TW200830616A - Electrode assembly and non-aqueous electrolyte battery - Google Patents

Abstract

An electrode assembly having a structure comprising a first microporous membrane separator comprising high-density polyethylene A having a terminal vinyl group concentration (measured by infrared spectroscopy) of 0.3 or more per 10,000 carbon atoms and ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1x10<SP>6</SP> or more, and a second microporous membrane separator comprising high-density polyethylene B having a terminal vinyl group concentration of 0.2 or less per 10,000 carbon atoms and said ultra-high-molecular-weight polyethylene, which are alternately sandwiched by an anode sheet and a cathode sheet, the difference in a shutdown temperature between said first and second separators being within 5 DEG C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode assembly for a battery which has a well-balanced safety, discharge capacity and cycleability, and a non-aqueous electrolyte battery including the electrode assembly. [Prior Art] A lithium ion secondary battery has an electrode composite including an anode and a cathode laminated through a separator. Specific examples of the electrode composite include a laminate in which a planar cathode and an anode are alternately laminated through a separator, a spiral tubular electrode in which an anode tape and a cathode tape are coated through a separator, and the like. The separator is usually composed of a microporous film of a thermoplastic resin. Since the effectiveness of the electrode composite affects performance, yield, and the safety of the battery is mainly determined by the effectiveness of the spacer, various proposals have been made to provide a combination of spacers having different properties, a spacer having an improved profile, and a chemical improvement. (for example, hydrophilized) separator or the like. Regarding an electrode assembly which provides a good battery life, JP 1 0- 1 995 02 A proposes an electrode composite comprising a molten laminate of a first separator and a second separator, wherein the first separator has a high Tensile strength (for example, polyene hydroxy non-woven fabric) and the second separator has good storage properties and electrolyte absorption (for example, polyethylene terephthalate), the composite has a cathode plate in contact with the first separator, and The structure in which the anode plate is in contact with the second separator. A secondary battery that does not suffer from an internal short circuit caused by the detachment of the active material from the electrode plate, JP 2000-3 1 5489 A proposes a rectangular non-aqueous electrolyte secondary battery including alternating laminated planar 200830616 Cathode and planar anode, planar anodes are placed in isolation pockets with good breaking properties, planar cathodes are placed in isolation pockets with good meltdown properties, each is made of porous polypropylene Or made of porous polyethylene. Regarding a secondary battery having good self-discharge resistance and cycleability, JP 2003-257474 A proposes a nickel-hydrogen secondary battery comprising a laminate in which a planar anode and a planar cathode are passed through a separator. In the electrode assembly, the separator is formed by alternately arranging the first and second separators, and each of the first separators is grafted with a vinyl monomer having a carboxylic acid group or treated with an acid having a sulfate group. The polyolefin non-woven fabric, and each of the second separators is a polyolefin non-woven fabric treated by corona discharge or fluorine gas. Regarding a non-aqueous electrolyte battery having good cycleability and internal short-circuit resistance between an anode and a cathode, JP 2004- 1 93 1 1 6 A proposes a non-aqueous electrolyte battery having a spiral tubular composite structure, the first of which The separator (for example, a porous polyethylene film having a diameter mode of 0.3 /zm or less when measured by a mercury intrusive pore meter) is in contact with the outer surface of the cathode strip, and the second separator (for example, intrusion with mercury) When the pore meter is measured, the porous polyethylene film having a diameter mode of 〇·5/zm or more is in contact with the inner surface of the cathode strip, and the lithium ion permeability of the first separator is smaller than that of the second separator. Regarding a non-aqueous electrolyte battery that does not cause thermal runaway due to excessive charging or abnormal heating, JP 2005-93077 A proposes a non-aqueous electrolyte battery including a spiral tubular electrode composite and a non-aqueous electrolyte, The spiral tubular electrode composite system is formed by laminating anode and cathode through first and second separators (for example, microporous polyethylene film) having different permeability and 200830616, and first contacting the outer surface of the cathode The separator has a permeability of 180 sec/100 cm3 or more, and the second separator in contact with the inner surface of the cathode has a permeability of 120 sec/100 cm3 or less. Regarding a non-aqueous electrolyte battery which is not subjected to thermal runaway due to excessive charging or abnormal heating, JP 2005-93078 A proposes a non-aqueous electrolyte battery comprising a spiral tubular electrode composite and a non-aqueous electrolyte, The spiral tubular electrode composite system is formed by laminating an anode and a cathode through first and second separators (for example, microporous polyethylene membranes) having different properties, and the first separator is in contact with the outer surface of the cathode. It has a permeability of 400 sec/100 cm3 or more, and the second separator which is in contact with the inner surface of the cathode has a heat shrinkage ratio of 30% or less after being measured at 150 ° C for 3 hours. However, any of the electrode composites disclosed in JP 10-199502 A, JP 2000-315489 A, JP 2003 -257474 A, JP 2004- 1 93 1 1 6 A, JP 2005-93077 A and JP 2005-93078 A are disclosed. The battery of the body does not have a well-balanced safety, discharge capacity and cycle. Therefore, it is desirable to have an electrode composite which provides good balance of battery balance, discharge capacity, and cycleability. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an electrode composite which can provide a good balance of safety, discharge capacity and cycleability in a battery. Another object of the present invention is to provide a non-aqueous electrolyte battery comprising such an electrode composite. From the above-mentioned results, the inventors found that: (1) composite separators with well-balanced permeability, mechanical strength, heat shrinkage resistance, open circuit 200830616 properties, meltdown properties, and compression resistance can be borrowed The first microporous membrane comprising high density polyethylene A is combined with a second microporous membrane comprising high density polyethylene B, wherein the high density polyethylene A has a terminal ethylene of 0.3 or more per 10,000 carbon atoms The base concentration (measured by infrared spectroscopy) and having an ultrahigh molecular weight polyethylene having a weight average molecular weight of 1x1 06 or more, the high density polyethylene B having a terminal vinyl concentration of 0.2 or less per 10,000 carbon atoms and an ultrahigh molecular weight polyethylene. (2) A battery having a well-balanced safety, discharge capacity, and cyclability can be obtained by using an electrode composite which alternately laminates an anode sheet and a cathode sheet through two kinds of the above-mentioned microporous membranes. Into. The present invention has been completed based on the above findings. Therefore, the battery composite of the present invention has a structure in which the first separator including the high-density polyethylene A and the second separator including the high-density polyethylene B are alternately sandwiched between the anode sheet and the cathode sheet, and the first The second separator has a shutdown temperature difference of less than 5 ° C, wherein the high density polyethylene A has a terminal vinyl concentration of 0.3 or more per 10 carbon atoms (measured by infrared spectroscopy) and has a weight The ultrahigh molecular weight polyethylene having an average molecular weight of 1x10 or more, and the high density polyethylene B having a terminal vinyl concentration of 0.2 or less per 10,000 carbon atoms (measured by infrared spectroscopy), and ultrahigh molecular weight polyethylene. In a preferred embodiment of the invention the battery composite system is in the form of a spiral tube. In order to provide better needle penetration safety of the battery, it is preferred to dispose the first microporous membrane separator on the inner surface of the cathode sheet while disposing the second microporous separator on the outer side of the cathode sheet. The non-aqueous electrolyte battery of the present invention includes the above electrode composite. 200830616 [Embodiment] Description of the preferred embodiment [1] Composition of the spacer material The first spacer material is formed of a microporous film made of the first polyolefin, and the second spacer material is made of the second polyolefin. The resulting microporous membrane is formed. (A) The first polyolefin first polyolefin is (a) a high-density polyethylene A having a terminal vinyl concentration of 0.3 or more per 10 carbon atoms (measured by infrared spectroscopy) and having a weight average a mixture of ultrahigh molecular weight polyethylene (polyethylene composition A) having a molecular weight (Mw) of 1 x 16 or more, or (b) a polyethylene composition A and a polymerization other than high density polyethylene A and ultra high molecular weight polyethylene a mixture of ethylene (polyethylene composition A').

