CN100511514C - Metal foil for capacitor, solid electrolytic capacitor using the foil and production methods of the foil and the capacitor - Google Patents
Metal foil for capacitor, solid electrolytic capacitor using the foil and production methods of the foil and the capacitor Download PDFInfo
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- CN100511514C CN100511514C CNB038205831A CN03820583A CN100511514C CN 100511514 C CN100511514 C CN 100511514C CN B038205831 A CNB038205831 A CN B038205831A CN 03820583 A CN03820583 A CN 03820583A CN 100511514 C CN100511514 C CN 100511514C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
Abstract
A metal foil for capacitor element is produced through a process comprising steps of etching and then electrochemically forming a metal foil after making cut lines each in a shape of a capacitor element with at least a part of a portion predetermined to be an anode-leading-outpart left uncut. The step of etching the foil is preferably performed with the anode-leading-out-parts being protected by protective material. Solid electrolytic capacitor elements prepared by using the metal foil have narrow variation in capacitance.
Description
The cross reference of related application
The application according to 35 U.S.C.119 (e) (1), requires the right according to the submission day that is defined in the provisional application of submitting on September 5th, 2,002 60/407,974 of 35 U.S.C.111 (b) based on the regulation of 35 U.S.C.111 (a).
Technical field
The present invention relates to a kind of production method (described tinsel be used for use capacitor) of tinsel and the capacitor that uses this paillon foil to produce at various electronic instruments.More specifically, the present invention relates to the method and the solid electrolytic capacitor that uses the tinsel that obtains by this method that a kind of etching and electrochemistry are formed for the tinsel of multi-layer solid electrolytic capacitor.
Background technology
Chip class or Small electronic component are developing rapidly with the miniaturization that solves electronic instrument, the High Density Packaging of printed panel, the raising of packaging efficiency etc.Be accompanied by above-mentioned development, improve producing as the chip class of element or the demand of small electrical electrolysis condenser.From this point and consider easy operability, the development and the popularization of the solid electrolytic capacitor of electrolytic solution have appearred rapidly not using in recent years.
Usually, chip class solid electrolytic capacitor is by forming the oxide dielectric film on etched valve acting (valveacting) tinsel, and form grooving (all with the element form) thereon (referring to JP-A-5-283304, the meaning of term used herein " JP-A " is " not examining open Japanese patent application "), or by wherein being installed on the metallic carrier at the paillon foil that each is cut into component shape, and form the cathode conductive layer that comprises carbon paste and silver paste thereon after forming solid electrolyte thereon, and formation is with the method formation of the housing parts of integrally closed.
In the metal such as aluminium, tantalum, niobium and titanium of valve acting, aluminium is favourable, because it is easy to by etch processes surface area be increased, and can be with by using aluminium to be used as dielectric material as the sull that the anodization (electrochemistry formations) of anode forms from the teeth outwards, therefore compare with other capacitor, can under low cost, produce small capacitor with big electric capacity.According to these characteristics, be extensive use of the solid aluminium electrolytic capacitor that is used in particular for low-voltage.
At present, the electrode foil plate that is used for solid aluminium electrolytic capacitor is an aluminium foil, and to increase surface area, the shape and the electrochemistry that then it are struck out product sample form the crop part with described aluminium foil electrochemistry or chemical etching.
The method of etching aluminium foil comprises DC (direct current) electrolytic etching method (wherein comprising in the electrolytic solution of the chloride ion-containing aqueous solution that wherein adds phosphoric acid, sulfuric acid, nitric acid etc., using aluminium foil as anodal and make the DC electric current by with etching aluminum foil with the electrode of aluminium foil placed adjacent as negative pole); And AC (alternating current) electrolytic etching method, wherein comprising in the electrolytic solution of the aqueous solution of the chloride ion-containing that wherein adds materials such as phosphoric acid, sulfuric acid, nitric acid, electrode (supply indirectly) or aluminium foil and each electrode of placing on its both sides (directly supply) that the AC electric current is placed by the aluminium foil both sides are with etching aluminum foil).
In the DC electrolytic etching, forming the erosion trace of channel-like in the crystalline orientation in the etched while.On the other hand, in the etching of AC current electroanalysis, form the erosion trace that is linked in sequence with random direction as beading simultaneously etched, and this is favourable for increasing surface area (area increase).Therefore, be the etching aluminium foil, mainly carry out the AC electrolytic etching; However, also proposed the method for described two kinds of methods combination and improved AC voltage method (referring to JP-A-11-307400) gradually.In addition, also proposed to comprise and regulated AC waveform, amplitude etc. with the method (JP-A-7-235456) improving effective area and increase with wherein use and comprise the method (JP-A-7-169657) of aluminium of corroding particulate metal of starting point as etching.
After the tinsel of the valve acting that the metal forming chip of valve acting is formed porous by chemical etching or after forming dielectric layer thereon, when paillon foil is cut into the shape of capacitor element, can produce the crack near the porous layer that cut surface, forms, and in the crop part, produce burr and cause this part roughening by etching.
These cracks that produce on the surface, cut edge when cutting, burr etc. will cause the capacitor specific characteristics deterioration.
In conducting polymer being connected on the paillon foil with the step that forms cathode portion, in order to suppress to move to the anode leader branch on the Treatment Solution, the interface between anode extension and the cathode portion applies shelters.But conducting polymer is easy to spread to outside the masking material towards anode part, and this causes leakage current to increase.
WO 02/063645 has proposed a kind of method, wherein forms etch layer on the surface, cut edge of the paillon foil that is cut into the capacitor element shape by electrolytic etching, and will dissolve at the burr on the part of cut edge simultaneously.But, in said method, etching may be confined on the crop part of paillon foil, and this makes that being difficult to Control current distributes, and the problem that comprises another, promptly make the cut edge be partly dissolved or make the intensity of described part to descend so fast, be difficult to a large amount of etched paillon foils of producing with stability property so that reduced the effective area of element.
Summary of the invention
The purpose of this invention is to provide the paillon foil that a kind of chemistry of the capacitor that is used to produce the homogeneous shape with narrow capacitance variations forms and the production method of this paillon foil.
Another object of the present invention provides capacitor element and the production method thereof of using this paillon foil.
The inventor has finished the present invention based on following discovery, the production that promptly has the employed tinsel of capacitor of narrow capacitance variations can realize by the method that may further comprise the steps: mark in the tinsel material of valve acting and manyly have the line of cut of predetermined minute widths so that each cutting part has the shape of capacitor element anode, thereby produce a large amount of capacitor elements simultaneously; With tinsel surface and cut edge surface etching; With carry out electrochemistry and form.
And; the inventor finds; carrying out etching after the part that etch layer can only divide by the anode leader that adopts protective materials protection will becoming capacitor element on the part that will become cathode portion forms; so that conducting polymer is connected in the step of cathode portion subsequently; anode leader divides and can suppress move on the Treatment Solution by sheltering satisfactorily, and can realize having stable electric capacity thus and the production of the capacitor of the characteristic of the leakage current that reduced.
