WO2005101432A1 - 電気化学素子用セパレータ - Google Patents
電気化学素子用セパレータ Download PDFInfo
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- WO2005101432A1 WO2005101432A1 PCT/JP2005/007315 JP2005007315W WO2005101432A1 WO 2005101432 A1 WO2005101432 A1 WO 2005101432A1 JP 2005007315 W JP2005007315 W JP 2005007315W WO 2005101432 A1 WO2005101432 A1 WO 2005101432A1
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- Prior art keywords
- separator
- mass
- fibrillated
- fiber
- heat
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a separator for an electrochemical element which realizes an electrochemical element having excellent heat resistance and low resistance and a highly reliable electrochemical element.
- an electric double layer capacitor using an organic solvent-based electrolytic solution even a small amount of moisture mixed in causes a decrease in withstand voltage and voltage maintenance ratio, and adversely affects the capacitor characteristics. It is common practice to dry at a high temperature for a long time in a state of being wound or laminated together to remove moisture contained in these members. Therefore, the separator is required to have heat resistance that can withstand a high-temperature atmosphere for a long time.
- the process of manufacturing an aluminum solid electrolytic capacitor using a conductive polymer as the dielectric includes a so-called re-chemical treatment, in which high-temperature heat treatment is performed in a state where the chemically treated aluminum foil and the separator are wound or laminated together. The separator is required to have heat resistance.
- the separator since there is a step of impregnating and polymerizing the conductive polymer monomer solution after the re-chemical treatment, the separator is required to be impregnated with the conductive polymer monomer solution even after the high-temperature heat treatment.
- a separator for an electric double layer capacitor composed of a fiber sheet containing fibers having fibrils and fine polyester fibers having a fineness of 0.45 dtex or less (for example, see Patent Document 1), and a separator mainly composed of polyamide fibers are used. (See, for example, Patent Document 2).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2001-244150
- Patent Document 2 JP 2002-198263
- An object of the present invention is to provide an electrochemical element having excellent heat resistance and low resistance and high reliability! Another object of the present invention is to provide a separator for an electrochemical device that realizes an electrochemical device.
- the fibril-dani heat-resistant fiber, fibril-dani cellulose, and non-fibril-dani fiber are essential components, and the physical properties after heat treatment are within a suitable range. It was found that by designing and manufacturing to meet these requirements, a separator for an electrochemical element that is excellent in heat resistance and realizes a low-resistance electrochemical element and a highly reliable electrochemical element can be obtained. Reached.
- the present invention relates to a wet nonwoven fabric containing fibrillated heat-resistant fiber having a softening point, a melting point, and a pyrolysis temperature of 250 ° C or more and 700 ° C or less.
- a wet nonwoven fabric containing fibrillated heat-resistant fiber having a softening point, a melting point, and a pyrolysis temperature of 250 ° C or more and 700 ° C or less.
- MD machine direction
- CD direction perpendicular to MD
- the fibrillar dani heat-resistant fiber strength be a wholly aromatic polyamide fiber.
- the fibrillar drier heat-resistant fiber strength be a wholly aromatic polyester fiber.
- the cellulosic cell be obtained from parenchymal cells of a fibrillated cellulose plant.
- the electrochemical element according to the present invention includes a manganese dry battery, an alkaline manganese battery, a silver oxide battery, a lithium battery, a lead storage battery, a nickel cadmium storage battery, a nickel-hydrogen storage battery, a nickel zinc storage battery, a silver zinc storage battery, and a lithium ion storage battery.
- Batteries, lithium polymer batteries, various gel electrolyte batteries, zinc-air storage batteries, iron-air storage batteries, aluminum-air storage batteries, fuel cells, solar cells, sodium-sulfur batteries, polyacene batteries, electrolytic capacitors, electric Refers to multilayer capacitors.
- any of a pair of electric double layer electrodes, one of an electric double layer electrode, the other being a redox electrode, and a pair of a redox electrode may be used.
- the electric double-layer electrode of the electric double-layer capacitor include carbon materials such as activated carbon, activated carbon fibers, carbon nanotubes, and non-porous carbon
- examples of the redox-type electrode include ruthenium oxide and oxidized carbon. Examples include metal oxides such as indium and tungsten oxide, and conductive polymers such as polypyrrol, polythiophene, polyaline, polyacetylene, polyacene, and derivatives thereof.
- the electrolyte includes an aqueous solution in which an ion dissociable salt is dissolved, propylene carbonate (PC), ethylene carbonate (EC), dimethinorecarbonate (DMC), getyl carbonate (DEC), acetonitrile (AN), ⁇ - Butymouth ratataton (BL), dimethylformamide (DMF), tetrahydrofuran (THF), dimethoxyethane (DME), dimethoxymethane (DMM), sulfolane (SL), dimethylsulfoxide (DMSO), ethylene glycol, propylene glycol, etc.
