CN100338702C - Niobium powder for capacitor, sintered body thereof and capacitor using the sintered body - Google Patents
Niobium powder for capacitor, sintered body thereof and capacitor using the sintered body Download PDFInfo
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- CN100338702C CN100338702C CNB018044131A CN01804413A CN100338702C CN 100338702 C CN100338702 C CN 100338702C CN B018044131 A CNB018044131 A CN B018044131A CN 01804413 A CN01804413 A CN 01804413A CN 100338702 C CN100338702 C CN 100338702C
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Abstract
The present invention relates to a nobium powder for capacitors, which contains from 0.05 to 20% by mass of niobium monoxide crystal and from 0.05 to 20% by mass of hexaniobium monoxide crystal; a sintered body thereof; and 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 provided on the dielectric material. A capacitor manufactured from a sintered body of a niobium powder of the present invention is favored with good high-temperature characteristics.
Description
Mutual reference to related application
The application is with the basis that is defined as of the 35th piece of the 111st (a) bar of United States code, according to the 35th piece of the 119th (e) (1) of United States code bar, requirement obtains according to the regulation of the 35th piece of the 111st (b) bar of United States code, in the U.S. Provisional Application No.60/268 of submission on February 16 calendar year 2001, the interests of 964 the applying date.
Technical field
The niobium powder for capacitor that the present invention relates to is used to make and has the big unit mass electric capacity and the capacitor of good high-temperature performance.The present invention also relates to niobium powder, niobium sintered body simultaneously and uses the capacitor of this sintered body.
Background technology
Be applied to the capacitor of electronic instrument such as mobile phone and PC, need small size and big electric capacity.In these capacitors, preferred tantalum capacitor, because with respect to its volume, its electric capacity is big and functional.In tantalum capacitor, the sintered body of tantalum powder is usually as anode part.In order to increase the electric capacity of tantalum capacitor, be necessary to increase the deal of sintered body or use the sintered body that surface area increases by grinding the tantalum powder.
Preceding a kind of method that increases the sintered body deal will inevitably relate to the expansion of capacitor shape, so just can not satisfy the demand that reduces size.On the other hand, increase by grinding the tantalum powder that surface area causes reducing in the aperture of sintering stage tantalum sintered object or lipostomous increases in a kind of method in back, infiltration negative electrode reagent becomes difficult in the operation of back thereby make.As a kind of method that addresses these problems, just studying the capacitor method of dielectric constant of using greater than the powdery sintered body of the material of tantalum.This material with big dielectric constant comprises niobium.
, use the capacitor of the sintered body that makes by these materials not have enough high-temperature behaviors, can not be applied to reality.Initial capacitance C under the definition room temperature
0With by capacitor is left standstill in 105 ℃ environment 2,000 hours and applies simultaneously voltage, then get back to room temperature after the ratio of resulting capacitor C, i.e. (C-C
0)/C
0Be high-temperature behavior.With the sintered body electrolytic oxidation, combine with another part electrode then when making capacitor, as long as use the tantalum powder, then high-temperature behavior usually can be in ± 20% scope.If but use conventional niobium powder, the high-temperature behavior of some capacitors can't be in ± 20% scope.
So, the reliability that the capacitor of use niobium powder is rated as at room temperature is low, and Just because of this, it is defective that these capacitors are judged as useful life, not practical application.
At technical elements related to the present invention, the existing use passed through in the presence of hydrogen niobium pentaoxide (Nb
2O
5) heat-treat and niobium oxide, the preparation of the partial reduction that obtains have the scheme (referring to WO00/15555) of the capacitor of big electric capacity and excellent leakage current characteristic., when the present inventor with test in the niobium oxide that obtains make capacitor, and when at high temperature it being carried out accelerated test, the decreased performance of capacitor can not be satisfactory.
