CN1467764A - Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same electrolyte - Google Patents
Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same electrolyte Download PDFInfo
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- CN1467764A CN1467764A CNA03142421XA CN03142421A CN1467764A CN 1467764 A CN1467764 A CN 1467764A CN A03142421X A CNA03142421X A CN A03142421XA CN 03142421 A CN03142421 A CN 03142421A CN 1467764 A CN1467764 A CN 1467764A
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Abstract
Provided is an electrolytic capacitor having low impedance and high temperature life performance by making electrical conductivity high by water and suppressing deterioration in hydration of electrode foil. In electrolyte for driving electrolytic capacitor, water is made to be a main solvent, an electrolytic acid component is set to be carboxylic acid and/or inorganic acid, and a base component is set to be ammonia. A basic compound except for ammonia is added. Thus, electrolyte for driving electrolytic capacitor, in which pH of electrolyte at 30[deg.]C is controlled to 6.0 to 8.5 is obtained.
Description
Technical field
The present invention relates to have Low ESR, the high reliability electrolytic capacitor driving electrolytic solution of character steady in a long-term and use the electrolytic capacitor of this electrolyte under hot environment.
Background technology
The electrolytic capacitor driving electrolytic solution (hereinafter referred to as " electrolyte ") that electrolytic capacitor that Low ESR is up to now used uses is to use with gamma-butyrolacton as solvent, and the quaternary ammonium salt of phthalic acid and maleic acid etc. is as the electrolyte of electrolyte (solute). In recent years, caused gazing at of people with ethylene glycol and water as the electrolyte of solvent.
But, use with gamma-butyrolacton as solvent, quaternary ammonium salt as electrolyte (solute) though the electrolytic capacitor of electrolyte have high electrical conductivity, under hot environment, also can obtain stable reliability, if but continuously energising under the high environment of humidity, the problem that electrolyte escapes to the capacitor outside appears in the highly basic composition that then can produce owing to the negative electrode position and encapsulant is etched light. And on the other hand, though ethylene glycol and water have high electrical conductivity as the electrolyte of solvent, when the electrolytic capacitor with the aluminium electrode occurring using, under hot environment, can not get the problem of stable reliability. That is, under hot environment, water and aluminium electrode generation hydration reaction have been accelerated the deteriorated of its characteristic, thereby can not have been satisfied desired performance.
Summary of the invention
Electrolytic capacitor driving electrolytic solution of the present invention, its main solvent is water, and electrolytical sour composition is carboxylic acid and/or inorganic acid, and the alkali composition is ammonium, it is characterized in that, contain beyond the ammonia alkali compounds and under 30 ℃ of conditions the pH of electrolyte in the scope of 6.0-8.5. Because this composition is as main solvent with water, therefore can obtain high electrical conductivity, also owing to the scope of the pH under 30 ℃ of conditions at 6.0-8.5, when therefore using electrolytic capacitor, even under hot environment, drive, also can suppress to obtain stable performance because that the aquation of electrode foil causes is deteriorated.
Better be the alkali compounds that adds in this electrolytic capacitor driving electrolytic solution beyond the ammonia, its addition is for respect to more than the equimolar amounts as the carboxyl in the carboxylic acid that do not dissociate of the ammonium of alkali composition. This forms available bases composition neutralizing acid composition, thereby further suppresses the oxidation reaction of electrode foil. In addition, even in the situation that ammonium evaporates in hot environment, because the superfluous alkali composition neutralizing acid composition that exists also can make the aluminum oxidation reaction that occurs rapidly under hot environment be inhibited.
Alkali compounds beyond the ammonia is if be selected from least a kind of compound of ammonium compounds, amines, imidazoline salt compound, pyridine compounds, alkali metal compound, then because these alkali compounds are stronger than the heat endurance of ammonium, even also evaporation is few under the environment of high temperature, the pH deflection that therefore can suppress electrolyte is acid.
If the alkali compounds beyond the ammonia is selected from hydroxyl ammonium, dihydroxy ammonium, methylamine, ethamine, monoethanolamine, hydroxymethyl aminomethane, dihydroxymethyl aminomethane, trishydroxymethylaminomethane, trihydroxyethyl aminomethane, dimethylamine, diethylamine, diethanol amine, trimethylamine, triethylamine, triethanolamine, tetramethyl-ammonium, tetraethyl ammonium, 1,2,3,4-tetramethyl imidazoline salt, 1-picoline at least a kind, then result of use is better.
If the carboxylic acid of acid composition is selected from formic acid, acetic acid, lactic acid, glycolic, oxalic acid, butanedioic acid, malonic acid, adipic acid, benzoic acid, salicylic acid, p-nitrobenzoic acid, glutaric acid, azelaic acid, EDDA, ethylenediamine tetra-acetic acid, trimethyladipic acid, 1,6-decane dicarboxylic acid, 1,7-octane dicarboxylic acids, fourth octane dicarboxylic acids, decanedioic acid at least a kind, then when using electrolytic capacitor, can improve the oxidation membrane repair that forms at electrode foil, it is deteriorated to suppress hydration.
If the inorganic acid of acid composition is selected from least a kind of phosphoric acid, phosphorous acid, hypophosphorous acid, boric acid, sulfamic acid, then when using electrolytic capacitor, can have high electrical conductivity, under hot environment, drive and also can obtain stable reliability.