More particularly, the present invention relates to the following production method that is used for the tinsel of the valve acting of capacitor, the solid electrolytic capacitor that uses this paillon foil and paillon foil and capacitor:
1) a kind of production method that is used for the tinsel of capacitor, it is included in the line of cut of the shape that marks capacitor element in the tinsel of valve acting and the small part that arrives is predefined for the uncut step of part that anode leader is divided, the surface portion of the tinsel of surface, the cut edge that produces in the abovementioned steps and valve acting is carried out the step of etched step and electrochemistry formation tinsel;
2), wherein be etched in and adopt protective materials will be predefined for part that the capacitor element anode leader divides to carry out after protecting as the above 1 described production method that is used for the tinsel of capacitor;
3) as the above 2 described production methods that are used for the tinsel of capacitor, wherein after etching, remove protective materials, carry out electrochemistry then and form step;
4), wherein after forming, the electrochemistry of etched paillon foil removes protective materials as the above 2 described production methods that are used for the tinsel of capacitor;
5) as the above 2 described production methods that are used for the tinsel of capacitor, wherein after etching, remove protective materials, and in that carry out will become before the step that forms of the electrochemistry in zone of cathode portion, the antianode extension and it on formation shelter as the interface between the zone with solid electrolytic layer of cathode portion;
6) as each described production method that is used for the tinsel of capacitor among the above 1-3, wherein each cutting part is to contain not quadrangle, U-shaped (shape of a hoof) or the semicircle of cutting part;
7) as the above 1 described production method that is used for the tinsel of capacitor, wherein the surface, cut edge is 30 ° or bigger with respect to the interior acute angle A on tinsel surface;
8) as the above 1 described production method that is used for the tinsel of capacitor, wherein line of cut width d is 2 times of tinsel thickness or still less;
9), wherein produce a plurality of tinsels that are used for capacitor with single batch of method by a plurality of lines of cut that in the tinsel of a valve acting, mark each shape that all has capacitor element as the above 1 described production method that is used for the tinsel of capacitor;
10) as the above 1 described production method that is used for the tinsel of capacitor, wherein paillon foil comprises at least a metal that is selected from the valve acting of aluminium, niobium and tantalum;
11) as the above 1 described production method that is used for the tinsel of capacitor, wherein the thickness of the tinsel of valve acting is 0.05-1mm;
12) as the above 1 described production method that is used for the tinsel of capacitor, wherein the tinsel of valve acting is the aluminium foil that contains the element of at least a Si of being selected from, Fe, Cu, Zn, Ni, Mn, Ti, Pb, B, P, V and Zr;
13), wherein except aluminium, with regard to atom, be 1-1,000 quality ppm at the total content of contained element in the paillon foil as the above 12 described production methods that are used for the tinsel of capacitor;
14) as the above 12 described production methods that are used for the tinsel of capacitor, wherein aluminium foil contains the Fe of Si, 1-100 quality ppm of 1-100 quality ppm and the Cu of 1-100 quality ppm;
15) as the above 1 described production method that is used for the tinsel of capacitor, wherein etching is to use the AC electrolytic etching of at least a waveform that is selected from sine wave, square wave and triangular wave;
16) as the above 1 described production method that is used for the tinsel of capacitor, wherein etching is the AC electrolytic etching, wherein on the metal of valve acting and placing on the electrode of metal both sides of valve acting terminal is provided, and the terminal that provides on the metal of valve acting directly is provided the AC electric current;
17) as the above 1 described production method that is used for the tinsel of capacitor, wherein etching is the DC electrolytic etching;
18) tinsel that is used for capacitor that obtains by each described production method among the above 1-17;
19) as the above 18 described tinsels that are used for capacitor, the radius of curvature r of a side that wherein will become the part of negative electrode is 0.1-500 μ m;
20) as the above 18 described tinsels that are used for capacitor, be included in the surface of tinsel and the porous layer on the surface, cut edge, described porous layer is formed at and will forms on the part of solid electrolyte, wherein the porous layer thickness T 2 on the surface, cut edge is greater than 1 μ m, and has following relation with porous layer thickness T 1 on the surface of tinsel:
T2/T1≤2；
21) a kind of solid electrolytic capacitor element is included in successively as solid electrolyte layer and conductive layer on each described tinsel among the above 18-20;
22) as above 21 described solid electrolytic capacitor element, wherein solid electrolyte layer comprises conducting polymer;
23) as above 22 described solid electrolytic capacitor element, the monomer that wherein forms conducting polymer is the monomeric compound that contains the monomeric compound of 5 Yuans rings of heterocycle or contain the aniline skeleton;
24) as above 23 described solid electrolytic capacitor element, the monomeric compound that wherein contains 5 Yuans rings of heterocycle is the compound that is selected from pyrroles, thiophene, furans, many episulfide and substitutive derivative thereof;
25) as above 23 described solid electrolytic capacitor element, the monomeric compound that wherein contains 5 Yuans rings of heterocycle is the compound by following formula (I) expression:
Wherein, substituent R
1And R
2Represent monoradical independently of one another, described monoradical is selected from hydrogen atom, have the straight chain of 1-10 carbon or branching, saturated or undersaturated hydrocarbyl group, oxyl, alkyl ester group, halogen, nitro, cyano group, primary, the second month in a season or uncle's amino, CF
3Group, phenyl and substituted-phenyl, R
1And R
2Hydrocarbon chain can locate at an arbitrary position to be bonded to each other be formed for by radicals R
1And R
2The carbon atom that is replaced forms the divalence chain of the saturated or unsaturated hydrocarbons ring structure of at least one 3-, 4-, 5-, 6-or 7-person together, and the loop chain of combination can contain the key of carbonyl, ether, ester, acid amides, sulfide, sulfinyl, sulfonyl or imino group arbitrarily;
26) as above 23 described solid electrolytic capacitor element, the monomeric compound that wherein contains 5 Yuans rings of heterocycle is for being selected from 3,4-ethylidene dioxy thiophene and 1, the compound of 3-dihydro isothianaphthene;
27) by multi-layer solid electrolytic capacitor as a plurality of capacitor elements stacks being obtained as described in above 21;
28) a kind of production method of solid electrolytic capacitor is included in the line of cut that marks each shape that all has capacitor element in the tinsel of valve acting and the small part that arrives is predefined for the uncut step of part that anode leader is divided; Etched step is carried out on surface to the tinsel of surface, the cut edge that produces in the abovementioned steps and valve acting; Electrochemistry formed etched tinsel to form the step of oxide dielectric film after the paillon foil part of wherein all cutting with component shape paillon foil being cut into each bar that is pectination linked together in anode leader is divided; On the oxide dielectric thin layer, form the step of solid electrolyte layer; On solid electrolyte layer, form the step of conductive layer; And by in the anode leader of each piece is divided, cutting the step of paillon foil piece that is the shape of capacitor element with use
The accompanying drawing summary
Fig. 1 is the schematic diagram of the production method of the explanation tinsel that is used for capacitor of the present invention.
Fig. 1 (A) be expression in order to prepare a plurality of capacitor elements by a tinsel, have a plurality of each all have the state diagram of tinsel of valve acting of the line of cut of capacitor element shape.
Fig. 1 (B) is the state diagram of tinsel of the valve acting of Fig. 1 (A) with part that the anode leader that is predefined for capacitor element divides of expression, and described anode leader is divided and adopted protective materials to protect.
Fig. 1 (C) is the state diagram of tinsel of the valve acting of presentation graphs 1 (B), and the part of after the whole paillon foil of etching protective materials being divided from the anode leader that becomes capacitor element is removed.