Summary of the invention
As the result to the broad research that addresses the above problem, the present inventor finds when the niobium powder that comprises columbium monoxide crystal and an oxidation six niobate crystals is used as the starting material niobium powder of niobium powder, niobium sintered body, the capacitor that can obtain having the good high-temperature performance.The present invention just is being based on above-mentioned discovery and is finishing.
More particularly, the capacitor that the purpose of this invention is to provide following niobium powder for capacitor and sintered body thereof and this sintered body of use.
1. niobium powder for capacitor comprises columbium monoxide crystal and an oxidation six niobate crystals.
2. as above-mentioned 1 described niobium powder for capacitor, the content of its columbium monoxide crystal is between 0.05-20 quality %.
3. as above-mentioned 1 described niobium powder for capacitor, the content of one oxidation six niobate crystals is between 0.05-20 quality %.
4. as each described niobium powder for capacitor among the above-mentioned 1-3, it comprises the niobium powder of part nitrogenize.
5. as above-mentioned 4 described niobium powder for capacitor, its nitrogenize amount is 10-100,000ppm (quality).
6. sintered body, it uses each described niobium powder for capacitor among the above-mentioned 1-5.
7. capacitor, it is by above-mentioned 6 described sintered bodies as a part of electrode, is formed at the dielectric substance on sintered body surface and another part electrode of being positioned on this dielectric substance is constituted.
8. as above-mentioned 7 described capacitors, its dielectric substance mainly is made of niobium oxide.
9. as above-mentioned 8 described capacitors, its niobium oxide forms by electrolytic oxidation.
10. as each described capacitor among the above-mentioned 7-9, its another part electrode is at least a material that is selected from electrolytic solution, organic semiconductor or inorganic semiconductor.
11. as above-mentioned 10 described capacitors, its another part electrode is made up of organic semiconductor, this organic semiconductor is selected from least a in the following organic semiconductor: the organic semiconductor that comprises benzopyrrole quinoline tetramer and chloranil, the organic semiconductor that mainly comprises four thio naphthacene, the organic semiconductor that mainly comprises four cyano quinone bismethane, and the organic semiconductor that mainly comprises following electric conductive polymer, described electric conductive polymer makes by dopant is mixed polymer, and the polymer that is impregnated in dopant comprises the two or more repetitives by following chemical formula (1) or (2) expression:
(in the formula, R
1-R
4Can be identical, also can be different, and each represents the alkyl of hydrogen atom, a 1-6 carbon atom or the alkoxyl of 1-6 carbon atom; X represents oxygen atom, sulphur atom or nitrogen-atoms; R
5Exist only in X when being nitrogen-atoms, the alkyl of expression hydrogen or 1-6 carbon atom; R
1With R
2, and R
3With R
4Can interosculate into ring.)
12. as above-mentioned 11 described capacitors, its organic semiconductor is to be selected from least a in polypyrrole, polythiophene and their substitutive derivative.
The detailed description of invention
Niobium powder of the present invention is to comprise the columbium monoxide crystal and an oxidation six niobate crystals are feature.
Be formed at aspect oxide dielectric film on the sintered body stable, the niobium powder is not as the tantalum powder, and this difference is at high temperature obvious especially.Its reason has many, and one of them reason is considered to because the composition of oxide dielectric film is different with the composition of niobium, and because the deterioration of oxide dielectric film has been quickened in the thermal strain under the high temperature.
On the other hand, when columbium monoxide crystal and an oxidation six niobate crystals mixed in the niobium powder, by inference, the thermal stress under the high temperature was slowed down.Therefore, its thermal stability of capacitor that is made by the niobium powder has increased.
A kind of execution mode that obtains niobium powder of the present invention is described below.
