TW200845464A - Separator for electric accumulator and electricity accumulation device - Google Patents

Abstract

A separator for electricity accumulation device is characterized in including a cellulose polymer. The film thickness of that separator is 1 μm - 30 μm, the porosity is 20%-90%, and the maximum hole size is smaller than 2 μm. Further, the appearing activation energy (-ΔG) with respect to the ions conduction is given with positive value in the temperature range of 120 DEG C to 180 DEG C.

Description

[Technical Field] The present invention relates to a separator for an electric storage device and a storage 7L member in which the separator is disposed. In particular, the electric double layer capacitor and the aluminum electrolytic capacitor 4 are separators for a storage element which are useful for a nonaqueous electrolyte battery such as an ion battery and which are excellent in heat resistance, and an electric storage element composed of the separator. . [Prior Art] In recent years, power storage components have been developed in the direction of low weight and miniaturization, and electronic devices such as mobile phones and computers have been utilized. In the field of power storage components, there will be a trend toward further miniaturization and high capacity. As a storage element

In terms of degree, a small pore diameter having high heat resistance is preferred. According to the viewpoint of miniaturization and high capacity of the storage element, the separator is used, from the viewpoint of the performance surface,

As long as the high resistance loss 121060.doc 200845464 can be reduced, from the performance point of view, the electric moon element j as the better electric energy component liquid 0 electric storage 70 pieces of internal resistance is green "... electric bow lead wire The resistance, the connection resistance of the lead and the mooring, the dielectric body έ0 . ^ ^ ^ ^ The sum of the electric 1 Μ and the electrolyte resistance, and the 4 j shell series resistance. Among them, the film thickness of the cow is on the electrolyte resistance class. Therefore, how to make the film thickness thin without impairing the performance becomes an important part. 先前 Previously as a separator for storage elements, general Nila hemp paper and forged cellulose have good feelings. ,,, and horse paper. The cellulose formed by the warfare and the like, in general, the separator of the refined paper: 'because of its thicker' is not conducive to the small size of the capacitor: the thinner of the electrolytic paper formed by the fiber, However, the thickness is limited to a minimum of 40 μm. The common disadvantage of the paper-based separators is that the holes are only large when they are thin and cannot be fully captured from the electrode, κι a ♦~. The life of the particles that are prone to short-term is significantly shortened. For example, in the publication of the Japanese Patent Laid-Open Patent Publication No. Hei No. 4, a laminated film of a fibrous micro-porous film and a polyethylene microporous film using a perforation method is disclosed. It is a small active material for the electrode active material necessary for the battery material. However, the thickness of the cellulose paper is thicker, and if it is strong, "*...bei! The early maturity area becomes thicker and becomes a requirement for a small pore size and a small pore size. Therefore, the ',, and the method satisfy the thickness ^.., for the fiber In the case of plain paper and polyethylene, the formation of laminated enamel, there will also be a problem that the whole area becomes thicker and becomes a larger pore size. In this publication, poly 121060.doc 200845464 Ethylene microporous membrane The opening is caused by laser perforation, and the aperture of the film is as large as 10 μηι.

In Japanese Laid-Open Patent Publication No. Hei 9-213296, a separator for a battery formed by laminating paper, a polyolefin-free nonwoven fabric, a woven fabric or a microporous film is disclosed. Since the mixed paper is a cellulose fiber and a synthetic fiber, there is a problem that the thickness becomes thick, or even if the thickness is thin, there is a problem that the thickness per unit area becomes large and becomes a large pore diameter. The thickness of the separator disclosed in the eighth report is 46-9 _, so that the volume occupied by the two spacers is increased, which is disadvantageous for the capacity of the battery. In Japanese Laid-Open Patent Publication No. Hei 7-22〇71〇, it is disclosed that an electric knife spacer 4 formed by multilayering a cellulose paper, a polyethylene microporous film or a microparticle layer is necessary. The trapping ability of the electrode active material: the separator is required to have a small pore diameter, and on the other hand, the film of the knife spacer is required to be a film in order to achieve high capacity. However, since the blade member disclosed in the publication uses cellulose paper, there is a problem that the overall film thickness becomes thick or the unit area becomes thick and becomes a large diameter. In Japanese Laid-Open Patent Publication No. Hei 10-256088, there is an electric double layer capacitor which uses a cellulose paper as a separator. However, in general, the thickness of the Fibrous knife spacer is 50 μm to 100 μm, which is disadvantageous for miniaturization of the electric grid because of its thick thickness. Further, although it has a thin cellulose paper, since not only the holding amount of the electrolytic solution is often not good, but also the retention of the electrolytic solution is low, there is a tendency that the electrolytic solution moves below the capacitor, and the electrolytic solution in the separator is generated. Unevenness - When it is severe, t appears as the gate of the electrolyte from the outflow θ ^ Τ ; Further, when the thickness of the separator is thinned, the diameter of the separator is increased, and the metal particles which are detached from the electrode cannot be caught, and the short circuit is likely to occur, thereby causing a problem that the life of the capacitor is remarkably shortened. On the other hand, when a microporous membrane is used as the separator, the small pore diameter is sufficiently maintained to capture the detached metal particles, so that the thickness of the separator can be reduced, which is advantageous for miniaturization or high capacity of the capacitor and electrolysis. The advantage of high liquid retention.

In the battery separator, a film composed of regenerated cellulose is used as a separator for a battery using a cellulose-based film, as disclosed in Japanese Laid-Open Patent Publication No. Hei. In this publication, it is actually revealed that the porosity is 0 /. A technique in which cell phantom (registered trademark) is immersed in ethanol and swelled, and dried to make it porous. However, as shown in the following Comparative Example 4 and Comparative Example 5, in the above method, the porosity of the actually obtained microporous film stayed at a level of several %, and there was no permeability at all, and it was not utilized as a separator for a battery. value. In the Japanese Patent Publication No. Hei 11-86827 and Japanese Patent Laid-Open No. 2000-4, it is disclosed that there is a non-porous film on the surface of the slufen, and the pores of the squeegee and the shovel; The facts indicated are well known to those skilled in the art of cellulose technology. It is also well known that the metal ions having the angstrom scale are transmitted because the swell of the sulphonate upon contact with the aqueous test solution. The heat resistance of the spacer is also indispensable at this time. On the other hand, it is as important as thinning that heat resistance is one of the properties of the component when it is molded. A capacitor having a microporous membrane as a separator is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The microporous membrane used in this publication has a film thickness of 25 and has a low electrical resistance, which is advantageous for downsizing or high capacity. An electric double layer capacitor using a microporous film such as a polyethylene resin as a separator is disclosed in Japanese Laid-Open Patent Publication No. Hei-4-74405. An electrolytic capacitor using a hydrophilic polyethylene or polypropylene resin microporous film as a separator is disclosed in Japanese Laid-Open Patent Publication No. SHO 59-140429. An electrolytic capacitor using a microporous membrane made of ABS resin (acrylonitrile-butadiene-styrene, acrylonitrile, butadiene, styrene copolymer) as a separator is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 0-35852. In the "Electrical Double Layer Capacitor and Power Storage System" published by Yukamura Diff (published by Nikkan Kogyo Shimbun, issued on March 31, 1999, pages 66 to 68), it is revealed that the polytetrafluoroethylene resin is micro. The porous film is used as an example of a separator of the electric double layer capacitor 5|. In general, in the production step of the organic electrolytic solution capacitor, the step of removing the moisture contained in the organic electrolytic solution by the absolute drying treatment is included. Since the absolute drying process is at 15 〇. (The above-mentioned high temperature is required, and the separator is required to have heat resistance under the high-temperature condition. However, the above-mentioned Japanese Patent Laid-Open No. 51-18851, Japanese Patent Laid-Open No. Hei-4-74405, and the Japanese Patent Application No. Microporous 121060.doc -10- 200845464 film using polyacetal resin or polypropylene resin disclosed in Kai-A 59-14〇 429A, since the crystalline melting point of the resin is 130 < t 135 (t or 16 (TC ~ 165 °c or so, the heat is not sufficient. That is, since the temperature is much lower than the temperature of the refining point, the transmission function of the separator is impaired. Therefore, the current situation is that the general capacitor cannot be widely used. Further, in the above-mentioned Japanese Patent Laid-Open Publication No. SHO-47-35852, it is disclosed that the ABS resin constituting the microporous film has heat resistance characteristics, but actually, the glass transition point is about 115. The thermoplastic resin is not sufficient in heat resistance. f For the polytetrafluoroethylene resin disclosed in "Okamoto Capacitor and Power Storage System" by Okamura Diff, the crystal melting point of the resin is 35 〇. However, since the microporous film made of a polytetrafluoroethylene resin is difficult to form, it is liable to cause a problem of unevenness in performance such as a film thickness. A nonaqueous electrolyte such as a lithium metal secondary battery or a lithium ion secondary battery is used. The battery is equipped with a safety valve, a temperature fuse, a current fuse, etc. when the battery is short-circuited between the positive and negative terminals of the battery to cause the battery temperature to rise, or when an abnormal situation such as heating is applied from the outside. Various protective mechanisms such as PTC (P〇Sitive Temperature Coefficient) components. In addition to the above-described protective mechanism, there is a separator having a function of a thermal fuse. The separator is composed of a polyolefin microporous membrane. When the temperature of the battery rises, the polyolefin softens or melts, so it has the function of blocking the separator and blocking the ion current between the electrodes. The so-called temperature fuse function refers to the high temperature region, accompanied by the blockage of the hole, the impedance. Rise and rise, thereby blocking the ion current between the positive and negative electrodes to prevent the battery temperature of 121060.d Oc -11 - 200845464 升之 function. With this temperature fuse ^ - ^ ^, the separator of the knives is necessary for lithium gold. The battery of the non-aqueous electrolyte is especially for small-capacity batteries, even if the battery is positively φ There is a short circuit in the anus, and the temperature of the battery rises. The temperature of the partition is limited. w ☆ No fuse can also function to limit the temperature rise. Therefore, before, such as j < knife spacers can be sufficient Respond. Then, when the small-capacity battery is heated from the outside, it is heated, or for the battery.

