CN100383900C - Niobium monoxide powder, niobium monoxide sintered product and capacitor using niobium monoxide sintered product - Google Patents

Abstract

The present invention provides (1) a niobium monoxide powder for capacitors, which is represented by the formula: NbOx (x=0.8 to 1.2), may contain from 50 to 200,000 ppm of other element, and has a tapping density of 0.5 to 2.5 g/ml, an average particle size of 10 to 1,000 mum, an angle of repose of 10 to 60 DEG , a BET specific surface area of 0.5 to 40 m2/g and a plurality of pore diameter peak tops in the pore distribution, and a production method thereof; (2) a niobium monoxide sintered body obtained by sintering the niobium monoxide powder, which has a plurality of pore diameter peak tops in the range from 0.01 to 500 mum, wherein preferably, out of the plurality of pore diameter peak tops, peak tops of two peaks having a highest relative intensity are present in the range from 0.2 to 0.7 mum and in the range from 0.7 to 3 mum, respectively, and the peak top of the peak having a highest relative intensity is present in the larger diameter side than the peak top of the peak having a next highest relative intensity, and a production method thereof; (3) a capacitor using the sintered body, and a production method thereof; and (4) an electronic circuit and an electronic instrument each using the capacitor.

Description

Niobium monoxide powder, columbium monoxide sintered body and the capacitor that uses the columbium monoxide sintered body

Relation with related application

This application is based on that the regulation of United States code the 35th volume the 111st (a) proposes, and requires the applying date of No. 60/331200, the U.S. Provisional Application that proposes according to No. 60/291925, the U.S. Provisional Application that proposes in May 21 calendar year 2001 of the 111st (b) regulation of this method with in November 9 calendar year 2001 according to the regulation of the 119th (e) (1st) of this method.

Technical field

The present invention relates to that stably manufacturer's quality electric capacity is big, (ESR) is low for equivalent series resistance, and niobium monoxide powder, the columbium monoxide sintered body of the capacitor that leakage current characteristic, moisture-proof are good use their capacitor and manufacture method thereof.

Background technology

The capacitor that is used for electronic instruments such as mobile phone or PC is preferably small-sized and jumbo.In these capacitors, tantalum capacitor because of showing big and functional being used of electric capacity more with respect to its size.

And electronic device in recent years requires the work under the low-voltage, work and the low noiseization under the high frequency, even therefore also require lower ESR (equivalent series resistance) for solid electrolyte capacitators.

Usually use the anode bodies of the sintered body of tantalum powder as tantalum capacitor.By back sintering this powder that is shaped, it is by integrated and form so-called sintered body electrode.In this sintered body inside, the particle of above-mentioned powder forms electricity, the 3 D complex shape of combination mechanically.After forming the dielectric film layer on the surface that comprises the internal voids surface of this sintered body, dipping constitutes capacitor as the material to electrode.The electric capacity of the capacitor of making is as long as the dielectric film layer just depends on the contact condition to electrode material and dielectric film layer largely equably attached to the surface of sintered body inside and outside on microcosmic.

In order to improve the electric capacity of this tantalum capacitor, needing increases Sintered Quality, perhaps uses the sintered body that has increased tantalum powder surface area by micronizing.

With the method that increases Sintered Quality, will inevitably increase the shape of capacitor and can't satisfy the requirement of miniaturization.On the other hand, increase tantalum powder method for specific area by micronizing, the aperture of tantalum sintered object will diminish, and increase at sintering stage blind hole, and it is difficult that the dipping of the negative electrode agent in subsequent handling becomes.

For example, if in the time of will using the phosphate aqueous solution conduct to electrode material, the contact condition of solution and dielectric film layer is complete, the electric capacity of this moment is apparent to be decided to be 100% than (also being negative electrode agent impregnation rate), when the tough electrode material of use especially solid electrode material, be difficult to make the apparent ratio of this electric capacity to reach 100%.That is, the average grain diameter of tantalum powder is little, and difficulty increased when perhaps the shape of the sintered body of being made by the tantalum powder was big, apparent ratio of electric capacity even less than 50% sometimes under extreme case.In addition, under the situation of the apparent ratio of this low electric capacity, the capacitor of making can't obtain sufficient moisture-proof.

In addition, the fine pore that has when the tantalum powder that is used to make tantalum sintered object hour, the fine pore that sintered body has also diminishes inevitably, makes electric capacity apparent than reducing.Its result, generation can't reduce the problem of ESR.Can consider the electrode material that uses the dielectric bigger than the dielectric constant of tantalum to obtain as one of method that addresses this problem, making can access the sintered body of the apparent ratio of high capacitance, with its capacitor as electrode.

As such electrode material that can be supplied in industrial productionization, known have a niobium bigger than the tantalum dielectric constant and that reserve is also Duoed.

The spy opens and discloses the manufacture method of capacitor with the sintered body element in the clear 55-157226 communique, wherein the particle diameter 2.0 μ m that form by the aggegation powder of press molding or following rectified action metal fine powder end, and sintering, should the severing of shaping sintered body be tiny, be connected to after the conductor part sintering again.But the manufacture method and the characteristic that do not have niobium capacitor in this communique are elaborated.

United States Patent (USP) 4,084 discloses a kind of hydrogenation and has pulverized the niobium powder that the niobium ingot obtains average grain diameter 5.1 μ m in No. 965 communiques, and the capacitor that its sintering is used.But the leakage current of disclosed capacitor (or the following LC that abbreviates as sometimes) value is big, lacks practicality.

Disclose by the part of nitrided niobium powders in the Te Kaiping 10-242004 communique and improved the LC value.

The spy opens to disclose in the 2000-119710 communique and a kind of niobium pentaoxide is put in the molten magnesium after the reduction reaction, take out the NbOx (x=0.5～1.5) that generates, then the NbOx (x=0.5～1.5) that will generate puts into and carries out reduction reaction in the molten magnesium and obtain metal niobium, the manufacture method of the high-purity niobium powder by two stage reduction reactions.

The tap density that is used for the niobium powder such as columbium monoxide of capacitor is important factor in the operation of shaping niobium powder, product up to the present, and tap density is greater than 2.5g/ml, for about 4g/ml, it is abundant inadequately to be used for being shaped.

Promptly be shaped when also the such niobium monoxide powder of sintering is made sintered body, niobium monoxide powder is poor to the flowability of mould by the forming machine hopper, generally is difficult to measure a certain amount of niobium monoxide powder and is sent to mould.Therefore, the shape of formed body is generally all fully stable inadequately, the undercapacity of formed body, sintered body, and the result causes producing the poor capacitor of LC with high-frequency.In addition, if use the special building mortion of the powder that can handle mobile difference, the shaping cost is too high, thereby impracticable.

Therefore, existing known capacitor is not adapted to progressive forming with niobium monoxide powder very much, has the low problem of productivity of capacitor.

Disclosure of an invention

The object of the present invention is to provide a kind of unit mass electric capacity big, (ESR) is low for equivalent series resistance, the capacitor that the leakage current characteristic is little and moisture-proof is good, can access the sintered body of the apparent ratio of high capacitance as its electrode material, preferably good fluidity and the easily progressive forming in forming operation of this sintered material, and niobium monoxide powder and manufacture method thereof that can the steady production capacitor.

Present inventors' above-mentioned problem of having concentrated on studies.It found that, if will have the columbium monoxide sintered body of specific pore size distribution, when especially the columbium monoxide sintered body of its pore-size distribution with a plurality of apertures peak value is used for electrode for capacitors, can produces and to obtain the apparent ratio of high capacitance, leakage current is low, moisture-proof is good capacitor.Further find, especially tap density is 0.5～2.5g/ml, further, especially average grain diameter is the niobium monoxide powder of 10～1000 μ m, its good fluidity, but progressive forming is suitable as above-mentioned sintered material, if use this niobium monoxide powder just can stably produce the low capacitor of leakage current value.

Also find, if further preferably wide by the emptying aperture distribution, aperture peak value is a plurality of, its aperture peak value all is used for electrode for capacitors at the columbium monoxide sintered body that 0.5 μ m or above niobium monoxide powder are made, and then can also realize low ESR when realizing the apparent ratio of high capacitance.

Promptly the present invention relates to following niobium monoxide powder, columbium monoxide sintered body, the capacitor that uses it and manufacture method thereof.

[1] by formula: NbOx (x=0.8～1.2) expression, and tap density is the capacitor niobium monoxide powder of 0.5～2.5g/ml.

[2] as the niobium monoxide powder of preceding paragraph [1] record, wherein further contain at least a other elements that are selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, selenium and the tellurium.

[3] as the niobium monoxide powder of preceding paragraph [1] or [2] record, wherein, other elements and niobium form composite oxides.

[4] as the niobium monoxide powder of preceding paragraph [2] or [3] record, wherein, the content of other elements is 50～200,000ppm.

[5] as the niobium monoxide powder of any record in the preceding paragraph [1] to [4], its average grain diameter is 10～1000 μ m.

[6] as the niobium monoxide powder of any record in the preceding paragraph [1] to [5], its angle of repose is 10～60 degree.

[7] as the niobium monoxide powder of any record in the preceding paragraph [1] to [6], its BET specific area is 0.5～40m ²/ g.

[8] as the niobium monoxide powder of any record in the preceding paragraph [1] to [7], has the pore-size distribution that in 0.01 μ m～500 mu m ranges, has the aperture peak value.

[9] as the niobium monoxide powder of preceding paragraph [8] record, wherein, pore-size distribution has a plurality of apertures peak value.

[10] as the niobium monoxide powder of preceding paragraph [8] or [9] record, wherein, being in all in 0.5 μ m～100 mu m ranges of aperture peak value.

[11] sintered body of the niobium monoxide powder of any record in the use preceding paragraph [1] to [10].

[12] as the sintered body of preceding paragraph [11] record, has the pore-size distribution that in 0.01 μ m～500 mu m ranges, has the aperture peak value.

[13] a kind of columbium monoxide sintered body, this sintered body is an electrode for capacitors columbium monoxide sintered body, it is characterized in that: the pore-size distribution of columbium monoxide sintered body is to have a plurality of apertures peak value.

[14] as the columbium monoxide sintered body of any record in the preceding paragraph [11] to [13], its pore-size distribution is to be made of two aperture peak values.

[15] as the columbium monoxide sintered body of preceding paragraph [13] or [14] record, in its a plurality of apertures peak value, the peak value at two peaks of relative intensity maximum is in 0.2～0.7 μ m and 0.7～3 mu m range respectively.

[16] as the columbium monoxide sintered body of preceding paragraph [13] record, in its a plurality of apertures peak value, the peakedness ratio relative intensity at the peak of the relative intensity maximum secondly peak value at big peak is in major diameter one side.

[17] as the columbium monoxide sintered body of any record in the preceding paragraph [11] to [16], this sintered body comprises that the pore void volume has 10mm ³Or above volume.

[18] as the columbium monoxide sintered body of any record in the preceding paragraph [11] to [17], this sintered body has 0.2～7m ²The specific area of/g.

[19] as the columbium monoxide sintered body of any record in the preceding paragraph [11] to [18], the part of this sintered body is by nitrogenize.

[20] as the columbium monoxide sintered body of any record in the preceding paragraph [11] to [19], this sintered body is the sintered body that is obtained by the columbium monoxide formed body that can give the sintered body of the CV value with 40000～200000 μ FV/g when 1400 ℃ of sintering.

[21] a kind of capacitor is characterized in that: by with the columbium monoxide sintered body of any record in the preceding paragraph [11] to [20] as a lateral electrode, and constitute between it and to the dielectric between the electrode.

[22] as the capacitor of preceding paragraph [21] record, wherein, the principal component of dielectric is a niobium pentaoxide.

[23] as the capacitor of preceding paragraph [21] record, wherein, be at least a material that is selected from electrolyte, organic semiconductor and the inorganic semiconductor to electrode.

[24] capacitor of putting down in writing as preceding paragraph [23], wherein, to electrode is organic semiconductor, and this organic semiconductor is to be selected from the organic semiconductor that is made of the benzopyrrole quinoline tetramer and chloranil, organic semiconductor that four sulphur aphthacenes are principal component, organic semiconductor that four cyano quinone bismethane is principal component and at least a material in the electroconductive polymer.

[25] as the capacitor of preceding paragraph [24] record, wherein, electroconductive polymer is at least a material that is selected from polypyrrole, polythiophene, polyaniline and the substitutive derivative thereof.

[26] as the capacitor of preceding paragraph [24] record, wherein, electroconductive polymer is the electroconductive polymer of dopant of having mixed in the polymer that contains by the repetitive shown in following general formula (1) or the general formula (2),

(in the formula, R ¹～R ⁴Expression independently of one another is selected from saturated or unsaturated alkyl, alkoxyl or the alkyl ester group of straight or branched of hydrogen atom, carbon number 1～10 or halogen atom, nitro, cyano group, primary, the second month in a season or uncle's amino, CF ₃Univalent perssad in the phenyl of base, phenyl and replacement.R ¹And R ²And R ³And R ⁴Also combination at an arbitrary position mutually of hydrocarbon chain, form the divalence chain, this divalence chain forms the circulus of at least one or above 3～7 yuan of ring fillings or unsaturated hydrocarbons with the carbon atom that is replaced by this group; Above-mentioned ring-type marriage chain can contain the key of carbonyl, ether, ester, acid amides, thioether, sulfinyl, sulfonyl, imino group at an arbitrary position; X represents oxygen, sulphur or nitrogen-atoms, R ⁵Only exist during for nitrogen-atoms at X, expression is selected from the saturated or unsaturated alkyl of the straight or branched of hydrogen atom or carbon number 1～10 independently).