Niobium powder for capacitor of the present invention is to obtain by primary particles shape niobium powder (being designated hereinafter simply as initial powder) is ground to suitable size.Initial powder can grind with conventionally known method.For example, a kind of method is that initial powder is statically placed in the vacuum under 500-2000 ℃ high temperature, then with dry method or wet method cracking; A kind of method is that initial powder and suitable adhesive such as acrylic resin or polyvinyl alcohol are mixed cracking then.Can freely control the particle diameter of nodular powder by the degree of grinding and cracking.The average particulate diameter of normally used porous and granular powder arrives between thousands of μ m at number μ m.After grinding and cracking, can be with the nodular powder classification.After the grinding, also can be with the on-granulated powder of nodular powder and Sq.
Initial powder raw material can be the commercially available prod.For example, can use following material: the initial powder that obtains with the halide of magnesium or sodium reduction niobium; By the initial powder that obtains with sodium reduction fluoro potassium niobate; The initial powder that melting salt (NaCl+KCl) electrolysis by the fluoro potassium niobate on nickel cathode obtains; Use hydrogen or by hydrogen being imported in the metal niobium ingot, then grinding and dehydrogenation and the initial powder that obtains.In these initial powder, for example can use the initial powder of average grain diameter as the tens of μ m of 0.1-.
The niobium powder that the present invention uses makes by in advance columbium monoxide crystal and an oxidation six niobate crystals being mixed with above-mentioned niobium powder.
For example, these fine-powdered crystal (average grain diameter: be about 0.1-1,000 μ m) are mixed with the niobium powder with the amount (the preferably amount of 0.05-10 quality %) of 0.05-20 quality % separately, thereby make niobium powder for capacitor of the present invention.
If columbium monoxide crystal and an oxidation six niobate crystals surpass 20 quality %, then initial capacitance value C separately
0To decline to a great extent unfriendly.Niobium powder of the present invention also can by mix above-mentioned crystal and initial powder, milled mixtures makes then.
One oxidation, six niobate crystals can be by using conventional reduction agent well known in the prior art (as hydrogen, alkali metal, alkaline-earth metal, NaBH
4Or LiBH
4) reduction columbium monoxide, columbium dioxide or niobium pentaoxide and make.The generation of one oxidation, six niobate crystals can be determined by x-ray diffraction pattern.
The initial niobium powder of a part of using among the present invention preferably passes through nitrogenize.
The nitrogenize amount is 10ppm-100000ppm.By this part nitrogenize, can improve leakage current (LC) performance of the capacitor that makes.More particularly, the nitrogenize amount is preferably between the 300-7000ppm, to reduce the LC value.The LC value is after making sintered body and dielectric substance with the niobium powder and being formed at this sintered body surface, measures in phosphate aqueous solution.
" nitrogenize amount " used herein is meant the amount of reacting and make it nitrogenize with the niobium powder, but do not comprise the nitrogen that is adsorbed on the niobium powder.
The nitriding method of niobium powder comprises liquid nitriding, ionitriding, gas nitriding method or their combination.Wherein, the preferred gas nitriding method under blanket of nitrogen is because its equipment is simple and easy operating.
By being statically placed in the blanket of nitrogen, the niobium powder can carry out gas nitriding.In nitriding atmosphere,, can obtain having the niobium powder of target nitrogenize amount with not being higher than 2000 ℃ temperature and a few hours with interior time of repose.At high temperature handle and to shorten the processing time.With the condition of determining by the nitriding temperature of the material of need nitrogenize and nitridation time being made a preliminary test etc., can easily control by the amount of the niobium powder of nitrogenize.
Even with after these crystal mix, nitridation reaction also can carry out at initial powder or niobium powder.
The another kind of execution mode that obtains niobium powder of the present invention is described below.