- PC propylene carbonate
- EC ethylene carbonate
- DMC dimethinorecarbonate
- DEC getyl carbonate
- AN acetonitrile
- AN ⁇ - Butymouth ratataton
- BL dimethylformamide
- DME dimethoxyethane
- DM dimethoxymethane
- SL di
- Examples thereof include those in which an ion dissociable salt is dissolved in an organic solvent, and ionic liquids (solid molten salts), but are not limited thereto.
- the organic solvent type is preferable because the withstand voltage of the aqueous solution type is low.
- Lithium ion batteries, lithium polymer batteries, electric double layer capacitors, electrolytic capacitors, etc. use a conductive polymer film such as polypyrrole, polythiophene, polyaline, polyacetylene, polyacene, or their derivatives instead of the electrolytic solution. Good,.
- heat-resistant fibers having a softening point, a melting point, and a thermal decomposition temperature of 250 ° C. or more and 700 ° C. or less (hereinafter sometimes simply referred to as heat-resistant fibers) are all used.
- Aromatic polyamide wholly aromatic polyester, wholly aromatic polyester amide, wholly aromatic polyether, Wholly aromatic polycarbonate, wholly aromatic polyazomethine, polyphenylene sulfide (PPS), poly p-phenylene benzobisthiazole (PBZT), polybenzoimidazole (PBI), polyetheretherketone (PEEK), polyamideimide (PAI), polyimide, polytetrafluoroethylene (PTFE), poly p-phenyl-2,6-benzobisoxazole) (PBO) and the like. These may be used alone or in combination of two or more. .
- P BZT may be either a trans type or a cis type.
- the softening point and melting point are not clear, but the thermal decomposition temperature is 250 ° C. Also included are those that are not less than C and not more than 700 ° C. Examples include wholly aromatic polyamides and PBO. Among these fibers, wholly aromatic polyamides, particularly para-based wholly aromatic polyamides and wholly aromatic polyesters are preferable because they are easily fibrillated because of their liquid crystallinity.
- the heat-resistant fiber used in the present invention preferably has a softening point, a melting point and a thermal decomposition temperature of 260 ° C to 650 ° C, more preferably 270 ° C to 600 ° C. More preferred 2 80 ° C to 550 ° C is most preferred! /.
- Para-based wholly aromatic polyamides include poly (para-phenylene-terephthalamide), poly (parabenzamide), poly (para-amide hydrazide), and poly (para-phenylene-terephthalamide) 1,4-diphenyl ether terephthalate Amide), poly (4,4'benzalidetidephthalamide), poly (paraphenylene 4,4'-biphenylene diphenol), poly (paraphenylene 1,6 naphthalenedicarboxylic acid amide), poly (para (2) p-phenyleneterephthalamide), copolyparaphenylene 3,4'-oxydiphene-leterephthalamide, etc. Powers not limited to these.
- the wholly aromatic polyester is synthesized by changing the composition ratio by combining monomers such as aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids.
- monomers such as aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids.
- aromatic diols such as aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids.
- aromatic hydroxycarboxylic acids include, but are not limited to, copolymers of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
- the fibril in the present invention is a fiber having a portion mainly divided very finely in a direction parallel to the fiber axis, and at least a part of which has a fiber diameter of 1 ⁇ m or less.
- the manufacturing method and the shape are different from those of a hybrid.
- a fibrid is formed by coagulating and sedimenting an aramide polymer solution in a precipitant that is being stirred at a high speed. US Pat. : described as l.
- the fibrils in the present invention preferably have a length to width aspect ratio ranging from 20: 1 to 100000: 1 and a Canadian standard freeness ranging from Oml to 500 ml.
- the fiber has a weight average fiber length of 0.1 mm or more and 2 mm or less and a specific surface area of 1 to 20 m 2 Zg.
- the weight average fiber length can be determined by using a commercially available fiber length measuring device utilizing the polarization characteristics obtained by irradiating the fiber with laser light.
- the specific surface area can be determined by measuring according to the BET one-point method.
- fibrillated cellulose it may be in the form of a film when dried, and it may be difficult to measure by the BET one-point method.
- the fibrillated cellulose in the present invention refers to bacterial cellulose or cellulose that has been mechanically fibrillated.
- the former refers to bacterial cellulose produced by microorganisms.
- This bacterial cellulose contains cellulose and a heteropolysaccharide having cellulose as a main chain, and contains glucans such as j8-1,3, ⁇ -1,2.
- the constituent components other than cellulose include hexoses such as mannose, fructose, galactose, xylose, arabinose, rhamnose, and glucuronic acid, pentoses, and organic acids.
- These polysaccharides may be composed of a single substance, but may be composed of two or more polysaccharides bonded by hydrogen bonds or the like, and any of them may be used.
