CN1711614A - Electrolytic capacitor - Google Patents
Electrolytic capacitor Download PDFInfo
- Publication number
- CN1711614A CN1711614A CN 200380102903 CN200380102903A CN1711614A CN 1711614 A CN1711614 A CN 1711614A CN 200380102903 CN200380102903 CN 200380102903 CN 200380102903 A CN200380102903 A CN 200380102903A CN 1711614 A CN1711614 A CN 1711614A
- Authority
- CN
- China
- Prior art keywords
- electrolytic capacitor
- electrolyte
- electrode foil
- foil
- cathode electrode
- 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
Images
Abstract
An electrolytic capacitor having a low impedance characteristic, having a high withstand voltage characteristic of 100 V class, wherein the electrolytic capacitor provides an excellent high temperature life characteristic and an excellent leakage characteristic. The electrolyte solution containing the aluminum tetrafluoride salt is used. The electrolytic capacitor of the present invention has a low impedance characteristic, a high withstand voltage characteristic, and an excellent high temperature life characteristic. Moreover, the aforementioned electrolyte solution is used, and a foil showing noble potential at least in the electrolyte solution than the electrode potential of the cathode tab, or a cathode electrode foil subjected to chemical treatment is used as the cathode electrode foil, so as to obtain an excellent leakage characteristic.
Description
Technical field
The present invention relates to electrolytic capacitor, particularly a kind of electrolytic capacitor with low impedance characteristic, high withstand voltage characteristic.
Background technology
Electrolytic capacitor generally has structure as shown in Figure 1.Just, highly purified aluminium foil to band shape carries out chemistry or electrochemical etch processes, when aluminium foil surface is enlarged, this aluminium foil carried out chemical conversion and handle in chemical conversion solutions such as ammonium borate aqueous solution after, form the anode electrode paper tinsel 2 of oxide film layer on the surface and by the cathode electrode foil 3 that only forms, its coiling is formed capacitor element 1 by the dividing plate 11 that forms by Manila paper etc. through the high-purity aluminium foil of etch processes.Then, be full of the electrolytic capacitor driving electrolytic solution in this capacitor element 1 after, receive and to be contained in the external shell of making by aluminium etc. that bottom tube-like is arranged 10.Peristome at external shell 10 is installed the seal body 12 that is made of elastic caoutchouc, by deep-draw processing sealing external shell 10.
As shown in Figure 2, on anode electrode paper tinsel 2, cathode electrode foil 3, connecting lead-out wire 4,5 respectively by methods such as seam weldering, ultrasonic bonding, as be used for electrode with each the two poles of the earth lead to the outside the electrode ejector.As the lead-out wire the 4, the 5th of each electrode ejector, the electrode slice 9 of the aluminum that constitutes by: round bar part 6 with the connecting portion 7 of the two poles of the earth electrode foil 2,3 butts, but and the external connecting 8 that forms by weld metal that is fixed on round bar part 6 front ends constitute.
Wherein, drive the electrolyte of usefulness as the electrolytic capacitor that in capacitor element, is full of with high conductivity, use at present to be main solvent, to be cation constituent as the cationic imidazoline cation that ring-type amidine compound quaternary saltization is formed and glyoxaline cation, to be that the salt of anion component is dissolved in wherein electrolyte as solute with the conjugate base of acid with γ one butyrolactone.
(opening flat 08-321440 communique and the flat 08-321441 communique of Te Kai) with reference to the spy.
Yet in recent years, electronic message unit just is digitized, so as the high speed of the driving frequency of the microprocessor of the heart portion of these electronic message units also in continuous progress.Therewith correspondingly, also in development, the increaseization of ripple current becomes significantly the increaseization of the electric power that the electronic unit of peripheral circuit consumes thus, and the electrolytic capacitor that is used for this circuit requires to have low impedance characteristic.
In addition, particularly in automotive field, be accompanied by the high mechanization of automotive performance, for having relatively high expectations of aforementioned low impedance characteristic.In addition, the driving voltage of vehicle mounted circuit is 14V, but along with the increase that consumes electric power, and it is just towards the 42V development, must be at 28V, more than the 84V corresponding to the voltage-resistent characteristic of the electrolytic capacitor of this driving voltage.And then therefore the requirement that has high temperature to use in this field requires to have life characteristics at high temperature for electrolytic capacitor.
In addition, the aforementioned electric electrolysis condenser can not corresponding this low impedance characteristic, and in addition, its proof voltage is 30V, though can corresponding 28V, can not satisfy the requirement of the above high withstand voltage of 84V.In addition, also has electrolyte is used for drawing the through hole leakage of the lead-out wire 5 that negative electrode uses easily from seal body 12 tendency, because the electrolyte leakage causes the deterioration of the electrology characteristics such as capacitance reduction of electrolytic capacitor, the result just has the shortcoming of the lost of life of electrolytic capacitor.
Therefore, the present invention aims to provide a kind ofly has the high withstand voltage characteristic of low impedance characteristic and 100V level, the electrolytic capacitor that life characteristics at high temperature is also good, and then also provides a kind of leakage characteristic also good electrolytic capacitor.
