CN1478287A - Powder for capacitor, sintered body thereof and capacitor using sintered body - Google Patents
Powder for capacitor, sintered body thereof and capacitor using sintered body Download PDFInfo
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- CN1478287A CN1478287A CNA01819611XA CN01819611A CN1478287A CN 1478287 A CN1478287 A CN 1478287A CN A01819611X A CNA01819611X A CN A01819611XA CN 01819611 A CN01819611 A CN 01819611A CN 1478287 A CN1478287 A CN 1478287A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Abstract
A powder for capacitors, which contains 0.01 to 15 atom % of zirconium and mainly comprises niobium and/or tantalum having an average particle size of from 0.2 to 5 mu m; a sintered body thereof; an a capacitor fabricated from the sintered body as one part electrode, a dielectric material formed on the surface of the sintered body, and another part electrode provided on the dielectric material. A capacitor manufactured from the sintered body of a powder for capacitors of the present invention have a large capacitance per unit mass and good leakage current characteristics.
Description
The mutual reference of related application
The application is based on the application of the regulation of 35 U.S.C. the 111st (a) bars, 119 (e) (1) clause according to 35 U.S.C., U.S. Provisional Application sequence number 60/267 is enjoyed in requirement, the rights and interests of the applyings date of 411 applications, and this provisional application is to propose on February 9 calendar year 2001 that is specified in according to 35 U.S.C.111 (b).
Technical field
The present invention relates to a kind of mud acid metal (mainly being niobium or tantalum) powder, can generate by this powder and have big capacitance per unit volume and good electrical flows the Lou capacitor of characteristic.Or rather, the present invention relates to niobium powder, tantalum powder and niobium-tantalum alloy powder, every kind of zirconium that all contains specified quantitative wherein, and relate to sintered body that uses this powder and the capacitor that uses this sintered body.
Background technology
Be used for requiring to have small size and big electric capacity such as the capacitor of the electronic instrument of cell-phone and PC.In these capacitors, tantalum capacitor preferably is because it has bigger electric capacity of its size and good performance.In tantalum capacitor, the sintered body of using tantalum powder usually is as anode part.In order to improve the electric capacity of these tantalum capacitors, need to increase the quality of sintered body, or use by pulverizing the sintered body that tantalum powder increases surface area.
The method of described increase sintered body weight must relate to the increase of capacitor shape, thereby can not satisfy the requirement that reduces size.On the other hand, in the method for described pulverizing tantalum powder with the increase surface area, the hole dimension of tantalum sintered object reduces, or increases at sintering stage blind hole, and therefore the immersion of negative electrode reagent becomes difficult in subsequent technique.In order to address these problems, to study in the sintering stage and reducing the method for closed pore and use the manufacture of materials capacitor method of dielectric constant greater than tantalum.Material with big dielectric constant comprises niobium.
JP-A-55-157226 (term " JP-A " refers to " not examining open Japanese patent application ") discloses the method that a kind of production is used for the sintered component of capacitor, it wherein is coalescent powder mold pressing under pressure of 2.0 μ m or littler niobium fine powder granules (initial powder) with particle diameter, sintered body with this moulded parts is cut into shred then, with conductor element and sintering once more after it is connected.But this patent application does not have the performance of the capacitor of this sintered component manufacturing of detailed public use.
United States Patent (USP) 4,084,965 disclose a kind of capacitor that uses niobium powder, and this powder is by hydrogenation and pulverize the acquisition of niobium ingot, and grain is through being 5.1 μ m.But the electric current leakage value of this niobium sintered body is big (being designated hereinafter simply as the LC value), and therefore practicality is relatively poor.
JP-A-10-242004 (United States Patent (USP) 6115235) discloses a kind of technology of the LC of improvement value, for example, and by part niobium nitride powder.But,, produce capacitor sometimes with big especially LC value making under the situation of large value capacitor by the sintered body of the niobium powder that uses fine grain.
Therefore, the purpose of this invention is to provide a kind of powder that is used for capacitor, this powder can provide the capacitor with big unit mass electric capacity and little electric current leakage value.Purpose of the present invention comprises provides sintered body that uses this powder and the capacitor that uses this sintered body.
Summary of the invention
Carried out extensive studies for addressing the above problem, the inventor finds by the zirconium of specified quantitative is sneaked into niobium, tantalum or niobium-tantalum alloy as a result, the powder that promptly is used in sintering has tiny average grain diameter and also can keep big specific area, and when using this sintered body to produce capacitor, can obtain to have the high power capacity of low LC value and stable capacitor.Based on above-mentioned discovery, the present invention is accomplished.
More specifically say, the present invention relates to following powder, its sintered body of capacitor and the capacitor that uses this sintered body of being used for.
1. powder that is used for capacitor, it contains zirconium and mainly comprises niobium and/or tantalum.
2. as above-mentioned the 1st the described powder that is used for capacitor, it contains 0.01-15 atom (atom)
% zirconium and mainly comprise niobium and/or tantalum.
3. as the above-mentioned the 1st or the 2nd the described powder that is used for capacitor, it mainly comprises niobium.
4. as the above-mentioned the 1st or the 2nd the described powder that is used for capacitor, it mainly comprises tantalum.
5. as above-mentioned the 1st the described powder that is used for capacitor, it mainly comprises niobium-tantalum alloy.
6. as any described powder that is used for capacitor among the above-mentioned 1-5, wherein average grain diameter is 0.2-5 μ m.
7. as any described powder that is used for capacitor among the above-mentioned 1-5, wherein specific area is 0.5-15m
2/ g.
8. as any described powder that is used for capacitor among the above-mentioned 1-5, wherein part niobium and/or tantalum combine with at least a element that is selected from nitrogen, carbon, boron or sulphur.
9. as above-mentioned the 8th the described powder that is used for capacitor, wherein the binding capacity of above-mentioned element is 50～200,000ppm.
10. powder that is used for capacitor, its average grain diameter is 20-500 μ m, obtains by any described powder that is used for capacitor among granulation such as the above-mentioned 1-9.
11. a sintered body wherein uses any described powder that is used for capacitor among the above-mentioned 1-10.
12. as above-mentioned the 11st described sintered body, wherein specific area is 0.5-5m
2/ g.
13. a capacitor is wherein by as the sintered body as above-mentioned the 11st or 12 description of a lateral electrode, the dielectric material that forms on this sintered body surface and the opposite side electrode manufacturing that provides on dielectric material.
14. as above-mentioned the 13rd described capacitor, wherein dielectric material contains niobium oxide and/or tantalum pentoxide
15. as above-mentioned the 14th described capacitor, wherein niobium oxide and/or tantalum pentoxide form by electrolytic oxidation.
16. as above-mentioned the 13rd described capacitor, wherein the opposite side electrode is at least a material that is selected from electrolyte, organic semiconductor or inorganic semiconductor.
