CN101692412B - New type solid electrolytic capacitor and manufacturing method thereof - Google Patents
New type solid electrolytic capacitor and manufacturing method thereof Download PDFInfo
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- CN101692412B CN101692412B CN2009101026008A CN200910102600A CN101692412B CN 101692412 B CN101692412 B CN 101692412B CN 2009101026008 A CN2009101026008 A CN 2009101026008A CN 200910102600 A CN200910102600 A CN 200910102600A CN 101692412 B CN101692412 B CN 101692412B
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Abstract
The invention relates to a new type solid electrolytic capacitor and a manufacturing method thereof, particularly to an electrical apparatus element and a low equivalent series resistance (ESR) manufactured by using six processing steps with high volume efficiency and excellent impedance frequency characteristic, wherein the ESR value can be kept stably in the range of 10 KHZ to 1000 KHZ, for meeting the demand of high-frequency solid electrolytic capacitor of modern electrical equipment. A key step 4 is a manufacturing method for a catholyte layer. The catholyte layer has an electroconductive macromolecular compound layer which is formed by compounding inorganic manganese dioxide electrolyte layer 4b or chemical polymerized electroconductive macromolecular layer 4b and electrolytic polymerized electroconductive macromolecular polymer layer 4c. The capacitor element is packed in the manner of leading an electrode on bottom.
Description
Technical field: the present invention relates to a kind of electronic component and manufacture method thereof, specifically a kind of manufacture method of new type solid electrolytic capacitor.
Background technology: along with all kinds of multimedia messages treatment facilities to miniaturization, high speed processingization and low-power consumption direction develop, and cause demand miniaturized component, height integrated level LSIC (high-frequency, low-voltage) circuit, and require the circuit intermittent work.Propose a series of new new demands for the capacitor that uses like this,, proposed low ESR (ESR), better the requirement of frequency characteristic especially for the tantalum electrolytic capacitor that is good at the big capacity of miniaturization.Semi-conductor electricity road direction high speed and low-voltage direction develop, in particularly high in fields such as military, space flight, aviation, weapons, boats and ships, the smart electronic equipment, clock frequency improves day by day, in order to suppress High-frequency Interference and voltage fluctuation, is badly in need of miniaturization and jumbo low 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 low 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 military 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.
Ten or twenty is in year recently, and 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 that the ideal of the electrolyte of solid electrolytic capacitor is selected.At present, conductive polymer material becomes the employed electrolytical exploitation trend of electrolytic capacitor of new generation already.
As the method that the electroconductive polymer polymer forms, known have chemical polymerization and an electrolysis polymerization method.Change polymerization and have the defective that intensity is low, it is in uneven thickness of the electroconductive polymer layer of formation, so extensively adopt the electrolysis polymerization method to form the electroconductive polymer layer at present.The good conductivity of the electroconductive polymer film that the general electroconductive polymer film ratio employing chemical polymerization that adopts the electrolysis polymerization method to form forms, and can form firm film.But, forming under the situation of solid electrolyte by the electroconductive polymer that adopts the electrolysis polymerization method to make, this solid electrolytic laminar surface becomes smoothly easily, makes this solid electrolytic layer and solid formation negative electrode thereon draw the contact performance variation of layer, causes the ESR of high-frequency region to increase.Except the low ESR of needs, it is stable that modern electronic equipment also needs to keep in the very big frequency range of the impedance behavior of electrolytic capacitor, needs that promptly external stress is had good stable.Particularly in the electrolytic capacitor preparation process, can produce very high mechanical stress during the anode of encapsulated capacitor (mold pressing resin encapsulation), to such an extent as to make the performance degradation of product.In order to alleviate external stress to the capacitor element Effect on Performance, just need on the capacitor anode piece, make the thicker outer dielectric substrate of one deck, wish that this electrolyte layers has enough mechanical strengths, can alleviate external stress again to the capacitor element Effect on Performance simultaneously.
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 shortcoming of these capacitors is to have 130m Ω and higher ESR.
