WO2016114175A1 - セパレータ及びアルミニウム電解コンデンサ - Google Patents
セパレータ及びアルミニウム電解コンデンサ Download PDFInfo
- Publication number
- WO2016114175A1 WO2016114175A1 PCT/JP2016/050141 JP2016050141W WO2016114175A1 WO 2016114175 A1 WO2016114175 A1 WO 2016114175A1 JP 2016050141 W JP2016050141 W JP 2016050141W WO 2016114175 A1 WO2016114175 A1 WO 2016114175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separator
- fiber
- csf value
- electrolytic capacitor
- aluminum electrolytic
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 175
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 155
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 119
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 108
- 239000000835 fiber Substances 0.000 description 178
- 238000000034 method Methods 0.000 description 66
- 230000007547 defect Effects 0.000 description 62
- 238000010009 beating Methods 0.000 description 60
- 239000002994 raw material Substances 0.000 description 57
- 229920000433 Lyocell Polymers 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 47
- 239000008151 electrolyte solution Substances 0.000 description 37
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 28
- 238000002156 mixing Methods 0.000 description 23
- 239000000123 paper Substances 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 15
- 230000001965 increasing effect Effects 0.000 description 14
- 229920000297 Rayon Polymers 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002964 rayon Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 7
- 235000010980 cellulose Nutrition 0.000 description 7
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002994 synthetic fiber Polymers 0.000 description 6
- 239000012209 synthetic fiber Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229920001407 Modal (textile) Polymers 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- -1 generally Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 210000004754 hybrid cell Anatomy 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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 suitable for an aluminum electrolytic capacitor, and an aluminum electrolytic capacitor using the separator.
- Aluminum electrolytic capacitors occupy a large volume ratio among the components of inverter circuits, so there is a strong demand for further miniaturization of aluminum electrolytic capacitors.
- an electrolytic capacitor such as an aluminum electrolytic capacitor is formed by interposing a separator between an anode aluminum foil and a cathode aluminum foil, winding them to form a capacitor element, and impregnating the capacitor element with an electrolytic solution. It is manufactured by inserting into a case and sealing.
- the main role of the separator is to separate both electrode foils and hold the electrolyte.
- the material of the separator is required to have electrical insulation, and hydrophilicity and oleophilicity are required for holding various types of electrolytes. Therefore, a separator made of cellulose having both of these characteristics is used.
- natural cellulose fibers such as softwood kraft pulp, manila hemp pulp and esparto pulp, and regenerated cellulose fibers such as solvent-spun cellulose fibers are generally used.
- An effective technique for reducing the impedance of the separator is to reduce the basis weight of the separator, to reduce the density, and to reduce the thickness.
- various problems arise simply by reducing the basis weight of the separator, reducing the density, and reducing the thickness.
- the basis weight of the separator is low, the density is low, and the thickness is thin, the density of the separator is also lowered.
- the element short-circuit defect rate and the aging short-circuit defect rate increase, and even if the short-circuit defect does not occur, the short-circuit defect rate after being commercialized and put on the market increases. There is a difficulty that.
- the separator is required to have a high density that does not increase the short-circuit defect rate and a strength that does not cause paper breakage in each process even if the basis weight is low, the density is low, and the thickness is low.
- the separator for aluminum electrolytic capacitors is also required to have a strong tear strength.
- Patent Documents 1 to 7 Conventionally, various configurations have been proposed for the purpose of improving the characteristics of aluminum electrolytic capacitor separators (see, for example, Patent Documents 1 to 7).
- Patent Document 1 proposes a method of using beaten solvent-spun cellulose fibers in order to improve the density of the separator and improve the impedance performance.
- a separator using solvent-spun cellulose fibers with a high degree of beating has a high density and a microporous paper quality.
- Aluminum electrolytic capacitors made using this separator have both characteristics of impedance and short-circuit defect rate. improves.
- Patent Document 1 when a 100% by mass regenerated cellulose fiber separator that can be beaten is used, the tear strength is low, and thus the separator may break during the production process of the aluminum electrolytic capacitor. there were.
- the occurrence of breakage of the separator is considered to be due to the following reason.
- By increasing the degree of beating of the regenerated cellulose fiber that can be beaten fine fibrils of several tens of nm to several ⁇ m can be obtained.
- the obtained fibrillated fine fiber has high rigidity and is not easily crushed. Therefore, when it is made into paper, it does not bind in the form of a film unlike the fibrillated fine fiber of natural fiber. Therefore, by using the fibrillated fine fiber obtained by beating the regenerated cellulose fiber for the separator, an extremely dense separator in which fine fibers independent from each other are constituted by innumerable point adhesion (hydrogen bonding) is obtained. can get.
- the separator obtained in this way has a high density, it has a microporous paper quality due to its structure, and the fibril cross section has a shape close to a perfect circle, so that the natural fiber is relatively flat. Unlike, it does not hinder the flow of ions.
- an aluminum electrolytic capacitor manufactured using a separator containing a regenerated cellulose fiber beating raw material has improved impedance and short circuit defect characteristics.
- regenerated cellulose fibers that can be beaten increase the bond between fibers and improve the tensile strength by beating, but if the degree of beating of the fiber is further increased, the tear strength decreases rapidly.
- the tensile strength due to the bond between fibers and the tear strength are in a contradictory relationship, and the higher the beating, the higher the tensile strength, but the lower the tear strength.
- beating is suppressed in order to improve the tear strength, not only the tensile strength but also the denseness is lowered, so that the short-circuit defect rate of the aluminum electrolytic capacitor is increased.
- Patent Document 2 proposes a method of blending regenerated cellulose fibers and beaten natural cellulose fibers in order to improve the tear strength of the separator and suppress the breakage of the separator in the aluminum electrolytic capacitor manufacturing process.
- the regenerated cellulose fiber 10-30% by mass of the natural cellulose fiber and the remaining part beaten the natural cellulose fiber becomes a skeleton, and the regenerated cellulose fiber beaten between the skeletons fills the tear strength and denseness.
- a separator having excellent properties can be obtained.
- the separator of Patent Document 2 is less dense than the separator composed only of regenerated cellulose fibers having a high degree of beating as disclosed in Patent Document 1. For this reason, when the separator of patent document 2 is used for an aluminum electrolytic capacitor, the short-circuit defect rate also increases.
- Patent Document 3 a separator is proposed which is made of continuous cellulose fibers with a fiber diameter of 0.5 to 8.0 ⁇ m produced by the wet spunbond method, and can reduce impedance and short-circuit failure rate when used in aluminum electrolytic capacitors. Has been.
- the wet spunbond method has anisotropy in the fiber arrangement, and it is difficult to form a dense web as in the papermaking method.
- the problem is solved by using a continuous long fiber of uniform fineness, but it still affects the denseness of a separator made of regenerated cellulose fibrils with a high degree of beating. Absent.
- short-circuit defects increase, and it is possible to cope with the low impedance of aluminum electrolytic capacitors as recently requested. There wasn't.
- the fiber which comprises the separator of patent document 3 is a cupra rayon which uses the copper ammonia solution in the manufacture stage of a raw material, it contains the copper ion inside a fiber. Therefore, after an aluminum electrolytic capacitor is put on the market, there is a risk of short-circuiting when copper ions are deposited inside the aluminum electrolytic capacitor.
- Patent Document 4 a separator is proposed in which paper is made using beaten cellulose fibers as a raw material and impregnated with a paper strength enhancer to improve tensile strength while having low impedance. If this separator is used for an aluminum electrolytic capacitor, a capacitor with a low short-circuit defect rate and a low impedance can be realized.
- Patent Document 5 proposes a separator that uses regenerated cellulose fibers with controlled freeness and is excellent in strength when an electrolytic solution adheres thereto.
- the separator described in Patent Document 5 has a lower degree of beating of the fiber than the separator described in Patent Document 1. For this reason, in the area
- Patent Document 6 proposes a separator that simultaneously improves denseness and impedance characteristics by blending esparto fiber, which is a natural fiber having a small cross-sectional diameter and a nearly circular shape.
- esparto fiber which is a natural fiber having a small cross-sectional diameter and a nearly circular shape.
- the denseness of the separator made of esparto fiber pulp does not reach the denseness of the separator made of regenerated cellulose fiber fibrils with a high degree of beating.
- the separator described in Patent Document 6 it cannot be said that the density of the separator is sufficient for the recent demand for a reduction in short-circuit defect rate.
- Patent Document 7 proposes a separator that reduces a short-circuit defect and improves impedance characteristics by using a two-layer separator of a natural cellulose layer having a high degree of beating and a layer having a low degree of beating.
- the separator described in Patent Document 7 has a natural cellulose layer with a high degree of beating, it is effective in reducing the short-circuit defect rate, but compared with the separator described in Patent Document 1, etc. The characteristic was easy to deteriorate. For this reason, further reduction of impedance is required.
- the denseness, impedance performance, tear strength, and the like required for the separator are in a complex relationship with each other, and it has been difficult to improve all of these performances at the same time.
- the present invention has been made in view of the above problems, and an object thereof is to provide a separator excellent in tear strength, denseness, and impedance performance. Another object of the present invention is to provide an aluminum electrolytic capacitor that is excellent in impedance performance, improves the short-circuit defect rate, and improves the yield by using this separator.
- the separator of the present invention is a separator interposed between an anode and a cathode, and is made of beating regenerated cellulose fiber.
- the separator has a CSF value X [ml] and a specific tear strength Y [mN ⁇ m 2 / g. Is in a range that simultaneously satisfies the following formulas 1 to 3.
- Formula 1 0 ⁇ X ⁇ 300
- Formula 2 15 ⁇ Y ⁇ 100
- Formula 3 Y ⁇ 0.175X ⁇ 2.5
- the CSF value X and the specific tear strength Y of the separator are in a range satisfying the following formulas 1 to 4.
- Formula 1 0 ⁇ X ⁇ 300
- Formula 2 15 ⁇ Y ⁇ 100
- Formula 3 Y ⁇ 0.175X ⁇ 2.5
- Formula 4 Y ⁇ 0.05X + 45
- the CSF value X and the specific tear strength Y of the separator are in a range that simultaneously satisfies the following formulas 2 to 5.
- Formula 2 15 ⁇ Y ⁇ 100
- Formula 3 Y ⁇ 0.175X ⁇ 2.5
- Formula 4 Y ⁇ 0.05X + 45
- Formula 5 0 ⁇ X ⁇ 100
- the thickness is more preferably 10 to 50 ⁇ m.
- the density is more preferably 0.25 to 0.70 g / cm 3 .
- the “CSF value” is a value measured according to “JIS P8121-2 Pulp-Freeness test method-Part 2: Canadian Standard Freeness Method”.
- the “specific tear strength” is a value calculated by dividing the tear strength by the basis weight.
- the specific tear strength in the transverse direction (CD) as defined in
- the separator when the separator is made of a mixed raw material of regenerated cellulose fibers having two types of beating of fiber A and fiber B, the separator has a CSF value X and a specific tear strength Y of Formula 1 It becomes possible to make it the range which satisfy thru
- the aluminum electrolytic capacitor of the present invention is formed by interposing a separator between an anode and a cathode, and the separator of the present invention is used as a separator.
- the separator for aluminum electrolytic capacitors excellent in tearing strength, denseness, and impedance performance can be provided. Further, by using the separator, it is possible to provide an aluminum electrolytic capacitor that has excellent impedance performance, improves the short-circuit defect rate, and can improve the yield.
- the separator of the present embodiment is made of regenerated cellulose fiber that can be beaten in a separator interposed between an anode and a cathode, and has a CSF value X [ml] and a specific tear strength Y [mN ⁇ m 2 / g]. Is in a range that simultaneously satisfies the following formulas 1 to 3, more preferably in a range that simultaneously satisfies the formulas 1 to 4, and still more preferably in a range that simultaneously satisfies the formulas 2 to 5.
- the aluminum electrolytic capacitor of this Embodiment is the structure which interposed the separator between the anode and the cathode using the separator of the said structure as a separator.
- Tear strength is the mass per 1 m 2 of the paper, it is known to be proportional to the basis weight. For this reason, the specific tear strength obtained by dividing the value of the tear strength by the basis weight is used as an index for comparison of the tear strength excluding factors such as the basis weight and thickness of the paper.
- the tear strength is mainly derived from the properties of the raw material. By comparing the specific tear strength, the specific tear strength is excellent in that not only the characteristics of the paper of the separator but also the characteristics of the raw materials can be compared at the same time.
- the specific tear strength varies greatly depending on the degree of beating of the raw material.
- the specific tear strength gradually increases as the degree of beating increases, but decreases as the degree of beating further increases.
- the equipment used for beating the fibers may be any equipment as long as it is usually used for preparing papermaking raw materials.
- a beater In general, a beater, a conical refiner, a disc refiner, a high-pressure homogenizer, and the like can be given.
- the fiber is refined by beating.
- the regenerated cellulose refined by beating is tried to be filtered on the sieve plate, it is affected by the fiber mat that is initially deposited on the sieve plate. Thereafter, the resistance of the suspension trying to pass through the sieve plate increases. For this reason, as the regenerated cellulose is refined by beating, the CSF value gradually decreases and reaches the lower limit.