Fig. 1 (D) is illustrated in the state diagram of cutting away the cathode portion of the capacitor element that electrochemistry forms after the tinsel of valve acting of Fig. 1 (C) with the shape of comb.
Fig. 2 is the enlarged drawing that is illustrated in the Fig. 1 (A) that cuts with the capacitor element shape in the tinsel of valve acting.
Fig. 3 is the viewgraph of cross-section of the x-x of Fig. 2.
Fig. 4 is the viewgraph of cross-section of solid electrolytic capacitor element of the present invention.
Fig. 5 is the viewgraph of cross-section by an embodiment of the multi-layer solid electrolytic capacitor of solid electrolytic capacitor element preparation of the present invention.
Detailed Description Of The Invention
Method of the present invention is described below.
(1) metal of valve acting
The tinsel that is used for valve acting of the present invention is the tinsel with valve action, such as aluminium, niobium, tantalum, aluminium alloy, niobium alloy and tantalum alloy. Be used for metal of the present invention and can be the form of plate and paillon foil. Preferred example comprises the paillon foil that can be used as the aluminum or aluminum alloy that volume or plate be purchased. If thickness can guarantee that after etching then this thickness is enough in the scope of the intensity that aluminium foil is enough. For example, thickness can be 0.05-1mm, preferred 0.08-0.4mm, more preferably 0.1-0.2mm.
Aluminium can contain the element of at least a Si of being selected from, Fe, Cu, Zn, Ni, Mn, Ti, Pb, B, P, V and Zr, and the amount of every kind of described element that preferred aluminium contains is 1-100 quality ppm, more preferably 10-50 quality ppm (based on the total amount of aluminium foil), condition is that the total amount of these elements is 1-1,000 quality ppm.
Especially, preferably contain the aluminium of the Cu of the Fe of Si, 1-100 quality ppm of 1-100 quality ppm and 1-100 quality ppm, and more preferably contain the aluminium of the Cu of the Fe of Si, 10-50 quality ppm of 10-50 quality ppm and 10-50 quality ppm.
The example of the aluminium alloy that mainly is made of aluminium comprises in aluminium and silicon, titanium, zirconium, tantalum, niobium and the hafnium one or more alloy.
There is no particular restriction for the size of the tinsel of the initial valve acting that cuts, as long as enough a plurality of for example like tabular capacitor element preparing greatly. Especially, the tinsel of valve acting preferably has for the enough large size of the capacitor element that takes out a plurality of fuel plates unit, each width of described cell is that 1-50mm and length are 1-50mm, more preferably width is that 2-20mm and length are 2-20mm, and more preferably width is that 2-5mm and length are 2-6mm.
(2) form line of cut
By the step of making line of cut in paillon foil is described with reference to the drawings.
In the embodiment shown in Fig. 1 (A), form and have predetermined live width and each all forms the line of cut (grooving) 5 of the shape of capacitor element in order to be amounted to 30 (in 10 row * 3 row) by a paillon foil (plate) preparation, at least part ofly will become the part that anode leader divides and not cut.
Enlarged drawing such as Fig. 1 (A) is shown in Figure 2, marks line of cut (grooving) 5, and stays and be predefined for that anode leader is divided or do not cut in the part 2 of final capacitor element Anodic outflow of bus current. In this embodiment, line of cut is the square shape of opening wide (not cutting) on one side, but line of cut can have any shape, is angled or circular quadrangle, U-shaped (shape of a hoof) and semicircle such as its turning, as long as it can form capacitor element. In Fig. 2, only shown a line of cut, but can be on the tinsel of valve acting simultaneously or form many lines of cut in batches, and the arrangement of line of cut to be not limited to shown in Fig. 1 (A) that a kind of, as long as in the step of back, do not have problems.
Fig. 3 is that expression is along the schematic diagram of the cross section of the x-x among Fig. 2. Line of cut width d (in the different situation of width between the forward and backward surface of paillon foil, d represents less width) should be the twice of foil thickness or less. For example, when electrolytic etching, because the meltage of the metal of valve acting mainly controls by electric weight, and the shape of the hole that forms in engraving method and groove affects by current density to a great extent, and it is important suitably regulating electric current.
In the engraving method that electricity consumption is directly supplied (wherein the tinsel at valve acting provides terminal), electric current back and forth flows between paillon foil and counterelectrode. Therefore, if paillon foil and electrode are parallel to each other, then electric current flows in the vertical direction of paillon foil and electrode surface. But, having at paillon foil in the situation of line of cut, electric current is not vertical directly flow but flow to cut edge or the cutting surfaces of line of cut. On the other hand, the route of current direction resistance decreasing. That is, the electric current that distributes near the electrode part the line of cut tends in the smooth surface that does not flow to paillon foil, and flows to cut edge or the cutting surfaces of line of cut. Therefore, line of cut is wider, and more electric currents concentrate on the cut edge with strong etching cut edge.
Foil surfaces is long-pending to be reduced by the line of cut width that forms on it, and strengthens by cutting surfaces is long-pending. That is, line of cut is narrower, and the cut edge and the electric current on the cutting surfaces that concentrate on line of cut are fewer, therefore suppresses the cut edge excessive dissolution.
Particularly, the thickness of supposing paillon foil is that t and line of cut width are d, if the cut edge Surface Vertical forms in the plane of paillon foil, the value that the paillon foil total surface area reduces is that the value of 2d and increase is 2t. Value added " 2t " than reduction value " 2d " is large must be more many, electric current more may concentrate on the cut edge. In order to suppress the excessive dissolution on surface, cut edge, preferred reduction value (2d) is the twice of value added (2t) or still less, i.e. 2t * 2 〉=2d. In other words, width d is that being formed with of the twice of foil thickness t or line of cut still less helps alleviate electric current and converge, thereby suppresses the excessive dissolution on surface, cut edge.
Usually, be used for tinsel of the present invention be 1mm or still less, preferred 0.4mm or still less, more preferably 0.2mm or still less. Therefore, the line of cut width be 2mm or still less, preferred 0.8mm or still less, more preferably 0.4mm or still less. If width surpasses 2mm, electric current concentrates on surface, cut edge and the dissolving of cut edge surface local, causes the element effective area to reduce with final electric capacity and reduces.
Line of cut can be for example by using cutter cutting, Thomson blade cuts, mold punching press or laser cutting to form. Cutting is carried out at a certain angle so that any one becomes interior obtuse angle in the front surface of paillon foil and the rear surface with cutting surfaces, acute angle A (in the embodiment depicted in fig. 3 in another surface became with cutting surfaces simultaneously, the front surface of paillon foil becomes interior obtuse angle with cutting surfaces, acute angle in the rear surface becomes with cutting surfaces simultaneously). In the present invention, acute angle A be preferably 30 ° or larger, more preferably 50 ° or larger. If angle is less than 30 °, etching partly begins to carry out from sharpened edge, and this part excessive dissolution, and the result has reduced effective area, and this causes wider capacitance variations scope.
(3) etching
After the tinsel of valve acting forms line of cut, when the etching metal paillon foil, by whole tinsel is immersed by carrying out etching in the electrolytic solution that adds the preparations such as phosphoric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid in the aqueous solution of chloride ion-containing.