In the electrolysis polymerization method to live, as shown in Figure 3, the top contact by the electrode member 2 that will be connected with the positive electrical of power supply makes the first dielectric substrate 4b form positive potential on the first dielectric substrate 4b.But, because the situation that contacts difference because of the electrode member 2 and the first dielectric substrate 4b, can not evenly distribute along the first dielectric substrate 4b current amount flowing in the electrolytic process, different capacitor elements then is difficult to formation is fixed and the uniform electrolysis polymerization thing of thickness layer, and the situation that very easily causes polyelectrolyte floor and capacitor anode body to peel off.
As one of technology that solves the above problems, there is the spy to open flat 11-121280 communique disclosed method.In the method, shown in Fig. 4 A, the first dielectric substrate 4b, except that covering anode dielectric oxide film 3, also cover the root of a part of anode tap 1, be the bottom of anode tap 1, near the anode tap that has just exposed the anode chunk partly, form the first certain electrolyte 4b conductive layer at the root of anode tap.Like this, when the anode lead-in wire imposes positive potential, can in the lump whole first dielectric substrate be formed positive potential as Fig. 4 B, thereby electrolytic oxidation polymerization takes place thereon.But, in the method, shown in Fig. 4 C, very easily around the anode tap root, form electroconductive polymer burr 17 in the electrolysis polymerization process.The isolation that this will seriously influence behind the capacitor anode and negative electrode in the production process causes the increase of final products leakage current, even can cause the short circuit of capacitor anode and negative electrode.
Summary of the invention: the objective of the invention is to overcome existing defective, a kind of new type solid electrolytic capacitor and manufacture method thereof are provided, produce and have extremely low equivalent series resistance (ESR) and very high volume efficiency solid electrolytic capacitor, make its ESR value in the 10KHZ-2000KHZ scope, keep stable, to satisfy the requirement of modern electronic equipment high frequencyization, chip type well.
The inventor's surprised discovery in experimental study, the electroconductive polymer polymeric layer that is first dielectric substrate and electrolysis polymerization with inorganic manganese dioxide dielectric substrate is the conductivity composite electrolyte layer that second dielectric substrate is composited; Or be that first dielectric substrate and electrolysis polymerization thing layer are that the conducting high polymers thing composite solid electrolyte layer that second dielectric substrate is composited is that the catholyte layer can finely satisfy above-mentioned requirements with the electroconductive polymer layer of chemical polymerization.On the capacitor element of the precoating conductive layer (first dielectric substrate) that the electroconductive polymer layer with inorganic manganese dioxide dielectric substrate or chemical polymerization is formed, form the conductive polymer coating of the thickness of making one deck densification, the stability of capacitor performance is improved greatly at 10-50 μ m by electrolysis polymerization.
According to above-mentioned discovery, purpose of the present invention realizes by following scheme:
The manufacturing of solid electrolytic capacitor comprises the following steps:
The step 2. porous sintered surface of anode adopts electrochemical method to form dielectric oxide film;
Step is the pre-protective layer of adhesive of covering dielectric oxidation film layer 3.;
4. step has the porous sintered surface of the anode of the pre-protective layer of adhesive to form conducting high polymers thing complex solid conductivity electrolysis matter layer, i.e. catholyte layer;
Step is coated graphite layer and silver slurry layer successively outside conducting high polymers thing complex solid conductivity electrolysis matter layer 5.;
6. step forms final products with resin by the mold pressing encapsulation.
Now be described below respectively: the 1. described valve metal of step is metal tantalum, niobium or titanium.The porous sintered body of above-mentioned valve metal powder formed band lead-in wire after mold pressing and vacuum-sintering, its sintered density is 5.2-5.8g.cm
-3, thickness is 0.6-1.2mm.
