CN113316830A - Spacer for solid electrolytic capacitor - Google Patents
Spacer for solid electrolytic capacitor Download PDFInfo
- Publication number
- CN113316830A CN113316830A CN202080009830.4A CN202080009830A CN113316830A CN 113316830 A CN113316830 A CN 113316830A CN 202080009830 A CN202080009830 A CN 202080009830A CN 113316830 A CN113316830 A CN 113316830A
- Authority
- CN
- China
- Prior art keywords
- fibers
- fiber
- spacer
- resistant fibers
- fibrillated heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000006850 spacer group Chemical group 0.000 title claims abstract description 44
- 239000003990 capacitor Substances 0.000 title claims abstract description 29
- 239000007787 solid Substances 0.000 title claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 91
- 239000012210 heat-resistant fiber Substances 0.000 claims abstract description 49
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 32
- 229920003043 Cellulose fiber Polymers 0.000 description 11
- 229920001940 conductive polymer Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229920001002 functional polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polyparaphenylene benzobisthiazole Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 241000270955 Achnatherum calamagrostis Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000011022 operating instruction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920006215 polyvinyl ketone Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- 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
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention provides a spacer for a solid electrolytic capacitor, which has small thickness unevenness, is not easy to generate internal short circuit, has no overhigh impedance and has high heat resistance. A solid electrolytic capacitor separator comprising a nonwoven fabric, wherein the nonwoven fabric contains fibrillated heat-resistant fibers and synthetic short fibers as essential components, the fibrillated heat-resistant fibers have a fiber length of 0.30 to 0.75mm, and the proportion of fibrillated heat-resistant fibers having a fiber width of 12 to 40 [ mu ] m is 55% or more and less than 75%.
Description
Technical Field
The present invention relates to a spacer for a solid electrolytic capacitor. Hereinafter, the "solid electrolytic capacitor spacer" may be abbreviated as "spacer". In addition, the "solid electrolytic capacitor" may be abbreviated as "capacitor".
Background
In a solid electrolytic capacitor (solid electrolytic capacitor) using a conductive polymer such as polypyrrole or polythiophene as a solid electrolyte, a wound element is formed by winding a foil-like anode electrode and a foil-like cathode electrode with a separator interposed therebetween, and a conductive polymer film completely covering the separator is formed by impregnating the separator in the wound element with a polymerization liquid of the conductive polymer and polymerizing the polymerization liquid or impregnating the separator with a conductive polymer dispersion liquid.
Conventionally, as a spacer for a capacitor, a paper-made spacer mainly composed of a pulp of natural cellulose fibers such as fine needle grass and hemp pulp, solvent-spun cellulose fibers, and regenerated cellulose fibers has been used (patent documents 1 and 2). The cellulose fibers in these paper spacers are reacted with an oxidizing agent used in polymerizing the conductive polymer to inhibit polymerization of the conductive polymer, and therefore, carbonization treatment is performed in advance so as not to inhibit polymerization. Therefore, the paper spacer is thermally shrunk and becomes brittle by carbonization treatment, and thus burrs of the electrode easily penetrate through the spacer, which causes a problem of high short-circuit defect rate.
Therefore, a separator using a nonwoven fabric mainly composed of synthetic fibers has been studied (patent documents 3 to 5). In capacitors, the temperature required for reflow heat resistance has recently increased, but the spacers of patent documents 3 and 4 may have large thermal shrinkage in an atmosphere of 260 ℃. The spacer of patent document 5 is characterized in that dimensional change rates in both MD (machine direction) and CD (direction perpendicular to MD) when heat-treated at 250 ℃ for 50 hours are-3% to + 1%. However, the fibrillated heat-resistant fibers used as a raw material are poor in dispersibility and therefore tend to form lumps, and if they are used as they are, they may have uneven thickness and high internal short-circuit defect rate and resistance.