17. as above-mentioned the 16th described capacitor, wherein the opposite side electrode is formed by organic semiconductor, this organic semiconductor is for being selected from the organic semiconductor that comprises the benzopyrrole quinoline tetramer and tetrachloroquinone (chloranile), the organic semiconductor that mainly comprises four thio naphthacene, the organic semiconductor that mainly comprises tetracyano-p-quinodimethane (tetracyanoquinodimethane), and mainly comprise by in the polymer that contains two or more repetitives by following general formula (1) or (2) expression, mixing at least a organic semiconductor of organic semi-conductor of the conducting polymer that dopant obtains:
(R wherein
1To R
4Can be identical or different, represent hydrogen atom separately, have the alkyl of 1-6 carbon atom or have the alkoxyl of 1-6 carbon atom, X represention oxygen atom, sulphur atom or nitrogen-atoms, R
5Only exist during for nitrogen-atoms, and represent hydrogen atom or have the alkyl of 1-6 carbon atom, every couple of R at X
1And R
2, and R
3And R
4Can mutually combine and form ring.)
18. as above-mentioned the 17th described capacitor, wherein organic semiconductor is to be selected from least a in polypyrrole, polythiophene and their substitutive derivative.Detailed Description Of The Invention
The present invention relates to be used for niobium powder, tantalum powder and the niobium-tantalum alloy powder of capacitor, wherein every kind all contains zirconium.These powder all show similar performance, therefore, will be that example is described the present invention below with the niobium powder.
The electric capacity of capacitor is generally represented with following formula:
(the C: electric capacity, 8: dielectric constant, S: specific area, d: interelectrode distance) of C=ε * (S/d).
Here, d=k * V (k: constant, V: form voltage), therefore, C=ε * (S/ (k * V)), and C * V=(ε/k) * S.Correspondingly, can improve the electric capacity of capacitor by increasing specific surface area (S).
First method that improves the specific area of the sintered body that is used for capacitor is the powder diameter that reduces to be used for this capacitor.In the present invention, the average grain diameter of the host grain that contains the zirconium niobium powder that is used to make sintered body is less than 5 μ m, and the specific area of this powder particle can be brought up to realistic scale like this.
As an example, following table 1 has shown the particle diameter that contains the zirconium niobium powder and the specific area of inventor's manufacturing (according to breaking method).
Table 1
| Average grain diameter (D 50) | Specific area (S) |
| ????5μm | ????0.5m 2/g |
| ????2μm | ????1.2 2/g |
| ????0.9μm | ????2.1 2/g |
| ????0.5μm | ????4.1 2/g |
| ????0.2μm | ????9.8 2/g |
Average grain diameter (the D that table 1 shows
50) particle size values of expression when the mass accumulation % that measures with particle size distribution measuring instrument (trade name " Microtrack ") is 50 quality %.The value of specific area for using the BET method to measure.
Obviously find out from table 1, the specific area that contains the zirconium niobium powder can be improved by reducing its average grain diameter, but, if the average grain diameter that contains the zirconium niobium powder is less than 0.2 μ m, pore-size diminishes and the closed pore increase when producing sintered body, the dipping of the negative electrode reagent in the subsequent step becomes difficult as a result, and the capacitor that obtains can not have big electric capacity and can not be applicable to practical use.On the other hand, if average grain diameter is 5 μ m or bigger, because specific area reduces to obtain big electric capacity.Therefore, in the present invention, the average grain diameter that contains the zirconium niobium powder is preferably from 0.2 μ m to less than 5 μ m.
Second method that improves the specific area of the sintered body that is used for capacitor is to use the powder with little average grain diameter to make sintered body, is suppressed at sintering stage generation closed pore simultaneously, so that do not reduce surface area.Usually, can keep specific area by reducing sintering temperature, still, if reduce sintering temperature, the intensity of sintered body can descend and be easy to cause and break.
In the present invention, make the zirconium of specified quantitative be included in niobium powder, tantalum powder or the niobium-tantalum alloy powder that is used for making sintered body, so that be enough to obtain to produce sintered body under the sintering temperature of necessary intensity with bigger serface.
Following table 2 has shown the specific area of the niobium sintered body that contains zirconium that the inventor as an example makes, and the specific area that does not contain the niobium sintered body of zirconium.
Table 2
| Sintering temperature | Specific area (S) | |
| Contain zirconium niobium sintered body (Nb: Zr=99.5: 0.5 (mole) | Niobium sintered body | |
| ??1300℃ | ????1.1m 2/g | ??0.7m 2/g |
| ??1250℃ | ????1.4m 2/g | ??0.9m 2/g |
| ??1200℃ | ????1.6m 2/g | ??1.0m 2/g |
| ??1150℃ | ????1.8m 2/g | ??1.2m 2/g |
Obviously find out from table 2,, contain the zirconium niobium powder and can keep being about the bigger serface that does not contain 1.5 times of zirconium niobium powder specific areas even sintering carries out under the high enough temp that obtains practical intensity.
And, even the zirconium niobium powder that contains that uses average grain diameter to reduce is made the high power capacity sintered body, do not see the special raising of LC value yet.Reason for this reason is not clear but suppose as follows.
Niobium and oxygen element have high bond joint strength, and therefore, the oxygen in the electrolytic oxidation thing film is easy to towards niobium metal side diffusion inside.But, in sintered body of the present invention, inner zirconium and niobium interact as keyed jointing, therefore, the oxygen in the electrolytic oxidation thing film is difficult for being keyed on the niobium metal of sintered body inside, and its diffusion to metal side is suppressed, the result, the stability of electrolytic oxidation thing film can be maintained, even and have under tiny particle diameter and the high power capacity situation at capacitor, the effect that reduces the LC value and reduce its dispersion also can reach.
In the present invention, the zirconium content that is used for producing the niobium powder of sintered body is important.Zirconium content is preferably 0.01-15 atom %.Have in mind from the electric capacity of institute's production capacitor and the balance between the electric current leakage value, more preferably 0.05-3 atom %.
If zirconium content is too little, the oxygen in the above-mentioned electrolytic oxidation thing film can not get suppressing to the diffusion of niobium metal side inside, and the result can not keep the stability of electrolytic oxidation thing film and the effect of reduction LC value to realize.On the other hand, if zirconium content is excessive, the content of niobium that contains the zirconium niobium powder descends, and electric capacity reduces.
In the present invention, be used to produce the average grain diameter that the zirconium niobium powder preferably has 0.2-5 μ m that contains of sintered body.
Average grain diameter can be for example by pulverizing the method acquisition of dehydrogenation then at the zirconium niobium powder that contains of above-mentioned scope to the hydride of niobium-zircaloy ingot, ball or powder.The average grain diameter that contains the zirconium niobium powder can be adjusted to the scope of needs by appropriate change hydrogenated niobium-zircaloy amount, pulverizing time, grinder etc.
Also can with thus obtained contain the zirconium niobium powder with do not contain in addition zirconium, average grain diameter is that 0.2 μ m mixes to the niobium powder less than 5 μ m, so that adjustment zirconium content.
This other niobium powder can obtain by the following method, for example: pulverize the also method of the hydride of ingot, ball or the powder of the processing of dehydrogenation subsequently niobium; The method of the sodium reduction product of potassium niobate is fluoridized in pulverizing; Or use the method for reduction-oxidation niobiums such as alkali metal, alkaline-earth metal, tantalum, niobium, aluminium, hydrogen, carbon.