[27] as the capacitor of preceding paragraph [26] record, wherein, electroconductive polymer is the electroconductive polymer that contains repetitive shown in the following general formula (3),

(in the formula, R ⁶And R ⁷Expression independently of one another is selected from the saturated or unsaturated alkyl or the combination at an arbitrary position mutually of this alkyl of straight or branched of hydrogen atom, carbon number 1～6, and expression forms the substituting group of the circulus of at least one or above 5～7 yuan of ring filling hydrocarbon that contain two oxygen elements; And can contain in above-mentioned circulus can substituted ethenylidene key, can substituted phenylene structure).

[28] as the capacitor of preceding paragraph [27] record, wherein, electroconductive polymer is at the electroconductive polymer that gathers the dopant that mixed in (3,4-ethylidene dioxy thiophene).

[29], wherein, be to constitute by the material that has a layer structure in a part at least to electrode as the capacitor of preceding paragraph [21] record.

[30] as the capacitor of preceding paragraph [21] record, wherein, be to contain the material of organic sulfonic acid anion as dopant to electrode.

[31] manufacture method of the niobium monoxide powder of any record in the preceding paragraph [1] to [10] is characterized in that: in the manufacture method of niobium monoxide powder, columbium monoxide or columbium monoxide compound are carried out activation processing (also being called " forming pore handles ").

[32] as the manufacture method of the niobium monoxide powder of preceding paragraph [31] record, it is characterized in that: the activation processing of columbium monoxide or columbium monoxide compound is to be undertaken by at least a operation that is selected from sintering circuit and the pulverizing process.

[33] as the manufacture method of the niobium monoxide powder of preceding paragraph [31] or [32] record, it is characterized in that: the activation processing of columbium monoxide or columbium monoxide compound is to use the mixture that contains columbium monoxide or columbium monoxide compound and activator to carry out.

[34] as the manufacture method of the niobium monoxide powder of any record in the preceding paragraph [31] to [33], it is characterized in that: being activated the columbium monoxide of processing or the average grain diameter of columbium monoxide compound is 0.01 μ m～10 μ m.

[35] as the manufacture method of the niobium monoxide powder of any record in the preceding paragraph [31] to [34], wherein, columbium monoxide or columbium monoxide compound are to contain 50～200, and 000ppm is selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, plumbous, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, the material of at least a element in selenium and the tellurium.

[36] as the manufacture method of the niobium monoxide powder of preceding paragraph [35] record, wherein, other elements that columbium monoxide or columbium monoxide compound contain and niobium formation composite oxides.

[37] as the manufacture method of the niobium monoxide powder of preceding paragraph [33] record, wherein, the mixture that contains columbium monoxide or columbium monoxide compound and activator is to use solvent mixed.

[38] as the manufacture method of the niobium monoxide powder of preceding paragraph [37] record, wherein, solvent is at least a solvent that is selected from water, alcohols, ethers, cellosolve class, ketone, aliphatic hydrocarbon, aromatic hydrocarbon based, the halogenated hydrocarbons.

[39] as the manufacture method of the niobium monoxide powder of preceding paragraph [33] record, wherein, activator uses 1～40 quality % with respect to the total amount of columbium monoxide or columbium monoxide compound.

[40] as the manufacture method of the niobium monoxide powder of preceding paragraph [33] or [39] record, wherein, the average grain diameter of activator is 0.01 μ m～500 μ m.

[41] as the manufacture method of the niobium monoxide powder of any record in preceding paragraph [33], [37], [39] and [40], wherein, the particle diameter peak value of activator is a plurality of.

[42] as the manufacture method of the niobium monoxide powder of any record in preceding paragraph [33], [37], [39] to [41], wherein, activator is at 2000 ℃ or the following material that can be removed as gas.

[43] as the manufacture method of the niobium monoxide powder of preceding paragraph [42] record, wherein, activator is to be selected from naphthalene, anthracene, quinone, camphor, polyacrylic acid, polyacrylate, polyacrylamide, polymethylacrylic acid, polymethacrylates, PMAm, polyvinyl alcohol, NH ₄Cl, ZnO, WO ₂, SnO ₂, MnO ₃In at least a.

[44] as the manufacture method of the niobium monoxide powder of any record in preceding paragraph [33], [37], [39] to [41], wherein, activator is to be selected from water-soluble substances, organic solvent solable matter, acid solution solable matter, alkaline solution solable matter, to form the material that becomes these solable matters behind the complex compound and at 2000 ℃ or followingly can become at least a in these solable matters.

[45] as the manufacture method of the niobium monoxide powder of preceding paragraph [44] record, wherein, activator is the compound that is selected from metal and carbonic acid, sulfuric acid, sulfurous acid, halogen, perhalogeno acid, hypohalogenous acids, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, perhaps at least a in metal, metal hydroxides and the metal oxide.

[46] as the manufacture method of the niobium monoxide powder of preceding paragraph [45] record, wherein, activator is to be selected from least a in metal carbonic acid thing, metal bicarbonate thing, metal hydroxides and the metal oxide.

[47] as the manufacture method of the niobium monoxide powder of preceding paragraph [46] record, wherein, activator is to be selected from least a in metal carbonic acid thing, metal bicarbonate thing, metal hydroxides and the metal oxide, and has the fusing point higher than the temperature in the sintering circuit.

[48] as the manufacture method of the niobium monoxide powder of preceding paragraph [44] record, wherein, activator is to be selected from lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, plumbous, arsenic, antimony, bismuth, selenium, tellurium, polonium, and at least a in their compound.

[49] as the manufacture method of the niobium monoxide powder of any record in the preceding paragraph [31] to [33], wherein, activation processing is the processing of removing activator by heating and/or decompression before sintering circuit or when sintering circuit.

[50] as the manufacture method of the niobium monoxide powder of any record in the preceding paragraph [31] to [33], wherein, activation processing is after sintering circuit, in the pulverizing process or behind the pulverizing process, makes sinter or crushed material solvent contact remove the processing of activator composition.

[51] as the manufacture method of the niobium monoxide powder of preceding paragraph [50] record, wherein, solvent is to be selected from water, organic solvent, acid solution, alkaline solution and to contain at least a in the solution of the part that forms soluble complexes.

[52] as the manufacture method of the niobium monoxide powder of preceding paragraph [51] record, wherein, acid solution is at least a solution that is selected from nitric acid, sulfuric acid, hydrofluoric acid and the hydrochloric acid.

[53] as the manufacture method of the niobium monoxide powder of preceding paragraph [51] record, wherein, alkaline solution contains and is selected from least a in alkali-metal hydroxide and the ammonia.

[54] as the manufacture method of the niobium monoxide powder of preceding paragraph [51] record, wherein, part is to be selected from least a in ammonia, glycine and the ethylenediamine tetra-acetic acid.

[55] a kind of manufacture method of nitrogenous niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the preceding paragraph [1] to [10] is handled with at least a method that is selected from bath nitriding, ionic nitriding and the gas nitriding method.

[56] a kind of manufacture method of carbon containing niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the preceding paragraph [1] to [10] is handled with at least a method that is selected from solid phase carbonization and the liquid carbonization method.

[57] a kind of manufacture method of boracic niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the preceding paragraph [1] to [10] is handled with at least a method that is selected from gas boronation and the solid phase boronation method.

[58] a kind of manufacture method of sulfur-bearing niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the preceding paragraph [1] to [10] is handled with at least a method that is selected from gas cure, ion sulfuration and the solid phase vulcanizing method.

[59] a kind of niobium monoxide powder, it is that manufacture method by any record in the preceding paragraph [31] to [58] obtains.

[60] a kind of manufacture method of columbium monoxide sintered body is characterized in that: the niobium monoxide powder that uses any record in preceding paragraph [1] to [10] and the preceding paragraph [59].

[61] a kind of manufacture method of capacitor, this method is as a lateral electrode with the columbium monoxide sintered body, contain the dielectric that is formed at this sintered body surface and be arranged at manufacture method on the above-mentioned dielectric, it is characterized in that: the sintered body that the niobium monoxide powder of any record obtains in the columbium monoxide sintered body has been a sintering preceding paragraph [1] to [10] and the preceding paragraph [59] the capacitor of electrode.

[62] as the manufacture method of the capacitor of preceding paragraph [61] record, wherein, dielectric forms by electrolytic oxidation.

[63] a kind of manufacture method of capacitor, this method is as a lateral electrode with the columbium monoxide sintered body, contain the dielectric that is formed at this sintered body surface and be arranged at the manufacture method to the capacitor of electrode on the above-mentioned dielectric, it is characterized in that: the columbium monoxide sintered body is the columbium monoxide sintered body of any record in the preceding paragraph [11] to [20].

[64] a kind of electronic circuit, this circuit have used the capacitor of any record in the preceding paragraph [21] to [30].

[65] a kind of electronic instrument, this instrument have used the capacitor of any record in the preceding paragraph [21] to [30].

The working of an invention scheme

Below to high capacitance, low ESR (ESR) and leakage current characteristic and the good capacitor of moisture-proof, can give the columbium monoxide sintered body that this characteristic obtains the apparent ratio of high capacitance, preferably as the good fluidity of this sintered material and niobium monoxide powder that can progressive forming, and their manufacture method describes.

Among the present invention, as the characteristic that satisfies above-mentioned capacitor, can improve the productive niobium monoxide powder that capacitor is made, using tap density is that the capacitor of 0.5～2.5g/ml is with niobium monoxide powder (abbreviation only is designated as niobium monoxide powder sometimes).

Capacitor is meant by formula with niobium monoxide powder: NbOx (x=0.8～1.2) is as principal component, and can become the raw-material material that is used to make capacitor.

The oxide of niobium is known three kinds of columbium monoxides, columbium dioxide, niobium pentaoxide.

The niobium oxide that x is between 0～1 is the state of metal niobium and columbium monoxide coexistence.Metal niobium is compared easy sintering with columbium monoxide, if metal niobium exists in a large number, then be difficult to increase the specific area of sintered body, causes the electric capacity of capacitor to diminish easily.

In addition, x is in the state that the niobium oxide between 1～2 is columbium monoxide and columbium dioxide coexistence.Columbium monoxide is a conductivity, and columbium dioxide is an insulating properties.If columbium dioxide exists in a large number, then be unfavorable for formation by the dielectric of electrolytic oxidation.

Consider these, the scope of x is preferred 0.8～1.2, and more preferably 0.9～1.1, preferred especially 0.95～1.05.

In niobium monoxide powder, for example can contain, can form at least a in the composition beyond the niobiums such as the composition of composite oxides or nitrogen, phosphorus, antimony, sulphur, selenium, tellurium with niobium.By containing such niobium composition in addition, can change agglutinating property, improve characteristic as capacitor.As the element beyond this niobium, for example can enumerate,, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, selenium and tellurium.

For example, can obtain the capacitor sintered body with following method by being shaped and the sintering niobium monoxide powder.

In the solution that the aftermentioned adhesive is dissolved in the organic solvents such as toluene or methyl alcohol, add the capacitor niobium monoxide powder, and fully mix with vibration mixer, V-Mixer etc.Under reduced pressure distill with drying machines such as taper driers then and remove organic solvent, make the columbium monoxide mixed powder that contains adhesive.This mixed powder is put into the automatic forming machine hopper.The columbium monoxide mixed powder is flow through from the conduit of hopper to forming machine mold automatically fall naturally and measure, be shaped with lead to mould.Make the columbium monoxide sintered body at 500 ℃～2000 ℃ sintering after this formed body under reduced pressure removed adhesive.

Then, for example with in the electrolytic solutions such as the phosphoric acid of columbium monoxide sintered body about 30～90 ℃ of temperature, concentration 0.1 quality %, adipic acid, up voltage to 20～60V carries out 1～30 hour chemical combination to be handled, and makes the dielectric layer based on niobium pentaoxide.On this dielectric layer, form solid electrolyte layers such as manganese dioxide, brown lead oxide, electroconductive polymer, then form graphite linings, silver paste layer.Then, thereon by behind connection such as welding cathode terminal, with the resin-sealed solid electrolytic capacitor of making.

During shaping, the mixed powder that does not have adequate liquidity or angle of repose is difficult to flow to mould from hopper, can't stable formation.Especially carry from hopper owing to methods such as using vibration, therefore the excessive or too small inhomogeneities of quality, sintered body intensity and the shape of formed body that all can make of the tap density of mixed powder or average grain diameter increases, phenomenon, leakage current value variation as a result such as thereby breach can take place, break.Therefore, the tap density of mixed powder, average grain diameter, flowability and angle of repose are key factors for making good sintered body and capacitor.