Being used for etched electrolytic solution is the solution that contains at least chlorion, and can be to the solution of the solution that wherein adds at least a sulphate-containing ion, phosphate anion, acetate ion, oxalate denominationby etc. and other alkali metal containing ion or alkaline-earth metal ions.
In the embodiment as shown in Fig. 1 (B); tinsel to single valve acting carries out etch processes; wherein mark 30 lines of cut 5 of each shape of all taking capacitor element with the arrangement of 3 row * 10 row, preferably adopt protective materials to protect 4a to being predefined for the part 2 that capacitor element divides with anode leader. The conservation treatment of employing protective materials can be such as the required forward and backward surface that imposes on paillon foil. This conservation treatment helps to reduce the defective goods ratio of getting an electric shock and causing owing to poor electricity in the process of the multi-layer solid electrolytic capacitor that a plurality of capacitor elements stacks are consisted of.
The protective materials that is used for etching step can be any material, if its can closely be connected to valve acting tinsel (such as aluminium foil) but upper and stable existence on the part that will protect and do not react with electrolytic solution (etching solution). The example of protective materials comprises acrylic resin, polyethylene sheets and anticorrosive additive material. The square rod of placing described material to be clamping relative section and to adopt pressure sensitive adhesive tape to be fixed, or described material is coated on the described part. The tinsel of using this protective materials is immersed electrolytic solution carry out etching, then as shown in Fig. 1 (C), protective materials is removed.
It is 1-1 that etching preferably is etched in frequency by AC, and 000Hz, current density are 0.025-4A/cm2And the etching electricity is 0.02-2,000C/cm2Condition under carry out. The preferred current density that increases gradually the AC electric current is carried out thereafter the AC electrolytic etching under constant electric current.
In the situation of AC electric current, electric current preferably has at least a waveform that for example comprises sinusoidal wave, triangular wave and square wave.
And, can be by at first carrying out the DC electrolytic etching, then carrying out the AC electrolytic etching and be combined with DC electrolytic etching and AC electrolytic etching. Also can only carry out etching by the DC electrolytic etching.
No matter use etching mode any of AC, DC or its combination, must make the electric current of input make the metal of valve acting play the electrode opposite with the electrode that places its both sides.
Etching is preferably undertaken by AC electrolytic etching method, wherein on the metal of valve acting and the electrode on the metal both sides that place valve acting terminal is provided, and alternating current directly is input between the metal and electrolysis of valve acting. According to the method, also etching cutting surfaces suitably.
After electrolytic etching, wash to remove the composition of electrolytic solution. Especially, in order to reduce residual chlorion, can after adopting the clean metal paillon foils such as salpeter solution, sodium aluminate solution, aluminium hydroxide solution, wash. Tinsel can further adopt to contain and be useful on the solution cleaning that forms the electrolytic solution of dielectric film by anodization.
And, can use chemical etching to increase surface area. In chemical etching, can use nitric acid, iron chloride etc.
In the tinsel that so obtains, the radius of curvature that the surface, cut edge has is 0.1-500 μ m, preferred 1-100 μ m, more preferably 2-50 μ m. If radius of curvature is less than 0.1 μ m, the surface, cut edge can not show the effect as curved surface, can not reduce electric leakage.
Porous layer thickness T 2 is preferably the twice of porous layer thickness T 1 in the tinsel plane surface or still less in the cut edge that obtains by etching. If T2 exceeds the twice of T1, the etch layer strength decreased in the cutting surfaces, and in etch layer owing to producing the crack in stack or the produced simultaneously pressure of sealed capacitor element. Fig. 1 (B) expression anode extension 2 is used the situation of protective materials 4a, and in the situation of the protection of not implementing to adopt protective materials, also divides on 2 in anode leader to form porous layer by etching.
(4) electrochemistry forms
If when etch processes, apply protective materials, can subsequently it be removed as shown in Fig. 1 (C). Then as shown in Fig. 1 (D), the tinsel of etched valve acting is cut into the metal forming slip 10 (aluminum foil strip of pectination) of pectination, then, with whole or at least zone 6 (everywhere all is predefined for has the solid electrolyte that forms cathode portion thereon, namely divides the part of 2 part (with following) shown in Fig. 2 except becoming anode leader) carry out electrochemistry and form. In addition, electrochemistry forms and can remove protective materials and to dividing 2 and form in the step in the back to apply as the interface portion between the zone of the solid electrolyte of cathode portion and carry out after sheltering thereon in anode leader, or can carry out in the situation of not removing protective materials.
Electrochemistry forms and can be undertaken by the whole bag of tricks, and there is no particular restriction to carry out condition that electrochemistry forms. For example, electrochemistry forms the electrolytic solution that can contain by use at least a ion such as oxalate, adipic acid root, borate or phosphate radical, is 0.05-20 quality % in electrolytic solution concentration, and temperature is 20-90 ℃, and current density is 0.01-600mA/cm2, voltage is to carry out under the condition of the electrochemistry that depends on the paillon foil of the processing numerical value that forms voltage. It is that 0.1-15 quality %, temperature are that 40-85 ℃, current density are 0.05-100mA/cm that condition preferably makes electrolytic solution concentration2。
After electrochemistry forms, if necessary, can carry out for example heat treatment of the impregnation process in phosphoric acid to improve water proofing property or film is strengthened.
By above treatment step, obtain the tinsel of valve acting of the present invention.
(5) shelter
Then, solid electrolyte is formed cathode portion.If necessary, implement to shelter 4b as preliminary treatment.Thereby shelter and have the Treatment Solution of preventing and on forming dielectric substrate and forming in the step of conductive layer, move on to the effect that the part of being sheltered insulate conductive layer (cathode portion) fully with anode part.
Operable masking material is general heat stable resin, preferably is dissolved in heat stable resin, its precursor that solvent maybe can adopt solvent swell or comprises inorganic powder and based on the composition (referring to JP-A-11-80596) of cellulosic resin.
Its example comprises PPSU (PPS), polyether sulfone (PES), cyanate ester resin, fluororesin (tetrafluoroethene, tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer etc.), low-molecular-weight polyimides and derivative thereof.Wherein preferred low-molecular-weight polyimides, polyether sulfone, fluororesin and precursor thereof, and more preferably low-molecular-weight polyimides.
With solution or the dispersion solution linear coating of above-mentioned material, make its thermal deformation form polymer by heat treatment, then with its curing as organic solvent.
Can implement to shelter by any method that polypropylene, polyester, silicone, the fluorine technology is propped up or analog is made band are adhered to up or the method that forms the resinous coat film portion.
Interface portion between the zone 3 of antianode extension 2 and formation solid electrolyte 7 applies shelters.
(6) formation of solid electrolyte
To the conducting polymer of the solid electrolyte that is formed for solid electrolytic capacitor of the present invention and unrestricted, but the preferred conducting polymer that uses, its example with pi-electron conjugated structure comprise as repetitive contain by the compound with thiophene skeleton, have many episulfide skeleton compound, have the compound of pyrrole skeleton, the conducting polymer that has the compound of furans skeleton or have the structure shown in the compound of aniline skeleton.