The initial powder that uses among the present invention is the metal that plays the valve effect that is similar to aluminium and tantalum.Therefore, its surface-coated one deck oxide that covered in air.Amount of oxidation changes according to the average grain diameter of niobium powder, and when average grain diameter when being 0.1 μ m to tens of μ m, the nitrogenize amount is generally 10,000-200,000ppm (quality).In this oxidiferous initial powder, grind the condition of initial powder when making the niobium powder by control, as heating rate, maximum temperature, time of repose and fall off rate when the maximum temperature, can make oxide part or crystallization fully.Crystallized product is the mixture of columbium monoxide crystal and an oxidation six niobate crystals.By detecting above-mentioned condition, also can adjust the columbium monoxide crystal in the crystallized product and the amount of an oxidation six niobate crystals.In this case, though the reason of not knowing, when using the initial powder of part nitrogenize, the amount of an oxidation six niobate crystals can increase sometimes.
When under those polishing progress, using method for crystallising according to crystallization condition, relation between condition when find grinding and each crystal amount of obtaining by oxide by preliminary test, thereby when obtaining containing the niobium powder of the columbium monoxide crystal that has above-mentioned scheduled volume separately and an oxidation six niobate crystals, can reduce the columbium monoxide crystal that tentatively mixes with niobate crystal and the amount of an oxidation six niobate crystals, perhaps those crystal do not need preliminary mixing.
Niobium sintered body of the present invention makes by the above-mentioned niobium powder of sintering.
Manufacture method to sintered body has no particular limits, and for example the extrusion forming of niobium powder can be become predetermined shape, then 10
-4-10
-1Heating a few minutes obtained sintered body by several hours under the temperature of the pressure of Pa, 500-2000 ℃.
Can make suitable shape and length with comprising such as niobium or the such lead that plays the valve effect of tantalum, and when carrying out the extrusion forming of above-mentioned niobium powder that this lead inserted mode system product of a part are inner and be compression molded into an integral body, so just this lead can be designed to the sintered body lead.
Capacitor of the present invention is by above-mentioned sintered body as a part of electrode, is formed at the dielectric substance on this sintered body surface and another part electrode of being positioned on the dielectric substance is constituted.
Capacitor comprises the dielectric substance of being made up of tantalum oxide, niobium oxide, polymer or ceramic compound with dielectric substance, wherein the dielectric substance of preferably being made up of niobium oxide.The dielectric substance of being made up of niobium oxide can obtain by the niobium powder, niobium sintered body that forms as a part of electrode with chemical method in electrolytic solution.When in electrolytic solution, forming niobium electrode, use protonic acid aqueous solution usually, as 0.1% phosphate aqueous solution or aqueous sulfuric acid with chemical method.By forming with chemical method in electrolytic solution under the situation that niobium electrode obtains the dielectric substance that niobium oxide forms, capacitor of the present invention is an electrolytic capacitor, and its niobium side is as anode.
In capacitor of the present invention, another part electrode is had no particular limits, for example can use at least a compound that is selected from the known electrolytic solution in aluminium electrolytic capacitor field, organic semiconductor and the inorganic semiconductor.
The object lesson of electrolytic solution comprises the dimethyl formamide-ethylene glycol mixtures of the isobutyl group tripropyl ammonium-tetrafluoride boron electrolyte that has dissolved 5 quality %, and the propene carbonate-ethylene glycol mixtures of having dissolved tetramethyl-ammonium-tetrafluoride boron of 7 quality %.
The organic semi-conductor object lesson comprises, the organic semiconductor that comprises benzene-pyrrolin tetramer and chloranil, the organic semiconductor that mainly comprises four thio naphthacene, the organic semiconductor that mainly comprises four cyano quinone bismethane, and the organic semiconductor that mainly comprises following electric conductive polymer, described electric conductive polymer makes by dopant is mixed polymer, and the polymer that is impregnated in dopant comprises the two or more repetitives by following chemical formula (1) or (2) expression:
(in the formula, R
1-R
4Can be identical, also can be different, and each represents the alkyl of hydrogen atom, a 1-6 carbon atom or the alkoxyl of 1-6 carbon atom; X represents oxygen atom, sulphur atom or nitrogen-atoms; R
5Exist only in X when being nitrogen-atoms, the alkyl of expression hydrogen or 1-6 carbon atom; R
1With R
2, and R
3With R
4Can interosculate into ring.)
