CN104409216B - Method for manufacturing Ta2O5-RuO2/Ta capacitor - Google Patents
Method for manufacturing Ta2O5-RuO2/Ta capacitor Download PDFInfo
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- CN104409216B CN104409216B CN201410720477.7A CN201410720477A CN104409216B CN 104409216 B CN104409216 B CN 104409216B CN 201410720477 A CN201410720477 A CN 201410720477A CN 104409216 B CN104409216 B CN 104409216B
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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 of electronic devices and components manufacture, more particularly to a kind of Ta2O5-RuO2The system of/Ta capacitors
Make method.
Background technology
High-energy tantalum mixed capacitor is with tantalum electrolytic capacitor as anode and the super large that constitutes for negative electrode of double layer capacitor
Capacity mixed capacitor, specifically by sintered type tantalum anode fuse, tantalum pentoxide (Ta2O5) medium, sulfuric acid solution electrolyte and tantalum
Base ruthenic oxide (RuO2) cathode sheets composition, sulfuric acid solution electrolyte and tantalio ruthenic oxide (RuO2) cathode sheets composition capacitor
Negative electrode, tantalio ruthenic oxide (RuO2) cathode sheets improve the contact area of sulfuric acid solution electrolyte, generate double layer capacitor,
Anode capacity is drawn to greatest extent can.High-energy tantalum mixed capacitor small volume, excellent electrical property, product reliability are good, and performance is steady
Fixed, life-span length, the energy density and power density of unit volume and Unit Weight are big, it is adaptable to Aeronautics and Astronautics, weapons, ship,
During electronics etc. has direct current, pulsation and the low ripple circuit of the Military Electronic Equipment of reliability requirement.
The focus technology of high-energy tantalum mixed capacitor is divided into the sintering of tantalum anode core, tantalum pentoxide (Ta2O5) medium system
Make, electrolyte quota, tantalio ruthenic oxide (RuO2) cathode sheets four aspects of making, wherein：
The sintering of tantalum anode core：Tantalum powder is suppressed into circular or square block, and then through 1300 DEG C～2100 DEG C
Under vacuum environment or atmosphere of inert gases, sintering is formed, and when tantalum powder is suppressed, needs to add a certain amount of Camphora, stearic acid etc.
Lubricant composition, makes the tightr of tantalum powder compacting.
Tantalum pentoxide (Ta2O5) medium making：After sintering in the oxidizing agent solution such as tantalum block insertion phosphoric acid, then carry out
Electrolysis forms tantalum pentoxide (Ta on tantalum block surface2O5) dielectric layer.Such as the patent of invention of Application No. 200910043202.3：
A kind of manufacture method of the non-solid electrolyte tantalum electric capacity of vast capacity, which is with tantalum sintered object as base material, and with the base material as sun
Pole 0.01～0.1% H3PO4Multipole formation is carried out in solution.
Electrolyte quota：Raw material is deionized water and sulfuric acid solution, and adds a certain amount of VOSO again in the solution4·
XH2O、Ag2SO4、CuSO4·5H2O、Fe2(SO4)3、VOSO4Deng transition metal salt, such as Application No. 201410122493.6 is sent out
Bright patent：Hybrid super tantalum capacitor high-pressure electrolysis matter and preparation method thereof.
Tantalio ruthenic oxide (RuO2) cathode sheets：Disperse in organic solvent, to add a certain amount of by powder ruthenium dioxide
Binding agent formed mixed liquor, mixed liquor is applied on tantalio piece, then drying, sintering, and repeat 6～13 times；Such as Shen
Please number for 201210370552.2 patent of invention：A kind of preparation method of ruthenium dioxide combination electrode for energy storage, and application
Number for 201210370552.2 patent of invention：Combined electrode supercapacitor and preparation method thereof.
In above-mentioned processing technology, tantalum pentoxide (Ta2O5) medium make and tantalio ruthenic oxide (RuO2) cathode sheets two
Step is the core technology of the ruthenium tantalum series capacitors, and the technical barrier in the field, and its reason mainly has at 2 points：One be by
In the special surface characteristic of tantalum pentoxide and ruthenic oxide material, cause the electrode surface being fabricated to easily to ftracture, cause with
Collector contact is not good, finally affects performance and the life-span of active material chemical property；Two is the electrification due to ruthenic oxide
Learn reaction and be concentrated mainly on the accurate three-dimensional space of two peacekeepings, therefore electrode can not be made to too thick, can otherwise have a strong impact on electrode
Performance, this means that prior art limits its application in some occasions for requiring high energy storage density.
The content of the invention
To solve above-mentioned technical problem, the invention provides a kind of manufacture method of Ta2O5-RuO2/Ta capacitors.
The present invention is achieved by the following technical programs.