The present invention contains the metal zirconium that the zirconium niobium powder can be no zirconium niobium powder and powder type or the mixture of zirconium compounds.The example of operable this zirconium compounds comprises alkoxide, zirconium boride, zirconium nitride, sulfuration zirconium, zirconium silicide, zircoium hydride, zirconium hydroxide, zirconium sulfate, zirconium silicate, zirconium halide, halogenation zirconia, oxo acetic acid zirconium and the zirconyl nitrate of zirconium carbide, zirconia (comprising stable zirconium dioxide), zirconium.These compounds may be used alone or two or more kinds used in combination.
The present invention contains the zirconium niobium powder also can be by using reduction-oxidation niobium and the acquisitions of zirconic mixture such as alkali metal, alkaline-earth metal, tantalum, niobium, aluminium, hydrogen, carbon.
Contain in the zirconium niobium powder in the present invention, the part contain the zirconium niobium powder can with at least a keyed jointing in nitrogen, carbon, boron and the sulphur so that further improve the electric current leakage value.This contains the zirconium niobium powder and can contain and anyly contain the zirconium niobium nitride, contain the zirconium niobium carbide, contain the zirconium niobium (Nb) boride and contain zirconium sulfuration niobium, and described these are respectively nitrogen, carbon, boron or the sulfide linkage things of practicing midwifery.These keyed jointing products can be separately or are comprised wherein with its two kinds, three kinds or four kinds of combinations.
Keyed jointing amount (total content of nitrogen, carbon, boron and sulphur) changes with the shape that contains the zirconium niobium powder, and still, under the situation of about 0.2-5 μ m, described total content is 50-200 in average grain diameter, 000ppm, preferred 200-20,000ppm.If described total content is lower than 50ppm, the LC characteristic can not get improving; Otherwise, if described content surpasses 200,000ppm, capacitance characteristic variation and be not suitable as capacitor.
The nitrogenize that contains the zirconium niobium powder can use the method for bath nitriding, ionic nitriding, gas nitriding or its mixing to carry out.Wherein, the preferred gas nitrogenize, this is because its facility is simple and easy operating.
Gas nitriding can be by placing blanket of nitrogen to carry out the above-mentioned zirconium niobium powder that contains.Keep a few hours under 2000 ℃ or lower nitriding atmosphere temperature, what can obtain to have target nitrogenize amount contains the zirconium niobium powder.Under higher temperature, carry out this processing and can shorten the processing time.
The carbonization that contains the zirconium niobium powder can be in gas carbonization, solid phase carbonization and the liquid carbonization any one.Containing the zirconium niobium powder can be by for example placing 2000 ℃ or more under the low temperature, under reduced pressure, several minutes to a few hours carbonization with it with material with carbon element or carbon source such as carbon containing organic material (for example methane).
The boronation that contains the zirconium niobium powder can be gas boronation or solid phase boronation.Containing the zirconium niobium powder can be by for example placing 2000 ℃ or more under the low temperature, under reduced pressure, several minutes to a few hours boronation with it with boron ball or boron source such as halogenation boron (for example boron trifluoride).
The sulfuration that contains the zirconium niobium powder can be any one in gas cure, ion sulfuration and the solid phase vulcanizing.For example, the gas cure in the sulphur gas atmosphere can place sulphur atmosphere to reach by containing the zirconium niobium powder.Be kept to less than tens of hours under 2000 ℃ or lower vulcanized gas temperature, what can obtain to have target sulfuration amount contains the zirconium niobium powder.Under higher temperature, carry out this processing and can shorten the processing time.
That uses in making sintered body is used for containing the zirconium niobium powder and can obtaining by following manner of capacitor: the niobium initial powder granulation that will contain zirconium is suitable shape, and further contains the zirconium niobium powder with the non-granulation of appropriate amount or niobium powder mixes after above-mentioned granulation.
The example of granulating method comprises: non-granulation is contained the zirconium niobium powder place high vacuum, be heated to the broken then method of proper temperature; Non-granulation is contained zirconium niobium powder and suitable bonding agent such as camphor, polyacrylic acid, polymethyl acrylate or polyethylene alcohol and solvent such as acetone, ethanol, acetic acid esters or water mix, then Po Sui method.
Contain the zirconium niobium powder by what use this granulation, the pressing mold performance in the sintered body production process improves.
The average grain diameter of granulated powder is preferably 20-500 μ m.Part is stopped up and to cause entering the flowability of metal die poor if the average grain diameter of granulated powder less than 20 μ m, can take place; Otherwise if surpass 500 μ m, the moulded parts after the mold pressing breaks in the corner easily.In addition, when the average grain diameter of granulated powder is 60-250 μ m, make in the process of capacitor behind sintered molded part, negative electrode reagent can easily flood and enter sintered body.
The niobium sintered body that contains zirconium that the present invention is used for capacitor contains the zirconium niobium powder or granulation contains the production of zirconium niobium powder by mold pressing and sintering are above-mentioned.The method of producing sintered body is not specifically limited, and still, this sintered body can for example be molded into reservation shape by containing the zirconium niobium powder, then at 500-2,000 ℃, preferred 900-1500 ℃, more preferably under 900-1300 ℃ 10
-5-10
2Pa pressure down heating several minutes obtained to a few hours.
The manufacturing of capacitor device is described below.
Capacitor of the present invention is by as the above-mentioned sintered body of a lateral electrode, the opposite side electrode manufacturing that is formed on the dielectric material on sintered body surface and provides on dielectric material.
For example, preparation has the plain conductor such as the valve acting of niobium or tantalum of containing of suitable shape and appropriate length, this lead is integrated in niobium powder sintering and mold pressing the part lead is inserted in the device of moulding, thereby makes lead become the lead-in wire of sintered body.
The dielectric material that is used for this capacitor is a kind of dielectric material of being made up of for example tantalum oxide, niobium oxide, polymer or ceramic compound, the preferred dielectric material of mainly being made up of niobium oxide, this material is by containing chemistry formation on the zirconium niobium sintered body in electrolyte.For chemistry in electrolyte forms niobium electrode, the protonic acid aqueous solution such as 0.1% phosphate aqueous solution, aqueous sulfuric acid, 1% acetic acid aqueous solution and the adipic acid aqueous solution commonly used.Containing under the situation that the zirconium niobium electrode obtains the niobium oxide dielectric material by forming in electrolyte with chemical method, capacitor of the present invention is an electrolytic capacitor, and contains zirconium niobium side as anode.
In capacitor of the present invention, the opposite side electrode does not have concrete restriction, for example can use at least a compound that is selected from the known electrolyte in aluminium electrolytic capacitor field, organic semiconductor and inorganic semiconductor.
The instantiation of electrolyte comprises and has dissolved the electrolytical dimethyl formamide of 5 quality % tetrafluoride boron isobutyl group 3 third ammoniums-ethylene glycol mixed solution, and the propene carbonate-ethylene glycol mixed solution of having dissolved 7 quality % tetrafluoride boron etamons.