According to electrolytic capacitor of the present invention, the specific volume of valve metal powder (CV value) is greater than 30,000 μ FV.g
-1, it is preferentially greater than 50,000 μ FV.g
-1The 2. described dielectric oxide film that forms in the porous sintered surface of band lead-in wire anode of step, be meant that above-mentioned valve metal powder is behind the anode porous sintered body that has lead-in wire that mold pressing becomes with vacuum high-temperature sintering, it is anodizing to 30～33V in the phosphoric acid,diluted aqueous solution, the dielectric oxide film layer of formation; The pre-protective layer of adhesive of the 3. described covering dielectric oxidation film layer of step mainly comprises the polymer of the organic bond that contains the bipolarity group; the adhesive that particularly contains hydroxyl; because hydroxyl can improve the bonding force of interlayer by attraction and/or key (as Van der Waals force, hydrogen bond, ionic bond, covalent bond etc.), this helps to improve the surface state of valve metal dielectric oxide film.It is optimum that what select for use is that the polymer that contains vinyl alcohol is used as adhesive, be particularly suitable for selecting for use the ethenol copolymer that contains other monomeric unit, ethenol copolymer can obtain in the copolymer hydrolysis by vinyl esters, for example the copolymer of vinyl esters and the unsaturated carboxylic acid (as propionic acid, methacrylic acid, ethylenediamine tetra-acetic acid etc.) that contains 3-30 carbon atom and other etc.In addition, also can use other material to improve the tack and the pliability of protective adhesive layer.The example of this material comprises acrylate or methacrylate; Polyurethane; Saturated or unsaturated fatty acid ester etc., the thin polymer film that these aliphatic acid can make aggregates into stable protective layer rapidly.
The pre-protective layer of adhesive may be made by various mode, as spin coating, silk-screen, impregnating.Be that the anode component that will have dielectric layer is impregnated in the solution that contains the protectiveness adhesive in an embodiment of the present invention, make yet handle by high temperature (about 150 ℃).Solvent in the solution is used to control the viscosity of solution, can use any solvent that can dissolve desired protectiveness adhesive, as water, glycol, glycol ether, glyceride, acid amides, sulfoxide or sulfone etc.Step is 4. described to form the composite conductive polyelectrolyte layers in the porous sintered surface of the anode that has the pre-protective layer of adhesive; be meant that the anode porous body forms the dielectric oxide film layer; and behind the pre-protective layer of treated formation adhesive, make the catholyte layer in the above.
Described solid electrolytic container catholyte layer is that second dielectric substrate of the electroconductive polymer polymer that formed by first dielectric substrate and electrolysis polymerization is composited, wherein, first dielectric substrate is that electroconductive polymer polymeric layer by inorganic manganese dioxide dielectric substrate or chemical polymerization constitutes.Described inorganic manganese dioxide first dielectric substrate is by flooding certain density manganese nitrate solution by the porous sintered body that will form, and at high temperature 300 ℃ of conditions are decomposed and formed.The preferred 0.8-1.3g/cm of the proportion of manganese nitrate solution wherein
3, 1.1-1.2g/cm more preferably
3Electroconductive polymer layer first dielectric substrate of described chemical polymerization, wherein the electroconductive polymer layer is a kind of pi-conjugated polymer, formed by chemical oxidation in-situ polymerization Chemical oxidative polymerization in site by polymer monomer and oxidant, the conducting polymer that obtains in this chemical oxidising polymerisation is to use the transition metal salt of the organic sulfonic acid of double as dopant and oxidant to obtain.The monomer of described pi-conjugated polymer is at least a in pyrroles, thiophene, aniline and the derivative thereof.The polymer monomer that the present invention uses is derivative 3, the 4-vinyl dioxy thiophene (EDT) of thiophene, oxidant is selected from the alkylbenzenesulfonate or the alkyl sulfonic acid (salt) of transition metal, as toluenesulfonic acid iron, DBSA iron, methanesulfonic acid iron, ethyl sulfonic acid iron, propane sulfonic acid iron, fourth sulfonic acid iron etc.
