CN104409216A - Method for manufacturing Ta2O5-RuO2/Ta capacitor - Google Patents
Method for manufacturing Ta2O5-RuO2/Ta capacitor Download PDFInfo
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- CN104409216A CN104409216A CN201410720477.7A CN201410720477A CN104409216A CN 104409216 A CN104409216 A CN 104409216A CN 201410720477 A CN201410720477 A CN 201410720477A CN 104409216 A CN104409216 A CN 104409216A
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Abstract
The invention provides a method for manufacturing a Ta2O5-RuO2/Ta capacitor, belongs to the technical field of electronic element manufacturing. A Ta2O5 anode medium layer and a RuO2 cathode medium layer of the Ta2O5-RuO2/Ta capacitor manufactured by using the method are stable in structure, relatively large in specific surface area, and excellent in electron conductivity and proton transmission capability, rapid charging and discharging can be realized, relatively high specific capacity and excellent large-current discharge property are achieved, and the energy density and the power density of an electrode are effectively increased.
Description
Technical field
The invention belongs to the technical field that electronic devices and components manufacture, particularly relate to a kind of Ta
2o
5-RuO
2the manufacture method of/Ta capacitor.
Background technology
High-energy tantalum mixed capacitor take tantalum electrolytic capacitor as the vast capacity mixed capacitor that anode and double electric layer capacitor form for negative electrode, specifically by sintered type tantalum anode fuse, tantalum pentoxide (Ta
2o
5) medium, sulfuric acid solution electrolyte and tantalum base ruthenic oxide (RuO
2) cathode sheets composition, sulfuric acid solution electrolyte and tantalum base ruthenic oxide (RuO
2) cathode sheets composition capacitor cathode, tantalum base ruthenic oxide (RuO
2) cathode sheets improves the electrolytical contact area of sulfuric acid solution, generate double electric layer capacitor, anode capacity can be drawn to greatest extent.High-energy tantalum mixed capacitor volume is little, excellent electrical property, product reliability is good, stable performance, life-span is long, the energy density of unit volume and Unit Weight and power density are large, and being applicable to Aeronautics and Astronautics, weapons, boats and ships, electronics etc. has in the direct current of the Military Electronic Equipment of reliability requirement, pulsation and low ripple circuit.
The focus technology of high-energy tantalum mixed capacitor is divided into the sintering of tantalum anode core, tantalum pentoxide (Ta
2o
5) medium making, electrolyte quota, tantalum base ruthenic oxide (RuO
2) making four aspects of cathode sheets, wherein:
The sintering of tantalum anode core: tantalum powder is pressed into circle or square block, then sinter under 1300 DEG C ~ 2100 DEG C vacuum environments or atmosphere of inert gases and form, when tantalum powder is suppressed, need to add the lubricant composition such as a certain amount of camphor, stearic acid, what tantalum powder was suppressed is tightr.
Tantalum pentoxide (Ta
2o
5) medium making: after sintering, tantalum block inserts in the oxidizing agent solutions such as phosphoric acid, then carries out electrolysis and forms tantalum pentoxide (Ta on tantalum block surface
2o
5) dielectric layer.If application number is the patent of invention of 200910043202.3: the manufacture method of a kind of vast capacity non-solid electrolyte tantalum electric capacity, it take tantalum sintered object as base material, and with this base material for anode 0.01 ~ 0.1% H
3pO
4multipole formation is carried out in solution.
Electrolyte quota: raw material is deionized water and sulfuric acid solution, and adds a certain amount of VOSO in the solution again
4xH
2o, Ag
2sO
4, CuSO
45H
2o, Fe
2(SO4)
3, VOSO
4deng transition metal salt, if application number is the patent of invention of 201410122493.6: hybrid super tantalum capacitor high-pressure electrolysis matter and preparation method thereof.
Tantalum base ruthenic oxide (RuO
2) cathode sheets: disperse in organic solvent by powder ruthenium dioxide, add a certain amount of binding agent and form mixed liquor, mixed liquor spread upon on tantalum substrate, then dry, sinter, and repeat 6 ~ 13 times; If application number is the patent of invention of 201210370552.2: a kind of preparation method of ruthenium dioxide combination electrode for energy storage, and application number is the patent of invention of 201210370552.2: combined electrode supercapacitor and preparation method thereof.
In above-mentioned manufacture craft, tantalum pentoxide (Ta
2o
5) medium makes and tantalum base ruthenic oxide (RuO2) cathode sheets two steps are core technologies of this ruthenium tantalum series capacitors, also be the technical barrier in this field, its reason mainly contains 2 points: one is due to tantalum pentoxide and the special surface characteristic of ruthenic oxide material, the electrode surface be made into is caused easily to ftracture, cause contacting with collector not good, finally affect performance and the life-span of active material chemical property; Two is because the electrochemical reaction of ruthenic oxide mainly concentrates on the accurate three-dimensional space of two peacekeepings, therefore electrode can not make too thick, otherwise can have a strong impact on electrode performance, this just means the application that prior art limits it and requires at some in the occasion of high energy storage density.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of manufacture method of Ta2O5-RuO2/Ta capacitor.
The present invention is achieved by the following technical programs.