- the lower limit value of the freeness varies depending on the fineness of the fiber used for beating and beating treatment conditions. For this reason, there is a case where the lower limit is reached before the CSF value decreases to 0 ml (that is, a value of +), and the CSF value does not increase immediately after the CSF value reaches 0 ml, and 0 ml is reduced.
- the CSF value may increase after a while.
- FIG. 1 is a graph showing the relationship between the total energy (kWh) of beating treatment and the CSF value (ml) for fibers (regenerated cellulose fibers) constituting the separator of the present invention.
- the CSF value gradually decreases and temporarily decreases to the lower limit (b state). Thereafter, by further beating, the fine fibers that pass through the holes in the sieve plate increase, so that the CSF value starts to increase. Then, when the CSF value increases and the CSF value increases, the state c is reached.
- the separator of this Embodiment is obtained by using the mixed raw material of the fiber (regenerated cellulose fiber) from which the fiber A and the fiber B differ in the degree of beating.
- the fiber A is the fiber with the lower beating degree
- the fiber B is the fiber with the higher beating degree.
- the fiber A a fiber having a CSF value of 500 to 0 ml is employed.
- the blending ratio of the fiber A is 20 to 80% by mass.
- the fiber B a fiber having a CSF value of 1 to 500 ml which is once beaten after the CSF value is once lowered to the lower limit value (0 ml or + value) and turned up is employed.
- the blending ratio of the fiber B is 20 to 80% by mass.
- the present embodiment can provide a separator for an aluminum electrolytic capacitor that is excellent in tear strength, compactness, and impedance performance. If this separator is used for an aluminum electrolytic capacitor, it is possible to improve the impedance performance, improve the short-circuit defect rate, and improve the yield in the aluminum electrolytic capacitor manufacturing process.
- a good result was obtained by mixing the regenerated cellulose fibers B having a CSF value of 1 to 500 ml whose CSF value started to increase at a rate of 20 to 80% by mass and making paper.
- fiber A and fiber B in the above ratio, and making paper it is possible to achieve both a conflicting relationship between tear strength and denseness. Is possible.
- the aluminum electrolytic capacitor using the separator of the present embodiment can be configured by impregnating and holding an electrolytic solution in the separator portion and separating the anode foil and the cathode foil with the separator.
- a plurality of separators may be interposed between the two electrodes as necessary within the allowable range of the outer diameter of the capacitor element.
- electrolyte solution may be used as long as it is a commonly used electrolyte solution.
- an electrolytic solution generally, ethylene glycol (hereinafter abbreviated as EG), ⁇ -butyrolactone (hereinafter abbreviated as GBL), dimethylformamide, sulfolane and the like are used as solvents, and boric acid, adipic acid, and maleic acid are used as these solvents. Or there exists what melt
- the electrolytic solution is not limited to the above examples and combinations thereof, and any electrolytic solution that is usually used may be used.
- the separator of this embodiment uses regenerated cellulose fibers that can be beaten, and the separator has a CSF value of X [ml] and a transverse tear (CD) specific tear strength of Y [mN ⁇ m 2 / g].
- the CSF value X and the specific tear strength Y are in a range that simultaneously satisfies the following formulas 1 to 3. More preferably, it is in a range that satisfies Formulas 1 to 4 simultaneously. More preferably, the separator is in a range that simultaneously satisfies Formulas 2 to 5.
- the “lateral direction (CD)” of the separator means the width direction of the separator wound in a long shape.
- Formula 5 0 ⁇ X ⁇ 100
- the separator When the expressions 1 to 3 are satisfied at the same time, the separator has an excellent tear strength and a high density, so that it can improve both the failure rate and the failure rate when used in an aluminum electrolytic capacitor. . Moreover, when Formula 1 thru
- the thickness of the separator is preferably 10 to 50 ⁇ m. When the thickness is less than 10 ⁇ m, short-circuit defects increase. On the other hand, if the thickness exceeds 50 ⁇ m, it may be difficult to reduce the size of the element, or the impedance performance may deteriorate.
- the density of the separator is preferably 0.25 to 0.70 g / cm 3 .
- the density is less than 0.25 g / cm 3 , the density of the separator is lowered and short-circuit defects are increased.
- the density exceeds 0.70 g / cm 3 , the impedance performance deteriorates.
- the present embodiment is made by mixing two types of fibers, fiber A and fiber B, with different degrees of beating using a raw material obtained by beating regenerated cellulose fibers that can be beaten.
- a separator is obtained.
- the reason why the fibers A and B having different beating degrees are mixed is to make the characteristics of the fibers A and B compatible.
- a separator using fiber A alone with a low degree of beating is excellent in tear strength but lacks denseness.
- a separator using a fiber B having a high degree of beating is excellent in denseness but weak in tearing strength.
- the separator formed into a sheet by mixing the fiber A and the fiber B of the present invention is compared with the separator formed into a sheet using a raw material beaten alone up to the same CSF value, the separator of the present invention has a denseness or tear strength. At least one of the characteristics is excellent. Since the raw material beaten alone is finer than fiber A, the tear strength is weak, and since it is not finer than fiber B, it is not dense.
- the role required for the fiber A is to improve the tear strength of the separator.
- Regenerated cellulose fibers having a lower degree of beating than fiber B are intertwined to form a three-dimensional network structure, and the entanglement point of this network structure is supported by fibrils and fibers B generated from fiber A. This improves the tear strength of the separator.
- it does not reach the fiber B with a high degree of beating since it is a regenerated cellulose fiber that has been beaten, the denseness and impedance of the separator are not impaired.
- the beaten raw material preferably has a CSF value of 500 to 0 ml.
- the CSF value is larger than 500 ml, the tear strength cannot be improved.
- a CSF value larger than 500 ml is a state in which there are many fibers with low beating degree, and since the bond between fibers is weak, even if a three-dimensional network structure is configured, the fibers are not pulled out.
- the resistance is weak.
- the degree of beating is increased until the CSF value once decreases to the lower limit value (0 ml or + value) and then starts to increase, the fiber becomes excessively fine. The resistance to pulling is weak, and the tear strength of the separator is significantly reduced.
- the mixing ratio of the fiber A is preferably 20 to 80% by mass. If the blending ratio is less than 20% by mass, the tear strength is lowered. When the blending ratio exceeds 80% by mass, the sheet obtained by papermaking becomes non-uniform, and the short circuit failure of the aluminum electrolytic capacitor increases.
- the role required for the fiber B is to improve the density of the separator. Since the regenerated cellulose fiber having a high degree of beating fills the gaps in the separator, the density of the separator is improved.
- the degree of beating of the fiber B is preferably 1 to 500 ml after the beating raw material CSF value is once lowered to the lower limit value (0 ml or + value) and further beaten and turned up.
- the CSF value of the fiber B reaches the lower limit value or before the lower limit value, the fineness of the fiber B is insufficient, and the formation of the sheet obtained by mixing with the fiber A becomes uneven. The number of short-circuit defects will increase.
- the CSF value once decreases to the lower limit value and starts to rise, it is further beaten. If the CSF value exceeds 500 ml, the fibers become too fine and are not suitable as a papermaking raw material.
- the blending ratio of fiber B is preferably 20 to 80% by mass. If the blending ratio is less than 20% by mass, the formation of the sheet obtained by papermaking becomes uneven, and the short circuit failure of the aluminum electrolytic capacitor increases. When the blending ratio exceeds 80% by mass, the tear strength of the separator is lowered.
- the reason for blending only regenerated cellulose fibers and not blending natural cellulose fibers or other synthetic fibers is as follows. Fibrils obtained by beating regenerated cellulose fibers have a small fiber diameter and high rigidity. Therefore, although fibers and fibrils are bonded by hydrogen bonding or the like at the entanglement point, since the fibers and fibrils are not bound to each other in a film shape with a surface or a line, there is a feature that impedance does not deteriorate.
- natural cellulose fiber has low rigidity and strong interfiber bonding force. That is, at the entanglement point between the natural celluloses, not only are they entangled, but the fibers are adsorbed by hydrogen bonding or the like in the process of drying the sheet, and are fused by surfaces, lines, or a combination thereof. As a result, the impedance deteriorates.
- Synthetic fibers unlike cellulose fibers, are only entangled at the entanglement points of the fibers, the bonding strength between fibers is weak, and various problems occur. For example, when blending synthetic fiber as fiber A, the tear strength is weak. This is because the resistance to pulling out the fibers is weak. Further, for example, when a fine synthetic fiber is blended as the fiber B, short-circuit defects increase.
- the sheet strength can be increased by using various binder fibers or the like, and heat-sealing or adhering, but when the number of fused parts increases, the impedance deteriorates.
- regenerated cellulose fiber a solution obtained by dissolving cellulose in a molecular form with an organic solvent such as copper ammonia regenerated cellulose fiber, viscose regenerated cellulose fiber and N-methylmorpholine-N-oxide by a wet spinning method is used as a spinning stock solution.
- Solvent-spun recycled cellulose fibers and the like.
- typical regenerated cellulose fibers that can be beaten include polynosic rayon as viscose regenerated cellulose fibers, and lyocell as solvent-spun regenerated cellulose fibers. By using these regenerated cellulose fibers, A fiber layer can be easily formed.
- cupra rayon which is a copper ammonia regenerated cellulose fiber
- cupra rayon is used as a separator for an aluminum electrolytic capacitor, there is a risk of short-circuiting such as precipitation of copper ions inside the capacitor after the aluminum electrolytic capacitor is put on the market. Therefore, cupra rayon is unsuitable as a material for aluminum electrolytic capacitor separators.
- the present invention is not limited to the above example, and any regenerated cellulose fiber that can be beaten may be used except for the case where there is a problem in terms of impurities, such as copper ammonia regenerated cellulose. It is not limited to polynosic rayon fiber or lyocell fiber showing a detailed configuration.
- the thickness of the separator may be adjusted by calendaring as necessary. Moreover, you may give paper strength reinforcement
- the separator configuration described above can provide a good separator in both the aluminum electrolytic capacitor manufacturing process and the aluminum electrolytic capacitor characteristics. That is, it is a good separator that has excellent impedance performance, improves the short-circuit defect rate, and improves the yield in the capacitor manufacturing process.
- the tear strength in the transverse direction (CD) of the separator was measured by the method specified in “JIS P 8116“ Paper—Tear Strength Test Method—Elmendorf Tear Tester Method ””. Next, the value of the obtained tear strength was divided by the basis weight of the separator to calculate the specific tear strength of the separator.
- the short-circuit defect rate is determined by counting the number of short-circuit defects during aging and aging of the winding element before impregnating with the electrolytic solution using the capacitor element that has been wound without breakage failure. By dividing by the number of elements wound without breakage failure, the percentage of short-circuit failure was obtained.
- the impedance of the produced aluminum electrolytic capacitor was measured at 20 ° C. and a frequency of 100 kHz using an LCR meter.
- each Example comprised the separator by the papermaking method using the regenerated cellulose fiber.
- Example 1 As fiber A, 20% by mass of lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 0 ml, and fiber B, the CSF value was once reduced to 0 ml (lower limit), and further beaten, and the CSF value of 500 ml turned to rise. Using a papermaking raw material in which 80% by mass of lyocell fiber, which is a regenerated cellulose fiber, is blended, a thickness of 10.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 17 mN ⁇ m 2 / g are obtained. A separator was obtained. The separator had a CSF value of 10 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 7.6 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and the aluminum of Example 1 An electrolytic capacitor was obtained.
- Example 2 As fiber A, 50% by mass of lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 0 ml, and fiber B, the CSF value was once reduced to 0 ml (lower limit) and further beaten, and the CSF value of 350 ml turned to rise.
- a separator was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 7.9 mm was formed, impregnated with a GBL-based electrolyte, inserted into a case, sealed, and the aluminum of Example 2 An electrolytic capacitor was obtained.
- Example 3 A separator having a thickness of 40.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 52 mN ⁇ m 2 / g was obtained by a circular net papermaking method using the same papermaking raw material as that of the separator of Example 2.
- the separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 8.5 mm was formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and aluminum of Example 3 An electrolytic capacitor was obtained.
- lyocell fiber which is a regenerated cellulose fiber with a CSF value of 10 ml
- fiber B after the CSF value is once reduced to 0 ml (lower limit), it is further beaten, and the CSF value of 350 ml that has started to rise is increased.
- a separator was obtained.
- the separator had a CSF value of 0 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 7.5 mm was formed, impregnated with a GBL-based electrolyte, inserted into a case, sealed, and the aluminum of Comparative Example 1 An electrolytic capacitor was obtained.
- Comparative Example 2 Using the same papermaking raw material as in Comparative Example 1, a sheet was obtained by the long net papermaking method. Subsequently, according to the method of Example 1 of Japanese Patent Application Laid-Open No. 2006-253728, the sheet was subjected to a paper strength enhancing process, a thickness of 16.0 ⁇ m, a density of 0.238 g / cm 3 , and a specific tear strength of 13 mN ⁇ m 2. / G separator was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 7.8 mm was formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and aluminum of Comparative Example 2 An electrolytic capacitor was obtained.