Patent document 6 describes that organic fibers having fibrils, which are beaten by a beating method with little mixing of metal foreign matter, are obtained by giving impact force at the time of breaking bubbles, which are generated by cavitation generated when a liquid jet is ejected from a nozzle or an orifice pipe to an organic fiber suspension, to the organic fibers in order to be applied to nonwoven fabrics for spacers and nonwoven fabrics for capacitors. However, patent document 6 only evaluates the tensile strength of a handsheet using an organic fiber having fibrils, and does not describe that the dispersion of the fiber having fibrils causes uneven thickness and a high internal short-circuit defect rate.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-267103
Patent document 2: japanese patent laid-open publication No. 2017-69229
Patent document 3: japanese patent laid-open No. 2001 and 332451
Patent document 4: japanese patent laid-open publication No. 2004-235293
Patent document 5: international publication No. 2005/101432 pamphlet
Patent document 6: japanese patent laid-open publication No. 2016-204798
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a spacer for a solid electrolytic capacitor having a small variation in thickness, a small possibility of internal short circuit, a small resistance, and a high heat resistance.
Means for solving the problems
The above technical problem is solved by the following means.
(1) A solid electrolytic capacitor separator comprising a nonwoven fabric, wherein the nonwoven fabric contains fibrillated heat-resistant fibers and synthetic short fibers as essential components, the fibrillated heat-resistant fibers have a fiber length of 0.30 to 0.75mm, and the proportion of fibrillated heat-resistant fibers having a fiber width of 12 to 40 [ mu ] m is 55% or more and less than 75%.
(2) The spacer for a solid electrolytic capacitor according to the item (1), wherein the fibrillated heat-resistant fibers have an average crimp rate (CURL) of 5 to 45%.
Effects of the invention
According to the present invention, the effects of high heat resistance, no excessive resistance, uniform texture, small thickness unevenness, and less internal short circuit can be achieved.
Detailed Description
< solid electrolytic capacitor >
In the present invention, the solid electrolytic capacitor refers to a solid electrolytic capacitor using a functional polymer having conductivity (conductive polymer) as an electrolyte. Examples of the functional polymer having conductivity include polypyrrole, polythiophene, polyaniline, polyacetylene, polyacene, and derivatives thereof. In the present invention, the solid electrolytic capacitor may be a hybrid electrolytic capacitor using these functional polymers and an electrolytic solution in combination. Examples of the electrolyte solution include, but are not limited to, an aqueous solution in which an ion-dissociable salt is dissolved, an organic solvent in which an ion-dissociable salt is dissolved, and an ionic liquid (solid molten salt). Examples of the organic solvent include Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Acetonitrile (AN), γ -Butyrolactone (BL), Dimethylformamide (DMF), Tetrahydrofuran (THF), Dimethoxyethane (DME), Dimethoxymethane (DMM), Sulfolane (SL), dimethyl sulfoxide (DMSO), ethylene glycol, and propylene glycol.
< spacer for solid electrolytic capacitor >
In the present invention, as the fibrillated heat-resistant fibers which are an essential component constituting the nonwoven fabric, fibers obtained by fibrillating heat-resistant fibers containing wholly aromatic polyamide, wholly aromatic polyester, polyimide, polyamideimide, polyether ether ketone, polyphenylene sulfide, polybenzimidazole, polyparaphenylene benzobisthiazole, polyparaphenylene benzobisoxazole, polytetrafluoroethylene, or the like can be used. Among these, the wholly aromatic polyamide is preferable because it has excellent affinity with the electrolyte.
In the present invention, the fiber length of the fibrillated heat resistant fiber is measured using kajaani fiber lab v3.5 (manufactured by Metso Automation) as an apparatus. The fiber length of the fibrillated heat resistant fiber is the length (1) in the projected fiber length (Proj) mode of the above-described apparatus, and is the length-weighted average fiber length. Further, only the fibrillated heat resistant fibers were used to measure the fiber length. The length of the fibrillated heat resistant fiber is 0.30 to 0.75mm, and more preferably 0.40 to 0.70 mm. If the fiber length is less than 0.30mm, the pores of the nonwoven fabric become too clogged, resulting in high impedance, and if the fiber length is longer than 0.75mm, the thickness unevenness due to the lumps, resulting in a decrease in heat resistance and the occurrence of internal short circuits.