A kind of Ta that the present invention is provided2O5-RuO2The manufacture method of/Ta capacitors, including tantalum anode core and tantalum cathode cylinder pressure
System and sintering, Ta2O5Medium film production, electrolyte quota, tantalio RuO2Cathode electrode layer makes, and capacitor assembling, its
In：
Ta2O5Deielectric-coating making step is：
(1) make oxidation and form liquid, using ethylene glycol：Deionized water ratio is 1：1～2 mixed liquor is solvent, is added
H3PO4Solution and Ag2SO4, make the mass concentration 0.08wt%～0.8wt% of phosphoric acid, Ag2SO4Mass concentration 0.01wt%～
0.05wt%；
(2) cool down oxidation and form liquid, the oxidation is formed at -5 DEG C～5 DEG C by the temperature control of liquid using cooling system；
(3) to tantalum anode core pretreatment, with the toluenesulfonic acid ferrous solution that concentration is 0.1wt%～3wt% to tantalum anode core
Carry out pretreatment, treatment temperature is 10～30min, its solvent is ethanol, methanol, the one kind in n-butyl alcohol；
(4) dielectric oxide film is made, anode pellet immersion oxidation is formed in liquid, anode pellet is powered, and
Boost current density is made in the range of 8mA/g～30mA/g, initial boost current density is 20mA/g～30mA/g, anode pellet
Upper voltage often boosts 12V, constant pressure 20min～30min, and boost current density is reduced 3～4mA/g after terminating by each constant pressure, most
It is little to be reduced to 8mA/g, until the positive and negative pole tension of capacitor anode pellet is raised to predetermined magnitude of voltage, after constant pressure 5h～6h, disconnect electricity
Source, described predetermined magnitude of voltage are 3～5 times of rated capacitor voltage；
(5) stable oxide-film, when voltage drops to below 1V in the anode pellet, will be formed with the anode of oxidation film layer
Pellet is formed in liquid from oxidation and is taken out, and is boiled and is washed 30min-120min, by anode pellet in being placed in the deionized water of 90 DEG C of temperature
Internal oxidation forms liquid and all boils wash clean；Vacuum is put into for 2 × 10-3More than Torr, temperature are 200～300 DEG C true
20～60min of heat treatment in empty stove；Then the anode pellet block immersion temperature through heat treatment is aoxidized for 160 DEG C～180 DEG C
Electrochemical treatments are carried out in agent solution 1～2 hour, applied voltage is 0.8 times～1.2 times of rated capacitor voltage, will pass through
The anode pellet of Passivation Treatment is cleaned, dry for standby.
Tantalio RuO2Cathode electrode making step is：
(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, six ammonium of tri-chlorination conjunction ruthenium, Asia
1 kind or 2 kinds of mixing in nitroxyl nitric acid ruthenium；
The cationic surfactant is cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecylamine hydrochloric acid
Salt, dioctadecylamine hydrochlorate, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl dimethyl benzyl chloride
Change 1 in ammonium, chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride
Kind or 2 kinds of mixing；
(2) in the solution of ruthenium source in the copper oxide of addition 1～5%, potassium oxide, manganese oxide, anhydrous cupric sulfate, potassium permanganate
One or more powder；
(3) 1～3% thickening agent is added, described thickening agent is polyacrylamide, titanate esters, Radix Acaciae senegalis, silicon coagulate
Glue；
(4) to tantalum cathode cylinder pretreatment, with the toluenesulfonic acid ferrous solution that concentration is 0.05wt%～1wt% to tantalum cathode cylinder
Inwall carries out pretreatment, and process time is 10～30min, is poured out after being disposed, and its solvent is ethanol, methanol, in n-butyl alcohol
One kind；
(5), in the cathode tube for pouring the solution that step (3) is obtained after step (4) is processed into, pouring volume is cathode tube volume
1/10～1/6, carry out centrifugation drying in being then placed in 60～70 DEG C of environment, described centrifugation drying is to be put into cathode tube
Dried on tachogenerator, and cathode tube is rotated around the centrage of cathode tube, during drying, needs to carry out tachogenerator
Speed governing, enables the solution that step (3) is obtained to be uniformly dispersed on the circular inner wall of cathode tube；
(6) will send in Muffle furnace by the cathode tube after step (5) process carries out high temperature sintering process, and temperature is 500～
600 DEG C, the time be 30min～120min, natural cooling after the completion of high-temperature heat treatment.
(7) Passivation Treatment, contains RuO to what step (6) was obtained2Step (2) is added to obtain in the cathode tube of cathode electrode layer
The solution passivation for arriving is processed, and being then fed again into Muffle furnace high temperature sintering carries out high temperature sintering process, and temperature is 500～600
DEG C, the time be 30min～120min, natural cooling after the completion of high-temperature heat treatment.
Electrolyte quota step is：
(1) deionized water by resistivity more than 5M Ω .cm is prepared with the sulphuric acid that mass percent concentration is more than 98%
Into the aqueous sulfuric acid that mass concentration is 25%-38%；
(2) the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15% is added in the aqueous sulfuric acid, is matched somebody with somebody
Make mixed solution；Need to add while using the organically-modified solvent dehydrated alcohol mixing of its 1/2～2 times of volume to make
With；It is described be higher than 140 DEG C property-modifying additive be ethylene glycol monomethyl ether, butyl glycol ether, dimethyl sulfoxide, N- crassitudes
One kind in the macromole organic solvent such as ketone, dimethylformamide, dimethyl acetylamide, sulfolane, HMPA or
Two kinds of mixing；
(3) in above-mentioned mixed solution, add the depolarizing agent of the 0.2%-1.0% of gross mass, Jing sonic oscillations uniformly to make
Obtain working electrolyte；The depolarizing agent is the one kind or two in the transition metal sulfates such as copper sulfate, sulphuric acid oxygen vitriol, iron sulfate
Plant and mix；
(4) gel electrolyte is formulated as：Part Working electrolyte is taken, 5%-15% high-purity gas are added by mass percentage
Aerosil, stirs, and gel electrolyte is obtained.
