, batteries containing such a membrane, and the use of such batteries as a power source in, e.g., electric and hybrid electric vehicles.
Microporous polyolefin 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 as a lithium ion battery separator, the membrane's performance significantly affects the properties, productivity and safety of the battery. Accordingly, the microporous polyolefin membrane should have suitably well-balanced permeability, mechanical properties, dimensional stability, shutdown properties, meltdown properties, etc. The term “well-balanced” means that the optimization of one of these characteristics does not result in a significant degradation in another.
As is known, it is desirable for the batteries to have a relatively low shutdown temperature and a relatively high meltdown temperature for improved battery safety, particularly for batteries exposed to high temperatures under operating conditions. Consistent dimensional properties, such as film thickness, are essential to high performing films. A separator with high mechanical strength is desirable for improved battery assembly and fabrication, and for improved durability. The optimization of material compositions, casting and stretching conditions, heat treatment conditions, etc. have been proposed to improve the properties of microporous polyolefin membranes.
In general, microporous polyolefin membranes consisting essentially of polyethylene (i.e., they contain polyethylene only with no significant presence of other species) have relatively low meltdown temperatures. Accordingly, proposals have been made to provide microporous polyolefin membranes made from mixed resins of polyethylene and polypropylene, and multi-layer, microporous polyolefin membranes having polyethylene layers and polypropylene layers in order to increase meltdown temperature. The use of these mixed resins can make the production of films having consistent dimensional properties, such as film thickness, all the more difficult.
U.S. Pat. No. 4,734,196 proposes a microporous membrane of ultra-high-molecular-weight alpha-olefin polymer having a weight-average molecular weight greater than 5×105, the microporous membrane having through holes 0.01 to 1 micrometer in average pore size, with a void ratio from 30 to 90% and being oriented such that the linear draw ratio in one axis is greater than two and the linear draw ratio is greater than ten. The microporous membrane is obtained by forming a gel-like object from a solution of an alpha-olefin polymer having a weight-average molecular weight greater than 5×105, removing at least 10 wt. % of the solvent contained in the gel-like object so that the gel-like object contains 10 to 90 wt. % of alpha-olefin polymer, orientating the gel-like object at a temperature lower than that which is 10° C. above the melting point of the alpha-olefin polymer, and removing the residual solvent from the orientated product. A film is produced from the orientated product by pressing the orientated product at a temperature lower than that of the melting point of the alpha-olefin polymer.
U.S. Patent Publication No. 2007/0012617 proposes a method for producing a microporous thermoplastic resin membrane comprising the steps of extruding a solution obtained by melt-blending a thermoplastic resin and a membrane-forming solvent through a die, cooling an extrudate to form a gel-like molding, removing the membrane-forming solvent from the gel-like molding by a washing solvent, and removing the washing solvent, the washing solvent having (a) a surface tension of 24 mN/m or less at a temperature of 25° C., (b) a boiling point of 100° C. or lower at the atmospheric pressure, and (c) a solubility of 600 ppm (on a mass basis) or less in water at a temperature of 16° C.; and the washing solvent remaining in the washed molding being removed by using warm water. The molten polymer is fed into a first inlet at an end of a first manifold and a second inlet at the end of a second manifold on the opposite side of the first inlet. Two slit currents flow together inside the die. It is theorized that due to the absence of flow divergence of the melt inside the manifold, it may be possible to achieve uniform flow distribution within the die. This is said to result in improved thickness uniformity in the transverse direction the film or the sheet.
JP Publication No. 2004-083866 proposes a method for producing a polyolefin microporous film that includes preparing a gel-like molded product by melting and kneading the polyolefin with a liquid solvent, extruding the molten and kneaded product from a die, simultaneously and biaxially drawing in the machine and vertical directions, subsequently drawing at a higher temperature than that of the simultaneous biaxial drawing to increase anisotropy against the primary drawing. The redrawing is carried out to satisfy both relations: 0<λ1t/λ2m≦10, wherein λ1t denotes a draw ratio of the biaxial drawing in the vertical direction and λ2m denotes a draw ratio of the redrawing in the machine direction, and 0<λ1m/λ2t≦10, wherein λ1m denotes a draw ratio of the biaxial drawing in the machine direction and λ2t denotes a draw ratio of the redrawing in the vertical direction.
WO 2004/089627 discloses a microporous polyolefin membrane made of polyethylene and polypropylene comprising two or more layers, the polypropylene content being more than 50% and 95% or less by mass in at least one surface layer, and the polyethylene content being 50 to 95% by mass in the entire membrane.
WO 2005/113657 discloses a microporous polyolefin membrane having conventional shutdown properties, meltdown properties, dimensional stability and high-temperature strength. The membrane is made using a polyolefin composition comprising (a) composition comprising lower molecular weight polyethylene and higher molecular weight polyethylene, and (b) polypropylene. This microporous polyolefin membrane is produced by a so-called “wet process”.
Despite these advances in the art, there remains a need for system and process capable of producing microporous polyolefin membranes and other high quality films or sheets.
Provided is a process for producing a microporous membrane. The process includes the steps of combining a polyolefin composition and at least one diluent (e.g., a solvent) to form a mixture (e.g., a polyolefin solution), the polyolefin composition comprising at least a first polyethylene having a crystal dispersion temperature (Tcd) and polypropylene, extruding the polyolefin solution through an extrusion die to form an extrudate, cooling the extrudate to form a cooled extrudate having a first area, orienting the cooled extrudate in at least a first direction by about one to about ten fold at a temperature of about Tcd+/−15° C. and further orienting the cooled extrudate in at least a second direction by about one to about five fold at a temperature about 10° C. to about 40° C. higher than the temperature employed in the first orienting step to form an extrudate having a second area≧10 fold larger than the first area.
In another aspect, a process for reducing transverse direction film thickness fluctuation in a film or sheet produced from a mixture (e.g., a polyolefin solution) is provided, the mixture comprising at least a first polyethylene having a crystal dispersion temperature (Tcd), a polypropylene and a solvent or diluent. The process includes the steps of extruding the polyolefin solution through an extrusion die to form an extrudate, cooling the extrudate to form a cooled extrudate, orienting the cooled extrudate in at least a first direction by about one to about ten fold at a temperature of about Tcd+/31 15° C. and further orienting the cooled extrudate in at least a second direction by about one to about five fold at a temperature about 10° C. to about 40° C. higher than the temperature employed in the first orienting step.
In one form, the oriented cooled extrudate is further processed to produce a membrane, utilizing the steps of removing at least a portion of the diluent to form a membrane, optionally stretching the dried membrane to a magnification of from about 1.1 to about 2.5 fold in at least one direction to form a stretched membrane, and heat-setting the membrane product of to form the microporous membrane.
