CN1369888A - Mfg. Method of solid electrolytic capacity and solid electrolytic capacity - Google Patents
Mfg. Method of solid electrolytic capacity and solid electrolytic capacity Download PDFInfo
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- CN1369888A CN1369888A CN 02104533 CN02104533A CN1369888A CN 1369888 A CN1369888 A CN 1369888A CN 02104533 CN02104533 CN 02104533 CN 02104533 A CN02104533 A CN 02104533A CN 1369888 A CN1369888 A CN 1369888A
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Abstract
An anode body is dipped into conductive macromolecular solution having a hydrophilic group in a polymer skeleton, and then is pulled up for heating treatment, thus forming a conductive macromolecular layer on the anode body. Then, the conductive macromolecular layer is covered with solution containing monomer made of a complex annular compound or its derivative, then monomer in solution containing the monomer is polymerized to form a polymerization film, and washing is made to remove residue remaining in the polymerization film, and then a first solid electrolyte layer is formed by drying. The invention is to provide the manufacturing method of a solid electrolytic capacitor for preventing performance from degrading due to residue that is generated when a solid electrolyte layer is formed, and for obtaining a product having improved performance, and to provide the solid electrolytic capacitor.
Description
Technical field
The present invention relates to be used for various e-machines utilization the manufacture method and the solid electrolytic capacitor of solid electrolytic capacitor of solid electrolyte layer.
Background technology
At first, describe with reference to the manufacture method of accompanying drawing in the past this solid electrolytic capacitor.
Fig. 8 is the profile of the formation of the above-mentioned solid electrolytic capacitor in the past of expression, in the figure, the 20th, by the tantalum metal powder pressing as valve metals is formed needed shape, carry out the anode bodies of the porous matter that sintering forms then, the 21st, the anode lead wire that constitutes by the tantalum lines that are embedded in this anode bodies 20.
The 22nd, the dielectric oxide film thereon layer that on described anode bodies 20 outer surfaces, forms, the 23rd, the solid electrolyte layer that on this dielectric oxide film thereon layer 22, forms, the 24th, the cathode layer that on this solid electrolyte layer 23, forms, this cathode layer 24 is to form by lamination carbon and silver coating, has so just constituted capacitor cell 25.The 26th, the anode terminal that is connected with the anode lead wire 21 of described capacitor cell 25, the 27th, utilize conductive adhesive 28 to be bonded in cathode terminal on the cathode layer 24, the 29th, the part of described anode terminal 26 and cathode terminal 27 is exposed to the potting resin of outer surface encapsulation capacitor cell 25, generally using epoxy is resin.In addition, the 30th, strengthen resin.
Below, with reference to Fig. 9 the manufacture method of the solid electrolytic capacitor in the past of such formation is described.Fig. 9 is a manufacturing procedure picture of representing solid electrolytic capacitor manufacture method in the past, as shown in the drawing, at first, in moulding, sintering circuit (S91), by being pressed, the tantalum metal powder that is embedded with the anode lead wire 21 that is made of the tantalum line forms needed shape, again it is carried out sintering, thereby produce the anode bodies 20 of porous matter.
Then, in formation process (S92), carry out anodized, on the outer surface of described anode bodies 20, form dielectric oxide film thereon layer 22 by using phosphoric acid.Then, in polymerization process (S93), by monomer solutions such as aniline, pyrroles, thiophene being evenly dispersed in the outer surface and the pore inside of described anode bodies 20, it is contacted with the solution that contains oxidant, perhaps on the contrary after oxidant is evenly disperseed, it is contacted with described monomer solution, thereby form the solid electrolyte layer 23 that constitutes by electroconductive polymer by chemical oxidising polymerisation.Then, form in the operation (S94), carry out carbon coating, silver coating coating, drying, form cathode layer 24, so just produce capacitor cell 25 at negative electrode.
Then, in assembling procedure (S95),, the anode lead wire 21 of described capacitor cell 25 is connected by being welded with the anode terminal 26 of COM terminal, and, utilize conductive adhesive 28 that cathode layer 24 is connected with cathode terminal 27.Then, in contour forming operation (S96), the part of described anode terminal 26 and cathode terminal 27 is shown out the surface respectively, with epoxy is that 29 pairs of capacitor cells of potting resin 25 carry out contour forming, at last, in finishing operation (S97), be divided into independently each sheet and check etc., finish manufacturing.
In addition, other method that forms described solid electrolyte layer for example spy is opened in the flat 10-321474 communique and has been put down in writing following technology, solid electrolyte layer is the solid electrolytic capacitor that is made of the 1st solid electrolyte layer and the 2nd solid electrolyte layer, wherein, the 1st solid electrolyte layer forms by the solution of heating polyaniline or derivatives thereof, the 2nd solid electrolyte layer forms by the polypyrrole or derivatives thereof being carried out electrolysis polymerization, owing to can form the uniform solid electrolyte layer of thickness, so can produce static capacity and impedance operator is good and reliability is good solid electrolytic capacitor.
But, adopt the manufacture method of described solid electrolytic capacitor in the past, in polymerization process, carry out chemical oxidising polymerisation in repeated multiple times, at the outer surface of anode bodies 20 and pore is inner when forming the solid electrolyte layer 23 that is made of polypyrrole, as Figure 10, shown in Figure 11, exist outer surface and the inner problem that generates the residue 31 of electroconductive polymer of pore at anode bodies 20.
The residue 31 of this electroconductive polymer is because polymerization slag, unpolymerized electroconductive polymer or the oxidant etc. when carrying out chemical oxidising polymerisation have destroyed the face shaping of capacitor cell 25, not only reduce the volume of capacitor cell 25 and accommodated efficient, make deterioration in characteristics, and in the worst case even the situation that residue 31 comes out from potting resin 29 can occur.Therefore, in order to remove this residue 31, form operation (S94) at cathode layer thus must carry out before removing the operation that residue 31 makes having an even surface of solid electrolyte layer 23 and proofreaies and correct face shaping with hairbrush or writing brush, not only reduced productivity ratio but exist, and, cause the worry of deterioration in characteristics because the state of removing of residue 31 damages electroconductive polymer layer 23.
In addition, in described polymerization process (S93), at monomer solution and containing in the solution of oxidant, when when being soaked in anode bodies 20 in wherein a kind of solution and being immersed in the another kind of solution again, because having soaked the solution of anode bodies 20 earlier is diffused into again in the another kind of solution, therefore, the solution concentration of anode bodies 20 inside reduces, the formation amount of the electroconductive polymer of anode bodies 20 inside reduces, thereby on dielectric oxide film thereon layer 22, can not cover the continuous solid electrolyte layer 23 that constitutes by electroconductive polymer, cause the problem of static capacity characteristic or impedance operator deterioration.
Therefore, in order to obtain to cover on the dielectric oxide film thereon layer 22 of anode bodies 20 inside with the continuous solid electrolyte layer 23 that constitutes by electroconductive polymer, draw original capacity fully, and the solid electrolytic capacitor that impedance operator is low, must tens of times form the operation of the solid electrolyte layer 23 that constitutes by electroconductive polymer repeatedly, have the extremely low problem of productivity ratio.
On the other hand, adopt the spy to open the disclosed technology of flat 10-321474 communique, in forming the 1st solid electrolyte layer, heat in the solution of the aniline or derivatives thereof by in containing the solvent of water, having dissolved the polymer shape and form, thereby when forming the 2nd solid electrolyte layer thereafter, there is the problem that is difficult for improving static capacity in the part dissolving of the 1st solid electrolyte layer.