In the present invention, the fiber width of the fibrillated heat resistant fiber is measured using kajaani fiber lab v3.5 (manufactured by Metso Automation) as an apparatus. The specific Fiber width ratio is the overall fraction (fibers) of the Fiber width (Fiber width) mode of the device. Further, the fiber width was measured using only the fibrillated heat resistant fibers. The proportion of the fibrillated heat-resistant fibers having a fiber width of 12 to 40 [ mu ] m is 55% or more and less than 75%, more preferably 60% or more, and still more preferably 65% or more. The fibrillated heat resistant fibers have a property of being poor in dispersibility and easily becoming lumps. If the proportion of the fibrillated heat-resistant fibers having a fiber width of 12 to 40 μm is less than 55%, problems such as reduction in heat resistance and occurrence of internal short circuits occur due to uneven thickness caused by lumps. When the content is 75% or more, the pores of the nonwoven fabric are too clogged, resulting in high impedance.
In the present invention, the average crimp ratio (CURL) of the fibrillated heat-resistant fiber is measured using kajaani fiber lab v3.5 (manufactured by Metso Automation) as a device. The CURL is the Fiber CURL (Fiber CURL) of the Fiber CURL distribution (Fiber CURL distribution) mode of the device described above.
The formula for the CURL calculation is described below in accordance with the operating instructions for the device described above.
Average crimp rate of fiber (CURLI)
CURLi(％)＝[Lc(n)i/Lp(n)i-1]×100
And (3) Curli: crimping of fibres
Lc (n) i: actual length of fiber (length along center line)
Lp (n) i: projected length of fibre (straight line measurement)
i: group (i 1 ~ 152)
Mean curvature of wrap (CURL, Fiber CURL)
CURL(％)＝∑(ni×CURLi)/∑ni
ni is the number of fibers in group i
In the present invention, only the average crimp rate (CURL) of the fibrillated heat-resistant fibers was measured. The fibrillated heat resistant fibers have an average crimp rate (CURL) of 5% or more and 45% or less, more preferably 10% or more and 35% or less, and still more preferably 15% or more and 25% or less. When the average crimp rate (CURL) of the fibrillated heat-resistant fibers is less than 5%, the entanglement of the fibers is too small, and the strength may be lowered. When the average crimp rate (CURL) of the fibrillated heat-resistant fibers exceeds 45%, dispersion of the fibers is excessively poor, and an internal short circuit may occur due to deterioration of texture.
The fibrillated heat-resistant fibers can be obtained by treatment with, for example, a fiber refiner, a beater, a mill, a attritor, a rotary blade homogenizer that imparts a shearing force with a high-speed rotary blade, a double-cylinder high-speed homogenizer that generates a shearing force between a cylindrical inner blade rotating at a high speed and a fixed outer blade, an ultrasonic crusher that refines the fibers by an impact caused by ultrasonic waves, a high-pressure homogenizer that imparts a pressure difference of at least 20MPa to a fiber suspension, makes the fiber suspension pass through a small-diameter orifice at a high speed, and collides and rapidly decelerates the fiber to impart a shearing force and a cutting force to the fiber, and the like.
In the present invention, examples of the synthetic short fibers which are essential components constituting the nonwoven fabric include short fibers containing resins such as polyolefin, polyester, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide, acrylic acid, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether, polyvinyl ketone, polyether, polyvinyl alcohol, diene, polyurethane, phenol, melamine, furan, urea, aniline, unsaturated polyester, fluorine, silicone, and derivatives thereof, and the above-mentioned heat-resistant fibers. The synthetic short fiber enhances the tensile strength and the puncture strength of the non-woven fabric.