" mainly comprising an electric conductive polymer " in this specification be meant, even can comprise the electric conductive polymer that contains the composition that the impurity from the organic semi-conductor starting monomer obtains.That is to say that " electric conductive polymer contains as main active ingredient.”
The polymer that comprises by the represented repetitive in structural formula (1) or (2) comprises: the derivative of polyaniline, polyphenylene oxide, polyphenylene sulfide, polythiophene, poly-furans, polypyrrole, poly-methyl pyrrole and these polymer.
The example of spendable dopant comprises: thioquinones is that dopant, anthracene list sulfonic acid are dopant and other various anion doped dose.Also can use the electron acceptor dopant, as NO
+Or NO
2 +Salt.
The object lesson of inorganic semiconductor comprises: mainly comprise the inorganic semiconductor of brown lead oxide or manganese dioxide, and the inorganic semiconductor that comprises tri-iron tetroxide.These semiconductors can use separately or two or more being used in combination.
When the organic or inorganic semiconductor that uses has 10
-2-10
3Scm
-1Conductivity the time, the capacitor that makes can have lower resistance value, and under the high frequency, electric capacity can have bigger increase.
When another part electrode is solid electrode, can conductive layer is placed on it, so that itself and outer conductor (for example: produce lead frame) and well electrically contact.
Conductive layer can form with following method, for example can be that conductive paste solidifies, electroplates, metallizes or form heat-resisting electroconductive resin.Preferable conductive paste comprises silver paste, copper cream, aluminium cream, carbon paste and nickel cream, and they can use separately or two or more being used in combination.When using two or more cream to starch, can be with cream slurry mixing or stacked mutually as the layer that separates.Then the conductive paste that applies is statically placed in the air or heating, makes it to solidify.Plating comprises nickel plating, copper facing, silver-plated and aluminize.The metal that is used for vapour deposition comprises aluminium, nickel, copper and silver.
In actual use, for example with carbon paste and silver paste lamination successively on another part electrode, and, constitute capacitor thus with the material mold pressing of epoxy resin and so on.This capacitor can have niobium or tantalum lead, and this lead is through sintering, and is compression molded into one with niobium sintered body or is welded on the niobium sintered body.
The capacitor of the present invention that makes is like this used such as resin moulded parts, resin enclosure, metal casing, resin impregnator or laminated film and is made overcoat, is used for various uses as capacitor product then.
When another part electrode is liquid, will put into for example container that is electrically connected with another part electrode with the capacitor that above-mentioned two electrodes and dielectric substance are made, constitute a complete capacitor.In this case, the electrode side of niobium sintered body derives by above-mentioned niobium or tantalum lead.Meanwhile, use electro-insulating rubber etc. that the electrode side of niobium sintered body and container are insulated.
Implement best way of the present invention
Below by embodiment and comparative example the present invention is described in more detail.
The method of test among each embodiment and evaluation physical property is described below.
(1) content of columbium monoxide crystal in the niobium powder and an oxidation six niobate crystals
These content are calculated by the calibration curve that is made of following condition.Described calibration curve according to the quality of each crystal, will respectively have the X-ray diffraction that carries out after initial niobium powder that the above-mentioned crystal of known quality reduces with the adsorb oxygen amount, that average grain diameter is 100 μ m mixes in testing 2 θ diffracted intensities and the quality of mixture draw.
(2) the nitrogenize amount of niobium powder
This nitrogenize amount is measured with the nitrogen oxygen analyzer that LEKO produces.
(3) high-temperature behavior of capacitor
Will with allow capacitor be statically placed in 105 ℃ the environment 2,000 hours and to apply simultaneously the voltage of 4V, to return to the ratio of resulting capacitor C after the room temperature, i.e. (C-C then
0)/C
0Be defined as high-temperature behavior.It is qualified that the capacitor of this ratio between ± 20% is assessed as, and estimate by the ratio of sample quantities and qualified element number.In each embodiment, prepared the sample of 50 unit.