This rerum natura of mixed powder is changing hardly with the front and back of mixing of adhesive, and the rerum natura of mixed powder is to be determined by the rerum natura of the capacitor that uses with niobium monoxide powder.Therefore, the tap density of the niobium monoxide powder of use, average grain diameter, flowability, angle of repose etc. are important.The flowability of niobium monoxide powder or angle of repose be because to be subjected to the influence of tap density or average grain diameter big, so tap density or average grain diameter become key factor.

For along with improving liquidity or productivity and sintered body intensity are improved in the angle of repose, and follow it to obtain the reduction effect of leakage current value, preferred 0.5～the 2.5g/ml of tap density among the present invention, further preferred 0.7～1.9g/ml, preferred especially 0.7～1.6g/ml.In addition, preferred 10～1000 μ m of the average grain diameter of niobium monoxide powder of the present invention, preferred especially 50～200 μ m.

For niobium monoxide powder is fallen to mould naturally from the forming machine hopper, the angle of repose of niobium monoxide powder of the present invention preferred 10～60 is spent, more preferably 10～50 degree.

Having as mentioned above, the niobium monoxide powder of rerum natura is, with contain niobium monoxide powder or columbium monoxide compound powder (below, these are recited as " raw material niobium monoxide powder ") and activator (also be called " form pore agent ", below be recited as " additive " sometimes) mixture as raw material, make through sintering circuit, pulverizing process at least successively.

Activator is removed in arbitrary operation of the sintering circuit of being made niobium monoxide powder of the present invention by raw mix or pulverizing process.The removal of activator also can be independent of above-mentioned sintering circuit or pulverizing process and carry out.

The method of removing activator can adopt various arbitrarily methods according to the chemical property of activator, can use a kind of or is used in combination the method for multiple easy removal activator.

As the method for removing activator, for example can enumerate, become gas to remove the method for activator by evaporation, distillation or thermal decomposition, the method that removes with the dissolution with solvents activator etc.

With the situation that activator is removed as gas, can in sintering circuit, carry out, the operation that removes activator by heating and/or decompression perhaps is set before sintering.

The situation of activator is removed in dissolving, by behind the raw materials for sintering mixture, or in pulverizing, or after pulverizing, solvent described later and sinter or its crushed material are contacted dissolve the removal activator.

In addition, making any operation of niobium monoxide powder of the present invention, nitrogenize, boronation, carbonization can be set or vulcanize the operation of a part of niobium monoxide powder from raw mix.

Below, the manufacture method of detailed description niobium monoxide powder of the present invention.

As the raw material niobium monoxide powder, can use be selected from columbium monoxide (NbOx:x=0.8～1.2) and, contain and be selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, plumbous, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, the columbium monoxide of at least a element in selenium and the tellurium, and at least a powder in the compound.In addition, also can be that these a part is further by the material of nitrogenize, sulfuration, carbonization or boronation.

The preferred 0.01 μ m of the average grain diameter～10 μ m that are used for raw material niobium monoxide powder of the present invention, more preferably 0.02 μ m～5 μ m, preferred especially 0.05 μ m～2 μ m.

In addition, in order to improve agglutinating property or capacitor produced electric property, preferred 50～500000 quality ppm of the amount of contained other elements, preferred especially 50～200000 quality ppm.

Acquisition becomes the method for the columbium monoxide of raw material niobium monoxide powder, for example can enumerate, as with niobium pentaoxide with calcium or magnesium etc. have the metallic reducing of reduction method, with the columbium dioxide powder in hydrogen stream, add thermal reduction method, mix the method that in argon gas, heats behind niobium metal powder and the columbium dioxide powder etc.

Acquisition becomes the method for the columbium monoxide that contains other elements of raw material niobium monoxide powder, for example can enumerate, will with the composite oxides of other compositions, the hopcalite of niobium pentaoxide and other elements, the oxides of columbium dioxide and other elements etc. heat in hydrogen stream as initiation material and reduce or use calcium, magnesium, yttrium, lanthanum, cerium, samarium, cerium alloy material etc. has the method for the metallic reducing of reduction, the method that the alloy of heating niobium and other elements carries out oxidation in air, the method of the mixture of heating niobium monoxide powder and other element compounds, make gas, solid, the method of other liquid elements and columbium monoxide reaction etc.These powders can be pulverized with usual way and regulate granularity.

For example, obtain containing the niobium monoxide powder that other elements are boron, can enumerate, mix the method that heats behind niobium (Nb) boride powder and the niobium monoxide powder, method or the boron of heated air shape and the method that columbium monoxide makes its reaction etc. that in air, heat the niobium (Nb) boride powder.

Activator is the material that can remove in the arbitrary operation by raw mix manufacturing niobium monoxide powder of the present invention.Usually in the niobium monoxide powder of the present invention, the removed part of activator forms pore.

The aperture of grain diameter influence's niobium monoxide powder of the present invention of activator, the aperture of niobium monoxide powder influences the aperture of columbium monoxide sintered body, and the aperture of sintered body influences the dipping of negative electrode agent in condenser capacitance and the capacitor manufacturing process.

The dipping of negative electrode agent has very big influence for the capacitor that making has high capacitance and low ESR.The columbium monoxide sintered body is owing to be that the press molding niobium monoxide powder is made, and therefore, the aperture of sintered body is inevitably less than the aperture of niobium monoxide powder.If consider degree of difficulty with respect to the negative electrode agent dipping property of the sintered body of making by powder with little peak, aperture, the preferred average diameter in the aperture that niobium monoxide powder has 0.5 μ m or more than, preferred especially 1 μ m or more than.

The preferred average diameter in these apertures is 0.01～500 μ m, more preferably 0.03～300 μ m, preferred especially 0.1～200 μ m.Therefore, preferred 0.01～500 μ m of the average grain diameter of activator, more preferably 0.03～300 μ m, preferred especially 0.1～200 μ m.

The aperture of most preferred niobium monoxide powder is, average diameter is 0.5 μ m～100 μ m, and in order to produce this aperture, the average grain diameter of most preferred activator is 0.5 μ m～100 μ m.

The little activator of particle diameter then can be used in its aperture if diminish, if become big, then can use the big activator of particle diameter.

In addition, can adjustment aperture distribute by the particle size distribution of adjusting activator.

For the capacitor that obtains there is not negative electrode agent dipping property problem and have abundant electric capacity, preferably the rerum natura according to the negative electrode agent suitably is provided with little of pore that can access desired electric capacity degree and the big fully pore of impregnated cathode agent degree that arrives in the columbium monoxide sintered body.

In order to adjust the pore-size distribution of niobium monoxide powder or columbium monoxide sintered body, for example, can use particle size distribution to have the activator (powder) of two or more peak values, making niobium monoxide powder have peak value is two or more pore-size distributions.Can obtain having the columbium monoxide sintered body that equal aperture peak value is two or more pore-size distribution by this niobium monoxide powder of sintering.At this moment, the aperture peak value preferably in the scope of 0.01～500 μ m, more preferably 0.03～300 μ m, further preferred 0.1～200 μ m, preferred especially 0.1～30 μ m, most preferably 0.2～3 μ m.

The niobium monoxide powder that can form this columbium monoxide sintered body has two or more apertures peak value.The two or more apertures peak value of this niobium monoxide powder preferably all 0.5 μ m or more than.For example, when being formed in 0.7 μ m and 3 μ m and having the columbium monoxide sintered body of two aperture peak values, two aperture peak values that niobium monoxide powder can be had for example are adjusted to, about 1.5 μ m and about 25 μ m.The average grain diameter of activator that is used to form the small-bore of about like this 1.5 μ m is about 1.5 μ m, and the average grain diameter that is used to form the wide-aperture activator of about like this 25 μ m is about 25 μ m.Usually the situation that is present in niobium monoxide powder for little pore and big pore, big pore is destroyed and diminish when press molding.Therefore, the large aperture peak value preferably 20 μ m or more than.For the aperture peak value is three situation, big aperture peak value also preferably 20 μ m or more than.In addition, 30 volume % of preferred full emptying aperture volume or abovely have 20 μ m or an above aperture, preferred especially 40 volume % or more than.

Activator with two or more particle size distribution peak values for example can obtain by mixing two kinds or the different activator of above particle size distribution peak value.

As the material that forms activator, for example can enumerate, at sintering temperature or the following material that becomes the material of gas or behind sintering, dissolve in solvent at least.

As at sintering temperature or the following material that becomes gas, for example can enumerate, become the material of gas etc. after evaporation, distillation or the thermal decomposition, even preferably also can not stay residue and become the material of the cheapness of gas easily at low temperature.As this material, for example can enumerate aromatic compound, camphor, NH such as naphthalene, anthracene, quinone ₄Cl, ZnO, WO ₂, SnO ₂, MnO ₃, the organic polymer thing.

As the organic polymer thing, for example can enumerate polyacrylic acid, polyacrylate, polyacrylamide, polymethylacrylic acid, polymethacrylates, PMAm, polyvinyl alcohol.

As being the material of solubility at least behind sintering, it is the material that the residue of activator or its pyrolysate dissolves in solvent, particularly preferably in the material that is dissolved in easily behind the sintering, in the pulverizing or after pulverizing in the solvent described later, by combination solvent, this material can be by selecting in the multiple material.

As this material, for example can enumerate the compound of metal and carbonic acid, sulfuric acid, sulfurous acid, halogen, perhalogeno acid, hypohalogenous acids, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, metal oxide, metal hydroxides and metal.

The preferred big compound of solubility in acid described later, alkali, ammonium salt solution equal solvent, for example can enumerate, contain the compound of at least a element in lithium, sodium, potassium, rubidium, caesium and francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, cerium, neodymium, erbium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, aluminium, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, selenium, tellurium, polonium, boron, silicon and the arsenic.Preferable alloy salt wherein, further preference as, barium monoxide, manganese nitrate (II), calcium carbonate etc.

These above-mentioned activators can use separately, also can make up two kinds or above use, without any problem.

Consider the pore that effective formation is specific, preferably the material that exists with solid in sintering temperature.This is for by existing with solid at the sintering temperature activator, and the columbium monoxide starting powder excessively coagulates integrated package, makes its welding between the contact generation columbium monoxide between the columbium monoxide.When sintering temperature existed with liquid or gas, the agglomerate effect was little, formed the pore less than desired pore sometimes.So when using high-melting-point material such as barium monoxide, calcium carbonate, aluminium oxide, magnesium oxide etc. as activator, fine pore is more stable when using low melting point such as zinc metal, tin metal, antimony oxide etc. as activator.

If the addition of activator is few, can make tap density and angle of repose become big, if tap density is diminished, sintering in the stage blind hole increase.In order to obtain not having the blind hole problem in the sintering stage, and the angle of repose is that 60 degree or following, tap density are 0.5～2.5g/ml, the addition of activator can change according to the average grain diameter of activator, but generally with respect to the raw material columbium monoxide be 1～40 quality % (below, when having specified otherwise quality % only is not designated as % simply), preferred 5～25%, more preferably 10～20%.

Raw mix can be product of mixing under the condition that does not have solvent between the powder with above-mentioned activator and above-mentioned columbium monoxide raw material, also can be to mix both dry products in back with appropriate solvent.

As spendable solvent, for example can enumerate water, alcohols, ethers, cellosolve class, ketone, aliphatic hydrocarbon, aromatic hydrocarbon based, halogenated hydrocarbons.

Also can use mixer during mixing.As mixer, can use device usually such as vibration mixer, V-Mixer, nauta mixer.Though the temperature during mixing is subjected to the boiling point of solvent, the restriction of solidifying point, be generally-50 ℃～120 ℃, preferred-50 ℃～50 ℃, more preferably-10 ℃～30 ℃.Mix required time so long as 10 minutes or abovely then do not do special restriction, but preferably carried out 1～6 hour usually.

When using solvent, use taper drier, chamber dryer etc. less than 80 ℃, preferably dry gained mixture under less than 50 ℃ condition.

Activator is in sintering temperature or following when becoming gas, can when sintering, remove activator, but also can according to the chemical property of activator under conditions such as the temperature of removing easily, pressure, time, before sintering, independently be provided with the operation of activator as the gas removal.At this moment, for example, 100 ℃～800 ℃, the decompression under, heat up in a steamer deactivator with several hrs.

Sintering circuit preferably under reduced pressure or in the reducing gas atmosphere such as argon gas, at 500 ℃～2000 ℃, preferred 800 ℃～1500 ℃, further preferred 1000 ℃～1400 ℃ are carried out.Preferably after sintering finishes, (abbreviate the columbium monoxide temperature as product temperature.) be cooled to 30 ℃ or following, be no more than inert gases such as the nitrogen that slowly feeds the oxygen that contains 0.01 volume %～10 volume %, preferred 0.1 volume %～1 volume % under 30 ℃ the condition or argon gas at product temperature, placed 8 hours or the taking-up of above back, obtain agglomerate.

Use pulverizer such as roll-type crushed machine that agglomerate is ground into suitable particle diameter in the pulverizing process.