L The internal temperature produces a large-capacity electricity of the temperature difference, and even if the pores of the separator are blocked by softening or melting, the temperature inside the battery does not rise, and soon the separator melts, flows, and ruptures. Budan I can cause the worst of the battery explosion. In recent years, it has been demanded that the separator has a heat-resistant function capable of withstanding an increase in temperature in the event of occurrence of the above-described battery failure, and the degree of demand is becoming higher and higher. Reducing the internal resistance of the battery has also become one of the methods for achieving a large capacity. Therefore, the requirements for high strength and thinning of the separator are also higher. The thinning of the 77 spacers has the effect of lowering the internal resistance, while the other side has in fact also has a side effect of impairing the heat resistance. Therefore, when making polyolefins, it is an epoch-making time to impart a potential heat-resistant function to the cellulose-based materials more effectively by notifying the separators, the strength of the film, the strength of the film, and the function of the temperature fuse. Excellent battery separator. W also has a technology that ensures the safety of the battery without using the above-mentioned thermal fuse function. For example, in Japanese Patent Laid-Open No. 2003-288946, No. 121060.doc -12-200845464, the following technique is not disclosed: as a separator that does not have a temperature fuse function, specifically, Weiyin secret (four) dimension line, set the voltage detection mechanism in the battery and the return current path ^ ^ ^ in conjunction with it, the bath is fine, so the heat of the overcharge is not enough. Further, the separator disclosed in the publication is a cellulose paper which is insufficient in terms of a film and a small pore diameter. It is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The electrical system disclosed in this publication is a meaningful proposal 'however', for example, when the temperature is far beyond the temperature exemplified by the function of the thermal fuse due to external heating, there is a lack of high-temperature reliability.

A non-aqueous electrolyte battery such as a (four) sub-secondary battery as a separator. However, the separator in the publication is also cellulose paper, which does not satisfy both the film and the small pore diameter. [Problems to be Solved by the Invention] An object of the present invention is to provide a separator for an electric component which is excellent in heat resistance. Further, an object of the present invention is to provide a storage element which is heat-treated in a component=step In the case of the internal heat generated during the failure and the heating of σρ outside the s-sister, it is highly resistant to exposure to high temperatures, and it is difficult to cause short-circuit failure due to the electrode (4) passing through metal particles, etc., and can be adapted to miniaturization and High capacity requirements. [Technical means for solving the problem] The inventors of the present invention have made intensive studies in order to solve the above problems, and it has been found that 'the specific cellulose-based microporous material is useful as a separator for a storage element.' When the separator is used, even if it is exposed to a high temperature of 121060.doc -13 - 200845464, no problem occurs, and an electric storage element which is advantageous for miniaturization and high capacity can be obtained, and the present invention has been completed. That is, the present invention is as follows. (1) A separator for a storage element, characterized in that it is composed of a cellulose microporous film having a film thickness of 1 μm to 30 μm, and pores

The degree is 20%~90%, the maximum pore control is below 2 μπι, and in the temperature range of i20 °C~180 °C, the apparent activation energy (_AG) related to ion conduction provides a positive value of 0 Γ 2 · In the separator for a storage element according to the above aspect, the apparent activation energy (_Δ(}) is 0.01 eV to 0.20 eV. 3_ The separator for a storage element according to 1 or 2 above, wherein the cellulose-based microporous membrane comprises regenerated fiber 4. The separator for a storage element according to any one of the above 1 to 3, wherein a breakdown strength per μ μ μm film thickness is 〇·〇 3 N or more. 5. The above 1 to 4 A separator for an electric storage device, wherein the component tether is selected from the group consisting of an electric double layer capacitor, an aluminum electrolytic capacitor, and a lithium ion battery. 6. A separator for a storage element, characterized in that it comprises a composite micro In the porous film, the composite microporous film comprises a cellulose-based microporous layer and a porous layer containing a polyolefin resin, and the polyolefin layer-containing porous layer has a replacement ratio per unit area of 3 〇 wt%. ~8〇wt%, the separator has a film thickness of 1 μχη~30 μηη, and a porosity of 20%~90%, most 7. The separator for a storage element according to the above-mentioned item 6, wherein the polyolefin resin is a polymer resin 121060.doc -14-200845464, and the storage element battery is used. 8. The separator for a storage element according to the above 7 The battery is a lithium ion battery. 9. An electric storage device, characterized in that the separator of any one of the above-mentioned 丨8 is interposed between the electrodes. 10. The electric storage device according to the above 9, wherein the electric storage device The component is selected from the group consisting of an aluminum non-solid electrolytic capacitor, an aluminum solid electrolytic capacitor, an electric double layer capacitor, and a lithium ion secondary battery. 11 · The livestock electrical component of the above 9 a solid electrolytic capacitor using an electrolyte containing at least one solvent selected from the group consisting of γ·butyrolactone, ethylene glycol, glycerol, ethylene glycol monomethyl ether, and hydrazine-methyl methacrylate 12. The storage element according to the above 9, wherein the storage element is an aluminum solid electrolytic capacitor using at least one electrolyte selected from the group consisting of tetracyanoquinone dioxane, polyacetylene, and poly Pyrrole, A polythiophene, a polydioxane, an ethyl oxime, a polyisothianaphthalene, or a polyaniline. The storage element according to the above 9, wherein the storage element is an electric double layer capacitor, and the capacitor is selected from the group consisting of An electrolyte of at least one of the following substances, namely, γ-butyrolactone, ethylene carbonate, propylene carbonate, cyclobutyl hydrazine, acetonitrile, 1,2-dimethoxy ethane, tetrafluoroborate Triethylmethanesulfonic acid, mercaptoethyl imidazole rust, and bis(trifluoromethanesulfonyl) quinone iminyl mercaptoethyl imidazole rust. 14. The electric storage device according to the above 9, wherein the electric storage device is a lithium ion secondary battery 121060.doc -15-200845464, the battery using an electrolyte containing at least one of a bath selected from the group consisting of γ- Butyrolactone, 2-methyl I·butyrolactone, hexamidine lactone, γ-valerolactone, dinonyl carbonate, diethyl carbonate, monopropyl sulphide, methyl ethyl sulphate, acid-breaking Ethyl ester, propylene acrylate, butyl butyrate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, cyclobutene, 1,2-dimethoxy ethane, 1 , 2-diethoxyethane, tetrahydrofuran, 2, mercaptotetrahydrofuran, and 3-mercapto-1,3-dioxime. The invention will be described in detail below.

