CN104409213A - Electrolyte glue solution for post-treatment of formed foil, electrode foil and capacitor - Google Patents
Electrolyte glue solution for post-treatment of formed foil, electrode foil and capacitor Download PDFInfo
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- CN104409213A CN104409213A CN201410638033.9A CN201410638033A CN104409213A CN 104409213 A CN104409213 A CN 104409213A CN 201410638033 A CN201410638033 A CN 201410638033A CN 104409213 A CN104409213 A CN 104409213A
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- capacitor
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- foil
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 239000003990 capacitor Substances 0.000 title claims abstract description 68
- 239000003292 glue Substances 0.000 title claims abstract description 67
- 239000011888 foil Substances 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 29
- 239000002322 conducting polymer Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- -1 silicon oxygen alkane Chemical class 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 17
- 229910000077 silane Inorganic materials 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000001993 wax Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002318 adhesion promoter Substances 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000012958 reprocessing Methods 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003252 repetitive effect Effects 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 2
- 229910001029 Hf alloy Inorganic materials 0.000 claims description 2
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001362 Ta alloys Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000756 V alloy Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001992 poloxamer 407 Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 34
- 239000011248 coating agent Substances 0.000 abstract description 33
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 abstract 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 238000012805 post-processing Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003756 stirring Methods 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
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- 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
-
- 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
- H01G9/15—Solid electrolytic capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses an electrolyte glue solution for post-treatment of formed foil, electrode foil and a capacitor. The main active constituents of the electrolyte glue solution comprise 25-99.5 parts by weight of conducting polymers, 0.5-40 parts by weight of water-dilutable resin, 0.1-5 parts by weight of silane coupling agents and 0.1-5 parts by weight of flatting agents. The electrolyte glue solution for the post-treatment of the formed foil can be used for treating the formed foil directly to obtain the electrode foil, subsequent capacitor manufacturing processes can be effectively simplified by means of the electrode foil, and thus production efficiency can be improved. In comparison with an existing capacitor manufacturing process, uncertainty of caused by EDOT (Ethylenedioxythiophene) monomers and oxidizing agent polymerization can be avoided, and further influences on the capacitor quality caused by the uncertainty can be avoided. Electrolyte layer structures produced by coating the electrolyte glue solution is compact in structure, firm in adhesion and good in electrical conductivity and contact with a metal oxidation layer. Meanwhile, good characteristics of a solid electrolytic capacitor can be maintained and high-frequency performance of the capacitor can be improved.
Description
Technical field
The application relates to capacitor electrode material field, particularly relates to a kind of electrolyte glue for Waste Acid From Hua Cheng Foil reprocessing, through the electrode foil that this electrolyte glue process obtains, and adopts the capacitor of this electrode foil.
Background technology
Electrolytic capacitor is one of indispensable components and parts in electronic product, and along with the development of electronic technology, packaging density and the integration degree of complete electronic set increase further.The discrete component of crucial not accessible site in aluminium electrolytic capacitor operation, just towards small size, Large Copacity, low cost, low impedance at high frequency future development.Aluminium electrolytic capacitor have function admirable, Large Copacity, cheap, be easy to processing, the feature such as easy to use, be therefore widely used in the electronic system products such as information electronic device, instrument, electromechanics, household electrical appliances.And as the newcomer in Lv electricity electrolytic capacitor family, solid-state aluminum electrolytic capacitor, its electrode material conductivity is high, can reach 100S/cm, relative ordinary liquid electrolytic conductivity 0.01S/cm, both conductivity differ 10000 times, therefore, the capacitor prepared has more excellent electrical property, especially in equivalent series resistance (being called for short ESR value), has more outstanding performance.Because electrode material is solid-state polymer compound, the risk of capacitorless blast, the stability of conduction high polymer is high, the life-span of prepared capacitor, also has more good performance compared with liquid aluminum electrolytic capacitor.For these reasons, aluminium solid electrolytic capacitor is subject to the welcome of vast complete-system vendor and user deeply.