When activator dissolves in solvent at least after sintering circuit, behind sintering, before pulverizing, pulverize in, pulverize the back or in these a plurality of operations, make appropriate solvent contact agglomerate or comminuted powder, the activator composition is removed in dissolving.Consider that from easy removal degree preferably the comminuted powder dissolving after pulverize is removed.

As solvent used herein, be the solvent that can access the solubility that needs dissolve activating agent fully, preferred cheap and be difficult for residual solvent.For example, activator is if water miscible, then make water, if the organic solvent solubility, then use methyl iso-butyl ketone (MIBK), ethanol, methyl-sulfoxide organic solvents such as (DMSO), if acid-solubility, then use nitric acid, sulfuric acid, phosphoric acid, boric acid, carbonic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, acid solutions such as organic acid, if alkali-soluble, then use alkali-metal hydroxide, the hydroxide of alkaline-earth metal, alkaline solutions such as ammonia, if the formation soluble complexes is then used the ammonia that can become its part, amines such as ethylenediamine, amino acidses such as glycine, polyphosphoric acid types such as sodium phosphate trimer, crown ether-like, thiosulfates such as sodium thiosulfate, solution such as chelating agent such as ethylenediamine tetra-acetic acid.

In addition, ammonium salt solution such as ammonium chloride, ammonium nitrate, ammonium sulfate or cation exchange resin, anion exchange resin etc. also are well suited for using.It is low that temperature is removed in the dissolving of wishing activator, preferred 50 ℃ or following.More preferably remove, carry out particularly preferably in 0 ℃～30 ℃-10 ℃～40 ℃ dissolvings.Preferably select few method of generating heat when in addition, dissolving is removed.For example, when in activator, using metal oxide or metal,, cause temperature too high if produce the heat of neutralization with the acid dissolving meeting of removal.Therefore, for example can select, make it to be dissolved in water or organic solvent method, use formation soluble complexes such as the ammonium salt aqueous solution or ethylenediamine tetra-acetic acid method, be dissolved in the method for the difficult heatings such as method of the solution that contains ion exchange resin.

The combination of activator and solvent more specifically for example can be enumerated, barium monoxide and water, calcium oxalate and hydrochloric acid, aluminium oxide and sodium hydrate aqueous solution, hafnium oxide and methyl iso-butyl ketone (MIBK), magnesium carbonate and the tetrasodium salt of EDTA aqueous solution etc.

Fully cleaning was also dry after activator was removed in dissolving.When removing barium monoxide, fully wash until cleaning electrical conductivity of water with ion exchange water and to reach 5 μ S/cm or following as water.Then under reduced pressure in 50 ℃ of product temperatures or following drying.Though the residual here activator or the amount of solvent composition are relevant with cleaning condition, are generally 100ppm or following.

For the niobium monoxide powder that obtains like this, above-mentioned agglomerate or columbium monoxide raw meal,, can further the part of niobium monoxide powder be carried out nitrogenize, boronation, carbonization, vulcanizes or carry out a plurality of these processing in order further to improve agglutinating property.

Also can contain the nitride of gained columbium monoxide, the boride of columbium monoxide, the carbide of columbium monoxide, sulfide or multiple these materials of columbium monoxide in the niobium monoxide powder of the present invention.Though its nitrogen, boron, carbon, and the content summation of each element of sulphur according to the shape of niobium monoxide powder and different, be generally 0ppm～200,000ppm, preferred 50ppm～100,000ppm, further preferred 200ppm～20,000ppm.If surpass 200, the 000ppm capacitance characteristic worsens, and is not suitable as capacitor.

The nitriding method of niobium monoxide powder can be implemented in bath nitriding, ionic nitriding, the gas nitriding etc. any one, perhaps makes up these methods and implements.So it is preferred because install easy processing ease by the gas nitriding in the nitrogen atmosphere.For example, by the method for the gas nitriding in the nitrogen atmosphere, can realize by above-mentioned niobium monoxide powder is positioned in the nitrogen atmosphere.The temperature of nitrogenize atmosphere gas is 2000 ℃ or following, standing time be 100 hours or in the time, can obtain the niobium monoxide powder of required nitrogenize amount.In addition, can be by shortening the processing time in higher Temperature Treatment.

The boronation method of niobium monoxide powder can be any one of gas boronation, solid phase boronation.For example, can be with the boron source of halogenation boron such as boron ball or boron trifluoride under reduced pressure with niobium monoxide powder, 2000 ℃ or following placement 1 minute～100 hours.

The carbonization of niobium monoxide powder can be any one of gas carbonization, solid phase carbonization, liquid carbonization.For example, can be with carbon sources such as carbonaceous organic material such as carbon source materials or methane under reduced pressure with niobium monoxide powder, 2000 ℃ or following placement 1 minute～100 hours.

The vulcanization process of niobium monoxide powder can be in gas cure, ion sulfuration, the solid phase vulcanizing etc. any one.For example, by the method for the gas cure in the sulfur gas atmosphere, can realize by above-mentioned niobium monoxide powder is positioned in the sulfur gas atmosphere.The temperature of atmosphere gas of sulfuration is 2000 ℃ or following, standing time be 100 hours or in the time, can obtain the niobium monoxide powder of required sulfuration amount.In addition, can be by shortening the processing time in higher Temperature Treatment.

The BET specific area of the niobium monoxide powder of the present invention that obtains as mentioned above is generally 0.5～40m ²/ g, preferred 0.7～10m ²/ g, further preferred 0.9～2m ²/ g.

Niobium monoxide powder of the present invention can mix the niobium monoxide powder that uses tap density, particle diameter, angle of repose, BET specific area, pore-size distribution, nitrogenize, boronation, carbonization, vulcanizing treatment to have nothing in common with each other.

The sintered body of the present invention that can be used for capacitor electrode, for example, the preferred foregoing niobium monoxide powder of the present invention of sintering is made.For example, be 10 after the given shape with the niobium monoxide powder press molding ^-5～10 ²Under the Pa, can obtain sintered body in 1 minute～10 hours at 500 ℃～2000 ℃, preferred 800 ℃～1500 ℃, further preferred 1000 ℃～1400 ℃ scope heating.

The pore-size distribution of the sintered body that is obtained by niobium monoxide powder of the present invention has the aperture peak value usually in 0.01 μ m～500 mu m ranges.

In addition, the pressurization by will be shaped the time is adjusted to given pressurization value, the aperture peak value that the aperture peak value number that sintered body is had have than niobium monoxide powder is Duoed.This pressurization value is different because of the press molding condition of the shape of the rerum natura of niobium monoxide powder, formed body or forming machine etc., but be in can press molding pressure or on, do not seal sintered body pore degree pressure or under scope in.Preferred pressurization value can be passed through preliminary experiment, combines with the factors such as rerum natura of the niobium monoxide powder that is shaped and decides, so that it can have a plurality of apertures peak value.Pressurization value for example, can by regulate forming machine to formed body increase the weight of regulate.

The pore-size distribution of sintered body preferably has at least two aperture peak values so that its contain obtain the little pore of desired electric capacity degree and, meet the rerum natura of negative electrode agent and the abundant big pore of impregnated cathode agent degree.Like this, it is good and electric capacity is apparent than high capacitor to obtain dipping to electrode from the sintered body that pore-size distribution has a plurality of peak values.

In addition, in the peak value of a plurality of apertures, the peak value when two peaks of relative intensity maximum is in 0.2～0.7 μ m and 0.7～3 μ m respectively, when preferably being in 0.2～0.7 μ m and 0.9～3 μ m respectively, the moisture-proof of the capacitor of being made by this sintered body is good, is preferred therefore.Further, in the peak value of a plurality of apertures, when the peak value at the peak that the peakedness ratio relative intensity at the peak of relative intensity maximum is secondly big is in major diameter one side, thus the time can access the better capacitor of moisture-proof, therefore preferred especially.

The specific area of the sintered body of Zhi Zuoing is generally 0.2m like this ²/ g～7m ²/ g.

Usually the shape of sintered body is big more, and is difficult more to the dipping of electrode.For example, when the size of sintered body at 10mm ³Or when above, the sintered body that pore-size distribution of the present invention has a plurality of peak values especially can effectively use.

Sintered body of the present invention also can be a part of by nitrogenize.As nitriding method, can adopt the method and the reaction condition that are applicable to above-mentioned niobium monoxide powder.Also can be first a nitrogenize part make the niobium monoxide powder of sintered body, the further sintered body made by this powder of a nitrogenize part again.

It is the oxygen element of 0.8～1.2 times of mole that this sintered body contains usually with respect to the niobium element.This comprise the oxygen that before sintering, is contained in the niobium monoxide powder and, the oxygen that when sintering, adds because of autoxidation.In addition, the content of element is generally 400 quality ppm or following beyond the element of the columbium monoxide in the sintered body of the present invention, interpolation, oxygen, the nitrogen.

Sintered body of the present invention is said for an example, and when 1400 ℃ of sintering, CV value (in the phosphate aqueous solution of 0.1 quality %, at the chemical combination magnitude of voltage of 80 ℃ of following chemical combination in the time of 120 minutes and product at the electric capacity of 120Hz) is 40000～200000 μ FV/g.

Below, the manufacturing of capacitor element is described.

For example, the lead that preparation is made of rectified action metals such as niobium or tantalums with suitable shape and length, when above-mentioned niobium monoxide powder press molding, it is integrally formed as a part that makes lead and is inserted into formed body inside, install so that lead becomes the lead-in wire of above-mentioned sintered body, or be designed to do not having to be shaped the lead that behind sintering, waits connection to prepare separately under the situation of lead with welding.

Can be it and the dielectric between the electrode is made capacitor by Jie with above-mentioned sintered body as a lateral electrode.For example, above-mentioned columbium monoxide sintered body as a lateral electrode, is gone up the formation dielectric on its sintered body surface (comprising the pore inner surface), on above-mentioned dielectric, be provided with, to constitute capacitor to electrode.

Here, as the dielectric of capacitor, preferably based on the dielectric of niobium oxide, further preferred niobium pentaoxide is the dielectric of main body.Niobium pentaoxide is the dielectric of main body, for example, can obtain by the columbium monoxide sintered body of electrolytic oxidation as a lateral electrode.During electrolytic oxidation columbium monoxide electrode, can use common protonic acid aqueous solution in electrolyte, the phosphate aqueous solution as 0.1%, aqueous sulfuric acid or 1% aqueous acetic acid, adipic acid aqueous solution etc. carry out.Like this, when chemical combination columbium monoxide electrode obtained the niobium oxide dielectric in electrolyte, capacitor of the present invention became electrolytic capacitor and the columbium monoxide electrode becomes anode.

In capacitor of the present invention, for the columbium monoxide sintered body electrode (to the utmost point) is not done special qualification, for example, can use at least a material (compound) in the known electrolyte of aluminium electrolytic capacitor industry, organic semiconductor and inorganic semiconductor.

Concrete example as electrolyte, can enumerate, dissolve the mixed solution of 5 quality % isobutyl group electrolytical dimethyl formamides of tripropyl ammonium tetrafluoroborate and ethylene glycol, the propylene carbonate that has dissolved 7 quality % tetraethyl ammonium tetrafluoroborates and the mixed solution of ethylene glycol etc.

As the organic semi-conductor concrete example, can enumerate, the organic semiconductor that is made of the benzopyrrole quinoline tetramer and chloranil, organic semiconductor, the four cyano quinone bismethane that four sulphur aphthacenes are principal component are the organic semiconductor of principal component or contain following general formula (1) or the electroconductive polymer of the repetitive of general formula (2) expression.

In the formula, R ¹～R ⁴Expression independently of one another is selected from saturated or unsaturated alkyl, alkoxyl or the alkyl ester group of straight or branched of hydrogen atom, carbon number 1～10 or halogen atom, nitro, cyano group, primary, the second month in a season or uncle's amino, CF ₃Univalent perssad in the phenyl of base, phenyl and replacement.R ¹And R ²And R ³And R ⁴Also combination at an arbitrary position mutually of hydrocarbon chain, form the circulus that the divalence chain is used for forming with the carbon atom that is replaced by this group at least one or above 3～7 yuan of ring fillings or unsaturated hydrocarbons.Above-mentioned ring-type marriage chain can contain keys such as carbonyl, ether, ester, acid amides, thioether, sulfinyl, sulfonyl, imino group at an arbitrary position.X represents oxygen, sulphur or nitrogen-atoms, R ⁵Only exist during for nitrogen-atoms at X, expression is selected from the saturated or unsaturated alkyl of the straight or branched of hydrogen atom, carbon number 1～10 independently.

Further, the R in above-mentioned general formula (1) or the general formula (2) among the present invention ¹～R ⁴Preferred saturated or unsaturated alkyl or the alkoxyl of representing the straight or branched of hydrogen atom, carbon number 1～6 independently of one another, R ¹And R ²And R ³And R ⁴Hydrocarbon chain can interosculate circlewise.

Further, in the present invention, the electroconductive polymer that contains the repetitive of above-mentioned general formula (1) expression preferably can be enumerated and contain with the construction unit of following general formula (3) the expression electroconductive polymer as repetitive.