The organic semi-conductor instantiation comprise the organic semiconductor that contains the benzopyrrole quinoline tetramer and tetrachloroquinone, mainly contain the organic semiconductor of four thio naphthacene, mainly contain the organic semiconductor of tetracyano-p-quinodimethane, and mainly contain organic semiconductor by the conducting polymer that obtains in the polymer that dopant is mixed the repetitive that contains following general formula (1) or (2) expression:
(R wherein
1To R
4Can be identical or different, represent hydrogen atom separately, have the alkyl of 1-6 carbon atom or have the alkoxyl of 1-6 carbon atom, X represention oxygen atom, sulphur atom or nitrogen-atoms, R
5Only exist during for nitrogen-atoms as X, and represent hydrogen atom or have the alkyl of 1-6 carbon atom, and every couple of R
1And R
2, and R
3And R
4Can mutually combine and form ring).For dopant, can use any known dopant, without limits.
The example that contains the polymer of the repetitive of representing in general formula (1) or (2) comprises polyaniline, polyoxygenated phenylene, polyphenylene oxide base, polythiophene, poly-furans, polypyrrole, poly-methyl pyrrole, and substitutive derivative and copolymer.Wherein, preferred polypyrrole, polythiophene and its substitutive derivative (for example, poly-(3,4-ethylene sulfo-thiophene)).
The term that uses in this specification " mainly contains conducting polymer " even in meaning that the conducting polymer that contains the component that impurity is derived in organic raw semiconductor monomer also can be included in, i.e. " conducting polymer is included in interior as basic effectively component ".
The example of spendable dopant comprises sulfo group quinonyl dopant, anthracene list sulfonic group dopant and other various anion doped dose.Also can use such as NO
+Or NO
2 +The electron acceptor dopant of salt.
The instantiation of inorganic semiconductor comprises the inorganic semiconductor that mainly contains brown lead oxide or manganese dioxide, and the inorganic semiconductor that contains tri-iron tetroxide.
These semiconductors can use separately or two or more are used in combination.
When used organic or inorganic semiconductor has 10
-2-10
3Scm
-1Conductivity the time, the capacitor of manufacturing can have less resistance value, and can further improve the electric capacity under the high frequency.
The opposite side electrode is under the situation of solid therein, and conductive layer can be provided thereon, so that reach good electrical contact with the lead (for example, lead frame) of outside.
Conductive layer can be by for example conductive paste curing, plating, metallization or the mode that forms heat-resisting electroconductive resin film form.The preferred embodiment of conductive paste comprises silver paste, copper cream, aluminium cream, carbon paste and nickel cream, and these cream can use separately or two or more are used in combination.Using under the situation of two or more cream, can be with cream mixed or a kind of cream overlapped form independent layer on the another kind of cream.Conductive paste can be placed air or heating that it is solidified then.The example of electroplating comprises nickel plating, copper facing, silver-plated and aluminize.The example of gas deposition metal comprises aluminium, nickel, copper and silver.
More specifically, for example carbon paste and silver paste are deposited on the opposite side electrode in order, and with the material compression molding such as epoxy resin, thereby constitute capacitor.This capacitor can have with niobium that contains zirconium niobium sintered body sintering and be embossed in or weld subsequently or tantalum lead-in wire.
The capacitor of the present invention that constitutes like this encapsulates with for example resin mouldings, resin shell, metal casing, resin impregnation or laminated film, is used as the capacitor product of various uses then.
At the opposite side electrode is under the situation of liquid, will form capacitor in the jar that for example is electrically connected with the opposite side electrode by the capacitor package that above-mentioned two kinds of electrodes and dielectric material constitute.In this case, the electrode side that contains the niobium sintered body of zirconium derives by above-mentioned niobium or tantalum lead-in wire, insulate with tank body with electro-insulating rubber etc. simultaneously.
Optimum implementation of the present invention
Followingly the present invention is described in more detail with reference to embodiment and Comparative Examples.But the present invention is not limited in these embodiment.In each embodiment and Comparative Examples, the electric capacity of sintered body and electric current leakage value and the electric capacity and the electric current leakage value that are worked into the capacitor in the chip are measured in accordance with the following methods and are assessed.(1) measurement of sintered body electric capacity
At the sintered body that immerses 30% sulfuric acid be placed between the tantalum material electrode in the sulfuric acid solution, connects a LCR instrument of making by Hewlett-Packard, measurement electric capacity and be set electric capacity under room temperature, 120Hz into this sintered body.(2) measurement of sintered body electric current leakage value
Under the room temperature, at the sintered body that immerses 20% phosphate aqueous solution be placed between the electrode in the phosphate aqueous solution, apply when being equivalent to form dielectric material the direct voltage (14V) 3 minutes that chemistry forms voltage 70% continuously, afterwards, measure electric current and be set electric current leakage value (LC value) into this sintered body.(3) measurement of condenser capacitance
Between the terminals of the chip of making, connect a LCR instrument of making by Hewlett-Packard, under room temperature, 120Hz, measure electric capacity and be set electric capacity into the capacitor of this processing chip.(4) measurement of condenser current leakage value
Direct voltage (6.3V) in the rated voltage (for example 2.5V, 4V, 6.3V, 10V, 16V, 25V, etc.), that chemistry forms the about 1/3-of voltage about 1/4 when forming dielectric material is applied to continuously between the terminals of the chip of making 1 minute, afterwards, measure electric current and be set electric current leakage value into the capacitor of this processing chip.Embodiment 1: the sintered body that contains the zirconium niobium powder:
Use 92g niobium ingot and 1g zirconium powder end, utilize arc-melting produce zirconium content be 1 mole of % contain zirconium niobium ingot.In a reactor of making of SUS 304, put into 50g gained ingot, and introduced hydrogen 10 hours continuously down at 400 ℃.After the cooling, the zirconium niobium piece that contains of hydrogenation is put into one and contained the jar of being made by SUS 304 of SUS matter ball and pulverized 10 hours.Afterwards, this hydride is mixed the slurry that forms 20 volume % with water, pack in the wet milk of making by SUS 304 waterproof pulverization 7 hours then with zirconia balls into.With centrifugation of gained slurry and decant, the product that obtains pulverizing.The vacuumize under the condition of 133Pa (1 holder) and 50 ℃ of this crushed products.Subsequently, the zirconium niobium powder that contains of this hydrogenation passes through at 400 ℃, 1.33 * 10
-2Pa (1 * 10
-4Holder) pressure heating dehydrogenation in 1 hour down.The average grain diameter that contains the zirconium niobium powder of being produced is 1.0 μ m, and zirconium content wherein is found to be 1 mole of % by the atom absorptiometry.What obtain thus contains the zirconium niobium powder at 1,000 ℃, 4 * 10
-3Pa (3 * 10
-5Holder) granulation under the vacuum.Afterwards, with the agglomerate fragmentation of granulation to obtain the granulated powder that average grain diameter is 120 μ m.