The synthetic staple fibers are non-fibrillatable fibers, and may be fibers (monofilaments) composed of a single resin or composite fibers composed of two or more resins. In addition, one kind of synthetic short fibers contained in the nonwoven fabric of the present invention may be used, or two or more kinds may be used in combination. Examples of the composite fiber include a sheath-core type, an eccentric core type, a side-by-side type, an island-in-sea type, an orange-lobe type, and a multiple bimetal type.
The fineness of the synthetic staple fibers is preferably 0.02 to 2.5dtex, more preferably 0.1 to 2.0 dtex. When the fineness of the synthetic staple fiber exceeds 2.5dtex, the fiber diameter becomes large and the number of fibers in the thickness direction becomes small, so that the synthetic staple fiber is difficult to be thin. When the fineness of the synthetic staple fiber is less than 0.02dtex, stable production of the fiber becomes difficult.
The synthetic staple fibers preferably have a fiber length of 1mm to 10mm, more preferably 1mm to 6 mm. When the fiber length exceeds 10mm, the texture may be poor. On the other hand, when the fiber length is less than 1mm, the mechanical strength of the nonwoven fabric may be weakened.
In the present invention, the total content of the fibrillated heat-resistant fibers and the synthetic short fibers in the nonwoven fabric is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass. When the total content is less than 50% by mass, the internal short-circuit defect rate may be high. Fibrillated heat-resistant fibers: the mass ratio of the synthetic short fibers is preferably 7: 1-1: 19, more preferably 5: 1-3: 17, and further preferably 4: 1-1: 5. Fibrillated heat-resistant fibers: when the mass ratio of the synthetic short fibers is within this range, the thermal shrinkage of the spacer is reduced, the heat resistance is excellent, the tensile strength of the nonwoven fabric is increased, the handleability of the nonwoven fabric is excellent, and the nonwoven fabric is not easily broken when the capacitor is manufactured.
In the present invention, the nonwoven fabric may contain fibers other than the fibrillated heat-resistant fibers and the synthetic staple fibers. For example, cellulose fibers; pulped and fibrillated cellulose fibers; fibrids, pulped products, fibrillated products containing synthetic resins; inorganic fibers, and the like. Examples of the inorganic fibers include glass, alumina, silica, ceramics, and rock wool. The cellulose fiber may be either natural cellulose fiber or regenerated cellulose fiber.
In the present invention, the weight per unit area of the nonwoven fabric is preferably 8 to 25g/m2More preferably 9 to 20g/m2More preferably 10 to 18g/m2. If the weight per unit area exceeds 25g/m2There is a time when the spacer becomes excessively thick and the weight per unit area is less than 8g/m2It may be difficult to obtain sufficient strength. The basis weight is based on JIS P8124: 2011 (paper and board basis weight measurement).
In the present invention, the thickness of the nonwoven fabric is preferably 8 to 60 μm, more preferably 10 to 55 μm, and still more preferably 12 to 52 μm. If the thickness exceeds 60 μm, the impedance may become too high, and if the thickness is less than 8 μm, the strength of the nonwoven fabric substrate may become too weak, and the nonwoven fabric substrate may be damaged during handling of the spacer or during production of the capacitor. The thickness is measured in accordance with JIS B7502: 2016, measured under a load of 5N.
In the present invention, the density of the spacer is preferably 0.25 to 0.70g/cm3More preferably 0.40 to 0.60g/cm3. When the density is less than 0.25g/cm3In this case, internal short-circuiting is liable to occur, and when it exceeds 0.70g/cm3When this occurs, the impedance sometimes becomes too high. The density is a value obtained by dividing the weight per unit area by the thickness (weight per unit area/thickness).