In the formula, R ⁶And R ⁷Represent the saturated or unsaturated alkyl or the combination at an arbitrary position mutually of this alkyl of the straight or branched of hydrogen atom, carbon number 1～6 independently of one another, expression forms the substituting group of the circulus of at least one or above 5～7 yuan of ring filling hydrocarbon contain two oxygen elements.In addition, above-mentioned circulus can contain can substituted ethenylidene key, can substituted phenylene structure.

Contain in the electroconductive polymer of this chemical constitution and be doped with dopant.Can use known dopant as dopant, not have particular determination.

As the concrete example of inorganic semiconductor, can enumerate with brown lead oxide or manganese dioxide be the inorganic semiconductor of principal component, the inorganic semiconductor that constitutes by tri-iron tetroxide etc.This semiconductor can use separately, also can make up two kinds or above use.

As the polymer of the repetitive that contains the expression of general formula (1) or general formula (2), for example can enumerate polyaniline, polyphenylene oxide, polyphenylene thioether, polythiophene, poly-furans, polypyrrole, poly-methyl pyrrole and substitutive derivative or copolymer.Wherein preferred polypyrrole, polythiophene and substitutive derivative thereof (for example, poly-(3,4-ethylidene dioxy thiophene) etc.).

If use conductivity 10 ^-2S/cm～10 ³The material of S/cm scope is as above-mentioned organic semiconductor and inorganic semiconductor, and then the resistance value of the capacitor of Zhi Zuoing will be littler, can further increase the electric capacity at high frequency.

As the method for making above-mentioned electroconductive polymer layer, can adopt will be as the method for polymerizable compound polymerization under the oxidant effect of the oxidation reaction that can fully carry out the oxidation of dehydrogenation bielectron of aniline, thiophene, furans, pyrroles, methylpyrrole or its substitutive derivative.From the polymerization reaction of polymerizable compound (monomer), gas-phase polymerization, polymerisation in solution of monomer for example etc. are arranged, be formed at the surface of columbium monoxide sintered body with dielectric.When but electroconductive polymer is the organic solvent soluble polymer of solution coating, can adopt the method that forms in surface applied.

Can enumerate method as a preferred manufacture method by polymerisation in solution, this method is that the columbium monoxide sintered body that will form dielectric layer impregnated in the solution (solution 1) that contains oxidant, then impregnated in the solution (solution 2) that contains monomer and dopant and carry out polymerization, form the method for electroconductive polymer layer on this surface.In addition, impregnated in solution 1 after also above-mentioned sintered body can being immersed in solution 2.In addition, in above-mentioned solution 2, also can be used as the monomer solution that does not contain dopant and be used for said method.In addition, when using dopant, it is coexisted with the solution that contains oxidant use.

By repeatedly once or above, preferred 3～20 these polymerization process operation, can easily form fine and close stratiform electroconductive polymer layer to above-mentioned columbium monoxide sintered body with dielectric.

In capacitor manufacture method of the present invention, oxidant can not use and bring the substance of going back dysgenic, this oxidant to become the oxidant that dopant can improve the conductivity of electroconductive polymer to capacitor performance, and easy-to-use compound is gone up in preferred industrial cheapness and manufacturing.

As this oxidant, specifically for example can enumerate FeCl ₃Or FeClO ₄, manganese class, 2 such as Fe (III) based compound class such as Fe (organic anion) salt or anhydrous Aluminum chloride/stannous chloride, alkali metal persulphate class, ammonium persulfate salt, peroxide, potassinm permanganate, 3-two chloro-5,6-dicyano-1,4-benzoquinones (DDQ), tetrachloro-1,4-benzoquinones, four cyano-1, sulfonic acid such as halogens such as quinones such as 4-benzoquinones, iodine, bromine, peracid, sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, fluosulfonic acid, sulfamic acid, ozone etc., and the combination of these a plurality of oxidants.

Wherein, as the basic compound of the organic anion that forms above-mentioned Fe (organic anion) salt, can enumerate organic sulfonic acid or organic carboxyl acid, organic phosphoric acid, organic boronic etc.As the concrete example of organic sulfonic acid, can use benzene sulfonic acid or p-methyl benzenesulfonic acid, methanesulfonic acid, ethyl sulfonic acid, alpha-sulfo naphthalene, β-sulfo group naphthalene, naphthalenedisulfonic acid, alkyl naphthalene sulfonic acid (alkyl is butyl, triisopropyl, di-t-butyl etc.).

On the other hand, as the concrete example of organic carboxyl acid, can enumerate acetic acid, propionic acid, benzoic acid, oxalic acid etc.Further, can also use macromolecule electrolytic anions such as polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, polyvinyl sulfuric acid, poly-Alpha-Methyl sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid in the present invention.These organic sulfonic acids or organic carboxyl acid example only are for example, are not limited thereto.In addition, above-mentioned anionic counter cation can be enumerated H ⁺, Na ⁺, K ⁺The ammonium ion that replaces Deng alkali metal ion or by hydrogen atom or tetramethyl, tetraethyl, the tetrabutyl, tetraphenyl etc. etc., but be not limited thereto.In the above-mentioned oxidant, especially preferably contain the oxidant of trivalent Fe based compound class or stannous chloride system, persulfuric acid alkaline metal salt, ammonium persulfate salt, acids, quinones.

In the polymer composition manufacture method of electroconductive polymer, Gong Cun the anion with dopant functionalities (oxidant go back anion beyond the substance anion) as required can use the electrolytic anion or other electrolytic anions that contain the oxidant anion that produced by above-mentioned oxidant (oxidant go back substance) in the antagonism ion.Specifically for example can enumerate PF ₆ ^-, SbF ₆ ^-, AsF ₆ ^-Halide anions, BF Deng 5B family element ₄ ^-Deng the halide anions of 3B family element, as I ^-(I ₃ ^-), Br ^-, Cl ^-Deng halogen anion, ClO ₄ ^-Deng perhalogeno acid anion, AlCl ₄ ^-, FeCl ₄ ^-, SnCl ₅ ^-Etc. Lewis acid anion or NO ₃ ^-, SO ₄ ^2-The sulfonic acid anions such as naphthalene sulfonic acids that replace Deng the alkyl of inorganic anion, p-methyl benzenesulfonic acid or naphthalene sulfonic acids, carbon number 1～5 (abbreviating C1～5 as), as CF ₃SO ₃ ^-, CH ₃SO ₃ ^-Deng organic sulfonic acid anion or CH ₃COO ^-, C ₆H ₅COO ^-Bronsted acid anion Deng carboxylate anion etc.

In addition, can enumerate equally, the electrolytical anion of macromolecule such as polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, polyvinyl sulfuric acid, poly-Alpha-Methyl sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid etc., but be not limited thereto.But, wherein preferred macromolecular and the low organic sulfonic acid compound of subsystem or the anion of polyphosphoric acid compound of dividing, the sulfoacid compound (neopelex, sodium naphthalene sulfonate etc.) that preferably uses fragrant family is as anionic compound is provided.

In addition, in the organic sulfonic acid anion,, can enumerate and have one or above sulfonic acid anion group (SO in the molecule as more effective dopant ₃ ^-) and the sulfo group naphtoquinone compounds or the rylnthracene sulfonin anion of quinone structure.

As the anionic basic framework of sulfo group quinone of above-mentioned sulfo group naphtoquinone compounds, can enumerate 1,4-benzoquinone, adjacent benzoquinones, 1,2-naphthoquinones, 1,4-naphthoquinones, 2,6-naphthoquinones, 9,10-anthraquinone, 1,4-anthraquinone, 1,2-anthraquinone, 1,4-

Quinone, 5,6- Quinone, 6,12-

Quinone, acenaphthenequinone, acenaphthene quinone, camphorquinone, 2,3-camphane diketone, 9,10-phenanthrenequione, 2,7-pyrene quinone etc.

When electrode (to the utmost point) is solid,, conductive layer can be set thereon in order to make as required electrically contacting of the outside lead that uses (as lead frame etc.) better.

As conductive layer, formation such as the curing of conductive paste, plating, metal evaporation, thermal endurance conductive resin membrane can for example be passed through.The preferred silver of conductive paste paste, copper paste, aluminium paste, carbon paste, nickel paste etc., these can use a kind of or use two kinds or more than.Use two kinds or when above, can mix use, also can make carry out behind the other individual course stacked.After using conductive paste, can be positioned in the air, perhaps heating makes it to solidify.As plating, can enumerate nickel plating, copper plating, silver plating, electroplated aluminum etc.In addition,, can enumerate aluminium, nickel, copper, silver etc. as evaporation metal.

Specifically, for example, lamination carbon paste, silver are stuck with paste the back with material seals such as epoxy resin successively on second electrode, constitute capacitor.These capacitors can also have with columbium monoxide sintered body thermal sintering be one, or at the niobium or the tantalum lead-in wire of welding thereafter.

As the capacitor of the present invention of above-mentioned manufacturing, can by as the dipping of resin mold, resin box, metallicity packing case, resin, laminated film etc. pack capacitor goods as various uses.

In addition, when electrode was liquid, the capacitor that is made of above-mentioned the two poles of the earth and dielectric for example can be, be contained in the jar that electrode is electrically connected in form capacitor.At this moment, the electrode side of columbium monoxide sintered body is arranged to by above-mentioned niobium or tantalum lead-in wire when derive the outside, by the insulation of realization such as insulating properties rubber and jar.

By using the niobium monoxide powder of making according to the embodiment of the present invention of above explanation to make the capacitor sintered body, make capacitor by this sintered body, can access the capacitor that leakage current values is little and reliability is good.

In addition, capacitor of the present invention is compared with existing tantalum capacitor, and is big with respect to the static capacity of volume, can access more small-sized capacitor goods.

Capacitor of the present invention with this specific character can also be as for example being used for the by-pass capacitor in analog circuit and the digital circuit, coupling capacitor, and existing tantalum capacitor more.General this capacitor is used in the electronic circuit more, therefore, if use capacitor of the present invention, will relax the configuration of electronic unit and the restriction of heat radiation, can be contained in than in the now narrower space by the electronic circuit that reliability is high.

Further, if use capacitor of the present invention, can obtain electronic instrument more small-sized than existing goods and that reliability is high, for example, mobile apparatus, tame electrical article, vehicle-mounted instrument, artificial satellite, communicating machines etc. such as computers such as computer, PC card periphery instrument, mobile phone.

The preferred plan that carries out an invention

Below, enumerate embodiment and comparative example is described more specifically the present invention, but the present invention is not limited to these examples.

The electric capacity of the tap density of the niobium monoxide powder in each example, angle of repose, average grain diameter and aperture and capacitor, leakage current values, the apparent ratio of electric capacity and moisture-proof value are measured by the following method.

(1) tap density is measured

Tap density is to use the method for jolt ramming device and determining instrument to measure in the apparent specific gravity determination method of the industrial monohydrate stipulated in JIS (JIS version in 2000) K1201-1 of benchmark.

(2) angle of repose is measured

The angle of repose is to use fluidity determining instrument and the sample size of stipulating among JIS (JIS version in the 2000) Z2504, from hopper lower height 6cm with respect to the horizontal plane niobium monoxide powder is fallen to horizontal plane, the inclined-plane angle with respect to the horizontal plane of horizontal plane is arrived as the angle of repose in the summit of generation circular cone.

(3) particle size determination

(HRA 9320-X100) device that uses マ イ Network ロ ト ラ Star Network company to make is measured particle size distribution with the laser diffraction and scattering method.Particle size values (the D that its cumulative volume % is equivalent to 50 volume % ₅₀μ m) as average grain diameter.

(4) pore size determination

The Poresier 9320 that uses Micro Meritics company to make measures pore-size distribution with mercury penetration method.

In the present invention, obtain maximum from the rate of change of the amount of being pressed into, with aperture shown in the maximum as peak value, with the size of maximum as the relative intensity at peak under this peak value.

(5) condenser capacitance is measured

In room temperature, between the terminal of the sheet of made, connect the LCR analyzer that ヒ ユ one レ Star ト パ Star カ one De company makes, solid measure value that will be when 120Hz is as the electric capacity of the capacitor of sheet processing.

(6) leakage current of capacitor is measured

At room temperature, will between the terminal of the sheet of made, apply current value that the 6.3V direct voltage measures after 1 minute leakage current values as processing capacitor in blocks.

(7) the apparent ratio of the electric capacity of capacitor

Will be in 0.1% phosphate aqueous solution, 1000 minutes sintered body of chemical combination under 80 ℃, 20V condition, the electric capacity of measuring in 30% sulfuric acid is represented with the ratio of the electric capacity after forming with capacitor as 100%.

(8) capacitor moisture-proof value

Under 60 ℃ of 95%RH conditions, place 500 hours off-capacity initial value 110% and 120% number is represented with the capacitor of made.The number of less than 110% is many more, illustrates that the moisture-proof value is good more.

(9) the ESR measured value of capacitor

In room temperature, between the terminal of the sheet of made, connect the LCR analyzer that ヒ ユ one レ Star ト パ Star カ one De company makes, ESR measured value that will be when 100kHz, 1.5VDC, 0.5Vrms. is as the ESR of processing capacitor in blocks.