A kind of Ta provided by the invention
2o
5-RuO
2the manufacture method of/Ta capacitor, comprises tantalum anode core and the compacting of tantalum cathode cylinder and sinters, Ta
2o
5deielectric-coating makes, electrolyte quota, tantalum base RuO
2cathode electrode layer makes, and capacitor assembling, wherein:
Ta
2o
5deielectric-coating making step is:
(1) make oxidation and form liquid, adopt ethylene glycol: deionized water ratio is 1:1 ~ 2 mixed liquor is solvent, adds H
3pO
4solution and Ag
2sO
4, make the mass concentration 0.08wt% of phosphoric acid ~ 0.8wt%, Ag
2sO
4mass concentration 0.01wt% ~ 0.05wt%;
(2) cooling oxidation forms liquid, adopts cooling system to control at-5 DEG C ~ 5 DEG C by the temperature that this oxidation forms liquid;
(3) to the preliminary treatment of tantalum anode core, carry out preliminary treatment with the toluenesulfonic acid ferrous solution that concentration is 0.1wt% ~ 3wt% to tantalum anode core, treatment temperature is 10 ~ 30min, and its solvent is the one in ethanol, methyl alcohol, n-butanol;
(4) dielectric oxide film is made, anode pellet being immersed oxidation is formed in liquid, antianode pellet is energized, and make boost current density be within the scope of 8mA/g ~ 30mA/g, initial boost current density is 20mA/g ~ 30mA/g, in anode pellet, voltage often boosts 12V, constant voltage 20min ~ 30min, after each constant voltage terminates, boost current density is reduced 3 ~ 4mA/g, minimumly be reduced to 8mA/g, until capacitor anode pellet both positive and negative polarity voltage is raised to predetermined magnitude of voltage, deenergization after constant voltage 5h ~ 6h, described predetermined magnitude of voltage is 3 ~ 5 times of rated capacitor voltage,
(5) stable oxide-film, when in anode pellet, voltage drop is to below 1V, the anode pellet being formed with oxidation film layer is taken out from oxidation formation liquid, and the deionized water being placed in temperature 90 DEG C boils and washes 30min-120min, the oxidation of anode pellet inside is formed liquid and all boils wash clean; Putting into vacuum degree is 2 × 10
-3more than Torr, temperature are heat treatment 20 ~ 60min in the vacuum furnace of 200 ~ 300 DEG C; Then will immerse temperature through heat treated anode pellet block is carry out electrochemical treatments 1 ~ 2 hour in 160 DEG C ~ 180 DEG C oxidizing agent solutions, applying voltage is 0.8 times ~ 1.2 times of rated capacitor voltage, anode pellet through Passivation Treatment is cleaned, dry for standby.
Tantalum base RuO
2cathode electrode making step is:
(1) make ruthenium source solution, ruthenium source is dissolved in aqueous isopropanol, adds cationic surfactant, dispersion;
Described ruthenium source is ruthenium trichloride, an isopropyl toluene ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium, tri-chlorination six ammonium close ruthenium, the mixing of in nitrosyl nitrate ruthenium a kind or 2 kinds;
Described cationic surfactant is the mixing of in cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecyl amine hydrochloride, dioctadecylamine hydrochloride, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl benzyl dimethyl ammonium chloride, chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride a kind or 2 kinds;
(2) in the solution of ruthenium source, add the oxidizability metal dust of 1 ~ 5%, described oxidizability metal dust is one or more in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, potassium permanganate;
(3) add 1 ~ 3% thickener, described thickener is polyacrylamide, titanate esters, gum arabic, Silica hydrogel;
(4) to the preliminary treatment of tantalum cathode cylinder, be that the toluenesulfonic acid ferrous solution of 0.05wt% ~ 1wt% carries out preliminary treatment to tantalum cathode cylinder inwall by concentration, processing time is 10 ~ 30min, pours out after being disposed, and its solvent is the one in ethanol, methyl alcohol, n-butanol;
(5) solution that step (3) obtains is poured in the cathode tube after step (4) process, pouring volume is 1/10 ~ 1/6 of cathode tube volume, then the environment putting into 60 ~ 70 DEG C carries out centrifugal oven dry, described centrifugal oven dry is dried for being put on tachogenerator by cathode tube, and cathode tube rotates around the center line of cathode tube, during oven dry, need to carry out speed governing to tachogenerator, the solution that step (3) is obtained is dispersed on the circular inner wall of cathode tube equably;
(6) carry out high temperature sintering process by sending in Muffle furnace by the cathode tube after step (5) process, temperature is 500 ~ 600 DEG C, and the time is 30min ~ 120min, naturally cools after high-temperature heat treatment completes.
(7) Passivation Treatment, what obtain to step (6) contains RuO
2the solution passivation process that step (2) obtains is added in the cathode tube of cathode electrode layer, and then high temperature sintering carries out high temperature sintering process in feeding Muffle furnace, temperature is 500 ~ 600 DEG C, and the time is 30min ~ 120min, naturally cools after high-temperature heat treatment completes.