In the present invention, the nonwoven fabric is preferably a wet nonwoven fabric produced by a wet papermaking method. The wet papermaking method is a method in which fibers are dispersed in water to prepare a uniform raw material slurry, and the raw material slurry is collected by a papermaking machine and dried to prepare a wet nonwoven fabric. Examples of the paper machine include a paper machine using a paper wire such as a cylinder wire, a fourdrinier wire, an inclined wire, or an inclined short wire, and a composite paper machine in which a plurality of paper wires are combined. In the step of producing the wet nonwoven fabric, water interlacing treatment may be performed as needed. The nonwoven fabric may be subjected to a processing treatment such as heat treatment, calendering, hot calendering.
[ examples ]
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples.
[ production of spacer ]
The raw materials in the parts shown in table 1 were disintegrated in water in a pulper, and a uniform raw material slurry (0.5 mass% concentration) was prepared under stirring with a stirrer. The raw material slurry was subjected to wet papermaking using a cylinder machine, and then both sides were brought into contact with metal rolls heated to 180 ℃ to perform heat treatment, and further subjected to calendering treatment to adjust the thickness, thereby producing a spacer made of a nonwoven fabric.
As the fibrillated heat resistant fibers, wholly aromatic polyamide pulp was used, and fibers having a fiber length and a fiber width shown in table 1 were produced and used by fibrillation treatment with a fiber refiner.
As the synthetic short fibers, oriented crystalline polyethylene terephthalate (PET) short fibers and binder PET short fibers are used. As the fibrillated natural cellulose fiber, fibrillated natural cellulose fiber in which natural cellulose is fibrillated by a high-pressure homogenizer and a proportion of fibers having a fiber length of 0.20mm or less is 75% is used. The parts are based on mass.
[ Table 1]
The following measurement and evaluation were performed on the spacers of examples and comparative examples, and the results are shown in table 2.
[ measurement: weight per unit area ]
According to JIS P8124: 2011 the weight per unit area is measured.
[ measurement: thickness ]
Using JIS B7502: 2016, the thickness of the outer micrometer was measured under a load of 5N.
[ evaluation: tensile strength
A sample of 50mm (CD) X200 Mm (MD) was prepared in accordance with JIS P8113: tensile strength (tensile strength) is measured 2006.
[ Heat resistance ]
The spacers were cut into pieces of 200mm (CD). times.200 Mm (MD), and left to stand in a thermostatic dryer at 260 ℃ for 3 hours to calculate the shrinkage in MD and CD.
Good: the average shrinkage in MD and CD is less than 0.8%.
Δ (Average): the average shrinkage of MD and CD is 0.8% or more and less than 1.0%.
X (difference: Poor): the average shrinkage of MD and CD is 1.0% or more.
[ evaluation: impedance (c)
The separator thus produced was immersed in an electrolyte (1M-LiPF)6Ethylene Carbonate (EC) + diethyl carbonate (DEC) + dimethyl carbonate (DMC) (1: 1, vol ratio)) was sandwiched between two substantially cylindrical copper electrodes, and the resultant was measured using an LCR tester (manufactured by Instec corporation, apparatus name: LCR-821), the resistance component of the ac impedance at 200kHz was measured.
[ evaluation: texture ]
The produced spacer was subjected to sensory evaluation for uniformity of texture when light was transmitted therethrough.
Very good (Excellent: Excellent): the uniformity of texture was very good and no thickness variation was observed.
Good: the uniformity of texture was good, and several thickness unevenness was observed.
Δ (Average): the uniformity of texture was poor and thickness unevenness was observed. Levels that can be used.
X (difference: Poor): the uniformity of texture was very poor, and the quality was concerned and could not be used.
[ evaluation: internal short-circuit defective rate
After the electrode group was produced by winding the produced separator between electrodes made of aluminum foil, the electrode group was examined for conduction between the electrodes with a tester without being immersed in an electrolyte solution, and the presence or absence of an internal short circuit was confirmed. The internal short defect rate was calculated from the number of internal short circuits with respect to the number of all electrode groups by examining 100 electrode groups.