Embodiment 1
0.6 μ m) and an oxidation six niobate crystals (average grain diameter: be that the initial powder (its surface coverage the native oxide of about 0.5 quality %) of 6 μ m mixes 0.7 μ m) with the columbium monoxide crystal (average grain diameter: that respectively is the amount of 2 quality % with average grain diameter.With the initial powder of this mixed crystal 6.7 * 10
-3Pa (5 * 10
-5Leave standstill under the temperature of vacuum Torr) and 1,050 ℃ and be thirty minutes long most, the heating rate with 10 ℃/min promotes temperature simultaneously.Then, the rate of temperature fall cooling with 80 ℃/min inwardly charges into argon gas simultaneously, and powder grinding, pulverizing with gained obtain the niobium powder.The content of each crystal in the niobium powder is shown in table 1.Then, take by weighing this niobium powder of 0.1g,, obtain the mechanograph that size is about 3mm * 4mm * 1.8mm with together mold pressing of niobium wire.With this mechanograph in 6.7 * 10
-3Pa (5 * 10
-5Leave standstill under the temperature of vacuum Torr) and 1,150 ℃ and reach 100 minutes most, and heat up, with the rate of temperature fall cooling of average 80 ℃/min, obtain sintered body thus then with the heating rate of 10 ℃/min.By this method, prepared this sintered body of 50 unit, all unit have been carried out electrochemical treatments (12V) in 0.1% phosphate aqueous solution, formed the oxide dielectric film that constitutes by niobium oxide on its surface.Then, each sintered body be impregnated in the equivalent mixed liquor of 30% ammonium persulfate aqueous solution and 30% lead acetate solution, dry then, this operation repeats repeatedly, forms by brown lead oxide and lead sulfate (brown lead oxide: another part electrode of forming 97 quality %) on the oxide dielectric film.Then, with carbon paste and silver paste coating according to the order of sequence, after being installed on the lead frame, they with the epoxy resin mold pressing, are made sheet-type capacitor.Hot properties (primary capacitance C to each capacitor of making
0(μ F) and high-temperature behavior) to estimate, it the results are shown in following table 1.
Embodiment 2-4 and comparative example 1-3:
With having made niobium powder and capacitor with embodiment 1 described identical mode, just changed the amount of each mixed crystal, its value is shown in table 1.
Embodiment 5-8:
With having made capacitor with embodiment 1 described identical mode, different is, to use average grain diameter be the primary particles (its surface coverage the natural oxide-film of about 2.5 quality %) of 1 μ m and this initial powder left standstill in nitrogen current 2 hours at 300 ℃, obtain the initial powder (nitrogenize amount: 2,800ppm (quality)) (embodiment 5) of part nitrogenize.In embodiment 6-8, use with embodiment 5 described identical modes and made capacitor, different is to use and be shown in the semiconductor of table 2 as another part electrode among the embodiment 5.