In yet another aspect, a system for reducing transverse direction film thickness fluctuation in a film or sheet produced from a polyolefin solution, the polyolefin solution comprising at least a first polyethylene having a crystal dispersion temperature (Tcd), a polypropylene and a solvent or diluent, is provided. The system includes an extruder for preparing the polyolefin solution, an extrusion die for receiving and extruding the polyolefin solution to form an extrudate, means for cooling the extrudate to form a cooled extrudate, a first stretching machine for orienting the cooled extrudate in at least a first direction by about one to about ten fold at a temperature of about Tcd+/31 15° C., a second stretching machine for further orienting the cooled extrudate in at least a second direction by about one to about five fold at a temperature about 10° C. to about 40° C. higher than the temperature employed by said first stretching machine, and a controller for regulating the temperature of the first stretching machine and the temperature of the second stretching machine, wherein the transverse direction film thickness fluctuation of a film or sheet produce by the system is reduced by at least 25%.
In one form, the first stretching machine is a roll-type stretching machine. In another form, the first stretching machine is a tenter-type stretching machine. In yet another form, the second stretching machine is a tenter-type stretching machine. In still yet another form, the polyolefin solution includes (i) at least about 5 wt. % high density polyethylene or at least about 6 wt. % high density polyethylene, or at least about 10 wt. % high density polyethylene, or at least about 30 wt. % high density polyethylene, and (ii) at least about 5 wt. % polypropylene or at least about 10 wt. % polypropylene or at least about 30 wt. % polypropylene, and (iii) at least about 4 wt. % ultra high molecular weight polyethylene or at least about 10 wt. % ultra high molecular weight polyethylene, the weight percents being based on the weight of the polyolefin solution.
In a further form, the polyolefin solution includes at least about 30 wt. % high density polyethylene, at least about 30 wt. % polypropylene and at least about 20 wt. % ultra high molecular weight polyethylene, the weight percents being based on the weight of the polyolefin solution.
In a still further form, the polyolefin of the polyolefin solution comprises from about 40% to about 100% or from about 20% to about 80% of the first polyethylene resin, the first polyethylene resin having a weight-average molecular weight (“Mw”) of from about 2×105 to about 9×105 and a molecular weight distribution (“MWD” defined as MWD) of from about 3 to about 50, from about 5% to about 60% or from about 15% to about 50% of a polypropylene resin having an Mw of from about 6×105 to about 4×106, an MWD of from about 3 to about 30 and a heat of fusion of 90 J/g or more, and from about 0% to about 40% of a second polyethylene resin having an Mw of from 1×106 to about 5×106, an MWD of from about 3 to about 30, with the percentages based upon the mass of the polyolefin composition.
In yet another form, the invention relates to a microporous membrane comprising polyethylene and polypropylene and having a thickness fluctuation standard deviation in at least one planar direction of ≦0.7 μm and a melt down temperature ≧150° C. In another form, the invention relates to a battery comprising a anode, a cathode, at least one separator located between the anode and the cathode, the separator comprising polyethylene and polypropylene and having a thickness fluctuation standard deviation in at least one planar direction of ≦0.7 μm and a melt down temperature ≧150° C. In still other embodiments, the invention relates to the use of such a battery as a power source for, e.g., computers, mobile telephones, electronic games, power tools, electric vehicles, and/or hybrid electric vehicles. The battery can be a lithium ion secondary battery.
These and other advantages, features and attributes of the disclosed processes and systems and their advantageous applications and/or uses will be apparent from the detailed description that follows, particularly when read in conjunction with the figures appended hereto.
The invention relates to a microporous membrane comprising polyethylene and polypropylene and having an improved balance of properties including improved melt down temperature and improved thickness variation in at least one planar direction. While the presence of polypropylene in the membrane can be advantageous for increasing the membrane's melt down temperature, the use of polypropylene can worsen other membrane properties such as the membrane's thickness fluctuation. It has been discovered that this difficulty can be overcome, as described below, so that a membrane having well-balanced properties can be produced.
Reference is now made to
Referring now to
The heated mixture is then extruded into a sheet 18 from a die 20 of extruder 12. The extruded sheet 18 is cooled by a plurality of chill rolls 22 to a temperature lower than the gelling temperature, so that the extruded sheet 18 gels. The cooled extrudate 18′ passes to a first orientation apparatus 24, which may be a roll-type stretching machine, as shown. The cooled extrudate 18′ is oriented with heating in the machine direction (MD) through the use of the roll-type stretching machine 24 and then the cooled extrudate 18′ passes to a second orientation apparatus 26, for sequential orientation in at least the transverse direction (TD), to produce a biaxially oriented film or sheet 18″. Second orientation apparatus 26 may be a tenter-type stretching machine and may be utilized for further stretching in the MD.
The biaxially oriented film or sheet 18″ next passes to a solvent extraction device 28 where a readily volatile solvent such as methylene chloride is fed in through line 30. The volatile solvent containing extracted diluent is recovered from a solvent outflow line 32. The oriented film or sheet 18″ next passes to a drying device 34, wherein the volatile solvent 36 is evaporated from the biaxially oriented film or sheet 18″.
Optionally, the biaxially oriented film or sheet 18″ next passes to dry orientation device 38 where the dried membrane is stretched to a magnification of from about 1.1 to about 2.5 fold in at least one direction to form a stretched membrane. Next, the biaxially oriented film or sheet 18″ next passes to the heat treatment device 44 where the biaxially oriented film or sheet 18″ is annealed so as to adjust porosity and remove stress left in the film or sheet 18″, after which biaxially oriented film or sheet 18″ is rolled up to form product roll 48.
Referring now to
The heated mixture (e.g., polymeric solution) is then extruded into a sheet 118 from a die 120 of extruder 112. The extruded sheet 118 is cooled by a plurality of chill rolls 122 to a temperature lower than the gelling temperature, so that the extruded sheet 118 gels. The cooled extrudate 118′ passes to a first orientation apparatus 124, which may be a tenter-type stretching machine, as shown. The cooled extrudate 118′ is oriented with heating in the machine direction (MD) and/or the transverse direction (TD) and then the cooled extrudate 118′ passes to a second orientation apparatus 126, for sequential orientation in the MD and/or TD, to produce an oriented film or sheet 118″. Second orientation apparatus 126 may also be a tenter-type stretching machine.
The oriented film or sheet 118″ next passes to a solvent extraction device 128 where a readily volatile solvent such as methylene chloride is fed in through line 130. The volatile solvent containing extracted diluent is recovered from a solvent outflow line 132. The biaxially oriented film or sheet 118″ next passes to a drying device 134, wherein the volatile solvent 136 is evaporated from the biaxially oriented film or sheet 118″.
Optionally, the oriented film or sheet 118″ next passes to dry orientation device 138 where the dried membrane is stretched to a magnification of from about 1.1 to about 2.5 fold in at least one direction to form a stretched membrane. Next, the oriented film or sheet 18″ next passes to the heat treatment device 144 where the oriented film (e.g., biaxially oriented film) or sheet 18″ is annealed so as to adjust porosity and remove stress left in the film or sheet 18″, after which biaxially oriented film or sheet 118″ is rolled up to form product roll 148.