Summary of the invention
First electrolytic capacitor of the present invention is following a kind of electrolytic capacitor: will be respectively and anode strip by dividing plate, anode electrode paper tinsel that cathode sheets connects and cathode electrode foil are reeled and are formed capacitor element, in this capacitor element, be full of electrolyte, when receiving capacitor element in the external shell that is contained in bottom tube-like, seal by the open end of seal body external shell, it is characterized in that: use the electrolyte contain tetrafluoride aluminium salt, the paper tinsel that uses the electrode potential in aforementioned electrolyte at least to compare with aforementioned cathode sheets to demonstrate noble potential (cathode potential) is as cathode electrode foil.
In addition, compare with aforementioned cathode sheets as the electrode potential in electrolyte and to demonstrate the noble potential cathode electrode foil, it is characterized in that: use on the surface of aluminium foil, be provided with by the metal nitride that is selected from titanium nitride, zirconium nitride, tantalum nitride, niobium nitride or be selected from the paper tinsel of layer of formed 0.02～0.1 μ m of metal of titanium, zirconium, tantalum, niobium.
Description of drawings
Fig. 1 is the internal cross section figure of the structure of demonstration electrolytic capacitor.
Fig. 2 is for showing the decomposition side view of capacitor element.
Embodiment
The structure of aluminium electrolytic capacitor has and identical in the past structure as shown in Figure 1, 2.Capacitor element 1 forms anode electrode paper tinsel 2 and cathode electrode foil 3 coilings by dividing plate 11.As shown in Figure 2, on anode electrode paper tinsel 2, cathode electrode foil 3, connecting lead-out wire 4,5 respectively, as anode ejector and negative electrode ejector.These lead-out wires the 4, the 5th by the connecting portion 7 that is connected with each paper tinsel and the round bar part 6 formed electrode slices 9 that are connected with connecting portion 7, and are welded on that external connecting 8 on the round bar part 6 constitutes.In addition, each paper tinsel and lead-out wire mechanically link together by seam weldering method, ultrasonic bonding etc.
What anode electrode paper tinsel 2 adopted is, after in acid solution, the aluminium foil of purity more than 99% being carried out the expansion faceization processing of chemistry or chemical etching, in the aqueous solution such as ammonium borate or ammonium adipate, carry out chemical conversion and handle, form the electrode foil of anodic oxidation film layer in its surface.
Then, the capacitor element 1 that will be full of electrolyte is received and is contained in the external shell of being made by aluminium etc. that bottom tube-like is arranged 10, on the open end of external shell 10, the seal body 12 that insertion has the through hole that is used to derive lead-out wire 4,5 carries out sealing of electrolytic capacitor by the end of tightening up external shell 10 again.
Then, in the present invention, cathode electrode foil 3 is same with anode electrode paper tinsel 2, uses the aluminium foil of purity more than 99% carried out etched electrode foil.Then, in the part on the surface of this cathode electrode foil 3 or form the paper tinsel of the layer of 0.02～0.1 μ m that forms by metal nitride or metal on the whole.As this metal nitride, can enumerate titanium nitride, zirconium nitride, tantalum nitride, niobium nitride etc., as metal, can enumerate titanium, zirconium, tantalum, niobium etc.And then, as cathode sheets, preferably use the raffinal of purity more than 99%.
Used electrolytic capacitor electrolyte contains tetrafluoride aluminium salt among the present invention.
Tetrafluoride aluminium salt is to be the salt of anion component with tetrafluoride aluminium, for this salt, and can be with ammonium salt, amine salt, quaternary ammonium salt or quaternary salt ring-type amidine ion as cation constituent.As the amine that constitutes amine salt, can enumerate primary amine (methylamine, ethamine, propylamine, butylamine, ethylenediamine, monoethanolamine etc.), secondary amine (dimethylamine, diethylamine, di-n-propylamine, methyl ethylamine, diphenylamines, diethanol amine etc.), tertiary amine (trimethylamine, triethylamine, tri-n-butylamine, triethanolamine etc.).In addition, as the quaternary ammonium that constitutes quaternary ammonium salt, can enumerate tetra-allkylammonium (tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA, methyl triethyl ammonium, dimethyl diethyl ammonium etc.), pyridine (1-picoline, 1-ethylpyridine, 1,3-parvoline etc.).
And then, be in the salt of cation constituent with quaternary salt ring-type amidine ion, quaternary salt ring-type amidine ion as cation constituent is to have N, N, the cation of the cyclic compound quaternary saltization of N '-replacement amidino groups is as having N, N, the cyclic compound of N '-replacement amidino groups can be enumerated following compound.Imidazoles monocyclic compound (1-methylimidazole, the 1-phenylimidazole, 1, the 2-methylimidazole, 1-ethyl-glyoxal ethyline, 2-ethyl-1-methylimidazole, 1,2-diethyl imidazoles, 1,2, imidazoles homologues such as 4-tri-methylimidazolium, 1-methyl-2-methoxyl group imidazoles, 1-methyl-alkoxyl derivatives such as 2-ethyoxyl imidazoles, nitro-derivatives such as 1-methyl-4 (5)-nitroimidazole, 1, amido derivatives such as 2-dimethyl-5 (4)-amido imidazoles etc.), benzimidazole compound (1-tolimidazole, 1-methyl-2-benzyl benzimidazole, 1-methyl-5 (6)-nitrobenzimidazole etc.), compound (1-methylimidazole quinoline with 2-imidazoline ring, 1,2-methylimidazole quinoline, 1,2,4-tri-methylimidazolium quinoline, 1-methyl-2-benzylimidazoline, 1-ethyl-glyoxal ethyline quinoline, 1,4-dimethyl-2-ethyl imidazol(e) quinoline, 1-methyl-2-ethoxyl methyl imidazoline etc.), compound (1-methyl isophthalic acid with tetrahydropyrimidine ring, 4,5, the 6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5, the 6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0]-the 7-endecatylene, 1,5-diazabicyclo [4,3,0]-5-nonene etc.) etc.