In the monomer of the starting material that is used as conducting polymer, the example with compound of thiophene skeleton comprises the compound of being represented by formula (I):
(wherein, substituent R
1And R
2Represent monoradical independently of one another, described monoradical is selected from hydrogen atom, have the straight chain of 1-10 carbon or branching, saturated or undersaturated hydrocarbyl group, oxyl, alkyl ester group, halogen, nitro, cyano group, primary, the second month in a season or uncle's amino, CF
3Group, phenyl and substituted-phenyl, R
1And R
2Hydrocarbon chain can locate at an arbitrary position to be bonded to each other and be formed for forming the divalence chain of the saturated or unsaturated hydrocarbons ring structure of at least one 3-, 4-, 5-, 6-or 7-person with the carbon atom that is replaced by radicals R 1 and R2, and the loop chain of combination can contain the key of carbonyl, ether, ester, acid amides, sulfide, sulfinyl, sulfonyl or imino group arbitrarily).
Its object lesson comprises such as 3 methyl thiophene, 3-ethylthiophene, 3-propyl group thiophene, 3-butyl thiophene, 3-amylic thiophene, 3-hexyl thiophene, 3-heptyl thiophene, 3-octyl group thiophene, 3-nonyl thiophene, 3-decylthiophene, 3-fluorine thiophene, 3-chlorothiophene, 3 bromo thiophene, 3-cyano thiophene, 3,4-thioxene, 3,4-diethyl thiophene, 3,4-butylidene thiophene, 3,4-methylene dioxy thiophene and 3, the derivative of 4-ethylidene dioxy thiophene.But these compounds can be the compound of buying on market, maybe can pass through known method (as at Synthetic Metals, the 15th volume, the method described in the 169th page (1986)) preparation.
Object lesson with compound of many episulfide skeleton comprises having 1, the compound of the many episulfide of 3-dihydro (being called 1 again, 3-dihydrobenzo [c] thiophene) skeleton and have 1, the compound of 3-dihydro-naphtho [2,3-c] thiophene skeleton.In addition, can use to have 1, the compound of 3-dihydro anthra [2,3-c] thiophene skeleton and have 1,3-dihydro aphthacene is the compound of [2,3-c] thiophene skeleton also.These compounds can pass through known method, the method preparation described in JP-A-8-3156.
In addition, can also use for example to have 1 the compound, 1 of 3-dihydro-naphtho [1,2-c] thiophene skeleton, 3-dihydro phenanthro-[2,3-c] thiophene derivant, have 1,3-dihydro three benzos [2,3-c] compound and 1 of thiophene skeleton, 3-dihydrobenzo [a] anthra [7,8-c] thiophene derivant.
Also can use the compound that in condensed ring, contains nitrogen or N-oxide arbitrarily, and its example comprises 1, the 3-dihydro-thiophene is [3,4-b] quinoxaline, 1 also, 3-dihydro-thiophene also [3,4-b] quinoxaline-4-oxide and 1, the 3-dihydro-thiophene is [3,4-b] quinoxaline-4 also, the 9-dioxide, but the present invention is not limited to this.
Object lesson with compound of pyrrole skeleton comprises such as 3-methylpyrrole, 3-N-ethyl pyrrole N-, 3-propyl pyrrole, 3-butyl pyrroles, 3-amyl group pyrroles, 3-hexyl pyrroles, 3-heptyl pyrroles, 3-octyl group pyrroles, 3-nonyl pyrroles, 3-decyl pyrroles, 3-fluorine pyrroles, 3-chlorine pyrroles, 3-bromine pyrroles, 3-cyanopyrrole, 3,4-dimethyl pyrrole, 3,4-diethyl pyrroles, 3,4-butylidene pyrroles, 3,4-methylene dioxy pyrroles and 3,4-ethylidene dioxy pyrroles's derivative, but the present invention is not limited to this.These compounds are commercially available compound, maybe can prepare by known method.
Object lesson with compound of furans skeleton comprises such as 3-methylfuran, 3-ethyl furan, 3-propyl group furans, 3-butyl furans, 3-pentyl furan, 3-hexylfuran, 3-heptyl furans, 3-octyl group furans, 3-nonyl furans, 3-decyl furans, 3-fluorine furans, 3-chlorine furans, 3-bromine furans, 3-cyano group furans, 3,4-dimethyl furan, 3,4-diethyl furans, 3,4-butylidene furans, 3,4-methylene dioxy furans and 3, the derivative of 4-ethylidene dioxy furans, but the present invention is not limited to this.These compounds are commercially available compound, maybe can prepare by known method.
Object lesson with compound of aniline skeleton comprises such as 2-aminotoluene, 2-MEA, 2-propyl group aniline, 2-butylaniline, 2-amyl aniline, 2-hexyl aniline, 2-heptyl aniline, 2-octyl group aniline, 2-nonyl aniline, 2-decyl aniline, 2-fluoroaniline, 2-chloroaniline, 2-bromaniline, 2-cyano-aniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2,3-butylidene aniline, 2,3-methylenedioxy benzene amine and 2, the derivative of 3-ethylidene dioxy aniline, but the present invention is not limited to this.These compounds are commercially available product, maybe can prepare by known method.
Also the compound that is selected from above-claimed cpd can be used in combination the solid electrolyte of formation as copolymer.In this case, the mixing ratio of polymerisable monomer etc. can change according to polymerizing condition etc., but preferred mixing ratio and polymerizing condition can be determined by simple test.The example of spendable method comprises the coating or be applied to simultaneously on the oxide film layer of tinsel and form the method for solid electrolyte (referring to JP-A-2-15611 and JP-A-10-32145 (United States Patent (USP) 6 in succession respectively of the monomer that wherein will all be preferably the solution form and oxidant for this reason, 214,930)).Usually, in conducting polymer, can use dopant, give reagent as alloy as the salt of benzene sulfonic acid, toluenesulfonic acid, naphthalene sulfonic acids, rylnthracene sulfonin or anthraquinone sulfonic acid (anthraquionenesulfonic acid) based on aryl sulfonic acid.
As shown in Figure 4, the conductive layer (not shown) that carbon paste layer and metal-containing powders are provided on the surface of solid electrolyte layer 7 is to form the cathode portion 8 of capacitor.The conductive layer of metal-containing powders closely is connected with solid electrolyte layer, and not only plays negative electrode, also works to connect the adhesive layer of final capacitor product (Fig. 5) cathode lead terminal 9.Conductive layer thickness to metal-containing powders is also unrestricted, but this thickness is generally 10-100 μ m level, preferred 10-50 μ m level.
Two or more capacitor elements in the application of the invention constitute under the situation of multi-layer solid electrolytic capacitor, as an embodiment shown in concrete among Fig. 5, the capacitor element of a plurality of stacks is welded in the anode leader office, and lead frame 11 is connected to the edge surface of welding portion.Lead frame 11 can be for fluting, that is, can have and wherein the edge corner part is cut out and therefore that it is smooth a little or make circular shape.
In addition, can make negative electrode coupling part relative and anode coupling part bear the role of lead terminal 9 and 13 with lead frame.
If the words of normally used material, there is no particular restriction with material to lead frame, but lead frame is preferably by based on the material (as Cu-Ni, Cu-Ag, Cu-Sn, Cu-Fe, Cu-Ni-Ag, Cu-Ni-Sn, Cu-Co-P, Cu-Zn-Mg or Cu-Sn-Ni-P alloy) of copper or adopt to constitute based on the material of the copper material with overlay coating, and when so constituting, the shape variation that for example makes lead frame is provided and has reduced the advantage of resistance with the good processability of the cutting that obtains lead frame.