The 1st form of electrolytic capacitor of the present invention is the device impregnation driving electrolytic solution that electrolytic paper is clipped in be rolled between anode foils and the Cathode Foil, then be inserted in the shell, seal with encapsulant again, it is characterized by: all in the scope of 65-100IRHD (rubber hardness degrees, international), above-mentioned driving electrolytic solution is the electrolytic capacitor driving electrolytic solution of above-mentioned composition to above-mentioned encapsulant by the hardness at isobutene isoprene rubber, EPT or its compositions of mixtures and any position. This structure can suppress the reduction of sealability in time, thereby seeing through of anti-sealing can obtain the few high reliability electrolytic capacitor of characteristic variations.
The anode foils that the 2nd form of electrolytic capacitor of the present invention is comprised of the aluminium foil that is formed with oxide-film, the Cathode Foil that aluminium foil forms and the electrolytic paper that contains driving electrolytic solution consist of, it is characterized by: process with phosphoric acid on the surface of above-mentioned anode foils and Cathode Foil, and above-mentioned driving electrolytic solution is each described electrolyte among the claim 1-6. This structure can make the resistance to water of anode foils and Cathode Foil be improved by the phosphorus atoms that adsorbs on alumite and the aluminium, and owing to Low ESR, therefore also can realize the electrolytic capacitor of stabilized driving under hot environment.
Such as above-mentioned electrolytic capacitor driving electrolytic solution of the present invention, its main solvent is water, electrolytical sour composition is carboxylic acid and/or inorganic acid, the alkali composition is ammonium, this electrolytic capacitor driving electrolytic solution contain beyond the ammonia alkali compounds and under 30 ℃ of conditions the pH of electrolyte in the scope of 6.0-8.5, use the electrolytic capacitor impedance of this electrolytic capacitor driving electrolytic solution low and under hot environment, also can obtain electrode and be difficult for deteriorated high performance electrolytic capacitor.
The specific embodiment
Below, the present invention is described in detail.
Electrolytic capacitor driving electrolytic solution of the present invention, its main solvent are water, and electrolytical sour composition is carboxylic acid and/or inorganic acid, and the alkali composition is ammonium. Main solvent makes water can improve electrical conductivity, the Low ESR when realizing using electrolytic capacitor. But as described in above-mentioned up to now routine, when driving the aluminium electrolutic capacitor that uses aqueous electrolyte under hot environment, usually, the aluminium foil and the water that consist of electrode can react sharp, produce gas, cause safety valve action. In addition, under the hot environment, because the ammonia that uses as solute is low boiling, optionally evaporation makes the pH of electrolyte be partial to acidity, and the solubilizing reaction of ammonium accelerates.
For this reason, electrolyte of the present invention contains the alkali compounds beyond the ammonium and adjusts, makes its pH under 30 ℃ of conditions is the scope of 6.0-8.5, thereby the hydration that suppresses aluminum electric pole foil is deteriorated. Because alkali compounds is stronger than the heat endurance of ammonium, even also evaporation is few under the environment of high temperature, the pH deflection that therefore can suppress electrolyte is acid. The addition of the alkali compounds beyond the ammonium can be done suitable adjustment according to the hydrogen ion concentration that contains in the electrolyte, and the pH of electrolyte is in the scope of 6.0-8.5 when making 30 ℃. The pH of electrolyte was less than 6.0 o'clock, because acid is carried out the oxidation reaction of ammonium, thereby the hydration that easily produces electrode is deteriorated, and pH surpasses at 8.5 o'clock, because alkali carries out the solubilizing reaction of ammonium, thereby easily produced electrode degradation. Therefore, the pH of electrolyte is being essential below 8.5 more than 6.0 under 30 ℃ of conditions.
If the alkali compounds beyond the interpolation ammonia, its addition are for for the waiting more than the mole of carboxyl in the carboxylic acid that do not dissociate of the ammonium of alkali composition, available bases composition neutralizing acid composition then suppresses the oxidation reaction of the ammonium that causes owing to sour composition. In addition, even in the situation that ammonium evaporates in hot environment, because the superfluous alkali composition neutralizing acid composition that exists also can make the aluminum oxidation reaction that occurs rapidly under hot environment be inhibited.
As above-mentioned, use the electrolytic capacitor of electrolyte of the present invention, because water is used as solvent, therefore, has high electrical conductivity, in addition, by adding ammonium alkali compounds in addition, the pH of the electrolyte under 30 ℃ of conditions is adjusted at the scope of 6.0-8.5, thus can suppress that hydration owing to electrode foil causes deteriorated, be the reliable electrolytic capacitor that has low-impedance performance and have character steady in a long-term under hot environment therefore.
In detail, electrolyte of the present invention is take water as main solvent, and the amount of water is in 35-100 % by weight in the solution. If amount less than 35 % by weight of water in the solution, then electrical conductivity descends, and resistivity increases, and can only obtain the characteristic with the same degree of electrolyte of using up to now the gamma-butyrolacton solvent.