- Lyocell fiber which is a regenerated cellulose fiber, is once beaten down to 0 ml (lower limit), then beaten, and a paper sheet raw material with a CSF value of 160 ml turned up is used to obtain a sheet by the long net papermaking method. It was. Subsequently, according to the method of Example 1 of Japanese Patent Application Laid-Open No. 2006-253728, the sheet was subjected to a paper strength enhancing process, a thickness of 20.0 ⁇ m, a density of 0.425 g / cm 3 , and a specific tear strength of 6 mN ⁇ m 2. / G separator was obtained. The separator had a CSF value of 150 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 7.9 mm is formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and the aluminum of Conventional Example 1 An electrolytic capacitor was obtained.
- a separator having a thickness of 40.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 43 mN ⁇ m 2 / g is obtained by a circular net papermaking method according to the method of Example 1 of JP-A-53-142652. It was.
- the separator had a CSF value of 620 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 6.3 V, a capacity of 1000 ⁇ F, and an element outer diameter of 8.5 mm is formed, impregnated with a GBL-based electrolyte, inserted into a case, sealed, and the aluminum of Conventional Example 2 An electrolytic capacitor was obtained.
- polynosic rayon fiber which is a regenerated cellulose fiber having a CSF value of 0 ml
- fiber B the CSF value is once lowered to 0 ml (lower limit value), and further beaten, and the CSF value is turned to 1 ml.
- a papermaking raw material containing 80% by mass of polynosic rayon fiber, which is a regenerated cellulose fiber a sheet was obtained by a long net papermaking method. Subsequently, the sheet was calendered to obtain a separator having a thickness of 25.0 ⁇ m, a density of 0.540 g / cm 3 , and a specific tear strength of 17 mN ⁇ m 2 / g.
- the separator had a CSF value of 0 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.0 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and the aluminum electrolytic capacitor of Example 4 It was.
- Example 5 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 100 ml, is 30% by mass. As fiber B, the CSF value is once lowered to 0 ml (lower limit), and further beaten, and the CSF value of 20 ml turned to rise. Using a papermaking raw material containing 70% by mass of lyocell fiber, which is a regenerated cellulose fiber, having a thickness of 30.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 24 mN ⁇ m 2 / g by the long net papermaking method. A separator was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.2 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed. It was.
- the separator had a CSF value of 55 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.2 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and an aluminum electrolytic capacitor of Comparative Example 3 It was.
- an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.3 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and an aluminum electrolytic capacitor of Comparative Example 4 It was.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 0 ml
- fiber B the CSF value is once lowered to 0 ml (lower limit), and further beaten, and the CSF value of 680 ml turned to rise.
- a papermaking raw material containing 20% by mass of lyocell fiber which is a regenerated cellulose fiber a thickness of 35.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 105 mN ⁇ m 2 / g by a circular net papermaking method.
- a separator was obtained.
- the separator had a CSF value of 0 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.3 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed, and the aluminum electrolytic capacitor of Comparative Example 5 It was.
- a lyocell fiber which is a regenerated cellulose fiber having a CSF value of 0 ml, as a papermaking raw material, a thickness of 30.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 7 mN ⁇ m 2 / g are obtained by the long net papermaking method.
- a separator was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.2 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed. It was.
- a separator having a thickness of 30.0 ⁇ m and a density of 0.333 g / cm 3 was obtained according to the method of Example 1 of JP-A-2009-158811. The specific tear strength of this separator was so large that it could not be measured. Moreover, since it consists of continuous long fibers, disaggregation was impossible.
- an aluminum electrolytic capacitor element having a rated voltage of 16 V, a capacity of 550 ⁇ F, and an element outer diameter of 9.2 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed. It was.
- a separator is produced using cupra rayon which is a copper ammonia regenerated cellulose fiber.
- Example 6 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 80 ml, is 40% by mass, and as fiber B, after the CSF value has once decreased to 0 ml (lower limit), it is further beaten, and the CSF value of 500 ml that has started to rise is increased.
- a papermaking raw material in which 60% by mass of lyocell fiber, which is a regenerated cellulose fiber, was blended, a thickness of 35.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 30 mN ⁇ m 2 / g were obtained.
- a separator was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.5 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed. It was.
- Example 7 As fiber A, lyocell fiber which is a regenerated cellulose fiber having a CSF value of 500 ml is 60 mass%, and fiber B is used. After the CSF value is once lowered to 0 ml (lower limit value), it is further beaten, and the CSF value of 20 ml turned to rise. Using a papermaking raw material containing 40% by mass of lyocell fiber, which is a regenerated cellulose fiber, a sheet was obtained by a long net papermaking method.
- the sheet was calendered to obtain a separator having a thickness of 35.0 ⁇ m, a density of 0.486 g / cm 3 , and a specific tear strength of 43 mN ⁇ m 2 / g.
- the separator had a CSF value of 56 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.5 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and the aluminum electrolytic capacitor of Example 7 It was.
- Example 8 A separator having a thickness of 40.0 ⁇ m, a density of 0.375 g / cm 3 , and a specific tear strength of 82 mN ⁇ m 2 / g was obtained by a circular net papermaking method using the same papermaking raw material as in Example 7.
- the separator had a CSF value of 56 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.6 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed, and the aluminum electrolytic capacitor of Example 8 It was.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.6 mm was formed, impregnated with a GBL-based electrolyte, inserted into a case, sealed, and an aluminum electrolytic capacitor of Comparative Example 6 It was.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 0 ml, is 15% by mass, and fiber B is used. After the CSF value is once reduced to 0 ml (lower limit value), it is further beaten and a CSF value of 340 ml that has started to rise.
- the separator had a CSF value of 5 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.5 mm was formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and an aluminum electrolytic capacitor of Comparative Example 7 It was.
- the conifer kraft pulp fiber which is a natural cellulose fiber having a CSF value of 500 ml
- fiber B after the CSF value has once decreased to 0 ml (lower limit), the CSF value has been further beaten and turned upward.
- a papermaking raw material in which 70% by mass of lyocell fiber, which is 200 ml of regenerated cellulose fiber, is blended, a thickness of 30.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 20 mN ⁇ m 2 / g separator was obtained.
- the separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an outer diameter of the element of 9.3 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, and sealed. It was.
- an aluminum electrolytic capacitor element having a rated voltage of 50 V, a capacity of 150 ⁇ F, and an element outer diameter of 9.5 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and the aluminum electrolytic capacitor of Conventional Example 6 It was.
- Example 9 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 400 ml, is 80% by mass, and fiber B is used. After the CSF value is once reduced to 0 ml (lower limit), it is further beaten, and the CSF value is 1 ml.
- a separator was obtained. The separator had a CSF value of 140 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.1 mm was formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- Example 10 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 500 ml, is 80% by mass, and fiber B is used. After the CSF value is once reduced to 0 ml (lower limit), it is further beaten, and the CSF value of 20 ml turned to rise. Using a papermaking raw material containing 20% by mass of lyocell fiber, which is a regenerated cellulose fiber, having a thickness of 40.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 55 mN ⁇ m 2 / g by the long net papermaking method. A separator was obtained. The separator had a CSF value of 260 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.1 mm was formed, impregnated with an EG-based electrolyte, and inserted into the case.
- the aluminum electrolytic capacitor of Example 10 was sealed.
- Example 11 As fiber A, lyocell fiber which is a regenerated cellulose fiber having a CSF value of 500 ml is 60 mass%, and fiber B is used. After the CSF value is once lowered to 0 ml (lower limit value), it is further beaten, and the CSF value of 20 ml turned to rise.
- a separator was obtained. The separator had a CSF value of 56 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.1 mm was formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- Example 12 A separator having a thickness of 45.0 ⁇ m, a density of 0.356 g / cm 3 , and a specific tear strength of 58 mN ⁇ m 2 / g was obtained by a circular net papermaking method using the same papermaking raw material as that of the separator of Example 9.
- the separator had a CSF value of 140 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.2 mm is formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- Example 13 A separator having a thickness of 45.0 ⁇ m, a density of 0.378 g / cm 3 , and a specific tear strength of 98 mN ⁇ m 2 / g was obtained by a circular net papermaking method using the same papermaking raw material as that of the separator of Example 10.
- the separator had a CSF value of 260 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.2 mm was formed, impregnated with an EG-based electrolytic solution, inserted into a case, sealed, and the aluminum electrolytic capacitor of Example 13 It was.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 620 ml is 70% by mass
- fiber B is used. After the CSF value is once lowered to 0 ml (lower limit value), it is further beaten, and the CSF value is turned to 10 ml.
- a thickness of 45.0 ⁇ m, a density of 0.367 g / cm 3 , and a specific tear strength of 105 mN ⁇ m 2 / g were obtained.
- a separator was obtained.
- the separator had a CSF value of 120 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an element outer diameter of 11.2 mm was formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- a sheet was obtained by a circular net papermaking method using lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 200 ml, as a papermaking material. Subsequently, according to the method of Example 1 of Japanese Patent Laid-Open No. 2006-253728, the sheet was subjected to a paper strength enhancing process, a thickness of 40.0 ⁇ m, a density of 0.325 g / cm 3 , and a specific tear strength of 107 mN ⁇ m 2. / G separator was obtained. The separator had a CSF value of 200 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 100 V, a capacity of 50 ⁇ F, and an outer diameter of the element of 11.1 mm is formed, impregnated with an EG-based electrolytic solution, inserted into a case, and sealed. It was.
- Example 14 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 500 ml, is 70% by mass, and fiber B is used. After the CSF value has once decreased to 0 ml (lower limit), it is further beaten, and the CSF value of 1 ml has started to rise. Using a papermaking raw material blended with 30% by mass of lyocell fiber, which is a regenerated cellulose fiber, having a thickness of 50.0 ⁇ m, a density of 0.300 g / cm 3 , and a specific tear strength of 48 mN ⁇ m 2 / g A separator was obtained. The separator had a CSF value of 95 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 200 V, a capacity of 120 ⁇ F, and an element outer diameter of 15.5 mm was formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 550 ml, is 80% by mass, and fiber B is used. After the CSF value is once lowered to 0 ml (lower limit), it is further beaten, and the CSF value of 1 ml turned up.
- a papermaking raw material blended with 20% by mass of lyocell fiber, which is a regenerated cellulose fiber a thickness of 55.0 ⁇ m, a density of 0.364 g / cm 3 , and a specific tear strength of 17 mN ⁇ m 2 / g are obtained by the long net papermaking method. A separator was obtained.
- the separator had a CSF value of 120 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 200 V, a capacity of 120 ⁇ F, and an element outer diameter of 15.7 mm was formed, and after being impregnated with an EG-based electrolytic solution, an attempt was made to insert it into the case. Therefore, it could not be inserted into a case having the same size as in Example 14. For this reason, it was inserted into a case having a size larger than that of Example 14 to obtain an aluminum electrolytic capacitor of Comparative Example 9.
- a separator having a thickness of 60.0 ⁇ m, a density of 0.600 g / cm 3 , and a specific tear strength of 35 mN ⁇ m 2 / g is obtained by a circular net papermaking method according to the method of Example 1 of JP-A-53-142652. It was.
- the separator had a CSF value of 450 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 200 V, a capacity of 120 ⁇ F, and an element outer diameter of 15.9 mm was formed. After impregnating with an EG-based electrolytic solution, an attempt was made to insert it into the case, but the element outer diameter was large. Therefore, it could not be inserted into a case having the same size as in Example 14. For this reason, it was inserted into a case having a size larger than that of Example 14 to obtain the aluminum electrolytic capacitor of Conventional Example 8.
- Example 9 According to the method of Example 2 of JP-A-6-168848, JP-thick 25.0, dense layer of density 0.800 g / cm 3, a thickness of 15.0 .mu.m, a low density layer of density 0.367 g / cm 3 A separator having a thickness of 40.0 ⁇ m, a density of 0.638 g / cm 3 and a specific tear strength of 14 mN ⁇ m 2 / g was obtained. The separator had a CSF value of 0 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 200 V, a capacity of 120 ⁇ F, and an element outer diameter of 15.2 mm is formed, impregnated with an EG-based electrolytic solution, and then inserted into a case and sealed. It was.
- Example 15 As fiber A, lyocell fiber, which is a regenerated cellulose fiber having a CSF value of 200 ml, is 80% by mass, and fiber B is used. After the CSF value is once reduced to 0 ml (lower limit), it is further beaten, and the CSF value is 1 ml. Using a papermaking raw material in which 20% by mass of lyocell fiber, which is a regenerated cellulose fiber, was blended, a thickness of 35.0 ⁇ m, a density of 0.457 g / cm 3 , and a specific tear strength of 20 mN ⁇ m 2 / g were obtained. A separator was obtained. The separator had a CSF value of 60 ml.
- an aluminum electrolytic capacitor element with a rated voltage of 450 V, a capacity of 50 ⁇ F, and an element outer diameter of 17.6 mm is formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and then carried out.