As shown in the viewgraph of cross-section of Fig. 5, lead terminal 13 is connected on the lead frame 11 that is connected with anode part 12, lead terminal 9 is connected on the cathode portion 8 of the conductive layer that comprises solid electrolyte layer 7, carbon paste layer and metal-containing powders, and integral body adopted insulating resin 15 (as epoxy resin) moulding, obtain solid electrolyte capacitators 14 thus.
Realize optimum implementation of the present invention
Below representative embodiment is described the present invention in more detail by reference.These embodiment are intended to explanation, and are not for the purpose that limit the invention to this fully.
Embodiment 1:
Make the step of line of cut
On the thick aluminium foil of 200 μ m (containing Si:20 quality ppm, Fe:24 quality ppm, Cu:33 quality ppm and Ti:0.9 quality ppm), form the rectangle line of cut that opens wide on one side, the width that each line of cut has is 200 μ m.Each the rectangle width that forms capacitor element in line of cut is that 3mm and length are 6mm.As shown in Fig. 1 (A), the line of cut that is used for 30 capacitor elements is arranged with 3 row * 10 row.
Etching step
Adopt the wide resin strip of 1mm to cover the forward and backward surface (Fig. 1 (B)) of the part that will be made into the anode leader branch as protective materials, then, aluminium foil is immersed down in first electrolytic solutions (aqueous sulfuric acid of the hydrochloric acid of 10 quality %+0.5 quality %) and carry out etching by the AC electrolytic etching under the condition shown in the table 1 at 60 ℃.
Electrochemistry forms step
Resin strip is removed (Fig. 1 (C)), and will be immersed the ammonium adipate aqueous solution by the pectination bar that cutter cuts from aluminium foil and apply 13V voltage and form the inchoate part of electrochemistry with electrochemistry, thus the formation dielectric film.
Masking steps
Be used for solid electrolyte 7 in order to control, with the carbon paste that forms and the zone of silver paste, along the side that anode leader is divided, the part of the terminal 5mm of part that will form solid electrolyte of adjusting the distance adopts the resin strip of 0.5mm to apply and shelters 4b.
Solid electrolyte forms as follows in the layer region that electrochemistry forms.
The capacitor element end immersion of aluminum foil strip is contained 3 of 20 quality %, in the aqueous isopropanol (solution 1) of 4-ethylidene dioxy thiophene, left standstill 5 minutes with its proposition and under 25 ℃ then.To adopt aluminium foil in the part that monomer solution handles to immerse then is prepared as in the aqueous solution that contains 30 quality % ammonium persulfate aqueous solutions that contains 2-sodium anthraquinone sulfonate (TokyoKasei production) concentration 0.07 quality %, descend dry 10 minutes at 60 ℃ then, thereby carry out oxidation polymerization.Repeat 25 times up to dipping in solution 2 and even the operation of carrying out oxidation polymerization from dipping solution 1, thereby form solid electrolyte layer.Coating carbon paste and silver paste on described solid electrolyte layer.Downcut aluminium foil from aluminum foil strip, the result obtains the solid electrolyte capacitators element 8 shown in Fig. 4.
The Computer-Assisted Design, Manufacture And Test of chip class multi-layer solid electrolytic capacitor
With two solid electrolytic capacitor element by on lead frame, using the silver paste articulamentum to gather into folds it, by welding anode lead terminal is connected to the part that does not form conductive polymer coating, integral body adopts molding for epoxy resin, and by apply rated voltage (6.3v) under 120 ℃ the capacitor element that obtains is worn out 2 hours.Adopt this mode, preparation is totally 150 chip class solid electrolytic capacitors.
By each capacitor being passed in temperature is that backflow test is carried out to the multi-layer solid electrolytic capacitor that obtains in zone 30 minutes under 230 ℃.Measurement applies after the rated voltage 1 minute leakage current, determining to have measuring the following measured value of voltage (6.3v) is the average leakage current (μ A) of 1CV or capacitor still less, with measured value be 0.04CV or more those capacitors be evaluated as the electric leakage defective, capacity ratio has been evaluated as the electric capacity defective by form the back in electrochemistry according to capacitance low 30% that capacitor element is immersed the estimated capacitor of the electric capacity that records in the ammonium adipate solution (15%) or more capacitor, the capacitor that is evaluated as the electric capacity defective is taken apart and checked, the part of output anode electricity has been evaluated as weld defect from those capacitors that lead-in wire breaks away from, and definite " amount of the amount of defective element/element to be evaluated ".It is resulting that the results are shown in Table 2.
With regard to r and T2/T1, by after the cutting surface finish of the solid electrolytic capacitor that will be obtained under light microscope actual measurement obtain above-mentioned numerical value.Under by the situation of cutting in the shape that after the etch processes paillon foil is struck out capacitor element, because the surface, cut edge does not almost form etch layer with the plane surface surface, cut edge vertical and exposure paillon foil core metal of paillon foil, numerical value r and T2 are 0.
Embodiment 2:
Adopt with embodiment 1 in identical method prepare the multi-layer solid electrolytic capacitor, but change the thickness of aluminium foil into 300 μ m from 200 μ m.Adopt the measurement and the backflow test that carry out leakage current in a like fashion.What obtain the results are shown in the table 2.
Embodiment 3:
Be used in embodiment 1 identical method and finish capacitor, but in etching step, the part that will not make the anode leader branch is protected with the protective materials resin strip among the embodiment 1.Adopt with embodiment 1 in identical method estimate the characteristic of these capacitor elements.What obtain the results are shown in the table 2.
Embodiment 4:
Be used in embodiment 1 identical method and finish capacitor, but use the pyrroles to replace 3 among the embodiment 1,4-ethylidene dioxy thiophene.Adopt with embodiment 1 in identical method estimate the characteristic of these capacitor elements.What obtain the results are shown in the table 2.
Embodiment 5:
Be used in embodiment 1 identical method and finish capacitor, but use furans to replace 3 among the embodiment 1,4-ethylidene dioxy thiophene.Adopt with embodiment 1 in identical method estimate the characteristic of these capacitor elements.What obtain the results are shown in the table 2.
Embodiment 6:
Be used in embodiment 1 identical method and finish capacitor, but use etching electric current to replace having sine-shaped etching electric current with triangular waveform.Adopt with embodiment 1 in identical method estimate the characteristic of these capacitor elements.What obtain the results are shown in the table 2.
Embodiment 7:
Be used in embodiment 1 identical method and finish capacitor, but use etching electric current to replace having sine-shaped etching electric current with square waveform.Adopt with embodiment 1 in identical method estimate the characteristic of these capacitor elements.What obtain the results are shown in the table 2.
Comparative example 1:
Adopt with embodiment 1 in identical method prepare the multi-layer solid electrolytic capacitor, but used thickness be 100 μ m aluminium foil, will not have the paillon foil etching of line of cut and etched paillon foil cut among the fritter replacement embodiment 1 with preliminary dimension and mark the etched then step of line of cut.Adopt the measurement and the backflow test that carry out leakage current in a like fashion.What obtain the results are shown in the table 2.
Comparative example 2:
Adopt with embodiment 1 in identical method prepare the multi-layer solid electrolytic capacitor, but in aluminium foil, cut so that acute angle A is 20 °.Adopt the measurement and the backflow test that carry out leakage current in a like fashion.What obtain the results are shown in the table 2.