(1) Polyethylene composition A

(i) High-density polyethylene A High-density polyethylene A has a terminal vinyl concentration (measured by infrared spectroscopy) of 0·3 or more per 10,000 carbon atoms (hereinafter referred to as "/10,000 C"). When the terminal vinyl concentration is less than 0.3/1 0,000 C, the breaking property of the first separator is insufficient. The terminal vinyl group concentration of the high density polyethylene crucible is preferably 0.4/10,000 C or more, more preferably 0.5/10, 〇〇〇 C or more. The terminal vinyl concentration is expressed as the number of terminal vinyl groups per one 〇 of one carbon atom in the high-density polyethylene A. The terminal vinyl concentration is measured by infrared spectroscopy. Specifically, the measurement is performed by (1) forming a sample having a thickness of about 1 mm by thermally pressing high-density polyethylene A, and (2) measuring the absorbance at 910 CHT1 A = log (I 〇 / I) , which is measured by Fourier transform red 200830616 external spectrometer. The intensity of the transmitted light indicating the blank groove 'and the intensity of the transmitted light of the sample cell' and (3) the equation for calculating the concentration of the terminal ethyl group (/10,000 C) = (1.14x absorbance A) / (high density poly B Density of A (g/cm3) x Thickness of Sample (mm) ° The weight average molecular weight (Mw) of high-density polyethylene A is preferably lxl〇4 to 5xl05, more preferably 1χ1〇5 to 5xl05' Good for 2xl05 to 4xl05° When the Mw of high density polyethylene is less than 5 X 1 05, the first spacer has a large average pore diameter. The density of the high density polyethylene crucible is usually from 0.90 to 0.98 g/cm3', preferably from 0.93 to 0.97 g/cm3, more preferably from 0.94 to 0.96 g/cm3. The high density polyethylene A is not limited to the ethylene homopolymer, but may be a copolymer containing a small amount of other olefin. The olefin other than ethylene is preferably propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, and Styrene. The high-density polyethylene A can be obtained by suspension polymerization, solution polymerization or gas phase polymerization using a catalyst loaded with a chromium compound in combination with an organometallic compound disclosed, for example, in JP 1 - 1 2777 B. (ii) Ultrahigh molecular weight polyethylene Ultrahigh molecular weight polyethylene has a Mw of 1 x 1 〇 6 or more. The ultrahigh molecular weight polyethylene may be an ethylene homopolymer or an ethylene·α-olefin copolymer containing a small amount of other olefins. The olefin other than ethylene is preferably propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate or Styrene. The Mw of the ultrahigh molecular weight polyethylene is preferably from IxlO6 to 15χ106, more preferably from 1x1〇6 to 5xl〇6, most preferably from 1x1 06 to 3x1 06. (iii) Formulation and weight average molecular weight -10- 200830616 The percentage of the ultrahigh molecular weight polyethylene in the polyethylene composition A is preferably 1% by mass or more, more preferably 2 to 60% by mass, most preferably 2 to 50% quality%. The Mw of the polyethylene composition A is preferably from 1 x 10 4 to 5 x 106, more preferably from 1 x 10 5 to 4 x 106, most preferably from 2 x 105 to 1.5 x 106. When the Mw of the polyethylene composition A is less than 1.5 x 10 6 , the first separator has a large average pore diameter. (b) Polyethylene composition Α' The polyethylene composition A' is a mixture of the polyethylene composition A and polyethylene other than the high-density polyethylene A and the ultrahigh molecular weight polyethylene. The polyethylene composition A can be the same as the foregoing. The polyethylene other than the high density polyethylene A and the ultra high molecular weight polyethylene is preferably at least one of the group consisting of medium density polyethylene, branched low density polyethylene, and linear low density polyethylene. Its Mw is preferably lxl 04 to 5x105. Other polyethylenes other than high-density polyethylene A and ultra-high molecular weight polyethylene are not limited to ethylene homopolymers, but may also contain small amounts of other α-olefins (for example, propylene, butene-1, hexene-1, etc.). Copolymer. In the polyethylene composition, the percentage of the polyethylene other than the high density polyethylene crucible and the ultrahigh molecular weight polyethylene is preferably 50% by mass or less, more preferably 20% by mass or less. (c) Molecular weight distribution Mw/Mn

Mw/Mn is a measure of molecular weight distribution; the larger the number, the wider the distribution of molecular weight. The Mw/Mn' of the first polyolefin is preferably from 5 to 300, more preferably from 5 to 100, most preferably from 5 to 30, in the ultrahigh molecular weight polyethylene and the other polyethylene. When Mw/Mn is less than 5, the percentage of the high molecular weight component is too high to be easily melt-extruded. On the other hand, when Mw/Mn is more than 30 Å, the percentage of the low molecular weight 200830616 component is too high, resulting in a decrease in the strength of the microporous membrane. The Mw/Μη of the polyethylene (the homopolymer or the ethylene·α-olefin copolymer) can be appropriately controlled by multistage polymerization. The multistage polymerization process is preferably a two-stage polymerization process comprising forming a high molecular weight polymer component in the first stage and forming a low molecular weight polymer component in the second stage. In the case of the polyethylene composition, the larger the Mw/Mn, the greater the difference in Mw present between the ultrahigh molecular weight polyethylene and the other polyethylene, and vice versa. The Mw/Mn of the ethylene composition can be appropriately controlled by the molecular weight and mixing ratio of the components. Φ (2) Other components The first polyolefin may contain, in addition to the aforementioned component (1), a polyolefin other than the first polyolefin which does not deteriorate the properties of the separator, or has a melting point of 170 ° C or higher or Heat resistance of glass transition temperature (Tg) (a) Other polyolefins Other than the first polyolefin may be at least one of the group consisting of: U) polypropylene, polybutene-1, Polypentene-1, ^ poly-4-methylpentene-1, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene, and ethylene·α- The olefin copolymers each having an Mw of from 1 x 4 to 4 χ 106, and (b) having a Mw of Mx from 1 x 10 3 to 1 x 10 4 . Polypropylene, polybutene-1, polypentene-1, poly-4-methylpentene-1, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, and Polystyrene, other polyolefins are not limited to the homopolymers' but may also be copolymers containing other α-olefins. (b) Heat-resistant resin The heat-resistant resin is preferably a crystalline tree -12-200830616 grease having a melting point of 17 CTC or more, which may be partially crystallized, and an amorphous resin having a Tg of 170 ° C or more. The melting point and Tg are measured by the differential scanning calorimetry (DSC) according to ns K7 121. Specific examples of the heat resistant resin include polyester (for example, polybutylene terephthalate (melting point: about 160 to 230 ° C), poly(p-butyl phthalate) (melting point: about 250-270 ° 〇, etc.), fluororesin , polydecylamine (melting point: 2 1 5-265 ° 〇, polycyclic aryl sulfide, polyimine (Tg: 280 ° C or above), polyamidimide (Tg: 28 0 ° C), Polyether oxime (Tg: 223 ° C), polyether ether ketone (melting point: 334 ° C), polycarbonate (melting point: 220-240 ° C), acetonitrile cellulose (melting point: 220 φ ° C), three Ethylene cellulose (melting point: 300 ° C), polyfluorene (Tg: 19CTC), polyether quinone (melting point: 216 ° C), etc. (B) second polyolefin

The first polyolefin is U) a mixture of high density polyethylene B having a terminal vinyl concentration of 0.2 or less per 10,000 carbon atoms (measured by infrared spectroscopy) and ultra high molecular weight polyethylene (polyethylene composition B), Or (b) a mixture of polyethylene composition B and polyethylene other than high density polyethylene B and ultra high molecular weight polyethylene (polyethylene composition B '). Φ (1) polyethylene composition B

(i) High-density polyethylene B High-density polyethylene B has a terminal vinyl concentration of 0.2/1 0,000 (or below) (measured by infrared spectroscopy). When the terminal vinyl concentration is greater than 0.2/1 0,000 C, the second spacer It has poor mechanical strength and meltdown properties. The terminal vinyl concentration of high density polyethylene B is preferably 0.15/10,000 C or less. The terminal vinyl concentration of high density polyethylene B is as in high density polyethylene A. The measurement is performed in the same manner. The Mw and density of high density polyethylene B can be the same as that of high density polyethylene A-13-200830616. When the Mw of high density polyethylene B is less than 5x1 Ο5, the second separator has a large average pore diameter. The high-density polyethylene crucible is preferably an ethylene homopolymer, but may also be a copolymer containing a small amount of other α-olefins. Other α-olefins may be the same as the foregoing. The aforementioned high-density polyethylene crucible may be used by using It is disclosed, for example, in suspension polymerization, solution polymerization or gas phase polymerization of a ruthenium catalyst containing a manganese compound of JP 1 - 2 2777. (ii) Ultrahigh molecular weight polyethylene