(10) content of nitrogen, oxygen, sulphur, each element of carbon

Analyze with oxygen nitrogen analysis device or analysis of carbon and sulfur device (two devices are LECO company and make).

(11) metal element content

Analyze with atomic absorption spectrum analysing arrangement, ICP apparatus for analyzing luminosity or ICP quality analysis apparatus (each device is Shimadzu Seisakusho Ltd.'s (strain) and makes).

(12) niobium oxide is formed

Calculate x value when niobium oxide represented with NbOx by obtaining the oxygen element content measured in above-mentioned (10) with respect to the mol ratio of the niobium element content of measuring in above-mentioned (11).

Embodiment 1:

Prepare with the cylindrical shape rustless steel container of tantalum piece liner 5 liters of internal diameter 150mm, the internal volumes of inboard.This container possesses supply that argon gas is arranged and discharge pipe, the supply machine of dusty material, mixer, adjustment machine, heater, cooler.400g magnesium metal flaking is put into cylindrical vessel, be heated to 750 ℃ (reduction temperatures) after filling with argon gas.After keeping this temperature to make the magnesium metal fusion in 15 minutes, the starting mixer.Nb by the about 10g of powder feeding machine input ₂O ₅Powder.Reactor temperature has risen about 30 ℃.After temperature reaches reduction temperature in the question response device, pass through the Nb of the about 10g of powder feeding machine input again ₂O ₅Powder.Carry out this operation repeatedly until adding Nb ₂O ₅The powder total amount reaches till the 350g.After adding end, continue to stir 30 minutes at reduction temperature.Then, reactor is cooled to 10 ℃ or following, stops to inject argon gas.After the decompression, slowly add air and make reactor temperature be no more than 50 ℃.Take out reaction product, with the mixed aqueous solution and the alternately cleaning of ion exchange water of hydrogen peroxide and nitric acid.The niobium monoxide powder that generates consist of NbO _0.98

After this niobium monoxide powder 200g put into niobium system jar, add entry, zirconia ball, pulverized 10 minutes.The average grain diameter of gained niobium monoxide powder is 1.0 μ m.In these slurries, add the polybutyl methacrylate 20g of average grain diameter 1 μ m.Mixed 1 hour with the vibration mixer, the mixture of having removed zirconia ball is put into the taper drier, 1 * 10 ²Carry out vacuumize under Pa, 80 ℃ of conditions.

Then, with this niobium monoxide powder 1 * 10 ^-2Heated 12 hours under Pa, 250～400 ℃ of conditions, decompose and remove polybutyl methacrylate, further 4 * 10 ^-3Sintering is 2 hours under the decompression of Pa, under 1200 ℃ of conditions.Be cooled to product temperature reach 30 ℃ or following after, slowly bubbling air makes product temperature be no more than 50 ℃.Pulverize gained columbium monoxide agglomerate with the roll-type crushed machine, obtain the niobium comminuted powder of average grain diameter 100 μ m.

The value of the physical property (tap density, average grain diameter, angle of repose, BET specific area, aperture peak value) that will measure this niobium monoxide powder is shown in table 1.

The niobium monoxide powder that obtains like this (about 0.1g) is put into tantalum element automatic forming machine (K.K. Seiken makes TAP-2R) hopper, with the niobium line automatic forming of 0.3mm ф, makes the formed body that size is about 0.3cm * 0.18cm * 0.45cm.The outward appearance of this formed body (breach, break, crooked) and the inhomogeneities of quality are shown in table 1.

Then by with this formed body 4 * 10 ^-3The Pa vacuum, under 1400 ℃ of conditions, place and obtained sintered body in 30 minutes.Prepare 100 these sintered bodies, 20V voltage electrolysis chemical combination 200 minutes, form the dielectric oxide-film on the surface with 0.1% phosphate aqueous solution.

Then, the dipping back forms as the manganese dioxide layer to electrode layer on the dielectric oxide-film in 30 minutes operation of 220 ℃ of heating in 60% manganese nitrate aqueous solution repeatedly.Then, lamination carbon-coating, silver are stuck with paste layer successively in the above.Then, be written into and wholely behind the lead frame use epoxy sealing, be made into sheet-type capacitor.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of leakage current values (being designated hereinafter simply as " LC ") are shown in table 1.

Embodiment 2

400g niobium ingot is put into the reaction vessel of SUS304 system, feed 10 hours hydrogen continuously at 400 ℃.After the cooling niobium piece that is hydrogenated being put into the SUS system jar that is placed with zirconia ball pulverized 10 hours.Then, in spike mill, put into slurries and the zirconia ball of the 20 volume % that water makes this hydride,, obtain the pulverizing slurries of hydrogenated niobium 40 ℃ or following case of wet attrition 7 hours, remove zirconia ball after, 1 * 10 ²Dry under Pa, the 50 ℃ of conditions.Then, with gained hydrogenated niobium powder 1 * 10 ^-2Heating made the hydrogenated niobium dehydrogenation in 4 hours under Pa, the 400 ℃ of conditions.Further in the presence of air,, obtain average grain diameter 0 200 ℃ of heating 5 hours.The niobium monoxide powder of 9 μ m.The columbium monoxide that generates consist of NbO _0.88

This niobium monoxide powder 830g and toluene 400g are put into niobium system jar, add the barium monoxide 170g of average grain diameter 1 μ m.Further add zirconia ball, mixed 1 hour with the vibration mixer.The mixture of removing zirconia ball is put into niobium tubbing, 1 * 10 ²Dry under Pa, the 50 ℃ of conditions.

Then, with dried mixture 4 * 10 ^-3Sintering is 3 hours under the decompression of Pa, under 1200 ℃ of conditions.Be cooled to product temperature reach 30 ℃ or following after, pulverize with the roll-type crushed machine and to be mixed with barytic columbium monoxide agglomerate, obtain the barytic columbium monoxide comminuted powder of being mixed with of average grain diameter 95 μ m.

This is mixed with the container that barytic columbium monoxide comminuted powder 500g and ion exchange water 1000g put into polytetrafluoroethylene system, is cooled to 15 ℃ or following.The aqueous solution of 60% nitric acid 600g, 30% hydrogen peroxide 150g, ion exchange water 750g of having prepared to be cooled to 15 ℃ or following mixing separately, when stirring this aqueous solution 1000g, be added drop-wise to and be mixed with in the barytic columbium monoxide comminuted powder aqueous suspension, so that water temperature is no more than 20 ℃.After drip finishing, further continue to stir 1 hour, leave standstill 30 minutes after, decant.Add ion exchange water 2000g, stir after 30 minutes, left standstill 30 minutes, then decant.Repeat this operation 5 times, further the columbium monoxide comminuted powder is put into the post of teflon system, cleaned 4 hours with the ion exchange water that flows.Clean electrical conductivity of water this moment is 0.9 μ S/cm.

With the columbium monoxide comminuted powder of the washing that is through with under reduced pressure, 50 ℃ down dry, obtain about 400g niobium monoxide powder.

Tap density, average grain diameter, angle of repose, BET specific area, the aperture peak value equivalence of this niobium monoxide powder are shown in table 1.

The niobium monoxide powder that obtains like this (about 0.1g) is put into tantalum element automatic forming machine (K.K. Seiken makes TAP-2R) hopper, with the niobium line automatic forming of 0.3mm ф, makes the formed body that size is about 0.3cm * 0.18cm * 0.45cm.The outward appearance of this formed body, the inhomogeneities of quality are shown in table 1.

Then by with this formed body 4 * 10 ^-3Place under the decompression of Pa, under 1400 ℃ of conditions and obtained sintered body in 30 minutes.Prepare 100 these sintered bodies, 20V voltage electrolysis chemical combination 200 minutes, form the dielectric oxide-film on the surface with 0.1% phosphate aqueous solution.

Then,, make it to contact the operation of pyrroles's steam by after repeating to make the dielectric oxide-film and the equivalent mixed liquor of 10% ammonium persulfate aqueous solution and the 0.5% anthraquinone sulfonic acid aqueous solution contacts at least 5 times, form by polypyrrole constitute to electrode (to the utmost point).

Then, in the above, lamination carbon-coating, silver are stuck with paste layer successively.Then, be written into lead frame after, whole use epoxy sealing, be made into sheet-type capacitor.Average (n=100) of the apparent ratio of the electric capacity of this capacitor, the electric capacity that reaches this sheet-type capacitor and LC value is shown in table 1.

Embodiment 3～10:

Use the method identical with embodiment 1, change average grain diameter, the addition of polybutyl methacrylate respectively, or the identical method of use and embodiment 2, change barytic average grain diameter, addition respectively, make niobium monoxide powder, its formed body, sintered body and capacitor.Electric capacity, the LC of outward appearance, quality inhomogeneities and the capacitor of the physical property of these niobium monoxide powders, formed body are shown in table 1.

Embodiment 11～22:

Embodiment 11～14 and 16～18 uses the method identical with embodiment 1, embodiment 15 and 19～22 uses the method identical with embodiment 2, activator replaces polybutyl methacrylate or barium monoxide shown in the use table 1 respectively, makes niobium monoxide powder, formed body and sintered body.Physical property, the outward appearance of formed body, the quality inhomogeneities of niobium monoxide powder are shown in table 1.

Then, by with this formed body 4 * 10 ^-3Place under the decompression of Pa, under 1400 ℃ of conditions and obtained sintered body in 30 minutes.Prepare 100 these sintered bodies, 20V voltage electrolysis chemical combination 200 minutes, form the dielectric oxide-film on the surface with 0.1% phosphate aqueous solution.

Then, be immersed in back taking-up in the aqueous solution (solution 1) that contains ammonium persulfate 25 quality %, 80 ℃ of dryings 30 minutes, the sintered body that then will form dielectric is immersed in and contains 3, take out aqueous isopropanol (solution 2) back of 4-ethylidene dioxy thiophene 18 quality %, places in 60 ℃ of atmosphere gas and carried out oxidation polymerization in 10 minutes.It is immersed in solution 1 once more, further carries out processing same as described above.Repeat 8 times and be immersed in solution 1 to the operation of carrying out oxidation polymerization, cleaned 10 minutes with 50 ℃ of warm water, 100 ℃ of dryings 30 minutes, form by conductive poly (3,4-ethylidene dioxy thiophene) constitute to electrode (electrode).

Then, in the above, lamination carbon-coating, silver are stuck with paste layer successively.Then, be written into lead frame after, whole use epoxy sealing, be made into sheet-type capacitor.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 23:

Obtain the niobium monoxide powder of average grain diameter 0.9 μ m with the method identical with embodiment 1.This columbium monoxide consist of NbO _1.02The 200g niobium monoxide powder is put into aluminium vessel, in nitrogen atmosphere, heated 2 hours at 300 ℃.The nitrogen amount that contains in the gained raw material niobium monoxide powder is 2100 quality ppm.In activator, use barium monoxide, use the method identical to obtain the nitrogenous columbium monoxide comminuted powder of average grain diameter 130 μ m, be made into body and sintered body with embodiment 2.Physical property, the outward appearance of formed body, the quality inhomogeneities of niobium monoxide powder are shown in table 1.Then use the method making sheet-type capacitor identical with embodiment 22.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 24:

Obtain the niobium monoxide powder of average grain diameter 0.9 μ m with the method identical with embodiment 1.This columbium monoxide consist of NbO _1.02Put into the platinum container made after 200g niobium monoxide powder and 5g sulphur powder fully mixed.Behind the argon replaces inside reactor, 250 ℃ of heating 2 hours.The sulfur content that contains in the gained raw material niobium monoxide powder is 2500 quality ppm.Use barium monoxide as activator, use the method identical to obtain the sulfur-bearing columbium monoxide comminuted powder of average grain diameter 200 μ m, be made into body and sintered body with embodiment 2.Physical property, the outward appearance of formed body, the quality inhomogeneities of niobium monoxide powder are shown in table 1.Then use the method identical to make sheet-type capacitor with embodiment 22.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 25:

Use boron powder to obtain the boracic niobium monoxide powder with the method identical with embodiment 24.The boron amount that contains in the gained raw material niobium monoxide powder is 1200 quality ppm.Use barium monoxide as activator, use the method identical to obtain the boracic columbium monoxide comminuted powder of average grain diameter 80 μ m, be made into body and sintered body with embodiment 2.Physical property, the outward appearance of formed body, the quality inhomogeneities of niobium monoxide powder are shown in table 1.Then use the method identical to make sheet-type capacitor with embodiment 22.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 26～29:

Use the method identical with embodiment 2, initiation material uses hydrogenated niobium-neodymium alloy powder, uses hydrogenated niobium-antimony alloy powder, uses hydrogenated niobium-ytterbium-boron alloy powder, uses hydrogenated niobium-yttrium-Zinc alloy powder at embodiment 29 at embodiment 28 at embodiment 27 at embodiment 26, obtains niobium monoxide powder.Composition separately is, is NbO at embodiment 26 _0.94, be NbO at embodiment 27 _0.96, be NbO at embodiment 28 _1.12, be NbO at embodiment 29 _1.08The niobium monoxide powder that contains other elements.Further use activator and the method identical, obtain the niobium monoxide powder that contains other elements of average grain diameter 70～250 μ m, be made into body and sintered body with embodiment 2.Physical property, the outward appearance of formed body, the quality inhomogeneities of niobium monoxide powder are shown in table 1.Then use the method identical to make sheet-type capacitor with embodiment 2.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Comparative example 1～3:

The cylindrical shape rustless steel container that internal diameter 150mm, the internal volume of preparation usefulness tantalum piece liner inboard is 5 liters.This container possesses supply that argon gas is arranged and discharge pipe, the supply machine of dusty material, mixer, adjustment machine, heater, cooler.400g magnesium metal flaking is put into cylindrical vessel, be heated to 750 ℃ (reduction temperatures) behind the injection argon gas.After this temperature keeps making the magnesium metal fusion in 15 minutes, the starting mixer.Nb by the about 10g of powder feeding machine input ₂O ₅Powder (using average grain diameter is the powder of 2～10 μ m).Reactor temperature rises to about 30 ℃.After temperature reaches reduction temperature in the question response device, pass through the Nb of the about 10g of powder feeding machine input again ₂O ₅Powder.Carry out this operation repeatedly until the interpolation Nb that finishes ₂O ₅Powder is all measured 350g.After adding end, continue to stir 30 minutes at reduction temperature.Then, cooling reactor to 10 ℃ or following stops argon gas and injects.After the decompression, slowly bubbling air makes reactor temperature be no more than 50 ℃.Take out reaction product, with the mixed aqueous solution and the alternately cleaning of ion exchange water of hydrogen peroxide and nitric acid.The columbium monoxide that generates consist of NbO _1.01, average grain diameter is 1.3～7 μ m.