Can enumerate alcohols and the non-proton organic solvents such as methyl alcohol, ethanol, propyl alcohol, butanols, cyclobutanol, cyclohexanol, ethylene glycol, propane diols, glycerine, methyl cellosolve, ethyl cellosolve, MPEG with the solvent that water uses. Non-proton organic solvent can be enumerated, N-METHYLFORMAMIDE, N, dinethylformamide, N-ethyl-formamide, N, N-DEF, N-methylacetamide, N, the acid amides such as N-dimethylacetylamide are that the cyclic amides such as the organic solvent that contains lactone such as organic solvent, α-valerolactone, gamma-valerolactone, ethylene carbonate, propylene carbonate are that the nitriles such as organic solvent, acetonitrile are oxide based organic solvent, the 3-methyl isophthalic acids such as organic solvent, dimethyl sulfoxide (DMSO), 3-azoles alkane-2-ketone, 1,3-diethyl-2-imidazolone, 1,3-dipropyl-2-imidazolone, 1-methyl-3-ethyl-2-imidazolone, 1,3,4-trimethyl-2-imidazolone, 1,3,4,5-tetramethyl-imidazolones such as 2-imidazolone are organic solvent.
The electrolyte of electrolyte of the present invention (solute) is that the amount in electrolyte better is the 20-90 % by weight generally in the 10-95 % by weight as the carboxylic acid of sour composition and/or inorganic acid with as the salt of the ammonium (ammonia or ammoniacal liquor) of alkali composition. If electrolytical amount is discontented with 10 % by weight or is surpassed 95 % by weight, then electrical conductivity significantly descends.
Because sour composition uses carboxylic acid, therefore can improve the oxidation membrane repair of ammonium, it is deteriorated to suppress hydration. In addition, if the acid that the molecular weight of molecular weight below the molecular weight (146) of adipic acid is little and use simultaneously greater than the acid of the molecular weight of adipic acid can obtain the electrolyte of these two characteristic goods of high conductivity and high-temperature stability.
The carboxylic acid that electrolyte of the present invention uses is polycarboxylic acid or the monocarboxylic acid of 2～4 valencys. The polycarboxylic acid of 2-4 valency can be enumerated, aliphatic polycarboxylic acid, aromatic multi-carboxy acid, ester ring type polycarboxylic acid and their alkyl (carbon number 1-3) substituent or nitro substituent and sulfur-containing compound. Aliphatic polycarboxylic acid can be enumerated, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, trimethyladipic acid, 1,6-decane dicarboxylic acid, 1,7-octane dicarboxylic acids, 5,6-decane dicarboxylic acid, butyl octane dicarboxylic acids, EDDA, nitrotrimethylolmethane acetic acid, ethylenediamine tetra-acetic acid, N, N-is two-the saturated polycarboxylic acids such as 2-ethoxy glycine, and the unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid. The aromatic multi-carboxy acid can enumerate, phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, PMA etc. and cyclohexane-1,2-dicarboxylic acids, cyclohexene-1, the ester ring type polycarboxylic acids such as 2-dicarboxylic acids, hexahydro-phthalic acid and above-mentioned polycarboxylic alkyl (carbon number 1-3) substituent or citraconic acid, dimethyl maleic acid, the nitrophthalic acid (polycarboxylic acid of the sulfur-bearing such as the nitro substituent such as 3-nitrophthalic acid, 4-nitrophthalic acid and propane thioic acid. )
Monocarboxylic acid can be enumerated aliphatic monocarboxylic acid that carbon number is 1-30, aromatic monocarboxylate, hydroxy acid etc. Aliphatic monocarboxylic acid can be enumerated the saturated mono carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, dodecoic acid, tetradecylic acid, stearic acid, behenic acid. The aromatic monocarboxylate can enumerate benzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid, cinnamic acid, naphthoic acid etc. Contain oxycarboxylic acid and can enumerate salicylic acid, flat acid, the resorcylic acid etc. chosen.
In above-mentioned carboxylic acid of the present invention, especially to be selected from formic acid, acetic acid, lactic acid, glycolic, oxalic acid, butanedioic acid, malonic acid, adipic acid, benzoic acid, salicylic acid, p-nitrobenzoic acid, glutaric acid, azelaic acid, EDDA, ethylenediamine tetra-acetic acid, trimethyladipic acid, 1,6-decane dicarboxylic acid, 1 is advisable at least for a kind of 7-octane dicarboxylic acids, butyl octane dicarboxylic acids, decanedioic acid.
The inorganic acid that uses as sour composition is advisable to be selected from phosphoric acid, phosphorous acid, hypophosphorous acid, boric acid, sulfamic acid a kind at least. By using above-mentioned inorganic acid, can obtain the electrolyte of these two characteristic goods of high conductivity and high-temperature stability.
Among the present invention, the alkali compounds beyond the ammonia can be enumerated ammonium compounds, amines, imidazoline salt compound, pyridine compounds, alkali metal compound, and above-claimed cpd can use separately, also can mix use.
Ammonium compounds specifically can be enumerated hydroxyl ammonium, dihydroxy ammonium etc.