The φ ultrahigh molecular weight polyethylene may be the same as the foregoing. The percentage of the ultrahigh molecular weight polyethylene in the polyethylene composition B may be the same as in the polyethylene composition A. The Mw of the polyethylene composition B can be the same as that of the polyethylene composition A. (b) Polyethylene composition B' The polyethylene composition B' is a mixture of polyethylene composition B and polyethylene other than high-density polyethylene B and ultrahigh molecular weight polyethylene. The polyethylene composition B can be the same as the foregoing. The polyethylene other than the high-density polyethylene B and 0 ultrahigh molecular weight polyethylene may be the same as the polyethylene other than the high-density polyethylene A and the ultra-high molecular weight polyethylene in the polyethylene composition A' described above. The percentage of the polyethylene other than the high-density polyethylene B and the ultrahigh molecular weight polyethylene is preferably 50% by mass or less, more preferably 20% by mass or less. (c) Molecular Weight Distribution Mw/Mn The Mw/Mn of the second polyolefin may be the same as that of the first polyolefin. (2) Other components The second polyolefin may contain, in addition to the aforementioned component (1), a polyolefin other than the second polyolefin, or having a temperature of 170 ° C or more, in which the total amount does not deteriorate the properties of the separator - 14 to 30,306,606. A heat-resistant resin having a melting point or a glass transition temperature (Tg). The polyolefin other than the second polyolefin may be the same as the other polyolefins except the first polyolefin described above. The heat resistant resin may be the same as the foregoing. [2] Method for producing spacer material (A) Method for manufacturing first spacer material The method for manufacturing the first spacer material includes the step (1) of melt-blending the first polyolefin and the φ film forming solvent to prepare a first polyolefin solution. (2) extruding the first polyolefin solution through the die, (3) cooling the extrudate to form a gel-like sheet, (4) stretching the gel-like sheet, and (5) removing the film-forming agent from the gel-like sheet, And (6) drying the obtained film. The film may be in the form of a strip if necessary (striping step (7)). After the step (6), if necessary, a stretching step (8) of the microporous film, a heat treatment step (9), a crosslinking step (10) using free radiation, a hydrophilization step (11), and the like can be carried out. (1) Preparation of Polyethylene Solution Φ The first polyolefin was melt-blended with a film forming solvent to prepare a first polyolefin solution. The first polyolefin may contain various additives such as an antioxidant, a cerium fine powder (a pore former), and the like, as long as the effects of the present invention are not deteriorated. The film forming solvent is preferably liquid at room temperature. The use of a liquid solvent enables high-rate stretching. The liquid solvent may be an aliphatic, alicyclic or aromatic hydrocarbon (for example, decane, decane, decahydronaphthalene, p-xylene, undecane, dodecane, liquid sarcophagus, etc.) having a boiling point similar to that of the aforementioned hydrocarbon An inorganic oil distillate, and a citric acid liquid at room temperature (for example, dibutyl phthalate, dioctyl phthalate-15-200830616, etc.). In order to obtain a colloidal laminate having a stable liquid solvent content, a nonvolatile liquid solvent such as liquid sarcophagus is preferably used. The solvent may be mixed with polyethylene in a melt blending state, but a solvent which is solid at room temperature may be mixed with a liquid solvent. Such solid solvents include stearyl alcohol, hexadecanol, sarcophagus and the like. However, when the sarcophagus is used alone, non-uniform stretching may occur. The viscosity of the liquid solvent is preferably from 30 to 500 cSt at 25 ° C, more preferably from 30 to 200 cSt. When the viscosity at 25 ° C is less than 30 cSt, the first polyolefin solution is easily foamed, causing difficulty in blending. On the other hand, when the viscosity is greater than φ 500 cSt, the removal of the liquid solvent may be difficult. Although not particularly limited, the uniform melt blending of the first polyolefin solution is preferably carried out using a twin-screw extruder to prepare a high-concentration polyolefin solution. The film forming solvent may be added before blending, or may be injected into the twin screw extruder at the intermediate portion during blending, although the latter is more preferred. The melt blending temperature of the polyolefin solution is preferably within the range of the melting point Tma + 10 ° C to Tma + 120 ° C of the first polyolefin. The melting point is measured by a differential scanning calorimetry (DSC) according to JIS K7121. Specifically, since the polyethylene compositions A and A' of the above φ have a melting point of about 1 30 to 40 ° C, the melt blending temperature is preferably from 140 to 250 ° C, more preferably from 170 to 240 ° C. The L/D ratio of the screw length L to the screw diameter D in the twin-screw extruder is preferably in the range of 20 to 100, more preferably in the range of 3 5 to 70. When L/D is less than 20, the melt blending system is insufficient. When the L/D is greater than 100, the residence time of the polyolefin solution in the twin-screw extruder is too long. The cylinder of the twin screw extruder preferably has an inner diameter of 40 to 100 mm. The percentage of the first polyolefin per 100% by mass of the polyolefin solution is preferably from 1 to 75% by mass, more preferably from 20 to 70% by mass. When the polyolefin is less than 1 -16·200830616% by mass, the yield is low. In addition, during the formation of the gel-like sheet, a large expansion or necking of the die exit occurs, causing the degree of formation and self-supporting of the gel-like sheet to decrease. On the other hand, when the polyolefin is more than 75% by mass, the formability of the gel-like sheet is deteriorated. (2) Extrusion The polyolefin solution melt-blended into the extruder was extruded from the mold immediately or after nine-granulation. The mold to be used is usually a sheet forming mold having a rectangular cross section opening, but a double cylinder hollow mold inflatable lip or the like can also be used. In the case where the sheet shape φ is molded, the mode gap is usually 0. 1-5 mm and it is heated to 1 40-250 ° C during extrusion. The pressing speed of the heated solution is preferably 0. 2 to 15 m/min. (3) Formation of gel-like sheet The polyolefin solution extruded from the mold was cooled to form a gel-like sheet. Cooling is preferably carried out at a condensation temperature of at least 50 ° C / min or more. The cooling is preferably carried out at 25 ° C or below. Such cooling fixes the microphase of the polyolefin isolated by the film forming solvent. In general, the lower the cooling rate, the larger the lattice unit of the colloidal sheet, resulting in a transition to a higher structure. On the other hand, the higher the cooling rate, the denser the lattice unit. A cooling rate of less than 50 ° C /min results in an increase in crystallinity such that it does not have suitable stretchability to provide a gel-like sheet. The cooling method that can be used is a method in which the extrudate is directly contacted with a cooling medium (e.g., cooling air, cooling water, etc.), and the extrudate is brought into contact with a cooled roll such as a cooling medium. (4) Stretching of the gel-like sheet The obtained gel-like sheet is stretched in at least one direction. The gel-like sheet can be uniformly stretched because it contains a film forming solvent. After the gelatinized sheet is heated, -17-200830616 is stretched to a predetermined multiple by a tenter method, a roll method, an aeration method, or a combination thereof. Stretching can be carried out uniaxially or biaxially, although a biaxial stretching system is preferred. In the case of biaxial stretching, any simultaneous biaxial stretching, continuous stretching or multi-stage stretching (for example, a combination of simultaneous biaxial stretching and continuous stretching) may be used, although the synchronous biaxial stretching system is Preferably. In the uniaxial stretching, the stretching ratio is preferably 2 times or more, more preferably 3 · 30 times. In the biaxial stretching, the stretching ratio is preferably 3 times or more in any direction (preferably, the area magnification is 9 times or more, more preferably 16 times or more, and most φ is preferably 25 times or more). When the area ratio is 9 times or more, the pinhole strength of the microporous film is improved. When the area magnification is more than 400 times, stretching equipment, stretching conditions, and the like are limited. The stretching temperature is preferably the melting point of the first polyolefin Tnu + 10 ° C or less, more preferably in the range of the crystal dispersion temperature Tcda of the first polyolefin or more and less than Tma. When the stretching temperature is higher than Tma + 10 ° C, the first polyolefin melts and the molecular chains cannot be aligned by stretching. When the stretching temperature is lower than Tcda, the first polyolefin is insufficiently softened, so that the microporous film is easily broken at the time of stretching, and the high-magnification stretching is achieved without the φ method. The polyethylene compositions A and A' have a Tma of about 1 30 to 140 ° C and a Tcda of about 90 to 100 ° C. Tcda is determined by measuring the temperature properties of the dynamic viscoelasticity of the polyethylene resin in accordance with ASTM D 4065. Therefore, the stretching temperature is from 90 to 140 ° C, preferably from 1 〇 〇 -1 30 °C. Such stretching causes splitting between the polyethylene layers, making the polyethylene phase finer and forming a large number of filaments. The filaments form a three-dimensional network structure (a three-dimensional irregular network structure). Stretching improves the mechanical strength of the microporous membrane and enlarges its pores, making the microporous membrane particularly suitable for use in battery separators. -18- 200830616 According to the desired properties, the stretching can be carried out in a thickness distribution in the thickness direction to provide a microporous polyolefin film having excellent mechanical strength. The details of this method are described in Japanese Patent No. 3,347,854. (5) Removal of film forming solvent For the purpose of removing (washing off) the film forming solution, a lotion was used. Since the first polyolefin phase is separated from the film forming solvent phase, the removal of the film forming solvent provides a microporous film. The removal (washing off) of the film forming solvent can be carried out by using a known washing liquid. The washing liquid includes volatile solvents such as saturated hydrocarbons (such as φ such as pentane, hexane, heptane, etc.), chlorinated hydrocarbons (such as dichloromethane, carbon tetrachloride, etc.), ethers (such as diethyl ether, dioxane). Etc.), ketone (such as methyl ethyl ketone, etc.), linear fluorinated carbon (such as trifluoroethane, C6Fm, C7F16, etc.), cyclic hydrofluorocarbon (such as C5H3F7, etc.), hydrofluoroether (such as C4F9〇CH3, C4F9〇) C2H5, etc.), perfluoroether (for example, C4F9〇CF3, C4F9〇C2F5, etc.). The cleaning of the microporous membrane after stretching can be carried out by immersing in a washing liquid and/or rinsing with a washing liquid. The washing liquid to be used is preferably from 300 to 30,000 parts by mass per 100 parts by mass of the stretched film. The cleaning temperature is usually 15-3 (TC, and φ can be heated during the cleaning if necessary. The heating temperature during the cleaning is preferably 80 ° C or less. The washing of the washing liquid is preferably carried out until the residual film forming solvent The total amount is less than 1% by mass of the added amount. (6) Drying The microporous polyolefin film obtained by stretching and removal of the film forming solvent is dried by a heat drying method, an air drying method, or the like. The amount of the micro-porous film is less than or equal to or less than the above-mentioned Tcda, in particular, Tcda (: or below). The drying system is carried out until the residual washing liquid becomes preferably 5% by mass or less per 100% by mass (dry). More preferably, it is 3% by mass. Insufficient drying -19·200830616 may result in undesirably reducing the porosity of the microporous membrane due to subsequent heat treatment, resulting in poor transmittance. (7) Strip-dried microporous of microporous membrane The film is stripped. A known cutter can be used. If necessary, the width of the separator can be appropriately controlled. The width of the separator is preferably 5 to 200 mm. (8) Tensile dry microporous of microporous membrane The film can be pulled at least in a single axis (re-stretching). The re-stretching φ can be carried out by a tenter method or the like when the microporous film is heated as described above. The re-stretching can be uniaxial or biaxial. In the case of biaxial stretching, 甩 can be obtained. Synchronous biaxial stretching or continuous biaxial stretching, although synchronous biaxial stretching is preferred. Incidentally, since re-stretching is usually performed on a microporous film in the form of a long sheet, it is by stretching a gel sheet. Therefore, the direction of stretching in the longitudinal direction and the transverse direction is the same as that in the case of stretching the gelatinous sheet. This is also the same in other manufacturing methods. The stretching temperature of the microporous film is preferably the melting point Tma or less of the first polyolefin. More preferably, it is in the range of Tcda to Tnu. The polyethylene compositions A and A' φ have a Tma of about 1 30 - 40 ° C. Therefore, the stretching temperature is 90 - 1 3 5 ° C, preferably 95 - 1 30 ° C. The uniaxial re-stretching ratio is 1. 1 -1.  8 times. In the case of uniaxial stretching, the re-stretching ratio in the longitudinal or transverse direction is 1.  1 -1 · 8 times. In the case of biaxial stretching, the re-stretching magnification in both the longitudinal and transverse directions is 1. 1-1. 8 times, the re-drawing magnification in the longitudinal direction and the transverse direction may be the same or different, although the re-drawing magnification is preferably the same in both directions. When the microporous film has a draw ratio of less than 1. At 1 time, the obtained film had insufficient transmittance, electrolyte absorption and compression resistance. When this magnification is greater than 1. 