As solvent used in the electrolyte of the present invention, can use protic polar solvent, non-protonic solvent and composition thereof.As the protic polar solvent, can enumerate monohydric alcohol (ethanol, propyl alcohol, butanols, amylalcohol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzylalcohol etc.), polyalcohol and hydroxyl alcoholic compound (ethylene glycol, propylene glycol, glycerine, methyl cellosolve, ethyl cellosolve, MPEG, dimethoxy propyl alcohol etc.) etc. typically.In addition, as non-proton property polar solvent, can enumerate acid amides system (N-methylformamide, N, dinethylformamide, the N-ethyl-formamide, N, the N-diethylformamide, the N-methylacetamide, N, the N-dimethylacetylamide, the N-ethyl acetamide, N, the N-diethyl acetamide, hexamethyl phosphoramide etc.), lactone (gamma-butyrolacton, δ-Wu Neizhi, gamma-valerolactone etc.), sulfolane system (sulfolane, the 3-methyl sulfolane, 2,4-dimethylsulfolane etc.), cyclic amide (N-N-methyl-2-2-pyrrolidone N-etc.), carbonates (ethylene carbonate, the propylene glycol carbonic ester, propylene carbonate etc.), nitrile (acetonitrile etc.), sulfoxide class (methyl-sulfoxide etc.), 2-imidazolone system [1,3-dialkyl group-2-imidazolone (1,3-dimethyl-2-imidazolone, 1,3-diethyl-2-imidazolone, 1,3-two (n-pro-pyl)-2-imidazolone etc.), 1,3,4-trialkyl-2-imidazolone (1,3,4-trimethyl-2-imidazolone etc.)] etc.Wherein, if use gamma-butyrolacton then can improve low impedance characteristic, therefore preferred, if use sulfolane, 3-methyl sulfolane, 2, the 4-dimethylsulfolane then can promote hot properties, and is therefore preferred, if it is make spent glycol then can improve voltage-resistent characteristic, therefore preferred.
Wherein, for being solvent with gamma-butyrolacton, being the electrolyte of solute with quaternary salt ring-type amidine salt, it has this problem of electrolyte from leaking between the round bar part 6 of seal body 12 and lead-out wire in life test, but in electrolytic capacitor of the present invention, this phenomenon of leakage can not take place.That is, be shown as noble potential because the current potential of dipping naturally of the cathode terminal 5 of common electrolytic capacitor is compared with the current potential of dipping naturally of cathode electrode foil 3, under the DC load state, compare with cathode electrode foil, cathode current flows to cathode terminal more.In addition, when placing, constitute local cell by cathode terminal and cathode electrode foil under no-load condition, cathode current flows to cathode terminal.Thus, under load, non-loaded both of these case, cathode current all flows to cathode terminal, consequently, partly generates hydroxide ion at the round bar part 6 of cathode terminal and the electrolyte interface of connecting portion 7.
Then, hydroxide ion of Sheng Chenging and quaternary salt ring-type amidine reaction thus, the open loop of quaternary salt ring-type amidine becomes secondary amine.On the other hand, if produce hydroxide ion, as the gamma-butyrolacton of solvent also with the hydroxide ion reaction, generate gamma-hydroxybutyric acid, pH reduces.If pH is reduced, the secondary amine closed loop that generates by the open loop of quaternary salt ring-type amidine then, generate quaternary salt ring-type amidine salt once more, because this quaternary salt ring-type amidine salt does not have volatility, and moisture absorption height, the quaternary salt ring-type amidine salt moisture absorption that generates once more between the round bar part of cathode terminal and seal body becomes the leakage state.
Yet in the present invention, the paper tinsel that uses the electrode potential in aforementioned electrolyte at least to compare with aforementioned cathode sheets to demonstrate noble potential is as cathode electrode foil, with the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound as solute.Therefore, cathode current flows to cathode electrode foil, and most hydroxide ion produces on cathode electrode foil.And then if use highly purified aluminium on cathode sheets, then the potential difference of cathode electrode foil and cathode sheets further increases, and can reduce the generation of hydroxide ion on cathode sheets.Further, think that the reactivity of the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound and hydroxide ion is lower, because these collaborative effects can prevent the leakage state.Equally also can prevent the leakage under no-load condition.
It is also good and then the leakage characteristic is also good that above electrolytic capacitor of the present invention has high withstand voltage characteristic, a life characteristics at high temperature of low impedance characteristic and 100V level.
Below second electrolytic capacitor of the present invention is described.Electrolytic capacitor of the present invention is characterised in that: pass through dividing plate, the negative electrode ejector that will be formed by the aluminium of purity 99.9% or more by the anode electrode paper tinsel with anode ejector and having, the cathode electrode foil that is formed by the aluminium that passes through the chemical conversion processing wind up and form capacitor element, be full of the electrolyte that contains tetrafluoride aluminium salt in this capacitor element, receipts are contained in the external shell.