The separator for the electric storage device of the present invention is preferably in the form of a sheet or a film and a composite of the above. Further, it is preferable that the structure is a film in which a large number of minute holes are formed, and a microporous film is particularly preferable. The shape of the separator is a microporous film, which can be made thinner and has a structure having uniform pores, so that the disadvantage of the short circuit of the element can be reduced. The separator for an electric storage device of the present invention substantially contains a cellulose-based polymer such as natural cellulose or regenerated cellulose. The natural cellulose may, for example, be pulp, cotton, cotton linters, bacterial cellulose (bacterial cellul: chemically and physically modified natural cellulose after regeneration) = vitamins, viscose ("regenerated cellulose, recycled fiber" The cellulose used in the eight-knife separator for the electric storage device of the present invention is an exaggerated cellulose, and is also the same as the knife. The best regenerated cellulose. In the present invention, the weight of the cellulose is 50,000 to 250,000, and the knives 1 are preferably 30,000 to 30, more preferably 100,000. ~ 2 million. When the weight is flat 121060.doc 16· 200845464 The average molecular weight is internally short-circuited and formed. This Qimingzhong 'because of the partition material raw material fiber Xinfu Gu Bazi has the following effect. μ Jingyi a knife, thus the first effect For the heat resistance is excellent, in the group 妒萱 _ heat treatment does not produce 孰 shrinkage, size = 1 7L parts of the step of adding U shrink 'size stability, so it can prevent damage

The U π component characteristic β, in the case of failure in the generation of a lithium ion secondary battery, is also durable, so that the membrane of the separator can be prevented from being damaged. It is also heat-resistant when subjected to any external heating in the use environment of the component, so that the component characteristics are prevented from being impaired. The second action is that the affinity with the electrolyte is good, and the cellulose-based polymer has the property of rapidly permeating all the electrolytes under normal temperature and pressure, and is chemically stable. The separator for an electric storage device of the present invention has a film thickness of from 1 μm to 30 μm, preferably from 5 μm to 30 μm, preferably from 7 μm to 30 μm. When the film thickness is less than i, the strength of the microporous film is insufficient, and the trapping of the detached metal particles is insufficient. When the film thickness exceeds 30 (1111, the volume occupied by the storage element is increased, which is disadvantageous to the miniaturization or high capacity of the element. The porosity of the separator for an electric storage device of the present invention is 2% to 9〇. %, preferably 疋25%~75%, preferably 30%~60%. When the porosity is less than 2〇〇/0, the ion permeability is insufficient, and the electrical resistance becomes high, which is disadvantageous for the storage element. Further, when the porosity exceeds 9〇%, the mechanical strength of the separator is lowered, so that the reliability of the failure such as a short circuit cannot be ensured. 121060.doc -17- 200845464 The largest separator for the storage element of the present invention The pore diameter is 2 _ or less, preferably 〇·〇1 μιη~1 μ„ι' is preferably 〇〇2 〇~〇2 _. When the maximum pore diameter exceeds 2 _, not only the electrolyte retention is insufficient Moreover, the metal particles or the carbon particles constituting the electrode are easily passed through the micropores to cause a short circuit. Further, when the maximum pores; X g Λ Λ ^ are less than 〇·〇1 μιη, sufficient porosity cannot be ensured, and thus electrolysis is performed. The liquid retention is insufficient.

C ϋ The electrical resistance of the separator for a storage element of the present invention is preferably 20 or less. More preferably, 15 or less is preferably 1 〇. When the electrical resistance is within the above range, power storage having excellent capacity can be obtained. In the separator for an electric storage device of the present invention, the puncture strength per ΐμη film thickness is preferably 0.03 Å or more, more preferably 〇〇4 Ν or more, and most preferably 0.05 Ν or more. The strength is required for the maximum load in the breakdown test, and the value of 1 is determined by the film thickness of the micro-emulsion film. Therefore, the thinner part of the invention is evaluated for the practical strength of the separator material. The better index 疋' is based on the breakdown strength of the thickness of the parent unit. The breakdown strength is too low, which is easy to produce a short circuit. The membrane factory gives it: the invention uses the separator for the storage element at 15 〇t... , ~ view 'better is.%~25%, and then good, 0〇/〇~20./., the best is 〇%~1〇%. 疋^ ^ ^ and the cross section of the knife spacer A in the biaxial direction shrinkage rate is good, and the vertical and horizontal directions are all in the _ direction.

Heat: If the shrinkage rate is too high, it cannot cope with the use environment of the storage element or the manufacturing process. - Heat treatment or stepping up the temple, so there is a short circuit caused by the dimensional change of the 121060.doc -18- 200845464 microporous film. Or the tendency of internal resistance to increase. On the other hand, the heat shrinkage rate is too low, meaning that the separator will thermally expand, but this is rare. The apparent activation energy of the partition of 70 pieces of electricity stored in Ming Dynasty must be positive, preferably 0.01 eV~0.20 eV, more preferably e2 eV~〇2〇ev, and most preferably 0.02 eV~ 0.15 eV. (

The positive or negative of the apparent activation energy indicates the temperature dependence of the ionic conductivity, and the energy level indicates the degree of dependence. When the apparent activation energy is positive, the temperature rises and the ion conductivity increases. When the apparent activation energy is negative, if the temperature rises, the opposite means that the ion conductivity decreases. That is, the absolute value of energy indicates the temperature dependence. For the separator having (4) heat, the apparent activation energy becomes a measure of high-temperature durability, and for the polyolefin-based separator having a shutdown function, the apparent activation energy Become an indicator of the operation of the shutdown function. Therefore, in the present invention, in the extremely high temperature range of i2 (rc~18 (rc), the apparent activation energy must be a positive value. When the apparent activation energy exceeds 〇·2~, it can be considered to be far more than ion movement or diffusion. The activation energy level may cause internal short-circuiting of the separator, melting of the separator, dissolution, etc., as another aspect of the present invention, and may further laminate the porous layer containing the polyolefin resin. The separator for a storage element according to another aspect of the invention is characterized in that the separator for a storage element includes a composite microporous membrane in which a cellulose microporous layer and a porous layer containing a polyolefin resin are combined. The porous layer containing the polyolefin resin has a weight fraction of 30 wt% to 80 wt% per unit of 121060.doc •19-200845464, and the film thickness of the separator is i μηι 30 30 μιη, and the porosity is 20%. ～90%, the maximum pore diameter is 2 μηι or less. As the polyolefin resin, a polyethylene resin is preferred, and a high-density polyethylene resin and/or an ultra-high molecular weight polyethylene resin are preferred. The polyethylene resin has咼 strength material, into It has a suitable crystal melting point for displaying the function of the temperature fuse. The weight average molecular weight of the polyolefin resin is preferably from 1 to 10,000 to 10,000, more preferably from 150,000 to 3,000,000, and most preferably 2 〇. When the weight average molecular weight is in the above range, the mechanical durability is sufficient, and the separator is easily formed. The crystalline melting point of the polyolefin resin is preferably 1 〇 (rc 165 C > c, More preferably, it is 100 ° C to 140 ° C, and the best *13 (rc 14 14 (rc.) If the melting point of the crystal is in the above range, the pores are clogged when the temperature of the battery rises, thereby effectively blocking the ion current. The function (the function of the so-called fuse temperature) prevents the rise of the battery temperature and does not limit the battery use temperature to a low temperature. From the separator containing the composite microporous film of the present invention, the porous layer containing the polyolefin resin is The weight fraction per unit area is preferably 3〇wt%~8〇wt%, more preferably 40 wt%~8〇, and most preferably 5〇(9)~(9) wt%. When the weight per unit area When the fraction exceeds (four) wt%, the amount of heat shrinkage increases, but it is not hot. On the other hand, when the weight fraction per unit area is less than 30 Wt%, there is a concern that the pore clogging at a high temperature is insufficient, which is not preferable. In the present invention, 'as a storage element, for example, an electric double layer Electrochemical capacitors such as capacitors or redox capacitors; non-solid electrolytic capacitors or electrolytic capacitors such as aluminum solid electrolytic capacitors; and non-aqueous electrolyte batteries such as lithium metal secondary batteries or lithium ion secondary batteries Among them, an electric double layer capacitor, an aluminum non-solid electrolytic capacitor, an aluminum solid electrolytic capacitor, and a clock ion secondary battery are preferable. The so-called aluminum non-solid electrolytic capacitor refers to an aluminum box for the anode and the cathode, and the like. The dielectric uses an aluminum oxide film 'and uses an electrolyte containing an electrolyte as a true cathode. 0 as the electrolyte, preferably a primary, secondary, or tertiary boronic acid, a saturated aliphatic dicarboxylic acid, an unsaturated aliphatic dicarboxylic acid, an aromatic monocarboxylic acid, an aromatic dicarboxylic acid, or an aromatic oxidized carboxylic acid. Grade or quaternary ammonium salt. Further, as the solvent of the electrolyte, a polyvalent alcohol, a lactone, an ether, a guanamine or a cyclic carbonate is preferred, and more preferably, 丫_丁内酉曰, E2 is used alone. An alcohol, glycerin, ethylene glycol monomethyl ether, and N-methyl decylamine may be used by mixing the above two or more. The method of assembling an aluminum non-solid electrolytic capacitor as a preferred storage element of the present invention is shown below. The anode foil is an aluminum foil formed in such a manner that electrochemical etching treatment is performed on both sides, and thereafter, an ammonium adipic acid aqueous solution is used for chemical conversion treatment to form an aluminum foil having an oxide film having a thickness of about 1 Å on the surface. . The cathode foil is an aluminum foil having a thickness of about 6 〇 μηι after electrochemical etching on both sides. The anode foil, the separator, the cathode foil, and the separator were alternately stacked in this order, and wound into a coil shape to produce a cylindrical element. The cylindrical element was housed in a metal can, and an electrolytic solution was injected and sealed to obtain an electrolytic capacitor. 121060.doc 200845464