Table 1
| The content quality % of columbium monoxide crystal | The content quality % of one oxidation, six niobate crystals | Primary capacitance C 0 μF | High-temperature behavior (qualified unit/sample number) | |
| Embodiment 1 | 2.00 | 2.00 | 185 | 50/50 |
| Embodiment 2 | 0.50 | 0.30 | 190 | 50/50 |
| Embodiment 3 | 17.20 | 1.30 | 188 | 50/50 |
| Embodiment 4 | 6.85 | 18.80 | 183 | 50/50 |
| Embodiment 5 | 3.20 | 2.25 | 645 | 50/50 |
| Embodiment 6 | 3.30 | 2.20 | 640 | 50/50 |
| Embodiment 7 | 3.25 | 2.35 | 635 | 50/50 |
| Embodiment 8 | 3.20 | 2.30 | 638 | 50/50 |
| Comparative example 1 | ＜0.05 | ＜0.05 | 181 | 47/50 |
| Comparative example 2 | ＜0.05 | 23.25 | 135 | 50/50 |
| Comparative example 3 | 20.55 | ＜0.05 | 127 | 50/50 |
Table 2
| Another part electrode | The electrode generation type | |
| Embodiment 6 | The anionic polypyrrole of doping sulfo group aromatic compound | Oxidation repeatedly in pyrroles's gas |
| Embodiment 7 | Manganese dioxide | To nitrogenized manganese thermal decomposition repeatedly |
| Embodiment 8 | The anionic polythiofuran derivative of doping sulfo group aromatic compound | Oxidation repeatedly in thiophene derivant solution |
As can be seen, when each was present in the niobium powder with the amount more than 0.05% when columbium monoxide crystal and an oxidation six niobate crystals, the high-temperature behavior of capacitor was improved from the contrast of embodiment 1-8 and comparative example 1.In addition, as can be seen, when the crystal amount surpassed 20 quality %, primary capacitance had reduced from the contrast of embodiment 1 and comparative example 2 and comparative example 3.
Industrial applicability
When using the niobium powder that contains the columbium monoxide crystal that respectively has 0.05-20 quality % and an oxidation six niobate crystals of the present invention in capacitor, the capacitor of gained has large unit mass electric capacity and good high-temperature behavior.
Claims (10)
1. niobium powder for capacitor, it comprises the columbium monoxide crystal of 0.05-20 quality % and an oxidation six niobate crystals of 0.05-20 quality %.
2. niobium powder for capacitor as claimed in claim 1, it comprises the niobium powder of part nitrogenize.
3. niobium powder for capacitor as claimed in claim 2, its nitrogenize amount is at 10-100, between the 000ppm, in mass.
4. sintered body, it uses as each described niobium powder among the claim 1-3.
5. capacitor, it be by as the sintered body as claimed in claim 4 of a part of electrode, be formed at the dielectric substance on this sintered body surface and another part electrode of being positioned on this dielectric substance is constituted.
6. capacitor as claimed in claim 5, its dielectric substance mainly is made of niobium oxide.
7. capacitor as claimed in claim 6, its niobium oxide forms by electrolytic oxidation.
8. as each described capacitor among the claim 5-7, its another part electrode is at least a material that is selected from electrolytic solution, organic semiconductor or inorganic semiconductor.
9. capacitor as claimed in claim 8, its another part electrode is made up of organic semiconductor, this organic semiconductor is selected from least a in the following organic semiconductor: the organic semiconductor that comprises benzopyrrole quinoline tetramer and chloranil, the organic semiconductor that mainly comprises four thio naphthacene, the organic semiconductor that mainly comprises four cyano quinone bismethane, and the organic semiconductor that mainly comprises following electric conductive polymer, described electric conductive polymer makes by dopant is mixed polymer, and the polymer that is impregnated in dopant comprises the two or more repetitives by following chemical formula (1) or (2) expression:
In the formula, R
1-R
4Can be identical, also can be different, and each represents the alkyl of hydrogen atom, a 1-6 carbon atom or the alkoxyl of 1-6 carbon atom; X represents oxygen atom, sulphur atom or nitrogen-atoms; R
5Exist only in X when being nitrogen-atoms, the alkyl of expression hydrogen or 1-6 carbon atom; R
1With R
2, and R
2With R
4Can interosculate into ring.
10. capacitor as claimed in claim 9, its organic semiconductor are at least a organic semiconductors that is selected from polypyrrole, polythiophene or their substitutive derivative.