8 -20- 200830616 times, forming too fine filaments, reducing heat shrinkage resistance and electrolyte absorption. (9) Heat treatment The dried microporous film is preferably subjected to heat treatment to stabilize the crystal to obtain a uniform thin layer. The heat treatment can include heat setting and/or annealing. The heat setting is preferably carried out by a tenter method or a roll method. The heat setting temperature is preferably in the range of the aforementioned crystal dispersion temperature Tcda to the melting point Tma, more preferably in the range of the stretching temperature of the microporous film of 5 ° C, preferably at the stretching temperature of the microporous film ± 3 ° C In the range. The annealing of φ to the heat treatment without applying a load on the microporous film can be carried out by using a heating chamber having a conveyor belt or a blowing type heating chamber. Annealing can be carried out continuously after the thermal relaxation of the tenter relaxation. The annealing temperature is preferably a melting point Tnu or less. Such annealing provides high penetration and strength of the microporous membrane. (10) Crosslinking of microporous membrane The microporous membrane can be crosslinked by free radiation (e.g., α-ray, /3 -ray, r-ray, electron beam, etc.). In the case of a radiation electron beam, the total amount of electron beams is preferably 0. The 1-100 Mrad acceleration voltage is preferably φ 1 00-300 kV. The cross-linking treatment increases the meltdown temperature of the microporous polyolefin film. (11) Hydrophilization treatment The microporous membrane can be subjected to a hydrophilization treatment (treatment of adding a hydrophilic property). The hydrophilization treatment may be a monomer graft treatment, a surfactant treatment, a corona discharge treatment, or the like. The monomer graft treatment is preferably carried out after the crosslinking treatment. In the case of surfactant treatment, any nonionic surfactant, cationic surfactant, anionic surfactant, and amphoteric surfactant may be used, and a nonionic surfactant is preferred. The microporous membrane is impregnated in an aqueous surfactant or a surfactant solution of a lower alcohol (e.g., methanol, ethanol, isopropanol, etc.) or by a doctor blade method. (B) Method of Manufacturing Second Separator In addition to the use of the second polyolefin, the second spacer can be manufactured in the same manner as the first spacer. The melt blending temperature of the second polyolefin solution in the step (1) is preferably in the range of the melting point Tnu + 10 to Tnu + 120 ° C of the second polyolefin. In the step (4), the stretching temperature is preferably 前述πη + 10 ° C or less as described above, more preferably in the range of the crystal dispersion temperature Tech to Tnu of the second polyolefin. In the step (6), the drying temperature is preferably φ equal to or less than the aforementioned Tcdb, particularly less than Tech by 5 ° C or more. In the step (8), the stretching temperature of the microporous film is preferably Tnu or less as described above, more preferably in the range of Tech to Tnu described above. In the step (9), the heat setting temperature is preferably in the range of the aforementioned Tech to Tnu, more preferably in the range of the stretching temperature of the microporous film ± 5 ° C, preferably in the stretching temperature of the microporous film. Within the range of ±3 °C. The annealing temperature is preferably Tnu or less as described above. The polyethylene compositions B and B' have a Tnu of about 1 30-140 ° C and a Tech of about 90-10 CTC. 0 In the method of manufacturing the second separator, in order to further improve the meltdown property, a fluororesin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polypropylene, poly can be formed on at least one side of the microporous polyethylene film. A porous coating layer of guanamine, polyarylene sulfide or the like. [3] Electrode Sheet The anode sheet includes a current collector and an anode active material layer, and the cathode sheet includes a current collector and a cathode active material layer. Depending on the form of the secondary battery (lithium ion secondary battery, nickel-hydrogen secondary battery, nickel-cadmium secondary battery, nickel-zinc secondary battery, silver-zinc secondary battery, etc.), a known material can be used as -22- 200830616 Current collector, anode active material and cathode active material. The anode and cathode sheets in a lithium ion secondary battery and the manner of manufacturing the same will be explained below. (A) Anode sheet Specific examples of the current collector of the anode sheet include metal foils of aluminum, copper, nickel, stainless steel, titanium, etc., and aluminum foil is preferred. The anode active material is a material that can absorb and release lithium ions. Specific examples of the anode active material may be inorganic compounds such as transition metal oxides, composite oxides of lithium and transition metals (lithium composite oxides), transition metal sulfides, and the like. The transition metal 肇 may be V, η η, F e, C 〇, N i or the like. An example of a preferred lithium composite oxide is a sheet-like lithium composite oxide containing at least one transition metal. Specific examples of the sheet-like lithium composite oxide include lithium nickelate, lithium cobaltate, lithium manganate, LiMn2〇4, Li(Ni-Mn-Co)〇2 and the like. The anode sheet is obtained by coating an anode active material paste, a binder and a solvent on a current collector, drying and pressing. The paste preferably contains a conductive additive, which may be flake graphite, carbon black or the like. The binder may be a fluorinated compound such as polyvinylidene fluoride, polytetrafluoroethylene or the like. The solvent may be, for example, φ N-methyl-2-pyrrolidone or the like. Although not particularly limited, the coating method may be, for example, a doctor blade method or the like. The anode active material layer is formed on one or both sides of the current collector' depending on the desired structure of the electrode composite. Although not particularly limited, the thickness of the current collector is preferably 5 to 60 // m, more preferably 8 to 40 // m, and the thickness of the anode active material layer is preferably 20 to each side of the anode sheet. 300/zm, more preferably 40 to 150/ζιη. (B) Cathode Sheet The material of the current collector for the cathode sheet can be the same as the above-mentioned metal foil -23-200830616, and copper foil is preferred. Specific examples of the cathode active material may be carbonaceous materials such as metastable phase carbon particles, natural graphite, artificial graphite, coal char, carbon black, and the like. Further examples may be Si, Sn, Si-C, and the like. The cathode sheet is obtained by coating a cathode active material paste, a binder and a solvent on a current collector, drying and pressing. The paste preferably contains a conductive additive, which may be flake graphite, carbon black or the like. The binder, conductive additive and solvent can be the same as those in the anode sheet. The binder for the cathode sheet may be an aqueous dispersion of rubber (styrene-butadiene rubber or the like). Although there is no particular limitation, the coating method may be, for example, a doctor blade method or the like. The cathode active material layer is formed on one or both sides of the current collector&apos; depending on the desired structure of the electrode composite. The thickness of the current collector of the cathode sheet can be the same as that of the anode sheet. The thickness of the cathode active material layer may be the same as that of the anode in the active material layer. The current collectors of the anode and cathode sheets may not have the same thickness. The anode active material layer and the cathode active material layer may not have the same thickness. [4] Structure of electrode composite φ Figs. 1 to 4 show an example of a cylindrical lithium ion secondary battery including the electrode composite of the present invention. This battery has a spiral tubular electrode composite 1 including a second separator 11, a cathode sheet 13, a first separator 10 and an anode sheet 12. In order to provide improved needle penetration safety of the battery, the spiral tubular electrode assembly 1 is preferably such that the second spacer 11 is disposed on the outer side surface of the cathode sheet 13, while the first spacer 10 is disposed on the inner side of the cathode sheet 13. Winding on the surface. As shown in Fig. 2, the second spacer 11 in this example is disposed on the inner side surface of the spiral tubular electrode assembly 1. As shown in Fig. 3, in the present example, the anode active material layer 12b is formed on -24-200830616 on both sides of the current collector 12a, and the cathode active material layer 13b is formed on the current collector 13a. On both sides. As shown in Figs. 2 and 4, the anode lead 20 connects the terminal end of the anode tab 12 to the battery cover 27, and the cathode lead 21 connects the terminal end of the cathode tab 13 to the battery can 23. When the spiral tubular electrode assembly 1 is used for a rectangular lithium ion secondary battery, the composite 1 is wound into a cylindrical shape. In the case of a lithium ion secondary battery having a laminated structure including an anode 12 and a cathode 13 which are alternately arranged, the first and second separators 1 and 11 are alternately planar anodes i 2 ^ and cathode 1 3 folders. The electrode composite 1 includes (a) a first separator 1 including a high density polyethylene A having excellent shutdown properties, and (b) a high density polyethylene B including excellent mechanical strength and meltdown properties. Two spacers. In addition, the table 1 and the table-separator 1 〇, 11 are also excellent in permeability, heat shrinkage resistance, and compression resistance. The shutdown temperature difference between the first and second separators 1 and 11 is within 5 °C. When this difference is greater than 5 ° C, the battery has low safety. The shutdown temperature of the first and second insulation materials 10, Η is preferably 125. ^ or on φ for excellent battery safety. [5] Non-aqueous electrolyte battery A lithium ion secondary battery having the electrode assembly 1 described above. The first and second separators contain an electrolyte solution. The electrolyte solution is obtained by dissolving a lithium salt in an organic solvent. The lithium salt may be LiCICU, LiPF6, LiAsF6, LiSbF6, LiBF4, LiCFsSCh, LiN(CF3S〇2)2, LiC(CF3S〇2)3, Li2Bi〇Cl1〇, LiN(C2F5S〇2)2, L i PF 4 ( CF 3) 2, L i PF 3 (C 2 F 5) 3. Low-grade fatty acid salt of lithium, li A 1 C14, and the like. The lithium salts may be used singly or in combination. The organic solvent may be an organic solvent having a high boiling range of -25,306,016 points and a high dielectric constant, such as ethylene carbonate, carbon@爱丙酯, ethyl methyl carbonate, r-butyrolactone, etc.; having a low boiling point And a low viscosity organic solvent such as tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dioxolane, dimethyl carbonate, diethyl carbonate, and the like. These organic solvents may be used singly or in combination. Since an organic solvent having a high dielectric constant has a local viscosity, and an organic solvent having a low viscosity has a low dielectric constant, a mixture thereof is preferably used. When the battery is assembled, the anode piece 1 2, the cathode piece 13 and the first and second separators 1 and 11 are immersed in the electrolyte solution, so that the separators 1 and 11 (microporous film) provide ion permeability. The immersion treatment is usually carried out by immersing the electrode assembly 1 in an electrolyte solution at room temperature. The cylindrical lithium ion secondary battery can be insulated by injecting the electrolyte solution into the battery can 23' by insulating the spiral tubular electrode assembly 1 (see FIGS. 1 to 4) at the bottom of the battery case 23 having the insulating plate 2 2 . The plate 22 covers the electrode assembly 1, and is formed by sealing the battery case 23 with the battery cover 27 through the spacer 28. The battery cover 27 has a current interrupting device 24, a curved plate 25 and a PTC device 26, thereby having the function of a φ anode electrode. The non-aqueous electrolyte battery including the electrolyte battery of the present invention has a discharge capacity of 1,500 mAh or more, and a capacity recovery rate of 60% or more, and a preferable capacity recovery rate of 75% or more. Although the electrode composite of the present invention and the non-aqueous electrolyte battery have been explained using a lithium ion secondary battery as an example, the electrode of the present invention is not limited thereto, and can be applied to other forms of non-aqueous electrolyte batteries. The electrode composite and the non-aqueous electrolyte battery of the present invention are not limited to the foregoing examples, and any modifications may be added thereto unless departing from the gist of the present invention. -26-200830616 [Embodiment] The present invention will be explained in more detail by way of the following examples, but the invention is not limited thereto. Example 1 (1) Preparation of the first separator Dry blending 100 parts by mass of the polyethylene composition A and 0. 2 parts by mass of antimony [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, wherein the polyethylene composition A includes 20% by mass The ultrahigh molecular weight polyethylene (UHMWPE) having a weight average molecular weight (Mw) of 2.0 χ 106 and a molecular weight distribution Mw/Mn of 8, and a terminal vinyl concentration of 80% by mass of 0. 6/1 0,000 C, Mw is 3. 5xl05, Mw/Mn is 13. 5 high density polyethylene A (HDPE-A). The terminal vinyl concentration of HDPE-A was measured by measuring the absorbance at 910 CHT1 A = log (I 〇 / I), which was measured by a Fourier transform infrared spectroscopy (FREEXACT-II from Horiba, Ltd). . Indicates the intensity of the transmitted light in the blank slot, and I represents the intensity of the transmitted light in the sample cell, and then calculates the formula for the terminal vinyl concentration (/1〇, 〇〇〇 C) = (1. The 14x absorbance A) / (the density of the high density polyethylene A (g / cm3) x the thickness (mm) of the sample) is determined. Polyethylene composition A has 6. 8x1 05 Mw, 21. Mw/Mn of 5, Tma of 134 °C and TccU of 100 °C. Mw and Mw/Mn of UHMWPE, HDPE and polyethylene compositions were measured by gel permeation chromatography (GPC) under the following conditions: Measuring instrument: GPC from Warers C 〇r ρ 〇rati ο η 1 5 0 C Column: obtained from Showa Denko S·Κ·Shodex UT806M Column temperature: 135t: Solvent (mobile phase): o-dichlorobenzene-27- 200830616 Solvent flow rate: 1. 0 ml/min Sample concentration: 0. 1% by weight (dissolved in 135 ° C for 1 hour), Injection: 500 // 1 Detector: Differential refractive index calibration curve from Waters Corp.: from standard polyethylene samples using predetermined conversion constants The monodisperse reduction curve. 