As indicated, the system disclosed herein is useful in forming microporous polyolefin membrane films and sheets. These films and sheets have reduced thickness variation in the transverse direction and find particular utility in the critical field of battery separators. The films and sheets disclosed herein provide a good balance of key properties, including high meltdown temperature, improved surface smoothness and improved electrochemical stability while maintaining high permeability, good mechanical strength and low heat shrinkage with good compression resistance. Of particular importance when used as a battery separator, the microporous membranes disclosed herein exhibit excellent heat shrinkage, melt down temperature and thermal mechanical properties; i.e., reduced maximum shrinkage in the molten state.
While the focus of the system described hereinabove has been with respect to the production of monolayer films and sheets, it is within the scope of this disclosure to provide multilayer laminated films and sheets produced in accordance herewith, as those skilled in the art can plainly understand. In an embodiment, the invention relates to a first microporous membrane comprising polyethylene and polypropylene and having a thickness fluctuation standard deviation in at least one planar direction of ≦0.7 μm and a melt down temperature ≧150° C., and at least a second membrane (e.g., a coating or layer) in contact with the first membrane. The second membrane is generally microporous and can comprise one or more of, e.g., ceramic, polymer (e.g., polyolefin), etc. The second membrane can be in face-to-face (e.g., planar) contact with the first membrane.
Starting materials (which are generally combined and used in the form of a polymer composition such as a polyolefin composition) having utility in the production of the afore-mentioned films and sheets will now be described. The finished membrane generally comprises the polymer(s) used to produce the membrane. As will be appreciated by those skilled in the art, the selection of a starting material is not critical. In one form, the starting material contains polyethylene and polypropylene. In another form, the starting materials contain polypropylene (PP-1) and at least one of (i) a first polyethylene (“PE-1”) having an Mw value<1×106 and (ii) a second polyethylene (“UHMWPE-1”) having an Mw value≧1×106.
In one form of the above (ii) and (iv), UHMWPE-1 can preferably have an Mw in the range of from 1×106 to about 15×106 or from 1×106 to about 5×106 or from 1.2×106 to about 3×106. When the amount of UHMWPE-1 in the membrane is in the range of 0 wt. % to about 40 wt. %, or about 1 wt. % to about 30 wt. %, or about 1 wt. % to 20 wt. %, on the basis of total amount of PE-1 and UHMWPE-1 in the membrane, it is less difficult to obtain a finished membrane having a hybrid structure defined in the later section. In one form, UHMWPE-1 can be, for example, one or more of (i) an ethylene homopolymer or (ii) a copolymer (random or block) of ethylene one or more of a-olefins such as propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, and styrene, etc.; and diolefins such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc. The amount of comonomer is generally less than 10% by mol based on 100% by mol of the entire copolymer.
In one form, PP-1 is present in the membrane in an amount in the range of about 5 wt. % to about 60 wt. %, or about 30 wt. % to 50 wt. %, or no more than about 60 wt. %, on the basis of the total weight of the microporous film or sheet material. The polypropylene can be, for example, one or more of (i) a propylene homopolymer or (ii) a copolymer (random or block) of propylene and one or more of α-olefins such as ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, and styrene, etc.; and diolefins such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc. The amount of the comonomer is generally less than 10% by mol based on 100% by mol of the entire copolymer. Optionally, the polypropylene has one or more of the following properties: (i) the polypropylene has an Mw ranging from about 1×104 to about 4×106, or about 3×105 to about 3×106, or about 6×105 to about 1.5×106, (ii) the polypropylene has an MWD (defined as Mw/Mn) in the range of from about 1.01 to about 100, or about 1.1 to about 50, or about 3 to about 30; (iii) the polypropylene's tacticity is isotactic; (iv) the polypropylene has a heat of fusion of at least about 90 Joules/gram or about 100 J/g to 120 J/g; (v) polypropylene has a melting peak (second melt) of at least about 160° C., (vi) the polypropylene has a Trouton's ratio of at least about 15 when measured at a temperature of about 230° C. and a strain rate of 25 sec−1; and/or (vii) the polypropylene has an elongational viscosity of at least about 50,000 Pa sec at a temperature of 230° C. and a strain rate of 25 sec−1. Optionally, the polypropylene has an MWD in the range of from about 1.01 to about 100, or from about 1.1 to about 50.
In one form, the polyolefin in the microporous film or sheet material can have an Mw of about 1.5×106 or less, or in the range of from about 1.0×105 to about 2.0×106 or from about 2.0×105 to about 1.5×106 in order to obtain a microporous film or sheet having a hybrid structure defined in the later section.
In one form, PE-1 can preferably have an Mw ranging from about 1×104 to about 9×105, or from about 2×105 to about 8×105, and can be one or more of a high-density polyethylene, a medium-density polyethylene, a branched low-density polyethylene, or a linear low-density polyethylene. In one form, PE-1 can be, for example, one or more of (i) an ethylene homopolymer or (ii) a copolymer (random or block) of ethylene one or more of α-olefins such as propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, and styrene, etc.; and diolefins such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc. The amount of comonomer is generally less than 10% by mol based on 100% by mol of the entire copolymer.
In one form, the microporous film or sheet has a hybrid structure, which is characterized by a pore size distribution exhibiting relatively dense domains having a main peak in a range of 0.01 μm to 0.08 μm and relatively coarse domains exhibiting at least one sub-peak in a range of more than 0.08 μm to 1.5 μm or less in the pore size distribution curve. The ratio of the pore volume of the dense domains (calculated from the main peak) to the pore volume of the coarse domains (calculated from the sub-peak) is not critical, and can range, e.g., from about 0.5 to about 49.
Mw and MWD of the polyethylene and polypropylene are determined using a High Temperature Size Exclusion Chromatograph, or “SEC”, (GPC PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). The measurement is made in accordance with the procedure disclosed in “Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001)”. Three PLgel Mixed-B columns available from (available from Polymer Laboratories) are used for the Mw and MWD determination. For polyethylene, the nominal flow rate is 0.5 cm3/min; the nominal injection volume is 300 μL; and the transfer lines, columns, and the DRI detector are contained in an oven maintained at 145° C. For polypropylene, the nominal flow rate is 1.0 cm3/min; the nominal injection volume is 300 μL; and the transfer lines, columns, and the DRI detector are contained in an oven maintained at 160° C.
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. The same solvent is used as the SEC eluent. Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of the TCB solvent, and then heating the mixture at 160° C. with continuous agitation for about 2 hours. The concentration of polymer solution was 0.25 to 0.75 mg/ml. Sample solution are filtered off-line before injecting to GPC with 2 μm filter using a model SP260 Sample Prep Station (available from Polymer Laboratories).
The separation efficiency of the column set is calibrated with a calibration curve generated using a seventeen individual polystyrene standards ranging in Mp (“Mp” being defined as the peak in Mw) from about 580 to about 10,000,000. The polystyrene standards are obtained from Polymer Laboratories (Amherst, Mass.). 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.
The microporous film or sheet material can optionally contain one or more additional polyolefins, identified as the seventh polyolefin, which can be, e.g., one or more of polybutene-1, polypentene-1, poly-4-methylpentene-1, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene and an ethylene α-olefin copolymer (except for an ethylene-propylene copolymer) and can have an Mw in the range of about 1×104 to about 4×106. In addition to or besides the seventh polyolefin, the microporous film or sheet material can further comprise a polyethylene wax, e.g., one having an Mw in the range of about 1×103 to about 1×104.
