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, the round bar part 6 that is connected with connecting portion 7 and be 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 9 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.
Also have, in the present invention, when making the electrode ejector, at first, the aluminium wire of intermittent pressurized processing is cut off the size that becomes regulation, make the aluminium conductor that forms by round bar part 6 and par 7, carry out chemical conversion then and handle, form anodic oxidation film from the teeth outwards.Thereafter on the end face of this aluminium conductor, the external connecting 8 that welding is formed by the CP line constitutes lead-out wire 4,5.
Wherein, for aluminium conductor, carry out ceramic coating as the negative electrode ejector.That is, to as the round bar part 6 of the above-mentioned aluminium conductor that forms anodic oxidation film from the teeth outwards on, spray the coating agent of forming by metal alkoxide system pottery, apply, aforementioned coating agent is then sprayed in heat treatment then once more, after applying,, on aluminium conductor, form overlay once more by heat treatment.
As being used for the pottery that metal alkoxide is a pottery, can enumerate Al
2O
3, SiO
2, ZrO
2, TiO
2, MgO, H
2BO
3, Cr
2O
3, BaTiO
3, PbTiO
3, KTaO
3Deng.In addition, as pottery used herein,, be preferably selected from Al if consider the coating characteristic
2O
3, SiO
2, ZrO
2In one or more, and then, if consider intensity, preferably by Al
2O
3, SiO
2The mixture of forming.
In addition, as coating method, can enumerate that round bar part 6 is immersed in the method that applies in the coating agent.Just, aluminium conductor is immersed in the coating agent, heat treatment then, then be immersed in the aforementioned coating agent once more after, heat treatment once more forms overlay thus on aluminium conductor.Then, par 7 is immersed in the methanol solution, removes overlay, the only method of residual overlay on round bar part 6 by ultrasonic wave etc.Yet by this method, the adjustment when removing overlay is not easy to carry out, for the ground of pinpoint accuracy on round bar part forms overlay, the method for preferred aforementioned injection, coating.
The par 7 of the lead-out wire of as above making 4,5 mechanically links together with electrode foil 2,3 by seam weldering method, ultrasonic bonding etc.Wherein, also can carry out ceramic coating, but if consider the coating accuracy, the ceramic coating layer be pre-formed before capacitor manufacturing process preferably at lead-out wire 5 with after cathode electrode foil 3 is connected.And then in order to obtain anti-fully leakage effect, it must form on the round bar part at least 6 of lead-out wire 5.
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, 1-phenylimidazole, 1,2-methylimidazole, 1-ethyl-2-methylimidazole, 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-2-methylimidazole quinoline, 1,4-dimethyl-2-ethyl imidazol(e) quinoline, 1-methyl-2-ethoxyl methyl imidazoline etc.), compound (1-methyl-1 with tetrahydropyrimidine ring, 4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0]-and 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 monomethyl formamide, N, the N dimethyl formamide, N one ethyl-formamide, N, N one diethylformamide, N monomethyl acetamide, N, N one dimethylacetylamide, N one ethyl acetamide, N, N one diethyl acetamide, hexamethyl phosphoramide etc.), lactone (γ-butyrolactone, γ-valerolactone, δ-valerolactone etc.), sulfolane system (sulfolane, 3-methyl sulfolane, 2,4-dimethylsulfolane etc.), cyclic amide (N monomethyl-2-pyrrolidones 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 one dialkyl group-2-imidazolone (1,3-dimethyl-2-imidazolone, 1,3-diethyl-2-imidazolone, 1,3-two (n-pro-pyl)-2-imidazolones etc.), 1,3,4-trialkyl-2-imidazolone (1,3,4 one trimethyls, one 2 one imidazolones etc.)] etc.Wherein, if use γ-butyrolactone then can improve low impedance characteristic, therefore preferred, if it is use sulfolane, 3-methyl sulfolane, 2,4-dimethylsulfolane then can promote hot properties, therefore preferred, if it is make spent glycol then can improve voltage-resistent characteristic, therefore preferred.