30 parts by mass of the obtained mixture was charged with an inner diameter of 5 8 mm and an L/D of 52. A vigorously blended twin-screw extruder of 5 was then supplied with 70 parts by mass of liquid paraffin [50 cst (40 ° C)] through a side feeder φ to a twin-screw extruder. Melt blending was carried out at 23 (TC and 250 rpm to prepare a polyethylene solution. This polyethylene solution was extruded from a T-die mounted at the tip of a twin-screw extruder and controlled by cooling at 5 °C. The rolls are stretched and cooled while being taken up to form a gel-like sheet. Using a tenter-stretching machine, the gel-like sheets are simultaneously biaxially stretched at 1 15 ° C, so that the stretching ratio is in the machine direction (MD) and the transverse direction. (TD) Both are 5 times. The stretched gel-like piece is immersed in a bath controlled at 25 ° C in dichloroethene, and washed with a vibration of 10 0 rp m for 3 minutes to remove Liquid sarcophagus. The obtained film was air-dried at room temperature, and the dried film was fixed in a tenter-stretching machine while being thermally fixed at 124 ° C for 30 seconds to prepare a microporous polyethylene film. The porous polyethylene film was striped to obtain a first separator 1 having a width of 6 mm (see Fig. 1). (2) Preparation of the second separator 1 part by mass of the polyethylene composition B With 0. 2 parts by mass of the aforementioned antioxidant dry blending, wherein the polyethylene composition B comprises 3 〇 mass% of the aforementioned UHMWPE and 70% by mass of the terminal vinyl group concentration is 〇1/1 〇, 〇〇〇-28- 200830616 C, Mw is 3 · Ox 105 and M w/Mn is 8. 6 B (HDPE-B). The polyethylene composition B has a crystal dispersion temperature Tcdb of 135 ° C, 8. Mw/Mn of U105. The microporous polymer 11 having a width of 60 Inm is prepared in the same manner as described above except that the polyethylene composition B is used and the degree is 1 27 °C. (3) Preparation of the anode sheet will be 2. 7 parts by mass of lithium cobalt composite oxide φ parts of acetylene carbon and 3 . 1 part by mass of polyvinylidene fluoride N-methyl-2-pyrrolidone, and the raw material paste was mixed by stirring. The anode active material paste was applied to the thickness of the aluminum foil current collector by a doctor blade method to obtain a uniform thickness to obtain an anode sheet 12 on both sides of the current collector. (4) Preparation of cathode sheet φ 8 8 parts by mass of metastable phase carbon particles, 10 parts by mass and 2 parts by mass of PVDF were added to N-methyl-2-3⁄4) to prepare a cathode active material paste. A layer for smoothing the copper foil current having a thickness of 10/zm by a doctor blade method. The layers are dried to produce a cathode sheet 13 which is in the current collecting cathode active material layer. (5) Preparation of the electrode composite sequentially laminating the second spacer 1 of 60 mm width, the high density polyethylene of the first spacers 10 and 55 of the sheet 13, 60 mm wide: the melting point Tnu, 100 Mw and 17. 2 The second isolated microporous membrane of the vinyl membrane is prepared by a fixed temperature method. (LiCoCh), 4. 2 Mass Ethylene (PVDF) was added to the hour to prepare the anode to have a layer of 20 // m. The layers are dried to a mass fraction of acetylene carbon of the active material layer: ketone, and mixed with a cathode active material paste applicator to obtain a cathode having a width of 1, 57 mm on both sides of the thickness concentrator The mm wide anode sheet 12 -29- 200830616 was used to prepare the electrode composite 1. The electrode assembly 1 is wound so that the second separator 1 1 is disposed on the outer surface of the cathode sheet 13. (6) Preparation of electrolyte solution 1 mol/liter of LiPF6 was added to a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a volume ratio of 40/60 to prepare an electrolyte solution. (7) Assembly of the battery The anode lead 20 is attached to the end of the anode φ sheet 12 in the spiral tubular electrode assembly 1, and the cathode lead 2 1 is attached to the cathode sheet 13 in the spiral tubular electrode assembly 1. The end. When the spiral tubular electrode assembly 1 is placed in the battery case 23 having the insulating plate 22 at the bottom, the anode lead 20 is connected to the battery cover 27, and the battery case 23 is connected to the cathode lead 20. After the electrolyte solution prepared in the above step (6) is injected into the battery can 23, the spiral tubular electrode composite 1 is covered with an insulating plate 22, and the battery cover 27 is sealed by the gasket 28 to prepare the battery case 23 to prepare 1 8650. A cylindrical lithium ion secondary battery having a diameter of 18 mm and a height of 6 5 mm. φ Example 2 except that the concentration of the polyethylene solution was 25% by mass, the stretching temperature was 1 17 ° C, and the annealing was performed at 125 ° C to make the lateral length 0. The first separator 10 was prepared in the same manner as in Example 1 except for 9 times. This first separator 10 was used to prepare a lithium ion secondary battery in the same manner as in Example 1. Example 3 100 parts by mass of the polyethylene composition A, which comprises 30% by mass of the aforementioned UHMWPE and 70% by mass of the aforementioned HDPE-A, with 0. 2 parts by mass The aforementioned antioxidant was dry blended. Polyethylene composition A has 134 ° (: -30 - 200830616 melting point Tnu, 100 ° C crystal dispersion temperature TccU, 8. Mw of 4xl05 and 2 3. 8 of Mw / Μ η. The first separator 10 was stretched in the transverse direction by a tenter-stretching machine by using a polyethylene composition A, a stretching temperature of 114 ° C, and a microporous film at 123 ° C. It was obtained in the same manner as in Example 1 except that the fixing temperature of the microporous film was 123 °C. A lithium ion secondary battery was prepared in the same manner as in Example 1 using this first separator 10. Example 4 100 parts by mass of the polyethylene composition A, which comprises 5% by mass of the aforementioned φ UHMWPE and 95% by mass of the aforementioned HDPE-A, with 0. 2 parts by mass of the aforementioned antioxidant was dry blended. The polyethylene composition A has a melting point Tma of 133 ° C, a crystal dispersion temperature TccL of 100 ° C, Mw of 4. 3 χ 105, and 15. 9 Mw / Mn. Except that the polyethylene composition A, the polyethylene solution had a concentration of 35 mass%, the stretching temperature was 116 ° C, and the microporous film was stretched in the transverse direction by a tenter-stretching machine at 126 ° C. The first separator 10 was prepared in the same manner as in Example 1 except that the fixing temperature of the microporous film was 126 °C. A lithium ion secondary battery was produced in the same manner as in Example 1 using this first separator 1 φ. Example 5 Except that the concentration of the polyethylene solution was 25 mass%, the microporous film was stretched in the transverse direction by a tenter-stretching machine at 1 27 °C. One time, and annealing at 1 27 °C, the length of the transverse direction becomes 〇.  A second separator 11 was prepared in the same manner as in Example 1 except for 9 times. A lithium ion secondary battery was produced in the same manner as in Example 1 using this second separator 11. Example 6 A first separator 10 was prepared in the same manner as in Example 2, and a second separator 11 was prepared in the same manner as in Example No. 31-200830616. Lithium Ion Secondary Battery This first and second separators 1 and 11 were produced in the same manner as in Example 1 to prepare 10,000 parts by mass of the polyethylene composition B, which included 5% by mass of UHMWPE and 95% by mass of the foregoing. HDPE-B, with 0. 2 mass The antioxidant is described as dry blending. The polyethylene composition B has a Tnu of 134 ° C, a crystal dispersion temperature of 100 ° C, Tcdb, 3. Mw of 8xl05 and Mw/Mn of. In addition to using this polyethylene composition B, the stretching temperature was φ ° C, and the microporous film was at 130 ° C in the transverse direction by a tenter-stretching machine. A second spacer Π was prepared in the same manner as in Example 1 except that the fixing temperature of the microporous film was 1 30 °C. Lithium ion secondary battery This second separator 1 was produced in the same manner as in Example 1. Example 8 A first separator 10 was obtained in the same manner as in Example 1 except that the stretching temperature was 1 14 °C. The first separator 11 was obtained in the same manner as in Example 1 except that the stretching temperature was 1 1 3 °C. The lithium ion secondary φ was produced in the same manner as in Example 1 using this first and second separators 10, 11. Comparative Example 1 A lithium ion secondary battery was prepared in the same manner as in Example 1 except that the electrode assembly was laminated in the order of the first separator 1 〇, the cathode sheet 13 , the first separator, and the anode sheet 1 2 . Comparative Example 2 was used except that the second separator 1 1 , the cathode sheet 13, the second separator, and the anode sheet 1 2 were laminated in this order to form an electrode composite. The previous melt. 6 117 Stretching and solidification in a battery mode 10, a lithium ion secondary battery was prepared in the same manner as in Example 1 and -32-200830616. Comparative Example 3 In addition to using only the aforementioned HDPE-B, the concentration of the polyethylene solution was 40% by mass, the stretching temperature was 114 ° C, and the microporous film was stretched in the transverse direction by a tenter-stretching machine at 128 ° C. 1. A separator was prepared in the same manner as the second separator 1 in Example 1, except that the fixing temperature of the microporous film was 128 °C. A lithium ion secondary battery was prepared in the same manner as in Example 1 except that this separator was used instead of the second separator 11. Φ Comparative Example 4 100 parts by mass of the polyethylene composition B, which comprises 3% by mass of the aforementioned UHMWPE and 97% by mass of the aforementioned HDPE-B, with 0. 2 parts by mass of the aforementioned antioxidant was dry blended. The polyethylene composition B had a melting point Tnu of 135 ° C, a crystal dispersion temperature Tech of 100 ° C, Mw of 3.5 χ 105, and Mw / Mn of 9,8. In addition to the use of the polyethylene composition B, the polyethylene solution concentration was 40% by mass, the stretching temperature was 119 ° C, and the microporous film was stretched in the transverse direction by a tenter-stretching machine at 130 ° C. A second separator 11 was prepared in the same manner as in Example 1 except that the solidification temperature of the microporous film was 130 °C. A lithium ion secondary battery was produced in the same manner as in Example 1 using this second separator 11. Comparative Example 5 The electrode composite was laminated in the order of the first separator 1 , the cathode sheet 13 , the second separator 11 , and the anode sheet 1 2 , and the first separator 10 was placed on the cathode sheet 13 A lithium ion secondary battery was prepared in the same manner as in Example 1 except for the outer surface. The properties of the microporous polyethylene film obtained in Examples 1-8 and Comparative Examples 1 - 5 were measured in the following manner. The results are shown in Table 1. (1) Average thickness (//m) The thickness of each microporous film was obtained by averaging the width of 30 cm by a contact length gauge at a pitch of 5 mm. (2) Gas permeability (sec/100cm3/20 // m) According to IS P8 117, the gas permeability P! is measured for each microporous film having a thickness Ti, and then converted into a thickness of 20 by the equation P2 = (PlX20)/Ti. Breathability P2 at μ m. • (3) Porosity (%) is measured by the gravimetric method. (4) Pin punching strength (mN/20 // m) For each microporous film having a thickness Ti, a needle having a round end surface having a diameter of 1 mm is used (curvature radius R: 〇. 5mm) puncture at 2mm/sec and measure its maximum load. The measured maximum load is converted to the maximum load L2 at a thickness of 20 μm using the equation = and used as the pinning strength. φ (5 ) Thermal Shrinkage Ratio (%) The shrinkage ratio of each (three-layer) microporous film in the length and width directions was measured by exposure to 10 5 t: 8 hours, and then averaged to obtain a heat shrinkage ratio. (6) Pore radius is measured by a mercury intrusive pore meter. (7) Shutdown temperature (it) As shown in Fig. 5, the test piece τρ having a size of 3 mm and 10 mm in the stretching direction MD and TD, respectively, was cut from the microporous film 10〇. Use thermomechanical analyzer (available from Seiko Instrument sine. TMA/SS 6000) -34- 200830616 The test piece was heated from room temperature at a rate of 5\:/min, the upper end 100a was clamped by the support 3, and the lower end 100b was attached to the 2 g weight 4. The temperature point at which the recursion is observed near the melting point is defined as the shutdown temperature. (8) Melting temperature (°C) Using a thermomechanical analyzer as described above, test pieces of 10 mm (TD) and 3 mm (MD) were applied with a load of 2 g according to the method shown in Fig. 5, at room temperature of 5 °C. /min to speed. The temperature at which the test piece TP is broken due to melting is referred to as "melting temperature". Φ (9) Gas permeability after hot compression (sec/100 cm3/20 # m) The microporous film sample was sandwiched between a pair of highly flat plates, and pressed at 90 ° C by a press machine. The pressure of 2 MPa (22 kgf/cm2) was heat-compressed for 5 minutes. The heat-compressed microporous film having a thickness T!' was measured for gas permeability P!' in accordance with nS P8117. The measured gas permeability Pi' is converted into a gas permeability P2' at a thickness of 20 / z m by the equation P^WPi'xaOVIV. The properties of the battery obtained in Example 8 and Comparative Example 1 - 5 were measured in the following manner. The results are shown in Table 1. m (10) Discharge capacity The battery is charged to 4. at a constant current of 900 mA by using a charge/discharge tester. 2V, further charging until the charging current drops to 4. 2V is 10mA at voltage, and then discharged at a constant current of 260mA at 25 °C. 0V. The measured initial capacity is taken as the discharge capacity (mAh). (1 1) Overcharge test The battery is charged at a current of 800 mA at 25 °C by using a charge/discharge tester (charge: 0. 5 C) Charge to 5V to check for smoke and burning. 0 -35- 200830616 (12) Needle-punch test Charge the battery to a constant current of 900 mA by using a charge/discharge tester. 2V, further charging until the charging current drops to 25 °C. 10V at a constant voltage of 2V. A stainless steel nail having a diameter of 3 mm was heated to 25 ° C and pierced at a radial center at a speed of 9 mm/sec to verify whether smoke and combustion occurred. (1 3) Capacity recovery rate after recovery test (recovery) The battery is charged to 4. with a constant current of 1,600 mA (amount of electricity: φ 1 C) by using a charge/discharge tester. 2V, further charging until the charging current drops to 4. Under the constant voltage of 2V, i〇mA, then discharge at a constant current of 1,600mA (electricity: 1C) to 3. 0V to check the discharge capacity (initial capacity) at 25 °C. Repeat this charging/discharging operation 1 time (recovery test). The discharge capacity was measured in the same manner to determine the capacity recovery rate after the resilience test (%). The capacity recovery rate (%) of the battery was determined by the following formula: Capacity recovery rate (%) = [(recovery capacity after test) / (initial capacity)]xl〇〇