In one form, a method for producing a microporous polyolefin membrane is provided. The method comprises the steps of (1) combining (e.g., by melt-blending) a polyolefin composition and at least one diluent (e.g. a membrane-forming solvent) to prepare a mixture (e.g., polyolefin solution), (2) extruding the mixture through a die to form an extrudate, (3) cooling the extrudate to form a gel-like sheet (cooled extrudate), (4) sequentially orienting the cooled extrudate through the use of a first orientation or stretching step and a second orientation or stretching step, (5) removing the membrane-forming solvent from the gel-like sheet to form a solvent-removed gel-like sheet, and (6) drying the solvent-removed gel-like sheet in order to form the, microporous membrane. An optional hot solvent treatment step (7) can be conducted between steps (4) and (5), if desired. After step (6), an optional step (8) of stretching the microporous membrane, an optional heat treatment step (9), an optional cross-linking step with ionizing radiations (10), and an optional hydrophilic treatment step (11), etc., can be conducted. While the invention will be described in terms of a polyolefin composition combined with a membrane-forming solvent to produce a polyolefin solution, which is then extruded, the invention is not limited thereto.
The polyolefin composition comprises polyolefin resins as described above that can be combined, e.g., by dry mixing or melt blending with an appropriate diluent to produce the mixture. Optionally, mixture can contain various additives such as one or more antioxidant, fine silicate powder (pore-forming material), etc., provided these are used in a concentration range that does not significantly degrade the desired properties of the, microporous membrane.
The diluent (e.g., a membrane-forming solvent) is preferably a solvent that is liquid at room temperature. While not wishing to be bound by any theory or model, it is believed that the use of a liquid solvent to form the polyolefin solution makes it possible to conduct stretching of the gel-like sheet at a relatively high stretching magnification. In one form, the membrane-forming solvent can be at least one of aliphatic, alicyclic or aromatic hydrocarbons such as nonane, decane, decalin, p-xylene, undecane, dodecane, liquid paraffin, etc.; 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. In one form where it is desired to obtain a gel-like sheet having a stable liquid solvent content, non-volatile liquid solvents such as liquid paraffin can be used, either alone or in combination with other solvents. Optionally, a solvent which is miscible with polyethylene in a melt blended state but solid at room temperature can be used, either alone or in combination with a liquid solvent. Such solid solvent can include, e.g., stearyl alcohol, ceryl alcohol, paraffin waxes, etc.
The viscosity of the liquid solvent is not a critical parameter. For example, the viscosity of the liquid solvent can range from about 30 cSt to about 500 cSt, or from about 30 cSt to about 200 cSt, at 25° C. Although it is not a critical parameter, when the viscosity at 25° C. is less than about 30 cSt, it can be more difficult to prevent foaming the polyolefin solution, which can lead to difficulty in blending. On the other hand, when the viscosity is greater than about 500 cSt, it can be more difficult to remove the liquid solvent from the microporous polyolefin membrane.
In one form, the resins, etc., used to produce to the polyolefin composition are melt-blended in, e.g., a double screw extruder or mixer. For example, a conventional extruder (or mixer or mixer-extruder) such as a double-screw extruder can be used to combine the resins, etc., to form the polyolefin composition. The membrane-forming solvent can be added to the polyolefin composition (or alternatively to the resins used to produce the polyolefin composition) at any convenient point in the process. For example, in one form where the polyolefin composition and the membrane-forming solvent are melt-blended, the solvent can be added to the polyolefin composition (or its components) at any of (i) before starting melt-blending, (ii) during melt blending of the first polyolefin composition, or (iii) after melt-blending, e.g., by supplying the membrane-forming solvent to the melt-blended or partially melt-blended polyolefin composition in a second extruder or extruder zone located downstream of the extruder zone used to melt-blend the polyolefin composition.
When melt-blending is used, the melt-blending temperature is not critical. For example, the melt-blending temperature of the polyolefin solution can range from about 10° C. higher than the melting point Tm1 of the polyethylene in the first resin to about 120° C. higher than Tm1. For brevity, such a range can be represented as Tm1+10° C. to Tm1+120° C. In a form where the polyethylene in the first resin has a melting point of about 130° C. to about 140° C., the melt-blending temperature can range from about 140° C. to about 250° C., or from about 170° C. to about 240° C.
When an extruder such as a double-screw extruder is used for melt-blending, the screw parameters are not critical. For example, the screw can be characterized by a ratio L/D of the screw length L to the screw diameter D in the double-screw extruder, which can range, for example, from about 20 to about 100 or from about 35 to about 70. Although this parameter is not critical, when L/D is less than about 20, melt-blending can be more difficult, and when L/D is more than about 100, faster extruder speeds might be needed to prevent excessive residence time of the polyolefin solution in the double-screw extruder, which can lead to undesirable molecular weight degradation. Although it is not a critical parameter, the cylinder (or bore) of the double-screw extruder can have an inner diameter of in the range of about 40 mm to about 100 mm, for example.
The amount of the polyolefin composition in the polyolefin solution is not critical. In one form, the amount of polyolefin composition in the polyolefin solution can range from about 1 wt. % to about 75 wt. %, based on the weight of the polyolefin solution, for example from about 20 wt. % to about 70 wt. %.
A monolayer extrusion die can be used to form an extrudate. In one form, the extrusion die is connected to an extruder, where the extruder contains the polyolefin solution. The die gap is generally not critical. For example, the extrusion die can have a die gap of about 0.1 mm to about 5 mm. Die temperature and extruding speed are also non-critical parameters. For example, the die can be heated to a die temperature ranging from about 140° C. to about 250° C. during extrusion. The extruding speed can range, for example, from about 0.2 m/minute to about 15 m/minute.
A gel-like sheet can be obtained by cooling, for example. Cooling rate and cooling temperature are not particularly critical. For example, the gel-like sheet can be cooled at a cooling rate of at least about 50° C./minute until the temperature of the gel-like sheet (the cooling temperature) is approximately equal to the gel-like sheet's gelatin temperature (or lower). In one form, the extrudate is cooled to a temperature of about 25° C. or lower in order to form the gel-like sheet.
In one form, the membrane-forming solvent is removed (or displaced) from the gel-like sheet in order to form a solvent-removed gel-like sheet. A displacing (or “washing”) solvent can be used to remove (wash away, or displace) the first and second membrane-forming solvents. The choice of washing solvent is not critical provided it is capable of dissolving or displacing at least a portion of the first and/or second membrane-forming solvent. Suitable washing solvents include, for instance, one or more of volatile solvents such as 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, C6F14, C7F16, etc.; cyclic hydrofluorocarbons such as C5H3F7, etc.; hydrofluoroethers such as C4F9OCH3, C4F9OC2H5, etc.; and perfluoroethers such as C4F9OCF3, C4F9O C2H5, etc.