Amines can be enumerated, the methylamine of primary amine class, ethamine, carbinolamine, monoethanolamine, hydroxymethyl aminomethane, dihydroxy methylamino methane, trishydroxymethylaminomethane, trihydroxyethyl aminomethane, the dimethylamine of secondary amine class, diethylamine, dimethanolamine, diethanol amine, the trimethylamine of tertiary amines, dimethyl amine, methyl-diethyl-amine, triethylamine, triethanolamine, dimethyl n-propylamine, dimethyl isopropylamine, Methylethyl n-propylamine, Methylethyl isopropylamine, diethyl n-propylamine, diethyl isopropylamine, three n-propylamine, tri-isopropyl amine, three n-butylamine, three tert-butylamines etc., the tetramethyl-ammonium of quaternary ammonium salt, tetraethyl ammonium, contain the amine of phenyl, such as dimethylaniline, Methylethyl aniline, diethylaniline etc.
The imidazoline salt compound has 1,8-diazabicyclo (5,4,0) endecatylene-7,1,5-diazabicyclo (4,3,0) nonene-5,1,2-methylimidazole quinoline salt, 1,2,4-tri-methylimidazolium quinoline, 1-methyl-2-ethyl-imidazoline, 1,4-dimethyl-2-ethyl-imidazoline, 1,2,3,4-tetramethyl imidazoline salt, 1-methyl-2-heptyl imidazoline, 1-methyl-2-(3 ' heptyl) imidazoline, 1-methyl-2-lauryl imidazoline, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methylimidazole, 1-tolimidazole.
Pyridine compounds has 1-picoline, 1-ethylpyridine, 1-methyl-3-ethylpyridine.
Alkali metal compound can be enumerated potassium hydroxide, NaOH, lithium hydroxide etc.
In the alkali compounds beyond the above-mentioned ammonia, be selected from hydroxyl ammonium, dihydroxy ammonium, methylamine, ethamine, monoethanolamine, hydroxymethyl aminomethane, dihydroxymethyl aminomethane, trishydroxymethylaminomethane, trihydroxyethyl aminomethane, dimethylamine, diethylamine, diethanol amine, trimethylamine, triethylamine, triethanolamine, tetramethyl-ammonium, tetraethyl ammonium 1,2,3,4-tetramethyl imidazoline salt, 1-picoline, at least a kind, result of use is good among the present invention.
In the electrolyte of the present invention, in the scope of not damaging its physical property, also can add all additives. Additive can be enumerated the nitro compounds such as the boric acid based compounds such as complex, o-nitrophenol, m-nitrophenol, p-NP of complex, boric acid and the polyalcohol (ethylene glycol, glycerine etc.) of phosphorus series compound, boric acid and the polysaccharides such as phosphate (mannitol, D-sorbite). By adding above-mentioned additive the sparking potential of electrolyte is risen, reasonable situation produces effect.
Electrolytic capacitor of the present invention uses the electrolytic capacitor driving electrolytic solution of above-mentioned composition.
The present invention specifically makes device that electrolytic paper is rolled into, soaks the driving electrolytic solution of the present invention that contains such as above-mentioned composition between anode foils and Cathode Foil, be inserted in the box, with the electrolytic capacitor of encapsulant sealing, the encapsulant among the present invention better by isobutene isoprene rubber, EPT and composition thereof form, the hardness at any position is all in the scope of 65-100 I RHD. If the hardness of encapsulant is less than 65IRHD, then does not produce by force from sealing leakage owing to pressing when rising sealing force at high temperature, if the hardness of encapsulant surpasses 100IRHD, then because the spring rate under the high temperature reduces encapsulant is chapped, thereby the phenomenon of leakage occurs.
If by above-mentioned structure, then as above-mentioned because the reduction of sealing force does not in time occur, therefore, under hot environment, also can prevent electrolyte from the spilling of wire portion, but can obtain the high reliability capacitor that rejection characteristic changes. If make the hardness of encapsulant of at least a portion more than 75IRHD, then can suppress by the physical strength that encapsulant self has since when internal pressure rises the appearance deformation of incident sealing surface.
Other structure of electrolytic capacitor of the present invention can be enumerated, the anode foils that is comprised of the aluminium foil that is formed with oxide-film, Cathode Foil and the driving electrolytic solution that aluminium foil forms consist of, use the electrolyte of the present invention such as above-mentioned composition, the surface of anode foils and the Cathode Foil acid-treated electrolytic capacitor of phosphorus.
If such as above-mentioned anode foils and the Cathode Foil of processing with phosphoric acid of using as electrode foil, then be improved owing to the phosphorus atoms that adsorbs on alumite and the aluminium makes resistance to water, therefore can realize using the effect that has good resistance to water such as pH of the present invention at the electrolytic capacitor of the electrolyte of 6.0-8.5 scope.
In addition, the present invention also has the electrolytic capacitor that the tectonic association processed with phosphoric acid such as the encapsulant of above-mentioned special physical property and anode foils and Cathode Foil surface forms.
Below, with embodiment the present invention is specifically described, but the present invention is not limited only to this. The mensuration of the various physics values in following examples, the comparative example is implemented by the following method.
(1) than resistance (Ω cm): use than EC-device and measuring element, measuring adjustment is the electrical conductivity of 30 ℃ electrolyte, and its inverse is as calculating than resistance.
(2) pH (-): using the pH determinator to measure adjustment is the pH of 30 ℃ electrolyte.