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：Suppressed with tantalum powder, and lubricant is added in tantalum powder；
(2) presintering, anode pellet is put in noble gases carries out presintering, and temperature is 200 DEG C～400 DEG C, pre-burning
Time is 20min～60min；
(3) sinter, anode pellet is put into into noble gases and is sintered, temperature is 1300 DEG C～2000 DEG C, sintering time
For 20min～60min, during sintering, the mode that anode pellet surface does not carry out physical contact with outer surface is sintered；
Tantalum cathode cylinder compacting sintering step be：
(1) suppress：Suppressed with tantalum powder, and lubricant is added in tantalum powder；
(2) presintering, tantalum cathode cylinder block is put in noble gases carries out presintering, and temperature is 100 DEG C～200 DEG C, in advance
The burning time is 20min～120min；
(3) sinter, tantalum cathode cylinder is put in noble gases and is sintered, temperature is 500 DEG C～900 DEG C, sintering time
For 20min～60min.
Further, described lubricant be Camphora, stearic acid and other soap matter fatty acids, Polyethylene Glycol, glyptal resin,
One or more in polyvinyl alcohol, microwax.
Further, described noble gases select the one kind in helium, neon, argon, krypton, xenon-133 gas, preferred argon.
Further, described capacitor number of assembling steps is：
(1) the capacitor anode pellet that the surface is formed with dielectric oxide film be impregnated in into prepared working electrolyte
In solution, dip time is 20min-60min, is then taken out, and heavily fortified point is directly positioned over stand-by in glass surface ware；
(2) tantalum shell deionized water is boiled and is washed, after drying in 120 DEG C of environment, be disposed vertically on assembling frame, injection
Working electrolyte solution impregnates 20min-60min at room temperature, then draws totally the electrolyte solution in cylinder with pipettor,
It is stand-by；
(3) gel electrolyte pipettor is injected in the tantalum shell impregnated of Working electrolyte according to consumption, Ran Hou
Teflon insulation packing ring on the anode pellet bottom pad of the Working electrolyte being impregnated with, which is vertically put in tantalum shell,
Capacitor assembly is obtained；
(4) above-mentioned capacitor assembly is carried out into slot rolling, laser sealing welding, plasma Jing after measurement correlation performance parameters
Electrolysis condenser product after the operations such as anode butt welding, that is, needed for making.
The beneficial effects of the present invention is：Ta is made by said method2O5-RuO2The Ta of/Ta capacitors2O5Anode medium
Layer and RuO2Cathode electrode Rotating fields are stable, have larger specific surface area, excellent electronic conduction and proton transport ability, filling
During electric discharge, discharge and recharge can be rapidly performed by, have higher specific capacity and excellent heavy-current discharge performance, can be effectively
Improve the energy density and power density of electrode.And specification is the Ta of 75V1000 μ F2O5-RuO2/ Ta capacitors 220 DEG C,
Under conditions of 30V after 100h, 200h life-span stress test, Ta2O5-RuO2/ Ta capacitors ESR average out under the conditions of 100Hz
135m Ω, 10.6 μ A of leakage current average out to, energy density 12.4J/cm under room temperature3；Pass through 500h under conditions of 220 DEG C, 30V
Life-span stress test after, capacitor performance keeps stable.
Specific embodiment
Be described further below technical scheme, but claimed scope be not limited to it is described.
A kind of Ta that the present embodiment is provided2O5-RuO2The manufacture method of/Ta capacitors, comprises the following steps：
First, the compacting of tantalum anode core and sintering
Tantalum anode core is suppressed and is sintered and conventional mould can be adopted to be suppressed, and is then sintered in sintering furnace, this
Embodiment preferably following preferred version：
1.1st, suppress
Suppressed with tantalum powder；By the size according to product casing, the mould of special anode pellet is designed, by one
Definite proportion is held the tantalum powder of (i.e. certain particle size) and is formed with certain pressure compacting.Gained anode bodies can be the shape of any requirement,
Such as cylinder, square, rectangle, circle, ellipse, triangle, hexagon, octagon, heptagon, pentagon etc..Anode
Body can also have in " groove " shape, groove includes one or more grooves, groove, low-lying or depression, to increase surface area-volume
Than present invention preferably employs cylindrical structural.
In order that the compacting of tantalum anode core is even closer, before compaction, lubricant is added in tantalum powder, to improve the stream of tantalum powder
Dynamic property and caking property, it is ensured that when anode bodies are compressing, each granule is equably bonded together each other, the anode bodies for being formed
The Density Distribution of each several part, just can guarantee that the sintering stress that each position is subject in high-temperature sintering process is consistent, reduces deformation；Institute
During the lubricant stated is Camphora, stearic acid and other soap matter fatty acids, Polyethylene Glycol, glyptal resin, polyvinyl alcohol, microwax
One or more, lubricant is dissolved in volatile organic solvent as lubricant during use by the present invention preferably glyptal resin
In, it is dehydrated alcohol, acetone that the present invention selects volatile organic solvent, the one of which solvent in carbon tetrachloride, and the present invention is excellent
Dehydrated alcohol is selected as solvent；The 0.1%-8% of the percentage composition that lubricant is added about gross weight, the present embodiment are preferred
0.5%.