The method for removing the membrane-forming solvent is not critical, and any method capable of removing a significant amount of solvent can be used, including conventional solvent-removal methods. For example, the gel-like sheet can be washed by immersing the sheet in the washing solvent and/or showering the sheet with the washing solvent. The amount of washing solvent used is not critical, and will generally depend on the method selected for removal of the membrane-forming solvent. In one form, the membrane-forming solvent is removed from the gel-like sheet (e.g., by washing) until the amount of the remaining membrane-forming solvent in the gel-like sheet becomes less than 1 wt. %, based on the weight of the gel-like sheet.
In one form, the solvent-removed gel-like sheet obtained by removing the membrane-forming solvent is dried in order to remove the washing solvent. Any method capable of removing the washing solvent can be used, including conventional methods such as heat-drying, wind-drying (moving air), etc. The temperature of the gel-like sheet during drying (i.e., drying temperature) is not critical. For example, the drying temperature can be equal to or lower than the crystal dispersion temperature Tcd. Tcd is the lower of the crystal dispersion temperature Tcd1 of the polyethylene in the first resin and the crystal dispersion temperature Tcd2 of the polyethylene in the second resin. For example, the drying temperature can be at least 5° C. below the crystal dispersion temperature Tcd. The crystal dispersion temperature of the polyethylene can be determined by measuring the temperature characteristics of the kinetic viscoelasticity of the polyethylene according to ASTM D 4065. In one form, the polyethylene has a crystal dispersion temperature in the range of about 90° C. to about 100° C.
Although it is not critical, drying can be conducted until the amount of remaining washing solvent is about 5 wt. % or less on a dry basis, i.e., based on the weight of the dry microporous polyolefin membrane. In another form, drying is conducted until the amount of remaining washing solvent is about 3 wt. % or less on a dry basis.
Prior to the step of removing the membrane-forming solvents, the gel-like sheet is stretched (i.e., oriented) in at least a first step and a second step, sequentially, in order to obtain a stretched, gel-like sheet.
In one form, the stretching can be accomplished by one or more of tenter-stretching, roller-stretching, or inflation stretching (e.g., with air). Although the choice is not critical, the stretching can be conducted monoaxially (i.e., in either the machine or transverse direction) or biaxially (both the machine and transverse direction). In the case of biaxial stretching (also called biaxial orientation), the stretching can be simultaneous biaxial stretching, sequential stretching along one planar axis and then the other (e.g., first in the transverse direction and then in the machine direction), or multi-stage stretching (for instance, a combination of the simultaneous biaxial stretching and the sequential stretching).
The first stretching magnification is not critical. The first stretching magnification (in at least one lateral (e.g., planar, when the membrane is flat) direction of the extrudate) can be, e.g., about 1.5 fold or more, or about 1.5 to about 10 fold. When biaxial stretching is used for the first stretching, the linear stretching magnification can be, e.g., about 1.5 fold or more, or about 1.5 fold to about 16 fold in each of the stretching directions. The second stretching magnification (in at least one lateral (e.g., planar, when the membrane is flat) direction of the extrudate) can be, e.g., about 1.5 fold or more, or about 1.5 to about 10 fold. When biaxial stretching is used for the second stretching, the linear stretching magnification can be, e.g., about 1.5 fold or more, or about 1.5 fold to about 16 fold in each of the stretching directions.
The total stretching magnification resulting from the first and second stretching generally results in an increase in membrane area of 10 fold or more, e.g., in the range of 15 fold to 50 fold, such as 20 fold to 30 fold. In an embodiment, the total stretching magnification resulting from the first and second stretching is 25 fold in area. The first and second stretching steps can be called “wet” stretching steps to distinguish them from dry orientation steps that are conducted after the diluent is removed.
The temperature of the gel-like sheet during the first orientation or stretching step can be about (Tm+10° C.) or lower, or optionally in a range that is higher than Tcd−15° C. but lower than Tcd+15° C. (or lower than Tm, wherein Tm is the lesser of the melting point Tm1 of the polyethylene in the first resin and the melting point Tm2 of the polyethylene in the second resin). In one form, the temperature of the gel-like sheet during the first orientation or stretching step can be about Tcd+/−15° C., or about Tcd−10° C. to about Tcd+10° C., or about 90° C. to about 100° C.
In accordance herewith, the temperature of the gel-like sheet during the second orientation or stretching step can be about 10° C. to about 40° C. higher than the temperature employed in the first orientation or stretching step. In one form, the temperature of the gel-like sheet during the first orientation or stretching step can be about 115° C. to about 130° C., or about 120° C. to about 125° C.
The stretching makes it easier to produce a relatively high-mechanical strength microporous polyolefin membrane with a relatively large pore size. Such microporous membranes are believed to be particularly suitable for use as battery separators.
Although it is not required, the gel-like sheet can be treated with a hot solvent. When used, it is believed that the hot solvent treatment provides the fibrils (such as those formed by stretching the gel-like sheet) with a relatively thick leaf-vein-like structure. The details of this method are described in WO 2000/20493.
In one form, the dried microporous membrane can be stretched, at least monoaxially. The stretching method selected is not critical, and conventional stretching methods can be used such as by a tenter method, etc. When the gel-like sheet has been stretched as described above the stretching of the dry microporous polyolefin membrane can be called dry-stretching, re-stretching, or dry-orientation.
The temperature of the dry microporous membrane during stretching (the “dry stretching temperature”) is not critical. In one form, the dry stretching temperature is approximately equal to the melting point Tm or lower, for example in the range of from about the crystal dispersion temperature Tcd to the about the melting point Tm. In one form, the dry stretching temperature ranges from about 90° C. to about 135° C., or from about 95° C. to about 130° C.
When dry-stretching is used, the stretching magnification is not critical. For example, the stretching magnification of the microporous membrane can range from about 1.1 fold to about 2.5 or about 1.1 to about 2.0 fold in at least one lateral (planar) direction.
In one form, the membrane relaxes (or shrinks) in the direction(s) of stretching to achieve a final magnification of about 1.0 to about 2.0 fold compared to the size of the film at the start of the dry orientation step.
In one form, the dried microporous membrane can be heat-treated. In one form, the heat treatment comprises heat-setting and/or annealing. When heat-setting is used, it can be conducted using conventional methods such as tenter methods and/or roller methods. Although it is not critical, the temperature of the dried microporous polyolefin membrane during heat-setting (i.e., the “heat-setting temperature”) can range from the Tcd to about the Tm, or from about 120° C. to about 130° C.
Annealing differs from heat-setting in that it is a heat treatment with no load applied to the microporous polyolefin membrane. The choice of annealing method is not critical, and it can be conducted, for example, by using a heating chamber with a belt conveyer or an air-floating-type heating chamber. Alternatively, the annealing can be conducted after the heat-setting with the tenter clips slackened. The temperature of the microporous polyolefin membrane during annealing can range from about the melting point Tm or lower, from about 60° C. to (Tm−10° C.), or in a range of from about 60° C. to (Tm−5° C.).
In one form, the microporous polyolefin membrane can be cross-linked (e.g., by ionizing radiation rays such as a-rays, (3-rays, 7-rays, electron beams, etc.) or can be subjected to a hydrophilic treatment (i.e., a treatment which makes the microporous polyolefin membrane more hydrophilic (e.g., a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc.))).