Electrolyte quota step is:
(1) resistivity is greater than the deionized water of 5M Ω .cm and mass percent concentration be more than 98% sulfuric acid be mixed with the aqueous sulfuric acid that mass concentration is 25%-38%;
(2) in described aqueous sulfuric acid, add the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15%, be mixed with mixed solution; While this organically-modified solvent of use, need the absolute ethyl alcohol adding its 1/2 ~ 2 times of volume used in combination; The described property-modifying additive higher than 140 DEG C is one or both mixing in the large molecule organic solvent such as EGME, butyl glycol ether, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, sulfolane, HMPA;
(3) in above-mentioned mixed solution, the depolarizing agent of the 0.2%-1.0% of gross mass is added, through sonic oscillation evenly obtained working electrolyte; Described depolarizing agent be in the transition metal sulfates such as copper sulphate, sulfuric acid oxygen alum, ferric sulfate one or both mix;
(4) being formulated as of gel electrolyte: get some work electrolyte, add 5%-15% high-purity gas aerosil by mass percentage, stir, obtained gel electrolyte.
Further, the sintering concrete operation step of described tantalum anode core and the compacting of tantalum cathode cylinder is as follows:
The compacting of tantalum anode core and sintering step are:
(1) suppress: suppress with tantalum powder, and add lubricant in tantalum powder;
(2) presintering, puts into inert gas and carries out presintering by anode pellet, temperature is 200 DEG C ~ 400 DEG C, and burn-in time is 20min ~ 60min;
(3) sinter, anode pellet is put into inert gas and sinters, temperature is 1300 DEG C ~ 2000 DEG C, and sintering time is 20min ~ 60min, and during sintering, physical contact is not carried out on anode pellet surface mode with outer surface sinters;
The sintering step of tantalum cathode cylinder compacting is:
(1) suppress: suppress with tantalum powder, and add lubricant in tantalum powder;
(2) presintering, puts into inert gas by tantalum cathode cylinder block and carries out presintering, and temperature is 100 DEG C ~ 200 DEG C, and burn-in time is 20min ~ 120min;
(3) sinter, tantalum cathode cylinder is put into inert gas and sinters, temperature is 500 DEG C ~ 900 DEG C, and sintering time is 20min ~ 60min.
Further, described lubricant is one or more in camphor, stearic acid and other soap matter aliphatic acid, polyethylene glycol, glyptal resin, polyvinyl alcohol, microwax.
Further, described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas.
Further, described capacitor number of assembling steps is:
(1) the capacitor anode pellet described surface being formed with dielectric oxide film impregnated in prepared working electrolyte solution, and dip time is 20min-60min, then takes out, and heavily fortified point is directly positioned in glass surface ware stand-by;
(2) tantalum shell deionized water is boiled wash, after drying in 120 DEG C of environment, be vertically positioned on assembling frame, inject working electrolyte solution and flood 20min-60min under room temperature, then the electrolyte solution in cylinder is drawn clean, stand-by with pipettor;
(3) gel electrolyte pipettor is injected the tantalum shell that impregnated of Working electrolyte according to consumption, then teflon insulation packing ring on padding bottom the anode pellet of the Working electrolyte be impregnated with, it is vertically put into tantalum shell, namely obtains capacitor assembly;
(4) by above-mentioned capacitor assembly through measuring after correlation performance parameters, after carrying out the operations such as slot rolling, laser sealing welding, the butt welding of plasma anode, namely make required electrolytic capacitor product.
Beneficial effect of the present invention is: make Ta by said method
2o
5-RuO
2the Ta of/Ta capacitor
2o
5anode dielectric layer and RuO
2cathode electrode Rotating fields is stablized, there are larger specific area, excellent electron conduction and proton transport ability, when discharge and recharge, discharge and recharge can be carried out fast, there are higher specific capacity and excellent heavy-current discharge performance, effectively can improve energy density and the power density of electrode.And specification is the Ta of 75V1000 μ F
2o
5-RuO
2/ Ta capacitor 220 DEG C, under the condition of 30V after 100h, 200h life-span load test, Ta
2o
5-RuO
2/ Ta capacitor is ESR average out to 135m Ω under 100Hz condition, leakage current average out to 10.6 μ A, energy density 12.4J/cm under room temperature
3; 220 DEG C, under the condition of 30V by the life-span load test of 500h after, capacitor performance keeps stable.
Embodiment
Further describe technical scheme of the present invention below, but described in claimed scope is not limited to.
A kind of Ta that the present embodiment provides
2o
5-RuO
2the manufacture method of/Ta capacitor, comprises the following steps:
One, the compacting of tantalum anode core and sintering
The compacting of tantalum anode core and sintering can adopt conventional mould to suppress, and then sinter in sintering furnace, the preferred following preferred version of the present embodiment:
1.1, suppress
Suppress with tantalum powder; By the size according to product casing, design the mould of special anode pellet, the tantalum powder of certain specific volume (i.e. certain particle size) is formed with the compacting of certain pressure.Gained anode bodies can be the shape of any requirement, as cylindrical, square, rectangle, circle, ellipse, triangle, hexagon, octagon, heptagon, pentagon etc.Anode bodies can also have " groove " shape, and comprise one or more groove, groove, low-lying or depression in groove, to increase surface area-to-volume ratio, the present invention preferably adopts cylindrical structural.