(3) electrostatic capacitance Cap (μ F): measure according to the method for putting down in writing among the C5120 of Japanese Industrial Standards
(4) dielectric loss angle tangent Tan δ (%): measure according to the method for putting down in writing among the C5120 of Japanese Industrial Standards
(5) leakage current LC (μ A): measure according to the method for putting down in writing among the C5120 of Japanese Industrial Standards
(6) rate of change of electrostatic capacitance (%): the difference of the electrostatic capacitance after the electrostatic capacitance at initial stage and the test is calculated with percentage.
(7) hardness (IRHD): measure with ウ オ レ one ス hardometer.
(8) impedance (m Ω): use the PRECISION LCR METER 4283A of HEWLETT PACKAD company system, measure under the condition of frequency 120kHz, voltage 0.5Vrms. Measuring circuit is the AC bridge method.
Composition and the physical property of the electrolyte that uses in following embodiment, the comparative example represent in table 1.
(table 1) 1/3
| Electrolyte forms (numerical value in the bracket is % by weight) | A | B (IRHD) | C (Ωcm) | pH (30℃) | ||
| ex.1 | I | Water (70) ethylene glycol (15) | Have | 75 | 18 | 8.5 |
| II | Ammonium formate (5) adipic acid 2 ammoniums (6) | |||||
| III | Triethanolamine (4) | |||||
| ex.2 | I | Water (60) ethylene glycol (18) | Have | 75 | 21 | 6.4 |
| II | Ammonium formate (5) adipic acid 2 ammonium (5) 1,6-decane dicarboxylic acids 2 ammoniums (8) | |||||
| III | Diethylamide (4) | |||||
| ex.3 | I | Water (70) ethylene glycol (8) | Have | 75 | 13 | 7.1 |
| II | Ammonium formate (8) adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (8) ethylenediamine tetra-acetic acid 2 ammoniums (2) | |||||
| III | Trishydroxymethylaminomethane (2) | |||||
| ex.4 | I | Water (70) ethylene glycol (6) | Have | 75 | 16 | 8.5 |
| II | Ammonium formate (8) adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (5) ethylenediamine tetra-acetic acid 2 ammoniums (2) | |||||
| III | Trishydroxymethylaminomethane (4) | |||||
| ex.5 | I | Water (50) ethylene glycol (30) | Have | 75 | 40 | 6.2 |
| II | Adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (5) trimethyladipic acids (5) hypophosphorous acid (3) | |||||
| III | Hydroxyl ammonium (2) | |||||
| ex.6 | I | Water (70) glycerine (5) | Have | 75 | 20 | 6.0 |
| II | Ammonium acetate (10) adipic acid 2 ammoniums (5) glutaric acids (8) | |||||
| III | Diethanol amine (2) | |||||
Ex: embodiment
I: solution A: the phosphorus of anode foils, Cathode Foil is acid-treated to be had or not
II: acid, alkali composition B: the hardness of sealing rubber
III: alkali compounds C: compare resistance
(table 1) 2/3
| Electrolyte forms (numerical value in the bracket is % by weight) | A | B (IRHD) | C (Ωcm) | pH (30℃) | ||
| ex.7 | I | Water (50) ethylene glycol (25) | Have | 75 | 28 | 6.7 |
| II | Ammonium formate (7) adipic acid 2 ammoniums (10) 1,7-octane dicarboxylic acids, 2 ammoniums (5) | |||||
| III | 1,2,3,4-tetramethyl imidazoline salt (3) | |||||
| ex.8 | I | Water (40) ethylene glycol (35) | Have | 75 | 33 | 7.9 |
| II | Ammonium formate (11) butyl octane dicarboxylic acids ammonium (13) | |||||
| III | Potassium hydroxide (1) | |||||
| ex.9 | I | Water (70) ethylene glycol (15) | Have | 75 | 22 | 6.5 |
| II | Ammonium borate (7) ammonium sebacate (7) | |||||
| III | Tetraethyl ammonium (1) | |||||
| ex.10 | I | Water (70) ethylene glycol (8) | Have | 75 | 13 | 8.5 |
| II | Ammonium formate (8) adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (5) ammonium hypophosphites (1) | |||||
| III | Trishydroxymethylaminomethane (3) | |||||
| ex.11 | I | Water (70) ethylene glycol (8) | Nothing | 75 | 13 | 8.5 |
| II | Ammonium formate (8) adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (5) ammonium hypophosphites (1) | |||||
| III | Trishydroxymethylaminomethane (3) | |||||
| ex.12 | I | Water (70) ethylene glycol (8) | Have | 60 | 13 | 8.5 |
| II | Ammonium formate (8) adipic acid 2 ammoniums (5) 1,7-octane dicarboxylic acids, 2 ammoniums (5) ammonium hypophosphites (1) | |||||
| III | Trishydroxymethylaminomethane (3) | |||||
Ex: embodiment
I: solution A: the phosphorus of anode foils, Cathode Foil is acid-treated to be had or not
II: acid, alkali composition B: the hardness of sealing rubber
III: alkali compounds C: compare resistance
(table 1) 3/3
| Electrolyte forms (numerical value in the bracket is % by weight) | A | B (IRHD) | C (Ωcm) | pH (30℃) | ||
| co.1 | I | Water (70) ethylene glycol (19) | Have | 75 | 17 | 7.0 |
| II | Ammonium formate (5) adipic acid 2 ammoniums (6) | |||||
| co.2 | I | Water (70) ethylene glycol (15) | Have | 75 | 20 | 5.5 |
| II | Ammonium formate (5) adipic acid (6 | |||||
| III | Triethanolamine (0.5) | |||||
| co.3 | I | Water (70) ethylene glycol (15) | Have | 75 | 21 | 9.3 |
| II | Ammonium formate (5) adipic acid (6) | |||||
| III | Triethanolamine (10) | |||||
| co.4 | I | Water (50) ethylene glycol (69) | Have | 75 | 71 | 6.6 |
| II | Ammonium formate (5) adipic acid (6 | |||||
Co: embodiment
I: solution A: the phosphorus of anode foils, Cathode Foil is acid-treated to be had or not
II: acid, alkali composition B: the hardness of sealing rubber
III: alkali compounds C: compare resistance
Embodiment 1-embodiment 10
Use the electrolyte of the composition transitivity shown in the table 1, make the device of the impregnation electrolyte that electrolytic paper is clipped in be rolled between anode foils and the Cathode Foil. Then from anode foils and each exit electrode of anode foils, insert aluminium shell, seal with caulking gum. Sealing rubber uses hardness to be the butyl rubber of the peroxide over cure of 75IRH. The aluminium foil that consists of the aluminium foil of electrode foil and be formed with oxide-film in 3% aqueous solution of 60 ℃ phosphoric acid, flood 2 minutes, carry out the phosphoric acid processing. The electrolytic capacitor rated voltage 6.3V-electrostatic capacitance 1500 μ F, the size that obtain: diameter 10mm * L16mm.