Summary of the invention
The objective of the invention is to solve this problem in the past, a kind of productivity ratio height is provided, simultaneously can stably make low impedance characteristic and the leakage current characteristic is good, and the manufacture method and the solid electrolytic capacitor of the solid electrolytic capacitor of static capacity height, reliability good quality production.
In order to solve described problem, the 1st invention of the present invention is a kind of manufacture method of solid electrolytic capacitor, the surface that is included in the anode bodies of valve metals formation forms the operation of dielectric oxide film thereon layer, this anode bodies is immersed in the electroconductive polymer aqueous solution that has hydrophilic group in the polymer backbone, then with its taking-up, carry out heat treated, thereby on described dielectric oxide film thereon layer, form the operation of electroconductive polymer layer, on described electroconductive polymer layer, cover the solution that contains the monomer that constitutes by the heterocyclic compound or derivatives thereof, by being carried out polymerization, the monomer in the solution that contains this monomer forms polymeric membrane then, be used to remove the washing that remains in the residue on this polymeric membrane then, then by it being carried out the dry operation that forms the 1st solid electrolyte layer, with the operation that on described the 1st solid electrolyte layer, forms cathode layer, has following effects according to this method: can boost productivity, can stably make low impedance characteristic, the product that leakage current characteristic good and static capacity are high.
The 2nd invention is a kind of manufacture method, be in the 1st invention, the electroconductive polymer that has hydrophilic group in the polymer backbone is any one derivative of the aniline of monomer, pyrroles, thiophene, furans, has following effects according to this method: can obtain high conductivity, can be manufactured on the good solid electrolytic capacitor of impedance operator of high-frequency region.
The 3rd invention is a kind of manufacture method, be in the 2nd invention, the electroconductive polymer that has hydrophilic group in the polymer backbone is for having sulfonic self rubber cement type electroconductive polymer, the 4th invention is a kind of manufacture method, have the anil of the electroconductive polymer of hydrophilic group in the polymer backbone, have following effects: impedance operator and leakage current characteristic good and the high solid electrolytic capacitor of proof voltage that can make high-frequency region by simple operation according to this method for expression in (changing 2).
[changing 2]
Wherein, the R that (changes 2) represents hydrogen, alkyl, alkoxyl, hydroxyl or nitro.
The 5th invention is a kind of manufacture method, is in the 1st invention, and the surface tension of the aqueous solution that has the electroconductive polymer of hydrophilic group in the polymer backbone is 70 * 10
-3Below the N/m, have following effects, can improve impregnability to the dielectric oxide film thereon layer according to this method.
In addition, if the surface tension of the aqueous solution surpasses 70 * 10
-3N/m, to the impregnability variation of dielectric oxide film thereon layer, thereby undesirable.
The 6th invention is a kind of manufacture method, is in the 1st invention, carries out heat treated in 160～250 ℃ temperature range, has following effects according to this method, and a part of hydrophilic group of electroconductive polymer layer is separated, and reduces the dissolubility with respect to water.
In addition, when the temperature of heat treated was lower than 160 ℃, the electroconductive polymer layer was with respect to the dissolubility height of water, can not improve static capacity and proof voltage, in addition, if above 250 ℃, to the thermal stress height of conductivity macromolecule layer, leakage current characteristic variation, thereby undesirable.
The 7th invention is a kind of manufacture method, be in the 1st invention, use oxidant to carry out the formation of the 1st solid electrolyte layer by chemical oxidising polymerisation, the 8th invention is a kind of manufacture method, the operation that forms the 1st solid electrolyte layer as described below: anode bodies with in any one solution that is immersed in monomer solution or oxidizing solution preset time, and then described anode bodies formed polymeric membrane to be immersed in preset time in the another kind of solution, carry out at least repeatedly the reparation operation of dielectric oxide film thereon then repeatedly, in addition, the 9th invention is a kind of manufacture method, the temperature that makes oxidizing solution has following effects according to this method: impedance operator and the leakage current characteristic good and the high solid electrolyte layer of conductivity that can produce high-frequency region for below the temperature that keeps in air.
The 10th invention is a kind of manufacture method, be in the 1st invention, carry out the formation of the 1st solid electrolyte layer with electrolysis polymerization, in addition, the 11st invention is a kind of manufacture method, electrolysis polymerization is that pH at the monomer that contains the heterocyclic compound or derivatives thereof at least, pH conditioning agent and water carries out polymerization in less than 5 the aqueous solution, has following effects according to this method: can improve polymerization speed, even and can produce at initial and electric capacity and be placed on the also good solid electrolytic capacitor of impedance operator under the condition in the high temperature.
The 12nd invention is a kind of manufacture method, be in the 1st invention, as the washing that is used to remove residue, at least remove the washing of anode bodies outer surface residue or remove in the washing that remains in the inner residue of anode bodies pore any one, the 13rd invention is a kind of manufacture method, as the washing of removing anode bodies outer surface residue or remove the washing that remains in the inner residue of anode bodies pore carry out following any one: use cold water, hot water, liquid such as organic solvent, air, the spray washing of any one in the gas, or utilize the ultrasonic washing of described liquid, or purge, has following effects according to this method: can more effectively obtain the effect of the 8th invention, and can reduce the leakage current characteristic of solid electrolyte layer.
The 14th invention is a kind of manufacture method, be in the 1st invention, after the operation that forms the 1st solid electrolyte layer, be arranged under the condition that is different from the condition that forms the 1st solid electrolyte layer the 2nd solid electrolyte layer that forms solid electrolyte layer and form operation, have following effects: can obtain the high solid electrolyte layer of conductivity that the leakage current characteristic has reduced according to this method.
The 15th invention is a kind of manufacture method, be in the 1st invention, after the operation that forms the 1st solid electrolyte layer, be arranged on the operation that the 2nd solid electrolyte layer that forms solid electrolyte layer under the condition that is different from the condition that forms the 1st solid electrolyte layer forms operation and forms the 3rd solid electrolyte layer of the solid electrolyte layer that is made of the electroconductive polymer that is different from the 1st solid electrolyte layer and the 2nd solid electrolyte layer, the 16th invention is a kind of manufacture method, this operation that forms the 3rd solid electrolyte layer is for carrying out following operation more than at least 1 time repeatedly: anode bodies is contained monomer to be immersed in preset time, operation in the suspension-turbid liquid of oxidant and electroconductive polymer particle and then described anode bodies is taken out the operation that keeps preset time outside solution from solution, in addition, the 17th invention is a kind of manufacture method, suspension-turbid liquid is to generate the electroconductive polymer particle by monomer that mixes specified rate and oxidant, and then the material of adding monomer, have following effect according to this method: can more effectively obtain by the 14th effect that invention obtains.
The 18th invention is a kind of manufacture method, be in the 15th invention, carry out the formation of the 3rd solid electrolyte layer with electrolysis polymerization, in addition, the 19th invention is a kind of manufacture method, electrolysis polymerization is for carrying out polymerization at the pH of the monomer that contains the heterocyclic compound or derivatives thereof at least, pH conditioning agent and water in less than 5 the aqueous solution, has following effects according to this method: can improve polymerization speed, be placed on the also good solid electrolytic capacitor of impedance operator under the condition in the high temperature even can produce at initial and electric capacity.
The 20th invention is a kind of manufacture method, be in the 1st, 14 or 15 invention, as the operation that forms the 1st solid electrolyte layer, before removing the washing that remains in the residue on the polymeric membrane, carry out the reparation of dielectric oxide film thereon, have following effects: can further reduce leakage current according to this method.
The 21st invention is a kind of manufacture method, be in the 1st, 14 or 15 invention, after forming operation, cathode layer heat-treats, in addition, the 22nd invention is a kind of manufacture method, in 230～280 ℃ temperature range, heat-treat, have following effects: can improve the adaptation of solid electrolyte layer and cathode layer, improve Low ESR and leakage current characteristic.