Tightr in order to make tantalum anode core suppress, before compaction, lubricant is added in tantalum powder, to improve mobility and the caking property of tantalum powder, ensure that each particle is bonded together each other equably when anode bodies is compressing, the density distribution of the anode bodies each several part formed, the guarantee sintering stress that each position is subject in high-temperature sintering process is consistent, reduces distortion; Described lubricant is one or more in camphor, stearic acid and other soap matter aliphatic acid, polyethylene glycol, glyptal resin, polyvinyl alcohol, microwax, the preferred glyptal resin of the present invention is as lubricant, during use, lubricant is dissolved in volatile organic solvent, the present invention selects volatile organic solvent to be wherein a kind of solvent in absolute ethyl alcohol, acetone, carbon tetrachloride, and the preferred absolute ethyl alcohol of the present invention is as solvent; The percentage composition that lubricant adds is approximately the 0.1%-8% of total weight, the present embodiment preferably 0.5%.
1.2, presintering
Anode pellet is put into inert gas and carries out presintering, temperature is 200 DEG C ~ 400 DEG C, burn-in time is 20min ~ 60min, when presintering process is main, lubricant in tantalum pressing block is therefrom evaporated, when avoiding subsequent high temperature to sinter, its lubricant composition high temperature occurs sharply to evaporate, the surface texture of anode pellet can be destroyed, lubricant is evaporated in the condition compared with low temperature by presintering, the reason that presintering is carried out under an inert gas is: (1) prevents lubricant from burning, destroy the structure of anode pellet, (2) prevent anode pellet oxidized under condition of uncertainty, described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas.
1.3, sinter
Anode pellet is put into inert gas sinter, temperature is 1300 DEG C ~ 2000 DEG C, sintering time is 20min ~ 60min, this sintering temperature is higher, the structure of anode pellet can be made to fix, anode pellet is through presintering process, lubricant is disposed, at sintering step, anode pellet surface there will not be rough curved surface, forms well-regulated curved surface, and the reason of carrying out under inert gas is: (1) prevents rest lubricant from burning, destroy the structure of anode pellet, (2) prevent tantalum powder uncontrollable oxidized; Described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas;
During sintering, because the ratio capacity rate of the valve metal powder for the formation of anode bodies is high, sintering causes the contraction of about 10%-20% sometimes.Along with the increase of anode bodies size, this contraction can cause anode construction generation moderate finite deformation, in embodiments of the present invention, for highly higher and diameter is less anode pellet, even also may occur macroscopic obviously bending.For this situation, it is believed that in theory, when anode bodies and outside rigid surface (surface as sintered crucible) physical contact, bend and can increase.More particularly, this rigid surface can in the contraction of physical contact place restriction anode bodies, thus cause the shrinkage ratio anode bodies other parts in physical contact region few.This contraction difference can cause anode bodies to bend conversely, forms curved shape (as crescent).In order to be down to minimum by this flexural deformation, the mode adopting anode body surface not carry out physical contact with outer surface (surface as sintered crucible) sinters.Such as, sintered crucible bottom even get out circular hole, then anode tap is inserted in the hole, make the unsettled handstand of anode bodies in sintered crucible, ensure that in sintering process, any surface does not directly form physical contact with other, limit Oxygen atom transfer to anode pellet on atmosphere in high temperature sintering time anode pellet can free shrink, not by physical restriction.Should also be understood that sintering can also adopt other various structure, and not by the restriction of this kind of structure.Such as, anode pellet may be adopted mode to be in suspension vertically put in heating furnace, then, after sintering process terminates, be put forward, thus obtain the capacitor anode pellet needed.
Two, the sintering of tantalum cathode cylinder compacting:
2.1, suppress
Suppress with tantalum powder, design the mould of special cathode tube, the tantalum powder of certain specific volume (i.e. certain particle size) is formed with the compacting of certain pressure.Gained anode bodies can be the shape of any requirement, as cylindrical, square, rectangle, circle, ellipse, triangle, hexagon, octagon, heptagon, pentagon etc.Anode bodies can also have " groove " shape, and comprise one or more groove, groove, low-lying or depression in groove, to increase surface area-to-volume ratio, the present embodiment preferably adopts cylindrical structural;
Tightr in order to make cathode tube suppress, before compaction, lubricant is added in tantalum powder, to improve mobility and the caking property of tantalum powder, ensure that each particle is bonded together each other equably when cathode tube is compressing, the density distribution of the cathode tube each several part formed is even, and the guarantee sintering stress that each position is subject in high-temperature sintering process is consistent, reduces distortion; Described lubricant is that the preferred glyptal resin of one or more the present embodiment in camphor, stearic acid and other soap matter aliphatic acid, polyethylene glycol, glyptal resin, polyvinyl alcohol, microwax is as lubricant, during use, lubricant is dissolved in volatile organic solvent, the present embodiment selection volatile organic solvent is the wherein a kind of solvent in absolute ethyl alcohol, acetone, carbon tetrachloride, and the preferred absolute ethyl alcohol of the present embodiment is as solvent; The percentage composition that lubricant adds is approximately the 0.1%-8% of total weight, the present embodiment preferably 0.5%.
2.2, presintering
Tantalum cathode cylinder is put into inert gas and carries out presintering, temperature is 100 DEG C ~ 200 DEG C, burn-in time is 20min ~ 120min, the lubricant in tantalum cathode cylinder is mainly removed in presintering at a lower temperature, the reason of carrying out under inert gas is: (1) prevents lubricant from burning, destroy the structure of anode pellet, (2) prevent tantalum powder uncontrollable oxidized; Described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas.