- the aluminum electrolytic capacitor of Example 15 was obtained.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 550 ml, is 80% by mass, and fiber B is used. After the CSF value is once lowered to 0 ml (lower limit), it is further beaten, and the CSF value of 1 ml turned up.
- the separator had a CSF value of 220 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 450 V, a capacity of 50 ⁇ F, and an element outer diameter of 17.6 mm is formed, impregnated with a GBL-based electrolytic solution, inserted into a case, sealed, and the aluminum electrolytic capacitor of Comparative Example 10 It was.
- lyocell fiber which is a regenerated cellulose fiber having a CSF value of 620 ml, is 80% by mass, and fiber B is used. After the CSF value is once lowered to 0 ml (lower limit), it is further beaten, and the CSF value of 1 ml that has started to rise is increased.
- the separator had a CSF value of 310 ml. Using this separator, an aluminum electrolytic capacitor element having a rated voltage of 450 V, a capacity of 50 ⁇ F, and an element outer diameter of 17.9 mm is formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and the aluminum electrolytic capacitor of Comparative Example 11 did.
- a separator having a thickness of 80.0 ⁇ m, a density of 0.400 g / cm 3 , and a specific tear strength of 95 mN ⁇ m 2 / g was obtained by a circular net papermaking method using the same papermaking raw material as that of the separator of Comparative Example 11.
- the separator had a CSF value of 310 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 450 V, a capacity of 50 ⁇ F, and an element outer diameter of 17.9 mm was formed, impregnated with a GBL electrolyte, inserted into a case, sealed, and the aluminum electrolytic capacitor of Comparative Example 12 did.
- a separator having a thickness of 90.0 ⁇ m, a density of 0.600 g / cm 3 , and a specific tear strength of 35 mN ⁇ m 2 / g is obtained by the circular net papermaking method according to the method of Example 1 of JP-A-53-142652. It was.
- the separator had a CSF value of 450 ml.
- an aluminum electrolytic capacitor element having a rated voltage of 450 V, a capacity of 50 ⁇ F, and an element outer diameter of 18.2 mm was formed, and after being impregnated with an EG electrolyte solution, an attempt was made to insert it into the case, but the element outer diameter was large. Therefore, it could not be inserted into the case of the same size as Example 15 and Comparative Examples 9 to 11. For this reason, it was inserted into a case having a size larger than that of Example 14 to obtain the aluminum electrolytic capacitor of Conventional Example 11.
- the fiber A for improving the tear strength and the fiber B for improving the denseness are blended, and the fiber A and the fiber B are made of regenerated cellulose fibers,
- the blending ratio to 20 to 80% and the blending ratio of fiber B to 20 to 80%, it is possible to provide a separator in which the CSF value X and specific tear strength Y of the separator satisfy the following formula.
- Formula 2 15 ⁇ Y ⁇ 100
- Table 1 shows the evaluation results of the separators of Examples 1 to 15 of the present embodiment described above, Comparative Examples 1 to 12, and Conventional Examples 1 to 11, and the performance evaluation results of the aluminum electrolytic capacitors.
- Table 1 in order to distinguish the difference in the degree of beating, the CSF value once reduced to 0 ml (lower limit value) and further beaten, and the CSF value turned to rise is marked with *.
- the thickness of the separator is described as “one thickness value ⁇ 2”.
- Each of the various measured values shows an average value of a plurality of samples.
- the aluminum electrolytic capacitors produced using the separators of Examples 1 to 3 have a low fracture failure rate of 0.0 to 0.4%, which is lower than 1%.
- the short-circuit defect rate is 0.2 to 0.5%, which is lower than 1%.
- the impedance is also sufficiently low at 0.110 to 0.140 ⁇ .
- the separator of Comparative Example 1 is as thin as 9.0 ⁇ m, the fracture failure rate is as high as 1.1% and the short-circuit failure rate is as high as 8.5%. This shows that the thickness of the separator is preferably 10 ⁇ m or more.
- the separator of Comparative Example 2 has a low density of 0.238 g / cm 3 , the fracture failure rate is as high as 1.1% and the short-circuit failure rate is as high as 8.0%. From this, it can be seen that the density of the separator is preferably 0.25 g / cm 3 or more. And the separator of the prior art example 1 uses only the raw material which becomes CSF value 160ml turned into the rise by further beating after the CSF value of a lyocell fiber once fell to 0 ml (lower limit). . For this reason, the specific tear strength of the separator is 6 mN ⁇ m 2 / g, which is lower than the range of Equation 2, and the fracture failure rate is as high as 1.1%.
- the separator of Conventional Example 2 has a high CSF value of 620 ml. For this reason, the density of the separator is low, and the short-circuit defect is as high as 11.5%. Furthermore, the separator is composed of only natural fibers, and the impedance is deteriorated to three times or more that of the first embodiment.
- the aluminum electrolytic capacitors produced using the separators of Examples 4 and 5 have low failure rates of 0.1 to 0.2%, which are lower than 1%.
- the short-circuit defect rate is 0.2 to 0.3%, which is lower than 1%.
- the impedance is also sufficiently low at 0.120 to 0.125 ⁇ .
- the separator of Comparative Example 3 has a CSF value of 20 ml, after the CSF value of the fiber A is once lowered to 0 ml (lower limit) and further beaten and turned up. For this reason, the specific tear strength of the separator is below the range of Formula 2, and the fracture failure rate is as high as 3.0%.
- the separator of the comparative example 4 has a CSF value of the fiber B of 5 ml, and the degree of beating is low.
- the specific tear strength exceeds the range of Formula 2, and the denseness of the separator is low. For this reason, the short-circuit defect rate of the aluminum electrolytic capacitor is as high as 2.2%.
- the separator of Comparative Example 5 has a CSF value of 680 ml, which was further beaten and turned up after the CSF value of the fiber B once decreased to 0 ml (lower limit value). For this reason, in the papermaking process of a separator, the excessively refined fiber in the fiber B has fallen off from the papermaking wire. As a result, the separator of Comparative Example 5 has a specific tear strength that exceeds the range of Formula 2, and the short-circuit defect rate is as high as 2.0%.
- the separator of Conventional Example 3 has a specific tear strength that is lower than the range of Formula 2, and has a high fracture failure rate of 11.0%.
- the CSF value of the separator of Conventional Example 3 is 0 ml, which is the same as the CSF value of the separators of Example 4 and Example 5, but both the breakage failure rate and the short-circuit failure rate are the same as those of Example 4 and Example 5. The result is better. From this, rather than a single beaten raw material, as in the present invention, it is possible to improve both the compactness and tear strength by mixing raw materials with different degrees of beating, and as a result, It can be seen that both the fracture failure rate and the short-circuit failure rate of the aluminum electrolytic capacitor can be reduced.
- the separator of Conventional Example 4 is a regenerated cellulose separator formed by a wet spunbond method, and its specific tear strength is so high that it cannot be measured. For this reason, no fracture failure occurred.
- the aluminum electrolytic capacitor of Conventional Example 4 has a high short-circuit defect rate of 10.0%. This is because the spunbond method is more likely to be non-uniform than the papermaking method, and is subjected to denseness.
- this prior art example 4 uses the cupra rayon which is a copper ammonia reproduction
- the aluminum electrolytic capacitors produced using the separators of Examples 6 to 8 have a fracture failure rate of 0.0 to 0.3%, which is lower than 1%, which is low.
- the short-circuit defect rate is 0.1 to 0.3%, which is lower than 1%.
- the impedance is also sufficiently low at 0.130 to 0.140 ⁇ .
- the separator of Example 7 is obtained by making a long-mesh paper using the same papermaking raw material as in Example 8.
- the separator of Example 7 satisfies Expression 4, and the separator of Example 8 does not satisfy Expression 4.
- the capacitor of Example 7 has a lower short-circuit defect rate.
- the separator of Comparative Example 6 contains 85 mass% of fiber A and 15 mass% of fiber B, and the specific tear strength exceeds the range of Formula 2.
- the aluminum electrolytic capacitor of Comparative Example 6 has a high short-circuit defect rate of 1.1%. This is presumably because the density was not improved because the ratio of the fiber B was small.
- the separator of Comparative Example 7 contains 15 mass% of fiber A and 85 mass% of fiber B, and the specific tear strength is below the range of Formula 2.
- the separator of Comparative Example 7 has a high fracture failure rate of 1.2%. This is considered because the ratio of the fiber A which improves tear strength is small.
- Conventional Example 5 is a softwood kraft pulp having a CSF value of 500 ml as the fiber A, and a regenerated cellulose fiber having a CSF value of 200 ml that has been beaten and turned upward after the CSF value has once decreased to 0 ml (lower limit) as the fiber B. It is blended. Compared with Examples 6 to 8, the impedance value is 0.200 ⁇ , which is 30% or more higher than Examples 6 to 8, due to the influence of softwood kraft pulp.
- Conventional Example 6 is a separator in which acrylic fiber is blended, but the specific tear strength is as low as 13 mN ⁇ m 2 / g, which is below the range of Formula 2.
- the aluminum electrolytic capacitors produced using the separators of Examples 9 to 13 have a low fracture failure rate of 0.0 to 0.2%, which is lower than 1%.
- the short-circuit defect rate is 0.0 to 0.5%, which is lower than 1%.
- the impedance is also sufficiently low at 0.255 to 0.280 ⁇ .
- the impedance of the aluminum electrolytic capacitors of Examples 9 to 13 is slightly higher than the impedance of the aluminum electrolytic capacitor of Conventional Example 7.
- the value of the impedance of the aluminum electrolytic capacitor varies depending on the rated voltage, capacity, etc. of the capacitor, and in the case of an aluminum electrolytic capacitor having a rated voltage of 100 V and a capacity of 50 ⁇ F, the ninth to thirteenth examples are used.
- the impedance value is sufficient.
- the short-circuit defect rate of the aluminum electrolytic capacitor produced using the separator of Example 9 is slightly lower.
- the aluminum electrolytic capacitor manufactured using the separator of Example 10 has a slightly lower short-circuit defect rate. This is the same reason as Example 7 and Example 8, and it can be seen that a separator that not only satisfies Formulas 2 and 3 but also satisfies Formula 4 is preferable from the viewpoint of improving the short-circuit defect rate.
- the short-circuit defect rate of the aluminum electrolytic capacitor produced using the separator of Example 11 is slightly lower.
- the separator of Comparative Example 8 has a large specific tear strength of 105 mN ⁇ m 2 / g, which exceeds the range of Formula 2. This is a result of a low degree of beating of the fiber A. For this reason, the short-circuit defect rate is as high as 1.1%.
- the separator of Conventional Example 7 is a separator made of paper using a raw material obtained by beating a regenerated cellulose fiber alone having a CSF value of 200 ml. Since the CSF value of the regenerated cellulose fiber was large, the specific tear strength was very high, and no fracture failure occurred. However, the specific tear strength exceeds the range of Formula 2, and the short-circuit defect rate is as high as 1.4%.
- the aluminum electrolytic capacitor produced using the separator of Example 14 has a failure rate of less than 0.1% and 1%, which is low. Moreover, the short-circuit defect rate is 0.2%, which is lower than 1% and is low. Furthermore, the impedance is sufficiently low at 0.440 ⁇ .
- the separator of Comparative Example 9 has a specific tear strength as small as 17 mN ⁇ m 2 / g, which is below the range of Equation 3. For this reason, the fracture failure rate is as high as 1.9%. Moreover, since it was thicker than the separator of Example 14 and the element outer diameter was large, it was inserted into a case having a size larger than that of Example 14.
- a thickness of 50 ⁇ m or less is preferable in order to reduce the size of the capacitor. Since the separator of Conventional Example 8 is thicker than the separator of Example 14 and has a large element outer diameter, it is inserted into a case having a size larger than that of Example 14. The separator has a high CSF value of 450 ml. As a result, the density of the separator is low and the short circuit defect is high at 15.2%. Moreover, it is comprised only with the natural fiber and the impedance has deteriorated twice as much as Example 14.
- the separator of the present embodiment is used, even if a separator thinner than the conventional one is used, short-circuit defects do not increase, and the element can be downsized at the same time.
- the separator of Conventional Example 9 has a natural fiber layer with a high degree of beating. For this reason, although the short circuit defect does not occur, the impedance performance is greatly deteriorated to 2.110 ⁇ . Further, since both fibers A and B have low resistance to fiber drawing, the value of specific tear strength is small and the fracture failure rate is as high as 2.5%.
- the aluminum electrolytic capacitor produced using the separator of Example 15 has a fracture failure rate of 0.7% and less than 1%, which is low. Moreover, the short-circuit defect rate is 0.1% and below 1%, which is low. Furthermore, the impedance is sufficiently low at 0.052 ⁇ .
- the separator of Comparative Example 10 has a specific tear strength as small as 28 mN ⁇ m 2 / g, which is below the range of Equation 3. For this reason, the fracture failure rate is as high as 1.0%.