-36- 200830616

Table 1 No. Example 1 Example 2 Type of spacer material First second first second polyethylene composition UHMWPE Mw (1) Mw/Mn (2) Mass % 2.0 xlO6 8 20 2.0 X 106 8 30 2.0 X 106 8 20 2.0 X 106 8 20 HDPE -A terminal vinyl content (3) (/10,000 C) Mw Mw/Mn mass % 0.6 3.5 X 105 13.8 80 - 0.6 3.5 X 105 13.5 80 - HDPE-B terminal vinyl content (/10,000 C) Mw Mw/Mn mass% - 0.1 3.0 X 105 8.6 70 - • 0.1 3.0 X 105 8.6 70 Mw 6.8 X 105 8,1 X 105 6.8 X 105 8.1 X 105 Mw/Mn 21.5 17.2 21.5 17.2 TmfC)(4) 134 135 134 135 Tcd(°C)( 5) 100 100 100 100 Manufacturing conditions Concentration (6) (% by mass) 30 30 25 30 Stretching temperature of gelatinous sheet ΓΟ Magnification (MD X TD) i7) 115 5x5 115 5x5 117 5x5 115 5x5 Stretching of microporous sheet Temperature (°C) / direction / magnification -1 - 1 - -AA ·/·/_ Heating fixed temperature rc) / time (seconds) 124/30 127/30 127/30 Annealing temperature rc) / direction / magnification 125 / TD/0.9 Microporous film Properties Average thickness (//m) 20 20 20 20 Gas permeability (seconds/100cm3/20"m) 500 550 450 550 Porosity (%) 38 38 36 38 Pin punch strength (mN/20 /m) 4,508 5, 880 3,920 5,880 MD/TD heat shrinkage (%) 6/5 6/5 6/3 6/5 Pore radius (nm) 40 40 40 40 Breaking temperature (.C) Breaking temperature difference ΓΟ , 129 132 130 132 3 2 Melting temperature ΓΟ 148 152 153 152 Gas permeability after heat compression (sec/100cm3/20/zm) 1,100 1,000 1,200 1,000 Layer structure of battery-shaped spiral tubular electrode composite (8) (II) / cathode / (IV anode (II) / Cathode / (I) / Anode needle penetration test No smoke and no burning No smoke and no combustion Overcharge test No smoke and no combustion No smoke and no combustion discharge capacity (mAh) 1,590 1,580 Battery capacity recovery rate ( %) 80 80 -37- 200830616