2.3, sinter
Tantalum cathode cylinder is put into inert gas sinter, temperature is 500 DEG C ~ 900 DEG C, and sintering time is 20min ~ 60min; Through presintering process, disposed by lubricant, at sintering step, the structure of tantalum cathode cylinder can be fixed by higher temperature, and tantalum cathode cylinder surface there will not be rough curved surface, forms well-regulated curved surface; The reason of carrying out under inert gas is: (1) prevents remaining lubricant from burning, and destroy the structure of anode pellet, (2) prevent tantalum powder uncontrollable oxidized; Described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas.
Three, Ta
2o
5deielectric-coating makes
3.1, make oxidation and form liquid
Adopt ethylene glycol: deionized water ratio is 1:1 ~ 2 mixed liquor is solvent, and preferred proportion is 1:1; Add H
3pO
4solution and Ag
2sO
4, make the mass concentration 0.08wt% ~ 0.8wt% of phosphoric acid, preferred 0.5wt%, Ag
2sO
4mass concentration 0.01wt% ~ 0.05wt%, be preferably 0.2wt%; Increase Ag
2sO
4effect be increase oxidation to form the conductive ion of liquid.
3.2, cooling oxidation forms liquid
Cooling system is adopted to control at-5 DEG C ~ 5 DEG C by the temperature that this oxidation forms liquid;
3.3, to the preliminary treatment of tantalum anode core
With the toluenesulfonic acid ferrous solution that concentration is 0.1wt% ~ 3wt%, preliminary treatment is carried out to tantalum anode core, the preferred 1wt% of concentration of toluenesulfonic acid ferrous solution, treatment temperature is 10 ~ 30min, and its solvent is the one in ethanol, methyl alcohol, n-butanol, and toluenesulfonic acid ferrous solution is 0.1wt% ~ 3wt%.
3.4, dielectric oxide film is made
Anode pellet being immersed oxidation is formed in liquid, antianode pellet is energized, and make boost current density be within the scope of 8mA/g ~ 30mA/g, initial boost current density is 20mA/g ~ 30mA/g, in anode pellet, voltage often boosts 12V, constant voltage 20min ~ 30min, after each constant voltage terminates, boost current density is reduced 3 ~ 4mA/g, minimumly be reduced to 8mA/g, until capacitor anode pellet both positive and negative polarity voltage is raised to predetermined magnitude of voltage, deenergization after constant voltage 5h ~ 6h, described predetermined magnitude of voltage is 3 ~ 5 times of rated capacitor voltage; Adopt the dielectric oxide film uniform close more that the method makes.
3.5, stable oxide-film
When voltage drop is to below 1V in anode pellet, the anode pellet being formed with oxidation film layer is formed liquid from oxidation and takes out, and the deionized water being placed in temperature 90 DEG C boils and washes 30min-120min, the oxidation of anode pellet inside is formed liquid and all boils wash clean; Putting into vacuum degree is 2 × 10
-3more than Torr, temperature are heat treatment 20 ~ 60min in the vacuum furnace of 200 ~ 300 DEG C; Then will be carry out electrochemical treatments 1 ~ 2 hour in the oxidizing agent solution of 160 DEG C ~ 180 DEG C through heat treated anode pellet block immersion temperature, applying voltage is 0.8 times ~ 1.2 times of rated capacitor voltage, anode pellet through Passivation Treatment is cleaned, dry for standby is more stable by the medium oxidizing membrane structure of the method process.
Four, tantalum base RuO
2cathode electrode makes
4.1, ruthenium source solution is made
Ruthenium source is dissolved in aqueous isopropanol, adds cationic surfactant, dispersion;
Described ruthenium source is ruthenium trichloride, an isopropyl toluene ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium, tri-chlorination six ammonium close ruthenium, the mixing of in nitrosyl nitrate ruthenium a kind or 2 kinds, the preferred ruthenium trichloride of the present embodiment;
Described cationic surfactant is the mixing of in cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecyl amine hydrochloride, dioctadecylamine hydrochloride, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl benzyl dimethyl ammonium chloride, chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride a kind or 2 kinds, the preferred benzalkonium chloride of the present embodiment.
4.2, oxidizability metal dust is added
The oxidizability metal dust of 1 ~ 5% is added in the solution of ruthenium source, described oxidizability metal dust is one or more in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, potassium permanganate, the mixed oxidization metal dust of the preferred anhydrous cupric sulfate of the present embodiment and potassium permanganate.
4.3, thickener is added
Add 1 ~ 3% thickener, described thickener is polyacrylamide, titanate esters, gum arabic, Silica hydrogel, the present embodiment optimization polypropylene acid amides.
4.4, to the preliminary treatment of tantalum cathode cylinder
Be that the toluenesulfonic acid ferrous solution of 0.05wt% ~ 1wt% carries out preliminary treatment to tantalum cathode cylinder inwall by concentration, the preferred 0.5wt% of the concentration of toluenesulfonic acid ferrous solution in the present embodiment, processing time is 10 ~ 30min, pour out after being disposed, its solvent is the one in ethanol, methyl alcohol, n-butanol, the preferred n-butanol of the present embodiment.