Current solid-state aluminum electrolytic capacitor aluminium foil preparation technology roughly comprises: and light paper tinsel-pre-treatment-one-level corrosion-secondary corrosion-reprocessing-one-level changes into-and secondary changes into.After processing above, obtain the solid-state low-voltage aluminium foil for aluminium electrolytic capacitor.Downstream producer obtains the low-voltage aluminium foil changed into through two-stage, namely after Waste Acid From Hua Cheng Foil, also needs the process route grown just can be prepared into complete capacitor very.Roughly route comprises: open paper tinsel-riveted joint-winding-pre-treatment-carbonization-impregnation monomer-impregnation oxidant-be polymerized-seal-change into.As can be seen from process route, adopt existing Waste Acid From Hua Cheng Foil, its capacitor preparation technology operation be more, more complicated; Further, there is more uncertainty with the polymerization reaction of oxidant in EDOT monomer (i.e. 3,4-rthylene dioxythiophene), affects the performance of capacitor, even affect the qualification rate of capacitor.
Summary of the invention
The object of the application provides a kind of brand-new electrolyte glue, the electrode foil obtained by this electrolyte glue process, and the capacitor prepared by this electrode foil for a kind of post-processing approach of Waste Acid From Hua Cheng Foil of improvement.
To achieve these goals, the application have employed following technical scheme:
This application discloses a kind of electrolyte glue for Waste Acid From Hua Cheng Foil reprocessing, the main active of this electrolyte glue comprises the levelling agent of the conducting polymer of 25-99.5 weight portion, the water-base resin of 0.5-40 weight portion, the silane coupler of 0.1-5 weight portion and 0.1-5 weight portion.
It should be noted that, the electrolyte glue of the application proposes based on a kind of post-processing approach of Waste Acid From Hua Cheng Foil.The post-processing approach of this Waste Acid From Hua Cheng Foil is included in the metal oxide layer surface-coated electrolyte glue of Waste Acid From Hua Cheng Foil, forms dielectric substrate; The key of this post-processing approach is, the process of coated electrolyte glue is carried out on Waste Acid From Hua Cheng Foil basis originally again, forms dielectric substrate, thus makes electrode foil; Through the electrode foil that this post-processing approach obtains, when preparing for follow-up capacitor, without the need to carrying out the operations such as pre-treatment, carbonization, impregnation EDOT monomer, impregnation oxidant and polymerization; Directly open paper tinsel, namely riveted joint, winding, impregnation, sealing be assembled into solid aluminum electrolytic capacitor; Thus simplify the technique that electrode foil makes capacitor.In addition, in existing technique, impregnation EDOT monomer, impregnation oxidant and be polymerized this three operations, in fact be exactly that polymerization is formed conducting polymer, and be attached on Waste Acid From Hua Cheng Foil, and conducting polymer is directly coated on Waste Acid From Hua Cheng Foil as glue by the application, and, in order to the adhesive force increasing conducting polymer also added out the component beyond conducting polymer, as water-base resin and silane coupler; Thus avoid the uncertainty of EDOT monomer and oxidant polymerization reaction, improve quality and the production stability of capacitor.In addition, in order to ensure the smooth, smooth of the coating that the coating of electrolyte glue obtains, the application is also creationary with the addition of levelling agent, to ensure the outward appearance of coating and electrode foil in electrolyte glue.
In addition, in the application, the preparation of electrolyte glue, can with reference to the preparation of the coating solution of routine, as added water or the mixing of isopropanol liquid cement agitation, is not specifically limited at this, as long as according to the formulated of the application; As for mode electrolyte glue being coated to Waste Acid From Hua Cheng Foil surface, also with reference to the coating of the coating solution of routine, can be not specifically limited at this.
Also it should be noted that, in the application, conducting polymer, water-base resin, silane coupler and levelling agent etc. can adopt the conventional reagent used in production, the key of the application is just the creationary electrolyte glue utilizing these preparation of reagents to become special, thus realize the application for applying the object preparing electrode foil, but not invent a kind of new reagent.But, in the preferred version of the application, for the Special use demand of the application, respectively conducting polymer, water-base resin, silane coupler and levelling agent are limited.
Preferably, conducting polymer is for having the polymer of the repetitive of general formula (I) or (II), or the polymer of the repetitive of general formula (I) and (II);
Wherein,
A represents the optional C1-C5 alkylidene replaced;
R represents at least one in optional the straight or branched C1-C18 alkyl, the C5-C12 cycloalkyl optionally replaced, the C6-C14 aryl optionally replaced, the C7-C18 aralkyl of optional replacement, the C1-C4 hydroxy alkyl of optional replacement or the hydroxyl that replace;
X value is the integer in 0-8.
Preferably, conducting polymer is polythiophene.
Preferably, conducting polymer is poly-(3,4-ethyldioxythiophene).