1.2nd, presintering
Anode pellet is put in noble gases carries out presintering, and temperature is 200 DEG C～400 DEG C, and burn-in time is 20min
Lubricant in tantalum pressing block is therefrom evaporated when presintering process is main by～60min, it is to avoid when subsequent high temperature is sintered, its
Lubricant composition high temperature occurs drastically to evaporate, and can destroy the surface texture of anode pellet, and presintering will be moistened in the condition compared with low temperature
Lubrication prescription is evaporated, and the reason for presintering is carried out under an inert gas is：(1) prevent lubricant from burning, destroy anode pellet
Structure, (2) prevent anode pellet to be oxidized under condition of uncertainty；Described noble gases select helium, neon, argon, krypton, xenon-133 gas
In one kind, preferred argon.
1.3rd, sinter
Anode pellet is put into noble gases to be sintered, temperature be 1300 DEG C～2000 DEG C, sintering time be 20min～
60min, the sintering temperature are higher, fix can the structure of anode pellet, and anode pellet is processed through presintering, by lubricant
Dispose, in sintering step, anode pellet surface is not in rough curved surface, form well-regulated curved surface, indifferent gas
The reason for carrying out under body be：(1) prevent rest lubricant from burning, destroy the structure of anode pellet, (2) prevent tantalum powder uncontrollable
It is oxidized；Described noble gases select the one kind in helium, neon, argon, krypton, xenon-133 gas, preferred argon；
During sintering, as the ratio capacity rate of the valve metal powder for forming anode bodies is high, sintering is sometimes resulted in about
The contraction of 10%-20%.With the increase of anode bodies size, this contraction can cause anode construction that moderate finite deformation occurs, at this
It is in inventive embodiments, for the higher and less anode pellet of diameter of height or even it is also possible that macroscopic substantially curved
It is bent.In this case, in theory it is believed that when anode bodies are connect with outside rigid surface (such as the surface of sintered crucible) physics
When tactile, bending can increase.More specifically, this rigid surface can limit the contraction of anode bodies at physical contact, so as to lead
Cause the shrinkage ratio anode bodies other parts in physical contact region few.This contraction difference can cause anode bodies to bend in turn, shape
Into curved shape (such as crescent).In order to this flexural deformation is minimized, using anode body surface not with outer surface (as burnt
The surface of knot crucible) mode that carries out physical contact is sintered.For example, sintered crucible bottom even get out circular hole,
Then anode tap is inserted in the hole, makes anode bodies vacantly stand upside down in sintered crucible, it is ensured that in sintering process not with other
What surface directly forms physical contact, limit Oxygen atom transfer to anode pellet on atmosphere high temperature sinter when anode core
Block can free shrink, not by physical restriction.It should also be understood that sinter that other various structures are adopted, and and
Do not limited by this kind of structure.For example, it may be possible to anode pellet is vertically put in heating furnace using mode in suspension, then,
After sintering process terminates, put forward, so as to obtain the capacitor anode pellet of needs.
2nd, the sintering of tantalum cathode cylinder compacting：
2.1st, suppress
Suppressed with tantalum powder, designed the mould of special cathode tube, by the tantalum powder of certain specific volume (i.e. certain particle size)
Formed with certain pressure compacting.Gained anode bodies can be the shape of any requirement, such as cylinder, square, rectangle, circle
Shape, ellipse, triangle, hexagon, octagon, heptagon, pentagon etc..Anode bodies can also have bag in " groove " shape, groove
One or more grooves, groove, low-lying or depression are included, to increase surface area-to-volume ratio, the present embodiment is preferably using cylinder
Structure；
In order that cathode tube compacting is even closer, before compaction, lubricant is added in tantalum powder, to improve the flowing of tantalum powder
Property and caking property, it is ensured that when cathode tube is compressing, each granule is equably bonded together each other, and the cathode tube for being formed is each
Partial Density Distribution is uniform, just can guarantee that the sintering stress that each position is subject in high-temperature sintering process is consistent, reduces deformation；
During described lubricant is Camphora, stearic acid and other soap matter fatty acids, Polyethylene Glycol, glyptal resin, polyvinyl alcohol, microwax
The preferred glyptal resin of one or more the present embodiment as lubricant, during use, lubricant is dissolved in volatile organic
In solvent, the present embodiment selects volatile organic solvent for the one of which solvent in dehydrated alcohol, acetone, carbon tetrachloride, sheet
The preferred dehydrated alcohol of embodiment is used as solvent；The 0.1%-8% of the percentage composition that lubricant is added about gross weight, this enforcement
Example preferably 0.5%.
2.2nd, presintering
Tantalum cathode cylinder is put in noble gases carries out presintering, and temperature is 100 DEG C～200 DEG C, and burn-in time is 20min
～120min, presintering mainly remove the lubricant in tantalum cathode cylinder at a lower temperature, the reason for carrying out under noble gases
It is：(1) prevent lubricant from burning, destroy the structure of anode pellet, (2) prevent tantalum powder uncontrollable oxidized；Described inertia
Gas selects the one kind in helium, neon, argon, krypton, xenon-133 gas, preferred argon.