4.5, RuO smeared by tantalum cathode cylinder
2
The solution that step 4.3 is obtained pour into step 4.4 process after cathode tube in, pouring volume is 1/10 ~ 1/6 of cathode tube volume, the present embodiment preferably 1/8, then the environment putting into 60 ~ 70 DEG C carries out centrifugal oven dry, described centrifugal oven dry is dried for be put on tachogenerator by cathode tube, and cathode tube rotates, during oven dry around the center line of cathode tube, need to carry out speed governing to tachogenerator, the solution that step 4.4 is obtained is dispersed on the circular wall of cathode tube equably; This step can disposable target cylinder inwall be coated with wipe RuO
2, and be uniformly distributed and be distributed on the inwall of cathode tube.
4.6, high temperature sintering
To process high temperature sintering in cathode tube feeding Muffle furnace by step 4.5 and carry out high temperature sintering process, temperature is 500 ~ 600 DEG C, and the time is 30min ~ 120min, naturally cools after high-temperature heat treatment completes.
4.7, Passivation Treatment
What obtain to step 4.6 contains RuO
2the solution passivation process that step 4.2 obtains is added in the cathode tube of cathode electrode layer, and then high temperature sintering carries out high temperature sintering process in feeding Muffle furnace, temperature is 500 ~ 600 DEG C, time is 30min ~ 120min, naturally cool after high-temperature heat treatment completes, this step can stablize the RuO of cathode tube inwall further
2dielectric layer.
Five, electrolytic capacitor solution makes
5.1, resistivity is greater than the deionized water of 5M Ω .cm and mass percent concentration be more than 98% sulfuric acid be mixed with the aqueous sulfuric acid that mass concentration is 25%-38%, the present embodiment preferably 30%;
5.2, in described aqueous sulfuric acid, add the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15%, be mixed with mixed solution, the present embodiment is preferably 10%; While this organically-modified solvent of use, need the absolute ethyl alcohol adding its 1/2 ~ 2 times of volume used in combination, the present embodiment is 1 times of volume preferably; The described property-modifying additive higher than 140 DEG C is one or both mixing in the large molecule organic solvent such as EGME, butyl glycol ether, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, sulfolane, HMPA, and the present embodiment is preferably EGME.
5.3, in above-mentioned mixed solution, add the depolarizing agent of the 0.2%-1.0% of gross mass, the present embodiment is preferably 0.5%, through sonic oscillation evenly obtained working electrolyte; Described depolarizing agent is that one or both in the transition metal sulfates such as copper sulphate, sulfuric acid oxygen alum, ferric sulfate mix, this enforcements preferably ferric sulfate.
5.4, gel electrolyte is prepared: get some work electrolyte solution, add 5%-15% high-purity gas aerosil by mass percentage, the present embodiment is preferably 10%, stirs, obtained gel electrolyte.
Six, capacitor assembling
6.1, the capacitor anode pellet described surface being formed with dielectric oxide film impregnated in prepared working electrolyte solution, and dip time is 20min-60min, then takes out, and is positioned in glass surface ware stand-by;
6.2, tantalum shell deionized water is boiled wash, after drying in 120 DEG C of environment, be vertically positioned on assembling frame, inject working electrolyte solution and flood 20min-60min under room temperature, then the electrolyte solution in cylinder is drawn clean, stand-by with pipettor;
6.3, gel electrolyte pipettor is injected the tantalum shell that impregnated of Working electrolyte according to consumption, then teflon insulation packing ring on padding bottom the anode pellet of the Working electrolyte be impregnated with, it is vertically put into tantalum shell, namely obtains capacitor assembly;
6.4, by above-mentioned capacitor assembly through measuring after correlation performance parameters, after carrying out the operations such as slot rolling, laser sealing welding, the butt welding of plasma anode, namely make required electrolytic capacitor product.
The present embodiment is also to the Ta made with above-described embodiment simultaneously
2o
5-RuO
2/ Ta capacitor detects, detection method and result as follows:
By the Ta made
2o
5-RuO
2/ Ta capacitor is placed in the environment higher than predetermined work ambient temperature and processes, this experimental selection is continuous firing 100h, 200h, 500h under the condition of selection 220 DEG C, 30V, then equivalent series resistance ESR and the conventional earth leakage stream K value of capacitor assembly is measured, when ESR≤1 Ω being detected, time K≤0.0008CV (μ A), up to standard; Then (energy density is usually according to formula E=1/2CV electrolytic capacitor up to standard to be placed on the mensuration energy density E when operating frequency 120Hz and temperature 25 DEG C
2determine, wherein C is the electric capacity represented with farad (F), and V is the capacitor working pressure represented with volt (V)), when being measured to 5≤E≤20J/cm
3time, this electrolytic capacitor is up to standard.
This capacitor specifications is 75V1000 μ F after tested, at 220 DEG C, capacitor ESR average out to 135m Ω under 100Hz condition under the condition of 30V after 100h, 200h life-span load test, and leakage current average out to 10.6 μ A, energy density 12.4J/cm under room temperature
3, conventional earth leakage stream K value is lower than 0.0008VC (μ A); 220 DEG C, under the condition of 30V by the life-span load test of 500h after, capacitor performance keeps stable.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., be all included within protection scope of the present invention.