Preferably, water-base resin is waterborne polyurethane resin and/or acrylic emulsion.
Preferably, silane coupler is KH560 or A-187.
Preferably, levelling agent is selected from least one in dimethyl silicone polymer, polyester resin change properties of organic silicon oxygen alkane and organic-silicon-modified dimethyl silicone polymer.The effect of levelling agent is levelling, and for coating or similar coating method, levelling agent can make coating smooth, smooth, thus ensures the outward appearance of coating and electrode foil.
Preferably, electrolyte glue also comprises at least one in ethylene glycol, wax emulsion, surfactant, defoamer, film forming agent, adhesion promoter and isopropyl alcohol.
Wherein, the effect of ethylene glycol improves conductance, and therefore, its consumption can determine according to Production requirement, is not specifically limited at this.
It should be noted that, the effect of wax emulsion is the smooth degree, water-fast, the wear-resisting and resistance to blocking that improve coating, can select to add according to the specific requirement of electrode foil or capacitor; Surfactant can improve the surface activity of coating, can select according to demand to add, and but, generally all can add; The foam in electrolyte glue is eliminated in the effect of defoamer, avoids foam to impact coating; The effect of film forming agent improves film forming, can select according to demand to add; The effect of adhesion promoter is the adhesive force improved further between coating and Waste Acid From Hua Cheng Foil, is having water-base resin to increase on the basis of adhesive force, can select according to demand to add adhesion promoter; The effect of isopropyl alcohol reduces surface tension, improves the compatibility of each component, also has the effect of dilution, can select according to demand to add, but generally all can add; In addition, in order to dilute electrolyte glue, appropriate deionized water can also be added, be not specifically limited at this.
Preferably, the consumption of wax emulsion is 0.5-20 weight portion, and the consumption of surfactant is 0.1-5 weight portion, and the consumption of defoamer is 0.1-3 weight portion, and the consumption of film forming agent is 0.1-5 weight portion, and the consumption of adhesion promoter is 0.1-5 weight portion.
Preferably, wax emulsion is that the material such as native paraffin and synthetic wax is scattered in the emulsion of a kind of heterogeneous system in water in the effect of emulsifying agent; Surfactant is selected from least one in polyvinylpyrrolidone, Pluronic F-127 laurate ether, polyethylene glycol, lauryl sodium sulfate, neopelex, glycerin monostearate and polysorbate; Defoamer is selected from least one in organic silicon modified by polyether oxygen alkane, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene; Film forming agent is selected from acrylic resin and/or polyurethane resin; Adhesion promoter is selected from amino modified silane compound and/or epoxy-modified silane compound.
The another side of the application discloses a kind of electrode foil, and this electrode foil comprises metal level, is positioned at the metal oxide layer of layer on surface of metal, and is positioned at the dielectric substrate on metal oxide layer surface; The material of metal level is at least one in the alloy of tantalum, niobium, aluminium, titanium, zirconium, hafnium, vanadium or these metals or compound; Metal oxide layer is after being changed into by described metal level, in the oxide layer that its surface is formed; Dielectric substrate is coated on metal oxide layer surface by the electrolyte glue of the application and is formed.It should be noted that, the thickness of dielectric substrate can according to use or Production requirement from Row sum-equal matrix, and the application is preferred, and dielectric substrate thickness is 1-100 μm can meet common user demand substantially.
On the basis of the electrode foil of the application, capacitor prepared by the electrode foil that the another side of the application also discloses a kind of the application of employing.
It should be noted that, the capacitor of the application, its quality and production technology are obtained for raising; The first, with regard to production technology, owing to have employed the electrode foil of the application, directly carry out out paper tinsel, riveted joint, winding, impregnation electrolyte and sealing process, make capacitor, without the need to operations such as pre-treatment, carbonization, impregnation EDOT monomer, impregnation oxidant and polymerizations; The production technology of capacitor is simplified.The second, due to the polymerization reaction without the need to carrying out EDOT monomer and oxidant, avoiding the unsteadiness of this polymerization reaction to the impact of capacitor quality, thus improve the quality of production of the capacitor of the application.