Make 10 these aluminium electrolutic capacitors, be determined at 105 ℃ of high-temperature load characteristics of 3000 hours, try to achieve its mean value.
The measurement result of the aluminium electrolutic capacitor that obtains represents in table 2.
(table 2)
| The initial stage characteristic | 105 ℃ after 3000 hours | |||||||
| Cap (μF) | Tanδ (％) | Z (mΩ) | LC (μA) | ΔCap (％) | Tanδ (％) | Z (mΩ) | LC (μA) | |
| ex.1 | 1540 | 5.2 | 13 | 12 | -18 | 5.5 | 15 | 11 |
| ex.2 | 1565 | 5.8 | 14 | 11 | -19 | 5.9 | 16 | 12 |
| ex.3 | 1594 | 5.2 | 10 | 10 | -19 | 5.5 | 13 | 12 |
| ex.4 | 1573 | 5.8 | 11 | 12 | -20 | 6.1 | 14 | 11 |
| ex.5 | 1567 | 5.7 | 30 | 11 | -18 | 5.9 | 32 | 11 |
| ex.6 | 1533 | 5.1 | 15 | 11 | -18 | 5.4 | 17 | 10 |
| ex.7 | 1587 | 6.0 | 19 | 11 | -22 | 6.2 | 22 | 13 |
| ex.8 | 1535 | 6.1 | 22 | 11 | -21 | 6.3 | 24 | 12 |
| ex.9 | 1569 | 5.2 | 16 | 12 | -19 | 5.5 | 18 | 11 |
| ex.10 | 1544 | 5.2 | 10 | 12 | -17 | 5.5 | 13 | 11 |
| ex.11 | 1544 | 5.2 | 10 | 12 | -25 | 5.8 | 16 | 18 |
| ex.12 | 1544 | 5.2 | 10 | 12 | -28 | 5.7 | 17 | 22 |
| co.1 | 1585 | 5.2 | 12 | 12 | Because produce gas, till 500 hours, all safety valves are opened. | |||
| co.2 | 1545 | 5.3 | 15 | 12 | Because produce gas, till 500 hours, all safety valves are opened. | |||
| co.3 | 1557 | 5.3 | 15 | 11 | Because produce gas, till 500 hours, all safety valves are opened. | |||
| co.3 | 1545 | 6.9 | 65 | 11 | Because produce gas, till 500 hours, all safety valves are opened. | |||
Ex: embodiment
Co: comparative example
Cap: electrostatic capacitance
Tan δ: dielectric loss angle tangent
Z: impedance
LC: leakage current
Δ Cap: the rate of change of static capacity
Embodiment 11
Except the phosphoric acid that does not carry out Cathode Foil and anode foils was processed, other made aluminium electrolutic capacitor with the method identical with embodiment 1.
The measurement result of the aluminium electrolutic capacitor that obtains represents in table 2.
Embodiment 12
Except the hardness of sealing rubber is the 60IRHD, other makes aluminium electrolutic capacitor with the method identical with embodiment 10.
The measurement result of the aluminium electrolutic capacitor that obtains represents in table 2.
Among the embodiment 1-10, because take water as main solvent, electrolytical sour composition is that carboxylic acid and/or inorganic acid, alkali composition are the ammonium salt of ammonium, and use and be adjusted to that pH is the electrolyte of 6.0-8.5 under 30 ℃ condition, process with phosphoric acid on the surface of electrode foil, has therefore obtained the deteriorated electrolytic capacitor that is inhibited of hydration of Low ESR and aluminum electric pole foil. In addition, since used by butylene isoprene form and the hardness of arbitrary portion all at the sealing rubber of the scope of 65-100IRHD, even the action of the safety valve that therefore causes in the generation that under hot environment, also can not occur owing to gas, thus can be accomplished the electrolytic capacitor of stabilized driving.