Physical propertys such as the tap density of this niobium monoxide powder, average grain diameter, angle of repose, BET specific area, average pore size are shown in table 1.

The niobium monoxide powder (about 0.1g) that obtains is like this put into tantalum element automatic forming machine (K.K. Seiken make TAP-2R) hopper, carry out the automatic forming test with the niobium line of 0.3mm ф, the result can't be shaped.

Comparative example 4～9:

Change the barytic addition of average grain diameter 1 μ m, use the method identical to obtain the niobium monoxide powder of tap density 0.2～0.4g/ml and 2.6～3.3g/ml with embodiment 2.Its physical property is shown in table 1.

The niobium monoxide powder that obtains like this (about 0.1g) is put into tantalum element automatic forming machine (K.K. Seiken makes TAP-2R) hopper, with the niobium line automatic forming of 0.3mm ф, makes the formed body that size is about 0.3cm * 0.18cm * 0.45cm.The outward appearance of this formed body, the inhomogeneities of quality are shown in table 1.

Then by with this formed body 4 * 10 ^-3Place under the vacuum of Pa, under 1400 ℃ of conditions and obtained sintered body in 30 minutes.Prepare 100 these sintered bodies, 20V voltage electrolysis chemical combination 200 minutes, form the dielectric oxide-film on the surface with 0.1% phosphate aqueous solution.

Then,, make the operation of its contact pyrroles steam by after repeating to make the dielectric oxide-film and the equivalent mixed liquor of 10% ammonium persulfate aqueous solution and the 0.5% anthraquinone sulfonic acid aqueous solution contacts at least 5 times, form by polypyrrole constitute to electrode (to the utmost point).

Then, in the above, lamination carbon-coating, silver are stuck with paste layer successively.Then, be written into lead frame after, whole use epoxy sealing, be made into sheet-type capacitor.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 30:

Obtain niobium monoxide powder with the method identical with embodiment 2.The average grain diameter of this niobium monoxide powder is 0.6 μ m, and it consists of NbO _0.95Add absolute methanol to concentration of slurry and reach 60 quality % and fully suspension.These slurries are joined in the niobium system jar, be respectively the average grain diameter 1.4 μ m of 15 quality % and 10 quality % and the barium monoxide of 23 μ m with respect to columbium monoxide in interpolation.Further add zirconia ball, mixed 1 hour with the vibration mixer.The mixture of removing zirconia ball is put into niobium tubbing, 1 * 10 ²Dry under Pa, the 50 ℃ of conditions.

With obtaining being mixed with barytic columbium monoxide agglomerate and columbium monoxide comminuted powder with embodiment 2 identical operations.

In 1000g is cooled to 15 ℃ or following ion exchange water, add 500g while stirring and should be mixed with barytic columbium monoxide comminuted powder, make water temperature be no more than 20 ℃.Add to finish the back and continue to stir 1 hour, leave standstill 30 minutes after, decant.Add ion exchange water 2000g, stir and left standstill 30 minutes after 30 minutes, then decant.Repeat this operation 5 times, further the columbium monoxide comminuted powder is put into teflon system post, cleaned 4 hours with the ion exchange water that flows.Clean electrical conductivity of water this moment is 0.5 μ S/cm.

With the columbium monoxide comminuted powder of the washing that is through with under reduced pressure, 50 ℃ down dry, obtain about 350g niobium monoxide powder.

Tap density, average grain diameter, angle of repose, BET specific area, the average pore size equivalence of this niobium monoxide powder are shown in table 1.

With being made into body, sintered body with embodiment 2 identical operations.The outward appearance of this formed body, the inhomogeneities of quality are shown in table 1.

Further, use form dielectric film with embodiment 2 identical operations after, form electrode, and lamination carbon-coating, silver are stuck with paste layer.Then, be written into lead frame after, whole use epoxy sealing, be made into sheet-type capacitor.The electric capacity of the apparent ratio of the electric capacity of this capacitor and this sheet-type capacitor and average (n=100) of LC value are shown in table 1.

Embodiment 31～37:

With the method identical with embodiment 30, change add activator kind, mix the average grain diameter and the addition of two kinds, obtain the columbium monoxide comminuted powder of hybrid activator.The solvent of stripping activator is selected from water, acid, alkali, contains the solution of ion exchange resin, ammonium nitrate solution, contains the solution of ethylenediamine tetra-acetic acid, uses the method stripping activator identical with embodiment 30, obtains niobium monoxide powder.Its physical property is shown in table 1.

Further use the method identical to be made into body, sintered body, and make sheet-type capacitor with embodiment 30.With the outward appearance of formed body, the inhomogeneities of quality, the electric capacity of capacitor and LC on average are shown in table 1.

Embodiment 38～40:

With the method identical with embodiment 30, initiation material uses hydrogenated niobium-ashbury metal powder, uses niobium-tungsten alloy powder, uses niobium-tantalum alloy powder at embodiment 40 at embodiment 39 at embodiment 38, obtains containing the niobium monoxide powder of other compositions respectively.Its physical property is shown in table 1.

Further use the method identical to be made into body, sintered body, and make sheet-type capacitor with embodiment 30.With the outward appearance of formed body, the inhomogeneities of quality, the electric capacity of capacitor and LC on average are shown in table 1.

Embodiment 41～51:

Use is at the niobium monoxide powder that embodiment 30～40 makes, and uses the method identical with embodiment 2 to make the columbium monoxide sintered body.The pore-size distribution of this sintered body is shown in table 2.

Embodiment 52～62:

Make 100 columbium monoxide sintered bodies of in embodiment 41～51, making respectively, with each sintered body in 0.1% phosphate aqueous solution 80 ℃, 20V chemical combination 1000 minutes, form the dielectric oxide-film on the sintered body surface.Repeat on reacted sintered body, to adhere to ammonium persulfate and anthraquinone sulfonic acid then, then carry out operation by the gas-phase polymerization of pyrroles's steam, impregnated cathode agent polypyrrole (below, be called negative electrode agent according to the A method) after, lamination carbon paste, silver are stuck with paste successively, and seal with epoxy resin, be made into sheet-type capacitor.Apparent ratio of the electric capacity of made capacitor and ESR are shown in table 3.

Embodiment 63～68:

Obtain the columbium monoxide predecessor of average grain diameter 0.8 μ m with the method identical with embodiment 2.Sintering, pulverize this predecessor and obtain columbium monoxide granulation powder.This granulation powder of 0.1g is put into mould (4.0mm * 3.5mm * 1.8mm), with as shown in table 4 the increasing the weight of of tantalum element automatic forming machine (K.K. Seiken makes TAP-2R), be made into body with the niobium line of the long 10mm for preparing separately, thick 0.3mm.Then obtained required sintered body in 30 minutes at 1400 ℃ of sintering.By regulating increasing the weight of of forming machine, make sintered body with pore-size distribution shown in the table 4.The size of the sintered body of embodiment 63, specific area, CV value are followed successively by 24.7mm respectively ³, 1.1m ²/ g, 86000 μ FV/g, every numerical value of other examples also embodiment 63 ± 2% in.

Embodiment 69～71:

Except the average grain diameter that makes predecessor by the classification predecessor 0.5 μ m, with embodiment 63～65 identical sintered bodies that obtain.The size of the sintered body of embodiment 69, specific area, CV value are followed successively by 24.9mm respectively ³, 1.5m ²/ g, 126000 μ FV/g, every numerical value of other examples also embodiment 69 ± 1% in.The pore-size distribution of the sintered body made is shown in table 4.

Embodiment 72:

Except use with the embodiment 4 identical niobium monoxide powders replacement granulation powder that obtain, with the embodiment 68 identical sintered bodies that obtain.The size of the sintered body of embodiment 72, specific area, CV value are followed successively by 24.8mm respectively ³, 1.2m ²/ g, 79000 μ FV/g.The pore-size distribution of the sintered body made is shown in table 4.

Comparative example 10～12:

Except using the niobium monoxide powder that obtains with the magnesium-reduced niobium pentaoxide the columbium monoxide granulation powder that the niobium monoxide powder that 1200 ℃ of heat treatments obtain replaces using among the embodiment 63～65, with embodiment 63～65 identical sintered bodies that obtain.Size, specific area, the CV value of the sintered body of the comparative example 10 made are followed successively by 24.3mm respectively ³, 0.8m ²/ g, 85000 μ FV/g, every numerical value of other comparative examples also comparative example 10 ± 2% in.The pore-size distribution of the sintered body made is shown in table 4.

Embodiment 73:

Be used among embodiment 30 and the embodiment 63～72 method of making sintered body, make each 60 of identical sintered bodies, make each sintered body in 0.1% phosphate aqueous solution 80 ℃, 20V chemical combination 1000 minutes, at sintered body surface formation dielectric oxide-film.Should be divided into per 30 one group respectively by reacted sintered body then, make it to flood the polypyrrole negative electrode agent according to the A method of record among the embodiment 52～62 for each 30 group sintered bodies, or the negative electrode agent that constitutes of the mixture by brown lead oxide and lead sulfate of the operation of repeated impregnations lead acetate and ammonium persulfate mixed liquor (brown lead oxide is 98 quality %) (below be called according to the B method negative electrode agent), lamination carbon paste, silver are stuck with paste successively, and seal with epoxy resin, be made into sheet-type capacitor.Apparent ratio of the electric capacity of made capacitor and moisture-proof value are shown in table 5.

Comparative example 13:

Be used in the comparative example 9～12 method of making sintered body, make each 60 of identical sintered bodies, make each sintered body in 0.1% phosphate aqueous solution 80 ℃, 20V chemical combination 1000 minutes, at sintered body surface formation dielectric oxide-film.Sintered body behind this chemical combination is divided into separately 30 every group then, after the polypyrrole negative electrode agent according to the A method for record among each 30 the group sintered body dipping embodiment 52～62, lamination carbon paste, silver are stuck with paste successively, and seal with epoxy resin, are made into sheet-type capacitor.Apparent ratio of the electric capacity of made capacitor and moisture-proof value are shown in table 5.

Comparative example 14～17:

Make 100 columbium monoxide sintered bodies of in comparative example 9～12, making respectively, make each sintered body in 0.1% phosphate aqueous solution 80 ℃, 20V chemical combination 1000 minutes, form the dielectric oxide-film on the sintered body surface.After then will this reacted sintered body being immersed in the polypyrrole negative electrode agent according to the A method of record among the embodiment 52～62, lamination carbon paste, silver are stuck with paste successively, and seal with epoxy resin, are made into sheet-type capacitor.Apparent ESR when is shown in table 3 with the electric capacity of made capacitor.

Table 2

Table 3

Table 4

Table 5

Utilizability on the industry

By formula: NbOx (x=0.8～1.2) expression, tap density is 0.5～2.5g/ml, and average grain diameter is 10～1000 μ m, and the angle of repose is 10～60 degree, and the BET specific area is 0.5～40m²/ g Capacitor of the present invention with the good fluidity of niobium monoxide powder and can progressive forming, by will The pore-size distribution that this niobium monoxide powder of sintering obtains is for to have the hole in 0.01 μ m～500 mu m ranges The footpath peak value, the niobium sintered body that preferably has a plurality of apertures peak value is used for electrode for capacitors, and can produce can Obtain that the apparent ratio of high capacitance, equivalent series resistance (ESR) are low, leakage current characteristic, moisture-proof be good Good capacitor.