Owing to adopting above technical scheme, the beneficial effect of the application is:
The electrolyte glue of the application, can meet the user demand of Waste Acid From Hua Cheng Foil reprocessing, this electrolyte glue is coated in the metal oxide layer surface of Waste Acid From Hua Cheng Foil, forms dielectric substrate, thus make electrode foil; When preparing capacitor with this electrode foil, not only effectively can simplify the production technology of capacitor, enhance productivity; And, due to the conducting polymer containing directly interpolation in dielectric substrate, compared with existing technique, avoid EDOT monomer and oxidant is polymerized the uncertainty brought, and the impact on capacitor quality caused thus.The electrolyte glue of the application applies in the porous metal oxide layer of electrode foil high-specific surface area, form dielectric substrate, this dielectric substrate compact structure, adhesion-tight is stablized, there is good conductivity and contact with metal oxide layer well, and while maintenance solid electrolytic capacitor good characteristic, improve its high frequency performance.
Embodiment
In the application, electrode foil refers to the paillon foil that can be directly used in capacitor and prepare, and is equivalent to the Waste Acid From Hua Cheng Foil mentioned in background technology; In fact, the electrode foil of the application is exactly process acquisition further on the basis of Waste Acid From Hua Cheng Foil, to facilitate follow-up capacitor preparation.Concrete, adopt the electrode foil of the application, first aspect, simplify follow-up capacitor preparation section, without the need to carrying out " pre-treatment-carbonization-impregnation monomer-impregnation oxidant-polymerization ", directly namely can be made into capacitor by " opening paper tinsel-riveted joint-winding-impregnation-sealing ", shorten the production time of capacitor producer, improve production efficiency; Second aspect, owing to adopting special electrolyte glue, without the need to carrying out being polymerized of EDOT monomer and oxidant in capacitor production technology, avoids the unsteadiness brought thus and the impact on capacitor performance and qualification rate thereof.
It should be noted that, the electrolyte glue of the application, in fact be based on Waste Acid From Hua Cheng Foil surface-coated one deck dielectric substrate to propose with the design simplifying follow-up capacitor production technology, this electrolyte glue is a kind of existence completely newly in solid electrolytic capacitor field, based on this electrolyte glue can realize the application Waste Acid From Hua Cheng Foil surface formed dielectric substrate, thus simplify capacitor production technology, improve capacitor production efficiency and quality of production stability.
Below by specific embodiment, the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
Embodiment one
The electrolyte glue of this example adds in order respectively by following deal: conducting polymer 50g, water-base resin 35g, wax emulsion 10g, surfactant 1g, levelling agent 1g, defoamer 1g, film forming agent 1g, adhesion promoter 1g, silane coupler 1g, isopropyl alcohol 6g, pure water 6g, interpolation limit, limit stirs, then electrolyte glue is coated in the metal oxide layer surface of Waste Acid From Hua Cheng Foil, coating thickness 50 μm, 150 DEG C of baking 5min, obtain electrode foil.
Then by electrode foil according to operation: open paper tinsel, riveted joint, winding, impregnation, sealing be assembled into solid aluminum electrolytic capacitor.Impregnation electrolyte step in the capacitor of wherein impregnation and traditional liquid state, this example is introduced into the preparation of solid aluminum electrolytic capacitor, certain repairing effect is had to electrode foil, make its performance better, the technique preparing capacitor of this example, compared with traditional solid capacitor preparation technology, eliminate operations such as " pre-treatment-carbonization-impregnation monomer-impregnation oxidant-polymerizations ".
Under the operating voltage of 25 volts, test the static capacity of capacitor, loss tangent and equivalent series resistance, test mode, with reference to the measurement of conventional solid electrolytic capacitor, tiredly to be stated at this.Test result is as shown in table 1.