- the latter is prepared by using various types of pulp including linters, lint, regenerated cellulose, solvent-spun cellulose, fibers obtained from parenchyma cells of plants, and the like, in the same manner as the fibrillated heat-resistant fibers described above. It refers to what has been fibrillated.
- the fibrillar cellulose alone is carbonized and decomposed by heat treatment and does not function as a separator.
- the fibrillar fiber When mixed with the fibrillar heat-resistant fiber as in the present invention, the fibrillar fiber is wound around the fibrillar heat-resistant fiber or hydrogen-bonded. A strong network is formed between self and other fibers, and the area exposed to the surface is reduced by the surrounding fibrillated heat-resistant fibers.
- fibrillated cellulose alone and fibrillated cellulose It is also evident from the difference in appearance after heat-treating the mixture of the fiber and the fibrillar dani heat-resistant fiber at 200 ° C or higher. That is, fibrillation cellulose alone causes carbonization decomposition, and is burnt and cannot maintain the original shape and becomes hard, whereas the mixture is suppressed from carbonization decomposition and the original shape and flexibility are maintained. .
- the effects exhibited by the fibrillated cellulose include strong tensile strength and piercing strength due to the strong network structure of the fibrillated cellulose, and favorable air permeability and pore size are maintained by the large specific surface area.
- fibrillated celluloses linter ⁇ parenchymal cell force Natural cellulose such as obtained fiber is highly uniform and easily formed into very fine fibrils, so that the thickness ⁇ pore size of the separator for electrochemical element becomes uniform. Immediate control of air permeability and pore size.
- Fibrillated cellulose obtained from regenerated cellulose or solvent-spun cellulose has poorer control of the air permeability and pore size of the separator for electrochemical devices, which is a thinner fiber than natural cellulose. The effect of strengthening is small.
- the fiber obtained in the present invention is mainly composed of cellulose obtained by treating a portion mainly containing parenchymal cells present in plant stems, leaves, fruits and the like with an alkali. , A fiber that is insoluble in water. Parenchymal cells have the characteristic of undeveloped secondary walls.
- the internal soft tissue of the stem, leaf mesophylls, fruits and the like may be crushed, but industrially, a food processing plant, a sugar factory, etc. It is best to use juice excreted from fruits, such as juice refuse from sugarcane and sugar beet.
- juice excreted from fruits such as juice refuse from sugarcane and sugar beet.
- sugarcane squeezed cake for example, using a cane separator manufactured by Amcaine
- the stalk strength of the sugarcane is separated and squeezed in advance by separating only the portion containing a large amount of softened cells, thereby softening the softened cells. It is possible to obtain a large amount of lees and it is efficient.
- sugar beet squeezed residue crushed root can be squeezed and the remaining residue can be used as it is.
- a kraft pulp diving method in which squeezed cake and the like are mixed with an alkali such as caustic soda and heated to decompose and remove lignin can be used.
- a soda pulping method can be used.
- Detailed pulping conditions may be appropriately determined in consideration of the properties of the raw material, the properties of the target fiber, the yield, and the like.
- wash the alkali After the removal, a bleaching treatment is performed if necessary.
- the bleaching agent hydrogen peroxide, chlorine dioxide, sodium hypochlorite, oxygen, ozone and the like can be used. After bleaching, it can be washed to obtain a fiber suspension.
- the fibrillated heat-resistant fiber and fibrillated cellulose according to the present invention are a refiner, a beater, a mill, a grinding device, a rotary blade homogenizer for applying a shearing force by a high-speed rotary blade, and a cylindrical type rotating at a high speed.
- Double cylindrical high-speed homogenizer that generates shear force between the inner blade and fixed outer blade, ultrasonic crusher that breaks down by ultrasonic impact, pressure difference of at least 3000 psi to fiber suspension And a high speed by passing through a small-diameter orifice and colliding with it to rapidly reduce the force obtained by processing the fiber using a high-pressure homogenizer or the like that can reduce the shearing force and cutting force.
- Finely manufactured with a jinizer ⁇ Preferable because fibrils can be obtained! / ⁇ .
- the non-fibrillar fibers used in the present invention include polyesters such as polyethylene terephthalate, polyethylene isophthalate and derivatives thereof, polyolefin, acrylic, polyamide, polyether sulfone (PES), polyvinylidene fluoride (PVDF) ), Poly (vinyl alcohol), ethylene-butyl alcohol copolymer, ethylene-butyl acetate copolymer, natural fiber, regenerated cellulose, solvent-spun cellulose, and other powerful single fiber-composite fiber, softening point, melting point, and thermal decomposition temperature.
- Heat-resistant fibers of 250 ° C or more and 700 ° C or less are mentioned.
- the fiber length of these non-fibrillated fibers is preferably from 0.1 to 15 mm, more preferably from 1 to 10 mm. If the fiber length is less than 0.1 mm, the fiber will fall off, and if it is longer than 15 mm, the fiber will be entangled and lump, and the thickness will easily become uneven.