Comparative example 3:
Adopt with embodiment 1 in identical method prepare the multi-layer solid electrolytic capacitor, but in aluminium foil, cut so that the line of cut width is 3mm.Adopt the measurement and the backflow test that carry out leakage current in a like fashion.What obtain the results are shown in the table 2.
Table 1
| Waveform | Frequency (Hz) | Current density (A/cm 2) | Electric weight (C/cm 2) | Width (mm) | Acute angle A (degree) | |
| |
Sinusoidal | 30 | 0.5 | 400 | 0.2 | 90 |
| |
Sinusoidal | 30 | 0.5 | 650 | 0.2 | 90 |
| |
Sinusoidal | 30 | 0.5 | 400 | 0.2 | 90 |
| Embodiment 4 | Sinusoidal | 30 | 0.5 | 400 | 0.2 | 90 |
| |
Sinusoidal | 30 | 0.5 | 400 | 0.2 | 90 |
| |
Triangle | 30 | 0.5 | 400 | 0.2 | 90 |
| |
Rectangle | 30 | 0.5 | 400 | 0.2 | 90 |
| Comparative example 1 | - | - | - | - | - | 90 |
| Comparative example 2 | Sinusoidal | 30 | 0.5 | 400 | 0.2 | 20 |
| Comparative example 3 | Sinusoidal | 30 | 0.5 | 400 | 3.0 | 90 |
Table 2
| r (μm) | T2/T1 | Average capacitance (μ F) | Electric capacity defective ratio ＊ | The weld defect ratio ＊ | Electric leakage defective ratio ＊ | Average leakage current (μ m) | |
| |
52 | 0.7 | 63.5 | 0/150 | 0/150 | 0/150 | 0.15 |
| |
52 | 0.7 | 93.2 | 0/150 | 0/150 | 0/150 | 0.18 |
| |
52 | 0.7 | 62.2 | 3/150 | 3/150 | 2/150 | 0.17 |
| Embodiment 4 | 52 | 0.7 | 63.6 | 0/150 | 0/150 | 0/150 | 0.15 |
| |
52 | 0.7 | 63.5 | 0/150 | 0/150 | 0/150 | 0.15 |
| |
48 | 0.6 | 61.0 | 0/150 | 0/150 | 0/150 | 0.10 |
| |
47 | 0.6 | 62.5 | 0/150 | 0/150 | 0/150 | 0.14 |
| Comparative example 1 | 0 | 0.0 | 27.1 | 5/150 | 5/150 | 22/150 | 1.89 |
| Comparative example 2 | 10 | 0.3 | 59.0 | 0/150 | 0/150 | 5/150 | 0.78 |
| Comparative example 3 | 89 | 2.8 | 50.7 | 1/150 | 0/150 | 10/150 | 0.95 |
*The quantity of the element of the quantity of defective element/to be evaluated
Industrial usability
According to the present invention, obtain following effect.
(1) marks line of cut by the local shape with capacitor element before etch process, the uniform capacitor element of the effective area tinsel of valve acting can be obtained, thereby the metal of the valve acting of the porous with narrow capacitance variations can be prepared.
Porous layer also can be formed on the surface, cut edge of metal of valve acting of the porous in the part that forms at least conducting polymer, and the corner part of cutting part sharpened edge is by the etching dissolving and form curved surface, can obtain the capacitor of high capacitance, and can suppress to produce defective goods owing to increase and the backflow of leakage current after the moulding.
(2) since porous layer be not formed on anode leader divides, thereby in chemical polymerization, there is not conducting polymer to be formed on anode leader divides by capillarity, therefore, do not have to occur owing to form conducting polymer short circuit and be beneficial to the welding of stack element, as a result, reduced owing to weld the capacitor that failed defective goods, contact resistance diminishes and can obtain to contain little equivalent serial resistance.
Claims (37)
1. production method that is used for the tinsel of capacitor, it is included in the line of cut of the shape that marks capacitor element in the tinsel of valve acting and the small part that arrives is predefined for the uncut step of part that anode leader is divided, the surface portion of the tinsel of surface, the cut edge that produces in the abovementioned steps and valve acting is carried out the step of etched step and electrochemistry formation tinsel.
2. the production method of the tinsel that is used for capacitor of claim 1 wherein is etched in part that the anode leader that adopts protective materials will be predefined for capacitor element divides and carries out after protecting.
3. the production method of the tinsel that is used for capacitor of claim 2 is wherein removed protective materials after etching, carries out electrochemistry then and forms step.
4. the production method of the tinsel that is used for capacitor of claim 2 is wherein removed protective materials after electrochemistry forms etched paillon foil.
5. the production method of the tinsel that is used for capacitor of claim 2, wherein after etching, remove protective materials, and in that carry out will become before the step that forms of the electrochemistry in zone of cathode portion, antianode extension and have formation thereon and shelter as the interface between the zone of the solid electrolytic layer of cathode portion.
6. the production method of each the tinsel that is used for capacitor among the claim 1-3, wherein each cutting part is to have not that quadrangle, the U-shaped of cutting part are the shape of a hoof or semicircle;
7. the production method of the tinsel that is used for capacitor of claim 1, wherein the surface, cut edge is 30 ° or bigger with respect to the interior acute angle A on tinsel surface.
8. the production method of the tinsel that is used for capacitor of claim 1, wherein line of cut width d is 2 times of tinsel thickness or still less.
9. the production method of the tinsel that is used for capacitor of claim 1 is wherein produced a plurality of capacitors by mark each many line of cut that all have the capacitor element shape in the tinsel of a valve acting with single batch of method.
10. the production method of the tinsel that is used for capacitor of claim 1, wherein paillon foil is made of at least a metal that is selected from the valve acting of aluminium, niobium and tantalum.
11. the production method of the tinsel that is used for capacitor of claim 1, wherein the thickness of the tinsel of valve acting is 0.05-1mm.
12. the production method of the tinsel that is used for capacitor of claim 1, wherein the tinsel of valve acting is the aluminium foil that contains at least a element that is selected from Si, Fe, Cu, Zn, Ni, Mn, Ti, Pb, B, P, V and Zr.
13. the production method of the tinsel that is used for capacitor of claim 12, wherein except aluminium, the total content of contained element is 1-1000 quality ppm in paillon foil.
14. the production method of the tinsel that is used for capacitor of claim 12, wherein aluminium foil contains the Fe of Si, 1-100 quality ppm of 1-100 quality ppm and the Cu of 1-100 quality ppm.
15. the production method of the tinsel that is used for capacitor of claim 1, wherein etching is to use the AC electrolytic etching of at least a waveform that is selected from sine wave, square wave and triangular wave.
16. the production method of the tinsel that is used for capacitor of claim 1, wherein etching is the AC electrolytic etching, wherein on the metal of valve acting and placing on the electrode of metal both sides of valve acting terminal is provided, and the terminal that provides on the metal of valve acting directly is provided the AC electric current.
17. the production method of the tinsel that is used for capacitor of claim 1, wherein etching is the DC electrolytic etching.
18. be used for the tinsel of capacitor, it is the tinsel of valve acting, comprising: form the line of cut of capacitor element shape, and at least a portion will become the part that the capacitor element anode leader divides and not be cut; With the porous layer that forms on the tinsel surface portion of cut edge surface by being etched in above-mentioned line of cut and above-mentioned valve acting; Oxide dielectric film on above-mentioned porous layer.