The structure of aluminium electrolytic capacitor has identical structure with first electrolytic capacitor, in the present invention, as cathode electrode foil 3, adopts to have the negative electrode ejector that is formed by the aluminium of purity more than 99.9% electrode foil that the aluminium of being handled by the process chemical conversion forms.Electrode foil of the present invention can obtain by the chemical conversion of carrying out 0.05～5V, preferred 0.5～3V through the aluminium foil that exchanges etch processes such as etching is handled.And then, preferably on the surface of the round bar part at least 6 of lead-out wire 4,5, form the alumina layer that forms by anodized by ammonium borate aqueous solution, ammonium phosphate solution or the ammonium adipate aqueous solution etc.
The mechanism of electrolyte leakage is identical with first electrolytic capacitor herein, in the present invention, the electrode foil that use has the negative electrode ejector that formed by the aluminium of purity more than 99.9%, formed by the aluminium of handling through chemical conversion is as cathode electrode foil, with the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound as solute.Therefore, the natural potential of cathode electrode foil is compared with the natural potential of negative electrode ejector and is demonstrated noble potential, because cathode current flows to cathode electrode foil, most hydroxide ion produces on cathode electrode foil.And then, if on the surface of the round bar part at least 6 of lead-out wire 4,5, forming alumina layer by anodized, the electric current that then flows to the negative electrode ejector is suppressed, and near the generation of the hydroxide ion the negative electrode ejector reduces.Further, think that the reactivity of the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound and hydroxide ion is lower, because these collaborative effects can prevent the leakage state.Equally also can prevent the leakage under no-load condition.
It is also good and then the leakage characteristic is also good that above electrolytic capacitor of the present invention has high withstand voltage characteristic, a life characteristics at high temperature of low impedance characteristic and 100V level.
Below the 3rd electrolytic capacitor of the present invention is described.Electrolytic capacitor of the present invention is a kind of, by anode electrode paper tinsel, cathode electrode foil and dividing plate are wound up, and be full of electrolyte and form capacitor element, the electrolytic capacitor that its receipts is contained in the external shell and forms, it is characterized in that using the electrolyte that contains tetrafluoride aluminium salt as aforementioned electrolyte, use the electrode foil of handling through peroxophosphoric acid as aforesaid anode electrode foil or cathode electrode foil.
The structure of electrolytic capacitor is identical with first electrolytic capacitor, as electrode foil, uses the electrode foil of handling through peroxophosphoric acid.Though also have effect of the present invention with one in anode electrode paper tinsel, the cathode electrode foil,, therefore use both usually if use both then can suppress the deterioration of two cube electrode paper tinsels.Usually highly purified aluminium foil is carried out chemistry or electrochemical etch process obtains etched foil, but as electrode foil of the present invention, use by in the etched pre-treatment of interchange, intermediate treatment or the last handling process in this etching work procedure, carry out the aqueous phosphatic impregnation process and the etched foil that obtains as cathode electrode foil.Then, with this etched foil, perhaps by the etched foil of not handling through peroxophosphoric acid is not carried out the phosphoric acid chemical conversion, and before chemical conversion, in the middle or last handling process, carry out phosphate impregnation and electrode foil as the anode electrode paper tinsel.
And then, can improve effect of the present invention if in aforementioned electrolyte for electrolytic capacitor, add phosphorus compound.As this phosphorus compound, can enumerate following material.Orthophosphoric acid, phosphorous acid, hypophosphorous acid and salt thereof, as its salt, can enumerate ammonium salt, aluminium salt, sodium salt, calcium salt, sylvite, in addition, can also enumerate phosphate cpds such as etherophosphoric acid, diethyl phosphate, butylphosphoric acid ester, dibutylphosphoric acid ester, 1-hydroxy ethylene-1, phosphinic acid compounds such as 1-di 2 ethylhexyl phosphonic acid, ATMP, phenyl-phosphonic acid etc.In addition, can also enumerate phosphinic compounds such as methyl phosphinic acids, phosphinic acids butyl ester.
And then, the condensed phosphoric acid that can also be listed below or its salt.The isothrausmatic condensed phosphoric acid of condensed phosphoric acid, metaphosphoric acid, hexa metaphosphoric acid of straight chain shapes such as pyrophosphoric acid, tripolyphosphate, four polyphosphoric acids is perhaps by the material of the condensed phosphoric acid be combined into of these chains, ring-type.In addition, as the salt of these condensed phosphoric acids, can use ammonium salt, aluminium salt, sodium salt, calcium salt, sylvite etc.
Addition is 0.05～3wt%, preferred 0.1～2wt%.
High withstand voltage characteristic, life characteristics at high temperature that above electrolytic capacitor of the present invention has low impedance characteristic and 100V level are also good.Promptly, when using tetrafluoride aluminium salt to carry out experiment of high-temperature load, moisture in the electrolyte exerts an influence to the characteristic of the reactivity increase of electrolyte and electrode foil, because electrolytic capacitor of the present invention uses the electrode foil of handling through peroxophosphoric acid, the reaction of electrolyte and electrode foil is suppressed, and life characteristics at high temperature is stable.