With the resulting niobium silk mold pressing that contains zirconium granulation niobium powder with diameter 0.3mm, obtain the moulded parts that size is approximately 0.3 * 0.18 * 0.45cm (about 0.1g).Then, with this moulded parts under 1,200 ℃ in 4 * 10
-3Pa (3 * 10
-5Holder) placed 30 minutes in the vacuum, obtain sintered body thus.Measure the tensile strength of niobium silk in this sintered body, be 3kg/cm
2(2.9 * 10
5Pa), thus illustrate that this sintered body has fully high intensity.Subsequently, the sintered body of gained by applying 20V voltage electrochemical treatments 200 minutes, forms dielectric layer on its surface in 0.1% phosphoric acid solution, under 80 ℃.Then, electric capacity and the electric current leakage value in 20% phosphate aqueous solution (be designated hereinafter simply as " LC ") of measurement in 30% sulfuric acid.Gained the results are shown in table 3.Embodiment 2-15: the sintered body that contains the niobium/tantalum powder of zirconium
Use zirconium powder end and niobium, tantalum or niobium-tantalum alloy ingot with the ratio of artificial setting, contain zirconium niobium ingot, contain zirconium tantalum ingot and contain zirconium niobium-tantalum ingot by the arc-melting preparation.
Use the facility identical, by adjusting the pulverizing time, obtain to have the containing the zirconium niobium powder, contain the zirconium tantalum powder and contain zirconium niobium-tantalum powder of particle diameter of needs by the various ingots of 50g with embodiment 1.Use these powder, make sintered body, and measure separately electric capacity and LC value in the mode identical with embodiment 1.The results are shown in table 3.Comparative Examples 1-6: niobium powder, tantalum powder and the niobium-tantalum alloy powder that does not contain zirconium:
By with embodiment 1 identical operations, preparation does not contain niobium powder, tantalum powder and the niobium-tantalum alloy powder of zirconium separately.Use these powder, make sintered body and measure separately electric capacity and LC according to the mode identical with embodiment 1.The results are shown in table 3.Comparative Examples 7 and 8: the niobium powder that contains excessive zirconium:
By with embodiment 1 identical operations, preparation zirconium content be 18.7 moles of % or 24.6 moles of % contain the zirconium niobium powder.Use these powder, make sintered body and measure separately electric capacity and LC according to the mode identical with embodiment 1.The results are shown in table 3.
Table 3
Embodiment 16-21: the sintered body that contains the niobium powder of zirconium
| Form (mol ratio) | Average grain diameter (μ m) | Electric capacity (μ FV/g) | LC(μA/g) | |||
| ?Nb | ??Ta | ????Zr | ||||
| Embodiment 1 | ?99 | ??- | ????1 | ????1.0 | ????139O00 | ????66 |
| Embodiment 2 | ?94 | ??5 | ????1 | ????1.0 | ????123000 | ????51 |
| Embodiment 3 | ?90 | ??9 | ????1 | ????1.0 | ????119000 | ????48 |
| Embodiment 4 | ?- | ??99 | ????1 | ????1.0 | ????39000 | ????6 |
| Embodiment 5 | ?99 | ??- | ????1 | ????0.5 | ????285000 | ????137 |
| Embodiment 6 | ?99 | ??- | ????1 | ????0.7 | ????185000 | ????92 |
| Embodiment 7 | ?99 | ??- | ????1 | ????1.3 | ????117000 | ????57 |
| Embodiment 8 | ?99 | ??- | ????1 | ????3.2 | ????55000 | ????20 |
| Embodiment 9 | ?99.98 | ??- | ????0.02 | ????1.0 | ????106000 | ????50 |
| Embodiment 10 | ?99.95 | ??- | ????0.05 | ????1.0 | ????110000 | ????53 |
| Embodiment 11 | ?99.5 | ??- | ????0.5 | ????1.0 | ????132000 | ????61 |
| Embodiment 12 | ?96.9 | ??- | ????3.1 | ????1.0 | ????133000 | ????64 |
| Embodiment 13 | ?93.8 | ??- | ????6.2 | ????1.0 | ????126000 | ????60 |
| Embodiment 14 | ?89.7 | ??- | ????10.3 | ????1.0 | ????123000 | ????63 |
| Embodiment 15 | ?86.3 | ??- | ????14.7 | ????1.0 | ????109000 | ????60 |
| Comparative Examples 1 | ?100 | ??- | ????- | ????0.5 | ????210000 | ????2210 |
| Comparative Examples 2 | ?100 | ??- | ????- | ????0.7 | ????139000 | ????1570 |
| Comparative Examples 3 | ?100 | ??- | ????- | ????1.0 | ????101000 | ????592 |
| Comparative Examples 4 | ?100 | ??- | ????- | ????1.3 | ????85000 | ????389 |
| Comparative Examples 5 | ?95 | ??5 | ????- | ????1.0 | ????88000 | ????321 |
| Comparative Examples 6 | ?- | ??100 | ????- | ????1.0 | ????31000 | ????8 |
| Comparative Examples 7 | ?81.3 | ??- | ????18.7 | ????1.0 | ????92000 | ????69 |
| Comparative Examples 8 | ?75.4 | ??- | ????24.6 | ????1.0 | ????84000 | ????79 |
In a reactor of making of SUS 304, put into 100g niobium ingot, and introduced hydrogen 10 hours continuously down at 400 ℃.After the cooling, the niobium piece of this hydrogenation is put into one contain the jar of making by SUS 304 of SUS matter ball and pulverized 10 hours.Afterwards, this hydride is mixed the slurry that forms 20 volume % with water, pack in the wet milk (trade name " Attritor ") that SUS 304 makes waterproof pulverization 7 hours then with zirconia balls into.With centrifugation of gained slurry and decant, the product that obtains pulverizing.The vacuumize under the condition of 133Pa (1 holder) and 50 ℃ of this crushed products.Subsequently, this hydrogenated niobium powder passes through at 400 ℃, 1.33 * 10
-2Pa (1 * 10
-4Holder) pressure heating dehydrogenation in 1 hour down.The average grain diameter of the niobium powder of being produced is 1.3 μ m.
According to the ratio of artificial setting, with the equal particle diameter of this niobium powder peace any one mixing in zirconia, zircoium hydride and the zirconium metal of about 1 μ m.With the various zirconium niobium powders that contain of gained at 1,000 ℃, 4 * 10
-3Pa (3 * 10
-5Holder) granulation under the vacuum.Afterwards, with the agglomerate fragmentation of granulation to obtain the granulated powder that average grain diameter is 190 μ m.
Contain zirconium granulation niobium powder separately with the niobium silk mold pressing of diameter 0.3mm with what obtain thus, obtain the moulded parts that size is approximately 0.3 * 0.18 * 0.45cm (about 0.1g).Then, with each moulded parts under 1,230 ℃ in 4 * 10
-3Pa (3 * 10
-5Holder) placed 30 minutes in the vacuum, to obtain sintered body.The sintered body of gained in 0.1% phosphoric acid solution, under 80 ℃ by applying 20V voltage electrochemical treatments 200 minutes, to form dielectric layer on its surface.Then, measure electric capacity in 30% sulfuric acid and the electric current leakage value in 20% phosphate aqueous solution.Gained the results are shown in table 4.