What embodiment 12 used is the less sealing rubber of hardness, but owing to use electrolyte of the present invention, therefore, even the spilling of the deteriorated electrolyte that causes because of sealing rubber do not occur under hot environment yet, thereby can be accomplished the electrolytic capacitor of stabilized driving.
Comparative example 1
Outside the alkali compounds except not adding ammonia, other makes the electrolyte that it forms expression in table 1 with the method identical with embodiment 1. Then, except using this electrolyte, other makes aluminium electrolutic capacitor with the method identical with embodiment 1.
The aluminium electrolutic capacitor measurement result that obtains represents in table 2.
Comparative example 2
Except having added the alkali compounds the ammonia, but make the pH of electrolyte be lower than scope of the present invention, have outside 5.5, other makes the electrolyte that it forms expression in table 1 with the method identical with embodiment 1. Then, except using this electrolyte, other makes aluminium electrolutic capacitor with the method identical with embodiment 1.
The aluminium electrolutic capacitor measurement result that obtains represents in table 2.
Comparative example 3
Except having added the alkali compounds the ammonia, but making the pH of electrolyte be higher than scope of the present invention, is outside 9.3, and other makes the electrolyte that it forms expression in table 1 with the method identical with embodiment 1. Then, except using this electrolyte, other makes aluminium electrolutic capacitor with the method identical with embodiment 1.
The aluminium electrolutic capacitor measurement result that obtains represents in table 2.
Comparative example 4
Outside the alkali compounds except not adding ammonia, other makes the electrolyte that it forms expression in table 1 with the method identical with embodiment 1. Then, except using this electrolyte, other makes aluminium electrolutic capacitor with the method identical with embodiment 1.
The aluminium electrolutic capacitor measurement result that obtains represents in table 2.
Therefore comparative example 1, even electrode surface is processed with phosphoric acid, improves the hardness of sealing rubber owing to do not add ammonia compound in addition, also produces bad effect owing to the gas that produces is opened whole safety valves till 500 hours.
Though comparative example 2 has added the alkali compounds beyond the ammonia, but because the pH of electrolyte is lower than scope of the present invention, in the comparative example 3, though added the alkali compounds beyond the ammonia, but because the pH of electrolyte is lower than scope of the present invention, all owing to opening whole safety valves, the gas of generation produces bad effect till above-mentioned two examples to 500 hour.
Though comparative example 4 is processed electrode surface with phosphoric acid, improved the hardness of sealing rubber, owing to do not add the compound beyond the ammonia, therefore, till 500 hours, because opening whole safety valves, the gas of generation produces bad effect.
Claims (8)
1 electrolytic capacitor driving electrolytic solution, its main solvent are water, and electrolytical sour composition is carboxylic acid and/or inorganic acid, and the alkali composition is ammonium, it is characterized in that, contain alkali compounds beyond the ammonia and the pH under 30 ℃ of conditions in the scope of 6.0-8.5.
2. electrolytic capacitor driving electrolytic solution according to claim 1 is characterized in that, adds the alkali compounds beyond the ammonia, and its addition is for respect to more than the equimolar amounts as the carboxyl in the carboxylic acid that do not dissociate of the ammonium of alkali composition.
3. electrolytic capacitor driving electrolytic solution according to claim 1 is characterized in that, the alkali compounds beyond the ammonia is selected from least a kind of compound of ammonium compounds, amines, imidazoline salt compound, pyridine compounds, alkali metal compound.
4. electrolytic capacitor driving electrolytic solution according to claim 1, it is characterized in that, alkali compounds beyond the ammonia is selected from hydroxyl ammonium, dihydroxy ammonium, methylamine, ethamine, monoethanolamine, hydroxymethyl aminomethane, dihydroxymethyl aminomethane, trishydroxymethylaminomethane, trihydroxyethyl aminomethane, dimethylamine, diethylamine, diethanol amine, trimethylamine, triethylamine, triethanolamine, tetramethyl-ammonium, tetraethyl ammonium, 1,2,3,4-tetramethyl imidazoline salt, 1-picoline, NaOH, lithium hydroxide, potassium hydroxide at least a kind.
5. electrolytic capacitor driving electrolytic solution according to claim 1, it is characterized in that, carboxylic acid as sour composition is selected from formic acid, acetic acid, lactic acid, glycolic, oxalic acid, butanedioic acid, malonic acid, adipic acid, benzoic acid, salicylic acid, p-nitrobenzoic acid, glutaric acid, azelaic acid, EDDA, ethylenediamine tetra-acetic acid, trimethyladipic acid, 1,6-decane dicarboxylic acid, 1,7-octane dicarboxylic acids, butyl octane dicarboxylic acids, decanedioic acid at least a kind.
6. electrolytic capacitor driving electrolytic solution according to claim 1 is characterized in that, is selected from phosphoric acid, phosphorous acid, hypophosphorous acid, boric acid, sulfamic acid at least a kind as the inorganic acid of sour composition.