In an embodiment, the membrane's thickness (average thickness, as described below) is generally in the range of from about 1 μm to about 100 μm, e.g., from about 5 μm to about 30 μm. The thickness of the microporous membrane can be measured by a contact thickness meter at 1 cm longitudinal intervals over the width of 20 cm, and then averaged to yield the membrane thickness. Thickness meters such as the Litematic available from Mitsutoyo Corporation are suitable. This method is also suitable for measuring thickness fluctuation and thickness variation after heat compression, as described below. Non-contact thickness measurements are also suitable, e.g., optical thickness measurement methods. In one form, the multi-layer microporous membrane has a thickness ranging from about 3 μm to about 200 μm, or about 5 μm to about 50 μm.
Optionally, the membrane is a monolayer membrane comprising:
(i) from about 20 wt. % to about 80 wt. % of the first polyethylene, the first polyethylene having an Mw of from about 2×105 to about 9×105 and an MWD of from about 3 to about 50;
(ii) from about 5 wt. % to about 60 wt. % of polypropylene having an Mw of from about 6×105 to about 4×106, an MWD of from about 3 to about 30, and a heat of fusion of 90 J/g or more; and
(iii) from about 0 wt. % to about 40 wt. % of the second polyethylene, the second polyethylene having an Mw of from 1×106 to about 5×106, an MWD of from about 3 to about 30, percentages based on the mass of the membrane.
Optionally, the microporous membrane has one or more of the following properties.
When the porosity is less than 25%, the microporous membrane generally does not exhibit the desired air permeability necessary for use as a battery separator. When the porosity exceeds 80%, it is more difficult to produce a battery separator of the desired strength, which can increase the likelihood of internal electrode short-circuiting. In an embodiment, the membrane has a porosity ≧25%, e.g., in the range of about 25% to about 80%, or 30% to 60%. The membrane's porosity is measured conventionally by comparing the membrane's actual weight to the weight of an equivalent non-porous membrane of the same composition (equivalent in the sense of having the same length, width, and thickness). Porosity is then determined using the formula: Porosity %=100×(w2−w1)/w2, wherein “w1” is the actual weight of the microporous membrane and “w2” is the weight of the equivalent non-porous membrane having the same size and thickness.
When the membrane's normalized air permeability of the microporous membrane (as measured according to JIS P8117) ranges from about 20 seconds/100 cm3 to about 400 seconds/100 cm3, it is less difficult to form batteries having the desired charge storage capacity and desired cyclability. When the air permeability is less than about 20 seconds/100 cm3, it is more difficult to produce a battery having the desired shutdown characteristics, particularly when the temperature inside the battery is elevated. Normalized air permeability is measured according to JIS P8117, and the results are normalized to a value at a thickness of 20 μm using the equation A=20 μm*(X)/T1, where X is the measured air permeability of a membrane having an actual thickness T1 and A is the normalized air permeability at a thickness of 20 μm. In an embodiment, the membrane's normalized air permeability is in the range of from about 100 seconds/100 cm3 to about 300 seconds/100 cm3.
The pin puncture strength (normalized to a 20 μm membrane thickness) is the maximum load measured when the microporous membrane is pricked with a needle 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 of the microporous membrane is less than 3,000 mN/20 μm, it is more difficult to produce a battery having the desired mechanical integrity, durability, and toughness. The pin puncture strength is preferably 3,500 mN/20 μm or more, for example, 4,000 mN/20 μm or more. In an embodiment, the membrane has a pin puncture strength in the range of 4,000 to 5,000 mN/20 μm. Pin puncture strength is defined as the maximum load measured when a microporous membrane having a thickness of T1 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 pin puncture strength (“S”) is normalized to a value at a membrane thickness of 20 μm using the equation S2=20 μm*(S1)/T1, where S1 is the measured pin puncture strength, S2 is the normalized pin puncture strength, and T1 is the average thickness of the membrane.
When the tensile strength of the microporous membrane is at least about 60,000 kPa in both longitudinal and transverse directions, it is less difficult to produce a battery of the desired mechanical strength. The tensile strength is preferably about 80,000 kPa or more, for example about 100,000 kPa or more. Tensile strength is measured in MD and TD according to ASTM D-882A. In an embodiment, the membrane's MD and TD tensile strength are each in the range of 80,000 kPa to 200,000 kPa.
When the tensile elongation according of the microporous membrane is 100% or more in both longitudinal and transverse directions, it is less difficult to produce a battery having the desired mechanical integrity, durability, and toughness. Tensile elongation is measured according to ASTM D-882A. In an embodiment, the membrane's MD and TD tensile elongation are each in the range of 100% to 200%.
When the heat shrinkage ratio measured after holding the microporous membrane at a temperature of about 105° C. for 8 hours exceeds 10% in both longitudinal and transverse directions, it is more difficult to produce a battery that will not exhibit internal short-circuiting when the heat generated in the battery results in the shrinkage of the separators. The membrane's heat shrinkage ratio is preferably 12% or less or 10% or less in MD and TD. For example, the membrane's MD 105° C. heat shrinkage can be 3.5%, e.g., in the range of 0.5% to 3.5%; and the 105° C. TD heat shrinkage can be 5%, e.g., in the range of 1% to 5%. The MD and TD heat shrinkage ratios are measured three times when exposed to 105° C. for 8 hours, and averaged to determine the heat shrinkage ratio. The membrane's heat shrinkage in orthogonal planar directions (e.g., MD or TD) at 105° C. is measured as follows: (i) Measure the size of a test piece of microporous membrane at ambient temperature in both MD and TD, (ii) expose the test piece to a temperature of 105° C. for 8 hours with no applied load, and then (iii) measure the size of the membrane in both MD and TD. The heat (or “thermal”) shrinkage in either the MD or TD can be obtained by dividing the result of measurement (i) by the result of measurement (ii) and expressing the resulting quotient as a percent.
In an embodiment, the membrane's 105° C. MD and TD heat shrinkages are each in the range of 1% to 5%.
When the thickness fluctuation of a battery separator exceeds 1.0 μm, it is more difficult to produce a battery with appropriate protection against internal short circuiting. Thickness fluctuation is expressed as a standard deviation. It is measured as follows: The thickness of the microporous membrane is measured by a contact thickness meter at 1 cm intervals in the area of 10 cm×10 cm of the membrane, to provide a membrane thickness at 100 data points. These 100 thickness values are then averaged to yield an average membrane thickness (as described above) and a thickness fluctuation represented by the standard deviation of the 100 thickness values.
In an embodiment, the membrane's thickness fluctuation in at least one planar direction is≦0.7 μm, e.g., in the range of 0.25 μm to 0.65 μm.
When the puncture strength fluctuation of a battery separator exceeds 10 mN, it is more difficult to produce a battery having appropriate durability and reliability. Pin puncture strength fluctuation is measured as follows: The maximum load is measured when each microporous membrane having a thickness of T1 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 L1 is converted to the maximum load L2 at a thickness of 20 μm by the equation of L2=(L1×20)/T1, and used as pin puncture strength. Twenty measured data in the area of 10 cm×10 cm of the membrane are averaged. Pin puncture strength fluctuation is the standard deviation of the strength measured at the 20 points.