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|---|---|---|---|
| JP366658/2000 | 2000-12-01 | ||
| JP2000366658A JP4521849B2 (en) | 2000-12-01 | 2000-12-01 | Niobium powder for capacitor, sintered body using the niobium powder, and capacitor using the sintered body |
| JP366658/00 | 2000-12-01 |
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| CNA2007101364433A Division CN101106022A (en) | 2000-12-01 | 2001-11-30 | Niobium powder for capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10347702B4 (en) * | 2003-10-14 | 2007-03-29 | H.C. Starck Gmbh | Sintered body based on niobium suboxide |
| KR101093502B1 (en) * | 2004-03-09 | 2011-12-13 | 가부시키가이샤 무라타 세이사쿠쇼 | Solid electrolytic capacitor and the use thereof |
| JP4177322B2 (en) * | 2004-11-30 | 2008-11-05 | ローム株式会社 | Solid electrolytic capacitor and manufacturing method thereof |
| GB0511321D0 (en) * | 2005-06-03 | 2005-07-13 | Starck H C Gmbh | Inorganic compounds |
| US7649730B2 (en) * | 2007-03-20 | 2010-01-19 | Avx Corporation | Wet electrolytic capacitor containing a plurality of thin powder-formed anodes |
| JP2008288561A (en) * | 2007-04-20 | 2008-11-27 | Sanyo Electric Co Ltd | Niobium solid electrolytic capacitor, and manufacturing method thereof |
| US7876548B2 (en) | 2007-04-20 | 2011-01-25 | Sanyo Electric Co., Ltd. | Niobium solid electrolytic capacitor and its production method |
| DE102011109756A1 (en) * | 2011-08-09 | 2013-02-14 | H.C. Starck Gmbh | Process for the preparation of electrolytic capacitors made of valve metal powders |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07508618A (en) * | 1993-04-26 | 1995-09-21 | キャボット コーポレイション | Improved method for producing tantalum powder and electrodes with high capacitance and low electrical leakage obtained from the powder |
| CN1240377A (en) * | 1996-11-07 | 2000-01-05 | 卡伯特公司 | Niobium powders and niobium electrolytic capacitors |
| WO2000015555A1 (en) * | 1998-09-16 | 2000-03-23 | Cabot Corporation | Methods to partially reduce a niobium metal oxide and oxygen reduced niobium oxides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3547484B2 (en) * | 1994-06-21 | 2004-07-28 | ニチコン株式会社 | Manufacturing method of capacitor element |
| US5993513A (en) * | 1996-04-05 | 1999-11-30 | Cabot Corporation | Method for controlling the oxygen content in valve metal materials |
| JP4263795B2 (en) * | 1998-12-22 | 2009-05-13 | 昭和電工株式会社 | Capacitor |
| 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 |
-
2000
- 2000-12-01 JP JP2000366658A patent/JP4521849B2/en not_active Expired - Fee Related
-
2001
- 2001-11-30 CN CNA2007101364433A patent/CN101106022A/en active Pending
- 2001-11-30 AT AT01998980T patent/ATE294991T1/en not_active IP Right Cessation
- 2001-11-30 CN CNB018044131A patent/CN100338702C/en not_active Expired - Fee Related
- 2001-11-30 DE DE60110573T patent/DE60110573T2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07508618A (en) * | 1993-04-26 | 1995-09-21 | キャボット コーポレイション | Improved method for producing tantalum powder and electrodes with high capacitance and low electrical leakage obtained from the powder |
| CN1240377A (en) * | 1996-11-07 | 2000-01-05 | 卡伯特公司 | Niobium powders and niobium electrolytic capacitors |
| WO2000015555A1 (en) * | 1998-09-16 | 2000-03-23 | Cabot Corporation | Methods to partially reduce a niobium metal oxide and oxygen reduced niobium oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE294991T1 (en) | 2005-05-15 |
| JP4521849B2 (en) | 2010-08-11 |
| CN101106022A (en) | 2008-01-16 |
| JP2002231583A (en) | 2002-08-16 |
| CN1397079A (en) | 2003-02-12 |
| DE60110573D1 (en) | 2005-06-09 |
| DE60110573T2 (en) | 2006-03-09 |
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