Electroconductive polymer polymer second dielectric substrate that described electrolysis polymerization forms is to be immersed in by the capacitor anode piece that will form first dielectric substrate that contain can be by in the electrolysis polymerization liquid of the metal ion of electrolytic oxidation and/or metal oxide, be dissolved with the monomer of a certain amount of pi-conjugated polymer in this electrolysis polymerization liquid, electrolysis polymerization reaction utilizes described metal and/or metal oxide ions to be produced oxidant by electrolytic oxidation to carry out electrochemical polymerization and form.Monomer concentration is more preferably used 0.01-0.1mol/L at 0.001-0.2mol/L in the described electrolysis polymerization liquid, and the polymerization voltage that electrolysis polymerization applied is more preferably used 2-3V at 1-6V.The second dielectric substrate electrolysis polymerization method mainly is the conducted electricity precoated shet 4d (shown in Fig. 2 A) that ring-type is set by the top at described capacitor anode lead-in wire, the precoated shet that can conduct electricity is connected with the positive pole of additional power source, with this anode as electrolysis polymerization carry out electrolysis polymerization as Fig. 2 B, the conducted electricity precoated shet 4d of the ring-type that forms of anode tap top in the method, impose positive potential when thereon, ring-type can be conducted electricity precoated shet and be formed by polymer fluid and the first dielectric substrate 4b and be electrically connected, whole first dielectric substrate will be on the positive potential of electrolysis system, thereby electrolytic oxidation polymerization takes place thereon, ring-type can be conducted electricity the bottom anode tap surface of precoated shet owing to be formed with the nonconducting insulation dielectric oxidation film layer of one deck in addition, therefore can not form electrolysis polymerization thing layer in its surface, though in whole electrolysis polymerization process, can around the ring-type on anode tantalum line top can be conducted electricity precoated shet, form the electroconductive polymer burr like this, as (17) among Fig. 2 C, but but guaranteed the clean of anode tap tantalum wire root and above fraction, reduce follow-up treatment process, the making of electrolytic capacitor is become be more prone to.
Solid electrolytic capacitor of the present invention, owing to become the composite conductive dielectric substrate of combining closely with the capacitor element dielectric oxide film in the capacitor main body surface topography, the first dielectric substrate electric conductivity height in this dielectric substrate, good springiness, can alleviate destruction or the damage of the stress that produces in the subsequent handling well to dielectric oxide film, adopt second dielectric substrate of electrolysis polymerization legal system to have compact structure simultaneously, the characteristic that intensity is high, again because it is the superficial growth along first dielectric substrate, therefore and between the negative electrode graphite linings of drawing, fine tack is arranged, and cover its edge well, so the relative mechanical stress of capacitor main body is very firm.Admittedly can obtain reliability height, electrolytic capacitor product that ESR is low.Step is 5. described to apply graphite linings and silver slurry layer successively and is meant on above-mentioned conducting high polymers solid conduction electrolyte skin and applies graphite linings and silver slurry layer successively outside the composite conductive dielectric substrate, make capacitor element.Then anode tap is connected on the anode terminal, uses electrically conducting adhesive that cloudy terminal is connected with cathode layer with lead frame with bottom surface extraction electrode.See Fig. 5.
According to the present invention, 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.Prepared solid electrolytic capacitor, under the test frequency of 100KHz, its ESR value＜30m Ω.It is stable that the ESR value can keep in the 10KHZ-1000KHZ scope, rate of change＜10%.
6. step forms final products by the mold pressing encapsulation, forms the mold pressing resin encapsulation with epoxy resin at last, as Fig. 1.
The invention will be further described below in conjunction with Figure of description and embodiment:
Description of drawings: Figure 1A is the structural representation of electrolytic capacitor of the present invention
Figure 1B is the A partial enlarged drawing among Figure 1A; Fig. 2 A is the anode bodies profile of explanation embodiments of the invention, is illustrated in when carrying out electrolysis polymerization, and the pre-conductive coating of ring-type is set at anode tap.
2B is the anode bodies profile of explanation embodiments of the invention, is illustrated in when carrying out electrolysis polymerization the state of dipping anode bodies in solution.
2C is the anode bodies profile of explanation embodiments of the invention, the anode bodies after the expression electrolysis polymerization finishes.
Fig. 3 capacitor element manufacturing process in the past forms the schematic diagram of cathodic conductivity polyelectrolyte layers with the electrolysis polymerization method.
Fig. 4 A is capacitor element manufacture method anode bodies profile in the past, and expression forms the state of dielectric coating and precoated shet.