The 23rd invention is a kind of solid electrolytic capacitor, manufacture method manufacturing by the solid electrolytic capacitor of any one record in the 1st～22 invention, the 24th invention is in the 23rd invention, the residue of electroconductive polymer layer is less than 5 weight %, have following effects by this structure: can stably produce low impedance characteristic, leakage current characteristic good, and the high product of static capacity.
Description of drawings
Fig. 1 is the manufacturing procedure picture of the solid electrolytic capacitor manufacture method of expression embodiment of the present invention 1.
Fig. 2 is the front section view of the wash mill of embodiment of the present invention 2.
Fig. 3 is the front view of capacitor cell behind the spray washing of this execution mode of expression.
Fig. 4 is the cutaway view of anode bodies pore inside behind the spray washing of expression embodiment of the present invention 3.
Fig. 5 is the manufacturing procedure picture of the solid electrolytic capacitor manufacture method of expression embodiment of the present invention 4.
Fig. 6 is the manufacturing procedure picture of the solid electrolytic capacitor manufacture method of expression embodiment of the present invention 6.
Fig. 7 is the performance plot of the solid electrolytic capacitor of embodiment of the present invention 10.
Fig. 8 is a profile of representing solid electrolytic capacitor structure in the past.
Fig. 9 is a manufacturing procedure picture of representing solid electrolytic capacitor manufacture method in the past.
The front view of Figure 10 residue that to be the solid electrolytic capacitor manufacture method of expression by in the past generate in anode body surface.
Figure 11 is that the profile of the manufacture method of solid electrolytic capacitor in the past at the inner residue that generates of pore of anode bodies passed through in expression.
Wherein, 1-capacitor cell, 2-anode lead wire, 3-configuration bar, 4A, 4B-spray spout, the water of 5-spray form, 6-water tank, 7-water, 8-pump, 9-pipe arrangement, 10-spray chamber main body, 11-lid.
Embodiment
Below, with reference to accompanying drawing, the manufacture method of the solid electrolytic capacitor of embodiment of the present invention is described.(execution mode 1)
Fig. 1 is the manufacturing procedure picture of the solid electrolytic capacitor manufacture method of expression embodiment of the present invention 1, at first in moulding, sintering circuit (S1), the tantalum metal powder pressure that is embedded with the anode lead wire that is made of the tantalum line is formed needed shape, thereby it is carried out the anode bodies that sintering is produced porous matter.Then, in formation process (S2), carry out anodized, on the outer surface of described anode bodies, form the dielectric oxide film thereon layer by utilizing phosphoric acid.
Then, the electroconductive polymer layer forms operation (S3) and the anode bodies that has formed described dielectric oxide film thereon layer is immersed in the electroconductive polymer aqueous solution that has hydrophilic group in the polymer backbone (S31), then it is taken out, and makes the water volatilization as solvent.Carry out heat treated (S32) then, form the electroconductive polymer layer.
Then, the 1st solid electrolyte layer forms the monomer solution that operation (S4) is made of heterocyclic compound and derivative thereof in the even dispersion of anode bodies outer surface that has formed described electroconductive polymer layer and pore inside, contact with oxidizing solution then, or on the contrary after evenly disperseing oxidizing solution, make its contact monomer solution, thereby form the polymeric membrane (S41) of heterocyclic compound by chemical oxidising polymerisation.Then, remove the residue (S42) on the polymeric membrane of remaining in that generates when forming this polymeric membrane, carry out drying (S43) by the polymeric membrane of this having been removed residue again, on anode bodies, formed the 1st solid electrolyte layer that constitutes by heterocyclic compound by washing.
Then, form in the operation (S5), on described anode bodies, carry out carbon coating, silver coating coating and dry, form cathode layer, produce capacitor cell thus at cathode layer.
In assembling procedure (S6),, again cathode layer is connected on the cathode terminal by conductive adhesive then by carrying out combination on the anode terminal that the anode lead wire of described capacitor cell is welded on the COM terminal.Then, in mold forming operation (S7), make the part of described anode terminal and cathode terminal be exposed to outer surface respectively, with the epoxies potting resin capacitor cell is formed, in finishing operation (S8), block into that monolithic is checked etc. at last, finish making.
By this manufacture method, can boost productivity, can stably produce low impedance characteristic, leakage current characteristic good and the high solid electrolytic capacitor of static capacity.
Below, be elaborated by embodiment.
[embodiment 1]
At first in moulding, sintering circuit (S1), the tantalum metal powder pressure that is embedded with the anode lead wire that is made of the tantalum line is formed needed shape, thereby it is carried out the anode bodies that sintering is produced porous matter.
Then, the formation of dielectric oxide film thereon layer (S2) is carried out anodized by utilizing phosphate aqueous solution, at the outer surface formation dielectric oxide film thereon layer of described anode bodies.
Then, the formation of electroconductive polymer layer (S3), it is 70 * 10 that the anode bodies that has formed described dielectric oxide film thereon layer is immersed in the surface tension of having dissolved polyaniline 10wt%
-3In the aqueous solution of N/m (S31), this polyaniline is obtained by the monomer that replaces the R in (changing 2) with ethyl, then it is taken out, and makes the water volatilization as solvent.Under 160 ℃, carry out 5 minutes heat treated (S32) then, form the electroconductive polymer layer.
Then, the formation of the 1st solid electrolyte layer (S4), behind described anode bodies outer surface and the inner evenly dispersion of pore pyrrole monomer solution, contact with oxidizing solution, thereby form the polymeric membrane (S41) of polypyrrole by chemical oxidising polymerisation, then, repair with the dielectric oxide film thereon layer of aqueous acetic acid antianode body.Remove the residue (S42) on the polymeric membrane of remaining in that generates when forming this polymeric membrane by washing then, again this polymeric membrane of having removed residue is carried out drying (S43), carry out this operation 3 times repeatedly, on anode bodies, form the 1st solid electrolyte layer that constitutes by polypyrrole.
In addition, pyrrole monomer solution uses in the aqueous solution that contains ethylene glycol 10wt% the dissolving pyrroles to make it to make it as 1.0mol/l, as dopant dissolving Negel the solution that is prepared from as 0.25mol/l, in addition, oxidizing solution uses in the aqueous solution that contains ethylene glycol 10wt% as oxidant dissolving ferric sulfate (III) and makes it to make it to make it as 0.05mol/l, as additive dissolving sulfuric acid as 0.75mol/l, as dopant dissolving Negel the solution that is prepared from as 0.75mol/l.
Then, carbon coating, silver coating coating and dry are carried out in the formation of cathode layer (S5) on described anode bodies, form cathode layer, produce capacitor cell thus.
Assembling procedure (S6) is connected cathode layer on the cathode terminal by conductive adhesive by carrying out combination on the anode terminal that the anode lead wire of described capacitor cell is welded on the COM terminal again then.Then, in mold forming operation (S7), make the part of described anode terminal and cathode terminal be exposed to outer surface respectively, with the epoxies potting resin capacitor cell is formed, in finishing operation (S8), block into that monolithic is checked etc. at last, produce solid electrolytic capacitor.