Clothing U槚) No. Example 3 Example 4 Type of spacer material First second first second polyethylene composition UHMWPE Mw(1) Mw/Mn (2) Mass% 2.0 X 106 8 30 2.0 X 106 8 30 2.0 X 106 8 5 2.0 X 106 8 30 HDPE-A End Vinyl Content (3) (/10,000 C) Mw Mw/Mn Mass % 0.6 3.5 X 105 13.5 70 - 0.6 3.5 X 105 13.5 95 - HDPE-B End Vinyl Content (/10,000 0 Mw Mw/Mn Mass % - 0.1 3.0 X 105 8.6 70 - 0.1 3.0 X 105 8.6 70 Mw 8.4 X 105 8.1 X 105 4.3 X 105 8.1 X 105 Mw/Mn 23.8 17.2 15.9 17.2 Tm(〇C)(4) 134 135 133 135 TccTCf 100 100 100 100 Manufacturing condition concentration (6) (% by mass) 30 30 35 30 Stretching temperature of gelatinous sheet (.〇 magnification (MD X TD) (7) 114 5x5 115 5x5 116 5x5 115 5x5 Microporous sheet stretching temperature (°C ) / direction / magnification 123 / TD / 1.1 126 / TD / I.3 - 1-1 - heating fixed temperature ( ° C) / time (seconds) 123 / 30 127 / 30 126 / 30 127 / 30 annealing temperature ( ° C)/direction/magnification-1-1- ·/-/- Properties of microporous film Average thickness (//m) 20 20 20 20 Gas permeability (sec/l〇〇cm3/20/zm) 330 550 320 550 Porosity (%) 43 38 41 38 pin Strength (mN/20/zm) 5,194 5,880 3,626 5,880 MDm) Heat shrinkage rate (%) 8/10 6/5 7/5 6/5 Pore radius (nm) 45 40 43 40 Breaking temperature (. 〇 Breaking temperature difference ΓΟ 131 132 133 132 1 Melting temperature (.〇152 152 149 152 Gas permeability after heat compression (#/l00cm3/20 β m) 950 1,000 950 1,000 Layer structure of battery-shaped spiral tubular electrode composite (8) (Π) / cathode /(I)/Anode (II)/Cathode/(I)/Anode Needle Penetration Test No smoke and no combustion No smoke and no combustion Overcharge test No smoke and no combustion No smoke and no combustion discharge capacity ( mAh) 1,600 1,580 Battery capacity recovery rate (%) 85 82 -38 - 200830616 Table 1 (continued)

No. Example 5 Example 6 Type of separator material First first - First 1 Second polyethylene composition UHMWPE Mw (1) Mw / Mn (2) Mass % 2.0 xlO6 8 20 2.0 X 106 8 30 2.0 X 106 8 20 2.0 xlO6 8 20 HDPE- A terminal vinyl content (3) (/10,000 C) Mw Mw/Mn mass % 0.6 3.5 X 105 13.5 80 - 0.6 3.5 X 105 13.5 80 - HDPE-B terminal vinyl content (/10,000 C) Mw Mw/Mn mass % - 0.1 3.0 X 105 8.6 70 - 0.1 3.0 X 105 8.6 70 Mw 6.8 X 105 8.1 X 105 6.8 X 105 8.1 X 105 Mw/Mn 2L5 17.2 21.5 17.2 TmfC)(4) 134 135 134 135 TcdfCf 100 100 100 100 Manufacturing condition concentration (6) (% by mass) 30 25 25 25 Stretching temperature of gelatinous sheet (. 〇 magnification (MD X TD) (7) 115 5x5 115 5x5 117 5x5 115 5x5 stretching temperature of microporous sheet (.〇/direction/magnification -1-1- 127/TD/1.1 127ΠΌ/1.1 Heating fixed temperature rev time (seconds) 124/30 -Α Annealing temperature (°C)/direction/magnification 127/TD/0.9 I 125ΠΌ/0.9 127TO0.9 Microporous Membrane properties Average thickness ("m) 20 20 20 20 Gas permeability (sec/lOOcm^O/zm) 500 350 450 350 Porosity (%) 38 41 36 41 Pin punch strength ( mN/20/zm) 4,508 4,214 3,920 4,214 MM3 heat shrinkage rate (%) . 6/5 7/3 6/3 7/3 Pore radius (_) 40 40 40 40 Breaking temperature 断 Breaking temperature difference (°C) 129 132 130 132 3 2 Meltdown temperature (.C) 148 150 153 150 Gas permeability after hot compression (sec/100cm3/20_) 1,100 1,000 1,200 1,000 Cell layer structure of spiral tubular electrode composite (8) (II) / Cathode / (I) / anode (II) / cathode / (I) / anode needle penetration test no smoke and no combustion no smoke and no combustion overcharge test no smoke and no combustion no smoke and no combustion discharge capacity (mAh ) 1,580 1,580 Battery capacity recovery rate (%) 81 80 -39- 200830616

... U" Example No. 7 Example 8 Type of spacer material First second first second polyethylene composition UHMWPE Mw (1) Mw / Mn (2) Mass % 2.0 X 106 8 20 2.0 xlO6 8 5 2.0 X 106 8 20 2.0 xlO6 8 30 HDPE-A End Vinyl Content (3) (/10,000 C) Mw Mw/Mn Mass % 0.6 3.5 X 105 13.5 80 - 0.6 3.5 X 105 13.5 80 - HDPE-B End Vinyl Content (/10,000 C) Mw Mw/Mn Mass % - 0.1 3.0 xlO5 8.6 95 - 0.1 3.0 X 105 8.6 70 Mw 6.8 X 105 3.8 x 105 6.8 X 105 8.1 X 105 Mw/Mn 21.5 10.6 21.5 17.2 TmfC)(4) 134 134 134 135 Tcd(°C)(5) 100 100 100 100 Manufacturing conditions Concentration (6) (% by mass) 30 30 30 30 Stretching temperature of gelatinous sheet (. 〇 magnification (MD X TD) (7) 115 5x5 117 5x5 114 5x5 113 5x5 stretching temperature of microporous sheet (.C)/direction/magnification-ΛΑ130ATD/L4 -1-1- Heating fixed temperature (.〇/time (seconds) 124/30 130/30 124/30 * 127/30 Annealing temperature (°C)/direction /magnification-1-1- -/-/- -1-1- Properties of microporous membranes Average thickness (#m) 20 20 16 16 Ventilation seconds / 100cm3/20//m) 500 240 380 430 Porosity (% ) 38 38 38 38 pin punch Strength (mN/20"m) 4,508 4,508 4,655 4,900 MDATD heat shrinkage (%) 6/5 2/2 6/6. 7/6 Pore radius (nm) 40 45 40 40 Breaking temperature 断 Breaking temperature difference (°C ) 129 133 128 131 /. 3 Melting temperature ΓΟ 148 147 148 149 Gas permeability after heat compression (seconds / 100cm3 / 20 / zm) 1,100 900 1,000 900 Battery layer structure of spiral tubular electrode composite (8) ω) / cathode Rib pole (8) / cathode / (I) / anode needle penetration test no smoke and no burning no smoke and no combustion overcharge test no smoke and no combustion no smoke and no combustion discharge capacity (mAh) 1,580 1,610 battery Capacity recovery rate (%) 80 83 -40- 200830616

Table 1 (continued) No. Comparative Example 1 Comparative Example 2 Type of separator material First second first second polyethylene composition UHMWPE Mw (1) Mw / Mn (2) Mass % 2.0 X 106 8 20 2.0 X 106 8 20 2.0 X 106 8 30 2.0 xlO6 8 30 HDPE-A End Vinyl Content (3) (/10,000 C) Mw Mw/Mn Mass % 0.6 3.5 X 105 13.5 80 0.6 3.5 X 105 13.5 80 - - HDPE-B End Vinyl Content (/ 10,000 C) Mw Mw/Mn mass % - - 0.1 3.0 X 105 8.6 70 0.1 3.0 X 105 8.6 70 Mw 6.8 X 105 6,8 X 105 8.1 X 105 8.1 X 105 Mw/Mn 21.5 21.5 17.2 17.2 ΤιηΓΟ (4) 134 134 135 135 Tcd(°C)(5) 100 100 100 v100 Manufacturing Condition Concentration (6) Reimbursement %) 30 30 30 30 Colloidal sheet stretching temperature fc) Magnification (MD X TD) (7) 115 5x5 115 5x5 115 5x5 115 5x5 Micro Stretching temperature of porous sheet (.〇/direction/magnification-1-1- _/一/_ -1-1- Heating fixed temperature (°C)/time (seconds) 124/30 124/30 127/30 127 /30 Annealing temperature ΓΟ/direction/magnification-1-1-1-11-1-1-1-- Properties of microporous film Average thickness (#m) 20 20 20 20 Gas permeability (seconds/100cm3/20//m ) 500 500 550 550 Porosity (%) 38 38 38 38 Impact strength (mN/20/zm) 4,508 4,508 5,880 5,880 MDATD heat shrinkage rate (%) 6/5 6/5 6/5 6/5 Pore radius (nm) 40 40 40 40 Breaking temperature (. 〇 Breaking temperature difference ( °C) 129 129 132 132 0 0 Melting temperature (.C) 148 148 152 152 Gas permeability after heat compression (sec/100cm3/20 // m) 1,100 1,100 1,000 1,000 Battery-like spiral tubular electrode composite Layer structure (8) (I) / cathode / 0) intestinal pole (II) / cathode / (8) / anode needle penetration test smoke no smoke and no combustion overcharge test no smoke and no combustion smoke discharge capacity (mAh) 1,590 1,580 battery capacity recovery rate (%) 79 80 -41 - 200830616