Fig. 4 B is the ideograph of capacitor element manufacture method in the past, electrolysis polymerization method schematic diagram
Fig. 4 C is capacitor element manufacture method anode bodies profile in the past, the state behind the expression electrolysis polymerization
Fig. 5 is bottom surface anode leading-out terminal and a cathode end welding schematic diagram in the embodiment of the invention
1. anode taps among the figure are called for short lead-in wire; 2. the anode porous sintered body is called for short anode bodies; 3. dielectric oxide film is called for short dielectric oxide film; 4. polyelectrolyte floor, or title conducting polymer comprises 4a, 4b and 4c; The pre-protective layer of 4a adhesive; 4b first dielectric substrate claims the precoating conductive layer again; 4c second dielectric substrate; 4d can conduct electricity precoated shet; 5. graphite linings; 6. silver slurry layer; 7. bonding silver slurry; 8. plastic packaging resin; 9. anode teflon gasket; 10. anode is drawn weld tabs (anode leading-out terminal); 11. negative electrode is drawn weld tabs (cathode end) 12. negative electrode teflon gaskets; 13. anode ultrasonic wave joint welding place; 14. negative electrode ultrasonic wave joint welding place; 15. anode tantalum wire pillow; 16. anode laser lap welding place; 17. burr; 20. negative electrode; 21. anode electrode.
Concrete execution mode:
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 1; be of a size of the porousness anode bodies 2 of 4.3mm * 3.1mm * 1.2mm; the direct voltage that anode bodies behind the sintering is applied 33V in the phosphoric acid,diluted aqueous solution carries out anode formation; form dielectric oxide film layer 3; the teflon gasket 9 that on anode tap is scurried, has insulation property then; prepared porousness anode bodies is impregnated in the solution that contains the protectiveness adhesive; (this solution is made up of the aqueous solution of the ethylenediamine tetra-acetic acid (EDTA) of polyvinyl alcohol that contains 1% weight portion and 1% weight portion); on the anode block, apply simultaneously the forward voltage of 20V; take out the anode block after 10 minutes; at room temperature place 10-15min; under 140-160 ℃ temperature dry 20 minutes then, the pre-protective layer 4a of adhesive.
Then this anode bodies is immersed in poly-ethylidene dioxy thiophene (EDT) monomer and 15wt% p-methyl benzenesulfonic acid iron mixed liquor of 2wt%, take out after 6 minutes, contain inferior enedioxy thiophene, p-methyl benzenesulfonic acid iron, n-butanol, aqueous isopropanol etc. in the mixed liquor, also contain 0.3% silane coupler.Impregnation is crossed the anode bodies of mixed liquor and at room temperature placed 10 minutes, be placed in 50 ℃ the constant temperature oven reaction 20 minutes, be warmed up to 120 ℃ of insulations then and finished polymerization reaction in 15 minutes.Then with this anode with ethanol and deionized water rinsing repeatedly, and in the p-methyl benzenesulfonic acid aqueous solution of 0.1wt%, change into again, dried is carried out at 120 ℃ in the back.Repeat aforesaid operations 3 times, on the tantalum anode block, obtain the first dielectric substrate 4b.Then, at the anode tap tantalum line end coated with conductive graphite slurry of the anode block that will finish above-mentioned steps, 120 ℃ of oven dry, to form the pre-conductive coating 4d of ring-type in tantalum line top ends.
Separate with aforesaid operations, will be (0.05mol/L), add in the water as the p-methyl benzenesulfonic acid (0.01mol/L) of dopant and as the ethylenediamine tetra-acetic acid (0.001mol/L) of chelating agent as the ethylidene dioxy thiophene (EDT) of monomer, mix, preparation forms the acidic electrolysis polymer fluid.The electrolysis polymerization liquid for preparing is poured in the electrolysis polymerization groove of stainless steel making.Then, the tantalum sintered object that has formed first dielectric substrate and the pre-conductive coating of ring-type be impregnated in the electrolysis polymerization liquid, notice that electrolysis polymerization liquid must have sufficient dipping and contact with the pre-conductive coating of ring-type.After this, the voltage that adds 2V between antianode and the negative electrode carries out electrolysis polymerization.Can form the electroconductive polymer layer that is formed by electrolysis polymerization after about 6 hours on first dielectric substrate is the second dielectric substrate 4C.
Then, on above-mentioned electroconductive polymer skin, apply graphite linings 5 and silver slurry layer 6 successively, make capacitor element.Then anode tap is connected on the anode terminal 10 with lead frame with bottom surface extraction electrode, use conductive adhesive that cathode terminal 11 is connected with cathode pads layer 12, and carry out mold pressing epoxy encapsulation 8 with epoxy resin, temperature during encapsulation is 180 ℃, anode and cathode terminal exposed parts only on the capacitor bottom surface, so just obtain final conducting polymer solid electrolytic capacitor.