Embodiment two
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 70g, water-base resin 30g, wax emulsion 2g, surfactant 2g, levelling agent 2g, defoamer 2g, film forming agent 2g, adhesion promoter 2g, silane coupler 2g, ethylene glycol 5g, isopropyl alcohol 5g.The coating thickness of this example is 60 μm, and 120 DEG C of baking 15min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment three
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 95g, water-base resin 25g, surfactant 1g, levelling agent 1g, defoamer 2g, silane coupler 2g.The coating thickness of this example is 100 μm, and 150 DEG C of baking 15min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment four
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 35g, water-base resin 20g, wax emulsion 20g, surfactant 5g, levelling agent 5g, defoamer 3g, film forming agent 5g, adhesion promoter 5g, silane coupler 5g, ethylene glycol 2g, pure water 2g.The coating thickness of this example is 30 μm, and 110 DEG C of baking 20min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment five
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 80g, water-base resin 40g, wax emulsion 0.5g, surfactant 0.1g, levelling agent 0.1g, defoamer 0.1g, film forming agent 0.1g, adhesion promoter 0.1g, silane coupler 0.1g, ethylene glycol 2g.The coating thickness of this example is 15 μm, and 100 DEG C of baking 20min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment six
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 10g, water-base resin 10g, wax emulsion 20g, surfactant 5g, levelling agent 4g, defoamer 2g, film forming agent 3g, adhesion promoter 2g, silane coupler 2g, ethylene glycol 1g, isopropyl alcohol 1g, pure water 1g.The coating thickness of this example is 1 μm, and 80 DEG C of baking 25min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment seven
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 25g, water-base resin 0.5g, surfactant 3g, levelling agent 2.5g, silane coupler 2.5g.The coating thickness of this example is 50 μm, and 110 DEG C of baking 25min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment eight
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 40g, water-base resin 10g, wax emulsion 5g, defoamer 1g, film forming agent 2g, adhesion promoter 3g, silane coupler 3g, levelling agent 2g, ethylene glycol 5g, isopropyl alcohol 5g.The coating thickness of this example is 65 μm, and 100 DEG C of baking 30min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment nine
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 50g, water-base resin 4g, surfactant 2g, levelling agent 2.5g, silane coupler 4g.The coating thickness of this example is 60 μm, and 90 DEG C of baking 40min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Embodiment ten
The technique of this example is identical with embodiment one with metering system, and just change electrolyte glue, coating thickness and baking condition, all the other are identical.
The electrolyte glue of this example adds respectively by following deal: conducting polymer 50g, water-base resin 1g, levelling agent 2g, silane coupler 5g.The coating thickness of this example is 50 μm, and 80 DEG C of baking 60min, obtain electrode foil.
The test result of this example is as shown in table 1 equally.
Comparative example one
By the aluminium anodes after anodization, i.e. Waste Acid From Hua Cheng Foil, immersing EDOT concentration is in the butanol solution of 24.35wt% 10 seconds, takes out and dries, namely; Immerse the 1.0mol/L p-methyl benzenesulfonic acid water solution 10 seconds of 0.1mol/L neopelex again, take out and dry, and be placed in air cooling 3 minutes, i.e. polymerization reaction 3 minutes.Repeat above-mentioned steps 6 times.
The aluminium chip completing above-mentioned steps being immersed EDOT concentration is in the butanol solution of 24.35wt% 10 seconds, takes out and dries; Immerse the 3.5mol/L p-methyl benzenesulfonic acid water solution 10 seconds of 0.2mol/L neopelex again, take out and dry, and be placed in air cooling 3 minutes, i.e. polymerization reaction 3 minutes.Repeat above-mentioned steps 6 times.Wherein conductive polymer membrane is obtained by the polymerization reaction of EDOT and oxide.
With washed with de-ionized water aluminium chip, impurity and the complete component of unreacted are cleaned up.
Aluminium chip is assembled into solid aluminum electrolytic capacitor by traditional technique.
Under the operating voltage of 25 volts, test the static capacity of capacitor, loss tangent and equivalent series resistance, test mode, with reference to the measurement of conventional solid electrolytic capacitor, tiredly to be stated at this.Test result is as shown in table 1.
Comparative example two
This example is identical with comparative example one, and difference is only, the time cooled in atmosphere is 50 seconds, and the thickness of conductive polymer membrane is 45nm.All the other are identical.
Comparative example three
This example is identical with comparative example one, and difference is only, the time cooled in atmosphere is 800 seconds, and the thickness of conductive polymer membrane is 1300nm.All the other are identical.
The test result of above embodiment and comparative example is as shown in table 1 below:
Table 1 solid aluminum electrolytic capacitor properties test result
Result shows, and under identical testing conditions, when static capacity is much the same, the loss tangent of comparative example and ESR are bigger than normal.Visible, be coated with the electrode foil of the electrolyte glue of the application, and the capacitor prepared thus, its ESR value is relatively little, for the power supply preparing high-quality is laid a good foundation.According to analysis, why the electrode foil of the application can obtain less loss tangent and ESR value, it is the dielectric substrate compact structure formed because of the electrolyte glue of the application, adhesion-tight is stablized, there is good conductivity and contact with metal oxide layer well, therefore, while maintenance solid electrolytic capacitor good characteristic, improve its high frequency performance.Compared with the operation of traditional repeatedly " impregnation monomer-impregnation oxidant-polymerization ", directly apply the electrolyte glue of the application, the polymerization reaction avoiding EDOT and oxide generates the uncertainty of conducting polymer, improves the quality of production.