步骤 In the step of assembling the electrolytic capacitor, when the separator composed of the cellulose paper is used, the electrolyte solution is poorly maintained due to the excessive pore size, and the electrolyte depletion failure such as dryness is liable to occur. However, when a separator having a small pore diameter composed of a cellulose-based polymer is used in the present invention, the electrolyte is introduced by the capillary effect, so that it is difficult to cause the above-mentioned trouble. Further, since the separator composed of the cellulose-based polymer has a thinner thickness than the paper and has a uniform pore structure, it has an advantage of contributing to an increase in the electrostatic capacitance of the capacitor and the reduction in the short-circuit defect. The solid electrolytic capacitor of Mingming refers to the use of the foil for the anode and the cathode, and the aluminum oxide film is used for the dielectric body, and the solid electrolyte is used as the true cathode. As the solid electrolyte, a low molecular organic conductor, an aliphatic coherent conductive polymer, a complex bicyclic coordinating conductive polymer, and a heterogeneous atomic conductive polymer are preferable, and more preferably, alone. Tetracyanate, dimethyl sulfonate (TCNQ complex), acetylene, polythiophene, polythiophene, polydioxyethylthiophene, polyisothionaphthalene, and polyaniline are used, or two or more of the above two types are used in combination. The electric double-layer capacitor refers to the application of the following electric double-layer principle, that is, when the conductor is immersed in the electrolyte, the thin insulating layer formed on the interface is sandwiched between the conductor and the f-solution.贞 charge. (4) A foil or the like having activated carbon or the like is used as the anode and the cathode. The electrolyte is preferably a quaternary ammonium salt, more preferably tetraethylammonium tetrafluoroborate, methyltriethylammonium tetrafluoroborate, & tetraethylammonium fluorophosphate or tetrafluoroborate tetra Ethyl scales. As the solvent of the electrolyte, it is preferably 121060.doc -22- 200845464 polyvalent alcohol, lactone or cyclic carbonate, cyclic sulfonate, ether, nitrile and ionic liquid, of which, more preferably, alone Use "butyrolactone, ethyl carbonate, propylene carbonate, sulfolane, acetonitrile, i, 2-dimethoxyethane, methyl ethyl imidazolium tetrafluoroborate, methyl ethyl imidazole trifluoromethanesulfonate And bis(difluoromethanesulfonyl) quinone imine methylethylimidazolium, or a mixture of two or more.

C The following shows a method of assembling an electric double layer capacitor as a preferred storage element of the present invention. Activated carbon and carbon black were supported on the aluminum mesh, and the separator was placed as a bipolar electrode (4) (four) pole and a cathode, and was wound into a cylindrical shape by a winder to form a coil-shaped element. The component is housed in a metal can, and after the electrolyte is injected, (10) is performed. c~15 (heating around rc, A completely removes moisture and seals, thereby obtaining an electric double layer capacitor. In the step of assembling the electric double layer capacitor, for example, when using a separator composed of polysmoke resin, heating The step separator will shrink, thereby causing a bad condition of the road. Moreover, in the use of the separator composed of cellulose paper, since the thickness is thick, the capacity does not become large. The film is separated from the cell layer by the polymer core, so it has heat resistance, so it will not be damaged during the heating step, and the thin film can be used to improve the capacity of the capacitor. The so-called lithium ion secondary battery refers to For example, a positive electrode material or a genus oxide' negative electrode active material uses carbon or graphite, and stores and releases lithium in the negative electrode as Reynolds first shell. Electrolyzed shell, preferably strong acid or super acid lithium salt, better in 121060.doc -23- 200845464 疋 'perchloric acid clock, lithium hexafluoroantimonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium double (two Fluorine Sulfhydryl) decylamine, lithium bis(pentafluoroethylsulfonyl) decylamine, monochamusic acid, lithium pentafluoroethanesulfonate, lithium octafluoropropane sulfonate, etc. As an electrolyte solvent, preferably It is a lactone, a carbonate, a carboxylate, a cyclic sulfonate or an ether. Among them, it is more preferable to use γ-butyrolactone, 2 methyl-γ-butyrolactone alone, and acetamidine.丫_butyrolactone, 丫-valerolactone, dimethyl hydrazine carbonate, acid Ύ ach, ,. Wenyiyi 6 曰, dipropyl carbonate, ethyl methyl carbonate, carbonic acid 乙 ◎ ® 曰, niacin Propylene ester, butylene carbonate, methyl acetate, ethyl acetate, propyl hydrazine, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxy B Burning, tetrahydrofuran, 2-methyltetrahydrofuran, and 3-mercapto-1,3- No. 1 ' either used in combination of two or more. Hereinafter, a lithium ion secondary battery is not assembled as a preferred storage element of the present invention. As the positive electrode active material, for example, a lithium metal oxide containing LiC〇2〇4 or LiMn2〇4 is used. The positive electrode is a substance formed in the following manner: (/f contains a metal oxide, acetylene black, polypredylene resin, and uses N_methyl tonalone as a dispersing medium to prepare a slurry, and the slurry is applied to:,,, and current collector The two sides of the foil of about 2 , are dried and compressed, thereby forming an active material layer having a thickness of 1 〇Q μιη on both sides of the aluminum foil. For example, a black-wound phase-phase pitch carbon microsphere of a reverse-phase material. The negative electrode uses a substance formed by using a carbon material, a polyvinylidene fluoride resin, and using a methylpyrrolidone as a dispersion medium to prepare a slurry. The slurry is applied to both sides of a steel box having a thickness of 14 121060.doc -24-200845464 : as a current collector, and is dried and shrunk, whereby the two sides of the tear are respectively formed into a thickness of just Active material layer.

On the positive electrode and the negative electrode, the positive electrode terminal and the negative electrode terminal are respectively set. The positive electrode, the separator, the negative electrode, and the separator were stacked in this order, and wound up in a cylindrical shape using a winder, and housed in a battery can. Used as a liquid, electrolyte! A hexafluorophosphate clock of about mol/liter is used, and a mixed solvent of methyl ethyl acetonate and ethyl carbonate is used in the solvent. In a battery can in which a cylindrical electrode was housed, an electrolyte solution was injected, and the battery was sealed by vacuum impregnation at a temperature of about right and left. In the step of assembling the battery, when the separator composed of the polyxanthene resin is used, the vacuum impregnation in the above-mentioned heating state must be performed, and the separation of the cellulose-based polymer is used in the present invention: The heat and the vacuum are not required, and the electrolyte has a characteristic of spontaneous permeation at normal temperature and pressure, so that the manufacturing steps of the battery can be simplified, which is useful. In the separator for a storage element according to the present invention, a method of producing a microporous film composed of a cellulose-based polymer may, for example, be a method consisting of the following steps: (a) Dissolving and doping the raw material cellulose a step in the copper ammonia solution; (b) a step of smoothly casting the above-mentioned dopant on the substrate; (c) after the above step (b), immersing it in the coagulating liquid to make the doping a step of coagulating the substance; (d) after the step (c) above, immersing it in the regenerant to regenerate the cellulose; (e) after the above step (b) and/or step (d), The step of immersing the solution in the cleaning solution 121060.doc -25-200845464 to remove the coagulating liquid and/or the regenerating liquid; and (f) the step of drying the organic solvent after replacing the washing liquid with an organic solvent. Further, an example of a method for producing a microporous film formed of a porous layer composed of a cellulose-based polymer and a porous layer composed of a polyolefin resin may be a method in which the production is high in cellulose. In the step (8) of the method of constituting the micro-fusible film, the dopant is cast on the poly-smoke microporous film.掺杂 The dopant used in the present invention refers to a cellulose-based polymer i WH5 Wt%, ammonia 4 wt% to 15 (four), and copper! The heart (a) pain is composed of a solution. In order to improve the solubility of cellulose, an alkali such as sodium oxysulfide may be further added, or an organic solvent such as acetone may be added for the purpose of phase separation control. Further, depending on the purpose, a composite material such as an inorganic filler, a crystal, a filament, or a short fiber may be added to the doping composition used in the present invention. In addition, C: winter anti-emulsifier, anti-static agent, flame retardant, 'slip agent, UV absorber, and other additives can also be mixed. The coagulating liquid used in the present invention may be a liquid in which ammonia is dissolved, particularly preferably hydrazine, water, aqueous sodium hydroxide solution, dilute sulfuric acid, and aqueous acetone solution. The term "solidification" refers to a decrease in the concentration of ammonia contained in the dopant, which causes the cellulose to undergo a phase-cracking phenomenon. By using the above coagulation liquid separately, it is possible to obtain a microporous film having various characteristics. For example, when the coagulation liquid is sodium oxychloride water, a microporous membrane having a porosity of 20% to 40% can be obtained; a microporous membrane having a porosity of 35% to 55% can be obtained for the water temple; _Aqueous solution 121060.doc -26- 200845464, a microporous membrane having a porosity of 50% to 70% can be obtained; and in the case of dilute sulfuric acid, a microporous membrane having a porosity of 70% or more can be obtained. The regenerating liquid used in the present invention may be an acid for dissolving copper which is mismatched with cellulose, and particularly preferably dilute sulfuric acid. The cleaning liquid used in the present invention is required to elute residual copper ions and wash the coagulating liquid or the regenerating liquid. Therefore, water is preferred.