[embodiment 2]
In described embodiment 1, the aqueous solution of the polyaniline 5wt% that is obtained by the monomer that replaces R in (changing 2) with ethyoxyl has been dissolved in use, under 180 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 3]
In described embodiment 1, the aqueous solution of the polyaniline 5wt% that is obtained by the monomer that replaces R in (changing 2) with ethyoxyl has been dissolved in use, under 200 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 4]
In described embodiment 1, use the aqueous solution that has dissolved the polyaniline 5wt% that obtains as the monomer of hydrogen by the R in (change 2), under 250 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 5]
In described embodiment 1, the aqueous solution of the polyaniline 5wt% that is obtained by the monomer that replaces R in (changing 2) with nitro has been dissolved in use, under 200 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 6]
In described embodiment 1, the aqueous solution of the polyaniline 5wt% that is obtained by the monomer that replaces R in (changing 2) with hydroxyl has been dissolved in use, under 200 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 7]
In described embodiment 1, the aqueous solution of the polyaniline 5wt% that is obtained by the monomer that replaces R in (changing 2) with ethyl has been dissolved in use, under 200 ℃, carry out 5 minutes heat treated, carry out the formation of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 8]
In described embodiment 1, use and to have added ethanol to make surface tension be 50 * 10
-3The aqueous solution of N/m carries out the formation (S3) of electroconductive polymer layer in addition similarly to Example 1, makes solid electrolytic capacitor.
[embodiment 9]
In described embodiment 1, use that to have added fluorine be that to make surface tension be 40 * 10 to surfactant
-3The aqueous solution of N/m carries out the formation (S3) of electroconductive polymer layer in addition similarly to Example 1, makes solid electrolytic capacitor.
[embodiment 10]
In described embodiment 1, the aqueous solution of the polyaniline 1wt% that is obtained by the monomer that replaces R in (changing 2) with methoxyl group has been dissolved in use, under 180 ℃, carry out 5 minutes heat treated, carry out the formation (S3) of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
[embodiment 11]
In described embodiment 1, the aqueous solution of the polyaniline 0.5wt% that is obtained by the monomer that replaces R in (changing 2) with methoxyl group has been dissolved in use, under 180 ℃, carry out 1,5,10,20,30 minute heat treated, carry out the formation (S3) of electroconductive polymer layer in addition similarly to Example 1, make the solid electrolytic capacitor of heat treated asynchronism(-nization).
[comparative example 1]
In described embodiment 1, in manganese nitrate 30% aqueous solution, soak, after the air dry, under 300 ℃, carry out 10 minutes thermal decomposition process and form manganese dioxide layer, carry out the formation (S3) of electroconductive polymer layer in addition similarly to Example 1, make solid electrolytic capacitor.
Solid electrolytic capacitor to described embodiment 1～11 and comparative example 1 wears out, and then the characteristic of electric capacity is measured.These results in (table 1), have been write down.This result measures 10 mean value respectively to each solid electrolytic capacitor.
[table 1]
In addition, the leakage current in (table 1) represents to add the current value of rated voltage after 1 minute.The voltage of the electrorheological limit when in addition, proof voltage is illustrated in and carries out voltage scanning with 0.2V/sec.
From (table 1) as can be seen, according to embodiment 1～11 and comparative example 1, by (S31) in the aqueous solution that is immersed in the electroconductive polymer that has hydrophilic group in the polymer backbone, then it is taken out and under 160～250 ℃, carry out heat treated (S32), thereby can suppress the dissolubility of electroconductive polymer layer with respect to water, even use the polymer fluid that contains water to form solid electrolyte layer (S4) subsequently, also can obtain good static capacity and impedance operator.
In addition, embodiment 8 is 50 * 10 by the surface tension that makes the electroconductive polymer aqueous solution that has hydrophilic group in the polymer backbone
-3N/m compares the impregnability that can improve to the dielectric oxide film thereon layer with embodiment 1, thereby has the effect that improves capacitance characteristic.
(execution mode 2)
In described execution mode 1, use wash mill shown in Figure 2 to constitute the washing procedure (S42) that the 1st solid electrolyte layer forms operation (S4) part.
Fig. 2 is the front cross-sectional view that is used to carry out the wash mill of described washing procedure, in the figure, the 1st, capacitor cell (forming the 1st solid electrolyte layer of polypyrrole), the 2nd, the anode lead wire of drawing from this capacitor cell 1, the 3rd, the anode lead wire 2 of capacitor cell 1 in many places with the configuration bar of given interval by solder bond.4A makes it towards capacitor cell 1 spray shape ground injection water in order described capacitor cell 1 to be carried out the spray spout that spray washing is provided with on capacitor cell 1 top, in the bottom of this figure groove or hole to be set, that is to say.The 5th, the spray form water that ejects from this spray spout 4A, the 6th, water tank, the 7th, be filled in the water in this water tank 6, the 8th, by pipe arrangement 9 water tank 6 interior water 7 are sent to the pump of spray spout 4A, the 10th, spray chamber main body, the 11st, lid.
Then, use the wash mill that constitutes like this, from spray spout 4A with 1.0kg/cm
2Pressure to capacitor cell 1 spray 10 second water 5, in case suspend, carry out same operation once more repeatedly, carry out spray washing.In addition, be 0.3kg/cm with described pressure change
2, 0.5kg/cm
2, 1.0kg/cm
2, 1.5kg/cm
2Residue and residual allowance when carrying out spray washing compares, and the result is shown in (table 2).
[table 2]
From (table 2) as can be seen, needing only from the pressure of spray spout 4A when capacitor cell 1 carries out spray washing is 0.5kg/cm
2Above pressure can obtain good effect.
Fig. 3 represents to have carried out the capacitor cell 1 that described spray washing has formed the 1st solid electrolyte layer, as shown in the drawing, the outer surface of the capacitor cell 1 that connects on configuration bar 3 has evenly formed the 1st solid electrolyte layer that is made of polypyrrole, and this residue is removed really.
The manufacture method of solid electrolytic capacitor of the present invention by being provided for removing the washing procedure that forms the residue that generates in the operation in polymeric membrane, can produce the solid electrolytic capacitor of fine qualities that forms the homogeneous solid dielectric substrate.
(execution mode 3)
The feature of embodiment of the present invention 3 is, as the washing that is used to remove residue (S42), remove the washing of anode bodies outer surface residue and remove the washing that remains in the inner residue of anode bodies pore, as described washing of removing anode bodies outer surface residue, use cold water, hot water, liquid such as organic solvent, air, the spray washing of any one of gas, or utilize the ultrasonic washing of described liquid, or in the purge any one, in addition, remove the washing that remains in the inner residue of anode bodies pore as described, adopt cold water, hot water, the manufacture method of the washing of liquid such as organic solvent or the solid electrolytic capacitor of ultrasonic washing, cooperate the effect of described execution mode 2 described inventions, can produce more high performance solid electrolytic capacitor.
Below, describe with reference to the manufacture method of accompanying drawing the solid electrolytic capacitor of embodiment of the present invention 3.
The residue of the polypyrrole polymeric membrane that in the operation (S4) that forms the 1st solid electrolyte layer, generates, roughly difference is residue that produces at the anode bodies outer surface and the residue that produces in anode bodies pore inside, the described residue that produces at the anode bodies outer surface can fully be removed by using the cold water (using the hot water better effects if) or the spray washing of air, and the residue that produces in anode bodies pore inside is then by using ultrasonic washing more effectively to remove.In addition, Fig. 3 represents to remove described anode bodies behind the residue that the anode bodies outer surface produces, and Fig. 4 represents to remove the state behind the inner residue that produces of anode bodies pore.
(execution mode 4)
The feature of embodiment of the present invention 4 is, form operation (S4) afterwards at the 1st solid electrolyte layer, be arranged on the manufacture method of the solid electrolytic capacitor of the formation operation (S4 ｀) of the 2nd solid electrolyte layer of formation solid electrolyte layer under the different conditions, cooperate the effect of described execution mode 1 described invention, can produce more high performance solid electrolytic capacitor.