- the average fiber diameter of these non-fibrillated fibers is preferably not less than 0.0002 ⁇ m and not more than 30 ⁇ m, more preferably not less than 0.01 ⁇ m and not more than 20 ⁇ .
- the fineness is preferably greater than or equal to 0.00dtex and less than or equal to 3dtex, more preferably greater than or equal to 0.005dtex and less than or equal to 2dtex.
- the average fiber diameter is less than 0.01 / zm, especially less than 0.0002 / zm, or the fineness is less than 0.005 dtex, especially less than 0.Old tex, the fiber is too thin to capture fibrillated heat-resistant fiber and fibrillated cellulose. In some cases, it is difficult to form the basic skeleton of the wet nonwoven fabric.
- the average fiber diameter is larger than 20 m, especially 30 m, or when the fineness is larger than 2 dtex, especially when it is larger than 3 dtex, fibrillation As soon as the heat-resistant fibers and the fibrillated cellulose fall off, pinholes may form and the formation may become uneven immediately.
- the cross-sectional shape of the non-fibrillar fibers used in the present invention may be any of a circle, an ellipse, a square, a rectangle, a star, a Y, and other irregular shapes.
- the fibrillated heat-resistant fibers, fibrillated cellulose and non-fibrillar fibers constituting the wet nonwoven fabric used in the present invention are, for example, 15% to 80% by mass of fibrillated heat-resistant fibers and 5% by mass of fibrillated cellulose. It is preferable to mix in an amount of from 35% by mass to 35% by mass and from 10% by mass to 75% by mass of non-fibrillated fiber. 30% by mass and 15% by mass to 70% by mass of non-fibrillar fibers, most preferably 25% to 60% by mass of fibrillated heat-resistant fibers, 10% to 20% by mass of fibrillated cellulose and non-fibrillar fibers.
- the dangling fiber is 20% by mass to 65% by mass.
- the separator for an electrochemical element of the present invention has a dimensional change in MD (machine direction) and CD (in a direction perpendicular to MD) when the wet nonwoven fabric is heat-treated at 250 ° C for 50 hours. All rates are -3% to + 1%. Even when heat-treated at a temperature lower than 250 ° C, it is within the range of 3% to + 1%. When the dimensional change is larger than ⁇ 3% on the minus side, it means that the separator for the electrochemical element has a large shrinkage, and the surface smoothness is significantly impaired. For this reason, the adhesion to the electrode is deteriorated, and the internal resistance of the electrochemical element is likely to increase.
- the conductive polymer film is likely to be formed unevenly and internal resistance is likely to be increased.
- the separator for an electrochemical element is made of a mixture of organic fibers and inorganic fibers, the surface after the heat treatment is uneven because the linear expansion coefficients of the organic fibers and the inorganic fibers upon heating differ greatly. , And the surface smoothness is liable to be significantly deteriorated.
- the separator for the electrochemical element shrinks too much, causing the element to come apart.
- the elements tend to vary.
- the amount of the fibril-dani heat-resistant fiber is 0% by mass or more, the melting point is less than 200 ° C.
- incorpororation of non-fibrillated fibers with certain components (2) When the blending amount of the fibrillated heat-resistant fiber is 15% by mass or more and less than 40% by mass, the non-fibrillated material having a component whose melting point is less than 200 ° C.
- non-fibrillated fiber having a component having a melting point of less than 200 ° C refers to a non-fibrillated fiber having a melting point of less than 200 ° C as a part of a single fiber or a composite fiber. Fiber! In the conjugate fiber, it is preferable that a part of the resin component having a melting point of less than 200 ° C is partially exposed on the fiber surface.
- a commercially available constant temperature dryer, an electric furnace, or the like can be used as a device for heating to 250 ° C used for the heat treatment.
- the atmosphere may be air, inert gas, or vacuum.
- the degree of vacuum should be higher than 10 _2 Torr. In the present invention, even if the physical properties after the heat treatment at 250 ° C. for 50 hours in the air are out of the preferable range, even if the heat treatment is performed in a vacuum, only insufficient properties as a separator for an electrochemical element can be obtained. That means.
- the separator for an electrochemical element of the present invention has a density after heat treatment of the wet nonwoven fabric at 250 ° C. for 50 hours of 0.25 gZcm 3 or more, 0.55 gZcm 3 or less, and a maximum pore size of 3. and a pressure of air permeability at a 0. LBARs is 0. 3LZminZcm 2 or more, if it has the properties of less than 3LZminZcm 2, it can be used as a separator for an electric double layer capacitor.
- the density is adjusted to a desired density by calendering or the like in advance before the heat treatment, if necessary. If at 250 ° C the density after 50 hours heat treatment of less than 0.