C The organic solvent used in the present invention must have the property of dissolving water and volatility. As the organic solvent, it is preferred that the solubility of water is 1 Wt/. In the above, it is preferred that the boiling point is from room temperature to 130 ° C. The organic solvent may, for example, be a ketone, an alcohol or a M ^ ^ ^ oxime as a ketone, and may have acetone or a methyl group. Ethyl ketone, methyl propyl ketone, methyl isopropanone, diethyl Siq, methyl _n-butanone, and methyl isobutyl ketone. /, as an alcohol, there are methanol, ethanol, n-propanol, isopropanol, butanol, 2 · butanol, isobutanol, butanol, indyl alcohol, % pentanol, 2 - methyl dibutyl Pre-t-pentanol, 3-methyl-2-butanol and neopentyl alcohol.

As scales, there are diethyl ether, divalent, tri-sonic, tetrahydroanthracene, H-methylmercaptoethane, 1,2,diethoxyethane, 2-methoxyethanol, and oxime-oxy- 2-propanol and the like. Examples of the S oxime include methyl acetate, ethyl acetate, ?-propyl acetate, and H i?. And as a guess, there are B guesses, C guesses, etc. Further, in consideration of adaptability, safety, and safety, the above solvents are alcohols and _. In the above-mentioned step, in the above step, in the step (e) of the use of the cleaning liquid, 121060.doc -27-200845464:, instead of continuing to dry the washing liquid, the organic solvent is used instead.

The step (7) of drying the organic solvent is carried out, whereby the porosity is effectively achieved. T. The separator for an electric storage device of the present invention may be subjected to heat treatment, crosslinking treatment, chemical modification, or the like. [Effects of the Invention] The separator for an electric storage device of the present invention has high heat resistance and is high in strength, and is extremely useful for use in a capacitor material, a capacitor material, and a clock ion battery. Furthermore, the electric storage element formed by using the separator has heat resistance even when exposed to a high temperature, so that it is difficult to cause a short-circuit failure due to the passage of metal particles, so that it is possible to achieve miniaturization and high capacity. Great use. [Embodiment] Hereinafter, the present invention will be further described based on examples. Further, the measurement method, evaluation method, and the like are as follows. (1) Film thickness The separator sample was cut into 10 cm squares, and the thickness of the nine positions was measured using a dial (dialgauge, peacock Ν ο 25), and the average thickness of the nine was taken as the film thickness. The measurement positions were randomly selected from 9 positions separated by more than 3 cm. Film thickness (μηι) = [sum of film thickness at 9 positions (μηι)] / 9 (2) Porosity (single layer structure film) The volume V (cm3) and mass W (g) of the separator are measured and utilized. The following formula is used to calculate the porosity ε (%). In the formula, the density p of cellulose is 1.45 (g/cm3). 121060.doc •28- 200845464 8=100x(l-W/(pxV)) (3) Mass fraction per unit area The multilayer structure of the separator sample was cut 10 cm square and its mass W (g) was measured. Secondly, pay attention to peeling so as not to damage the layers of the multilayer structure, measure the mass WA(g), WB(g) for each layer, and calculate the weight m (g/m2) per unit area of the whole sample and the weight per unit area of each layer by the following formula. mA (g/m2) and mB (g/m2), and obtain the weight fraction wA (wt%), wB (wt%) 〇 mA = l 〇 - 2xI (WAi + WA2 + ... + WAj) per unit area of each layer. mB=l〇-2xI(WBi + WB2+·······WBj) m=10'2xW wA= 1 00xmA/m wB= 1 00xmB/m (4) Porosity (multilayer structure film) The volume V (cm3) and the mass W (g), and using the mass fraction wA (wt%) per unit area in the above (3), wB (wt%), the porosity ε (%) is calculated by the following formula . In the formula, the cellulose density PA was 1.45 (g/cm3) as an empirical value, and the polyethylene density pB was 0.96 (g/cm3) as an empirical value. ε=100χ[(1·1 00x W)/(Vx(pAxwA+pBxwB))] (5) The breakdown strength is measured using a compression tester (KES-G5, manufactured by KATO TECH) with a radius of curvature of 0.5 at the tip of the needle. The breakdown test was performed under the test conditions of 2 mm/sec, and the measurement temperature was 23 ± 2 ° C, and the maximum load E(N) of the failure point was observed. From the maximum load E and the film thickness ί(μιη), the following formula is used: 121060.doc -29- 200845464 Normalization, as the breakdown strength S(N) per 1 μm film thickness. S = E / t (6) Maximum pore diameter Measured according to the bubble point method using a chlorofluorocarbon or alcohol having a surface tension γ of 9 mN/m to 24 mN/m as a wetting liquid. For the wet curve, the applied pressure and the amount of air permeation were measured in the boost mode, and the maximum pore diameter dBP (nm) was determined from the pressure pBp (Pa) of the initial bubble generated in the obtained wet curve by the following formula. ( Ο άβρ=106χ2.8 60χγ/ΡΒΡ (7) The heat shrinkage rate will be cut into a sample of about 1〇cm square, and placed in a constant temperature and humidity environment with a temperature of 23 ° 2 C and a humidity of 65 ° /. After 24 hours. After measuring the size, the sample was placed in a hot air circulating oven at 50 ° C for 2 hours for heat shrinkage test. After the test, the sample was cooled and placed in the above constant/JHL constant humidity environment. After the hour, the sample size was measured again. The aspect ratio of the sample before the test was set to Guangna and Guang (7). After the test, the longitudinal dimension of the sample was set to L1MD and litd, and the longitudinal and transverse heat shrinkage rates c(10) and cTD(%) were as follows. Defined as shown in the formula. CMd=1〇〇x(L°md.Limd)/l〇md

Ctd=1〇〇x(L0xd.L1td)/l〇td (8) In the measuring unit for electrical resistance, the diameter of the unit is set to N. The unit has an AC impedance measuring device and a measuring unit as shown in Fig. 1. Used to form a unit with two 2.0 cm diameter disc-shaped platinum electrodes with a 2.0 cm separator sample. 121060.doc -30- 200845464 Nothing. As an electrolytic solution, it is used in a propylene carbonate solvent and has 〇·8 mol. /. The tetraethylammonium tetrafluoroborate is dissolved as an electrolyte. After the measurement unit was filled with the electrolytic solution, dehydration and defoaming treatment were carried out for 1 hour in a vacuum drying set at 4 ° C, and the measurement was carried out in a constant temperature room of 23 ± 2 . When the frequency range is 40 Hz to 1 〇〇, the frequency is changed little by little, and the AC impedance is measured to obtain each |z|(impedance) and 0 (phase difference). Next, an electrochemical impedance analysis software (manufactured by S〇lartr〇n Co., Ltd.: trademark ZView) was used to obtain the actual electrical resistance r (q·coffee 2) of the separator sample. In this case, as an equivalent circuit, a mode shown in FIG. 2 in which Ri (separator resistance component), CPE (phaseing element), c (capacitor component), and R2 (device resistance component) are assembled is used. Perform assembly. The obtained electrical resistance Rl(Q) was normalized by the electrode area according to the following equation to define the electrical resistance Κ (Ω · cm2) of the separator. R = Rix (1.6 / 2) 2 x 3.1416 (9) Apparent activation energy An AC impedance measuring instrument and a measuring unit were used. In the measuring unit, a separator sample having a size of a metal cylinder was placed between two disk-shaped copper electrodes having a diameter of 1.6 cm to form a unit. The N unit has a configuration as shown in FIG. As the electrolytic solution, it is used in a propylene carbonate = vinegar solvent, and G. 8 m 〇 1% of tetrafluorinated tetraethyl hydride is dissolved as electricity. After the measurement unit is filled with the electrolyte, it is set to 4 〇. 〇之之处 121060.doc -31 · 200845464 Beverage for 1 hour of tax water, defoaming treatment. Next, the γ6 can be placed in the hot air circulation. Take the (four) line from the center and connect it to the AC impedance π tab (tabu) at a temperature of 6. . . ~200. . In the range of the temperature rise, at least every flow = step 2 is set to 'when the temperature is balanced and stabilized, the intersection is performed and the measurement is performed. Again, the measurement is in the frequency range of 40 Hz to 100. 'The frequency is changed little by little, and the AC impedance is measured, and Izl (impedance) and 0 (phase difference) at each temperature are obtained. • /, person, using the electrochemical impedance analysis software (manufactured by S〇lart^n Co., Ltd.: quotient 'ZVlew)' to determine the actual electrical resistance of the separator sample, coffee 2). In addition, 'this is the equivalent circuit' uses Ri (separator resistance into a knife), CPE (phased element), L (coil component), c (capacitor component), (device resistance component), and CPE2 The phase elements are assembled in the pattern shown in Figure 4. The obtained electric resistance R1 at each temperature ((4) was normalized by the electrode area and the film thickness ί (μπι) according to the following formula to define the ion conductivity σβ.πΓ1 of the separator). a=txl〇-2/{R1x(1.6/2)2x3.1416} The vertical axis takes the natural logarithm of the product of the obtained ion conductivity σ and the absolute temperature T(K), and the horizontal axis takes the absolute temperature Τ(Κ) The reciprocal is used to produce the Arrhenius ink dot, and the slope a and the intercept b are obtained based on the linearity. From the gas constant K (8.3145 JK^mol·1), the Avogadro constant ΝΑ(6·0221χ 1023 ιηοΓ1), and the slope a, the apparent activity is defined according to the following formula. 121060.doc -32- 200845464 Chemical-AG (eV).