Claims (5)
1. a Ta
2o
5-RuO
2the manufacture method of/Ta capacitor, is characterized in that: comprise tantalum anode core and the compacting of tantalum cathode cylinder and sinter, Ta
2o
5deielectric-coating makes, and electrolytic capacitor solution makes, tantalum base RuO
2cathode electrode layer makes, and capacitor assembling, wherein:
Ta
2o
5deielectric-coating making step is:
(1) make oxidation and form liquid, adopt ethylene glycol: deionized water ratio is 1:1 ~ 2 mixed liquor is solvent, adds H
3pO
4solution and Ag
2sO
4, make the mass concentration 0.08wt% of phosphoric acid ~ 0.8wt%, Ag
2sO
4mass concentration 0.01wt% ~ 0.05wt%;
(2) cooling oxidation forms liquid, adopts cooling system to control at-5 DEG C ~ 5 DEG C by the temperature that this oxidation forms liquid;
(3) to the preliminary treatment of tantalum anode core, carry out preliminary treatment with the toluenesulfonic acid ferrous solution that concentration is 0.1wt% ~ 3wt% to tantalum anode core, treatment temperature is 10 ~ 30min, and its solvent is the one in ethanol, methyl alcohol, n-butanol;
(4) dielectric oxide film is made, anode pellet being immersed oxidation is formed in liquid, antianode pellet is energized, and make boost current density be within the scope of 8mA/g ~ 30mA/g, initial boost current density is 20mA/g ~ 30mA/g, in anode pellet, voltage often boosts 12V, constant voltage 20min ~ 30min, after each constant voltage terminates, boost current density is reduced 3 ~ 4mA/g, minimumly be reduced to 8mA/g, until capacitor anode pellet both positive and negative polarity voltage is raised to predetermined magnitude of voltage, deenergization after constant voltage 5h ~ 6h, described predetermined magnitude of voltage is 3 ~ 5 times of rated capacitor voltage,
(5) stable oxide-film, when in anode pellet, voltage drop is to below 1V, the anode pellet being formed with oxidation film layer is taken out from oxidation formation liquid, and the deionized water being placed in temperature 90 DEG C boils and washes 30min-120min, the oxidation of anode pellet inside is formed liquid and all boils wash clean; Putting into vacuum degree is 2 × 10
-3more than Torr, temperature are heat treatment 20 ~ 60min in the vacuum furnace of 200 ~ 300 DEG C; Then will immerse temperature through heat treated anode pellet is carry out electrochemical treatments 1 ~ 2 hour in 160 DEG C ~ 180 DEG C oxidizing agent solutions, applying voltage is 0.8 times ~ 1.2 times of rated capacitor voltage, anode pellet through Passivation Treatment is cleaned, dry for standby.
Tantalum base RuO
2cathode electrode making step is:
(1) make ruthenium source solution, ruthenium source is dissolved in aqueous isopropanol, adds cationic surfactant, dispersion;
Described ruthenium source is ruthenium trichloride, an isopropyl toluene ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium, tri-chlorination six ammonium close ruthenium, the mixing of in nitrosyl nitrate ruthenium a kind or 2 kinds;
Described cationic surfactant is the mixing of in cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecyl amine hydrochloride, dioctadecylamine hydrochloride, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl benzyl dimethyl ammonium chloride, chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride a kind or 2 kinds;
(2) in the solution of ruthenium source, add the oxidizability metal dust of 1 ~ 5%, described oxidizability metal dust is one or more in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, potassium permanganate;
(3) add 1 ~ 3% thickener, described thickener is polyacrylamide, titanate esters, gum arabic, Silica hydrogel;
(4) to the preliminary treatment of tantalum cathode cylinder, be that the toluenesulfonic acid ferrous solution of 0.05wt% ~ 1wt% carries out preliminary treatment to tantalum cathode cylinder inwall by concentration, processing time is 10 ~ 30min, pours out after being disposed, and its solvent is the one in ethanol, methyl alcohol, n-butanol;
(5) solution that step (3) obtains is poured in the cathode tube after step (4) process, pouring volume is 1/10 ~ 1/6 of cathode tube volume, then the environment putting into 60 ~ 70 DEG C carries out centrifugal oven dry, described centrifugal oven dry is dried for being put on tachogenerator by cathode tube, and cathode tube rotates around the center line of cathode tube, during oven dry, need to carry out speed governing to tachogenerator, the solution that step (3) is obtained is dispersed on the circular wall of cathode tube equably;
(6) will send into high temperature sintering in Muffle furnace by step (5) process cathode tube and carry out high temperature sintering process, temperature is 500 ~ 600 DEG C, and the time is 30min ~ 120min, naturally cools after high-temperature heat treatment completes.
(7) Passivation Treatment, what obtain to step (6) contains RuO
2the solution passivation process that step (2) obtains is added in the cathode tube of cathode electrode layer, and then high temperature sintering carries out high temperature sintering process in feeding Muffle furnace, temperature is 500 ~ 600 DEG C, and the time is 30min ~ 120min, naturally cools after high-temperature heat treatment completes.