Table 1 (continued) No. Comparative Example 3 Comparative Example 4 Type of separator material First first (9) First second polyethylene composition UHMWPE Mw (1) Mw / Mn (2) Mass % 2.0 X 106 8 20 - 2.0 X 106 8 20 2.0 X 106 8 3 HDPE-A End Vinyl Content (3) (/10,000 0 Mw Mw/Mn Mass % 0.6 3.5 X 105 13.5 80 _ 0.6 3.5 X 105 13.5 80 - HDPE-B End Vinyl Content (/10,000 C) Mw Mw /Mn mass % - 0.1 3.0 xlO5 8.6 100 - 0.1 3.0 X 105 8.6 97 Mw 6.8 X 105 - 6.8 X 105 3.5 X 105 Mw/Mn 21.5 - 21.5 9.8 Tm (°C) (4&gt; 134 134 134 135 TcdfCf) 100 100 100 100 Manufacturing condition Concentration i6) (% by mass) 30 40 30 40 Stretching temperature of gelatinous sheet (.C) Magnification (MD X TD) (7) 115 5x5 114 5x5 115 5x5 119 5x5 Extrusion of microporous sheet Temperature (°C)/direction/magnification mfTO/ΙΛ -1-1- 130/TD/1.4 Heating fixed temperature (°C)/time (seconds) 124/30 128/30 124/30 130/30 Annealing temperature (. 〇/direction/magnification-/-/- -1-1- Properties of microporous membrane Average thickness (#m) 20 20 20 20 Gas permeability (sec/100cm3/20/zm) 500 280 500 260 Porosity (%) 38 42 38 39 Pin punch strength (mN/20/zm 4,508 5,684 4,508 4,802 MD/TD heat shrinkage rate (%) 6/5 3/4 6/5 3/3 Pore radius (nm) 40 43 40 43 Breaking temperature (. 〇 Breaking temperature difference (.〇129 134 129 135 5 6 Meltdown temperature (.〇148 145 148 145 Gas permeability after heat compression (sec/100cm3/20 &quot; m) 1,100 900 1,100 900 Cell layer structure of spiral tubular electrode composite (8) (II) / cathode /(I)/anode (9)/cathode/(10)/anode needle penetration test smoke and smoke charge overcharge test no smoke and no smoke smoke discharge capacity (mAh) 1,580 1,590 battery capacity recovery rate (%) 81 80 -42- 200830616

Table 1 (continued) No. Comparative Example 5 Type of separator First and second polyethylene composition UHMWPE Mw (1) 2.0 X 106 2.0 X 106 Mw/Mn (2) 8 8% by mass 20 30 HDPE-A Terminal vinyl content (3) 0.6 - (/10,000 C) Mw 3.5 X 105 - Mw/Mn 13.8 - Mass % 80 - HDPE-B End Vinyl Content - 0.1 (/10,000 C) Mw - 3.0 X 105 Mw/Mn - 8.6 % by mass - 70 Mw 6.8 X 105 8.1 X 105 Mw/Mn 21.5 17.2 TmfC)(4) 134 135 Tcd(r)i5> 100 100 Manufacturing conditions Concentration (6) (% by mass) 30 30 Stretching temperature of gelatinous sheet (.〇115 115 magnification (MD X TD)(7) Stretching temperature of 5x5 5x5 microporous sheet (.〇/direction/magnification•1-1- Heating fixed temperature (°C)/time (seconds) 124/30 127/30 Annealing temperature (°C) /direction/magnification Microporous film Properties Average thickness (//m) 20 20 Gas permeability (sec/100cm3/20/zm) 500 550 Porosity (%) 38 38 Pin punch strength (mN/20/m) 4,508 5,880 MDATD heat shrinkage rate (%) 6/5 6/5 Pore radius (nm) 40 40 Breaking temperature ΓΟ 129 132 Breaking temperature difference (.〇3 meltdown temperature rc) 148 152 After hot compression Gasity 1,100 1 ΠΠΠ (sec/100cm3/20"m) 1 , 层 Battery layer structure of spiral tubular electrode composite (8) (I) / cathode / (9) / anode needle wear test smoke charge over test without risk Smoke and non-combustion discharge capacity (mAh) 1,590 Battery capacity recovery rate (%) 80 -43 - 200830616 Note: (1) M w represents the weight average molecular weight. (2) Mw / Mn represents the weight average molecular weight / # quantity average molecular weight Determined molecular weight distribution (3) The number of terminal vinyl groups per 10,000 carbon atoms (quantity / 10,000 C) (4) Tm represents the melting point of the polyethylene composition. (5) Ted represents the polyethylene composition The crystal dispersion temperature. (6) The concentration of the first polyethylene solution and the concentration of the second polyethylene solution (7) MD indicates the longitudinal direction, and TD indicates the lateral direction. (8) A laminate structure from the outside, wherein (I) represents a first separator, (II) represents a second separator, "cathode" represents a cathode sheet, and "anode" represents an anode sheet. (9) Although the spacer composed of HDPE-B in Comparative Example 3 is not classified as the first or second spacer, the series is in the field of the "second spacer". As clearly shown in Table 1, the electrode composites of Examples 1 to 8 including the first and second separators have well-balanced penetration, mechanical strength, heat shrinkage resistance, shutdown properties, meltdown properties, and compression resistance. Sex. In particular, the first spacer has excellent shutdown properties and the second spacer has excellent mechanical strength and meltdown properties. Therefore, the resulting battery provides excellent safety, discharge capacity and recovery. In Comparative Example 1, a battery having two sheets of HDPE-A-containing first separator and no HDPE-B-containing separator was smoked in the needle-punching test, indicating that the safety was worse than those of Examples 1 to 8. . In Comparative Example 2, a battery having two sheets of HDPE-B-containing second separator and no HDPE-A-containing separator was smoked in the overcharge test, indicating that it was safer than Examples 1 to 8 - 44 - 200830616 Poor. In Comparative Example 2, a battery having a piece of the first separator and other separators made only of hdPE-B and not containing UHMWPE smoked in the needle penetration test showed that the safety was inferior to those of Examples 1 to 8. In Comparative Example 4, the battery having the electrode assembly including the first and second spacers has a shutdown overflow difference of more than 5 ° C, and smokes in the needle penetration test and the overcharge test, indicating that the safety is compared with the example 1 To 8 is poor. In Comparative Example 5, a battery having an electrode composite having a first separator on the outer surface of the cathode sheet and a second separator on the inner surface of the cathode sheet smoked in the needle penetration test, indicating that the safety was compared with that of Example 1 to 8 is poor. EFFECTS OF THE INVENTION A battery having a well-balanced safety, discharge capacity and recovery can be obtained by using the electrode composite of the present invention. This electrode composite is suitable for non-aqueous electrolyte batteries. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partially cutaway perspective view showing a cylindrical lithium ion secondary battery including an electrode assembly of the present invention. Fig. 2 is a transverse sectional view of the battery of Fig. 1. Fig. 3 is an enlarged cross-sectional view showing a portion A of Fig. 2. Fig. 4(a) is a partial cross-sectional view showing the end portion of the anode piece in the electrode assembly of Fig. 1. Fig. 4(b) is a partial cross-sectional view showing the end portion of the cathode sheet in the electrode assembly of Fig. 1. Figure 5 is a graphical representation of the method of measuring the temperature of the circuit breaker and the temperature of the meltdown. [Main component symbol description] 1 Spiral tubular electrode composite -45- 200830616 3 4 10 11 12 Support weight First spacer Second spacer Anode sheet 12a Current collector 12b Anode active material layer

13 13a 13b 20 21 Cathode sheet Current collector Cathode active material layer, anode wire Cathode wire 22 Insulation plate 23

24 25 26 27 Battery case Current interrupter Bending plate PTC device Battery cover 2 8 100 100a 100b Gasket Microporous membrane Upper end of test piece Lower part of test piece 46-

Claims (1)

200830616 X. Patent Application Range: 1. An electrode composite comprising a first microporous membrane separator comprising high density polyethylene A and a second microporous membrane separator comprising high density polyethylene B, the first The anode separator and the cathode sheet are alternately sandwiched with the second separator, and the gap temperature difference of the separators is within 5 ° C, wherein the high density polyethylene A has 0.3 or more per 10,000 carbon atoms. The end vinyl concentration (measured by infrared spectroscopy) and has an average molecular weight of 1xl 〇6 or more of ultrahigh molecular weight polyethylene, and, high density polyethylene B has 每 every 10, 碳 carbon atoms. 2 or less terminal vinyl concentration (measured by infrared spectroscopy) and ultra high molecular weight polyethylene. 2 · The electrode composite of claim 1 of the patent scope is in the form of a spiral tube. 3. The electrode composite of claim 2, wherein the first spacer is disposed on an inner surface of the cathode sheet, and the second spacer is disposed on an outer surface of the cathode sheet. 4. A non-aqueous electrolyte battery having a discharge capacity of 1,500 mAh or more and a capacity recovery rate of 60% or more, comprising an electrode having a first microporous membrane separator and a second microporous membrane separator a composite body having a structure in which the first and second separators are alternately sandwiched between the anode sheet and the cathode sheet, and the difference in the open circuit temperature between the first and second separators is within 5 ° C, Among them, high-density polyethylene A has a temperature of 0.3 or more per 1 〇, and a carbon atom is -47-200830616 a terminal vinyl group (measured by infrared spectroscopy) and having an ultrahigh molecular weight polyethylene having a weight average molecular weight of lxl 06 or more, and a high density polyethylene B having a terminal vinyl concentration of 0.2 or less per 10,000 carbon atoms. Infrared spectroscopy) and ultra high molecular weight polyethylene. -48-