Table 4
Embodiment 22-26: the sintered body that contains the part niobium nitride powder of zirconium:
| The kind of zirconium | Zirconium content (mole %) | Electric capacity (μ F.V/g) | ??LC (μA/g) | |
| Embodiment 16 | Zirconia | ????0.2 | ????102000 | ????39 |
| Embodiment 17 | Zirconia | ????1.0 | ????116000 | ????55 |
| Embodiment 18 | Zircoium hydride | ????0.5 | ????104000 | ????43 |
| Embodiment 19 | Zircoium hydride | ????2.2 | ????115000 | ????53 |
| Embodiment 20 | Metal zirconium | ????0.05 | ????93000 | ????40 |
| Embodiment 21 | Metal zirconium | ????0.7 | ????112000 | ????51 |
In a reactor of being made by SUS 304, that puts into 10g zirconium content and be 1.2 moles of %, average grain diameter and be 0.9 μ m contains the zirconium niobium powder.This powder is to prepare according to the mode identical with embodiment 1.Under 300 ℃, introduced continuously nitrogen 0.5-20 hour to this reactor, contain the nitride of the niobium of zirconium with acquisition.
The nitrogen content of every kind of nitride is used the device measuring of the measurement nitrogen content of being made by LECO, and this equipment is measured nitrogen content according to thermal conductivity.This measured value is set to the nitrogenize amount with the ratio of the powder of independent measurement.Here nitrogenize amount is 0.02-0.89 quality %.The various nitride of zirconium niobium that contain of gained are according to mode granulation, mold pressing and the sintering identical with embodiment; and every kind of sintered body of gained is in 0.1% phosphoric acid solution; under 80 ℃ by applying 20V voltage electrochemical treatments 200 minutes, to form dielectric layer on its surface.Then, measure electric capacity in 30% sulfuric acid and the LC value in 20% phosphate aqueous solution.The results are shown in table 5.
Table 5
Embodiment 27-29: the sintered body that contains zirconium niobium powder/niobium powder mixture:
| Zirconium content (mole %) | Nitrogen content (quality %) | Electric capacity (μ F.V/g) | ????LC ??(μA/g) | |
| Embodiment 22 | ????1.2 | ????0.02 | ????142000 | ????65 |
| Embodiment 23 | ????1.2 | ????0.10 | ????141000 | ????58 |
| Embodiment 24 | ????1.2 | ????0.28 | ????143000 | ????55 |
| Embodiment 25 | ????1.2 | ????0.43 | ????141000 | ????55 |
| Embodiment 26 | ????1.2 | ????0.89 | ????139000 | ????70 |
In a nickel matter crucible, add 20g the fluoridizing potassium niobate and fluoridize the sodium of 10 times of potassium niobate moles of vacuum, 80 ℃ of following finish-dryings, make it in 1000 ℃, argon atmospher, carry out reductase 12 0 hour.After this reaction is finished, cool off this system and water, 95% sulfuric acid, water washing reduzate successively, then vacuumize and with the oxidation aluminium pot ball mill grinding that contains the silica alumina ball 40 hours.Also stir in 50% nitric acid of the product immersion 3: 2 (quality) of pulverizing and the mixed solution of 10% aqueous hydrogen peroxide solution.Afterwards, the product water of this pulverizing thoroughly washing reaches 7 removing impurity up to pH, and vacuumize.The average grain diameter of the niobium powder of being produced is 1.2 μ m.
Thus obtained niobium powder and according to embodiment 14 same way as preparations, average grain diameter is that 1.0 μ m, zirconium content are that the zirconium niobium powder that contains of 10 moles of % thoroughly mixes with the ratio of artificial setting; and with the various mixtures of gained according to mode granulation, mold pressing and the sintering identical, to obtain sintered body with embodiment 14.Measure the electric capacity and the LC value of each sintered body of gained, the results are shown in table 6.Embodiment 30-32: the sintered body that contains zirconium niobium powder/niobium powder mixture of part nitrogenize:
In a reactor of making by SUS 304, put into 50g niobium ingot, and introduced hydrogen 12 hours continuously down at 400 ℃.After the cooling, the niobium piece of hydrogenation is put into one contain the jar of making by SUS304 of irony ball and pulverized 10 hours.With reactor and the hydrogenation of making by SUS304 once more under these conditions same as described above of packing into of the product of this pulverizing.Afterwards, this hydride is mixed the slurry that forms 20 volume % with water, pack in the wet milk of making by SU S304 waterproof pulverization 6 hours then with zirconia balls into.With centrifugation of gained slurry and decant, the product that obtains pulverizing.This crushed products is 1.33 * 10
2Vacuumize under the condition of Pa (1 holder) and 50 ℃.Subsequently, this hydrogenated niobium powder passes through at 400 ℃, 1.33 * 10
-2Pa (10
-4Holder) pressure heating dehydrogenation in 1 hour down.The average grain diameter of the niobium powder of being produced is 1.0 μ m.
Ratio according to artificial setting; with thus obtained niobium powder and the average grain diameter for preparing according to the mode identical with embodiment 14 is that 0.9 μ m and zirconium content are that the zirconium niobium powder that contains of 10 moles of % thoroughly mixes; and behind the nitride that obtains by various mixtures according to the mode identical with embodiment 24, with various nitride granulations, mold pressing and sintering to obtain sintered body.Measure the electric capacity and the LC value of each sintered body, the results are shown in table 6.
Table 6
Embodiment 33-34: the manufacturing of capacitor device of the present invention and assessment:
| The kind of niobium powder | Mixing ratio (contains the zirconium niobium powder: niobium powder) | Electric capacity (μ F.V/g) | ??LC (μA/g) | |
| Embodiment 27 | Reduced powder | ????90∶10 | ??122000 | ??65 |
| Embodiment 28 | Reduced powder | ????50∶50 | ??128000 | ??61 |
| Embodiment 29 | Reduced powder | ????10∶90 | ??137000 | ??63 |
| Embodiment 30 | Comminuted powder | ????80∶20 | ??124000 | ??59 |
| Embodiment 31 | Comminuted powder | ????40∶60 | ??130000 | ??60 |
| Embodiment 32 | Comminuted powder | ????20∶80 | ??137000 | ??60 |
Embodiment 33 according to the mode identical with embodiment 11, respectively prepares 50 sintered bodies according to the mode identical with embodiment 1 and embodiment 34 respectively.
In the phosphate aqueous solution of each leisure 0.1% of these sintered bodies, by applying 20V voltage electrochemical treatments 200 minutes, to form the oxide dielectric film on its surface.Subsequently, repeat each sintered body is immersed 60% manganese nitrate solution, 30 minutes operations of heating under 220 ℃ then, form manganese dioxide layer on oxide dielectric film surface as another electrode layer.On this another electrode layer, pile up carbon-coating and silver paste layer in order.After installing lead frame, with this device as a whole with the epoxy resin mold pressing, to produce chip capacitor.The average capacitance of this chip capacitor and average LC value (among each embodiment, the n=50 sheet) are shown in table 7.Comparative Examples 8-10: the capacitor device that uses the sintered body that does not contain the zirconium niobium powder:
In a nickel matter crucible, 20g is fluoridized potassium niobate at vacuum, 80 ℃ of following finish-dryings, and pack into and fluoridize the sodium of 10 times of potassium niobate moles, make it in 1000 ℃, argon atmospher, carry out reductase 12 0 hour.After this reaction is finished, cool off this system and water, 95% sulfuric acid, water washing reduzate successively, then vacuumize and with the oxidation aluminium pot ball mill grinding that contains the silica alumina ball 40 hours.In 50% nitric acid that the product of pulverizing is immersed 3: 2 (quality) and the mixed solution of 10% aqueous hydrogen peroxide solution and stirring.Afterwards, the product water of this pulverizing thoroughly washing reaches 7 removing impurity up to pH, and vacuumize.The average grain diameter of the niobium powder of being produced is 1.3 μ m.