Below, describe with reference to the manufacture method of accompanying drawing the solid electrolytic capacitor of embodiment of the present invention 4.
Fig. 5 is the manufacturing procedure picture of solid electrolytic capacitor manufacture method of expression embodiment of the present invention 4, and present embodiment 4 is that the 1st solid electrolyte layer at described execution mode 1 forms operation (S4) afterwards, the 2nd solid electrolyte layer is set forms operation (S4 ').It is to form solid electrolyte layer under the condition different with described the 1st solid electrolyte layer formation operation (S4) that the 2nd solid electrolyte layer forms operation (S4 ｀), more particularly, the monomer solution that uses in the 2nd solid electrolyte layer formation operation uses in the aqueous solution that is containing ethylene glycol 10wt% and reaches 0.75mol/l as monomer dissolving pyrroles, reach the solution that 0.25mol/l is prepared from as dopant dissolving Negel, oxidizing solution uses in the aqueous solution that contains ethylene glycol 10wt% and reaches 0.75mol/l as oxidant dissolving ferric sulfate (III), reach 0.05mol/l as dopant dissolving Negel, reach the solution that 0.75mol/l is prepared from as additive dissolving sulfuric acid, after on the solid electrolyte layer that monomer solution is evenly dispersed in described the 1st solid electrolyte layer formation operation (S4) formation, it is contacted with oxidizing solution, thereby form the polymeric membrane of polypyrrole by chemical oxidising polymerisation.Remove remaining oxidant by cold water washing or hot water washing then, carry out the reparation of dielectric oxide film thereon layer then, carry out cold water washing or hot water washing then,, on anode bodies, form the solid electrolyte layer that constitutes by polypyrrole again by dry.
The condition that described the 2nd solid electrolyte layer forms operation (S4 ｀) form with respect to the 1st solid electrolyte layer operation condition changing the concentration of pyrrole monomer solution, but other ground also has and reduces the method that the 2nd solid electrolyte layer forms the pyrrole monomer solution concentration of operation.
Like this, form the condition of condition changing the 2nd solid electrolyte layer formation operation of operation with respect to the 1st solid electrolyte layer, suppress the chemical oxidising polymerisation reaction in the 2nd solid electrolyte layer formation operation, thereby owing to can be formed uniformly the solid electrolyte layer of electroconductive polymer to anode bodies pore inside, thereby can produce more high performance solid electrolytic capacitor.
(execution mode 5)
Embodiment of the present invention 5 is characterised in that, the 2nd solid electrolyte layer forms operation (S4 ｀) and carries out once the above operation that anode bodies is immersed in preset time in the monomer solution at least repeatedly, then described anode bodies is immersed in the operation of preset time in the oxidizing solution, then described anode bodies is taken out the manufacture method of the solid electrolytic capacitor of the operation that in air, keeps preset time from solution, cooperate the effect of described execution mode 4 described inventions, can produce more high performance solid electrolytic capacitor.
Below, the manufacture method of the solid electrolytic capacitor of embodiment of the present invention 5 is described.
In described execution mode 4, the 2nd solid electrolyte layer forms operation (S4 ｀) and monomer solution is evenly being disperseed the back contact with oxidizing solution, thereby forms the polymeric membrane of polypyrrole by chemical oxidising polymerisation.At this moment, in being immersed in monomer solution and oxidizing solution successively after, anode bodies is taken out from solution, in air, keep preset time.Can fully carry out the chemical oxidising polymerisation reaction of anode bodies pore inside like this.In addition, be higher than the temperature of oxidizing solution, can further promote the chemical oxidising polymerisation reaction by making the temperature that in described air, keeps.
Remove remaining oxidant by cold water washing or hot water washing then, carry out the reparation of dielectric oxide film thereon layer then, carry out cold water washing or hot water washing at last, drying.Carry out this sequence of operations by repeated multiple times, can obtain more uniform solid electrolyte layer.
(execution mode 6)
The feature of embodiment of the present invention 6 is, form operation (S4) afterwards at the 1st solid electrolyte layer, be arranged on and be different under this condition the 3rd solid electrolyte layer that the 2nd solid electrolyte layer that forms solid electrolyte layer forms the solid electrolyte layer that operation (S4 ｀) and formation is made of the electroconductive polymer that is different from the 1st solid electrolyte layer and the 2nd solid electrolyte layer and form the operation (manufacture method of the solid electrolytic capacitor of S4 "); cooperate the effect of described execution mode 4 described inventions, can produce more high performance solid electrolytic capacitor.
Manufacture method to the solid electrolytic capacitor of embodiment of the present invention 6 describes with reference to the accompanying drawings.
Fig. 6 is the manufacturing procedure picture of the solid electrolytic capacitor manufacture method of expression embodiment of the present invention 6, present embodiment 6 is to form operation (S4) at the 1st solid electrolyte layer of described execution mode 1 to be provided with afterwards that the 2nd solid electrolyte layer forms operation (S4 ｀) and the 3rd solid electrolyte layer forms operation (S4 ＂), and it is to form by being different from the operation of solid electrolyte layer that described the 1st solid electrolyte layer forms the electroconductive polymer formation of operation (S4) that described the 3rd solid electrolyte layer forms operation (S4 ＂).
More particularly, form operation (S4) as the 1st solid electrolyte layer, execution mode 1 is described as described, disperse pyrrole monomer solution equably in the anode body surface that has formed the dielectric oxide film thereon layer, make its catalytic oxidation solution then, or on the contrary after disperseing oxidant equably, make its contact pyrrole monomer solution, thereby form the polymeric membrane of polypyrrole by chemical oxidising polymerisation.Remove excess oxidant by cold water washing or hot water washing then, carry out the reparation of dielectric oxide film thereon layer then, remove the residue on the polymeric membrane of remaining in that generates when forming this polymeric membrane by washing then, this polymeric membrane of having removed residue is carried out drying, thereby on anode bodies, form the solid electrolyte layer that constitutes by polypyrrole.
Then, form operation (S4 ｀) as the 2nd solid electrolyte layer, execution mode 4 is described as described, after on the solid electrolyte layer that pyrrole monomer solution is evenly dispersed in the formation of the 1st solid electrolyte layer formation operation, catalytic oxidation solution, thus the polymeric membrane of polypyrrole formed by chemical oxidising polymerisation.Remove excess oxidant by cold water washing or hot water washing then, carry out the reparation of dielectric oxide film thereon layer then, carry out cold water washing or hot water washing then, drying, thus on anode bodies, form the solid electrolyte layer that constitutes by polypyrrole.
Then, the 3rd solid electrolyte layer forms operation (S4 ＂), use is dissolved ethylidene dioxy thiophene as suspension-turbid liquid and is reached 1.0mol/l in the aqueous solution that contains ethylene glycol 10wt%, reach 0.75mol/l as oxidant dissolving p-methyl benzenesulfonic acid iron, reach the solution that 0.15mol/l is prepared from as dopant dissolving Negel, described the 2nd solid electrolyte layer is formed the anode bodies that has formed solid electrolyte layer in the operation be immersed in preset time in the described suspension-turbid liquid, take out then, keep preset time after unnecessary suspension-turbid liquid is removed in subcooled water washing or hot water washing, carry out cold water washing or hot water washing then, drying, thus the solid electrolyte layer that constitutes by polythiophene on anode bodies, formed.
Like this,, separately use conductive polymer material, can produce more high performance solid electrolytic capacitor by using polythiophene as the 3rd solid electrolyte layer.