In(axT)=axT'1+b axT=ebxe-(Kxa)/(KxT) -AG=-Kxa/(NAx 1·6022χΐ〇,) (10) Heat resistance test..., V package low, Yabian As a solution, a solution of propylene carbonate tetraethylammonium tetrafluoroborate (4) (10) liter was used. Make simple components at the two poles. Will, when, according to before and after heating

The partition containing the electrolyte is placed between the recording and the treatment. The simple component is heated in an oven of i5〇°c to heat the ratio of 24/J AC impedance to evaluate the heat resistance. (11) The winding test anode is used in the following manner. The formed book is subjected to electrochemical (10) m treatment on both sides. Thereafter, (4) has been carried out by chemical treatment to form an aluminum box having a thickness of 1 〇〇μιη on the surface. The cathode crucible is used on both sides for electrochemical re-etching treatment with a thickness of 6 〇 _. The anode m pig μ spacer was cut into strips having a length of 7 〇cm and a width of 2.5 (10), and alternately overlapped in the order of yang (four), separator, cathode _, and sub-pieces. Make cylindrical components. The diameter and height of the cylindrical member were measured, the volume was calculated, and the degree of miniaturization was evaluated. (12) Fuse • Short-circuit test Use an AC impedance measuring device and a measuring unit. In the measuring unit, 'used in two circular plate-shaped copper electric wires with a diameter of h6 cm. 121060.doc -33- 200845464 \ The sample of the partition piece which is fixed by the metal cylinder is fixed. The composition shown in 3. In the electrolyte, Shan >; as a / trough [butyrolactone 5 〇 evaluation 10 /. In the mixed solvent of propylene carbonate 25/¥ and 酉夂«ethyl ester 25 wt%, 1 () m〇i / liter of tetrafluorinated acid clock is dissolved as an electrolyte. f After the measurement unit was filled with the electrolytic solution, the dehydration and defoaming treatment was performed for 1 hour in a vacuum oven set to a machine. Γ

The Lj-person's unit is placed in the hot air circulation type tank +, and a thermoelectric pair is installed for monitoring the temperature inside the unit. Remove the lead from the lead plate mounted on the unit and connect it to the AC impedance meter. In the range of 6 G ° C to 200 ° C, the temperature is raised at a temperature increase rate of 2 minutes, and the AC impedance is applied. Furthermore, the measurement is performed under the frequency] and the correlation of the electrical resistance bars at each temperature is obtained. In the correlation diagram between the temperature and the electrical resistance obtained by the enthalpy, it can be explained that the electric resistance rises sharply when viewed in the temperature rising direction, and the temperature fuse of the separator functions in the temperature range in which the electrical resistance is maintained. On the other hand, when the temperature is higher than the temperature indicated by the temperature fuse, the electrical resistance will be drastically reduced, and short-circuiting will soon be seen. ' ^ Test method can reliably display the function of the fuse, which is to evaluate the heat resistance of the separator which can withstand the souther temperature without short circuit. (13) The air permeability will cut the partition sample by 4 pieces of 5 cm square. According to JIS pm?, Gurley type air permeability tester (Toyo Seiki (4)) = 121060.doc -34 - 200845464. The measurement was carried out under the conditions of a pressure of 〇·0128 atm, a measured membrane area of 6.4 cm 2 , and an air permeation of 100 ml, and the average value was determined. Air permeability (seconds/100 cc) = [sum of measured values of 4 blocks] / 4 [Example 1] The cotton linters having a weight average molecular weight of 146,000 were dissolved in a copper ammonia solution towel prepared by a well-known method. Filtration was carried out 'defoaming to form cellulose rich f, ί; degree 8.0 wt% 'ammonia concentration was 61 wt%, and the copper concentration was 2. 9 grabs. Using an applicator, the above dopant was cast on a glass plate at a thickness of 25 Å, and immersed in 2 (TC water for 1 〇 minutes. Then, the 3 (tetra) aqueous sulfuric acid solution was dipped for 1 〇 minutes, after which The water was washed. Next, after dehydration in 2 (TC isopropanol for 2 hours), the isopropanol was evaporated and dried using a hot air circulating oven of 15 ° C to obtain a microporous membrane. The physical properties of the film ## 夕札膘 The physical properties are shown in Table 1, and the heat resistance analysis results are shown in Fig. 5. The apparent activation energy of the 12th generation to the time is positive, and is in The linearity of the high temperature side can be observed in the correlation diagram. From the above results, it can be clarified that the present embodiment - the spacer for the electric and electronic components of the ancient, w"" even if the same / under the dish 'the porous structure is also a helmet... b It has better heat resistance and therefore has better properties in terms of heat resistance. [Example 2] Using an applicator, the example was produced in the following: the thickness of 250 μηη in the thickness of the glass The board is cast, and it is 10 minutes in the middle of the river. Then, at 121060.doc -35- 200845464 Immersed in a 3 wt% aqueous solution of sulfuric acid at 20 ° C for 1 min, followed by water washing. Secondly, after dipping in ethanol at 20 ° C for 2 hours and dehydrating, 15 〇 was used. The hot air circulating oven was used to make ethanol. The microporous film was obtained by evaporation drying, and the physical properties of the obtained microporous film were as shown in Table 1. The apparent activation energy at UOt: 〜180 ° C was positive and had high heat resistance. Example 3]