- the separators of Comparative Example 11 and Comparative Example 12 have a CSF value of 310 ml, exceeding the range of Formula 1. For this reason, the short defect rate is as high as 1% or more.
- the separator of Conventional Example 11 is thicker than the separator of Example 15 and has a larger element outer diameter, it is inserted into a case having a size larger than that of Example 15.
- the separator has a high CSF value of 450 ml. For this reason, the density of the separator is low, and the short-circuit defect is as high as 16.0%. Moreover, it is comprised only with the natural fiber and the impedance has deteriorated twice or more of Example 15. Also from this example, it can be seen that if the separator of the present embodiment is used, even if a separator thinner than the conventional one is employed, the short-circuit defect does not increase, and the element can be miniaturized at the same time.
- each example of an Example and a comparative example the CSF value of a separator and specific tear strength are plotted, and it shows in FIG. In FIG. 2, a straight line at the boundary of the range of Expressions 1 to 5 is shown together with a plot of the values of each example.
- each example is in the range of Formulas 1 to 3, and each comparative example is out of at least one range of Formulas 1 to 3.
- the short-circuit defect rate is further reduced when not only equations 1 to 3 are satisfied but also equation 4 is simultaneously satisfied.
- Equation 5 is satisfied at the same time, the short-circuit defect rate is further reduced.
- the fiber A that improves the tear strength and the fiber B that improves the denseness are beaten to the following ranges, and the fiber A and the fiber B are regenerated cellulose.
- a separator can be provided.
- the separator thickness to 10 to 50 ⁇ m and the density to 0.25 to 0.70 g / cm 3 , it is possible to provide a separator for an aluminum electrolytic capacitor excellent in impedance characteristics, denseness, and tear strength.
- CSF value of fiber A CSF 500-0 ml
- CSF value of fiber B once lowered to 0 ml (lower limit), further beaten
- Formula 1 0 ⁇ X ⁇ 300
- Formula 2 15 ⁇ Y ⁇ 100
- Formula 3 Y ⁇ 0.175X ⁇ 2.5
- the separator of this Embodiment about the aluminum electrolytic capacitor was demonstrated.
- the description of the details of the other configuration and manufacturing method of the aluminum electrolytic capacitor is omitted, but in the aluminum electrolytic capacitor of the present invention, the electrode material and the electrolytic solution material are not particularly limited, and various types are available. Materials can be used.
- the CSF value of the fiber A is set to CSF 500 to 0 ml
- the CSF value of the fiber B is once lowered to 0 ml (lower limit), and then further beaten, and the CSF value 1 to 500 ml turned to rise. I was trying.
- the fiber produced from the same kind of regenerated cellulose fiber and having a different degree of beating was used for the fiber A and the fiber B.
- the structure of the regenerated cellulose fiber that can be beaten constituting the separator is such that the characteristics of the separator satisfy Formulas 1 to 3 simultaneously, Formulas 1 to 4 simultaneously, or Formulas 1 to As long as Formula 5 is satisfied simultaneously, there is no particular limitation.
- regenerated cellulose fibers having different degrees of beating are used as long as Formulas 1 to 3 are satisfied simultaneously, Formulas 1 to 4 are satisfied simultaneously, or Formulas 1 to 5 are satisfied simultaneously.
- the separator of the present invention is also applicable to various electric storage devices such as electric double layer capacitors, lithium ion capacitors, lithium ion batteries, lithium batteries, sodium ion batteries, solid electrolytic capacitors, etc. Is possible.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Abstract
Description
インバータ回路では、整流器から出力される直流に含まれている変動成分の平滑化を目的として、アルミニウム電解コンデンサが使用される。
同じ面積のアルミニウム箔を使用する場合、薄いセパレータを用いてコンデンサ素子を形成すれば、外径の小さなコンデンサ素子が作製できる。従って、薄いセパレータが求められている。
しかしながら、単に、セパレータの坪量を低く、密度を低く、厚さを薄くしたのみでは、様々な問題が発生する。
セパレータの坪量を低く、密度を低く、厚さを薄くした場合、セパレータの緻密性も低下する。このため、アルミニウム電解コンデンサに使用したときに、素子ショート不良率やエージングショート不良率が増大し、仮にショートしなかった場合でも、製品化されて市場に出された後のショート不良率が高くなる、という難点がある。
また、セパレータの坪量を低く、密度を低く、厚さを薄くした場合、セパレータの引裂強さの値も低下する。その結果、アルミニウム電解コンデンサの製造工程において、セパレータの破断が発生し、生産性や歩留りが低下する。
これらの理由により、セパレータには、低坪量、低密度、薄厚であっても、ショート不良率を増加させない高い緻密性、及び、各工程で紙切れを発生させない強度が、求められている。
しかしながら、セパレータの厚さを厚く、密度を高くすると、インピーダンスが悪化してしまう。
従って、セパレータの引裂強さが強いことも、アルミニウム電解コンデンサ用セパレータに求められている。
叩解可能な再生セルロース繊維の叩解の程度を高くすることによって、数10nm~数μmの微細なフィブリルが得られる。得られたフィブリル化微細繊維は、剛性が高く潰れにくいため、紙にしたときに、天然繊維のフィブリル化微細繊維のようにフィルム状に結合することがない。従って、再生セルロース繊維を叩解して得られたフィブリル化微細繊維をセパレータに使用することにより、互いに独立した微細繊維が無数の点接着(水素結合)により構成された、極めて緻密性の高いセパレータが得られる。このようにして得られたセパレータは、緻密性が高いにもかかわらず、その構造上微多孔質状の紙質となり、しかもフィブリル断面は真円に近い形状であるため、比較的扁平な天然繊維と異なり、イオンの流れを阻害することがない。その結果、再生セルロース繊維の叩解原料を配合したセパレータを用いて作製したアルミニウム電解コンデンサは、インピーダンス及びショート不良率の両特性が改善する。
しかしながら、叩解可能な再生セルロース繊維は、叩解することで繊維間結合が増加し引張強さが向上するが、さらに繊維の叩解の程度を高くすると、引裂強さは急激に低下する。即ち、繊維間結合による引張強さと、引裂強さとは、相反する関係にあり、叩解が高度になるほど、引張強さは向上するが、引裂強さは低下してしまうことになる。
ここで、引裂強さを向上するために叩解を抑制すると、引張強さだけでなく緻密性も低下してしまうため、アルミニウム電解コンデンサのショート不良率が増加してしまう。
これは、以下の理由によると考えられる。
再生セルロース繊維からは、前述の通り、剛性が高く断面が真円に近い形状のフィブリルが得られる。一方、天然セルロース繊維は、再生セルロース繊維に比べて断面が扁平かつ大きいため、イオンの流れを阻害してしまう。その結果、再生セルロース繊維の叩解原料及び天然セルロース繊維を配合したセパレータを用いて作製された、アルミニウム電解コンデンサは、インピーダンスが悪化してしまう。
さらに、特許文献2のセパレータは、特許文献1に示されていたような、叩解の程度の高い再生セルロース繊維のみで構成されたセパレータと比較して、緻密性が低下する。このため、特許文献2のセパレータは、アルミニウム電解コンデンサに使用した場合に、ショート不良率も増加してしまう。
さらに、特許文献3のセパレータを構成する繊維は、原材料の製作段階で銅アンモニア溶液を使用したキュプラレーヨンであるため、繊維内部に銅イオンを含有している。そのため、アルミニウム電解コンデンサが市場に出された後に、アルミニウム電解コンデンサの内部で銅イオンが析出した場合のショートの危険性を有している。
ここで、セパレータの緻密性を向上させるために、再生セルロース繊維のCSF値を低くすると、引裂強さが低下してしまう。
さらに、特許文献5に記載されているセパレータは、特許文献2に記載されているようなセパレータと比較して、繊維間の結合力が弱い。このため、コンデンサ素子を形成して電解液を含浸させた後の、例えば熱による膨張収縮といったような、激しい動きを伴わない変形には耐えられるが、コンデンサ素子の巻取り工程のような、動きの大きな工程では、セパレータが破断してしまう。
しかしながら、エスパルト繊維のパルプからなるセパレータの緻密性は、叩解の程度の高い再生セルロース繊維のフィブリルからなるセパレータの緻密性には及ばない。このため、特許文献6に記載されたセパレータでは、近年のショート不良率の低減の要望に対して、セパレータの緻密性が充分とは言えない。
特許文献7に記載されたセパレータでは、叩解の程度の高い天然セルロースの層を持つため、ショート不良率の低減に効果的であるものの、特許文献1に記載されたセパレータ等と比較して、インピーダンス特性が悪化しやすかった。このため、更なるインピーダンスの低減が求められている。
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
式4:Y≦0.05X+45
式2:15≦Y≦100
式3:Y≧0.175X-2.5
式4:Y≦0.05X+45
式5:0≦X≦100
また、「比引裂強さ」とは、引裂強さを坪量で除して算出される値であり、ここでは、「JIS P 8116 『紙-引裂強さ試験方法-エルメンドルフ形引裂試験機法』」に規定された、横方向(CD)の比引裂強さである。
また、該セパレータを用いることによって、インピーダンス性能に優れ、ショート不良率を改善すると共に、歩留りを向上させることが可能な、アルミニウム電解コンデンサを提供できる。
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
式4:Y≦0.05X+45
式5:0≦X≦100
また、本実施の形態のアルミニウム電解コンデンサは、セパレータとして上記構成のセパレータを使用して、陽極と陰極との間に、セパレータを介在させた構成である。
このため、引裂強さの値を坪量で除した比引裂強さは、紙の坪量や厚さ等の要因を排除した、引裂強さの比較のための指標として用いられる。
引裂強さは、主に原料の特性に由来する。比引裂強さを比較することで、セパレータの紙の特性の比較だけではなく、原料の特性の比較も同時に行える点で、比引裂強さが優れている。
叩解によって微細化された再生セルロースを、ふるい板上でろ過しようとすると、ふるい板上に初期に堆積する繊維マットの影響を受ける。その後、ふるい板を通過しようとする懸濁液の抵抗が大きくなる。このため、叩解により再生セルロースを微細化していくと、CSF値は次第に低くなり、下限に到達する。
CSF値が下限に達した状態から、更に叩解すると、ふるい板の孔を通過する程度の微細な繊維が増加し、CSF値は上昇に転じる。
なお、以下、繊維A及び繊維Bのうち、繊維Aを叩解の程度が低い方の繊維とし、繊維Bを叩解の程度が高い方の繊維とする。
また、繊維Aの配合割合は、20~80質量%とする。
繊維Bとしては、CSF値が一旦下限値(0mlもしくは+の値)まで低下した後、更に叩解し、上昇に転じたCSF値が1~500mlのものを採用する。
また、繊維Bの配合割合は、20~80質量%とする。
即ち、叩解の程度の異なる二種の再生セルロース繊維である、繊維Aと繊維Bを、上記割合で混合して抄紙することにより、相反する関係である、引裂強さと緻密性とを両立することが可能となる。
しかし、電解液は、以上の例及びその組み合わせに限定されるものではなく、通常使用される電解液であれば、いずれでも良い。
本実施の形態のセパレータは、叩解可能な再生セルロース繊維を用いて、セパレータのCSF値をX[ml]、横方向(CD)の比引裂強さをY[mN・m2/g]としたとき、CSF値Xと比引裂強さYとが、次に示す式1乃至式3を同時に満たす範囲にある。より好ましくは、式1乃至式4を同時に満たす範囲にある。さらに好ましくは、式2乃至式5を同時に満たす範囲にあるセパレータである。なお、セパレータの「横方向(CD)」とは、長尺状に巻回されたセパレータの幅の方向を意味する。
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
式4:Y≦0.05X+45
式5:0≦X≦100
また、式1乃至式4を同時に満足する場合、セパレータの緻密性がより向上し、ショート不良率を、より低減できる。
さらに、式2乃至式5を同時に満足する場合、セパレータの緻密性がさらに向上し、ショート不良率を、さらに低減できる。
一方、比引裂強さYが式2の下限を下回る場合、アルミニウム電解コンデンサの製造工程における、セパレータの破断不良が増加する。
叩解の程度の異なる繊維Aと繊維Bとを混合する理由は、繊維Aと繊維Bの特徴を両立させるためである。
叩解の程度が低い繊維Aを単独で用いたセパレータは、引裂強さに優れるものの、緻密性に欠ける。
一方、叩解の程度が高い繊維Bを単独で用いたセパレータは、緻密性に優れるものの、引裂強さが弱い。
本発明の繊維Aと繊維Bとを混合してシート化したセパレータと、同じCSF値まで単独叩解した原料を用いてシート化したセパレータを比較すると、本発明のセパレータは、緻密性あるいは引裂強さの少なくとも一方の特性が優れる。単独叩解した原料は、繊維Aに比べると微細化しているため、引裂強さが弱く、また、繊維Bに比べると微細化していないため、緻密性に欠けることとなる。
再生セルロース繊維の叩解により得られるフィブリルは、その繊維径が細く、剛性が高い。そのため、繊維やフィブリルが交絡点で水素結合等により結合するが、繊維やフィブリル同士が面や線でフィルム状に結着することが無いために、インピーダンスが悪化しない特徴がある。
中でも、叩解可能な再生セルロース繊維としては、ビスコース再生セルロース繊維としてのポリノジックレーヨン、及び、溶剤紡糸再生セルロース繊維としてのリヨセルが代表的なものとして挙げられ、これらの再生セルロース繊維を用いることで、容易に繊維層を形成できる。
また、必要に応じて、紙力増強加工を施しても良い。
さらに、必要に応じて、抄紙工程で通常使用される添加剤、例えば分散剤や消泡剤等を使用してもよい。
本実施の形態のセパレータ及びアルミニウム電解コンデンサの各特性の具体的な測定は、以下の条件及び方法で行った。
「JIS P8121-2 パルプ-ろ水度試験法-第2部:カナダ標準ろ水度法」に従って、セパレータのCSF値を測定した。