In an embodiment, the membrane's pin puncture strength fluctuation is in the range of 5 mN to 9 mN.
In one form, the melt down temperature can range from about 150° C. to about 190° C. The melt down temperature can be 160° C., e.g., in the range of from 160° C. to 190° C., e.g., from 170° C. to 190° C. Melt down temperature is measured by the following procedure: A rectangular sample of 3 mm×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 10 mm. The lower chuck is fixed and a load of 19.6 mN applied to the sample at the upper chuck. The chucks and sample are enclosed in a tube which can be heated. Starting at 30° C., the temperature inside the tube is elevated at a rate of 5° C./minute, and sample length change under the 19.6 mN load is measured at intervals of 0.5 second and recorded as temperature is increased. The temperature is increased to 200° C. The melt down temperature of the sample is defined as the temperature at which the sample breaks. In an embodiment, the membrane's melt down temperature is in the range of about 165° C. to about 200° C., such as about 170° C. to about 195° C.
The microporous membrane can exhibit a maximum shrinkage in the molten state (about 140° C.) of about 30% or less, preferably about 25% or less. In an embodiment, the membrane's maximum shrinkage in the molten state is in the range of 10% to 25%. Maximum shrinkage in the molten state in a planar direction of the membrane is measured by the following procedure.
Using the TMA procedure described for the measurement of melt down temperature, the sample length measured in the temperature range of from 135° C. to 145° C. are recorded. The membrane shrinks, and the distance between the chucks decreases as the membrane shrinks. The maximum shrinkage in the molten state is defined as the sample length between the chucks measured at 23° C. (L1 equal to 10 mm) minus the minimum length measured generally in the range of about 135° C. to about 145° C. (equal to L2) divided by L1, i.e., [L1−L2]/L1*100%. When TD maximum shrinkage is measured, the rectangular sample of 3 mm×50 mm used 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. When MD maximum shrinkage is measured, the rectangular sample of 3 mm×50 mm used is cut out of the microporous membrane such that the long axis of the sample is aligned with the machine direction of the microporous membrane as it is produced in the process and the short axis is aligned with the transverse direction.
The thickness variation ratio after heat compression at 90° C. under a pressure of 2.2 MPa for 5 minutes is generally 20% or less per 100% of the thickness before compression, e.g., ≦10%. Batteries comprising microporous membrane separators with a thickness variation ratio of 20% or less (e.g., in the range of 5% to 10%) have suitably large capacity and good cyclability. Thickness variation after heat compression is measured by subjecting the membrane to a compression of 2.2 MPa (22 kgf/cm2) in the thickness direction for five minutes while the membrane is exposed to a temperature of 90° C. The membrane's thickness variation ratio is defined as the absolute value of (average thickness after compression−average thickness before compression)/(average thickness before compression)×100. The result is expressed as an absolute value.
The microporous membranes disclosed herein, when heat-compressed at 90° C. under pressure of 2.2 MPa for 5 minutes, have an air permeability (as measured according to JIS P8117) of about 1000 sec/100 cm3 or less, e.g., 600 sec/100 cm3, such as from about 100 to about 600 sec/100 cm3. Batteries using such membranes have suitably large capacity and cyclability. The air permeability after heat compression may be, for example, 700 sec/100 cm3 or less. Air permeability after heat compression is measured according to JIS P8117 after the membrane is subjected to a compression of 2.2 MPa (22 kgf/cm2) in the thickness direction for five minutes while the membrane is exposed to a temperature of 90° C.
When a lithium ion secondary battery comprising a separator formed by a microporous membrane is stored at a temperature of 80° C. for 30 days, it is desired that the battery capacity recovery ratio [(capacity after high-temperature storing)/(initial capacity)]×100 (%) should be 70% or more, e.g., in the range of 70% to 85%. The battery capacity recovery ratio is preferably 75% or more. The capacity recovery ratio of a lithium ion battery containing the microporous membrane as a separator is measured as follows: First, the discharge capacity (initial capacity) of the lithium ion battery is measured by a charge/discharge tester before high temperature storage. After being stored at a temperature of 80° C. for 30 days, the discharge capacity is measured again by the same method to obtain the capacity after high temperature storage. The capacity recovery ratio (%) of the battery is determined by the following equation: capacity recovery ratio (%)=[(capacity after high temperature storage)/(initial capacity)]×100.
When a lithium ion secondary battery comprising a separator formed by a microporous membrane is manufactured, it is desired that the electrolytic solution absorption speed of the battery should be 2.5 or more (e.g., 3.0 or more). Electrolytic solution absorption speed is measured as follows: 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 LiPF6, 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 of the membrane is expressed by a relative value, assuming that the electrolytic solution absorption rate in the microporous membrane of Comparative Example 1 is 1. A membrane having a relatively high electrolytic solution absorption speed (e.g., ≧2.5) is desirable since less time is required for the separator to uptake the electrolyte during battery manufacturing, which in turn increases the rate at which the batteries can be produced. In an embodiment, the membrane has an electrolytic solution absorbtion speed 3.5, e.g., in the range of 3.5 to 8.
The invention will be illustrated with the following non-limiting examples.
Dry-blended were 99.8 parts by mass of a polyolefin composition comprising 20% by mass of ultra-high-molecular-weight polyethylene (UHMWPE) having an Mw of 1.9×106, an MWD of 5.09, a melting point (Tm) of 135° C., and a crystal dispersion temperature (Tcd) of 100° C., 50% by mass of high-density polyethylene (HDPE) having a Mw of 5.6×105 and MWD of 4.05, Tm of 135° C., and Tcd of 100° C., and 30% by mass of a polypropylene (PP) having a Mw of 6.6×105 and MWD of 11.4, and a heat of fusion of 103.3, and 0.2 parts by mass of tetrakis [methylene-3-(3,5-ditertiary-butyl-4-hydroxyphenyl)-propionate]methane as an antioxidant. The polyolefin composition had a MWD of 8.6, a Tm of 135° C., and Tcd of 100° C.
Thirty parts by mass of the resultant mixture was charged into a strong-blending double-screw extruder having an inner diameter of 58 mm and L/D of 52.5, and 70 parts by mass of liquid paraffin [50 cst (40° C.)] was supplied to the double-screw extruder via a side feeder. Melt-blending was conducted at 210° C. and 200 rpm to prepare a first polyolefin solution.
The polyolefin solution was supplied from its double-screw extruder to a monolayer-sheet-forming T-die at 210° C., to form an extrudate. The extrudate was cooled while passing through cooling rolls controlled at 15° C., to form a gel-like sheet. Using a first tenter-stretching machine, the gel-like sheet was biaxially stretched at 100.0° C., to 2 fold in both machine and transverse directions. Using a second tenter-stretching machine, the gel-like sheet was again biaxially stretched, this time at 120.0° C., to 2.5, fold in both machine and transverse directions.