Electrolytic capacitor solution making step is:
(1) resistivity is greater than the deionized water of 5M Ω .cm and mass percent concentration be more than 98% sulfuric acid be mixed with the aqueous sulfuric acid that mass concentration is 25%-38%;
(2) in described aqueous sulfuric acid, add the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15%, be mixed with mixed solution; While this organically-modified solvent of use, need the absolute ethyl alcohol adding its 1/2 ~ 2 times of volume used in combination; The described property-modifying additive higher than 140 DEG C is one or both mixing in the large molecule organic solvent such as EGME, butyl glycol ether, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, sulfolane, HMPA;
(3) in above-mentioned mixed solution, the depolarizing agent of the 0.2%-1.0% of gross mass is added, through sonic oscillation evenly obtained working electrolyte; Described depolarizing agent be in the transition metal sulfates such as copper sulphate, sulfuric acid oxygen alum, ferric sulfate one or both mix;
(4) being formulated as of gel electrolyte: get some work electrolyte solution, add 5%-15% high-purity gas aerosil by mass percentage, stir, obtained gel electrolyte.
2. Ta as claimed in claim 1
2o
5-RuO
2the manufacture method of/Ta capacitor, is characterized in that: the sintering concrete operation step of described tantalum anode core and the compacting of tantalum cathode cylinder is as follows:
The compacting of tantalum anode core and sintering step are:
(1) suppress: suppress with tantalum powder, and add lubricant in tantalum powder;
(2) presintering, puts into inert gas and carries out presintering by anode pellet, temperature is 200 DEG C ~ 400 DEG C, and burn-in time is 20min ~ 60min;
(3) sinter, anode pellet is put into inert gas and sinters, temperature is 1300 DEG C ~ 2000 DEG C, and sintering time is 20min ~ 60min, and during sintering, physical contact is not carried out on anode pellet surface mode with outer surface sinters;
The sintering step of tantalum cathode cylinder compacting is:
(1) suppress: suppress with tantalum powder, and add lubricant in tantalum powder;
(2) presintering, puts into inert gas by tantalum cathode cylinder block and carries out presintering, and temperature is 100 DEG C ~ 200 DEG C, and burn-in time is 20min ~ 120min;
(3) sinter, tantalum cathode cylinder is put into inert gas and sinters, temperature is 500 DEG C ~ 1000 DEG C, and sintering time is 20min ~ 60min.
3. Ta as claimed in claim 2
2o
5-RuO
2the manufacture method of/Ta capacitor, is characterized in that: described lubricant is one or more in camphor, stearic acid and other soap matter aliphatic acid, polyethylene glycol, glyptal resin, polyvinyl alcohol, microwax.
4. Ta as claimed in claim 1
2o
5-RuO
2the manufacture method of/Ta capacitor, is characterized in that: described inert gas selects the one in helium, neon, argon, krypton, xenon-133 gas, preferred argon gas.
5. Ta as claimed in claim 1
2o
5-RuO
2the manufacture method of/Ta capacitor, is characterized in that: described capacitor number of assembling steps is:
(1) the capacitor anode pellet described surface being formed with dielectric oxide film impregnated in prepared working electrolyte solution, and dip time is 20min-60min, then takes out, and is vertically placed in glass surface ware stand-by;
(2) tantalum shell deionized water is boiled wash, after drying in 120 DEG C of environment, be vertically positioned on assembling frame, inject working electrolyte solution and flood 20min-60min under room temperature, then the electrolyte solution in cylinder is drawn clean, stand-by with pipettor;
(3) gel electrolyte pipettor is injected the tantalum shell that impregnated of Working electrolyte according to consumption, then teflon insulation packing ring on pad is being impregnated with bottom the anode pellet of Working electrolyte, it is vertically put into tantalum shell, namely obtains capacitor assembly;
(4) by above-mentioned capacitor assembly through measuring after correlation performance parameters, after carrying out the operations such as slot rolling, laser sealing welding, the butt welding of plasma anode, namely make required electrolytic capacitor product.
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| CN105355432A (en) * | 2015-11-03 | 2016-02-24 | 铜陵市科峰电子有限责任公司 | High-temperature-resistant capacitor electrolyte |
| CN105405655A (en) * | 2015-12-09 | 2016-03-16 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing non-solid electrolyte tantalum capacitor cathode |
| CN109887750A (en) * | 2019-02-20 | 2019-06-14 | 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) | A kind of non-solid tantalum electrolytic capacitor Working electrolyte and preparation method thereof and non-solid tantalum electrolytic capacitor |
| CN113972073A (en) * | 2021-10-26 | 2022-01-25 | 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 inner wall capacity of tantalum shell of non-solid electrolyte tantalum capacitor |
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|---|---|---|---|---|
| CN105355432A (en) * | 2015-11-03 | 2016-02-24 | 铜陵市科峰电子有限责任公司 | High-temperature-resistant capacitor electrolyte |
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| CN109887750B (en) * | 2019-02-20 | 2020-10-16 | 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) | Working electrolyte of non-solid electrolyte tantalum capacitor, preparation method of working electrolyte and non-solid electrolyte tantalum capacitor |
| CN113972073A (en) * | 2021-10-26 | 2022-01-25 | 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 inner wall capacity of tantalum shell of non-solid electrolyte tantalum capacitor |
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| CN104409216B (en) | 2017-04-12 |
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