U The dopant prepared in Example 1 was cast on a glass plate at a thickness of 25 μm using an applicator, and immersed in a 30 wt% aqueous acetone solution at 2 ° C for 1 minute, and then washed with water. Then, at 2〇. The mixture was immersed in a 3 wt% aqueous sulfuric acid solution for 10 minutes, and then washed with water. Next, after dehydration by immersing in 20 c of isopropyl alcohol for 2 hours, the isopropanol was evaporated to dryness using a 150 C hot air circulating oven, thereby obtaining a microporous film. The physical properties of the obtained microporous membrane are shown in Table 。. 12 〇 < t 〜 i8 (the apparent activation energy at rc is a positive value and has high heat resistance. [Comparative Example 1], a commercially available polypropylene separator (Celgard 2500: manufactured by Celgard & The physical properties are shown in Table ,, and the results of analysis of heat resistance are shown in Fig. 6. From the above, it is clear that the apparent activation energy shifts to a negative value with (10) and C as a boundary, and does not fill the knife. This suggests that the porous structure changes from the temperature of the refining point far below the polypropylene resin to the direction of ion permeation and ecstasy + 艮. Further, when the temperature is above 15 5 C, the internal β ▲ knowledge occurs. The internal short circuit 'causes the phenomenon that the ion transmission V degree rises rapidly in the appearance. [Comparative Example 2] 121060.doc -36 - 200845464 Commercially available cellulose electrolytic paper (Sakamoto Height Paper Industry Co., Ltd. · TF4〇 _3〇) The physical properties are shown in Table 1. The physical properties were evaluated as a film thickness of 37 μηι, a porosity of 76%, a maximum pore diameter of 2.5 μηη, a gas permeability of 7 seconds, and a puncture strength of 0.016 每 per 1 μηι film thickness. In particular, as a separator for a storage element having a large aperture, the performance of preventing the penetration of electrode fine particles is poor. Comparative Example 3] - A commercially available cellulose acetate microporous membrane (manufactured by Toyo Filter Co., Ltd., p C〇2〇A, nominal pore size 〇·2〇μηι) was immersed in a 2 wt% aqueous sodium hydroxide solution. The mixture was hydrolyzed for 17 hours, washed with water, and then immersed in an aqueous solution of 3 sulfuric acid for 10 minutes, and further washed with water. Thereafter, it was immersed in 20 C of ethanol for 2 hours to be dehydrated, and then vacuum-dried under a vacuum to obtain micro In the porous film, as compared with the cellulose acetate microporous film, the weight of the obtained microporous film was reduced by 4% by weight, and it was confirmed that the ethyl sulfhydryl group as a substituent was detached and substantially regenerated. The physical properties of the obtained microporous film. Medium, film thickness 82, porosity ti 57 / 〇 maximum pore control 0.43 μηι, gas permeability 54 seconds, puncture strength 0.050 Ν. The microporous membrane obtained has a thick film thickness, so the separator for the storage element [Comparative Example 4] According to the same technique as disclosed in Japanese Patent Laid-Open No. Hei 10-3898, a commercially available Seymour (registered trademark) film (Second Village Chemical Industry Co., Ltd.) 1 · Ρ·5) After immersing in 40C ethanol for 1 hour, The hot air circulating oven is used to evaporate and dry the ethanol. The film thickness of the film obtained is 2〇μηη, the porosity is 4%, so it is completely opaque, and the air permeability cannot be measured. Therefore, it is not a microporous film which can be used as a separator for a storage element. [Comparative Example 5] A commercially available Sevilla (registered trademark) film (manufactured by Nakamura Chemical Co., Ltd.: • Ρ^1) was used. Other than this, it carried out in the same method as the comparative example 3. Since the obtained film has a film thickness of 20 μm and a porosity of 8%, it is completely non-transmissive and cannot measure the gas permeability. Therefore, it is not a microporous film which can be used as a separator for an electric storage device. C. [Reference Example 1] A high-density polyethylene having a weight average molecular weight of 250,000 and a density of 〇·956 was 4 〇 wt/. , 3 7.8 C dynamic viscosity 75·9 cSt of mobile paraffin 60 wt% and 2,6_di-t-butyl-p-cresol 0.3 wt% mixed in polyethylene, using a kneading machine to melt at 200 ° C Mixed. The kneaded material was formed into a sheet shape using a compression molding machine heated to 2 Torr: and then cooled and solidified using a water-cooled compression molding machine to form a sheet having a thickness of 1200 μm. ,Secondly, using a biaxial stretching machine, biaxial stretching was carried out at a temperature of 120° C. at 7×7 times in a vertical and horizontal direction. Further, it was immersed in isopropyl alcohol to extract and remove the paraffin wax, and then a hot air cycle of 130° C. was used. The oven was evaporated to dryness in an oven to obtain a polyethylene microporous membrane. _ The physical properties of the obtained poly-b-microporous membrane, the film thickness was 15 μm, and the porosity was 37%. [Comparative Example 6] The physical properties of the polyethylene microporous membrane obtained in Reference Example 1 were evaluated, as shown in Table 2 It is described that the heat shrinkage rate at 150 ° C is large, which is 67%. 121060.doc -38- 200845464 [Examples 4 to 6 and Comparative Example 7] A cellulose porous layer was formed on one surface of a polyethylene microporous film in the following manner. The cotton lining of 194,000 in the average knife was dissolved in a n-liquid towel prepared by a well-known method, and the cellulose concentration was 5.5 wt%, the ammonia concentration was 4·9 wt%, and the copper concentration was 2" Grab the change. Using the applicator, the obtained dopant was applied to one side of the polyethylene microporous film obtained in Reference Example, respectively, at a thickness of 5 μm (ratio: Example 7): Η) 0 μΐη (Example 4) 150 μηη (Example 5) and 2〇〇μιη (Example phantom and casting. Then, immersed in water of 20 〇 for 10 minutes, and at 2 〇. immersed in 3 wt% aqueous sulfuric acid solution; After a minute, the water was washed. Secondly, after immersing in 20 ° C of isopropanol for 2 hours and dehydrating, the isopropanol was evaporated and dried using a hot air circulating oven at 8 ° C, thereby obtaining a single surface. Microporous membrane of porous cellulose layer. In the microporous membrane obtained, the weight fraction per unit area of the polyethylene porous layer was 88 wt% (Comparative Example 7), 73 wt% (Example 4), 59 wt, respectively. (Example 5) and 52 wt% (Example 6) The physical properties of the obtained microporous film are shown in Table 2. Fig. 7 shows the heat shrinkage action of 1〇〇°c~2〇〇. The microporous membranes of Examples 4 to 6 having a weight fraction per unit area of the cellulose porous layer of 20% by weight or more have a good heat shrinkage rate at 150 ° C. Fig. 8 shows the action of the fuse/short test at 6 〇C~2 0 0 C. 121060.doc -39- 200845464 The comparison of the case 6 is at 15 (the heat shrinkage rate at TC is 67%). The porous film is used as a short circuit in the vicinity of 130. (: ~14 (). The temperature of the fuse is immediately short-circuited. The electrical resistance drops rapidly. Another-party, the sixth generation in Example 6

The microporous membrane having a small heat shrinkage rate of 5% is 13 〇t: 〜l4 (the short circuit does not occur after the rCB is near the temperature fuse, and the state of maintaining the (four) state is maintained up to 200 ° C. [Example 7 and 8] The cellulose porous layer is formed on one side of the polyethylene microporous membrane in the following manner: The cotton wool having a weight average molecular weight of η·30,000 is dissolved in a copper ammonia solution prepared by a well-known method. After the bubble, the cellulose concentration is 3.5 Wt% 'the ammonia concentration is wt%, and the copper concentration is 13 _. The change of the impurities obtained by using the applicator to make the obtained dopants in the phase One side of the microporous film was cast in a thickness of 1 〇〇 to Example 7) and 2 〇 0 μη (Example 8). Then, it was immersed in water of TC for 1 minute, and was immersed in an aqueous solution of sulphuric acid for 3 minutes in a state of TC. After washing for 1 minute, it was washed with water. It was immersed in 20 C of isopropanol for 2 hours. After dehydration, the isopropanol was evaporated to dryness using an 80 C hot air circulating oven, thereby obtaining a microporous membrane having a porous cellulose layer on one side. Among the microporous crucibles obtained, the polyethylene porous layer per unit The weight fraction of the area was 77% by weight in Example 7, which was ... in Example 8. The physical properties of the obtained microporous film were as shown in Table 2, and had a particularly low electrical resistance of 121060.doc -40-200845464. [Comparative Example 8] The method disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. An attempt was made to prepare a cellulose microporous film. A commercially available celluloid (registered trademark) film (manufactured by Nakamura Chemical Co., Ltd.: p_5) was immersed in ethanol at 4 ° C for 1 hour, and then 15 〇 was used. C hot air circulation type ^ drying phase to evaporate ethanol, the film of the obtained film Since it is 20 μm, the porosity is 4%, so it is completely impermeable, and the gas permeability cannot be measured, so it is not a cellulose microporous film. As described above, since the cellulose porous film cannot be produced by the technique disclosed in the publication, Therefore, the objective of obtaining a laminate of a polyethylene microporous membrane and a cellulose microporous membrane was obtained. [Comparative Example 9] For the purpose of preparing cellulose microporous ruthenium, a commercially available sericin (registered trademark) was used. Membrane (manufactured by Ermura Chemical Industry Co., Ltd.: PS-1) was used in the same manner as in the case of the vehicle parent example 2. The obtained film had a film thickness of 2 pm and a porosity of 8%. Therefore, it is completely opaque and it is impossible to measure the gas permeability. Therefore, * is not the target cellulose microporous film. [Reference Example 2] Polyvinyl resin (crystalline melting point 135t, Asahi Kasei Co., Ltd.: fi8〇) was used as the crystallinity. Thermoplastic resin. Using a closed kneading machine made by Toyo Seiki Co., Ltd., 40 wt% of polyethylene resin and 6 〇wt% s2 of flowing paraffin (the rc is melted and kneaded, and then the temperature has been adjusted to 2 〇〇. Compressed into 121060.doc -41 - 200845464 The machine is formed into a sheet having a thickness of 600 μηι. Next, using a tensile tester, biaxial stretching is carried out at a temperature of 5 C5 at 12 CTC, and then the mobile ant is removed by using a two-gas tortic extraction. The microporous film obtained has a film thickness of 20 μm, a porosity of 45%, a maximum pore diameter of Ο.ΙΟμπι, and 150. (: The heat shrinkage rate at the time is extremely large, being 8〇%. 9] A cellulose microporous membrane having a film thickness of 21 μm, a porosity of 44%, a maximum pore diameter of 〇·〇59 μηι and a heat shrinkage of 1% obtained in Example 1 was used as a separator. , heat resistance test. The ratio of the change in the AC impedance before and after the test was 1.0 times, so that there was almost no change and the heat resistance was good. [Comparative Example 10] Using a polyethylene resin microporous film obtained in Reference Example 2 as a separator, heat resistance test was carried out. After the test, the film of the separator was broken and short-circuited, so that heat resistance was insufficient. [Comparative Example 11] Microporous film made of polypropylene resin (celgard No. 2500 ·· celgar (Mi film thickness 27 μηι, porosity 52./〇, maximum pore diameter 0·13 μηι, and heat shrinkage at 150 C) 40%) As a separator, the heat resistance was measured. The ratio of change in the AC impedance after the test was 丨〇〇〇 or more, so the heat resistance was insufficient. [Example 10] The obtained in Example 1 was used. The cellulose microporous membrane was subjected to a winding test as a separator to prepare a cylindrical member. As a result, the element volume was 121060.doc -42 - 200845464 3.7 cm3, and compared with the following Comparative Example 12, the volume was reduced. [Comparative Example 12] A mandrel test was carried out by using a Manila paper (manufactured by Otsuka Paper Co., Ltd.: capacitor paper) having a thickness of 56 μm and a density of 52 g/cm 3 as a separator to prepare a cylindrical element. As a result, the component volume is 5 〇cm3. [Industrial Applicability]