「JIS C 2300-2 『電気用セルロース紙-第2部:試験方法』 5.1 厚さ」に規定された、「5.1.1 測定器及び測定方法 a外側マイクロメータを用いる場合」のマイクロメータを用いて、「5.1.3 紙を折り重ねて厚さを測る場合」の10枚に折り重ねる方法で、セパレータの厚さを測定した。
「JIS C 2300-2 『電気用セルロース紙-第2部:試験方法』 7.0A 密度」のB法に規定された方法で、絶乾状態のセパレータの密度を測定した。
「JIS P 8116 『紙-引裂強さ試験方法-エルメンドルフ形引裂試験機法』」に規定された方法で、セパレータの横方向(CD)の引裂強さを測定した。次に、得られた引裂強さの値をセパレータの坪量で除して、セパレータの比引裂強さを算出した。
それぞれのセパレータと所定の静電容量となるよう裁断したアルミ箔とを使用し、素子巻機にて巻き取って、コンデンサ素子を形成した。この操作を1000回行った後、セパレータの破断が無く巻き取れたコンデンサ素子を計数し、1000から減じて破断不良数を求めた。この破断不良数を1000で除して、百分率をもって破断不良率とした。
ショート不良率は、破断不良なく巻き取れたコンデンサ素子を用いて、電解液含浸前の巻取り素子の導通ショート及びエージング中のショート不良数を計数し、これらのショート不良となった素子数を、破断不良なく巻き取れた素子数で除して、百分率をもってショート不良率とした。
作製したアルミニウム電解コンデンサのインピーダンスは、LCRメータを用いて、20℃で100kHzの周波数で測定した。
なお、各実施例のセパレータは、再生セルロース繊維を使用して、抄紙法にてセパレータを構成した。
繊維Aとして、CSF値0mlの再生セルロース繊維であるリヨセル繊維を20質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値500mlの再生セルロース繊維であるリヨセル繊維を80質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ10.0μm、密度0.400g/cm3、比引裂強さ17mN・m2/gのセパレータを得た。このセパレータのCSF値は10mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径7.6mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例1のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値0mlの再生セルロース繊維であるリヨセル繊維を50質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値350mlの再生セルロース繊維であるリヨセル繊維を50質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ20.0μm、密度0.450g/cm3、比引裂強さ27mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径7.9mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例2のアルミニウム電解コンデンサとした。
実施例2のセパレータと同じ抄紙原料を用いて、円網抄紙法により、厚さ40.0μm、密度0.400g/cm3、比引裂強さ52mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径8.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例3のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値10mlの再生セルロース繊維であるリヨセル繊維を50質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値350mlの再生セルロース繊維であるリヨセル繊維を50質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ9.0μm、密度0.422g/cm3、比引裂強さ13mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径7.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例1のアルミニウム電解コンデンサとした。
比較例1と同じ抄紙原料を用いて、長網抄紙法によりシートを得た。続いて、特開2006-253728号公報の実施例1の方法に従って、このシートに紙力増強加工を施し、厚さ16.0μm、密度0.238g/cm3、比引裂強さ13mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径7.8mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例2のアルミニウム電解コンデンサとした。
再生セルロース繊維であるリヨセル繊維を、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値160mlである抄紙原料を用いて、長網抄紙法によりシートを得た。続いて、特開2006-253728号公報の実施例1の方法に従って、このシートに紙力増強加工を施し、厚さ20.0μm、密度0.425g/cm3、比引裂強さ6mN・m2/gのセパレータを得た。このセパレータのCSF値は150mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径7.9mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例1のアルミニウム電解コンデンサとした。
特開昭53-142652号公報の実施例1の方法に従って、円網抄紙法により、厚さ40.0μm、密度0.400g/cm3、比引裂強さ43mN・m2/gのセパレータを得た。このセパレータのCSF値は620mlであった。
このセパレータを用いて、定格電圧6.3V、容量1000μF、素子外径8.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例2のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値0mlの再生セルロース繊維であるポリノジックレーヨン繊維を20質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるポリノジックレーヨン繊維を80質量%配合した抄紙原料を用いて、長網抄紙法によりシートを得た。続いて、このシートにキャレンダー加工を施すことにより、厚さ25.0μm、密度0.540g/cm3、比引裂強さ17mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.0mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例4のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値100mlの再生セルロース繊維であるリヨセル繊維を30質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を70質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ30.0μm、密度0.400g/cm3、比引裂強さ24mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.2mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例5のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を40質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値80mlの再生セルロース繊維であるリヨセル繊維を60質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ30.0μm、密度0.400g/cm3、比引裂強さ5mN・m2/gのセパレータを得た。このセパレータのCSF値は55mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.2mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例3のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値30mlの再生セルロース繊維であるリヨセル繊維を20質量%、繊維Bとして、CSF値5mlの再生セルロース繊維であるリヨセル繊維を80質量%配合した抄紙原料を用いて、円網抄紙法により、厚さ35.0μm、密度0.371g/cm3、比引裂強さ105mN・m2/gのセパレータを得た。このセパレータのCSF値は20mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.3mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例4のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値0mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値680mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、円網抄紙法により、厚さ35.0μm、密度0.400g/cm3、比引裂強さ105mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.3mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例5のアルミニウム電解コンデンサとした。
抄紙原料として、CSF値0mlの再生セルロース繊維であるリヨセル繊維を用いて、長網抄紙法により、厚さ30.0μm、密度0.400g/cm3、比引裂強さ7mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.2mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例3のアルミニウム電解コンデンサとした。
特開2009-158811号公報の実施例1の方法に従って、厚さ30.0μm、密度0.333g/cm3のセパレータを得た。このセパレータの比引裂強さは、測定不可能なほどに大きかった。また、連続長繊維から成るため、離解も不可能であった。
このセパレータを用いて、定格電圧16V、容量550μF、素子外径9.2mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例4のアルミニウム電解コンデンサとした。
この従来例4は、銅アンモニア再生セルロース繊維であるキュプラレーヨンを使用して、セパレータを作製している。
繊維Aとして、CSF値80mlの再生セルロース繊維であるリヨセル繊維を40質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値500mlの再生セルロース繊維であるリヨセル繊維を60質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ35.0μm、密度0.400g/cm3、比引裂強さ30mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例6のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値500mlの再生セルロース繊維であるリヨセル繊維を60質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を40質量%配合した抄紙原料を用いて、長網抄紙法によりシートを得た。続いて、このシートにキャレンダー加工を施すことにより、厚さ35.0μm、密度0.486g/cm3、比引裂強さ43mN・m2/gのセパレータを得た。このセパレータのCSF値は56mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例7のアルミニウム電解コンデンサとした。
実施例7と同じ抄紙原料を用いて、円網抄紙法により、厚さ40.0μm、密度0.375g/cm3、比引裂強さ82mN・m2/gのセパレータを得た。このセパレータのCSF値は56mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.6mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例8のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値350mlの再生セルロース繊維であるリヨセル繊維を85質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を15質量%配合した抄紙原料を用いて、円網抄紙法により、厚さ40.0μm、密度0.425g/cm3、比引裂強さ112mN・m2/gのセパレータを得た。このセパレータのCSF値は190mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.6mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例6のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値0mlの再生セルロース繊維であるリヨセル繊維を15質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値340mlの再生セルロース繊維であるリヨセル繊維を85質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ35.0μm、密度0.400g/cm3、比引裂強さ12mN・m2/gのセパレータを得た。このセパレータのCSF値は5mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例7のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値500mlの天然セルロース繊維である針葉樹クラフトパルプ繊維を30質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値200mlの再生セルロース繊維であるリヨセル繊維を70質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ30.0μm、密度0.400g/cm3、比引裂強さ20mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.3mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例5のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値625mlの合成繊維であるアクリル繊維を25質量%、繊維Bとして、CSF値0mlの再生セルロース繊維であるリヨセル繊維を75質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ35.0μm、密度0.371g/cm3、比引裂強さ13mN・m2/gのセパレータを得た。このセパレータのCSF値は5mlであった。
このセパレータを用いて、定格電圧50V、容量150μF、素子外径9.5mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、従来例6のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値400mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ40.0μm、密度0.400g/cm3、比引裂強さ30mN・m2/gのセパレータを得た。このセパレータのCSF値は140mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.1mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例9のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値500mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ40.0μm、密度0.400g/cm3、比引裂強さ55mN・m2/gのセパレータを得た。このセパレータのCSF値は260mlであった
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.1mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例10のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値500mlの再生セルロース繊維であるリヨセル繊維を60質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlの再生セルロース繊維であるリヨセル繊維を40質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ40.0μm、密度0.400g/cm3、比引裂強さ43mN・m2/gのセパレータを得た。このセパレータのCSF値は56mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.1mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例11のアルミニウム電解コンデンサとした。
実施例9のセパレータと同じ抄紙原料を用いて、円網抄紙法により、厚さ45.0μm、密度0.356g/cm3、比引裂強さ58mN・m2/gのセパレータを得た。このセパレータのCSF値は140mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.2mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例12のアルミニウム電解コンデンサとした。