[ Table 2]
The spacers of examples 1 to 13 were made of a nonwoven fabric containing fibrillated heat-resistant fibers and synthetic short fibers as essential components, and the fibrillated heat-resistant fibers had a fiber length of 0.30 to 0.75mm and a proportion of fibrillated heat-resistant fibers having a fiber width of 12 to 40 μm of 55% or more and less than 75%, and therefore had high heat resistance, did not have excessively high resistance, and were able to achieve the effect of preventing internal short circuits. In addition, in the spacers of examples 1 to 9, since the average crimp rate of the fibrillated heat-resistant fibers was 5 to 45%, the effects of uniform texture and less thickness unevenness were also achieved.
Comparing examples 2, 10 and 11, the spacer of example 2 in which the average crimp rate of the fibrillated heat-resistant fibers was 5 to 45% had higher strength and uniform texture than the spacer of example 10 in which the average crimp rate of the fibrillated heat-resistant fibers was less than 5%. Further, the texture of the spacer of example 2 was uniform compared to the spacer of example 11 in which the average crimp rate of the fibrillated heat resistant fibers exceeded 45%.
Comparing examples 5, 12 and 13, the spacer of example 5 having an average crimp rate of the fibrillated heat-resistant fibers of 5 to 45% had higher strength and a uniform texture than the spacer of example 12 having an average crimp rate of the fibrillated heat-resistant fibers of less than 5%. Further, the texture of the spacer of example 5 was uniform compared to the spacer of example 13 in which the average crimp rate of the fibrillated heat resistant fibers exceeded 45%.
The spacers of comparative examples 1, 3 and 5 had a fiber length of less than 0.30mm and a proportion of fibrillated heat-resistant fibers having a fiber width of 12 to 40 μm of 75% or more, and therefore had higher resistance than the spacers of examples 1 to 13.
In the spacers of comparative examples 2, 4 and 6, the fiber length of the fibrillated heat-resistant fibers was longer than 0.75mm, and the proportion of the fibrillated heat-resistant fibers having a fiber width of 12 to 40 μm was less than 55%, so that the quality was very poor as compared with the spacers of examples 1 to 13, and the heat resistance was observed to be lowered due to uneven thickness at a level where quality was concerned, and as a result, the internal short-circuit defect rate was high.
Industrial applicability
The present invention can be suitably used as a spacer for solid electrolytic capacitors or a spacer for hybrid electrolytic capacitors.
Claims (2)
1. A spacer for a solid electrolytic capacitor, characterized in that,
a separator for a solid electrolytic capacitor comprising a nonwoven fabric, wherein the nonwoven fabric contains fibrillated heat-resistant fibers and synthetic short fibers as essential components, the length of the fibrillated heat-resistant fibers is 0.30mm to 0.75mm, and the proportion of the fibrillated heat-resistant fibers having a fiber width of 12 [ mu ] m to 40 [ mu ] m in the fibrillated heat-resistant fibers is 55% or more and less than 75%.