(execution mode 7)
The feature of embodiment of the present invention 7 is, in above-mentioned execution mode 6, form in the operation (S4 ＂) at the 3rd solid electrolyte layer, form solid electrolyte layer by electrolysis polymerization, can improve polymerization speed, even and in the early stage electric capacity is placed under the condition in the high temperature and also can accesses the good solid electrolytic capacitor of impedance operator.
Below, the manufacture method of the solid electrolytic capacitor of embodiment of the present invention 7 is described.
In above-mentioned execution mode 6, except being immersed in the aqueous solution that contains ethylidene dioxy thiophene 0.5mol/l and alkylnaphthalene sulfonate 0.1mol/l and be used for improving the isopropyl alcohol of liquid stabilising, by the part on the electroconductive polymer layer is contacted with active electrode, under the burning voltage of 3V, carry out 30 minutes electrolysis polymerization, make beyond the electroconductive polymer that is made of poly-ethylidene dioxy thiophene separates out equably, carry out the 3rd solid electrolyte layer equally with execution mode 6 and form operation (S4 ＂) and make solid electrolytic capacitor.
According to above-mentioned manufacture method, except the effect of above-mentioned execution mode 6 described inventions, can produce more high performance solid electrolytic capacitor.
(execution mode 8)
The feature of embodiment of the present invention 8 is, the 3rd solid electrolyte layer forms operation (S4 ＂) carries out soaking certain hour repeatedly in the suspension-turbid liquid that contains the monomer of anode bodies, oxidant and electroconductive polymer particle operation, and from solution, take out above-mentioned anode bodies, the operation that keeps certain hour outside solution is more than at least 1 time, make the method for solid electrolytic capacitor, except the effect of above-mentioned execution mode 6 described inventions, can produce more high performance solid electrolytic capacitor.
Below, the manufacture method of the solid electrolytic capacitor of embodiment of the present invention 8 is described.
In above-mentioned execution mode 6, form in the operation at described the 3rd solid electrolyte layer, in suspension-turbid liquid, soak certain hour, take out then, behind the maintenance certain hour, by washing with water or removing unnecessary suspension-turbid liquid with hot wash, wash or use hot wash then with water, drying.Several is carried out in these a series of operations repeatedly, can obtain the more uniform solid electrolyte layer that is made of polythiophene.
(execution mode 9)
The feature of embodiment of the present invention 9 is, in any one mode of above-mentioned execution mode 1 or 4 or 6, form operation (S5) afterwards at cathode layer, the manufacture method of the solid electrolytic capacitor that the anode bodies that has formed solid electrolyte layer is heat-treated, the organic substance and the curable solid electrolyte layer that adopt this method to remove fully to remain on the polymeric membrane, thereby have the effect of the solid electrolytic capacitor that can access capacity characteristic and ESR characteristic good.
Below, with embodiment the manufacture method of the solid electrolytic capacitor of embodiment of the present invention 9 is described.
[embodiment 12]
In above-mentioned execution mode 1, remove to form the 1st solid electrolyte layer, then form cathode layer after, beyond under 250 ℃ the anode bodies that has formed this solid electrolyte layer being heat-treated, with the execution mode 1 same solid electrolytic capacitor of making.
[embodiment 13]
In above-mentioned execution mode 4, remove to form the 2nd solid electrolyte layer, then form cathode layer after, beyond under 250 ℃ the anode bodies that has formed this solid electrolyte layer being heat-treated, with the execution mode 4 same solid electrolytic capacitors of making.
[embodiment 14]
In above-mentioned execution mode 6, remove to form the 2nd solid electrolyte layer, then form cathode layer after, beyond under 250 ℃ the anode bodies that has formed this solid electrolyte layer being heat-treated, with the execution mode 6 same solid electrolytic capacitors of making.
[comparative example 2]
Adopt the method for explanation in one of the above-mentioned background technology to make solid electrolytic capacitor.
For the solid electrolytic capacitor of the foregoing description 12～14 and comparative example 2, the capacity characteristic under the mensuration 120Hz, the result of the ESR characteristic under the 100kHz are shown in (table 3).
[table 3]
From (table 3) as can be seen, compare solid electrolytic capacitor capacity characteristic, the ESR characteristic good of embodiment 12～14 with comparative example.
After cathode layer forms operation, the anode bodies that has formed solid electrolyte layer is heat-treated like this, the solid electrolyte layer full solidification can be improved adaptation, therefore can obtain the solid electrolytic capacitor of capacity characteristic and ESR characteristic good.
In addition, the scope that heat treated temperature is preferred 230 ℃～280 ℃ can not the full solidification solid electrolyte layer when heat treatment temperature is lower than 230 ℃, and when surpassing 280 ℃, solid electrolyte layer changes, and can not obtain good capacity characteristic, ESR characteristic.
(execution mode 10)
The feature of embodiment of the present invention 10 is, makes the residue of the 1st solid electrolyte layer be lower than 5 weight %, has following effects: can obtain volume and accommodate the good high-performance solid electrochemical capacitor of efficient by reducing residue as far as possible.
Below, the solid electrolytic capacitor of embodiment of the present invention 10 is described.
From Fig. 7, can clearly find out, be suppressed at when being lower than 5 weight %, can reduce the deterioration of ESR by the 1st solid electrolyte layer being formed the residue of removing in the operation behind the residue.
(execution mode 11)
The feature of embodiment of the present invention 11 is, forms the 1st solid electrolyte layer by electrolysis polymerization, can improve polymerization speed like this, and stage in the early stage, also can obtain the good solid electrolytic capacitor of impedance operator even electric capacity is placed under the condition in the high temperature.
Below, the solid electrolytic capacitor manufacture method of embodiment of the present invention 11 is described.
[embodiment 15]
Use has the aluminium etched foil (aluminum etched foil) of lead-in wire as anode bodies.By it being carried out anodized, in the outer surface formation dielectric oxide film thereon of above-mentioned anode bodies with the 3% ammonium adipate aqueous solution.
Then, the formation of electroconductive polymer layer is that the anode bodies that will form above-mentioned dielectric oxide film thereon is immersed in the following aqueous solution, and the surface tension of promptly dissolving by the polyaniline 5wt% that replaces the monomer acquisition that R obtains in (changing 2) with ethyoxyl is 70 * 10
-3The aqueous solution of N/m takes out it then, vapors away the water as solvent.Under 200 ℃, carry out heat treated 5 minutes then, thereby form the electroconductive polymer layer.
Then, the formation of the 1st solid electrolyte is undertaken by following method, use in advance pyrrole monomer 0.5mol/l with after Negel 0.1mol/l mixes, adding is adjusted the propyl phosphate of agent as the water of solvent with as pH, and pH value is adjusted to 2 polymer fluid, makes polymerization begin with electrode and the aluminium etched foil is surperficial contacts, polymerization voltage with 2V carries out electrolysis polymerization, wash then, be used to remove the residue that remains on the polymeric membrane, drying.
Then, the formation of cathode layer (S5) is by carbon coating on above-mentioned anode bodies, applies silver coating, carries out drying, forms cathode layer, has so just obtained capacity cell.Encapsulate with epoxy resin then, make solid electrolytic capacitor.
[comparative example 3]
In the foregoing description 15, except the 1st solid electrolyte layer forms according to following method, make solid electrolytic capacitor similarly to Example 15.Described method is for to disperse pyrrole monomer solution equably in the outer surface and the pore inside of anode bodies, it is contacted with oxidizing solution, by the polymeric membrane of chemical oxidising polymerisation formation polypyrrole, repair with the dielectric oxide film thereon layer of aqueous acetic acid antianode body then.Then, remove the residue on the polymeric membrane of remaining in that generates by washing when forming this polymeric membrane, this is removed polymeric membrane drying behind the residue, this operation is carried out 3 times repeatedly.