- the internal resistance of the electrochemical device may increase.
- the maximum pore diameter is larger than 3.5 m, the electrode active material with a small particle diameter may pass through and an internal short circuit may occur. Therefore, the maximum pore size is preferably 3.5 ⁇ m or less, but more preferably 0.1 ⁇ m or more so as not to hinder ion permeability.
- the air permeability is less than 0. 3LZminZcm 2, ion permeability is deteriorated, electrochemical The internal resistance of the chemical element tends to increase.
- 3LZminZcm 2 or more to To to be less than 3LZminZcm 2, the following eight factors, namely (1) the degree of fibrillation of fibrillated heat-resistant fiber (a weight average fiber length , Aspect ratio, freeness, specific surface area), (2) compounding amount of fibrillated heat-resistant fiber, (3) thickness of non-fibrillated fiber, (4) compounding amount of non-fibrillated fiber, (5) fibrillated fiber Fibrillation degree (weight average fiber length, aspect ratio, freeness, specific surface area) of dani cellulose, (6) blending amount of fibrillated cellulose, (7) basis weight of wet nonwoven fabric, (8) density of wet nonwoven fabric Can be achieved by adjusting the relationship
- the electrochemical element separator of the present invention is characterized in that the wet nonwoven fabric is subjected to a heat treatment at 280 ° C for 60 minutes, and then a wet area formed by infiltration in a plane direction by a water drop dropped by the drop method of JIS L1907 for 60 seconds If it has the property that the longer major axis is 20 mm or more, it can be used as a separator for solid electrolytic capacitors. Naturally, even when heat-treated at a temperature lower than 280 ° C, it shows a longer diameter of 20 mm or more. One drop of water is dropped from a burette fixed at a height of 10 mm from the surface of the separator for electrochemical devices.
- the major axis of the wet region in the present invention refers to the major axis of the wet region that is formed in a pseudo-circular shape in a plane direction around the water droplet when the dropped water droplet penetrates the electrochemical element separator.
- the major axis of the wet area 60 seconds after the drop of the water droplet is used as an index. By using this method, evaluation can be performed with good reproducibility. If the long diameter of the wet area after 60 seconds in the present invention is less than 20 mm, the impregnating property of the conductive polymer monomer aqueous solution is poor, and it is difficult to form the conductive polymer film.
- fibers that become hydrophobic when heat-treated at 280 ° C for 60 minutes include strong polyester fibers such as polyethylene terephthalate, polyethylene isophthalate, and derivatives thereof.
- the separator for a solid electrolytic capacitor in the present invention the wet nonwoven fabric It is preferable that the air permeability after heat treatment at 250 ° C. for 50 hours is 0.25 gZcm 3 or more and 0.55 gZcm 3 or less and the air permeability at a pressure of 0.1 lbar is 3 LZminZcm 2 or more and less than 30 LZminZcm 2 .
- the air permeability is less than 3 LZminZcm 2
- the amount of fibers in the electrochemical element separator is too large, the formation of the conductive polymer film becomes uneven, and the internal resistance of the solid electrolytic capacitor may increase.
- LBARs is, 3LZminZcm 2 or more, to be less than 30LZminZcm 2, the following eight factors, namely (1) Fiburirui ⁇ heat fibers Fiburirui ⁇ ( (Weight average fiber length, aspect ratio, freeness, specific surface area), (2) amount of fibrillated heat-resistant fiber, (3) thickness of non-fibrillated fiber, (4) amount of non-fibrillated fiber , (5) fibrillation degree of fibrillation of cellulose (weight average fiber length, aspect ratio, freeness, specific surface area), (6) compounding amount of fibrillated cellulose, (7) basis weight of wet nonwoven fabric, (8) This can be achieved by adjusting the density relationship of the wet nonwoven fabric.
- the maximum pore diameter in the present invention means the maximum pore diameter measured in accordance with the bubble point method of ASTM F316-86.
- the measurement of the maximum pore size can be performed using a commercially available measuring instrument (Coulter Electronics Co., Ltd., Coulter Porometer).
- the air permeability in the present invention means the amount of air per unit time and per unit area passing through the sample when air is supplied to the sample at a pressure of 0.1 lbar.
- the measurement of the air permeability can be carried out using a commercially available measuring instrument (Coulter Electronics Co., Ltd., Coulter Porometer).
- the present inventors differed in the Fragile tester, which is not suitable for measurement of a sample having extremely low air permeability, or the Gurley air permeability meter, which is not suitable for measurement of a sample having extremely high air permeability (easy to permeate).
- the present inventors have found that it is possible to evaluate samples which are difficult to determine by measuring the air permeability at a pressure of 0.1 lbar, and have reached the present invention. Therefore, for example, a difference between samples can be more clearly identified by comparing both the maximum pore diameter and the air permeability at a pressure of 0.1 lbar, taking into account the physical properties.