2.3rd, sinter
Tantalum cathode cylinder is put in noble gases and is sintered, temperature be 500 DEG C～900 DEG C, sintering time be 20min～
60min；Process through presintering, lubricant is disposed, in sintering step, higher temperature can be solid by the structure of tantalum cathode cylinder
Fixed, tantalum cathode cylinder surface is not in rough curved surface, forms well-regulated curved surface；The reason for carrying out under noble gases
It is：(1) remaining lubricant burning is prevented, the structure of anode pellet is destroyed, (2) prevents tantalum powder uncontrollable oxidized；It is described
Noble gases select helium, neon, argon, krypton, the one kind in xenon-133 gas, preferred argon.
3rd, Ta2O5Medium film production
3.1st, make oxidation and form liquid
Using ethylene glycol：Deionized water ratio is 1：1～2 mixed liquor is solvent, is preferably in a proportion of 1：1,；Add H3PO4It is molten
Liquid and Ag2SO4, make the mass concentration 0.08wt%～0.8wt% of phosphoric acid, preferred 0.5wt%, Ag2SO4Mass concentration
0.01wt%～0.05wt%, preferably 0.2wt%；Increase Ag2SO4Effect be to increase oxidation and form the conductive ion of liquid.
3.2nd, cool down oxidation and form liquid
The oxidation is formed at -5 DEG C～5 DEG C by the temperature control of liquid using cooling system；
3.3rd, to tantalum anode core pretreatment
Pretreatment, toluenesulfonic acid ferrum are carried out to tantalum anode core with the toluenesulfonic acid ferrous solution that concentration is 0.1wt%～3wt%
The preferred 1wt% of concentration of solution, treatment temperature are 10～30min, and its solvent is ethanol, methanol, the one kind in n-butyl alcohol, toluene
Sulfonic acid ferrous solution is 0.1wt%～3wt%.
3.4th, make dielectric oxide film
Anode pellet immersion oxidation is formed in liquid, anode pellet is powered, and is made the boost current density be
In the range of 8mA/g～30mA/g, initial boost current density is 20mA/g～30mA/g, and in anode pellet, voltage often boosts 12V,
Boost current density is reduced 3～4mA/g after terminating by constant pressure 20min～30min, each constant pressure, and minimum is reduced to 8mA/g, directly
Predetermined magnitude of voltage is raised to the positive and negative pole tension of capacitor anode pellet, deenergization after constant pressure 5h～6h, described are predetermined
3～5 times for rated capacitor voltage of magnitude of voltage；The dielectric oxide film more uniform close made using the method.
3.5th, stable oxide-film
When voltage drops to below 1V in the anode pellet, the anode pellet for being formed with oxidation film layer is formed in liquid from oxidation
Take out, boil in being placed in the deionized water of 90 DEG C of temperature and wash 30min-120min, the oxidation inside anode pellet is formed into liquid complete
Boil wash clean in portion；Vacuum is put into for 2 × 10-3More than Torr, temperature be heat treatment 20 in 200～300 DEG C of vacuum drying oven～
60min；Then will immerse in the oxidizing agent solution that temperature is 160 DEG C～180 DEG C through the anode pellet block of heat treatment carries out electricity
Chemical treatment 1～2 hour, 0.8 times～1.2 times for rated capacitor voltage of applied voltage, by the anode through Passivation Treatment
Pellet is cleaned, dry for standby, and the medium oxidizing membrane structure by the method process is more stable.
4th, tantalio RuO2Cathode electrode makes
4.1st, make ruthenium source solution
Ruthenium source is dissolved in into aqueous isopropanol, cationic surfactant, dispersion is added；
Described ruthenium source is ruthenium trichloride, an isopropyl toluene ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium, six ammonium of tri-chlorination conjunction ruthenium, Asia
1 kind or 2 kinds of mixing in nitroxyl nitric acid ruthenium, the preferred ruthenium trichloride of the present embodiment；
The cationic surfactant is cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecylamine hydrochloric acid
Salt, dioctadecylamine hydrochlorate, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl dimethyl benzyl chloride
Change 1 in ammonium, chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride
Kind or 2 kinds of mixing, the preferred benzalkonium chloride of the present embodiment.
4.2nd, metal compound powders are added
To in the solution of ruthenium source in the copper oxide of addition 1～5%, potassium oxide, manganese oxide, anhydrous cupric sulfate, potassium permanganate
One or more, the mixed oxidization metal dust of the preferred anhydrous cupric sulfate of the present embodiment and potassium permanganate.
4.3rd, add thickening agent
Add 1～3% thickening agent, described thickening agent is polyacrylamide, titanate esters, Radix Acaciae senegalis, Silica hydrogel, this
The preferred polyacrylamide of embodiment.
4.4th, to tantalum cathode cylinder pretreatment
Pretreatment, this reality are carried out to tantalum cathode cylinder inwall with the toluenesulfonic acid ferrous solution that concentration is 0.05wt%～1wt%
The preferred 0.5wt% of concentration of toluenesulfonic acid ferrous solution in example is applied, process time is 10～30min, is poured out after being disposed, and which is molten
Agent is ethanol, methanol, the one kind in n-butyl alcohol, the preferred n-butyl alcohol of the present embodiment.