In addition, pyrrole monomer solution use dissolving pyrroles in the aqueous solution that contains ethylene glycol 10wt% reaches 1.0mol/l, dissolving reaches the formulated solution of 0.25mol/l as the Negel of dopant, oxidizing solution uses the ferric sulfate (III) that dissolves as oxidant in the aqueous solution that contains ethylene glycol 10wt% to reach 0.75mol/l in addition, dissolving reaches 0.05mol/l as the Negel of dopant, and dissolving reaches the formulated solution of 0.75mol/l as the sulfuric acid of additive.
[comparative example 4]
In the foregoing description 15, except being immersed in 30% the manganese nitrate aqueous solution, make it air dry after, under 300 ℃, carried out thermal decomposition process 10 minutes, form beyond the manganese dioxide layer, form the electroconductive polymer layer similarly to Example 16 and make solid electrolytic capacitor.
Solid electrolytic capacitor to the foregoing description 16 and comparative example 3 and 4 wears out, and measures the characteristic of electric capacity then.Its result is shown in (table 4).This result gets each solid electrolytic capacitor is tested 10 mean values that obtain respectively.
[table 4]
From (table 4) as can be seen, the solid electrolytic capacitor of embodiment 15 carries out electrolysis polymerization by using the low polymer fluid of pH, compare by the solid electrolytic capacitor that chemical oxidising polymerisation forms with comparative example 3, particularly significantly improvement is being arranged aspect impedance and the leakage current characteristic.And, compare by the solid electrolytic capacitor that carries out electrolysis polymerization formation solid electrolyte layer on the surface of manganese dioxide layer with comparative example 4, particularly also very good aspect static capacity and leakage current characteristic.
According to the present invention, by after anode bodies being immersed in the electroconductive polymer aqueous solution that has hydrophilic group in the polymer backbone, heat treated is carried out in its taking-up, form the operation of electroconductive polymer layer on the described anode bodies and on described electroconductive polymer layer, covering the solution that contains the monomer that constitutes by the heterocyclic compound or derivatives thereof, by being carried out polymerization, the monomer in the solution that contains this monomer forms polymeric membrane then, after being used to then remove the washing that remains in the residue on this polymeric membrane, it is carried out drying, form the operation of the 1st solid electrolyte layer, and when forming solid electrolyte layer, utilize method such as spray washing to remove the solid electrolyte residue that generates in the polymerization process, therefore, can produce uniform solid electrolyte layer of formation and the good solid electrolytic capacitor of reliability.
In addition, by after the 1st solid electrolyte layer forms operation, be arranged on the manufacture method that the 2nd solid electrolyte layer that forms solid electrolyte layer under the condition that is different from the 1st solid electrolyte layer formation operation forms operation, or after the 1st solid electrolyte layer forms operation, be arranged on the manufacture method that the 2nd solid electrolyte layer formation operation that forms solid electrolyte layer under the condition that is different from the 1st solid electrolyte layer formation operation and the 3rd solid electrolyte layer that forms the solid electrolyte layer that is made of the electroconductive polymer that is different from the 1st solid electrolyte layer and the 2nd solid electrolyte layer form operation, can improve capacity characteristic or ESR characteristic, produce the high product of reliability.
And, by after cathode layer forms operation, the anode bodies that has formed solid electrolyte layer being heat-treated, can remove the organic substance that remains on the polymeric membrane fully, simultaneously can be the solid electrolyte layer immobilization, therefore, the effect that has the solid electrolytic capacitor that can produce capacity characteristic and ESR characteristic good.
[changing 2]
[table 1]
Rated voltage 6.3WV (D size: 7.3 * 4.3 * 2.8mm)
[table 2]
[table 3]
[table 4]
| Static capacity (μ F) at120Hz | Impedance (m Ω) at100kHz | Leakage current (μ A) | Initial proof voltage (V) | ||
| Embodiment 1 | ????105 | ????36 | ????2.4 | ????15.4 | |
| Embodiment 2 | ????103 | ????34 | ????2.3 | ????15.5 | |
| Embodiment 3 | ????106 | ????33 | ????2.2 | ????15.7 | |
| Embodiment 4 | ????108 | ????31 | ????2.0 | ????15.9 | |
| Embodiment 5 | ????107 | ????34 | ????2.3 | ????15.5 | |
| Embodiment 6 | ????106 | ????33 | ????2.3 | ????15.4 | |
| Embodiment 7 | ????105 | ????35 | ????2.2 | ????15.5 | |
| Embodiment 8 | ????107 | ????33 | ????2.2 | ????15.6 | |
| Embodiment 9 | ????109 | ????32 | ????2.1 | ????15.6 | |
| Embodiment 10 | ????102 | ????33 | ????2.3 | ????15.6 | |
| Embodiment 11 | 1 minute | ????106 | ????32 | ????2.2 | ????15.3 |
| 5 minutes | ????107 | ????33 | ????2.0 | ????15.5 | |
| 10 minutes | ????108 | ????34 | ????1.9 | ????15.7 | |
| 20 minutes | ????110 | ????36 | ????1.8 | ????15.8 | |
| 30 minutes | ????112 | ????39 | ????1.7 | ????15.9 | |
| Comparative example 1 | ????94 | ????48 | ????3.8 | ????14.2 | |
| Nozzle | Spray pressure | Residual quantity |
| 4A | ?0.3kg/cm 2 | ??15wt％ |
| ?0.5kg/cm 2 | ??5wt％ | |
| ?1.0kg/cm 2 | ??2wt％ | |
| ?1.5kg/cm 2 | ??0wt％ |
| Capacity characteristic | The ESR characteristic | |
| Embodiment 12 | ????107 | ????36 |
| Embodiment 13 | ????113 | ????29 |
| Embodiment 14 | ????115 | ????24 |
| Comparative example 2 | ????97 | ????76 |
| Static capacity (μ F) at120Hz | Impedance (m Ω) at100kHz | Leakage current (nA) | |
| Embodiment 15 | ????25.4 | ????29 | ????145 |
| Comparative example 3 | ????23.6 | ????37 | ????850 |
| Comparative example 4 | ????20.2 | ????30 | ????300 |
Claims (24)
1, a kind of manufacture method of solid electrolytic capacitor, it is characterized in that, comprise: the operation that forms the dielectric oxide film thereon layer in the anode body surface that constitutes by valve metals, this anode bodies is immersed in the electroconductive polymer aqueous solution that has hydrophilic group in the polymer backbone, then with its taking-up, carry out heat treated, thereby on described dielectric oxide film thereon layer, form the operation of electroconductive polymer layer, on described electroconductive polymer layer, cover the solution that contains the monomer that constitutes by the heterocyclic compound or derivatives thereof, by being carried out polymerization, the monomer in the solution that contains this monomer forms polymeric membrane then, be used to remove the washing that remains in the residue on this polymeric membrane then, then it is carried out drying, thereby form the operation of the 1st solid electrolyte layer and on described the 1st solid electrolyte layer, form the operation of cathode layer.
2, the manufacture method of solid electrolytic capacitor according to claim 1 is characterized in that, the electroconductive polymer that has hydrophilic group in polymer backbone is any one the derivative in the aniline of monomer, pyrroles, thiophene, the furans.
3, the manufacture method of solid electrolytic capacitor according to claim 2 is characterized in that, the electroconductive polymer that has hydrophilic group in polymer backbone is for having sulfonic self rubber cement type electroconductive polymer.
4, the manufacture method of solid electrolytic capacitor according to claim 3 is characterized in that, has the anil of the electroconductive polymer of hydrophilic group for expression in (changing 1) in polymer backbone.
Change 1
5, the manufacture method of solid electrolytic capacitor according to claim 1 is characterized in that, the surface tension that has the electroconductive polymer aqueous solution of hydrophilic group in polymer backbone is 70 * 10
-3Below the N/m.
6, the manufacture method of solid electrolytic capacitor according to claim 1 is characterized in that, carries out heat treated in 160～250 ℃ temperature range.
7, the manufacture method of solid electrolytic capacitor according to claim 1 is characterized in that, uses oxidant to carry out the formation of the 1st solid electrolyte layer by chemical oxidising polymerisation.
8, the manufacture method of solid electrolytic capacitor according to claim 7, it is characterized in that, the operation that forms the 1st solid electrolyte layer is that anode bodies is immersed in preset time in any one solution in monomer solution or the oxidizing solution, and then described anode bodies is immersed in preset time in the another kind of solution, form polymeric membrane, carry out at least repeatedly the reparation operation of dielectric oxide film thereon then repeatedly.
9, the manufacture method of solid electrolytic capacitor according to claim 8 is characterized in that, the temperature of oxidizing solution is for below the temperature that keeps in air.
10, the manufacture method of solid electrolytic capacitor according to claim 1 is characterized in that, carries out the formation of the 1st solid electrolyte layer with electrolysis polymerization.
11, the manufacture method of solid electrolytic capacitor according to claim 10 is characterized in that, electrolysis polymerization is that pH at the monomer that contains the heterocyclic compound or derivatives thereof at least, pH conditioning agent and water carries out polymerization in less than 5 the aqueous solution.
12, the manufacture method of solid electrolytic capacitor according to claim 1, it is characterized in that, as the washing that is used to remove residue, remove the washing of anode bodies outer surface residue at least or remove in the washing that remains in the inner residue of anode bodies pore any one.
13, the manufacture method of solid electrolytic capacitor according to claim 12, it is characterized in that, as the washing of removing anode bodies outer surface residue or the washing of removing the residue that remains in anode bodies pore inside, use any one the spray washing in liquid, air, the gases such as cold water, hot water, organic solvent, or utilize the ultrasonic washing of described liquid, or in the purge any one.
14, the manufacture method of solid electrolytic capacitor according to claim 1, it is characterized in that, after the operation that forms the 1st solid electrolyte layer, be arranged on the 2nd solid electrolyte layer that forms solid electrolyte layer under the condition that is different from the condition that forms the 1st solid electrolyte layer and form operation.
15, the manufacture method of solid electrolytic capacitor according to claim 1, it is characterized in that, after the operation that forms the 1st solid electrolyte layer, be arranged on the 2nd solid electrolyte layer formation operation that forms solid electrolyte layer under the condition that is different from the condition that forms the 1st solid electrolyte layer and form operation with the 3rd solid electrolyte layer that forms the solid electrolyte layer that constitutes by the electroconductive polymer that is different from the 1st solid electrolyte layer and the 2nd solid electrolyte layer.
16, the manufacture method of solid electrolytic capacitor according to claim 15, it is characterized in that the operation that forms the 3rd solid electrolyte layer is to carry out repeatedly more than at least 1 time anode bodies being immersed in the operation of preset time in the suspension-turbid liquid that contains monomer, oxidant and electroconductive polymer particle and then described anode bodies being taken out the operation that keeps preset time outside solution from solution.
17, the manufacture method of solid electrolytic capacitor according to claim 16 is characterized in that, suspension-turbid liquid is to generate the electroconductive polymer particle by monomer that mixes specified rate and oxidant, and then adds the liquid of monomer.
18, the manufacture method of solid electrolytic capacitor according to claim 15 is characterized in that, carries out the formation of the 3rd solid electrolyte layer with electrolysis polymerization.
19, the manufacture method of solid electrolytic capacitor according to claim 18 is characterized in that, electrolysis polymerization is that pH at the monomer that contains the heterocyclic compound or derivatives thereof at least, pH conditioning agent and water carries out polymerization in less than 5 the aqueous solution.
20, according to the manufacture method of claim 1,14 or 15 described solid electrolytic capacitors, it is characterized in that, as the operation that forms the 1st solid electrolyte layer, before removing the washing that remains in the residue on the polymeric membrane, carry out the reparation of dielectric oxide film thereon.
21, according to the manufacture method of claim 1,14 or 15 described solid electrolytic capacitors, it is characterized in that, after cathode layer forms operation, heat-treat.
22, the manufacture method of solid electrolytic capacitor according to claim 21 is characterized in that, heat-treats 230～280 ℃ temperature range.
23, a kind of solid electrolytic capacitor adopts the manufacture method manufacturing of any described solid electrolytic capacitor in the claim 1～22.
24, solid electrolytic capacitor according to claim 23 is characterized in that, the residue of electroconductive polymer layer is less than 5 weight %.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1577656B (en) * | 2003-07-10 | 2010-05-26 | 三洋电机株式会社 | Method for producing capacitor elements |
| CN101894671A (en) * | 2010-06-23 | 2010-11-24 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer of solid electrolytic capacitor |
| CN101894672A (en) * | 2010-06-23 | 2010-11-24 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer by solid electrolytic capacitor |
| CN101203925B (en) * | 2005-06-27 | 2011-05-04 | 株式会社村田制作所 | Solid electrolytic capacitor and production method thereof |
| CN102396040A (en) * | 2009-12-18 | 2012-03-28 | 帝化株式会社 | Solid electrolytic capacitor |
| CN103733286A (en) * | 2011-08-17 | 2014-04-16 | 三菱丽阳株式会社 | Solid electrolyte capacitor and method for producing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2657932B2 (en) * | 1989-12-12 | 1997-09-30 | マルコン電子株式会社 | Method for manufacturing solid electrolytic capacitor |
| JP2937716B2 (en) * | 1993-11-18 | 1999-08-23 | 日本電気株式会社 | Tantalum solid electrolytic capacitor and method of manufacturing the same |
| JPH10303074A (en) * | 1997-04-23 | 1998-11-13 | Fujitsu Towa Electron Kk | Method for manufacturing solid electrolytic capacitor |
| JP3202668B2 (en) * | 1997-10-21 | 2001-08-27 | 富山日本電気株式会社 | Method for manufacturing solid electrolytic capacitor |
-
2002
- 2002-02-08 SG SG200200746A patent/SG111043A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1577656B (en) * | 2003-07-10 | 2010-05-26 | 三洋电机株式会社 | Method for producing capacitor elements |
| CN101203925B (en) * | 2005-06-27 | 2011-05-04 | 株式会社村田制作所 | Solid electrolytic capacitor and production method thereof |
| CN102396040A (en) * | 2009-12-18 | 2012-03-28 | 帝化株式会社 | Solid electrolytic capacitor |
| CN102396040B (en) * | 2009-12-18 | 2013-01-16 | 帝化株式会社 | Solid electrolytic capacitor |
| CN101894671A (en) * | 2010-06-23 | 2010-11-24 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer of solid electrolytic capacitor |
| CN101894672A (en) * | 2010-06-23 | 2010-11-24 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer by solid electrolytic capacitor |
| CN103733286A (en) * | 2011-08-17 | 2014-04-16 | 三菱丽阳株式会社 | Solid electrolyte capacitor and method for producing same |
| CN103733286B (en) * | 2011-08-17 | 2017-02-08 | 三菱丽阳株式会社 | Solid electrolyte capacitor and method for producing same |
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| Publication number | Publication date |
|---|---|
| CN1226760C (en) | 2005-11-09 |
| SG111043A1 (en) | 2005-05-30 |
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