- Wet nonwoven fabrics include a round paper machine, a fourdrinier paper machine, a short net paper machine, an inclined paper machine, and a combination paper machine made of a combination of the same or different kinds of paper machines. Used. It is preferable to use pure water such as ion-exchanged water or distilled water. The characteristics of the electrochemical element are affected! / Dispersing agents, thickeners, etc. should not be added as much as possible. In that case, a nonionic one is preferred.
- the basis weight of the separator for an electrochemical element of the present invention is not particularly limited, 5g / m 2 ⁇ : L00g / m 2 is preferred instrument 8g / m 2 ⁇ 50g / m 2 is more preferred.
- the thickness of the separator for an electrochemical device in the present invention is not particularly limited, but is set to a thickness having high uniformity! ⁇ 300 / zm force preferred, ⁇ 20 ⁇ ! ⁇ 150 m force ⁇ even more preferred! / ,. If it is less than 10 / zm, sufficient piercing strength cannot be obtained, and if it is thicker than 300 m, the electrode area force that can be stored in the electrochemical element may be reduced, and the capacity of the electrochemical element may be reduced.
- the electrochemical element separator of the present invention is subjected to processing such as calendering, thermal calendaring, and heat treatment as necessary.
- Nora-based wholly aromatic polyamide (manufactured by Teijin Techno Products, Twaron 1080, trade name, fineness: 1.2 dtex, fiber length: 3 mm, thermal decomposition temperature: 550 ° C) is dispersed in water to an initial concentration of 5% by mass. Using a double disc refiner, beating is repeated 15 times to obtain a weight average fiber length of 1.65 mm and a BET specific surface area of 13. A fibrillated para-based wholly aromatic polyamide fiber having a Canadian standard freeness of 80 ml was produced. Hereinafter, this is referred to as “Fibrillar d'ani heat-resistant fiber 1” or “FBI”.
- the fibrillated heat-resistant fiber 1 was beaten repeatedly 25 times with a high-pressure homogenizer under the condition of 500 kg Zcm 2 to obtain a weight average fiber length of 0.65 mm, a BET specific surface area of 17.8 m 2 Zg, and a Canadian standard freeness of Oml. Fibrillated para-based wholly aromatic polyamide fibers were prepared. Hereinafter, this is referred to as fibrillation heat-resistant fiber 2 or FB2.
- a wholly aromatic polyester fiber (Kuraray, Vectran NT, trade name, fineness 1.7 dtex, fiber length 3 mm, melting point 280 ° C) in water to an initial concentration of 5% by mass, and use a double disc After beating repeatedly 15 times, using a high-pressure homogenizer at 500 kgZcm 2 for 20 times, the weight average fiber length is 0.35 mm, BET ratio A fibrillar dani wholly aromatic polyester fiber having a surface area of 9.2 m 2 / g and a Canadian standard freeness of 150 ml was prepared. Hereinafter, this is referred to as fibrillation heat-resistant fiber 3 or FB3.
- fibrillation heat-resistant fiber 3 or FB3 fibrillation heat-resistant fiber 3
- PBO Polyp-phenylene 2,6 Benzobisoxazole
- Initial concentration 5 % By weight in water and repeatedly beaten for 20 times using a double disc refiner, and then repeatedly for 20 times using a high-pressure homogenizer at 500 kg / cm 2 to obtain a weight-average fiber length.
- this will be referred to as fibrillar heat resistant fiber 4 or FB4.
- fibrillated cellulose 1 fibrillated cellulose 1 or FBC1.
- a slurry was prepared using pulp according to the raw materials and contents shown in Table 1. At this time, ion-exchanged water was used.
- PET1 in Table 1 is a polyethylene terephthalate fiber with a fineness of 0.1 ldtex and a fiber length of 3 mm (Tijintetron Tepils TM04PN SD0.1X3, trade name, manufactured by Teijin Fibers)
- PET2 is a polyethylene terephthalate fiber with a fineness of 0.3 dtex and a fiber length of 3 mm (manufactured by Teijin Fibers Co., Ltd., Tijintetron Tepyrus TM04PN SD0.3 ⁇ 3, trade name), PET3 is a polyethylene terephthalate fiber with a fineness of 0.6 dtex and a fiber length of 5 mm (manufactured by Teijin Fibers, Tijintetron TA04N SDO. 6X5, trade name),
- PET4 is a polyester-sheath composite fiber with a fineness of 1. ldtex and a fiber length of 5 mm (manufactured by Teijin Fibers, Tijintetron TJ04CN SD1.1X5, trade name, core: polyethylene terephthalate, sheath: polyethylene terephthalate) And a copolymer of polyethylene isophthalate, melting point of the sheath 110 ° C),
- PET5 is a polyethylene terephthalate fiber with a fineness of 1.7 dtex and a fiber length of 5 mm (manufactured by Teijin Fibers, Tijintetron TJ04CN SD1.7X5, trade name, core: polyethylene terephthalate, sheath: polyethylene terephthalate and polyethylene isophthalate) , The melting point of the sheath is 110 ° C).