2. The spacer for a solid electrolytic capacitor according to claim 1,
the average crimp rate (CURL) of the fibrillated heat-resistant fibers is 5 to 45%.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2019-059101 | 2019-03-26 | ||
| JP2019059101 | 2019-03-26 | ||
| JP2020028178A JP6821071B2 (en) | 2019-03-26 | 2020-02-21 | Separator for solid electrolytic capacitors |
| JP2020-028178 | 2020-02-21 | ||
| PCT/JP2020/012170 WO2020196215A1 (en) | 2019-03-26 | 2020-03-19 | Separator for solid electrolytic capacitor |
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| CN113316830A true CN113316830A (en) | 2021-08-27 |
| CN113316830B CN113316830B (en) | 2022-12-23 |
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| JP (1) | JP6821071B2 (en) |
| KR (1) | KR102567592B1 (en) |
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| CN1942983A (en) * | 2004-04-16 | 2007-04-04 | 三菱制纸株式会社 | Separator for electrochemical element |
| JP2011228320A (en) * | 2010-04-15 | 2011-11-10 | Mitsubishi Paper Mills Ltd | Separator for solid electrolytic capacitor, and solid electrolytic capacitor using the same |
| JP2012195162A (en) * | 2011-03-16 | 2012-10-11 | Mitsubishi Paper Mills Ltd | Substrate for lithium secondary battery, and separator for lithium secondary battery |
| CN104425791A (en) * | 2013-08-30 | 2015-03-18 | 三菱制纸株式会社 | Separator for Electrochemical Element, Process for Producing Separator and Electrochemical Element Using Separator |
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| JP2017174928A (en) * | 2016-03-23 | 2017-09-28 | 三菱製紙株式会社 | Separator for solid electrolytic capacitor |
| JP2017199728A (en) * | 2016-04-25 | 2017-11-02 | 三菱製紙株式会社 | Separator for solid electrolytic capacitor |
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| WO2018123689A1 (en) * | 2016-12-27 | 2018-07-05 | 三菱製紙株式会社 | Lithium ion battery separator and lithium ion battery |
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| JP3466206B2 (en) | 1992-03-19 | 2003-11-10 | ニッポン高度紙工業株式会社 | Electrolytic capacitor |
| JP4707208B2 (en) | 2000-05-24 | 2011-06-22 | ニッポン高度紙工業株式会社 | Winding type electrolytic capacitor |
| JP4163523B2 (en) | 2003-01-29 | 2008-10-08 | 三菱製紙株式会社 | Separator for solid electrolytic capacitor |
| JP2007150122A (en) * | 2005-11-30 | 2007-06-14 | Mitsubishi Paper Mills Ltd | Separator for electric double layer capacitor |
| JP2010232202A (en) * | 2009-03-25 | 2010-10-14 | Tomoegawa Paper Co Ltd | Separator for electricity storage device |
| JP2016204798A (en) | 2015-04-28 | 2016-12-08 | 日本製紙パピリア株式会社 | Organic fiber having fibril |
| JP2018125272A (en) * | 2016-03-24 | 2018-08-09 | 三菱製紙株式会社 | Lithium ion battery separator |
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2020
- 2020-02-21 JP JP2020028178A patent/JP6821071B2/en active Active
- 2020-03-19 CN CN202080009830.4A patent/CN113316830B/en active Active
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| CN1942983A (en) * | 2004-04-16 | 2007-04-04 | 三菱制纸株式会社 | Separator for electrochemical element |
| JP2011228320A (en) * | 2010-04-15 | 2011-11-10 | Mitsubishi Paper Mills Ltd | Separator for solid electrolytic capacitor, and solid electrolytic capacitor using the same |
| JP2012195162A (en) * | 2011-03-16 | 2012-10-11 | Mitsubishi Paper Mills Ltd | Substrate for lithium secondary battery, and separator for lithium secondary battery |
| CN104425791A (en) * | 2013-08-30 | 2015-03-18 | 三菱制纸株式会社 | Separator for Electrochemical Element, Process for Producing Separator and Electrochemical Element Using Separator |
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| CN108140492A (en) * | 2015-09-28 | 2018-06-08 | 日本高度纸工业株式会社 | Electro chemical elements use separator and electrochemical element |
| JP2017174928A (en) * | 2016-03-23 | 2017-09-28 | 三菱製紙株式会社 | Separator for solid electrolytic capacitor |
| JP2017199728A (en) * | 2016-04-25 | 2017-11-02 | 三菱製紙株式会社 | Separator for solid electrolytic capacitor |
| WO2018123689A1 (en) * | 2016-12-27 | 2018-07-05 | 三菱製紙株式会社 | Lithium ion battery separator and lithium ion battery |
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| Publication number | Publication date |
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| JP6821071B2 (en) | 2021-01-27 |
| TW202044293A (en) | 2020-12-01 |
| KR102567592B1 (en) | 2023-08-16 |
| JP2020167386A (en) | 2020-10-08 |
| KR20210094098A (en) | 2021-07-28 |
| CN113316830B (en) | 2022-12-23 |
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