With the thus obtained niobium powder of the 30g reactor of making by SUS 304 of packing into, and under 300 ℃, introduced continuously nitrogen 0.5-4 hour, to obtain the nitride of niobium to this reactor.The nitrogen content of every kind of nitride is used the device measuring of the measurement nitrogen content of being made by LECO, and this equipment is measured nitrogen content according to thermal conductivity.The mass ratio of the powder of this measured value and independent measurement is set to the nitrogenize amount.As a result, nitrogenize amount here is 0.02-0.30 quality %.
With the nitride of various niobiums according to mode granulation, mold pressing and the sintering identical with embodiment 1 to obtain sintered body.
Use the sintered body of gained, make 50 chip capacitors, and measure the physical property of each chip capacitor of manufacturing according to the mode identical with embodiment 33 and 34.The results are shown in table 7.
Table 7
Embodiment 35-37: the manufacturing of capacitor device of the present invention and assessment:
| Nitrogen content (quality %) | Electric capacity (μ F) | ??LC ??(μA) | The LC value surpasses the sheet number of 100 μ A | |
| Embodiment 33 | ????- | ??625 | ??46 | ????0/50 |
| Embodiment 34 | ????- | ??594 | ??42 | ????0/50 |
| Comparative Examples 8 | ????0.02 | ??398 | ??46 | ????1/50 |
| Comparative Examples 9 | ????0.07 | ??392 | ??42 | ????1/50 |
| Comparative Examples 10 | ????0.30 | ??382 | ??30 | ????0/50 |
Embodiment 35 respectively prepares 50 slice sintered bodies according to the mode identical with embodiment 12 and embodiment 37 according to the mode identical with embodiment 24 according to the mode identical with embodiment 7, embodiment 36.Under each comfortable 20V voltage of these sintered bodies in 0.1% phosphoric acid solution electrochemical treatments 200 minutes, to form the oxide dielectric film on its surface.
Then, this oxide dielectric film is contacted with the equivalent mixed solution of 10% ammonium persulfate aqueous solution with the 0.5% anthraquinone sulfonic acid aqueous solution, then contact with pyrroles's steam, this operation repeats 5 times at least, contains the electrode of polypyrrole thereby form another on the oxide dielectric film.On this another electrode, pile up carbon-coating and silver paste layer in order.After installing lead frame, with this device as a whole with the epoxy resin mold pressing, to produce chip-shaped capacitor.The average capacitance of this chip capacitor and average LC value (among each embodiment, the n=50 sheet) are shown in table 8.Comparative Examples 11-13: use the capacitor device that does not contain zirconium niobium powder sintered body
In a reactor of making by SUS 304, put into 50g niobium ingot, and introduced hydrogen 12 hours continuously down at 400 ℃.After the cooling, the niobium piece of hydrogenation is put into one contain the jar of making by SUS304 of irony ball and pulverized 10 hours.With reactor and the hydrogenation of making by SUS304 once more under these conditions same as described above of packing into of the product of this pulverizing.Afterwards, this hydride is mixed the slurry that forms 20 volume % with water, pack in the wet milk of making by SUS 304 waterproof pulverization 6 hours then with zirconia balls into.With centrifugation of gained slurry and decant, the product that obtains pulverizing.This crushed products is 1.33 * 10
2Vacuumize under the condition of Pa (1 holder) and 50 ℃.Subsequently, this hydrogenated niobium powder passes through at 400 ℃, 1.33 * 10
-2Pa (1 * 10
-4Holder) pressure heating dehydrogenation in 1 hour down.The average grain diameter of the niobium powder of being produced is 1.0 μ m.
The niobium powder that 30g obtained of in a reactor of making by SUS 304, packing into, and under 300 ℃, introduced continuously nitrogen 0.5-3 hour to this reactor, to obtain the nitride of niobium.The nitrogen content of every kind of nitride is used the device measuring of the measurement nitrogen content of being made by LECO, and this equipment is measured nitrogen content according to thermal conductivity.The mass ratio of the powder of this measured value and independent measurement is set to the nitrogenize amount, and result, nitrogenize amount here are 0.03-0.28 quality %.
With the nitride of various niobiums according to mode granulation, mold pressing and the sintering identical with embodiment 1 to obtain sintered body.
Use the sintered body of gained, make 50 chip capacitors, and measure the physical property of each chip capacitor of manufacturing according to the mode identical with embodiment 35-37.The results are shown in table 8.
Table 8
Embodiment 38-39: the manufacturing of capacitor device of the present invention and assessment:
| Nitrogen content (quality %) | Electric capacity (μ F) | ????LC ??(μA) | Sheet number with excessive LC value | |
| Embodiment 35 | ????- | ??528 | ????46 | ????0/50 |
| Embodiment 36 | ????- | ??595 | ????45 | ????0/50 |
| Embodiment 37 | ????0.29 | ??642 | ????43 | ????0/50 |
| Comparative Examples 11 | ????0.02 | ??453 | ????48 | ????1/50 |
| Comparative Examples 12 | ????0.14 | ??444 | ????44 | ????0/50 |
| Comparative Examples 13 | ????0.28 | ??451 | ????40 | ????0/50 |
Embodiment 38 prepares 50 sintered bodies according to the mode identical with embodiment 8, embodiment 39 respectively according to the mode identical with embodiment 15.Under each comfortable 20V voltage of these sintered bodies in 0.1% phosphoric acid solution electrochemical treatments 200 minutes, to form the oxide dielectric film on its surface.Then, each sintered body is immersed the mixed solution (1: 1 volume) of 35% acetic acid lead solution and 35% ammonium persulfate aqueous solution and it was reacted under 40 ℃ 1 hour, repeat this operation on the oxide dielectric film, to form the mixed layer of brown lead oxide and lead sulfate as another electrode.On this another electrode layer, pile up carbon-coating and silver paste layer in order.After installing lead frame, with this device as a whole with the epoxy resin mold pressing, to produce chip capacitor.The average capacitance of this chip capacitor and average LC value (among each embodiment, the n=50 sheet) are shown in table 9.
Table 9
| Nitrogen content (quality %) | Electric capacity (μ F) | ???LC ??(μA) | Sheet number with excessive LC value | |
| Embodiment 38 | ????- | ??247 | ????14 | ????0/50 |
| Embodiment 39 | ????- | ??491 | ????45 | ????0/50 |
Industrial applicibility
The capacitor that is used for the sintered powder manufacturing of capacitor by the present invention advantageously has large electric capacity, good current leakage (LC) characteristic, the low dispersion and high reliability, and wherein powder of the present invention contains the zirconium of specified quantitative and mainly comprises niobium and/or zirconium.
Claims (18)
1. powder that is used for capacitor, wherein this powder contains zirconium and mainly comprises niobium and/or tantalum.
2. the powder that is used for capacitor according to claim 1, it contains 0.01-15 atom % zirconium and mainly comprises niobium and/or tantalum.
3. the powder that is used for capacitor according to claim 1 and 2, wherein this powder mainly contains niobium.