- PET6 means a wholly aromatic polyester fiber (Kuraray, Vectran HHA, trade name) with a fineness of 1.7 dtex and a fiber length of 5 mm.
- A1 is an acrylic fiber having a fineness of 0.1 ldtex and a fiber length of 3 mm (manufactured by Mitsubishi Rayon, Bonnell MV P, trade name, acrylonitrile-based copolymer composed of three components of acrylonitrile, methyl acrylate, and methacrylic acid derivative),
- A2 is an acrylic fiber having a fineness of 0.4 dtex and a fiber length of 3 mm (manufactured by Mitsubishi Rayon, Bonnell MV P, trade name, acrylonitrile-based copolymer composed of three components of acrylonitrile, methyl acrylate, and methacrylic acid derivative),
- PA1 is an aromatic polyamide fiber with a fineness of 0.08 dtex and a fiber length of 3 mm (manufactured by Kuraray, Dienestar, trade name, melting point 255 ° C, softening point 230 ° C),
- PA2 is a para-type wholly aromatic polyamide fiber with a fineness of 0.75 dtex and a fiber length of 5 mm (manufactured by Teijin Tetano Products, Technora, trade name, copolyparaphenylene-1,3,4'-oxydiphenyleneterephthalamide),
- PA3 is a para-type wholly aromatic polyamide fiber with a fineness of 1.2 dtex and a fiber length of 5 mm (manufactured by Teijin Tetano Products, Twaron 1080, trade name),
- N1 is a nylon 6,6 fiber with a fineness of 0.5 dtex and a fiber length of 5 mm (made by Asahi Kasei Fiber, Leona, trade name),
- N2 is a nylon 6 fiber with a fineness of 0.6 dtex and a fiber length of 5 mm (made by UTICA, ⁇ 601>, Product name),
- PB01 means PBO fiber (Toyobo, Zylon AS, trade name) with a fineness of 1.7 dtex and a fiber length of 6 mm.
- G1 means micro glass fiber (manufactured by Manville, 106, trade name) having an average fiber diameter of 0.65 / zm.
- Electrochemical element separators 1 to 8 and 17 to 19 were laminated between the positive electrode and the negative electrode, and spirally wound using a winding machine to produce a spiral element.
- the spiral type element is housed in an aluminum case, and the positive terminal and the negative terminal After welding the positive electrode lead and negative electrode lead to the case, the case was sealed leaving the electrolyte injection port
- Each case was subjected to a vacuum heat treatment at 250 ° C for 50 hours to remove water contained in the electrodes and the separator for electrochemical elements. After allowing this to cool to room temperature in a vacuum, an electrolyte was injected into the case, and the injection port was sealed to produce electric double layer capacitors 1 to 8 and 17 to 19.
- (C H) (CH) NBF was added so that 1.5 mol Zl was added to propylene carbonate.
- a solution obtained by dissolving 2 5 3 3 4 was used.
- Electrochemical element separators 9 to 17 and 20 with a width of 2 mm were arranged on the dielectric layer of the anode, and wound together with the cathode to form an element.
- This element was heat-treated at 280 ° C for 60 minutes, cooled, immersed in an aqueous solution for polymerization in which a predetermined amount of thiophene, an oxidizing agent and a surfactant were dissolved, chemically polymerized, and integrated with the polythiophene solid electrolyte.
- a solid electrolytic capacitor element was formed. After the device was dried, it was housed in a case and the opening was sealed to produce solid electrolytic capacitors 9 to 17 and 20.
- Electrochemical element separators 1 to 20 were cut into 200 mm width and 250 mm length. This was placed in a thermostat dryer (DHS82, manufactured by Yamato Scientific) and heat-treated at 250 ° C for 50 hours. The dimensions before and after the heat treatment were measured, and the rate of change in MD and CD relative to the original dimensions was determined.
- DHS82 thermostat dryer
- the maximum pore sizes of the separators 1 to 20 for electrochemical devices were measured.
- a Coulter porometer manufactured by Coulter-Elect Co., Ltd. Nitas
- the air permeability per unit time and unit area at a pressure of 0.1 lbar was measured.
- a Coulter porometer manufactured by Coulter Electronics Corporation
- Electrochemical element separators 1 to 20 were cut into 200 mm squares, placed in a thermostatic dryer (manufactured by Yamato Scientific, DHS82), and heat-treated at 280 ° C for 60 minutes. After the heat treatment, the sample was fixed to a sample holding frame specified in JIS L1907, fixed so that the height from the sample surface to the tip of the burette was 10 mm, and one drop of water was dropped from the burette. The force when the water droplet reached the sample surface was also measured for the long diameter of the wet area after 60 seconds. Similar measurements were performed at four locations per sample, and the smallest values are shown in the table. Numeral 6 in the table indicates the size of the water droplet, which means that the water droplet did not penetrate at all after 60 seconds.