Claims (65)

1. a capacitor niobium monoxide powder is represented by formula: NbOx, and wherein x=0.8～1.2, and tap density are 0.5～2.5g/ml.

2. as the niobium monoxide powder of claim 1 record, wherein further contain at least a other elements that are selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, selenium and the tellurium.

3. as the niobium monoxide powder of claim 2 record, wherein, other elements and niobium form composite oxides.

4. as the niobium monoxide powder of claim 2 or 3 records, wherein, the content of other elements is 50～200,000ppm.

5. as the niobium monoxide powder of any record in the claim 1 to 3, its average grain diameter is 10～1000 μ m.

6. as the niobium monoxide powder of any record in the claim 1 to 3, its angle of repose is 10～60 degree.

7. as the niobium monoxide powder of any record in the claim 1 to 3, its BET specific area is 0.5～40m ²/ g.

8. as the niobium monoxide powder of claim 1 record, has the pore-size distribution that in 0.01 μ m～500 mu m ranges, has the aperture peak value.

9. as the niobium monoxide powder of claim 8 record, wherein, described pore-size distribution has a plurality of apertures peak value.

10. as the niobium monoxide powders of claim 8 or 9 records, wherein, being in all in 0.5 μ m～100 mu m ranges of aperture peak value.

11. sintered body that has used the niobium monoxide powder of any record in the claim 1 to 10.

12. the sintered body as claim 11 record has the pore-size distribution that has the aperture peak value in 0.01 μ m～500 mu m ranges.

13. as the sintered body of claim 11 record, it is characterized in that: this sintered body is an electrode for capacitors columbium monoxide sintered body, and the pore-size distribution of this columbium monoxide sintered body has a plurality of apertures peak value.

14. as the sintered body of any record in the claim 11 to 13, its pore-size distribution is made of two aperture peak values.

15. as the sintered body of claim 13 record, in its a plurality of apertures peak value, the peak value at two peaks of relative intensity maximum is in respectively in the scope of 0.2～0.7 μ m and 0.7～3 μ m.

16. as the sintered body of claim 13 record, in its a plurality of apertures peak value, the peakedness ratio relative intensity at the peak of the relative intensity maximum secondly peak value at big peak is in major diameter one side.

17. as the sintered body of any record in the claim 11～13,15～16, this sintered body comprises that the pore void volume has 10mm ³Or above volume.

18. as the sintered body of any record in the claim 11～13,15～16, this sintered body has 0.2～7m ²The specific area of/g.

19. as the sintered body of any record in the claim 11～13,15～16, the part of this sintered body is by nitrogenize.

20. as the sintered body of any record in the claim 11～13,15～16, this sintered body is the sintered body that is obtained by the columbium monoxide formed body that can give the sintered body of the CV value with 40000～200000 μ FV/g when 1400 ℃ of sintering.

21. a capacitor is characterized in that: by with the sintered body of any record in the claim 11 to 20 as a lateral electrode, and constitute between it and to the dielectric between the electrode.

22. as the capacitor of claim 21 record, wherein, the principal component of dielectric is a niobium pentaoxide.

23., wherein, be at least a material that is selected from electrolyte, organic semiconductor and the inorganic semiconductor to electrode as the capacitor of claim 21 record.

24. capacitor as claim 23 record, wherein, to electrode is organic semiconductor, and this organic semiconductor is to be selected from the organic semiconductor that is made of the benzopyrrole quinoline tetramer and chloranil, organic semiconductor that four sulphur aphthacenes are principal component, organic semiconductor that four cyano quinone bismethane is principal component and at least a material in the electroconductive polymer.

25. as the capacitor of claim 24 record, wherein, electroconductive polymer is at least a material that is selected from polypyrrole, polythiophene, polyaniline and the substitutive derivative thereof.

26. as the capacitor of claim 24 record, wherein, electroconductive polymer is the electroconductive polymer of dopant of having mixed in the polymer that contains by the repetitive shown in following general formula (1) or the general formula (2),

In the formula, R ¹～R ⁴Expression independently of one another is selected from saturated or unsaturated alkyl, alkoxyl or the alkyl ester group of straight or branched of hydrogen atom, carbon number 1～10 or halogen atom, nitro, cyano group, primary, the second month in a season or uncle's amino, CF ₃Univalent perssad in the phenyl of base, phenyl and replacement; R ¹And R ²And R ³And R ⁴Also combination at an arbitrary position mutually of hydrocarbon chain, form the divalence chain, this divalence chain forms the circulus of at least one or above 3～7 yuan of ring fillings or unsaturated hydrocarbons with the carbon atom that is replaced by this group; Above-mentioned ring-type marriage chain can contain the key of carbonyl, ether, ester, acid amides, thioether, sulfinyl, sulfonyl, imino group at an arbitrary position.X represents oxygen, sulphur or nitrogen-atoms, R ⁵Only exist during for nitrogen-atoms at X, expression is selected from the saturated or unsaturated alkyl of the straight or branched of hydrogen atom or carbon number 1～10 independently.

27. as the capacitor of claim 26 record, wherein, electroconductive polymer is the electroconductive polymer that contains repetitive shown in the following general formula (3),

In the formula, R ⁶And R ⁷Expression independently of one another is selected from the saturated or unsaturated alkyl or the combination at an arbitrary position mutually of this alkyl of straight or branched of hydrogen atom, carbon number 1～6, and expression forms the substituting group of the circulus of at least one or above 5～7 yuan of ring filling hydrocarbon that contain two oxygen elements; And can contain in above-mentioned circulus can substituted ethenylidene key, can substituted phenylene structure.

28. as the capacitor of claim 27 record, wherein, electroconductive polymer is at the electroconductive polymer that gathers the dopant that mixed in (3,4-ethylidene dioxy thiophene).

29., wherein, be to constitute by the material that has a layer structure in a part at least to electrode as the capacitor of claim 21 record.

30., wherein, be to contain the material of organic sulfonic acid anion as dopant to electrode as the capacitor of claim 21 record.

31. the manufacture method of the niobium monoxide powder of any record in the claim 1 to 10 is characterized in that: in the manufacture method of niobium monoxide powder, columbium monoxide or columbium monoxide compound are carried out activation processing.

32. as the manufacture method of the niobium monoxide powder of claim 31 record, it is characterized in that: the activation processing of columbium monoxide or columbium monoxide compound is to be undertaken by at least a operation that is selected from sintering circuit and the pulverizing process.

33. the manufacture method of niobium monoxide powders as claim 31 or 32 records is characterized in that: the activation processing of columbium monoxide or columbium monoxide compound is to use the mixture that contains columbium monoxide or columbium monoxide compound and activator to carry out.

34. the manufacture method as the niobium monoxide powder of any record in the claim 31 to 32 is characterized in that: being activated the columbium monoxide of processing or the average grain diameter of columbium monoxide compound is 0.01 μ m～10 μ m.

35. manufacture method as the niobium monoxide powder of any record in the claim 31 to 32, wherein, columbium monoxide or columbium monoxide compound are to contain 50～200, and 000ppm is selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, plumbous, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, the material of at least a element in selenium and the tellurium.

36. as the manufacture method of the niobium monoxide powder of claim 35 record, wherein, other elements that columbium monoxide or columbium monoxide compound contain and niobium formation composite oxides.

37. as the manufacture method of the niobium monoxide powder of claim 33 record, wherein, the mixture that contains columbium monoxide or columbium monoxide compound and activator is to use solvent mixed.

38. as the manufacture method of the niobium monoxide powder of claim 37 record, wherein, solvent is at least a solvent that is selected from water, alcohols, ethers, cellosolve class, ketone, aliphatic hydrocarbon, aromatic hydrocarbon based, the halogenated hydrocarbons.

39. as the manufacture method of the niobium monoxide powder of claim 33 record, wherein, activator uses 1～40 quality % with respect to the total amount of columbium monoxide or columbium monoxide compound.

40. as the manufacture method of the niobium monoxide powder of claim 33 record, wherein, the average grain diameter of activator is 0.01 μ m～500 μ m.

41. as the manufacture method of the niobium monoxide powder of claim 33 record, wherein, the particle diameter peak value of activator is a plurality of.

42. as the manufacture method of the niobium monoxide powder of claim 33 record, wherein, activator is at 2000 ℃ or the following material that can be removed as gas.

43. manufacture method as the niobium monoxide powder of claim 42 record, wherein, activator is to be selected from naphthalene, anthracene, quinone, camphor, polyacrylic acid, polyacrylate, polyacrylamide, polymethylacrylic acid, polymethacrylates, PMAm, polyvinyl alcohol, NH ₄Cl, ZnO, WO ₂, SnO ₂, MnO ₃In at least a.

44. manufacture method as the niobium monoxide powder of claim 33 record, wherein, activator is to be selected from water-soluble substances, organic solvent solable matter, acid solution solable matter, alkaline solution solable matter, to form the material that becomes these solable matters behind the complex compound and at 2000 ℃ or followingly can become at least a in these solable matters.

45. manufacture method as the niobium monoxide powder of claim 44 record, wherein, activator is the compound that is selected from metal and carbonic acid, sulfuric acid, sulfurous acid, halogen, perhalogeno acid, hypohalogenous acids, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, perhaps at least a in metal, metal hydroxides and the metal oxide.

46. as the manufacture method of the niobium monoxide powder of claim 45 record, wherein, activator is to be selected from least a in metal carbonic acid thing, metal bicarbonate thing, metal hydroxides and the metal oxide.

47. manufacture method as the niobium monoxide powder of claim 46 record, wherein, activator is to be selected from least a in metal carbonic acid thing, metal bicarbonate thing, metal hydroxides and the metal oxide, and has the fusing point higher than the temperature in the sintering circuit.

48. manufacture method as the niobium monoxide powder of claim 44 record, wherein, activator is to be selected from lithium, sodium, potassium, rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, plumbous, arsenic, antimony, bismuth, selenium, tellurium, polonium, and at least a in their compound.

49. as the manufacture method of the niobium monoxide powder of any record in the claim 31 to 32, wherein, activation processing is the processing of removing activator by heating and/or decompression before sintering circuit or when sintering circuit.

50. as the manufacture method of the niobium monoxide powder of any record in the claim 31 to 32, wherein, activation processing is after sintering circuit, in the pulverizing process or behind the pulverizing process, makes sinter or crushed material solvent contact remove the processing of activator composition.

51. as the manufacture method of the niobium monoxide powder of claim 50 record, wherein, solvent is to be selected from water, organic solvent, acid solution, alkaline solution and to contain at least a in the solution of the part that forms soluble complexes.

52. as the manufacture method of the niobium monoxide powder of claim 51 record, wherein, acid solution is at least a solution that is selected from nitric acid, sulfuric acid, hydrofluoric acid and the hydrochloric acid.

53. as the manufacture method of the niobium monoxide powder of claim 51 record, wherein, alkaline solution contains and is selected from least a in alkali-metal hydroxide and the ammonia.

54. as the manufacture method of the niobium monoxide powder of claim 51 record, wherein, part is to be selected from least a in ammonia, glycine and the ethylenediamine tetra-acetic acid.

55. the manufacture method of a nitrogenous niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the claim 1 to 10 is handled with at least a method that is selected from bath nitriding, ionic nitriding and the gas nitriding method.

56. the manufacture method of a carbon containing niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the claim 1 to 10 is handled with at least a method that is selected from solid phase carbonization and the liquid carbonization method.

57. the manufacture method of a boracic niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the claim 1 to 10 is handled with at least a method that is selected from gas boronation and the solid phase boronation method.

58. the manufacture method of a sulfur-bearing niobium monoxide powder is characterized in that: the niobium monoxide powder of any record in the claim 1 to 10 is handled with at least a method that is selected from gas cure, ion sulfuration and the solid phase vulcanizing method.

59. a niobium monoxide powder, it is that manufacture method by any record in the claim 31 to 58 obtains.

60. the manufacture method of a columbium monoxide sintered body is characterized in that: the niobium monoxide powder that uses any record in claim 1 to 10 and the claim 59.

61. the manufacture method of a capacitor, this method is as a lateral electrode with the columbium monoxide sintered body, contain the dielectric that is formed at this sintered body surface and be arranged at manufacture method on the above-mentioned dielectric, it is characterized in that: the sintered body that the niobium monoxide powder of any record obtains in columbium monoxide sintered body claim 1 to 10 that has been sintering and the claim 59 capacitor of electrode.

62. as the manufacture method of the capacitor of claim 61 record, wherein, dielectric forms by electrolytic oxidation.

63. the manufacture method of a capacitor, this method is as a lateral electrode with the columbium monoxide sintered body, contain the dielectric that is formed at this sintered body surface and be arranged at the manufacture method to the capacitor of electrode on the above-mentioned dielectric, it is characterized in that: the columbium monoxide sintered body is the columbium monoxide sintered body of any record in the claim 11 to 20.

64. an electronic circuit, this circuit has used the capacitor of any record in the claim 21 to 30.

65. an electronic instrument, this instrument has used the capacitor of any record in the claim 21 to 30.