Embodiment two:
To have 50, the tantalum powder of 000 μ FV/g, compacting is in blocks, and is forming the porousness anode bodies 2 that is of a size of 4.3mm * 3.0mm * 0.6mm, anode bodies behind the sintering is applied the 30V direct voltage carry out anode formation in the phosphoric acid,diluted aqueous solution, form dielectric oxide film layer 3.Make the pre-protective layer 4a of adhesive according to the method for embodiment 1 then.It is 1.15g/cm that the tantalum anode block that will have the pre-protective layer of adhesive then impregnated in proportion
3Manganese nitrate solution in, dipping temperature is controlled at about 65 ℃, the about 6min of dip time, take out then anode block is positioned in the high temperature drying case, and make the temperature in the drying box within 1min, be elevated to 300 ℃, and in drying box, pour supersaturation water steam behind the insulation 5min, after the 2min sample is taken out cooling, after repeat said process again one time, thereby on the tantalum anode block, obtain the first dielectric substrate 4b that forms by the manganese dioxide of thermal decomposition gained.The capacitor anode block with first dielectric substrate that is obtained immersed the voltage with 24V changes into again in the glacial acetic acid solution contain 0.05wt%.Make second dielectric substrate and polymeric outer layer 4c according to the method electrolysis of embodiment one then, on the conducting polymer skin, apply low-temperature conductive graphite linings 5, conductive silver slurry layer 6 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.
Tantalum anode in the embodiment of the invention forms dielectric oxide film after dilute phosphoric acid solution changes into, the wet survey of each example capacitance is 110 μ F, finishes all processes among the embodiment, and 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 is respectively to implement the mean value of 20 samples:
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 10 and cathode end 11 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 (10)
1. the manufacture method of a solid electrolytic capacitor, its processing step is followed successively by:
Step is anode 1., the anode porous sintered body (2) that has lead-in wire (1) that valve metal tantalum or niobium powder are formed through mold pressing and vacuum-sintering;
2. step adopts electrochemical method to form dielectric oxide film layer (3) on anode porous sintered body (2) surface;
Step is the pre-protective layer of adhesive (4a) of covering dielectric oxidation film layer (3) 3., and wherein the pre-protective layer of adhesive comprises the polymer of the repetitive with bipolarity base;
6. step forms final products by the mold pressing encapsulation, it is characterized in that all the other processing steps are:
Step is the conducting high polymers thing composite solid electrolyte layer of solid electrolytic capacitor 4., i.e. the preparation of first dielectric substrate (4b) of catholyte layer and second dielectric substrate (4c);
The cathode conductive layer that 5. step covers first dielectric substrate (4b) and second dielectric substrate (4c) is graphite linings (5) and silver slurry layer (6);
Described catholyte layer is that second dielectric substrate (4c) of the electroconductive polymer polymerization that formed by first dielectric substrate (4b) and electrolysis polymerization is composited, and wherein first dielectric substrate is that electroconductive polymer polymeric layer by inorganic manganese dioxide dielectric substrate or chemical polymerization constitutes.
2. the manufacture method of a kind of solid electrolytic capacitor according to claim 1 is characterized in that the inorganic manganese dioxide layer of described first dielectric substrate (4b) is that to impregnated in proportion by the porous sintered body that forms by first three steps be 0.8～1.3g/cm
3Manganese nitrate solution, and at high temperature 300 ℃ of conditions are decomposed and are formed.
3. the manufacture method of a kind of solid electrolytic capacitor according to claim 1, the electroconductive polymer polymeric layer that it is characterized in that described first dielectric substrate (4b) chemical polymerization is a kind of pi-conjugated polymer, formed by the chemical oxidation in-situ polymerization by polymer monomer and oxidant, the conducting polymer that obtains in this chemical oxidation in-situ polymerization is to use the transition metal salt of the organic sulfonic acid of double as dopant and oxidant to obtain; The monomer of described pi-conjugated polymer is at least a in pyrroles, thiophene, aniline and the derivative thereof;
4. the manufacture method of a kind of solid electrolytic capacitor according to claim 1, described second dielectric substrate (4c) is to be immersed in by the capacitor anode piece that will form first dielectric substrate (4b) that contain can be by in the electrolysis polymerization liquid of the metal ion of electrolytic oxidation and/or metal oxide, be dissolved with the monomer of 0.001～0.2mol/L-conjugated polymer in this electrolysis polymerization liquid, electrolysis polymerization reaction utilizes described metal and/or metal oxide ions to be produced oxidant by electrolytic oxidation to carry out electrochemical polymerization and form.