In addition, owing to using the electrolyte glue of the application, make the electrode foil prepared, in the preparation of follow-up capacitor, avoid the operation of traditional repeatedly " impregnation monomer-impregnation oxidant-polymerization ", simplify the preparation technology of capacitor.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made, all should be considered as the protection range belonging to the application.
Claims (10)
1. for an electrolyte glue for Waste Acid From Hua Cheng Foil reprocessing, it is characterized in that: the main active of described electrolyte glue comprises the levelling agent of the conducting polymer of 25-99.5 weight portion, the water-base resin of 0.5-40 weight portion, the silane coupler of 0.1-5 weight portion and 0.1-5 weight portion.
2. electrolyte glue according to claim 1, it is characterized in that: described conducting polymer is for having the polymer of the repetitive of general formula (I) or (II), or the polymer of the repetitive of general formula (I) and (II);
Wherein,
A represents the optional C1-C5 alkylidene replaced;
R represents at least one in optional the straight or branched C1-C18 alkyl, the C5-C12 cycloalkyl optionally replaced, the C6-C14 aryl optionally replaced, the C7-C18 aralkyl of optional replacement, the C1-C4 hydroxy alkyl of optional replacement or the hydroxyl that replace;
X value is the integer in 0-8.
3. electrolyte glue according to claim 2, is characterized in that: described conducting polymer is polythiophene, is preferably, poly-(3,4-ethyldioxythiophene).
4. electrolyte glue according to claim 1, is characterized in that: described water-base resin is waterborne polyurethane resin and/or acrylic emulsion.
5. electrolyte glue according to claim 1, is characterized in that: described silane coupler is KH560 or A-187; Described levelling agent is selected from least one in dimethyl silicone polymer, polyester resin change properties of organic silicon oxygen alkane and organic-silicon-modified dimethyl silicone polymer.
6. the electrolyte glue according to any one of claim 1-5, is characterized in that: described electrolyte glue also comprises at least one in ethylene glycol, wax emulsion, surfactant, defoamer, film forming agent, adhesion promoter and isopropyl alcohol.
7. electrolyte glue according to claim 6, it is characterized in that: the consumption of described wax emulsion is 0.5-20 weight portion, the consumption of surfactant is 0.1-5 weight portion, the consumption of defoamer is 0.1-3 weight portion, the consumption of film forming agent is 0.1-5 weight portion, and the consumption of adhesion promoter is 0.1-5 weight portion.
8. electrolyte glue according to claim 6, is characterized in that: described wax emulsion is that the material such as native paraffin and synthetic wax is scattered in the emulsion of a kind of heterogeneous system in water in the effect of emulsifying agent; Described surfactant is selected from least one in polyvinylpyrrolidone, Pluronic F-127 laurate ether, polyethylene glycol, lauryl sodium sulfate, neopelex, glycerin monostearate and polysorbate; Described defoamer is selected from least one in organic silicon modified by polyether oxygen alkane, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene; Described film forming agent is selected from acrylic resin and/or polyurethane resin; Described adhesion promoter is selected from amino modified silane compound and/or epoxy-modified silane compound.
9. an electrode foil, is characterized in that: comprise metal level, be positioned at the metal oxide layer of layer on surface of metal, and be positioned at the dielectric substrate on metal oxide layer surface;
The material of described metal level is at least one in the alloy of tantalum, niobium, aluminium, titanium, zirconium, hafnium, vanadium or these metals or compound;
Described metal oxide layer is after being changed into by described metal level, in the oxide layer that its surface is formed;
Described dielectric substrate is coated on described metal oxide layer surface by the electrolyte glue described in any one of claim 1-8 and is formed.
10. the capacitor adopting electrode foil according to claim 9 to prepare.
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| CN201410638033.9A CN104409213A (en) | 2014-11-12 | 2014-11-12 | Electrolyte glue solution for post-treatment of formed foil, electrode foil and capacitor |
| PCT/CN2015/089165 WO2016074526A1 (en) | 2014-11-12 | 2015-09-08 | Electrolyte glue solution for post-treatment of formed foil, electrode foil and capacitor |
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| CN108269702A (en) * | 2017-12-15 | 2018-07-10 | 益阳艾华富贤电子有限公司 | Mixed solution, solid aluminum electrolytic capacitor impregnation and production method |
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