7. electrolytic capacitor, it is the device impregnation driving electrolytic solution that electrolytic paper is clipped in be rolled between anode foils and the Cathode Foil, then be inserted in the shell, the electrolytic capacitor that forms with the encapsulant sealing again, it is characterized in that, all in the scope of 65-100IRHD, above-mentioned driving electrolytic solution is each described electrolytic capacitor driving electrolytic solution among the claim 1-6 to above-mentioned encapsulant by the hardness at isobutene isoprene rubber, EPT or its compositions of mixtures and any position.
8. electrolytic capacitor, possess the anode foils of the aluminium foil formation that is formed with oxide-film, the Cathode Foil that aluminium foil consists of and the electrolytic paper that contains driving electrolytic solution, it is characterized in that, process with phosphoric acid on the surface of above-mentioned anode foils and Cathode Foil, and above-mentioned driving electrolytic solution is each described electrolytic capacitor driving electrolytic solution among the claim 1-6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002163936 | 2002-06-05 | ||
| JP2002163936A JP4039129B2 (en) | 2002-06-05 | 2002-06-05 | Electrolytic solution for electrolytic capacitor driving and electrolytic capacitor using the same |
| JP2002-163936 | 2002-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1467764A true CN1467764A (en) | 2004-01-14 |
| CN100419929C CN100419929C (en) | 2008-09-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03142421XA Expired - Lifetime CN100419929C (en) | 2002-06-05 | 2003-06-05 | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same electrolyte |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4039129B2 (en) |
| CN (1) | CN100419929C (en) |
| MY (1) | MY142367A (en) |
| TW (1) | TWI271760B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057306B (en) * | 2004-09-07 | 2010-09-08 | 松下电器产业株式会社 | Electrolyte for electrolytic capacitor and electrolytic capacitor utilizing the same |
| CN101840790A (en) * | 2010-05-31 | 2010-09-22 | 福建国光电子科技股份有限公司 | Processing method of aluminum foil in manufacturing process of solid aluminum electrolytic capacitor |
| CN101341559B (en) * | 2005-11-15 | 2012-03-28 | 日本贵弥功株式会社 | Electrolytic capacitor |
| CN104538183A (en) * | 2014-12-10 | 2015-04-22 | 南通瑞达电子材料有限公司 | Electrolyte for medium and high voltage of electrolytic capacitor and preparation method of electrolyte |
| CN113628885A (en) * | 2020-05-07 | 2021-11-09 | 深圳新宙邦科技股份有限公司 | Electrolyte for solid-liquid mixed electrolytic capacitor and electrolytic capacitor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005303062A (en) * | 2004-04-13 | 2005-10-27 | Rubycon Corp | Electrolytic capacitor and electrolytic solution for driving the same |
| JP2007115947A (en) * | 2005-10-21 | 2007-05-10 | Nichicon Corp | Electrolyte for driving electrolytic capacitor |
| JP4862602B2 (en) * | 2006-10-13 | 2012-01-25 | パナソニック株式会社 | Aluminum electrolytic capacitor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0684620B1 (en) * | 1993-12-03 | 2003-06-04 | Sanyo Chemical Industries, Ltd. | Electrolytic solution and electrochemical element prepared therefrom |
-
2002
- 2002-06-05 JP JP2002163936A patent/JP4039129B2/en not_active Expired - Lifetime
-
2003
- 2003-06-02 TW TW92114898A patent/TWI271760B/en not_active IP Right Cessation
- 2003-06-04 MY MYPI20032067 patent/MY142367A/en unknown
- 2003-06-05 CN CNB03142421XA patent/CN100419929C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057306B (en) * | 2004-09-07 | 2010-09-08 | 松下电器产业株式会社 | Electrolyte for electrolytic capacitor and electrolytic capacitor utilizing the same |
| US7859828B2 (en) | 2004-09-07 | 2010-12-28 | Panasonic Corporation | Electrolytic solution for electrolytic capacitor, and electrolytic capacitor using the same |
| CN101341559B (en) * | 2005-11-15 | 2012-03-28 | 日本贵弥功株式会社 | Electrolytic capacitor |
| CN101840790A (en) * | 2010-05-31 | 2010-09-22 | 福建国光电子科技股份有限公司 | Processing method of aluminum foil in manufacturing process of solid aluminum electrolytic capacitor |
| CN101840790B (en) * | 2010-05-31 | 2012-09-05 | 福建国光电子科技股份有限公司 | Processing method of aluminum foil in manufacturing process of solid aluminum electrolytic capacitor |
| CN104538183A (en) * | 2014-12-10 | 2015-04-22 | 南通瑞达电子材料有限公司 | Electrolyte for medium and high voltage of electrolytic capacitor and preparation method of electrolyte |
| CN113628885A (en) * | 2020-05-07 | 2021-11-09 | 深圳新宙邦科技股份有限公司 | Electrolyte for solid-liquid mixed electrolytic capacitor and electrolytic capacitor |
| CN113628885B (en) * | 2020-05-07 | 2023-04-18 | 深圳新宙邦科技股份有限公司 | Electrolyte for solid-liquid mixed electrolytic capacitor and electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200402075A (en) | 2004-02-01 |
| JP4039129B2 (en) | 2008-01-30 |
| MY142367A (en) | 2010-11-30 |
| TWI271760B (en) | 2007-01-21 |
| CN100419929C (en) | 2008-09-17 |
| JP2004014666A (en) | 2004-01-15 |
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