4.5th, RuO is smeared on tantalum cathode cylinder2
In the cathode tube that the solution that step 4.3 is obtained is poured into after step 4.4 is processed, pouring volume for cathode tube volume 1/
10～1/6, the present embodiment preferably 1/8 carries out centrifugation drying in being then placed in 60～70 DEG C of environment, described centrifugation drying is
Cathode tube is put on tachogenerator and is dried, and cathode tube is rotated around the centrage of cathode tube, during drying, needed
Speed governing is carried out to tachogenerator, the solution that step 4.4 is obtained is uniformly dispersed on the circular wall of cathode tube；The step can
RuO is wiped disposably to apply to the inwall of cathode tube2, and be uniformly distributed and be distributed on the inwall of cathode tube.
4.6th, high temperature sintering
Cathode tube will be processed by step 4.5 and send into Muffle furnace high temperature sintering carries out high temperature sintering process, and temperature is 500～
600 DEG C, the time be 30min～120min, natural cooling after the completion of high-temperature heat treatment.
4.7th, Passivation Treatment
Contain RuO to what step 4.6 was obtained2The solution passivation for adding step 4.2 to obtain in the cathode tube of cathode electrode layer
Process, being then fed again into Muffle furnace high temperature sintering carries out high temperature sintering process, and temperature is 500～600 DEG C, the time is
30min～120min, natural cooling after the completion of high-temperature heat treatment, the step can further stablize the RuO of cathode tube inwall2It is situated between
Matter layer.
5th, electrolytic capacitor solution makes
5.1st, by resistivity more than 5M Ω .cm deionized water and the preparation of sulphuric acid that mass percent concentration is more than 98%
Into the aqueous sulfuric acid that mass concentration is 25%-38%, the present embodiment preferably 30%；
5.2nd, the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15% is added in the aqueous sulfuric acid,
Mixed solution is configured to, the present embodiment is preferably 10%；Need while using the organically-modified solvent add its 1/2～2
The dehydrated alcohol of times volume is used in mixed way, preferably 1 times volume of the present embodiment；It is described be higher than 140 DEG C property-modifying additive be second two
Alcohol methyl ether, butyl glycol ether, dimethyl sulfoxide, N-Methyl pyrrolidone, dimethylformamide, dimethyl acetylamide, sulfolane,
One or two mixing in the macromole organic solvent such as HMPA, the present embodiment are preferably ethylene glycol monomethyl ether.
5.3rd, in above-mentioned mixed solution, add the depolarizing agent of the 0.2%-1.0% of gross mass, the present embodiment to be preferably
0.5%, Jing sonic oscillation is uniformly obtained working electrolyte；The depolarizing agent is the transition such as copper sulfate, sulphuric acid oxygen vitriol, iron sulfate
One or two mixings in metal sulfate, this enforcement are preferably iron sulfate.
5.4th, prepare gel electrolyte：Part working electrolyte solution is taken, adds 5%-15% high-purity by mass percentage
Aerosil, the present embodiment are preferably 10%, stir, and gel electrolyte is obtained.
6th, capacitor assembling
6.1st, the capacitor anode pellet that the surface is formed with dielectric oxide film be impregnated in into prepared work electrolysis
In matter solution, dip time is 20min-60min, is then taken out, and is positioned over stand-by in glass surface ware；
6.2nd, tantalum shell deionized water is boiled and is washed, after drying in 120 DEG C of environment, be disposed vertically on assembling frame, note
Enter working electrolyte solution and impregnate 20min-60min at room temperature, then the electrolyte solution in cylinder is drawn with pipettor dry
Only, it is stand-by；
6.3rd, gel electrolyte pipettor is injected in the tantalum shell impregnated of Working electrolyte according to consumption, Ran Hou
Teflon insulation packing ring on the anode pellet bottom pad of the Working electrolyte being impregnated with, which is vertically put in tantalum shell,
Capacitor assembly is obtained；
6.4th, above-mentioned capacitor assembly is carried out into slot rolling, laser sealing welding, plasma Jing after measurement correlation performance parameters
Electrolysis condenser product after the operations such as anode butt welding, that is, needed for making.
While Ta of the present embodiment also to being made with above-described embodiment2O5-RuO2/ Ta capacitors are detected, detection method
And result is as follows：
The Ta by made by2O5-RuO2/ Ta capacitors are processed in being placed on the environment higher than predetermined work ambient temperature, this
Experimental selection is selecting 220 DEG C, continuous firing 100h, 200h, 500h under conditions of 30V, then measure capacitor assembly etc.
Effect series resistance ESR and conventional earth leakage stream K values, it is when ESR≤1 Ω is detected, during K≤0.0008CV (μ A), up to standard；Then will reach
Target electrolysis condenser is placed on and determines energy density E in 25 DEG C of operating frequency 120Hz and temperature (energy density is generally according to public affairs
Formula E=1/2CV2It is determined that, wherein C is the electric capacity represented with farad (F), and V is the capacitor working represented with volt (V)
Pressure), when being measured to 5≤E≤20J/cm3When, the electrolysis condenser is up to standard.
Jing tests the capacitor specifications for 75V1000 μ F, 100h, 200h life-span load examination under conditions of 220 DEG C, 30V
Capacitor after testing ESR average out to 135m Ω under the conditions of 100Hz, 10.6 μ A of leakage current average out to, energy density under room temperature
12.4J/cm3, conventional earth leakage stream K values are less than 0.0008VC (μ A)；By the life-span load of 500h under conditions of 220 DEG C, 30V
After test, capacitor performance keeps stable.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., be all contained within protection scope of the present invention.