And then, in first to the 3rd electrolytic capacitor of the present invention, use in the butyl rubber polymer that the copolymer by isobutene, isoprene and divinylbenzene forms, add as the peroxide of crosslinking agent and the partial cross-linked butyl rubber of peroxide, with this as seal body.As the vulcanizing agent that in peroxide cure, uses, can enumerate ketone peroxide class, ketal peroxide class, hydroperoxide type, dialkyl peroxide class, diacyl peroxide class, peroxide two carbonates, peroxy esters class etc.Specifically can enumerate, 1,1-di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane, normal-butyl-4,4-di-t-butyl peroxide valerate, dicumyl peroxide, t-butyl peroxy benzoic ether, di-tert-butyl peroxide, benzoyl peroxide, 1,3-two (t-butyl peroxy isopropyl) benzene, 2,5-dimethyl-2,5-di-t-butyl peroxide-3-hexin, tert-butyl hydroperoxide cumene, α, α '-two (t-butyl peroxy) diisopropyl benzene etc.
As implied above, owing to electrolytic capacitor of the present invention uses the partial cross-linked butyl rubber of peroxide that in the butyl rubber polymer that the copolymer by isobutene, isoprene and divinylbenzene forms interpolation gets as the peroxide of crosslinking agent as seal body, and the electrolyte that contains tetrafluoride aluminium salt, the seal body high withstand voltage characteristic, that be used for the present invention and electrolyte with low impedance characteristic and 100V level have the good high-temperature characteristic, have therefore further improved life characteristics at high temperature.
In addition, for existing quaternary salt ring-type amidine compound, has the tendency of leakage by hydroxide ion reaction with near the generation negative electrode ejector, and in the present invention, good sealing property between the through hole of seal body and the lead-out wire, and think the reactive low of used electrolyte and hydroxide ion among the present invention, further improve the leakage characteristic by its synergy.
(embodiment)
Below by enumerating embodiment the present invention is described.Because the structure of electrolytic capacitor has and identical in the past structure, describes with reference to Fig. 1, Fig. 2.Form capacitor 1 by dividing plate 11 coiling anode electrode paper tinsels 2 and cathode electrode foil 3.In addition, as shown in Figure 2, on anode electrode paper tinsel 2, cathode electrode foil 3, connecting the lead-out wire 5 that is used to draw the lead-out wire 4 of anode and is used to draw negative electrode respectively.
This lead-out wire the 4, the 5th, the electrode slice 9 that forms by the round bar part 6 that becomes one with the connecting portion 7 of electrode foil butt with this connecting portion 7, and be fixed on the external connecting 8 of round bar part 6 front ends and constitute.In addition, connecting portion 7 and round bar part 6 are to be formed by 99% aluminium, and external connecting 8 is formed by coppered steel wire (hereinafter referred to as the CP line).On the surface of the round bar part at least 6 of this lead-out wire 4,5, form the anodic oxidation film of aluminium oxide by anodized by ammonium phosphate solution.This lead-out wire 4,5 makes connecting portion 7 link to each other with anode electrode paper tinsel 2, cathode electrode foil 3 respectively in conductive mode by methods such as seam weldering, ultrasonic bonding.
What anode electrode paper tinsel 2 adopted is, after in acid solution, the aluminium foil of purity 99.9% being carried out the expansion faceization processing of chemistry or chemical etching, in the ammonium adipate aqueous solution, carry out chemical conversion and handle, form the electrode foil of anodic oxidation film layer in its surface.
Then, capacitor element 1 receipts that have been full of electrolyte are contained in the external shell made of aluminum 10, at the peristome of external shell 10 seal body 12 are installed, simultaneously by the end of external shell 10 being carried out deep-draw processing with sealing external shell 10.Seal body 12 is formed by elastic caoutchoucs such as for example butyl rubbers, and has the through hole of deriving lead-out wire 4,5 respectively.
Cathode electrode foil 3 and anode electrode paper tinsel 2 be same adopt aluminium foil to purity 99.9% to carry out etching and electrode foil.Then, on the surface of this cathode electrode foil 3, integrally cover titanium nitride or the titanium of 0.1 μ m by vapour deposition method.In addition, the thin layers such as titanium nitride among this embodiment have covered the whole surface of cathode electrode foil 3, can for example only cover metal nitride on the one side of cathode electrode foil 3 only on the part of cathode electrode foil 3 where necessary.
In addition, for electrolyte A, employing with gamma-butyrolacton (75 parts) as solvent, dissolved with 1-ethyl-2,3-methylimidazole tetrafluoride aluminium salt (25 parts) is as the electrolyte of solute, as electrolyte B, with gamma-butyrolacton (80 parts) as solvent, dissolved with 1-ethyl-2,3-methylimidazole tetrafluoride aluminium salt (20 parts) is as the electrolyte of solute.In addition, electrolyte C as a comparative example, employing, has been dissolved with 1-ethyl-2 as solvent with gamma-butyrolacton (75 parts), and 3-methylimidazole diphenate is as the electrolyte of solute.
As above the rated voltage of the electrolytic capacitor of Gou Chenging is, uses the 16V that is of electrolyte A, C, uses the 100V that is of electrolyte B.Estimate the characteristic of these electrolytic capacitors.Experimental condition is 125 ℃, load in 2000 hours, 105 ℃, and 2000 hours are non-loaded.Its result is shown in (table 1-1)～(table 1～4).