実施例10のセパレータと同じ抄紙原料を用いて、円網抄紙法により、厚さ45.0μm、密度0.378g/cm3、比引裂強さ98mN・m2/gのセパレータを得た。このセパレータのCSF値は260mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.2mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例13のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値620mlの再生セルロース繊維であるリヨセル繊維を70質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値10mlの再生セルロース繊維であるリヨセル繊維を30質量%配合した抄紙原料を用いて、円網抄紙法により、厚さ45.0μm、密度0.367g/cm3、比引裂強さ105mN・m2/gのセパレータを得た。このセパレータのCSF値は120mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.2mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、比較例8のアルミニウム電解コンデンサとした。
抄紙原料として、CSF値200mlの再生セルロース繊維であるリヨセル繊維を用いて、円網抄紙法によりシートを得た。続いて、特開2006-253728号公報の実施例1の方法に従って、このシートに紙力増強加工を施し、厚さ40.0μm、密度0.325g/cm3、比引裂強さ107mN・m2/gのセパレータを得た。このセパレータのCSF値は200mlであった。
このセパレータを用いて、定格電圧100V、容量50μF、素子外径11.1mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、従来例7のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値500mlの再生セルロース繊維であるリヨセル繊維を70質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を30質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ50.0μm、密度0.300g/cm3、比引裂強さ48mN・m2/gのセパレータを得た。このセパレータのCSF値は95mlであった。
このセパレータを用いて、定格電圧200V、容量120μF、素子外径15.5mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、実施例14のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値550mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ55.0μm、密度0.364g/cm3、比引裂強さ17mN・m2/gのセパレータを得た。このセパレータのCSF値は120mlであった。
このセパレータを用いて、定格電圧200V、容量120μF、素子外径15.7mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースへの挿入を試みたが、素子外径が大きいため、実施例14と同じサイズのケースには挿入できなかった。このため、実施例14よりも大きなサイズのケースに挿入し、比較例9のアルミニウム電解コンデンサとした。
特開昭53-142652号公報の実施例1の方法に従って、円網抄紙法により、厚さ60.0μm、密度0.600g/cm3、比引裂強さ35mN・m2/gのセパレータを得た。このセパレータのCSF値は450mlであった。
このセパレータを用いて、定格電圧200V、容量120μF、素子外径15.9mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースへの挿入を試みたが、素子外径が大きいため、実施例14と同じサイズのケースには挿入できなかった。このため、実施例14よりも大きなサイズのケースに挿入し、従来例8のアルミニウム電解コンデンサとした。
特開平6-168848号公報の実施例2の方法に従って、厚さ25.0μm、密度0.800g/cm3の高密度層、厚さ15.0μm、密度0.367g/cm3の低密度層を持つ、厚さ40.0μm、密度0.638g/cm3、比引裂強さ14mN・m2/gのセパレータを得た。このセパレータのCSF値は0mlであった。
このセパレータを用いて、定格電圧200V、容量120μF、素子外径15.2mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースに挿入、封口し、従来例9のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値200mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ35.0μm、密度0.457g/cm3、比引裂強さ20mN・m2/gのセパレータを得た。このセパレータのCSF値は60mlであった。
このセパレータを、両極間に二枚用いて、定格電圧450V、容量50μF、素子外径17.6mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、実施例15のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値550mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ70.0μm、密度0.300g/cm3、比引裂強さ28mN・m2/gのセパレータを得た。このセパレータのCSF値は220mlであった。
このセパレータを用いて、定格電圧450V、容量50μF、素子外径17.6mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例10のアルミニウム電解コンデンサとした。
繊維Aとして、CSF値620mlの再生セルロース繊維であるリヨセル繊維を80質量%、繊維Bとして、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1mlの再生セルロース繊維であるリヨセル繊維を20質量%配合した抄紙原料を用いて、長網抄紙法により、厚さ80.0μm、密度0.400g/cm3、比引裂強さ50mN・m2/gのセパレータを得た。このセパレータのCSF値は310mlであった。
このセパレータ用いて、定格電圧450V、容量50μF、素子外径17.9mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例11のアルミニウム電解コンデンサとした。
比較例11のセパレータと同じ抄紙原料を用いて、円網抄紙法により、厚さ80.0μm、密度0.400g/cm3、比引裂強さ95mN・m2/gのセパレータを得た。このセパレータのCSF値は310mlであった。
このセパレータ用いて、定格電圧450V、容量50μF、素子外径17.9mmのアルミニウム電解コンデンサ素子を形成し、GBL系電解液を含浸後、ケースに挿入、封口し、比較例12のアルミニウム電解コンデンサとした。
特開昭53-142652号公報の実施例1の方法に従って、円網抄紙法により、厚さ90.0μm、密度0.600g/cm3、比引裂強さ35mN・m2/gのセパレータを得た。このセパレータのCSF値は450mlであった。
このセパレータを用いて、定格電圧450V、容量50μF、素子外径18.2mmのアルミニウム電解コンデンサ素子を形成し、EG系電解液を含浸後、ケースへの挿入を試みたが、素子外径が大きいため、実施例15や比較例9乃至11と同じサイズのケースには挿入できなかった。このため、実施例14よりも大きなサイズのケースに挿入し、従来例11のアルミニウム電解コンデンサとした。
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
表1では、叩解の程度の違いを区別するために、CSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値に、*を付けて記載している。また、両極間に二枚のセパレータを使用したアルミニウム電解コンデンサの場合、セパレータの厚さを「一枚の厚さの値×2」と記載している。各種の測定値は、いずれも複数個の試料の平均値を示している。
一方、比較例1のセパレータは、厚さが9.0μmと薄いため、破断不良率が1.1%、ショート不良率が8.5%と高くなっている。このことより、セパレータの厚さは10μm以上が好ましいとわかる。
また、比較例2のセパレータは、密度が0.238g/cm3と低いため、破断不良率が1.1%、ショート不良率が8.0%と高くなっている。このことより、セパレータの密度は0.25g/cm3以上が好ましいとわかる。
そして、従来例1のセパレータは、リヨセル繊維のCSF値が一旦0ml(下限値)まで低下した後、更に叩解することで、上昇に転じたCSF値160mlとなっている原料のみを使用している。このため、セパレータの比引裂強さが6mN・m2/gと、式2の範囲を下回っており、破断不良率が1.1%と高くなっている。
また、従来例2のセパレータは、セパレータのCSF値が620mlと高い。このため、セパレータの緻密性が低く、ショート不良が11.5%と高くなっている。さらに、セパレータが天然繊維のみで構成されており、インピーダンスが実施例1の3倍以上に悪化している。
比較例3のセパレータは、繊維AのCSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値20mlである。このため、セパレータの比引裂強さが式2の範囲を下回っており、破断不良率が3.0%と高い。
そして、比較例4のセパレータは、繊維BのCSF値が5mlであり、叩解の程度が低い。そのため、比引裂強さが式2の範囲を超過しており、セパレータの緻密性が低くなっていることがわかる。このため、アルミニウム電解コンデンサのショート不良率が2.2%と高い。
また、比較例5のセパレータは、繊維BのCSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値680mlである。このため、セパレータの抄紙工程において、繊維B中の過度に微細化された繊維が抄紙ワイヤーから抜け落ちてしまっている。結果として、比較例5のセパレータは、比引裂強さが式2の範囲を超過しており、ショート不良率が2.0%と高い。
従来例3のセパレータは、比引裂強さが式2の範囲を下回っており、破断不良率が11.0%と高い。また、従来例3のセパレータのCSF値は0mlであり、実施例4及び実施例5のセパレータのCSF値と同じであるが、破断不良率、ショート不良率共に、実施例4及び実施例5の方が優れる結果となっている。このことから、単一で叩解した原料よりも、本発明のように、叩解程度の異なる原料を混合してセパレータとした方が、緻密性、引裂強さともに向上させることができ、その結果、アルミニウム電解コンデンサの破断不良率、ショート不良率共に低減できるとわかる。
従来例4のセパレータは、湿式スパンボンド法によりシート形成した再生セルロースセパレータで、比引裂強さが測定不能なほど高い。このため、破断不良は発生しなかった。しかしながら、従来例4のアルミニウム電解コンデンサはショート不良率が10.0%と高い。これは、スパンボンド法は抄紙法に比べ、シートが不均一になりやすく緻密性にかけるためである。
また、この従来例4は、銅アンモニア再生セルロース繊維であるキュプラレーヨンを使用して、セパレータを作製しているため、繊維内部に銅イオンを含有している。そのため、キュプラレーヨンを使用したセパレータを用いたアルミニウム電解コンデンサは、長期間使用した際、コンデンサ内部で銅イオンが析出し、ショート不良が発生する危険性が懸念される。
実施例7のセパレータは、実施例8と同じ抄紙原料を用いて長網抄紙したものである。実施例7のセパレータは式4を満たしており、実施例8のセパレータは、式4を満たさない。実施例7と実施例8のコンデンサを比較すると、実施例7のコンデンサの方が、ショート不良率が低い。このことから、式2及び式3を満たすのみでなく、さらに式4も満たす場合、ショート不良率をさらに低減できることがわかる。
比較例6のセパレータは、繊維Aを85質量%、繊維Bを15質量%配合しており、比引裂強さが式2の範囲を超えている。そして、比較例6のアルミニウム電解コンデンサは、ショート不良率が1.1%と高くなっている。これは繊維Bの割合が少ないため、緻密性が向上しなかったためと考えられる。
比較例7のセパレータは、繊維Aを15質量%、繊維Bを85質量%配合しており、比引裂強さが式2の範囲を下回っている。そして、比較例7のセパレータは破断不良率が1.2%と高くなっている。これは、引裂強さを向上させる繊維Aの割合が少ないためと考えられる。
従来例5は、繊維AとしてCSF値500mlの針葉樹クラフトパルプを、繊維BとしてCSF値が一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値200mlの再生セルロース繊維を配合している。実施例6乃至実施例8と比較すると、針葉樹クラフトパルプの影響で、インピーダンス値が0.200Ωと、実施例6乃至8と比較して30%以上高くなっている。
従来例6は、アクリル繊維を配合したセパレータであるが、比引裂強さが13mN・m2/gと低く、式2の範囲を下回っている。これは合成繊維を配合した結果、繊維間結合力が低下したためである。また、同じ理由でセパレータの遮蔽性も低下し、破断不良率、ショート不良率がそれぞれ1.2%、1.1%と高い結果となった。
実施例9乃至実施例13のアルミニウム電解コンデンサのインピーダンスは、従来例7のアルミニウム電解コンデンサのインピーダンスよりも僅かに高くなっている。しかしながら、アルミニウム電解コンデンサのインピーダンスの値は、コンデンサの定格電圧や容量等によって期待される値の範囲が異なるものであり、定格電圧100V・容量50μFのアルミニウム電解コンデンサでは、実施例9乃至実施例13のインピーダンスの値でも十分である。
実施例12と比較して、実施例9のセパレータを用いて作製したアルミニウム電解コンデンサは、ショート不良率がわずかに低くなっている。また、実施例13と比較して、実施例10のセパレータを用いて作製したアルミニウム電解コンデンサは、ショート不良率がわずかに低くなっている。これは、実施例7及び実施例8と同じ理由であり、式2及び式3を満たすのみでなく、さらに式4も満たすセパレータの方が、ショート不良率改善の点から好ましいとわかる。
実施例9と比較して、実施例11のセパレータを用いて作製したアルミニウム電解コンデンサは、ショート不良率がわずかに低くなっている。このことから、式1の範囲を満たすのみでなく、より狭い、式5の範囲を満たすセパレータの方が、ショート不良率改善の点から好ましいとわかる。
比較例8のセパレータは、比引裂強さが105mN・m2/gと大きく、式2の範囲を超えている。これは繊維Aの叩解の程度が低い結果であるが、このため、ショート不良率が1.1%と高い。
従来例7のセパレータは、再生セルロース繊維をCSF値200mlの単独叩解した原料を用いて抄紙したセパレータである。再生セルロース繊維のCSF値が大きいため、比引裂強さが非常に高く、破断不良は発生しなかった。しかしながら、比引裂強さが式2の範囲を超えており、ショート不良率が1.4%と高くなっている。
比較例9のセパレータは、比引裂強さが17mN・m2/gと小さく、式3の範囲を下回っている。このため、破断不良率が1.9%と高くなっている。また、実施例14のセパレータに比べ厚く、素子外径が大きかったため、実施例14よりも大きなサイズのケースに挿入している。このことから、コンデンサの小型化を追求するには、厚さ50μm以下である事が好ましいと分かる。
従来例8のセパレータは、実施例14のセパレータに比べ厚く、素子外径が大きかったため、実施例14よりも大きなサイズのケースに挿入している。また、セパレータのCSF値が450mlと高い。このことにより、セパレータの緻密性が低く、ショート不良が15.2%と高くなっている。また、天然繊維のみで構成されており、インピーダンスが実施例14の2倍に悪化している。この例から、本実施の形態のセパレータを用いれば、従来よりも薄いセパレータを採用してもショート不良が増加することなく、同時に素子の小型化も可能であるとわかる。
従来例9のセパレータは、叩解の程度の高い天然繊維の層を持つ。このため、ショート不良は発生していないが、インピーダンス性能が2.110Ωと大きく悪化している。また、繊維A、B共に繊維の引き抜きに対する抵抗力が弱いため、比引裂強さの値も小さく、破断不良率も2.5%と高い。
比較例10のセパレータは、比引裂強さが28mN・m2/gと小さく、式3の範囲を下回っている。このため、破断不良率が1.0%と高くなっている。
比較例11及び比較例12のセパレータは、CSF値が310mlと、式1の範囲を超えている。このため、いずれもショート不良率が1%以上と高い。
従来例11のセパレータは、実施例15のセパレータに比べ厚く、素子外径が大きかったため、実施例15よりも大きなサイズのケースに挿入している。また、セパレータのCSF値が450mlと高い。このため、セパレータの緻密性が低く、ショート不良が16.0%と高くなっている。また、天然繊維のみで構成されており、インピーダンスが実施例15の2倍以上に悪化している。この例からも、本実施の形態のセパレータを用いれば、従来よりも薄いセパレータを採用してもショート不良が増加することなく、同時に素子の小型化も可能であることがわかる。
図2より、各実施例は式1乃至式3の範囲に入っており、各比較例は式1乃至式3の少なくとも一つの範囲から外れている。
また、同定格電圧、同容量のコンデンサで比較した場合、式1乃至3を満たすのみでなく、さらに式4も同時に満たす場合、ショート不良率が、より低減する。
さらに、式5も同時に満たす場合、ショート不良率がさらに低減する。
繊維AのCSF値:CSF500~0ml
繊維BのCSF値:一旦0ml(下限値)まで低下した後、更に叩解し、上昇に転じたCSF値1~500ml
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5
アルミニウム電解コンデンサの他の構成、製造方法の詳細についての説明は省略したが、本発明のアルミニウム電解コンデンサにおいて、電極材料及び電解液材料については、特別に限定を必要とすることはなく、種々の材料を用いることができる。
本発明においては、セパレータを構成する、叩解可能な再生セルロース繊維の構成は、セパレータの特性が、式1乃至式3を同時に満たす、もしくは、式1乃至式4を同時に満たす、あるいは、式1乃至式5を同時に満たす限り、特に限定されるものではない。式1乃至式3を同時に満たす、もしくは、式1乃至式4を同時に満たす、あるいは、式1乃至式5を同時に満たす限りは、例えば、叩解の程度の異なる3つ以上の再生セルロース繊維を使用することや、CSF値が実施の形態のCSF値の範囲外である再生セルロース繊維を使用することや、繊維Aと繊維Bとで異なる再生セルロース繊維を原料とすることも可能である。
また、素子外径が許容する限り、本発明のセパレータを複数枚、または本発明のセパレータを一枚以上用いて複数枚重ねて使用することも可能である。
Claims (6)
- 陽極と陰極との間に介在させるセパレータであって、
叩解可能な再生セルロース繊維からなり、
CSF値X[ml]と比引裂強さY[mN・m2/g]が、下記式1乃至式3を満たす範囲にある
ことを特徴とするセパレータ。
式1:0≦X≦300
式2:15≦Y≦100