4. the powder that is used for capacitor according to claim 1 and 2, wherein this powder mainly contains tantalum.
5. the powder that is used for capacitor according to claim 1, wherein this powder mainly contains niobium-tantalum alloy.
6. according to any described powder that is used for capacitor among the claim 1-5, wherein average grain diameter is 0.2-5 μ m.
7. according to any described powder that is used for capacitor among the claim 1-5, its specific area is 0.5-15m
2/ g.
8. according to any described powder that is used for capacitor among the claim 1-5, wherein part niobium and/or tantalum combine with at least a element that is selected from nitrogen, carbon, boron or sulphur.
9. the powder that is used for capacitor according to claim 8, wherein the amount of the element of above-mentioned combination is 50～200,000ppm.
10. powder that is used for capacitor, its average grain diameter is 20-500 μ m, and obtains by any described powder that is used for capacitor among the granulation claim 1-9.
11. a sintered body wherein uses any described powder that is used for capacitor among the claim 1-10.
12. sintered body according to claim 11, its specific area are 0.5-5m
2/ g.
13. a capacitor is wherein by as the sintered body according to claim the 11 or 12 descriptions of a lateral electrode, the dielectric material that forms on this sintered body surface and the opposite side electrode manufacturing that provides on dielectric material.
14. capacitor according to claim 13, wherein dielectric material contains niobium oxide and/or tantalum pentoxide
15. capacitor according to claim 14, wherein niobium oxide and/or tantalum pentoxide form by electrolytic oxidation.
16. capacitor according to claim 13, wherein the opposite side electrode is at least a material that is selected from electrolyte, organic semiconductor or inorganic semiconductor.
17. capacitor according to claim 16, wherein the opposite side electrode is formed by organic semiconductor, this organic semiconductor be selected from the organic semiconductor that comprises the benzopyrrole quinoline tetramer and tetrachloroquinone, mainly comprise the organic semiconductor of four thio naphthacene, mainly comprise the organic semiconductor of tetracyano-p-quinodimethane, and mainly comprise by in the polymer that contains two or more repetitives by following general formula (1) or (2) expression, mixing at least a organic semiconductor of organic semi-conductor of the conducting polymer that dopant obtains:
R wherein
1To R
4Can be identical or different, and represent hydrogen atom separately, have the alkyl of 1-6 carbon atom or have the alkoxyl of 1-6 carbon atom, X represention oxygen atom, sulphur atom or nitrogen-atoms, R
5Only exist during for nitrogen-atoms, and represent hydrogen atom or have the alkyl of 1-6 carbon atom at X, and every couple of R
1And R
2, and R
3And R
4Can mutually combine and form ring.
18. capacitor according to claim 17, wherein organic semiconductor is to be selected from least a in polypyrrole, polythiophene and their substitutive derivative.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000366039A JP4683512B2 (en) | 2000-11-30 | 2000-11-30 | Capacitor powder, sintered body using the same, and capacitor using the same |
| JP366039/2000 | 2000-11-30 | ||
| JP366039/00 | 2000-11-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1478287A true CN1478287A (en) | 2004-02-25 |
| CN100401436C CN100401436C (en) | 2008-07-09 |
Family
ID=18836718
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01819611XA Expired - Fee Related CN100401436C (en) | 2000-11-30 | 2001-11-30 | Powder for capacitor, sintered body thereof and capacitor using sintered body |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4683512B2 (en) |
| CN (1) | CN100401436C (en) |
| AT (1) | ATE336073T1 (en) |
| DE (1) | DE60122205T2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112735830A (en) * | 2014-11-24 | 2021-04-30 | Avx 公司 | Wet electrolytic capacitor for implanted medical device |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19953946A1 (en) * | 1999-11-09 | 2001-05-10 | Starck H C Gmbh Co Kg | Capacitor powder |
| EP1505611B9 (en) * | 2003-07-22 | 2012-12-05 | H.C. Starck GmbH | Method of making capacitors |
| US7729104B2 (en) | 2004-04-15 | 2010-06-01 | Jfe Mineral Company, Ltd. | Tantalum powder and solid electrolyte capacitor including the same |
| WO2008108462A1 (en) * | 2007-03-08 | 2008-09-12 | Rohm Co., Ltd. | Composite material, capacitor using the same, and their production methods |
| US8107218B2 (en) * | 2009-06-02 | 2012-01-31 | Micron Technology, Inc. | Capacitors |
| CN105493212A (en) * | 2013-08-30 | 2016-04-13 | 昭和电工株式会社 | Tungsten powder and positive electrode body of capacitor |
| CN103934452B (en) * | 2014-05-12 | 2016-07-06 | 宁夏东方钽业股份有限公司 | A kind of dough method of superelevation specific volume tantalum powder and the tantalum powder prepared by the method |
| KR102220538B1 (en) | 2014-09-23 | 2021-02-24 | 경희대학교 산학협력단 | Electrode including organic semiconducting material, method for manufacturing electrode and supercapacitor including the electrode |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849124A (en) * | 1969-12-05 | 1974-11-19 | Norton Co | Capacitor powder |
| US4084965A (en) * | 1977-01-05 | 1978-04-18 | Fansteel Inc. | Columbium powder and method of making the same |
| JPS55157226A (en) * | 1979-05-25 | 1980-12-06 | Matsushita Electric Ind Co Ltd | Method of manufacturing sintered element for capacitor |
| JP2745875B2 (en) * | 1991-06-29 | 1998-04-28 | 日本ケミコン株式会社 | Cathode materials for electrolytic capacitors |
| JP3254163B2 (en) * | 1997-02-28 | 2002-02-04 | 昭和電工株式会社 | Capacitor |
| WO2000067936A1 (en) * | 1998-05-06 | 2000-11-16 | H.C. Starck, Inc. | Metal powders produced by the reduction of the oxides with gaseous magnesium |
| AU2571200A (en) * | 1999-02-16 | 2000-09-04 | Showa Denko Kabushiki Kaisha | Niobium powder, niobium sintered body, capacitor comprised of the sintered body,and method for manufacturing the capacitor |
| TW479262B (en) * | 1999-06-09 | 2002-03-11 | Showa Denko Kk | Electrode material for capacitor and capacitor using the same |
-
2000
- 2000-11-30 JP JP2000366039A patent/JP4683512B2/en not_active Expired - Fee Related
-
2001
- 2001-11-30 DE DE60122205T patent/DE60122205T2/en not_active Expired - Lifetime
- 2001-11-30 CN CNB01819611XA patent/CN100401436C/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112735830A (en) * | 2014-11-24 | 2021-04-30 | Avx 公司 | Wet electrolytic capacitor for implanted medical device |
| US11282652B2 (en) | 2014-11-24 | 2022-03-22 | KYOCERA AVX Components Corporation | Wet electrolytic capacitor for an implantable medical device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100401436C (en) | 2008-07-09 |
| DE60122205D1 (en) | 2006-09-21 |
| ATE336073T1 (en) | 2006-09-15 |
| JP4683512B2 (en) | 2011-05-18 |
| JP2002173371A (en) | 2002-06-21 |
| DE60122205T2 (en) | 2007-07-05 |
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