(table 1-1)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 125 ℃ of loads in-2000 hours | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 1 | ??A | The TiN evaporation | ??401 | ??0.028 | ??-12.1 | ??0.043 | ??0/25 |
| Embodiment 2 | ??A | The Ti evaporation | ??402 | ??0.028 | ??-11.9 | ??0.044 | ??0/25 |
| Comparative example 1 | ??C | ?????- | ??405 | ??0.046 | ??-10.0 | ??0.142 | ??7/25 |
(table 1-2)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 105 ℃-2000 hours non-loaded | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 1 | ??A | The TiN evaporation | ??402 | ??0.028 | ??-5.4 | ??0.034 | ??0/25 |
| Embodiment 2 | ??A | The Ti evaporation | ??402 | ??0.029 | ??-5.2 | ??0.035 | ??0/25 |
| Comparative example 1 | ??C | ????- | ??406 | ??0.046 | ??-4.2 | ??0.052 | ??6/25 |
(table 1-3)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 125 ℃ of loads in-2000 hours | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 3 | ??B | The TiN evaporation | ??22.9 | ??0.011 | ??-6.5 | ??0.026 | ??0/25 |
| Embodiment 4 | ??B | The Ti evaporation | ??22.8 | ??0.012 | ??-6.3 | ??0.028 | ??0/25 |
(table 1-4)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 105 ℃-2000 hours non-loaded | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 3 | ??B | The TiN evaporation | ??22.9 | ??0.011 | ??-0.9 | ??0.014 | ??0/25 |
| Embodiment 4 | ??B | The Ti evaporation | ??22.7 | ??0.013 | ??-0.8 | ??0.015 | ??0/25 |
As can be seen, compare with comparative example from (table 1-1), (table 1-2), the tan δ of the electrolytic capacitor of embodiment is lower, and 125 ℃ tan δ changes less, and life characteristics at high temperature is good, can also prevent leakage.And then, by among (table 1-3), (the table 1-4) as can be seen, initial stage characteristic, life characteristic during rated voltage 100V are also good, have realized having the electrolytic capacitor of the 100V level of unexistent low impedance characteristic in the past.
Below by enumerating embodiment second electrolytic capacitor of the present invention is described.The structure of electrolytic capacitor has the structure identical with first electrolytic capacitor, the evaluating characteristics content is also identical, but cathode electrode foil 3 uses have negative electrode ejector that is formed by the aluminium foil of purity more than 99.9% and the electrode foil that is formed by the aluminium that carries out the chemical conversion processing after exchanging etching under 2V.In addition, on the surface of the round bar part at least 6 of lead-out wire 4,5, form alumina layer by anodized by ammonium phosphate solution.Adopt aluminium foil to carry out etched electrode foil as a comparative example, similarly on the surface of the round bar part at least 6 of lead-out wire 4,5, form alumina layer by anodized by ammonium phosphate solution to purity 99.6%.Its result is shown in (table 2-1)～(table 2～4).
(table 2-1)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 125 ℃ of loads in-2000 hours | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 5 | ??A | The chemical conversion paper tinsel | ??402 | ??0.029 | ??-12.1 | ??0.044 | ??0/25 |
| Comparative example 2 | ??C | ??????- | ??408 | ??0.046 | ??-10.0 | ??0.143 | ??7/25 |
(table 2-2)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 105 ℃-2000 hours non-loaded | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 5 | ??A | The chemical conversion paper tinsel | ??401 | ??0.026 | ??-5.2 | ??0.033 | ??0/25 |
| Comparative example 2 | ??C | ???????- | ??407 | ??0.046 | ??-4.2 | ??0.053 | ??6/25 |
(table 2-3)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 125 ℃ of loads in-2000 hours | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 6 | ??B | The chemical conversion paper tinsel | ??22.6 | ??0.010 | ??-6.4 | ??0.024 | ??0/25 |
(table 2-4)
| Electrolyte | Cathode electrode foil | The initial stage characteristic | 105 ℃-2000 hours non-loaded | Leakage | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||||
| Embodiment 6 | ??B | The chemical conversion paper tinsel | ??22.9 | ??0.011 | ??-0.9 | ??0.012 | ??0/25 |
As can be seen, compare with comparative example from (table 2-1), (table 2-2), the tan δ of the electrolytic capacitor of embodiment is lower, and 125 ℃ tan δ changes less, and life characteristics at high temperature is good, can also prevent leakage.And then, by among (table 2-3), (the table 2-4) as can be seen, initial stage characteristic, life characteristic during rated voltage 100V are also good, have realized having the electrolytic capacitor of the 100V level of unexistent low impedance characteristic in the past.
Below by enumerating embodiment the 3rd electrolytic capacitor of the present invention is described.The structure of electrolytic capacitor has the structure identical with first electrolytic capacitor, in the present invention, use is carried out the etched foil of phosphate impregnation processing as Cathode Foil in etching work procedure, use has formed the chemical conversion film of anode chemical conversion film to this etched foil by the phosphoric acid chemical conversion, as anode foils.As a comparative example, use the electrode foil of not this phosphate impregnation processing of process, phosphoric acid chemical conversion.
In addition, used electrolyte for electrolytic capacitor is shown in table (table 3-1).
Use the rated value of the electrolytic capacitor that the electrolyte of as above embodiment constitutes to be 100WV-22 μ F, estimate the characteristic of these electrolytic capacitors.Experimental condition is load in 125 ℃, 500 hours.Its result is shown in table (3-2).