5. the manufacture method of described a kind of solid electrolytic capacitor according to claim 4 is characterized in that monomer concentration is at 0.01～0.1mol/L in the electrolysis polymerization liquid, and the polymerization voltage that electrolysis polymerization applied is at 1-6V.
6. the manufacture method of a kind of solid electrolytic capacitor according to claim 1, it is characterized in that being provided with the conducted electricity precoated shet (4d) of ring-type by top at described lead-in wire (1), the precoated shet (4d) that can conduct electricity is connected with the positive pole (21) of additional power source, carries out electrolysis polymerization with this anode as electrolysis polymerization.
7. the manufacture method of a kind of solid electrolytic capacitor according to claim 1 is characterized in that: silver slurry layer (6) that cathode conductive layer is used and the bonding silver-colored low-temperature silver slurry of starching (7) for the tool high conduction performance, the electric conductivity＜0.015 Ω .m of this silver slurry
-2, curing temperature＜80 ℃.
8. the manufacture method of a kind of solid electrolytic capacitor according to claim 1 is characterized in that: what anode leading-out terminal (10) that links to each other with lead-in wire (1) and cathode end (11) that is connected with cathode conductive layer all used is bottom surface electrode form down.
9. the solid electrolytic capacitor that manufacture method according to claim 1 is made is characterized in that its impedance frequency characteristic is good, and it is stable that its ESR value can keep in the 10KHZ-1000KHZ scope, rate of change＜10%.
10. solid electrolytic capacitor that manufacture method according to claim 1 is made, it is characterized in that: the used graphite of cathode conductive layer is the low temperature graphite of tool high conduction performance, the electric conductivity of this graphite＜15 Ω .m
-2, curing temperature＜80 ℃.
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| CN101923966B (en) * | 2010-08-20 | 2012-04-18 | 电子科技大学 | Solid tantalum electrolytic capacitor and preparation method thereof |
| CN101916672B (en) * | 2010-08-20 | 2012-07-18 | 电子科技大学 | Solid tantalum electrolytic capacitor and preparation method thereof |
| DE102012004692A1 (en) * | 2012-03-12 | 2013-09-12 | Heraeus Precious Metals Gmbh & Co. Kg | Addition of polymers to thiophene monomers in in situ polymerization |
| CN102800480B (en) * | 2012-08-24 | 2016-01-13 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of preparation method for cathode of Nb capacitor |
| CN103295787B (en) * | 2013-05-28 | 2016-01-20 | 中国振华（集团）新云电子元器件有限责任公司 | The processing method of electrolytic capacitor manufacture process medium oxide-film |
| CN104240955A (en) * | 2014-09-09 | 2014-12-24 | 中国振华（集团）新云电子元器件有限责任公司 | Tantalum electrolytic capacitor and manufacturing method thereof |
| CN105428069B (en) * | 2015-08-19 | 2018-02-16 | 中国科学院福建物质结构研究所 | A kind of solid electrolytic capacitor with composite solid electrolyte and preparation method thereof |
| CN106710882B (en) * | 2015-08-19 | 2019-03-08 | 中国科学院福建物质结构研究所 | A kind of solid electrolytic capacitor and preparation method thereof with composite solid electrolyte |
| CN109887749B (en) * | 2019-01-25 | 2022-06-21 | 南通瑞泰电子有限公司 | All-solid-state aluminum electrolytic capacitor and preparation method thereof |
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| CN114068190A (en) * | 2021-11-16 | 2022-02-18 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Method for improving insulation strength of tantalum capacitor |
| CN114974898A (en) * | 2022-06-14 | 2022-08-30 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Capacitor core and manufacturing method thereof, electrolytic capacitor and manufacturing method thereof |
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