Claims (5)
1. a kind of Ta2O5-RuO2The manufacture method of/Ta capacitors, it is characterised in that：Including tantalum anode core and the compacting of tantalum cathode cylinder
And sintering, Ta2O5Medium film production, electric capacity electrolyte make, tantalio RuO2Cathode electrode layer makes, and capacitor assembling, its
In：
Ta2O5Deielectric-coating making step is：
(1) make oxidation and form liquid, using ethylene glycol：Deionized water ratio is 1：1～2 mixed liquor is solvent, adds H3PO4It is molten
Liquid and Ag2SO4, make the mass concentration 0.08wt%～0.8wt% of phosphoric acid, Ag2SO4Mass concentration 0.01wt%～
0.05wt%；
(2) cool down oxidation and form liquid, the oxidation is formed at -5 DEG C～5 DEG C by the temperature control of liquid using cooling system；
(3) to tantalum anode core pretreatment, tantalum anode core is carried out with the toluenesulfonic acid ferrous solution that concentration is 0.1wt%～3wt%
Pretreatment, process time are 10～30min, and its solvent is ethanol, methanol, the one kind in n-butyl alcohol；
(4) dielectric oxide film is made, anode pellet immersion oxidation is formed in liquid, anode pellet is powered, and is made liter
Piezoelectricity current density is that, in the range of 8mA/g～30mA/g, initial boost current density is 20mA/g～30mA/g, electricity in anode pellet
Press the 12V that often boosts, constant pressure 20min～30min, each constant pressure that boost current density is reduced 3～4mA/g after terminating, minimum subtracts
It is little to 8mA/g, until the positive and negative pole tension of capacitor anode pellet is raised to predetermined magnitude of voltage, deenergization after constant pressure 5h～6h,
3～5 times for rated capacitor voltage of described predetermined magnitude of voltage；
(5) stable oxide-film, when voltage drops to below 1V in the anode pellet, will be formed with the anode pellet of oxidation film layer
Formed in liquid from oxidation and taken out, boiled in being placed in the deionized water of 90 DEG C of temperature and wash 30min-120min, inside anode pellet
Oxidation form liquid and all boil wash clean；Vacuum is put into for 2 × 10-3More than Torr, temperature are 200～300 DEG C of vacuum drying oven
Middle 20～60min of heat treatment；Then it is 160 DEG C～180 DEG C oxidizing agent solutions the anode pellet through heat treatment to be immersed temperature
In carry out electrochemical treatments 1～2 hour, applied voltage is 0.8 times～1.2 times of rated capacitor voltage, will be at passivation
The anode pellet of reason is cleaned, dry for standby；
Tantalio RuO2Cathode electrode layer making step be：
(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, six ammonium of tri-chlorination conjunction ruthenium, nitrosyl
1 kind or 2 kinds of mixing in base nitric acid ruthenium；
The cationic surfactant is cetyl trimethyl quaternary ammonium bromides, lauryl amine, octadecyl amine hydrochloride, double
Octadecyl amine hydrochloride, benzalkonium chloride, dodecyl dimethyl phenyl phosphonium bromide, dodecyl dimethyl benzyl ammonium chloride,
1 kind or 2 in chlorination dococylpyridinium, tetrabutylammonium chloride, tri-n-octyl dimethyl ammonium chloride, benzyltriethylammoinium chloride
The mixing planted；
(2) add in the solution of ruthenium source 1～5% copper oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, in potassium permanganate one
Plant or various powders；
(3) 1～3% thickening agent is added, described thickening agent is polyacrylamide, titanate esters, Radix Acaciae senegalis, Silica hydrogel；
(4) to tantalum cathode cylinder pretreatment, with the toluenesulfonic acid ferrous solution that concentration is 0.05wt%～1wt% to tantalum cathode cylinder inwall
Carry out pretreatment, process time is 10～30min, is poured out after being disposed, its solvent is ethanol, methanol, in n-butyl alcohol one
Kind；
(5) in the cathode tube for pouring the solution that step (3) is obtained after step (4) is processed into, pouring volume for cathode tube volume 1/
10～1/6, centrifugation drying is carried out in being then placed in 60～70 DEG C of environment, described centrifugation drying is that cathode tube is put into rotating speed
Dried on machine, and cathode tube is rotated around the centrage of cathode tube, during drying, needs to adjust tachogenerator
Speed, enables the solution that step (3) is obtained to be uniformly dispersed on the circular wall of cathode tube；
(6) will process cathode tube by step (5) and send into Muffle furnace high temperature sintering carries out high temperature sintering process, and temperature is 500～
600 DEG C, the time be 30min～120min, natural cooling after the completion of high-temperature heat treatment；
(7) Passivation Treatment, contains RuO to what step (6) was obtained2What in the cathode tube of cathode electrode layer, addition step (2) was obtained is molten
Liquid Passivation Treatment, being then fed again into Muffle furnace high temperature sintering carries out high temperature sintering process, and temperature is 500～600 DEG C, the time
For 30min～120min, natural cooling after the completion of high-temperature heat treatment；
Electric capacity electrolyte making step is：
(1) deionized water by resistivity more than 5M Ω .cm is configured to matter with the sulphuric acid that mass percent concentration is more than 98%
Aqueous sulfuric acid of the amount concentration for 25%-38%；
(2) the organically-modified solvent higher than 140 DEG C of boiling points of total amount 5%-15% is added in the aqueous sulfuric acid, is configured to
Mixed solution；Need to add the dehydrated alcohol of its 1/2～2 times of volume to be used in mixed way while using the organically-modified solvent；
It is described be higher than 140 DEG C of boiling points organically-modified solvent be ethylene glycol monomethyl ether, butyl glycol ether, dimethyl sulfoxide, N- methylpyrroles
One kind in alkanone, dimethylformamide, dimethyl acetylamide, sulfolane, HMPA macromole organic solvent or
Two kinds of mixing；
(3) in above-mentioned mixed solution, add the depolarizing agent of the 0.2%-1.0% of gross mass, Jing sonic oscillations that work is uniformly obtained
Make electrolyte；The depolarizing agent is copper sulfate, sulphuric acid oxygen vitriol, one or two in iron sulfate transition metal sulfate are mixed
With；
(4) gel electrolyte is formulated as：Part working electrolyte solution is taken, 5%-15% high-purity gas are added by mass percentage
Aerosil, stirs, and gel electrolyte is obtained.