19. the tinsel that is used for capacitor of claim 18, wherein the radius of curvature r at cutting part edge is 0.1-500 μ m.
20. the tinsel that is used for capacitor of above claim 18, it is included in the lip-deep porous layer in surface and cut edge of tinsel, described porous layer is formed at and will forms on the part of solid electrolyte, wherein the porous layer thickness T 2 on the surface, cut edge is greater than 1 μ m, and has following relation with lip-deep porous layer thickness T 1 at tinsel:
T2/T1≤2。
21. a solid electrolytic capacitor element, it comprises among the claim 18-20 solid electrolyte layer and conductive layer on each the tinsel successively.
22. the solid electrolytic capacitor element of claim 21, wherein solid electrolyte layer comprises conducting polymer.
23. the solid electrolytic capacitor element of claim 22, the monomer that wherein forms conducting polymer are the monomeric compound that contains the monomeric compound of 5 yuan of rings of heterocycle or have the aniline skeleton.
24. the solid electrolytic capacitor element of claim 23, the monomeric compound that wherein contains 5 yuan of rings of heterocycle are the compound that is selected from pyrroles, thiophene, furans, many episulfide and substitutive derivative thereof.
25. the solid electrolytic capacitor element of claim 23, the monomeric compound that wherein contains 5 yuan of rings of heterocycle is the compound by following formula (I) expression:
Substituent R wherein
1And R
2Represent monoradical independently of one another, described monoradical is selected from hydrogen atom, have the straight chain of 1-10 carbon or branching, saturated or unsaturated alkyl group, oxyl, alkyl group, halogen, nitro, cyano group, primary, the second month in a season or uncle's amino, CF
3Group, phenyl and substituted-phenyl, R
1And R
2Hydrocarbon chain can be bonded to each other at an arbitrary position being formed for forming the divalence chain of the saturated or unsaturated hydrocarbons ring structure of at least one 3-, 4-, 5-, 6-or 7-unit with the carbon atom that is replaced by radicals R 1 and R2, and the loop chain of combination can contain the key of carbonyl, ether, ester, acid amides, sulfide, sulfinyl, sulfonyl or imino group arbitrarily.
26. the solid electrolytic capacitor element of claim 23, the monomeric compound that wherein contains 5 yuan of rings of heterocycle is for being selected from 3,4-ethylidene dioxy thiophene and 1, the compound of 3-dihydro isothianaphthene.
27. the multi-layer solid electrolytic capacitor, it is by obtaining a plurality of capacitor element stacks according to claim 21.
28. the production method of a solid electrolytic capacitor, be included in the line of cut that marks each shape that all has capacitor element in the tinsel of valve acting and the small part that arrives is predefined for the uncut step of part that anode leader is divided, etched step is carried out on surface to the tinsel of surface, the cut edge that produces in abovementioned steps and valve acting, paillon foil being cut into the bar that is pectination wherein all with the paillon foil part of component shape cutting after the anode leader branch links together, etched tinsel is carried out electrochemistry to be formed to form the step of oxide dielectric film, on the oxide dielectric thin layer, form the step of solid electrolyte layer, on solid electrolyte layer, form the step of conductive layer, and by in the anode leader of each piece is divided, cutting the step of paillon foil piece that is the shape of capacitor element with use.
29. the tinsel that is used for capacitor of claim 18, wherein each cutting part is to have not quadrangle, U-shaped or the semicircle of cutting part;
30. the tinsel that is used for capacitor of claim 18, wherein the surface, cut edge is 30 ° or bigger with respect to the interior acute angle A on tinsel surface.
31. the tinsel that is used for capacitor of claim 18, wherein line of cut width d is 2 times of tinsel thickness or still less.
32. the tinsel that is used for capacitor of claim 18 is wherein produced a plurality of capacitors by mark each many line of cut that all have the capacitor element shape in the tinsel of a valve acting with single batch of method.
33. the tinsel that is used for capacitor of claim 18, wherein paillon foil is made of at least a metal that is selected from the valve acting of aluminium, niobium and tantalum.
34. the tinsel that is used for capacitor of claim 18, wherein the thickness of the tinsel of valve acting is 0.05-1mm.
35. the tinsel that is used for capacitor of claim 33, wherein the tinsel of valve acting is the aluminium foil that contains at least a element that is selected from Si, Fe, Cu, Zn, Ni, Mn, Ti, Pb, B, P, V and Zr.
36. the tinsel that is used for capacitor of claim 33, wherein except aluminium, the total content of contained element is 1-1000 quality ppm in paillon foil.
37. the tinsel that is used for capacitor of claim 33, wherein aluminium foil contains the Fe of Si, 1-100 quality ppm of 1-100 quality ppm and the Cu of 1-100 quality ppm.
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| US7768773B2 (en) * | 2008-01-22 | 2010-08-03 | Avx Corporation | Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor |
| JP5137631B2 (en) * | 2008-03-12 | 2013-02-06 | 三洋電機株式会社 | Method for producing metal foil for electrolytic capacitor, and electrolytic capacitor |
| CN108292564B (en) * | 2015-11-30 | 2021-04-23 | 松下知识产权经营株式会社 | Method for manufacturing electrode foil and method for manufacturing capacitor |
| CN108701547B (en) * | 2016-03-10 | 2020-10-30 | 松下知识产权经营株式会社 | Solid electrolytic capacitor and method for manufacturing the same |
| CN106670735B (en) * | 2016-08-31 | 2019-02-01 | 北京时代民芯科技有限公司 | A kind of high-precision weld tabs cutting method |
| CN107492450B (en) * | 2017-08-09 | 2020-01-21 | 乳源东阳光优艾希杰精箔有限公司 | Soft aluminum foil for low-voltage anode of aluminum electrolytic capacitor and manufacturing method thereof |
| CN107790895A (en) * | 2017-11-01 | 2018-03-13 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | The cutter device and its cutting method of electrode foil |
| CN111048318A (en) * | 2018-10-12 | 2020-04-21 | 钰冠科技股份有限公司 | Valve metal foil and method for manufacturing same |
| CN110444401B (en) * | 2019-08-30 | 2021-05-07 | 丰宾电子（深圳）有限公司 | Solid electrolyte sheet type laminated aluminum electrolytic capacitor and manufacturing method thereof |
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| US5500101A (en) * | 1993-12-28 | 1996-03-19 | Nihon Chikudenki Kogyo Kabushiki Kaisha | Method of etching aluminum foil for electrolytic capacitor |
| JP2802730B2 (en) * | 1993-12-28 | 1998-09-24 | 日本蓄電器工業株式会社 | Etching method of aluminum foil for electrolytic capacitor |
| JPH11307400A (en) * | 1998-04-21 | 1999-11-05 | Matsushita Electric Ind Co Ltd | Manufacture of electrode foil for solid electrolytic capacitor |
-
2003
- 2003-08-29 CN CNB038205831A patent/CN100511514C/en not_active Expired - Fee Related
- 2003-08-29 KR KR1020057002876A patent/KR100988802B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050058389A (en) | 2005-06-16 |
| KR100988802B1 (en) | 2010-10-20 |
| CN1679125A (en) | 2005-10-05 |
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