- the charge was calculated from the voltage drop immediately after the start of discharging when the electric double layer capacitors 1 to 8 and 17 to 19 were charged at a voltage of 2.7 V and then discharged at a constant current of 20 A.
- the failure rate In the fabrication of the solid electrolytic capacitor, the percentage of the elements that had fluctuated after heat treatment at 280 ° C for 60 minutes was defined as the failure rate.
- ESR equivalent series resistance
- the leakage current after applying a voltage of 6.3 V to solid electrolytic capacitors 9 to 17 and 20 was measured, and the average value per 1000 solid electrolytic capacitors was shown.
- the electrochemical element separators produced in Examples 1 to 15 each had a MD and CD dimensional change rates of 3% to + 1% after heat treatment at 250 ° C for 50 hours.
- the electrochemical element equipped with the separator has a very low rejection rate, a low internal resistance, and a very high voltage, as shown in Tables 4 and 5. It shows a high retention rate and a very small leakage current, achieving high reliability.
- the separators for electrochemical devices manufactured in Examples 1 to 8 had a density after heat treatment at 250 ° C. for 50 hours of 0.25 gZcm 3 or more, and a maximum pore size of 0.55 gZcm 3 or less. There 3. less, air permeability force 0. 5LZminZcm 2 or more when the pressure 0. LBARs, since less than 3L ZminZcm 2, preferably a dark especially as a separator for an electric double layer capacitor.
- the separators for electrochemical devices manufactured in Examples 9 to 15 were subjected to a heat treatment at 280 ° C for 60 minutes, and water droplets dropped by the dropping method of JIS L1907 were soaked in the plane direction. Since the long diameter of the wetted area after 60 seconds is 20 mm or more, the impregnating property of the conductive polymer in the monomer aqueous solution is very good, and it is particularly suitable as a separator for a solid electrolytic capacitor using a conductive polymer as a dielectric. Was.
- the separators for electrochemical devices manufactured in Comparative Examples 1 to 5 had a remarkably large dimensional change rate of MD and CD after heat treatment at 250 ° C for 50 hours, and had high heat resistance.
- the failure rate of the electrochemical element was extremely high or the voltage maintenance rate was low because of insufficient power, and the reliability was low.
- the electrochemical element separator of the present invention contains fibrillated heat-resistant fiber, fibrillated cellulose, and non-fibrillated fiber, and has a preferable range after heat treatment. And high reliability! ⁇ It is possible to realize an electrochemical device.
- Examples of utilization of the separator for an electrochemical element of the present invention include applications requiring heat resistance and low internal resistance, for example, separators for electric double layer capacitors, solid electrolytic capacitors, lithium ion batteries, and the like.
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- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05730630A EP1737004B1 (en) | 2004-04-16 | 2005-04-15 | Separator for electrochemical element |
KR1020067023628A KR101122500B1 (ko) | 2004-04-16 | 2005-04-15 | 전기 화학 소자용 세퍼레이터 |
JP2006512391A JP4377911B2 (ja) | 2004-04-16 | 2005-04-15 | 電気化学素子用セパレータ |
US11/547,630 US8252449B2 (en) | 2004-04-16 | 2005-04-15 | Separator for electrochemical element |
Applications Claiming Priority (2)
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JP2004-121440 | 2004-04-16 | ||
JP2004121440 | 2004-04-16 |
Publications (1)
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WO2005101432A1 true WO2005101432A1 (ja) | 2005-10-27 |
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ID=35150235
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PCT/JP2005/007315 WO2005101432A1 (ja) | 2004-04-16 | 2005-04-15 | 電気化学素子用セパレータ |
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Country | Link |
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US (1) | US8252449B2 (ja) |
EP (1) | EP1737004B1 (ja) |
JP (1) | JP4377911B2 (ja) |
KR (1) | KR101122500B1 (ja) |
CN (1) | CN100559526C (ja) |
WO (1) | WO2005101432A1 (ja) |
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Publication number | Publication date |
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EP1737004A1 (en) | 2006-12-27 |
EP1737004B1 (en) | 2012-09-05 |
KR101122500B1 (ko) | 2012-03-15 |
CN1942983A (zh) | 2007-04-04 |
JP4377911B2 (ja) | 2009-12-02 |
US20070287062A1 (en) | 2007-12-13 |
EP1737004A4 (en) | 2010-09-29 |
KR20070004965A (ko) | 2007-01-09 |
JPWO2005101432A1 (ja) | 2008-03-06 |
CN100559526C (zh) | 2009-11-11 |
US8252449B2 (en) | 2012-08-28 |
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