2. Ta as claimed in claim 12O5-RuO2The manufacture method of/Ta capacitors, it is characterised in that：Described tantalum anode core
Suppress with tantalum cathode cylinder and sintering concrete operation step is as follows：
Tantalum anode core is suppressed and sintering step is：
(1) suppress：Suppressed with tantalum powder, and lubricant is added in tantalum powder；
(2) presintering, anode pellet is put in noble gases carries out presintering, and temperature is 200 DEG C～400 DEG C, burn-in time
For 20min～60min；
(3) sinter, anode pellet is put into into noble gases and is sintered, temperature is 1300 DEG C～2000 DEG C, sintering time is
20min～60min, during sintering, the mode that anode pellet surface does not carry out physical contact with outer surface is sintered；
Tantalum cathode cylinder is suppressed and sintering step is：
(1) suppress：Suppressed with tantalum powder, and lubricant is added in tantalum powder；
(2) presintering, tantalum cathode cylinder block is put in noble gases carries out presintering, and temperature is 100 DEG C～200 DEG C, during pre-burning
Between be 20min～120min；
(3) sinter, tantalum cathode cylinder is put in noble gases and is sintered, temperature is 500 DEG C～1000 DEG C, sintering time is
20min～60min.
3. Ta as claimed in claim 22O5-RuO2The manufacture method of/Ta capacitors, it is characterised in that：Described lubricant is
One or more in Camphora, stearic acid and other soap matter fatty acids, Polyethylene Glycol, glyptal resin, polyvinyl alcohol, microwax.
4. Ta as claimed in claim 22O5-RuO2The manufacture method of/Ta capacitors, it is characterised in that：Described noble gases
One kind in selection helium, neon, argon, krypton, xenon-133 gas.
5. Ta as claimed in claim 12O5-RuO2The manufacture method of/Ta capacitors, it is characterised in that：Described capacitor bank
Filling step is：
(1) the capacitor anode pellet that surface is formed with dielectric oxide film is impregnated in prepared working electrolyte solution,
Dip time is 20min-60min, is then taken out, and is vertically placed on stand-by in glass surface ware；
(2) tantalum shell deionized water is boiled and is washed, after drying in 120 DEG C of environment, be disposed vertically on assembling frame, inject work
Electrolyte solution impregnates 20min-60min at room temperature, then draws totally the electrolyte solution in cylinder with pipettor, treats
With；
(3) gel electrolyte pipettor is injected in the tantalum shell impregnated of Working electrolyte according to consumption, then in dipping
There is teflon insulation packing ring on the anode pellet bottom pad of Working electrolyte, which is vertically put in tantalum shell, that is, is obtained
Capacitor assembly；
(4) above-mentioned capacitor assembly is carried out into slot rolling, laser sealing welding, plasma anode Jing after measurement correlation performance parameters
Electrolysis condenser product after the operations such as butt welding, that is, needed for making.
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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 |
| CN105405655B (en) * | 2015-12-09 | 2018-06-29 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of non-solid tantalum electrolytic capacitor cathode preparation method |
| 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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| CN101556869A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Method for preparing RuO2 film in internal wall of tantalum shell applied to tantalum capacitor |
| CN103560007A (en) * | 2013-10-18 | 2014-02-05 | 中国振华（集团）新云电子元器件有限责任公司 | Method for manufacturing solid electrolyte capacitor having high conductivity |
| CN103887085A (en) * | 2014-03-28 | 2014-06-25 | 贵州中航聚电科技有限公司 | High-voltage electrolyte for hybrid super tantalum capacitor and preparation method thereof |
| CN104021947A (en) * | 2014-06-20 | 2014-09-03 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556869A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Method for preparing RuO2 film in internal wall of tantalum shell applied to tantalum capacitor |
| CN103560007A (en) * | 2013-10-18 | 2014-02-05 | 中国振华（集团）新云电子元器件有限责任公司 | Method for manufacturing solid electrolyte capacitor having high conductivity |
| CN103887085A (en) * | 2014-03-28 | 2014-06-25 | 贵州中航聚电科技有限公司 | High-voltage electrolyte for hybrid super tantalum capacitor and preparation method thereof |
| CN104021947A (en) * | 2014-06-20 | 2014-09-03 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor |
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