式3:Y≧0.175X-2.5 - 前記CSF値Xと前記比引裂強さYが、さらに下記式4を満たす範囲にあることを特徴とする請求項1に記載のセパレータ。
式4:Y≦0.05X+45 - 前記CSF値Xと前記比引裂強さYが、さらに下記式5を満たす範囲にあることを特徴とする請求項2に記載のセパレータ。
式5:0≦X≦100 - 厚さが10~50μmであることを特徴とする請求項1乃至請求項3のいずれか1項に記載のセパレータ。
- 密度が0.25~0.70g/cm3であることを特徴とする請求項1乃至請求項3のいずれか1項に記載のセパレータ。
- 陽極と陰極との間に、セパレータを介在して成るアルミニウム電解コンデンサであって、
前記セパレータとして、請求項1乃至請求項5のいずれか1項に記載のセパレータが少なくとも一枚使用されている
ことを特徴とするアルミニウム電解コンデンサ。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/542,317 US10566141B2 (en) | 2015-01-16 | 2016-01-05 | Separator and aluminum electrolytic capacitor |
BR112017015015-8A BR112017015015B1 (pt) | 2015-01-16 | 2016-01-05 | Separador interposto entre um anodo e um catodo de um dispositivo de armazenamento, e, capacitor eletrolítico de alumínio |
CN201680005432.9A CN107210132B (zh) | 2015-01-16 | 2016-01-05 | 分隔件和铝电解电容器 |
KR1020177019736A KR102429448B1 (ko) | 2015-01-16 | 2016-01-05 | 세퍼레이터 및 알루미늄 전해 컨덴서 |
MYPI2017702544A MY182644A (en) | 2015-01-16 | 2016-01-05 | Separator and aluminum electrolytic capacitor |
EP16737246.5A EP3246927B1 (en) | 2015-01-16 | 2016-01-05 | Separator and aluminum electrolytic capacitor |
RU2017128987A RU2698471C2 (ru) | 2015-01-16 | 2016-01-05 | Сепаратор для аккумулирующего устройства и алюминиевый электролитический конденсатор |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015006664A JP6412805B2 (ja) | 2015-01-16 | 2015-01-16 | セパレータ及びアルミニウム電解コンデンサ |
JP2015-006664 | 2015-01-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016114175A1 true WO2016114175A1 (ja) | 2016-07-21 |
Family
ID=56405722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/050141 WO2016114175A1 (ja) | 2015-01-16 | 2016-01-05 | セパレータ及びアルミニウム電解コンデンサ |
Country Status (10)
Country | Link |
---|---|
US (1) | US10566141B2 (ja) |
EP (1) | EP3246927B1 (ja) |
JP (1) | JP6412805B2 (ja) |
KR (1) | KR102429448B1 (ja) |
CN (1) | CN107210132B (ja) |
BR (1) | BR112017015015B1 (ja) |
HU (1) | HUE050980T2 (ja) |
MY (1) | MY182644A (ja) |
RU (1) | RU2698471C2 (ja) |
WO (1) | WO2016114175A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107677582A (zh) * | 2017-09-19 | 2018-02-09 | 合肥国轩高科动力能源有限公司 | 一种锂离子电池隔膜透液率的测试方法及其装置 |
CN109750552A (zh) * | 2018-12-04 | 2019-05-14 | 株洲时代新材料科技股份有限公司 | 一种铝电解电容器纸 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6503201B2 (ja) * | 2015-03-12 | 2019-04-17 | ニッポン高度紙工業株式会社 | 蓄電デバイス用セパレータ及び該セパレータを用いた蓄電デバイス |
JP7048839B2 (ja) * | 2018-02-09 | 2022-04-06 | エルジー エナジー ソリューション リミテッド | 固体高分子電解質およびそれを含むリチウム二次電池 |
KR20220137914A (ko) * | 2020-02-21 | 2022-10-12 | 닛폰 고도시 코포레이션 | 알루미늄 전해 컨덴서용 세퍼레이터 및 알루미늄 전해 컨덴서 |
JP6850921B1 (ja) | 2020-03-16 | 2021-03-31 | ニッポン高度紙工業株式会社 | 電気化学素子用セパレータおよび電気化学素子 |
JP2022012525A (ja) * | 2020-07-01 | 2022-01-17 | ニッポン高度紙工業株式会社 | アルミニウム電解コンデンサ用セパレータ及びアルミニウム電解コンデンサ |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10504858A (ja) * | 1994-06-22 | 1998-05-12 | コートールズ ファイバーズ (ホールディングス)リミティド | リヨセル繊維及びその製造法 |
JP2010239094A (ja) * | 2009-03-31 | 2010-10-21 | Nippon Chemicon Corp | 電解コンデンサ用セパレータおよび電解コンデンサ |
JP2015004140A (ja) * | 2013-06-20 | 2015-01-08 | 王子ホールディングス株式会社 | 不織布及びその製造方法 |
JP2015088703A (ja) * | 2013-11-01 | 2015-05-07 | ニッポン高度紙工業株式会社 | キャパシタ用セパレータおよび該セパレータを用いたキャパシタ |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53142652A (en) | 1977-05-17 | 1978-12-12 | Nippon Kodoshi Kogyo Kk | Paper for electrolytic capacitor |
SU1739403A1 (ru) * | 1990-09-04 | 1992-06-07 | Научно-производственное объединение "Квант" | Сепаратор дл щелочного аккумул тора с цинковым анодом |
JP3466206B2 (ja) | 1992-03-19 | 2003-11-10 | ニッポン高度紙工業株式会社 | 電解コンデンサ |
JP3693299B2 (ja) | 1992-11-27 | 2005-09-07 | ニッポン高度紙工業株式会社 | 電解コンデンサ |
GB2324064A (en) * | 1997-04-11 | 1998-10-14 | Courtaulds Fibres | Modified lyocell fibre and method of its formation |
EP0933790A1 (en) * | 1998-02-02 | 1999-08-04 | Asahi Glass Company Ltd. | Electric double layer capacitor |
JP4787473B2 (ja) * | 2004-06-18 | 2011-10-05 | ニッポン高度紙工業株式会社 | アルカリ電池用セパレータ紙及びアルカリ電池 |
JP5032748B2 (ja) * | 2005-02-25 | 2012-09-26 | 株式会社クラレ | アルカリ電池用セパレータ及びアルカリ一次電池 |
JP4109697B2 (ja) | 2006-06-23 | 2008-07-02 | ニッポン高度紙工業株式会社 | 電解コンデンサ |
JP4938640B2 (ja) | 2007-12-27 | 2012-05-23 | 旭化成せんい株式会社 | セパレーター |
KR101702693B1 (ko) * | 2009-10-15 | 2017-02-06 | 미쓰비시 세이시 가부시키가이샤 | 리튬 2 차 전지용 기재 및 리튬 2 차 전지용 세퍼레이터 |
RU2427052C1 (ru) * | 2010-04-19 | 2011-08-20 | Открытое акционерное общество Воронежское специальное конструкторское бюро "Рикон" (ОАО ВСКБ "Рикон") | Электродный материал для конденсатора электрического, способ его изготовления и суперконденсатор электрический |
CN103081169B (zh) * | 2010-08-04 | 2016-06-01 | 日本高度纸工业株式会社 | 碱性电池用隔膜以及碱性电池 |
JP5594845B2 (ja) | 2011-04-04 | 2014-09-24 | 三菱製紙株式会社 | 電気化学素子用セパレーター |
KR101827617B1 (ko) * | 2012-12-26 | 2018-02-08 | 주식회사 쿠라레 | 전기 이중층 커패시터용 세퍼레이터 및 전기 이중층 커패시터 |
JP6775130B2 (ja) * | 2014-07-18 | 2020-10-28 | ニッポン高度紙工業株式会社 | 蓄電デバイス用セパレータおよび該セパレータを用いた蓄電デバイス |
JP6503201B2 (ja) * | 2015-03-12 | 2019-04-17 | ニッポン高度紙工業株式会社 | 蓄電デバイス用セパレータ及び該セパレータを用いた蓄電デバイス |
JP6674956B2 (ja) * | 2015-09-17 | 2020-04-01 | ニッポン高度紙工業株式会社 | 電気化学素子用セパレータおよび電気化学素子 |
HUE057888T2 (hu) * | 2015-09-29 | 2022-06-28 | Nippon Kodoshi Corp | Szeparátor elektrokémiai eszközhöz és elektrokémiai eszköz |
FI129075B (fi) * | 2016-03-24 | 2021-06-30 | Paptic Ltd | Menetelmä luonnonkuituja ja synteettisiä kuituja sisältävän kuituradan valmistamiseksi |
JP2017179677A (ja) * | 2016-03-31 | 2017-10-05 | 特種東海製紙株式会社 | 多孔性シート |
-
2015
- 2015-01-16 JP JP2015006664A patent/JP6412805B2/ja active Active
-
2016
- 2016-01-05 KR KR1020177019736A patent/KR102429448B1/ko active IP Right Grant
- 2016-01-05 RU RU2017128987A patent/RU2698471C2/ru active
- 2016-01-05 CN CN201680005432.9A patent/CN107210132B/zh active Active
- 2016-01-05 HU HUE16737246A patent/HUE050980T2/hu unknown
- 2016-01-05 WO PCT/JP2016/050141 patent/WO2016114175A1/ja active Application Filing
- 2016-01-05 US US15/542,317 patent/US10566141B2/en active Active
- 2016-01-05 EP EP16737246.5A patent/EP3246927B1/en active Active
- 2016-01-05 MY MYPI2017702544A patent/MY182644A/en unknown
- 2016-01-05 BR BR112017015015-8A patent/BR112017015015B1/pt not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10504858A (ja) * | 1994-06-22 | 1998-05-12 | コートールズ ファイバーズ (ホールディングス)リミティド | リヨセル繊維及びその製造法 |
JP2010239094A (ja) * | 2009-03-31 | 2010-10-21 | Nippon Chemicon Corp | 電解コンデンサ用セパレータおよび電解コンデンサ |
JP2015004140A (ja) * | 2013-06-20 | 2015-01-08 | 王子ホールディングス株式会社 | 不織布及びその製造方法 |
JP2015088703A (ja) * | 2013-11-01 | 2015-05-07 | ニッポン高度紙工業株式会社 | キャパシタ用セパレータおよび該セパレータを用いたキャパシタ |
Non-Patent Citations (1)
Title |
---|
See also references of EP3246927A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107677582A (zh) * | 2017-09-19 | 2018-02-09 | 合肥国轩高科动力能源有限公司 | 一种锂离子电池隔膜透液率的测试方法及其装置 |
CN109750552A (zh) * | 2018-12-04 | 2019-05-14 | 株洲时代新材料科技股份有限公司 | 一种铝电解电容器纸 |
Also Published As
Publication number | Publication date |
---|---|
MY182644A (en) | 2021-01-27 |
US20180315551A1 (en) | 2018-11-01 |
RU2698471C2 (ru) | 2019-08-27 |
HUE050980T2 (hu) | 2021-01-28 |
BR112017015015B1 (pt) | 2022-10-18 |
EP3246927A4 (en) | 2018-11-07 |
US10566141B2 (en) | 2020-02-18 |
RU2017128987A3 (ja) | 2019-03-20 |
KR102429448B1 (ko) | 2022-08-03 |
EP3246927B1 (en) | 2020-06-24 |
JP6412805B2 (ja) | 2018-10-24 |
JP2016134425A (ja) | 2016-07-25 |
EP3246927A1 (en) | 2017-11-22 |
CN107210132B (zh) | 2018-12-14 |
KR20170104483A (ko) | 2017-09-15 |
BR112017015015A2 (ja) | 2018-01-23 |
RU2017128987A (ru) | 2019-02-18 |
CN107210132A (zh) | 2017-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6412805B2 (ja) | セパレータ及びアルミニウム電解コンデンサ | |
JP6674956B2 (ja) | 電気化学素子用セパレータおよび電気化学素子 | |
US11063319B2 (en) | Separator for electrochemical element and electrochemical element | |
KR102404190B1 (ko) | 축전 디바이스용 세퍼레이터 및 상기 세퍼레이터를 사용한 축전 디바이스 | |
WO2016010085A1 (ja) | 蓄電デバイス用セパレータおよび該セパレータを用いた蓄電デバイス | |
KR102583728B1 (ko) | 전기 화학 소자용 세퍼레이터 및 전기 화학 소자 | |
JP7012425B2 (ja) | アルミニウム電解コンデンサ用セパレータ及びアルミニウム電解コンデンサ | |
JP6850921B1 (ja) | 電気化学素子用セパレータおよび電気化学素子 | |
JP2020113689A (ja) | アルミニウム電解コンデンサ用セパレータ及びアルミニウム電解コンデンサ | |
WO2022004851A1 (ja) | アルミニウム電解コンデンサ用セパレータ及びアルミニウム電解コンデンサ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16737246 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2016737246 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15542317 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20177019736 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2017128987 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112017015015 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112017015015 Country of ref document: BR Kind code of ref document: A2 Effective date: 20170713 |