The separator for electricity storage device of the present invention is used as a non-aqueous (four) liquid storage component, and has better performance in terms of capacitor use, capacitor use, and plasma ion battery use, and can contribute to heat resistance, safety, and reliability. Further, since the separator for the electric storage device of the present invention is available. It is excellent in the effect of impregnating the electrolyte and is easy to be immersed in the electrolyte. Bay/utilization 121060.doc 200845464 f I<hi Comparative Example 2 (N 卜 0.016 τ-Η rH +0.051 Comparative Example 1 (Ν 0.13 190 r - Η m 0079 Ο 〇i - 0.003 Example 3 m (N 0.097 340 00 (N 0.083 rH Η +0.026 Example 2 00 〇\ cn 0.038 2050 m cn 0.159 rH +0.073 Example 1 0.059 1840 cn 0.134 ▼Η rH +0.069 Film thickness (μιη) Porosity (%) Maximum aperture (μπι) Air permeability (seconds) Electrical resistance (Ω·οηι2) Breakdown strength (N) Apparent activation energy (eV) at 120 ° C to 180 ° C Thermal contraction rate (%) 121060.doc -44- 200845464 实施 Example 8 double layer Α / Β m (N < N 0.036 卜 \6 0.168 ^ 实施 Example 7 double layer Α / Β m (N τ - Η 0.039 inch 1 0.196 〇 \ Example 6 double layer Α / Β TO (N Vo m 0.027 00 1 0.185 Example 5 Double layer Α/Β ON (N (N 0.029 inch 0.207 ν 〇 Example 4 double layer Α / Β S rn 00 mc^) 0.030 ON On 0.261 s Comparative Example 7 Double layer Α / Β CN 00 00 0.028 0.267 m Comparative Example 6 Single layer Β 〇100 0.069 inch 0.221 Membrane structure φ $ r^nr 0s Lean ah M Le v0 SBf ?v Φ Film thickness (μιη) Porosity (°/〇) Most Aperture (μπι) Electrical resistance (Ω·οπι2) Breakdown strength (Ν) Thermal contraction rate (%) 121060.doc -45- 200845464 Brief description of the drawing] Fig. 1 is a view schematically showing a unit for measuring electrical resistance. 1 '1 is not a metal unit container, 2 is a metal unit cover, 3, a non-metal bullet 4 is a metal electrode sheet, $ is a box electrode, and a Teflon (tefl〇n, registered trademark) is a circle. Cartridge, 7 denotes a partitioning member, 8 denotes a butterfly-shaped screw, and 9 denotes an insulating lining of Teflon (registered trademark), which is not made of a fluorocarbon (registered trademark), and u denotes a guide plate.

Figure 2 is a diagram showing the equivalent circuit used in the analysis of electrical resistance. Fig. 3 is a view schematically showing an apparent activation energy measuring unit and a fuse. Short-circuit test and measurement unit. In Fig. 3, i denotes a metal unit container, 2 = a metal-free unit cover, 3 denotes a metal spring, 4 denotes a metal electrode pressure 2'15 denotes a copper electrode, 16 denotes a metal cylinder, and 17 denotes a ring double The surface tape, 7 indicates that the separator '8 indicates a thumb screw, 9 indicates an insulating liner made of Teflon (registered trademark), and 1 indicates a teflon ring made of Teflon (registered trademark), indicating a tab. Figure 4 is a graph showing the equivalent circuit used in the analysis of apparent activation energy. Fig. 5 is an Arrhenius plot of a separator for an electric storage device of the embodiment. Fig. 6 is an Arrhenius ink dot diagram of a separator for a storage element of Comparative Example 1. Fig. 7 is a view showing the heat shrinking operation of the battery separators of Examples 4 to 6 and Comparative Examples 6 to 7. Fig. 8 is a view showing the fuse and short-circuit operation of the separator for a battery of Example 6 and Comparative Example 6. [Main component symbol description] 121060.doc -46- 200845464 Γ:

2 3 4 5 6 7 8 9 10 11 15

16 17 C

CPE > CPE! > CPE

L

Ri R2 Metal Unit Container Metal Unit Cover Metal Spring Metal Electrode Piece Platinum Electrode Teflon Cylindrical Separator Butterfly Screw Teflon Insulation Liner Teflon 0 Ring Lead Plate Copper Electrode Metal Cylindrical ring double tape capacitor component phasing element coil component separator resistance component device resistance component 121060.doc -47-

Claims (1)

200845464 X. Patent application scope: A separator for storage elements, a pottery material A is recognized from a person, a person, and is characterized by a cellulose-based microporous membrane, the membrane of the partition N 丁心胜/予为 i μηι〜3〇(4), porosity is 20 to 9 〇, the largest pore; 〇_ takes X pore 仫 below 2 μηι, and in the temperature range of 12 (rc~i8〇〇c, The apparent activation energy (-AG) associated with the ion 偻暮 日 日 丁 V V provides a positive value of 0.2. The separator for the storage element of claim 1 wherein the apparent activation energy (ΔG) is 〇 〇1 eV 〜0.20 eV. The separator for a storage element according to claim 1 or 2, wherein the cellulose-based microporous membrane comprises regenerated cellulose. 4. The method according to any one of claims 1 to 3 A separator for a storage element, wherein a breakdown strength per unit thickness is 0.03 N or more. 5. The separator for an electric storage device according to any one of the preceding claims, wherein the above-mentioned member is selected from the group consisting of an electric double layer capacitor Any one of the electrolytic capacitors and the ion battery. 〇6· I is a separator for a storage element, The feature is ☆, which comprises a composite micro-porous film comprising a cellulose-based microporous layer and a porous layer of each polyolefin resin, the porous layer of the polyolefin-containing resin unit area The weight fraction is 30 wt% to 80 wt%, and the separator has a film thickness of 1 μm to 30 μm, a porosity of 2% to 9%, and a maximum pore diameter of 2 μm or less. The separator for a storage element, wherein the polyalkylene resin-based polyethylene resin is the battery element of the storage element. 8' The separator for an electric component, wherein the battery is separated from the 121060.doc 200845464 sub-battery. It is characterized in that it is used by interposing a separator according to any one of claims 1 to 10 between the electrodes. The power storage device of claim 9, wherein the storage element is selected from an aluminum non-solid electrolytic capacitor, aluminum. Any of a solid electrolytic capacitor, an electric double layer capacitor, and a lithium ion secondary battery. 11. The electric storage device of claim 9, wherein the storage element is an aluminum non-solid electrolytic capacitor containing a material selected from the group consisting of γ-butane, ethylene glycol, glycerin, ethylene glycol monomethyl ether, and hydrazine- An electrolyte of at least one solvent of methylformamide. 12. The storage element of claim 9, wherein the storage element is an aluminum solid electrolytic capacitor selected from the group consisting of tetracyanoquinone, polyethylidene, polypyrrole, polythiophene, and polydioxyethylthiophene. At least one electrolyte of polyisothionaphthalene and polyaniline. 13. The electric storage device according to claim 9, wherein the electric storage device is an electric double layer capacitor, wherein the electric storage element is selected from the group consisting of γ-butene, carbonic acid, propylene carbonate, and cyclopentide. Acetonitrile, 1,2-dimethoxyethane, tetraethylborate methylethylimidazolium, trifluoromethanesulfonate methylethylimidazole rust, and bis(trifluoromethanesulfonyl) fluorene imine methylethyl An electrolyte of at least one solvent in the 11 m. The storage element of claim 9, wherein the storage element is a lithium ion secondary battery, the battery comprising a substance selected from the group consisting of γ-butyrolactone, 2-methyl-γ-butyrolactone, and acetamidine-γ-butyl Lactone, γ-valerolactone, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, ethyl carbonate, ethyl phthalate 121060.doc 200845464 ester, butylene carbonate, acetic acid Ester, ethyl acetate, methyl propionate, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetra An electrolyte of at least one solvent of hydroquinone and 3_methyl-1,3-dioxime. 121060.doc