(table 3-1)
| ??GBL | ??A | ??B | ??C | Sparking voltage | Resistance coefficient | |
| Embodiment 7 | ??79.8 | ??20 | ??- | ??0.2 | ??205 | ??40 |
| Comparative example 3 | ??80 | ??- | ??20 | ??- | ??85 | ??91 |
GBL: gamma-butyrolacton
A: tetrafluoride aluminic acid 1-ethyl-2,3-methylimidazole quinoline
B: hydrogen phthalate 1-ethyl-2,3-methylimidazole quinoline
C: dibutylphosphoric acid ester
(table 3-2)
| Electrode foil | The initial stage characteristic | 125 ℃-500 hours | |||
| ??Cap ??(μF) | ??tanδ | ??ΔCap ??(％) | ??tanδ | ||
| Embodiment 8 | Handle through peroxophosphoric acid | ??23.1 | ??0.01 | ??-1.3 | ??0.01 |
| Comparative example 4 | Do not handle through peroxophosphoric acid | ??22.8 | ??0.01 | ??-4.3 | ??0.03 |
Cap: capacitance, tan δ: the tangent of dielectric loss, Δ Cap: the rate of change of capacitance
As can be seen, compare with the comparative example of prior art from (table 3-1), the sparking voltage of the electrolyte for electrolytic capacitor of embodiment is higher, and resistance coefficient is lower.Also have, as can be seen, use its tan δ of electrolytic capacitor of 100WV lower from (table 3-2), the rate of change of specific capacitance is lower mutually with comparative example, and tan δ also has only 1/3, and effect of the present invention is remarkable.
Thus, in first to the 3rd electrolytic capacitor, use is in the butyl rubber polymer that the copolymer by isobutene, isoprene and divinylbenzene forms, interpolation as the peroxide of crosslinking agent and the partial cross-linked butyl rubber of peroxide during as seal body, the leakage characteristic improves.
Industrial applicibility
By the first and second capacitors of the present invention, when use contains the electrolyte of four aluminum fluoride salt, the paper tinsel that uses the electrode potential in aforementioned electrolyte at least to compare with aforementioned negative electrode sheet to demonstrate noble potential is as cathode electrode foil, perhaps with having that the negative electrode that is formed by the aluminium of purity 99.9% or more is drawn device and through the cathode electrode foil that is formed by aluminium that chemical conversion is processed, can provide have low impedance characteristic, high withstand voltage characteristic, life characteristics at high temperature well and then also good electrolytic capacitor of leakage characteristic.
In addition, by the 3rd electrolytic capacitor of the present invention owing to use through four aluminum fluoride salt and the acid-treated electrode foil of phosphorus, can provide have low impedance characteristic, also good electrolytic capacitor of high withstand voltage characteristic, high temperature service life spy.
Claims (5)
1. electrolytic capacitor, it is to form capacitor element by anode electrode paper tinsel and cathode electrode foil coiling that dividing plate will be connected with anode strip, cathode sheets respectively, in this capacitor element, be full of electrolyte, when receiving capacitor element in the external shell that is contained in bottom tube-like, seal by the open end of seal body external shell, it is characterized in that: use the electrolyte contain tetrafluoride aluminium salt, the paper tinsel that uses the electrode potential in described electrolyte at least to compare with described cathode sheets to demonstrate noble potential is as cathode electrode foil.
2. electrolytic capacitor as claimed in claim 1, it is characterized in that: as cathode electrode foil, use is provided with by the metal nitride that is selected from titanium nitride, zirconium nitride, tantalum nitride, niobium nitride or is selected from the paper tinsel of layer of formed 0.02～0.1 μ m of metal of titanium, zirconium, tantalum, niobium on the surface of aluminium foil.
3. electrolytic capacitor, it is to pass through dividing plate, the negative electrode ejector that will form by the aluminium of purity 99.9% or more by the anode electrode paper tinsel with anode ejector and having and wind up by the cathode electrode foil that the aluminium that passes through the chemical conversion processing forms and to form capacitor element, in this capacitor element, be full of the electrolyte that contains tetrafluoride aluminium salt, receive and to be contained in the external shell and to form.
4. electrolytic capacitor, it is by anode electrode paper tinsel, cathode electrode foil and dividing plate are wound up, be full of electrolyte and form capacitor element, this capacitor element received be contained in the external shell and form, wherein use the electrolyte that contains tetrafluoride aluminium salt as described electrolyte, and use the electrode foil of handling through peroxophosphoric acid as described anode electrode paper tinsel or cathode electrode foil.