The stretched gel-like sheet was fixed to an aluminum frame of 20 cm×20 cm, and immersed in a bath of methylene chloride controlled at a temperature of 25° C. to remove the liquid paraffin with a vibration of 100 rpm for 3 minutes. The resulting membrane was air-cooled at room temperature. The dried membrane was re-stretched by a batch-stretching machine to a magnification of 1.4 fold in a transverse direction at 125° C. The re-stretched membrane, which remained fixed to the batch-stretching machine, was heat-set at 125° C. for 10 minutes to produce a microporous polyolefin membrane.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that the temperature of the second wet stretching of the gel-like sheet was conducted at 125° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that the magnification of the first wet stretching of the gel-like sheet was 5 fold in a machine direction and the magnification of the second wet stretching of the gel-like sheet was 5 fold in a transverse direction.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that there was no re-stretching of the dried membrane prior to heat-setting. Another exception from Example 1 for this Example 4 was that the heat setting temperature was 126° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that the polyolefin composition included 70% by mass of the first polyethylene resin and 30% by mass of the polypropylene resin. This polyolefin composition contains no second polyethylene resin.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that the polyolefin composition included 30% by mass of a polypropylene resin having an Mw of 1.1×106, an MWD of 5.0, and a heat of fusion of 114.0 J/g. Another exception from Example 1 for this Example 6 is that the heat setting temperature was 126° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 6 was repeated except that the temperature of the second wet stretching of the gel-like sheet was 125° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Example 1 was repeated except that the polyolefin composition employed included 72% by mass of the first polyethylene resin and 8% by mass of the polypropylene resin and 20% by mass of the second polyethylene resin having an Mw of 2×106 and MWD of 8.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 1.
Dry-blended were 99.8 parts by mass of a polyolefin composition comprising 20% by mass of ultra-high-molecular-weight polyethylene (UHMWPE) having an Mw of 1.9×106, an MWD of 5.09, a melting point (Tm) of 135° C., and a crystal dispersion temperature (Tcd) of 100° C., and 80% by mass of high-density polyethylene (HDPE) having a Mw of 5.6×105 and MWD of 4.05, Tm of 135° C., and Tcd of 100° C., and 0.2 parts by mass of tetrakis [methylene-3-(3,5-ditertiary-butyl-4-hydroxyphenyI)-propionate]methane as an antioxidant. The polyolefin composition had an MWD of 8.6, a Tm of 135° C., and Tcd of 100° C.
Thirty parts by mass of the resultant mixture was charged into a strong-blending double-screw extruder having an inner diameter of 58 mm and L/D of 52.5, and 70 parts by mass of liquid paraffin [50 cst (40° C.)] was supplied to the double-screw extruder via a side feeder. Melt-blending was conducted at 210° C. and 200 rpm to prepare a first polyolefin solution.
The polyolefin solution was supplied from its double-screw extruder to a monolayer-sheet-forming T-die at 210° C., to form an extrudate. The extrudate was cooled while passing through cooling rolls controlled at 0° C., to form a gel-like sheet. Using a tenter-stretching machine, the gel-like sheet was biaxially stretched at 115.0° C., to 5 fold in both machine and transverse directions.
The stretched gel-like sheet was fixed to an aluminum frame of 20 cm×20 cm, and immersed in a bath of methylene chloride controlled at a temperature of 25° C. to remove the liquid paraffin with a vibration of 100 rpm for 3 minutes. The resulting membrane was air-cooled at room temperature. The dried membrane was not re-stretched for this Example. The membrane, was fixed to the batch-stretching machine, and was heat-set at 126.8° C. for 10 minutes to produce a microporous polyolefin membrane. The resulting oriented membrane was washed with methylene chloride to remove residual liquid paraffin, followed by drying.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the gel-like sheet was biaxially stretched at 115.0° C., to 5 fold in both the machine and transverse directions. Another exception from Example 1 for this Comparative Example was that the heat setting temperature was 127.5° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the first stretching temperature of the gel-like sheet was 115.0° C. Another exception from Example 1 employed for this Comparative Example was that the heat setting temperature was 127.0° C.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the first stretching temperature of the gel-like sheet was conducted at 120.0° C., and the second stretching temperature was conducted at 100.0° C. Another exception from Example 1 for this Comparative Example was that the heat setting temperature was 126.5° C. for polyolefin composition.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the polyolefin composition employed included 20% by mass of the first polyethylene resin and 10% by mass of the second polyethylene resin. The gel-like sheet was broken in stretching.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the polyolefin composition employed included 20% by mass of the first polyethylene resin and 30% by mass of the polypropylene resin and 50% by mass of the second polyethylene resin.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the first gel-like sheet was biaxially stretched at 100.0° C. to 1.25 fold in both machine and transverse directions, and, likewise, the sheet was again biaxially stretched this time at 120.0° C. to 4 fold in both machine and transverse directions.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the polyolefin composition employed included 30% by mass of a polypropylene resin having an Mw of 2.5×105, an MWD of 3.5, and a heat of fusion of 69.2 J/g.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
Example 1 was repeated except that the polyolefin composition employed included 30% by mass of a polypropylene resin having an Mw of 1.6×106, an MWD of 3.2, and a heat of fusion of 78.4 J/g.
There was obtained a microporous membrane of polypropylene having the characteristic properties as shown in Table 2.
All patents, test procedures, and other documents cited herein, including priority documents, are fully incorporated by reference to the extent such disclosure is not inconsistent and for all jurisdictions in which such incorporation is permitted.
While the illustrative forms disclosed herein have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside herein, including all features which would be treated as equivalents thereof by those skilled in the art to which this disclosure pertains.
When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.
The invention will now be further described by the following non-limiting embodiments.
(a) an extruder for preparing the polyolefin solution;
(b) an extrusion die for receiving and extruding the polyolefin solution to form an extrudate;
(c) means for cooling the extrudate to form a cooled extrudate having a first area;
(d) a first stretching machine for orienting the cooled extrudate in at least a first direction by about one to about ten fold at a temperature of about 90° C. to about 125° C.;
(e) a second stretching machine for further orienting the cooled extrudate in at least a second direction by about one to about five fold at a temperature about 10° C. to about 40° C. higher than the temperature employed by said first stretching machine to a second area at least ten fold larger than the first area; and
(f) a controller for regulating the temperature of the first stretching machine and the temperature of the second stretching machine;
wherein the transverse direction film thickness fluctuation of a film or sheet produce by the system is reduced by at least 25%.
(i) from about 20% to about 80% of the first polyethylene, the first polyethylene having an Mw of from about 2×105 to about 5×105 and an MWD of from about 5 to about 50;
(ii) from about 5% to about 60% of a polypropylene having an Mw of from about 6×105 to about 4×106, an MWD of from about 3 to about 30; and
(iii) from about 0% to about 40% of a second polyethylene having an Mw of from about 1×106 to about 5×106, an MWD of from about 3 to about 30 a heat of fusion of 90 J/g more, percentages based on the mass of the polyolefin composition.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/073936 | 12/25/2008 | WO | 00 | 8/27/2010 |
| Number | Date | Country | |
|---|---|---|---|
| 61017820 | Dec 2007 | US |