Wherein, for being solvent with γ-butyrolactone, 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 9 and lead-out wire in life test, but in electrolytic capacitor of the present invention, this phenomenon of leakage can not take place.Promptly, because the current potential of dipping naturally of the cathode terminal 5 of electrolytic capacitor is compared with the current potential of dipping naturally of cathode electrode foil 3 and is shown as noble potential (cathode potential) usually, under the DC load state, to 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 γ-butyrolactone of solvent also with the hydroxide ion reaction, generate γ-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, also on negative electrode ejector and part that seal body contacts, form the ceramic coating layer, with the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound as solute.Therefore, the electric current that flows to the negative electrode ejector is suppressed, and almost can't see the generation of hydroxide ion near the negative electrode ejector.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.
Below second electrolytic capacitor of the present invention is described.Electrolytic capacitor of the present invention has: the anode electrode paper tinsel that will have the anode ejector by dividing plate winds up, is full of the capacitor element that electrolyte forms with the cathode electrode foil with negative electrode ejector, receive the external shell of this capacitor element of dress, and the seal body that this external shell is sealed, it is characterized in that: use to contain the electrolyte of tetrafluoride aluminium salt as aforementioned electrolyte, and on negative electrode ejector and part that seal body contacts, form the insulating properties synthetic resin layer.
The structure of electrolytic capacitor is identical with first electrolytic capacitor, in the present invention, to the aluminium conductor as the negative electrode ejector, carries out the coating of insulating properties synthetic resin layer.
As the resin synthetic material of insulating properties, for example can enumerate thermosetting resins such as epoxy resin, phenol resin, furane resins, melmac, xylene resin, guanamine resin; Thermoplastic resins such as fluororesin, polybutadiene, polyamide, polyamide-imide resin, polyacrylate, polyimides, Polyetherimide, polyether-ether-ketone, Merlon, polyvinyl dimethoxym ethane, polyphenylene sulfide, liquid crystal polymer, ketone resin, cumar resin, MBS resin.In addition, in these resins, can be with the ratio below the 10 weight %, for example add coupling agent such as silane system, titanate esters system and use.
Just, coupling agent is coated on the round bar part 6 of the aluminium conductor that is set forth in surperficial upward formation anodic oxidation film dry formation after the coupling agent layer, formation insulating properties synthetic resin layer on aluminium conductor; Perhaps when inapplicable coupling agent, by being injected on the round bar part 6 by heating or with the coating agent that the liquid molten thing of the insulating properties synthetic resin of appropriate solvent adjustment forms, apply,, on aluminium conductor, form the insulating properties synthetic resin layer then by dried.
Perhaps also the film that is configured as the synthetic resin film of hot melt property can be applied on the round bar part 6, carry out heat treated then and form.
In addition, as coating method, in addition round bar part 6 is immersed in the method that applies in the coating agent.Just, aluminium conductor is immersed in the overlay, dried forms overlay on aluminium conductor then.Then par 7 is immersed in the methanol solution, removes overlay, the only method of residual overlay on round bar part 6 by ultrasonic wave etc.Yet by this method, the adjustment when removing overlay is not easy to carry out, for the ground of pinpoint accuracy on round bar part forms overlay, the method for preferred aforementioned injection, coating.
The par 7 of the lead-out wire of as above making 4,5 mechanically links together with electrode foil 2,3 by seam weldering method, ultrasonic bonding etc.Wherein, also can carry out the coating of insulating properties synthetic resin, but if consider the coating accuracy, the insulating properties synthetic resin layer be pre-formed before capacitor manufacturing process preferably at lead-out wire 5 with after cathode electrode foil 3 is connected.And then in order to obtain anti-fully leakage effect, it must form on the round bar part at least 6 of lead-out wire 5.
The mechanism of electrolyte leakage is identical with first electrolytic capacitor herein, in the present invention, on negative electrode ejector and part that seal body contacts, forms the insulating properties synthetic resin layer, with the tetrafluoride aluminium salt of quaternary salt ring-type amidine compound as solute.Therefore, the electric current that flows to the negative electrode ejector is suppressed, and almost can't see the generation of hydroxide ion near the negative electrode ejector.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.
Below the 3rd electrolytic capacitor of the present invention is described.Electrolytic capacitor of the present invention has: the anode electrode paper tinsel that will have the anode ejector by dividing plate winds up with the cathode electrode foil with negative electrode ejector, the capacitor element that is full of electrolyte and forms, with the external shell of receiving this capacitor element of dress, and the seal body that this external shell is sealed, it is characterized in that: use to contain the electrolyte of tetrafluoride aluminium salt as aforementioned electrolyte, and use by isobutene, in the butyl rubber polymer that the copolymer of isoprene and divinylbenzene forms, add as the peroxide of crosslinking agent and the partial cross-linked butyl rubber of peroxide as seal body.
The structure of electrolytic capacitor is identical with first electrolytic capacitor, in 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 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 mentioned above, because electrolytic capacitor of the present invention uses 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 as seal body, use contains the electrolyte of tetrafluoride aluminium salt, so have the high withstand voltage characteristic of low impedance characteristic and 100V level, because the used good high-temperature characteristic that seal body and electrolyte had among the present invention, therefore the life characteristics at high temperature of electrolytic capacitor of the present invention also is good.
Further, for existing quaternary salt ring-type amidine compound, it has the tendency of leakage by the hydroxide ion reaction with near the generation negative electrode ejector, and in the present invention, has 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.
More than small-sized electrolytic capacitor is described, then the 4th large-scale electrolytic capacitor is described.
Electrolytic capacitor of the present invention is a kind of by dividing plate being inserted between anode electrode paper tinsel with anode ejector and the cathode electrode foil with negative electrode ejector and winding up in the capacitor element of formation, be full of the electrolyte that contains tetrafluoride aluminium salt, these capacitor element receipts are contained in the external shell of bottom tube-like, with being provided with that the sealing part that connects aforementioned cathode end and the rivet of the outside terminal open end to this housing seals and the electrolytic capacitor that forms, it is characterized in that: on the contact portion of aforementioned rivet and sealing part, form the ceramic coating layer.
Also have, for dividing plate being inserted between anode electrode paper tinsel with anode ejector and cathode electrode foil and winding up in the capacitor element of formation with negative electrode ejector, be full of the electrolyte that contains tetrafluoride aluminium salt, these capacitor element receipts are contained in the external shell of bottom tube-like, with being provided with that the sealing part that connects aforementioned cathode end and the rivet of the outside terminal open end to this housing seals and the electrolytic capacitor that forms, it is characterized in that: on aforementioned cathode end, form the ceramic coating layer.
The structure of aluminium electrolytic capacitor winds up formation capacitor element 1 by dividing plate with anode foils and Cathode Foil as shown in Figure 3.Be connected anode leading-out terminal 18, cathode end 19 respectively on this external anode foils and the Cathode Foil.
Anode foils adopts is after in acid solution the aluminium foil of purity more than 99.9% 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.
In addition, Cathode Foil and anode foils similarly adopt the aluminium foil of purity more than 99.9% are carried out etched electrode foil.Here with anode foils similarly, also can carry out the chemical conversion of 1~2V and handle.
Anode leading-out terminal 18, cathode end 19 use the aluminium foil of purity more than 99% respectively.
Then, will be embedded in by the rivet 14,15 that aluminium forms by elastomeric element subtends such as rigid insulation plate such as phenol resin laminated sheet and rubber slabs and fit and near the central portion of the sealing part 13 that forms.These rivets 14,15 are formed by round bar part 16 and head 17.
In the present invention, on the rivet 15 of cathode side, carry out the coating of ceramic coating layer.Just, spray the coating agent of forming by metal alkoxide system pottery, apply, carry out dried then, on aluminium conductor, form overlay by round bar part 16 to rivet 15.Wherein, prevent the leakage effect, then must on the round bar part at least 16 of rivet 15, form coating as if considering.In addition,, rivet is carried out chemical conversion handle, form anodic oxidation film from the teeth outwards, then can further use better if before coating.
About used here ceramic coating material and coating method, identical with first electrolytic capacitor.
The rivet of making according to the method described above 14,15 is embedded in by elastomeric elements such as rigid insulation plate such as phenol resin laminated sheet and rubber slabs and fits and near the central portion of the sealing part 13 that forms.On the head 17 of rivet 14,15, outside terminal 20 is set then,, fixes this outside terminal 20 by tightening up the end of rivet 14,15.
Here also can carry out same coating by target leading-out terminal 19, to replace cathode side rivet 15.
Then, as above in the capacitor element 1 of Gou Chenging, be full of the driving electrolytic solution of electrolytic capacitor.Electrolyte adopts and the same electrolyte of first electrolytic capacitor.
Electrode leads to client of the capacitor element that is full of electrolyte 1 as above is connected with the bottom of rivet 14,15, receives capacitor element 1 by the external shell made of aluminum 10 that bottom tube-like is arranged.Open end at external shell 10 inserts sealing part 13 then, and then deep-draw processing and crimping processing are carried out in the end of external shell 10, carries out sealing of electrolytic capacitor.
Even in this large-scale electrolytic capacitor, for the electrochemical relationship between aforesaid cathode terminal 5 and the Cathode Foil in the small electrical electrolysis condenser, think to be present in similarly between cathode side rivet 15 or cathode side leading-out terminal 19 and the Cathode Foil, thereby leakage takes place.On the other side, think in the present invention, because on cathode side rivet 15 or cathode side leading-out terminal 19, formed the ceramic coating layer, under load, non-loaded two sides' situation, electric current can not flow to cathode side rivet 15 or cathode side leading-out terminal 19, and leakage has obtained preventing.
More than electrolytic capacitor of the present invention have the high withstand voltage characteristic of low impedance characteristic and 100V level, the leakage characteristic is also good.Life characteristics at high temperature also is good in addition.
Below the 5th large-scale electrolytic capacitor is described.
Electrolytic capacitor of the present invention is a kind of by dividing plate being inserted between anode electrode paper tinsel with anode ejector and the cathode electrode foil with negative electrode ejector and winding up in the capacitor element of formation, be full of the electrolyte that contains tetrafluoride aluminium salt, these capacitor element receipts are contained in the external shell of bottom tube-like, with being provided with that the sealing part that connects aforementioned cathode end and the rivet of the outside terminal open end to this housing seals and the electrolytic capacitor that forms, it is characterized in that: on the contact portion of aforementioned rivet and sealing part, form the insulating properties synthetic resin layer.
Also have, for dividing plate being inserted between anode electrode paper tinsel with anode ejector and cathode electrode foil and winding up in the capacitor element of formation with negative electrode ejector, be full of the electrolyte that contains tetrafluoride aluminium salt, these capacitor element receipts are contained in the external shell of bottom tube-like, with being provided with that the sealing part that connects aforementioned cathode end and the rivet of the outside terminal open end to this housing seals and the electrolytic capacitor that forms, it is characterized in that: on aforementioned cathode end, form the insulating properties synthetic resin layer.
The structure of electrolytic capacitor is identical with the 4th electrolytic capacitor, in the present invention, on the rivet 15 of cathode side, carries out the coating of insulating properties synthetic resin layer.Just, spray the coating agent of forming by the synthetic resin material of insulating properties, apply, carry out dried then, on aluminium conductor, form overlay by round bar part 16 to rivet 15.Wherein, prevent the leakage effect, then must on the round bar part at least 16 of rivet 15, form coating as if considering.In addition,, rivet is carried out chemical conversion handle, form anodic oxidation film from the teeth outwards, then can further use better if before coating.
About used here insulating properties synthetic resin material and coating method, identical with second electrolytic capacitor.
The mechanism of the leakage of electrolyte is identical with the 4th electrolytic capacitor herein, in the present invention, because on cathode side rivet 15 or cathode side leading-out terminal 19, formed the insulating properties synthetic resin layer, under load, non-loaded two sides' situation, electric current can not flow to cathode side rivet 15 or cathode side leading-out terminal 19, and leakage has obtained preventing.
More than electrolytic capacitor of the present invention have the high withstand voltage characteristic of low impedance characteristic and 100V level, the leakage characteristic is also good.Life characteristics at high temperature also is good in addition.
And then, in first to the 5th electrolytic capacitor of the present invention,, use the electrode foil of handling through peroxophosphoric acid as electrode foil.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.
In addition, 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, phosphinic acid compounds such as 1-hydroxy ethylene-1,1-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.
(the 1st embodiment)
Below by enumerating embodiment first electrolytic capacitor of the present invention is described.Because the structure of electrolytic capacitor has and identical in the past structure, as shown in Figure 1 and Figure 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.
These lead-out wires the 4, the 5th are made of round bar part 6 that becomes one with the connecting portion 7 of electrode foil butt with this connecting portion 7 and the external connecting 8 that is fixed on round bar part 6 front ends.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 9 are installed, simultaneously by the end of external shell 10 being carried out deep-draw processing with sealing external shell 10.Seal body 9 is formed by elastic caoutchoucs such as for example butyl rubbers, and has the through hole of deriving lead- out wire 4,5 respectively.
Then, on the surface of the round bar part 6 of the aluminium conductor that is used for the negative electrode ejector, form the ceramic coating layer.By spraying Al to round bar part 6
2O
3And SiO
2The coating agent formed of metal alkoxide system pottery, 180 ℃ of 10 seconds of following heat treatment, and then after spraying aforementioned coating agent,, and then after 20 minutes, forming this ceramic coating layer 180 ℃ of following heat treatments once more 180 ℃ of 10 seconds of following heat treatment.
In addition, for electrolyte A, employing with γ-butyrolactone (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 γ-butyrolactone (80 parts) as solvent, dissolved with the electrolyte of 1-ethyl-2,3-methylimidazole tetrafluoride aluminium salt (20 parts) as solute.In addition, electrolyte C as a comparative example, employing, has been dissolved with the electrolyte of 1-ethyl-2,3-methylimidazole diphenate as solute as solvent with γ-butyrolactone (75 parts).
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)
(table 1-2)
(table 1-3)
(table 1-4)
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 in (table 1-3), (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.
(the 2nd embodiment)
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, and the electrolyte of use, evaluating characteristics content are also identical, in the present invention, on the surface as the round bar part 6 of the aluminium conductor of negative electrode ejector, forms the insulating properties film of synthetic resin.In 97 weight portion epoxy resin, mix 3 weight portion β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, by gunite, be coated on the round bar part after, dry this insulating properties synthetic resin layer that forms.Its result is shown in (table 2-1)~(table 2~4).
(table 2-1)
(table 2-2)
(table 2-3)
(table 2-4)
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 in (table 2-3), (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.
(the 3rd embodiment)
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 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.As a comparative example, use the butyl rubber polymer that the copolymer by isobutene and isoprene is formed to carry out the butyl rubber of quinoid sulfuration.
In addition, electrolyte is identical with first electrolytic capacitor.
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 1000 hours, 105 ℃, and 1000 hours are non-loaded.Its result is shown in (table 3-1)~(table 3~4).
(table 3-1)
(table 3-2)
(table 3-3)
(table 3-4)
As can be seen, compare with comparative example from (table 3-1), (table 3-2), 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 in (table 3-3), (table 3-4) 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.
(the 4th embodiment)
Below by enumerating embodiment the 4th large-scale electrolytic capacitor is described.As the structure of the electrolytic capacitor of embodiment 7 as shown in Figure 3, form capacitor element 1 by dividing plate being inserted between anode electrode paper tinsel and the cathode electrode foil and winding up.In addition, anode electrode paper tinsel, cathode electrode foil are connected with anode leading-out terminal 18, cathode end 19 respectively.
The anode electrode paper tinsel adopts is after in acid solution the aluminium foil of purity more than 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.
In addition, cathode electrode foil and anode electrode paper tinsel similarly adopt the aluminium foil to purity 99.9% to carry out etching, carry out the electrode foil that chemical conversion is handled under 1V.
Anode leading-out terminal 18, cathode end 19 adopt 99% aluminium foil.
In capacitor element 1 as constituted above, be full of the electrolyte that electrolytic capacitor drives usefulness.
Form the rivet of making by 99% aluminium, contain round bar part 16 and head 17 14,15 then.
On the surface of rivet 15 round bar parts 16 of cathode side, form the ceramic coating layer of embodiment 3 then.
Then, rivet 14,15 is embedded in by elastomeric elements such as rigid insulation plate such as phenol resin laminated sheet and rubber slabs and fits and near the central portion of the sealing part 13 that forms.Outside terminal 20 is set on head 17 then,, fixes this outside terminal 20 by tightening up the end of rivet 14,15.
In addition, as embodiment 8, on the surface of cathode end 19, form the ceramic coating layer, to replace the round bar part 16 of cathode side rivet 15.
In addition, about above-mentioned electrolyte and ceramic coating layer, identical with first electrolytic capacitor.
Then, the electrode leads to client of capacitor element 1 son and after the bottom of rivet 14,15 is connected, by the external shell made of aluminum 10 receipts capacitor elements 1 that bottom tube-like is arranged.
Open end at external shell 10 inserts sealing part 13 then, and then deep-draw processing and crimping processing are carried out in the end of external shell 10, carries out sealing of electrolytic capacitor.
As above the electrolytic capacitor of Gou Chenging compares with electrolytic capacitor 5, do not form the ceramic coating layer on rivet as a comparative example.Condition is passed judgment on the having or not of leakage of electrolyte afterwards for to reach 2000 hours at 105 ℃ of following load 16V.Its result is shown in table (4-1).In addition, placed 2000 hours down, similarly the having or not of leakage of electrolyte passed judgment at 105 ℃.Its result is shown in table (4-2).
(table 4-1)
|
Electrolyte |
Overlay |
Leakage |
Embodiment 7 |
A |
The negative electrode rivet |
0/25 |
Embodiment 8 |
A |
Cathode end |
0/25 |
Comparative example 5 |
C |
- |
5/25 |
(table 4-2)
|
Electrolyte |
Overlay |
Leakage |
Embodiment 7 |
A |
The negative electrode rivet |
0/25 |
Embodiment 8 |
A |
Cathode end |
0/25 |
Comparative example 5 |
C |
- |
5/25 |
As can be seen, under the situation aspect the load, non-loaded two, leakage does not take place in the present invention from (table 4-1), (table 4-2).
(the 5th embodiment)
Below by enumerating embodiment the 5th large-scale electrolytic capacitor is described.The structure of electrolytic capacitor is identical with the 4th electrolytic capacitor, in the present invention, on the surface of rivet 15 round bar parts 16 of cathode side, forms the insulating properties synthetic resin layer of embodiment 9.
In addition, as embodiment 10, on the surface of cathode end 19, form the insulating properties synthetic resin layer, to replace the round bar part 16 of cathode side rivet 15.As a comparative example 6, except not forming on the rivet the insulating properties synthetic resin layer, all the other and embodiment 9,10 similarly constitute electrolytic capacitor, are used for comparison.
In addition, identical with second electrolytic capacitor about above-mentioned electrolyte and insulating properties synthetic resin layer, the evaluating characteristics content is identical with the 4th electrolytic capacitor.Its result is shown in (table 5-1), (table 5~2).
(table 5-1)
|
Electrolyte |
Overlay |
Leakage |
Embodiment 9 |
A |
The negative electrode rivet |
0/25 |
Embodiment 10 |
A |
Cathode end |
0/25 |
Comparative example 6 |
C |
- |
5/25 |
(table 5-2)
|
Electrolyte |
Overlay |
Leakage |
Embodiment 9 |
A |
The negative electrode rivet |
0/25 |
Embodiment 10 |
A |
Cathode end |
0/25 |
Comparative example 6 |
C |
- |
5/25 |
As can be seen, under the situation aspect the load, non-loaded two, leakage does not all take place in the application's invention from (table 5-1), (table 5-2).
Thus, in first to the 5th above electrolytic capacitor, when using the electrode foil handled through peroxophosphoric acid as anode electrode paper tinsel or catholyte paper tinsel, life characteristics at high temperature further improves, and can also further improve life characteristics at high temperature if add phosphorus compound in electrolyte.