5. as each described electrolytic capacitor in the claim 1 to 4, wherein use in the butyl rubber polymer that the copolymer by isobutene, isoprene and divinylbenzene forms, add as the peroxide of crosslinking agent and the partial cross-linked butyl rubber of peroxide as seal body.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP326019/2002 | 2002-11-08 | ||
| JP326009/2002 | 2002-11-08 | ||
| JP326007/2002 | 2002-11-08 | ||
| JP326028/2002 | 2002-11-08 | ||
| JP2002326007A JP2004165203A (en) | 2002-11-08 | 2002-11-08 | Electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1711614A true CN1711614A (en) | 2005-12-21 |
| CN100550238C CN100550238C (en) | 2009-10-14 |
Family
ID=32805063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801029030A Expired - Fee Related CN100550238C (en) | 2002-11-08 | 2003-11-07 | Electrolytic capacitor |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2004165203A (en) |
| CN (1) | CN100550238C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8184429B2 (en) | 2006-09-07 | 2012-05-22 | Panasonic Corporation | Capacitor lead wire, its manufacturing method, and capacitor using the same |
| CN101755314B (en) * | 2007-07-19 | 2012-10-10 | 松下电器产业株式会社 | Electronic component, lead wire and their production methods |
| CN110993353A (en) * | 2020-01-06 | 2020-04-10 | 深圳市兴创嘉技术有限公司 | Winding method of electrolytic capacitor core cladding |
| CN112435856A (en) * | 2020-11-05 | 2021-03-02 | 肇庆绿宝石电子科技股份有限公司 | Aluminum electrolytic capacitor and manufacturing method and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101302728B1 (en) * | 2005-09-30 | 2013-09-03 | 니폰 케미콘 가부시키가이샤 | Electrolytic capacitor |
| JP4983073B2 (en) * | 2005-09-30 | 2012-07-25 | 日本ケミコン株式会社 | Electrolytic capacitor |
| JP4866586B2 (en) * | 2005-09-30 | 2012-02-01 | 三菱化学株式会社 | Electrolytic capacitor and electrolytic capacitor manufacturing method |
| JP7010350B1 (en) * | 2020-09-30 | 2022-01-26 | 日本ケミコン株式会社 | Cathode and electrolytic capacitors |
| JP7010351B1 (en) * | 2020-09-30 | 2022-01-26 | 日本ケミコン株式会社 | Cathode and electrolytic capacitors |
-
2002
- 2002-11-08 JP JP2002326007A patent/JP2004165203A/en active Pending
-
2003
- 2003-11-07 CN CNB2003801029030A patent/CN100550238C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8184429B2 (en) | 2006-09-07 | 2012-05-22 | Panasonic Corporation | Capacitor lead wire, its manufacturing method, and capacitor using the same |
| CN101512692B (en) * | 2006-09-07 | 2013-06-12 | 松下电器产业株式会社 | Condenser lead wire, its manufacturing method, and condenser using them |
| CN101755314B (en) * | 2007-07-19 | 2012-10-10 | 松下电器产业株式会社 | Electronic component, lead wire and their production methods |
| CN110993353A (en) * | 2020-01-06 | 2020-04-10 | 深圳市兴创嘉技术有限公司 | Winding method of electrolytic capacitor core cladding |
| CN112435856A (en) * | 2020-11-05 | 2021-03-02 | 肇庆绿宝石电子科技股份有限公司 | Aluminum electrolytic capacitor and manufacturing method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100550238C (en) | 2009-10-14 |
| JP2004165203A (en) | 2004-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1664968B (en) | Aluminum electrolytic capacitor | |
| KR101112019B1 (en) | Electrolytic capacitor | |
| CN1711614A (en) | Electrolytic capacitor | |
| KR20050088284A (en) | Electrolytic capacitor | |
| CN104952621A (en) | Electrolyte for aluminum electrolytic capacitor and aluminum electrolytic capacitor using same | |
| CN100481286C (en) | Electrolytic capacitor | |
| CN109791843A (en) | Electrode foil and electrolytic capacitor | |
| KR101112023B1 (en) | Electrolytic capacitor | |
| CN100452258C (en) | Electrolytic capacitor manufacturing method | |
| KR101112022B1 (en) | Electrolyte for electrolytic capacitor and electrolytic capacitor containing the same | |
| US20200135408A1 (en) | Electrolytic capacitor and method for manufacturing electrolytic capacitor | |
| JP4304384B2 (en) | Electrolytic capacitor | |
| JP2009088301A (en) | Electrolytic capacitor | |
| KR20050088286A (en) | Electrolytic capacitor manufacturing method | |
| JP2004165262A (en) | Electrolyte for electrolytic capacitor and electrolytic capacitor using it | |
| JP2006012984A (en) | Electrolytic solution for electrolytic capacitors | |
| JP2004165213A (en) | Electrolytic capacitor | |
| JP2004165264A (en) | Electrolytic capacitor | |
| JP2004186579A (en) | Electrolytic capacitor | |
| JP2004165261A (en) | Electrolytic solution for electrolytic capacitor and electrolytic capacitor using it | |
| JP2005294592A (en) | Electrolytic capacitor | |
| JP2004304078A (en) | Electrolyte for electrolytic capacitor and electrolytic capacitor using the same | |
| JP2004200657A (en) | Electrolytic capacitor | |
| JP2004165211A (en) | Electrolytic capacitor | |
| JP2004247419A (en) | Electrolytic solution for electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Co-patentee after: MITSUBISHI CHEMICAL Corp. Patentee after: NIPPON CHEMI-CON Corp. Address before: Tokyo, Japan Co-patentee before: MITSUBISHI RAYON Co.,Ltd. Patentee before: NIPPON CHEMI-CON Corp. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170929 Address after: Tokyo, Japan Co-patentee after: MITSUBISHI RAYON Co.,Ltd. Patentee after: NIPPON CHEMI-CON Corp. Address before: Tokyo, Japan Co-patentee before: MITSUBISHI CHEMICAL Corp. Patentee before: NIPPON CHEMI-CON Corp. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091014 Termination date: 20181107 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |