CN101350253A - Solid electrolyte capacitor with ultra-low equivalent series resistance and manufacturing method thereof - Google Patents
Solid electrolyte capacitor with ultra-low equivalent series resistance and manufacturing method thereof Download PDFInfo
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- CN101350253A CN101350253A CNA2008100689165A CN200810068916A CN101350253A CN 101350253 A CN101350253 A CN 101350253A CN A2008100689165 A CNA2008100689165 A CN A2008100689165A CN 200810068916 A CN200810068916 A CN 200810068916A CN 101350253 A CN101350253 A CN 101350253A
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Abstract
The invention relates to a solid electrolytic capacitor and the method for preparing the solid electrolytic capacitor, wherein the solid electrolytic capacitor takes solid conducting high molecular polymer as electrolyte and takes valve metals, such as tantalum, niobium, titanium, aluminum and the like as an anode. The solid electrolytic capacitor is characterized by sufficiently explaining the techniques for the design of the anode, the function assignment, the chemical oxidative in-situ polymerization, the dip-coating graphite silver paste, the making of bottom extraction electrode and the like, with the technical proposal of the invention, a high polymer film, a graphite layer and a silver layer can be compactly combined, the manufactured electrolytic capacitor can be provided with very low equivalent series resistance (ESR), very high volumetric efficiency and good impedance frequency characteristic, the ESR value can be stable in the range of 10KHz-1000KHz, and the requirements of the frequency of a modern electronic equipment can be satisfied.
Description
Technical field:
The present invention relates to a kind of solid electrolyte capacitators and manufacture method thereof, especially be anode with valve metals such as tantalum, niobium, titanium, aluminium, as electrolyte, outer surface adopts that insulating material encapsulation, leading-out terminal draw from the bottom surface cube shapedly has ultra-low equivalent series resistance (ESR) Solid electrolytic capacitor And Manufacturing approach with conducting polymer.
Background technology:
Along with the multimedia messages treatment facility develops to miniaturization, high speed processingization and low-power consumption direction, cause demand miniaturized component, height integrated level LSIC (high-frequency, low-voltage) circuit, and require the circuit intermittent work, therefore electrolytic capacitor is proposed a series of new demand, particularly tantalum electrolytic capacitor has been proposed big capacity miniaturization, low ESR (ESR), the better requirement of frequency characteristic.Semi-conductor electricity road direction high speed and low-voltage direction develop, and particularly in the high, precision and frontier electronic equipment, clock frequency improves day by day, in order to suppress High-frequency Interference and voltage fluctuation, are badly in need of miniaturization and jumbo ultralow ESR decoupling zero filter.Information processing mobile communication terminals such as PDA are high performance and multifunction day by day, and the variation of internal current is very big thus, in order to eliminate the interference of big electric current change, also needs the tantalum electrolytic capacitor of the ultralow ESR of big capacity.At present, the low impedance at high frequency chip tantalum capacitor has become one of electronic devices and components of modern electronic equipment first-selection.
For satisfying the requirement that modern electronic technology development improves constantly the performance of electrolytic capacitor, especially to the requirement of low impedance at high frequency, capacitor manufacturer is carrying out fruitful groping aspect the design of tantalum electrolytic capacitor and the material, and the copolymer solid electrolyte capacitor becomes one of final solution.
In the recent two decades, scientific research confirms that fully pi-conjugated conducting polymer rate is high especially, therefore is particularly suitable as solid electrolyte.Pi-conjugated polymer also claims conducting polymer or synthetic metal.Owing to its good processing characteristics has obtained using widely.Polypyrrole, polythiophene, polyaniline, polyphenylene etc. are the example of known pi-conjugated polymer.The latter half eighties 20th century, German Bayer AG has successfully developed a kind of new polythiofuran derivative poly-(3,4-ethylidene dioxy thiophene) and has been called for short PEDT.PEDT is a kind of polymer of indissoluble but has some interesting characteristics.Except that having high conductivity (about 300s/cm), the PEDT film almost is transparent and has high stability when the state of oxidation, thereby is with a wide range of applications, and also is the electrolyte of desirable solid electrolytic capacitor.At present, conducting polymer composite becomes the employed electrolytical exploitation trend of electrolytic capacitor of new generation already.
Described by 3 in European patent EP-A-340 512 specifications, the solid electrolyte that 4 ethylidene dioxy thiophene are made poly-3, the production method of 4 ethylidene dioxy thiophene (PEDT), and the purposes that PEDT is used for the solid electrolyte of electrolytic capacitor by the oxidation polymerization effect.PEDT is as the substitute of manganese dioxide in the solid electrolytic capacitor or charge transfer complex, because it has higher conductivity, therefore can reduce the equivalent series resistance of capacitor and improve frequency performance.Open flat 2-130906, U.S.Pat.Nos.5,729,428 the spy in addition; 5,968,417; 6,001,281; All relate to the manufacturing of electrostrictive polymer electrolysis condenser in many patents such as 6,059,999 and 6,674,635.Its main method all is after employing is flooded high polymer monomer and oxidizing agent solution (i.e. the two-step method of often saying) respectively with capacitor body, make the high polymer monomer polymerization under proper condition, remove unreacted monomer, oxidant or polymer residue by cleaning subsequently, so repeated multiple times is so that polymer film reaches enough thickness.Adopt the high polymer monomer and the oxidant of this method fully not to mix, therefore react inhomogeneous, can't make the polymer film of excellent electrical properties at capacitor surface.Based on this shortcoming, people form polymer fluid (i.e. the one-step method of often saying) after with high polymer monomer, dopant, oxidant and solvent mixed together, with the fuse direct impregnation of capacitor in the mixed polymerization liquid of monomer, oxidant and dopant is arranged, subsequently under certain condition, along with the volatilization of solvent, monomer will be directly at the inner electroconductive polymer polymer film that forms of capacitor body under the effect of oxidant.One-step polymerization method has overcome monomer and oxidant undercompounding in the two-step method, reacts uneven shortcoming, but because oxidant and monomer solution mix the meeting polymerization reaction take place, cause the inefficacy of mixing material, so the service time of mixing material is very short, waste very big, the cost height.
Except requiring low ESR value, also require the very big interior maintenance of frequency range of impedance behavior of electrolytic capacitor to stablize, need that promptly external stress is had good stable.Can produce very high mechanical stress when particularly in the electrolytic capacitor preparation process, capacitor being encapsulated, will make the performance degradation of product.In order to alleviate the influence of external stress, just need on the capacitor anode piece, make the thicker outer dielectric substrate of one deck to capacitor performance.The inventor's surprised discovery in experimental study is made the thick conductive polymer coating of one deck 10-50 μ m on capacitor anode piece surface, and the stability of capacitor performance is improved greatly.This also is the prerequisite that the present invention makes the high-frequency electrolysis capacitor.
US 6,001, and 281 have described in an embodiment and have solid electrolyte and outer field capacitor, and this solid electrolyte is generated by polyvinylene dioxy thiophene (PEDT/PSS) original position, and this skin is made by the PEDT/PSS complex compound.But the characteristics of these capacitors are to have 130m Ω and higher ESR.
Therefore, the ESR of modern electrolytic capacitor product still needs further reduction, and for improving the stability of product, this product is also used has fine and close outer polymeric layer.The solid electrolytic capacitor of ultralow ESR will be the main developing direction of electrolytic capacitor R﹠D and production.
Summary of the invention:
The objective of the invention is to overcome prior art " one-step method " and high polymer monomer, dopant, oxidant and solvent are mixed polymer fluid that thing forms exists oxidant and monomer is easy to generate polymerization reaction, the shortcoming that causes the polymer fluid instability and lost efficacy, and overcome that existing " one-step method " produce have solid electrolyte and outer field capacitor still has the shortcoming of high equivalent series resistance (ESR), provide a kind of manufacturing to have densified polymer layer and outer field, have the method for the solid electrolytic capacitor of utmost point low ESR (ESR) and very high volume efficiency.
The manufacture method of general solid electrolytic capacitor comprises the following steps: successively
A, the valve metal powder is become the anode porous sintered body that has lead-in wire through mold pressing and vacuum-sintering;
B, adopt electrochemical method to form dielectric oxide film in the porous sintered surface of anode;
C, form the conducting high polymers layer in the porous sintered surface of the anode that has dielectric oxide film;
D, outside conducting high polymers thing layer coated graphite layer and silver slurry layer successively;
E, form final products by mold pressing encapsulation.
Wherein a, valve metal are meant metal tantalum, niobium, titanium or aluminium, and with valve metal powder porous sintered of formed anode (abbreviation agglomerate) after mold pressing and vacuum-sintering, its sintered density is 5.2～5.8g.cm
-3, thickness is 0.6～1.2mm, wherein b, to adopt electrochemical method to form dielectric oxide film on porous sintered of anode surface be that agglomerate is immersed in the dilute phosphoric acid solution, the dielectric oxide film layer that forms through electrochemical reaction under the 33V voltage conditions.
Wherein d, the used graphite of negative electrode conducting shell are the low temperature graphite of tool high conduction performance.The electric conductivity of this graphite＜15 Ω .m
-2, curing temperature＜80 ℃.
Used silver slurry is the low-temperature silver slurry of tool high conduction performance.Electric conductivity＜0.015 Ω the .m of this silver slurry
-2, curing temperature＜80 ℃.
Wherein e, when forming final products by press mold encapsulation, what anode extraction electrode that links to each other with the capacity cell anode tap and cathode end that is connected with the capacity cell cathode conductive layer all used is bottom surface electrode form down.
Maximum characteristics of the present invention are step c, and step c comprises following operation successively:
The preparation of (1) first dielectric substrate;
The preparation of (2) second dielectric substrates;
(3) preparation of polymeric outer layer.
Wherein the preparation method of (1) first dielectric substrate is immersed in 5～10min in the polymeric solution (being called for short first polymer fluid) of first dielectric substrate with porous sintered of the anode that has dielectric oxide film (abbreviation agglomerate) under 0～10 ℃ of condition, the agglomerate that will flood first polymer fluid then places room temperature condition to dry 10min, be placed on again in 40～150 ℃ the baking oven and react 15～40min, make monomer fully polymerization under the oxidant effect, use deionized water wash again, and agglomerate is changed into 30～60min again with mend forming liquid, in deionized water, clean afterwards and drying, described dipping, polymerization, change into again with the cleaning-drying process need and repeat 2～4 times, make the 1st dielectric substrate thickness at 10～15nm
Wherein the preparation method of (2) second dielectric substrates is that the agglomerate that will have first dielectric substrate is immersed in 5～10min in the polymer fluid (being called for short second polymer fluid) of second dielectric substrate under 0～10 ℃ of condition, its dipping, polymerization, one-tenthization and cleaning-drying process are with the preparation of first dielectric substrate again, flood repeatedly, polymerization, change into and cleaning-drying process 2～4 times again, the thickness that makes second dielectric substrate is at 15～20nm.
Wherein the preparation method of (3) polymeric outer layer is with the agglomerate with first dielectric substrate and second dielectric substrate, under 0～10 ℃ of condition, be immersed in the polymer fluid of polymeric outer layer (being called for short outer polymer fluid), its dipping, polymerization, again change into identical with the cleaning-drying process with the preparation method of first dielectric substrate, flood repeatedly, polymerization, change into and cleaning-drying process 1～3 time again, the thickness that makes outer polymer layer is at 20～50 μ m.
Above-described benefit forms liquid, is meant that solution concentration is the aqueous solution of the p-methyl benzenesulfonic acid of 0.1wt%.Above-described first polymer fluid contains the polymer fluid that monomer, oxidant, solvent and coupling agent are formed, and wherein, monomer is meant pi-conjugated polymer, is selected from the pyrroles, and thiophene, aniline and derivative thereof be as 3, a kind of in the 4-vinyl dioxy thiophene (EDT); Oxidant is selected from the alkylbenzenesulfonate or the alkylsulfonate of transition metal iron, copper, manganese, chromium, cerium, as toluenesulfonic acid iron, DBSA iron, first sulphur ester iron, ethyl sulfonic acid iron, propane sulfonic acid iron, fourth sulfonic acid iron a kind of or two kinds, solvent is selected from n-butanol, isopropyl alcohol, absolute ethyl alcohol, oxolane, water, N-methyl pyrrolidone (NMP) a kind of or two kinds, coupling agent is a silane, in first polymer fluid, monomer accounts for polymer fluid 1～3wt%, silane coupler accounts for 0.1～0.5wt% of polymer fluid, and oxidant accounts for 30～35wt%, and all the other are solvent.
The above second dielectric substrate close liquid (second polymer fluid) suddenly, except that composition with preparation first dielectric substrate polymer fluid (first polymer fluid), also be added with the organic adhesive of the band five-membered ring structure as polyvinylpyrrolidone, in second polymer fluid, monomer accounts for polymer fluid 4～6wt%, bonding agent is 0.1～0.5wt%, and all the other are joined with first polymer fluid.
The polymer fluid of above-described polymeric outer layer (being called for short outer polymer fluid), composition is except that having the first polymer fluid composition, also be added with one or more high boiling solvents of N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), butyl carbitol, also add organic bond in addition, be selected from as acrylate, function silane, polyvinyl alcohol, polymethacrylates a kind of or two kinds, also be added with the polymerization reaction delayed-action activator, the polymerization reaction delayed-action activator is selected from the combination in any of imidazole, pyrazoles, pyridine or their derivative.In the outer polymer fluid, monomer accounts for 8-12wt%, and high boiling solvent accounts for 1～2wt%, and delayed-action activator accounts for 0.5～1wt%, and organic bond accounts for 0.1～0.5wt%, and all the other proportionings are with first polymer fluid.
Solid electrolytic capacitor with the inventive method is produced has ultra-low equivalent series resistance ERS value, under the test frequency of 100KHz, and its ESR value＜50m Ω.Its impedance frequency characteristic is good, and it is stable that its ESR value can keep in 10KHz～1000KHz scope, rate of change＜10%.
The invention provides a kind of is electrolyte with the solid conduction high molecular polymer, with valve metals such as tantalum, niobium, titanium, aluminium is solid electrolytic capacitor of anode and preparation method thereof, adopt technical scheme of the present invention, make between high polymer layer, graphite linings, the silver slurry layer and combine closely, thereby can manufacture out the solid electrolytic capacitor of ultra-low equivalent series resistance ESR and very high volume efficiency, can satisfy the requirement of modern electric equipment high frequencyization, back formulaization well.
The anode extraction electrode that links to each other with the capacity cell anode tap all adopts bottom surface electrode form down with cathode end that is connected with the capacity cell cathode conductive layer, improves the volume efficiency of capacitor with this.
Description of drawings:
Fig. 1 is the present invention's (adopting bottom surface electrode product down) structural representation; Fig. 2 is the partial enlarged drawing of Figure 1A, has illustrated the hierarchy of inside of tantalum electrolytic capacitor;
In the accompanying drawing: the tantalum wire 1 anode tantalum piece 2 polymer electrolytic layers 3 first dielectric substrate 3a second dielectric substrate 3b polymeric outer layer 3c graphite linings 4 silver slurry layers 5 bonding silver slurry 6 plastic packaging resins 7 teflon gaskets 8 anodes are drawn weld tabs 9 negative electrodes and are drawn weld tabs 10
Embodiment:
Embodiment 1: choosing the CV value is 50, the tantalum powder of 000 μ Fv/g, compacting in flakes, and sinter into 1390 ℃ of following high temperature high vacuum and to contain tantalum lead-in wire, be of a size of the anode porousness agglomerate (abbreviation agglomerate) of 4.3mm * 3.1mm * 1.2mm, agglomerate is anodizing to 33V in the phosphoric acid,diluted aqueous solution, form the dielectric oxide film layer, the teflon gasket that on anode tap is scurried, has insulation property then, then with the agglomerate of oxide skin layer under 0～10 ℃ of low temperature, immerse first polymer fluid, first polymer fluid contains the monomer 3 of 2wt%, 4-vinyl dioxy thiophene, the oxidant p-methyl benzenesulfonic acid iron that contains 40wt%, contain 0.3% silane coupler, all the other are solvent, n-butanol and isopropyl alcohol, n-butanol and isopropyl alcohol weight proportion 1: 1, after soaking 6 minutes, take out agglomerate, at room temperature placed 10 minutes, be placed in 50 ℃ of constant temperature ovens and react 20min, be warmed up to 120 ℃ of insulation 15min then and finish polymerization reaction, clean repeatedly with ethanol and deionized water then, and in mending the p-methyl benzenesulfonic acid aqueous solution that forms liquid 0.1wt% concentration, change into 40min again, in deionized water, clean afterwards and drying, repeat above-mentioned dipping, polymerization, change into again and cleaning-drying process 3 times, obtain first dielectric substrate, the agglomerate that will have first dielectric substrate then immerses second polymer fluid, second polymer fluid batching is added with 0.3wt% polyvinylpyrrolidone organic adhesive and monomer on first polymer fluid batching basis amount increases to 4wt%, all the other batchings are with first polymer fluid, it operates dipping, polymerization, clean, change into again and the operation of cleaning-drying with first dielectric substrate, 3 times repeatedly, obtain second dielectric substrate, thickness 15～20nm, the agglomerate that will have first dielectric substrate and second dielectric substrate then, under 0～10 ℃ of condition, be immersed in the outer polymer fluid, outer polymer fluid batching is added with the high boiling solvent N-methyl pyrrolidone (NMP) of 1wt% on the basis of first polymer fluid batching, 0.5% response delay agent imidazoles, monomer concentration rises to 10wt%, all the other batchings are with first polymer fluid, it operates dipping, polymerization, clean, change into again and the operation of cleaning-drying with first dielectric substrate, 2 times repeatedly, make polymeric outer layer thickness 20～50nm, on the conducting polymer skin, apply low-temperature conductive graphite linings, conductive silver slurry layer then, finish the preparation of conductive cathode.So just form the conducting polymer capacitor core.
Embodiment 2:
The tantalum powder that will have 50,000 μ FV/g, compacting is in blocks, and forming the porousness anode bodies that is of a size of 4.3mm * 3.0mm * 0.6mm, the anode bodies behind the sintering is anodizing to 30V in the phosphoric acid,diluted aqueous solution, forms the dielectric oxide film layer.Step in-situ chemical according to embodiment 1 applies first dielectric substrate, second dielectric substrate and polymeric outer layer then, just when making second dielectric substrate, the polyvinylpyrrolidone of the 0.3wt% in the polymer fluid is replaced to the polymethyl methyl esters of 0.4wt%.When making outer layer copolymer with outer polymer fluid in the dimethyl sulfoxide (DMSO) NMP of 1wt% replace to the DMSO of 1wt%.And, prepare the polymeric outer layer of the about 20 μ m of thickness～50 μ m through 2 above-mentioned dippings, polymerization, cleaning and formation process again.On the conducting polymer skin, apply low-temperature conductive graphite linings, conductive silver slurry layer then, finish the preparation of conductive cathode.The anode of lead frame and cathode weld are finished the encapsulation of resin bed then, form solid electrolytic capacitor.
Embodiment 3:
Make the anode porous sintered body according to embodiment 1, and burning surface formation dielectric oxide film, step in-situ chemical according to embodiment 1 applies first dielectric substrate, second dielectric substrate and polymeric outer layer then, just with the dipping of first dielectric substrate, polymerization, cleaning and again formation process change into 4 times, with the dipping of second dielectric substrate, polymerization, cleaning and again formation process change into 2 times, and polymeric solution at polymeric outer layer in add the neopelex of the butyl carbitol of 0.2wt% and 0.1wt% as surfactant.And the neopelex that adds simultaneously the butyl carbitol of 0.2wt% and 0.1wt% in black lead wash finishes graphite, silver slurry as surfactant, finishes the welding of lead frame, finishes the encapsulation of resin bed, forms electrolytic capacitor.
Comparative example 1:
Conventional now method is that the tantalum anode that will form dielectric oxide film immerses 5min～10min in the polymer fluid that monomer concentration is 3～6wt%, the tantalum core that will flood polymer fluid then places room temperature condition to dry about 10min, be placed on again in 40 ℃～60 ℃ the baking oven and react 15min, afterwards at 120 ℃ of heat treatment 10min.Again with this fuse of deionized water wash 30min, in the p-methyl benzenesulfonic acid aqueous solution of 0.1wt%, anode tantalum fuse is mended formation 30 minutes, rinsing and drying in deionized water repeat described dipping, drying, heat treatment and benefit forming process and obtain the conductive polymer coating that thickness is approximately 10 μ m 12 times afterwards.Then, on the half-finished conductive polymer coating that obtains, apply graphite silver slurry, carry out mold pressing then.Like this, just make and finished solid electrolytic capacitor.
Comparative example 2:
Make the anode porous sintered body according to embodiment 1, and burning surface formation dielectric oxide film, step in-situ chemical according to embodiment 1 applies first dielectric substrate then, second dielectric substrate is the dipping with first dielectric substrate, polymerization, clean and again formation process change into 4 times, dipping with second dielectric substrate, polymerization, clean and again formation process change into 6 times, do not carry out the preparation of polymeric outer layer, the anode that directly will have second dielectric substrate applies the low-temperature conductive graphite linings, conductive silver slurry layer, the product lead frame does not adopt the bottom surface towards bottom electrode, and use conventional side lead frame to weld, finish the encapsulation of resin bed, form electrolytic capacitor.
Comparative example 3:
Make the anode porous sintered body according to embodiment 1, and burning surface formation dielectric oxide film.The tantalum anode that will form dielectric oxide film then immerses earlier and contains in the above solution of oxidant 40wt% 10 minutes, taking-up under 50 ℃ temperature dry 30 minutes, immersed then in the solution contain monomer 5 minutes, room temperature was placed 30 minutes, polyase 13 0～60 minute under 40～80 ℃ temperature conditions then, remove unnecessary unreacted monomer and oxidant and residue with methyl alcohol, deionized water rinsing, change into again, and under 100～150 ℃ temperature, carry out drying.Repeat said process and obtain the conductive polymer coating that thickness is approximately 20 μ m 12～16 times.Select for use conventional manganese dioxide electrolytic condenser to produce used hot setting graphite and Yin Yin slurry (its curing temperature＞180 ℃), the product lead frame does not adopt the bottom surface towards bottom electrode, and use conventional side lead frame to weld, and finish the encapsulation of resin bed, form electrolytic capacitor.
Tantalum anode in the embodiment of the invention forms dielectric oxide film after dilute phosphoric acid solution changes into, the wet survey capacitance of removing embodiment 2 is 220 μ F, and the wet survey of other each example capacitance is 110 μ F, finishes all processes among the embodiment, capacitance is tested under 120Hz, and the average size extraction rate reaches 98%.Equivalent series resistance is tested under 10KHz, 100KHz, 1000KHz, 2000KHz respectively, and leakage current is tested 30 seconds readings under 1.2 times of rated voltages.Following table 1 is respectively to implement the mean value of 20 samples:
Table 1
Data by last table as can be seen, technical scheme polymerization cycle-index of the present invention is few, production efficiency greatly improves, negative electrode polymer electrolytic layer adopts three step manufacture crafts, both guaranteed the growth of polyeletrolyte in the anode bodies internal void, the adequate thickness and the intensity of outer layer copolymer have been guaranteed again, and adopt low-temperature conductive graphite linings, conductive silver slurry layer, anode and cathode end all use the bottom surface towards bottom electrode, have guaranteed that fully drawing with product of capacitance has extremely low ESR value and stable impedance frequency characteristic.
Claims (7)
1. the manufacture method of the solid electrolytic capacitor of a ultra-low equivalent series resistance comprises the following steps: successively
A, the valve metal powder is become the anode porous sintered body that has lead-in wire through mold pressing and vacuum-sintering;
B, adopt electrochemical method to form dielectric oxide film in the porous sintered surface of anode;
C, form the conducting high polymers layer in the porous sintered surface of the anode that has dielectric oxide film;
D, outside conducting high polymers thing layer coated graphite layer and silver slurry layer successively;
E, form final products by mold pressing encapsulation.
It is characterized in that step C is made up of following operation successively:
The preparation of (1) first dielectric substrate;
The preparation of (2) second dielectric substrates;
(3) preparation of polymeric outer layer.
2. the manufacture method of the solid electrolytic capacitor of ultra-low equivalent series resistance according to claim 1 is characterized in that in each operation of C step:
The preparation method of (1) first dielectric substrate is called for short agglomerate is immersed in first dielectric substrate under 0～10 ℃ of condition polymeric solution with porous sintered of the anode that has dielectric oxide film to be called for short 5～10min in first polymer fluid, the agglomerate that will flood first polymer fluid then places room temperature condition to dry 10min, be placed on again in 40～150 ℃ the baking oven and react 15～40min, make monomer fully polymerization under the oxidant effect, use deionized water wash again, and agglomerate is changed into 30～60min again with mend forming liquid, in deionized water, clean afterwards and drying, described dipping, polymerization, change into again with the cleaning-drying process need and repeat 2～4 times, make the 1st dielectric substrate thickness at 10～15nm;
The preparation method of (2) second dielectric substrates is that the agglomerate that will have first dielectric substrate is immersed in second dielectric substrate under 0～10 ℃ of condition polymer fluid is called for short 5～10min in second polymer fluid, its dipping, polymerization, one-tenthization and cleaning-drying process are with the preparation method of first dielectric substrate again, flood repeatedly, polymerization, change into and cleaning-drying process 2～4 times again, the thickness that makes second dielectric substrate is at 15～20nm;
(3) preparation method of polymeric outer layer is with the agglomerate with first dielectric substrate and second dielectric substrate, under 0～10 ℃ of condition, be immersed in and be called for short outer polymer fluid in the polymer fluid of polymeric outer layer, its dipping, polymerization, change into identical with the preparation method of first dielectric substrate again with the cleaning-drying process, flood repeatedly, polymerization, change into and cleaning-drying process 1～3 time again, the thickness that makes outer polymer layer is at 20～50 μ m;
Above-described additional formation liquid is meant that solution concentration is the aqueous solution of the p-methyl benzenesulfonic acid of 0.1wt%.
3. the manufacture method of the solid electrolytic capacitor of a kind of ultra-low equivalent series resistance according to claim 2, the polymer fluid of its feature first dielectric substrate i.e. first polymer fluid is meant the polymer fluid that monomer, oxidant, solvent and coupling agent are formed, wherein, monomer is meant pi-conjugated polymer, be selected from the pyrroles, thiophene, aniline and derivative thereof be as 3, a kind of in the 4-vinyl dioxy thiophene (EDT); Oxidant is selected from the alkylbenzenesulfonate or the alkylsulfonate of transition metal iron, copper, manganese, chromium, cerium, as toluenesulfonic acid iron, DBSA iron, methanesulfonic acid iron, ethyl sulfonic acid iron, propane sulfonic acid iron, fourth sulfonic acid iron a kind of or two kinds, solvent is selected from n-butanol, isopropyl alcohol, absolute ethyl alcohol, oxolane, water, N-methyl pyrrolidone (NMP) a kind of or two kinds, coupling agent is a silane, in first polymer fluid, monomer accounts for polymer fluid 1～3wt%, silane coupler accounts for 0.1～0.5wt% of polymer fluid, and oxidant accounts for 30～35wt%, and all the other are solvent;
The polymer fluid of second dielectric substrate i.e. second polymer fluid, except that having the preparation first dielectric substrate polymer fluid is the composition of first polymer fluid, also be added with the organic adhesive of the band five-membered ring structure as polyvinylpyrrolidone, in second polymer fluid, monomer accounts for polymer fluid 4～6wt%, bonding agent is 0.1～0.5wt%, and all the other proportionings are with first polymer fluid;
The polymer fluid of above-described polymeric outer layer is called for short outer polymer fluid, composition is except that having the first polymer fluid composition, also be added with one or more high boiling solvents of N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) or butyl carbitol, also add organic bond in addition, be selected from acrylate, function silane, polyvinyl alcohol, polymethacrylates a kind of or two kinds, also be added with the polymerization reaction delayed-action activator, the polymerization reaction delayed-action activator is selected from the combination in any of imidazoles, pyrazoles, pyridine or their derivative.In the outer polymer fluid, monomer accounts for 8-12wt%, and high boiling solvent accounts for 1～2wt%, and delayed-action activator accounts for 0.5～1wt%, and organic bond accounts for 0.1～0.5wt%, and all the other proportionings are with first polymer fluid.
4. according to the manufacture method of the solid electrolytic capacitor of claim 1 or 2 or 3 described a kind of ultra-low equivalent series resistances, it is characterized in that: above-mentioned valve metal is metal tantalum, niobium, titanium or aluminium, above-mentioned valve metal powder formed porous sintered body after mold pressing and vacuum-sintering, its sintered density is 5.2～5.8gcm
-3, thickness is 0.6～1.2mm.
5. according to the manufacture method of the solid electrolytic capacitor of claim 1 or 2 or 3 described a kind of ultra-low equivalent series resistances, it is characterized in that: the used graphite of cathode conductive layer has the low temperature graphite of high conduction performance, the electric conductivity of this graphite＜15m Ω cm
-2, curing temperature＜80 ℃;
The used silver slurry of cathode conductive layer is starched the electric conductivity＜15m Ω cm of this silver slurry for the low-temperature silver of tool high conduction performance
-2, curing temperature＜80 ℃.
6. according to the manufacture method of the solid electrolytic capacitor of claim 1 or 2 or 3 described a kind of ultra-low equivalent series resistances, it is characterized in that: what anode extraction electrode that links to each other with the capacity cell anode tap and cathode end that is connected with the capacity cell cathode conductive layer all used is bottom surface electrode form down.
7. the solid electrolytic capacitor of a ultra-low equivalent series resistance, it is characterized in that: the capacitor that the method according to this invention is produced, under the test frequency of 100KH2, its ESR value＜50m Ω, its impedance frequency characteristic, it is stable that the ESR value can keep in 10KHz～1000KHz scope, rate of change＜10%.
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916672A (en) * | 2010-08-20 | 2010-12-15 | 电子科技大学 | Solid tantalum electrolytic capacitor and preparation method thereof |
| CN101923964A (en) * | 2010-08-20 | 2010-12-22 | 电子科技大学 | Solid tantalum electrolytic capacitor and manufacturing method thereof |
| CN101923966A (en) * | 2010-08-20 | 2010-12-22 | 电子科技大学 | Solid tantalum electrolytic capacitor and preparation method thereof |
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