CN103219156B - Capacitor electrode, capacitor, manufacturing method thereof, electronic circuit and electronic device - Google Patents

Abstract

The present invention provides: (1) a capacitor electrode comprising niobium sintered body, wherein a plurality of pore diameter peak tops are in the pore distribution of the niobium sintered body; (2) a capacitor which comprises one electrode using the capacitor electrode, a counter electrode and dielectric material therebetween; (3) manufacturing method of the capacitor; and (4) an electronic circuit and electronic device using the above capacitor.

Description

Electrode for capacitors, capacitor and its production method, electronic circuit and electronic machine

It is on May 14th, 2002, Application No. 02801689.0, entitled " niobium powder, niobium sintered body the applying date that the application is With the capacitor using the sintered body " patent application and the applying date be May 14, Application No. in 2002 The patent of the 201010166871.2nd, entitled " electrode for capacitors, capacitor and its production method, electronic circuit and electronic machine " The divisional application of application.

Cross reference to related applications

This application is the application of the regulation based on 35U.S.C. 111 (a) sections, and it is according to 35U.S.C. 119 (e) (1) The regulation of section, it is desirable to the U.S. Provisional Application No.60/ that the regulation according to 35U.S.C.111 (b) is proposed in May 21 calendar year 2001 The rights and interests of 291,925 and the No.60/331,200 proposed in the November 9 calendar year 2001 applying date.

Technical field

The present invention relates to niobium powder and its sintered body, it can be stably produced with unit mass high capacitance, good The capacitor of leak current characteristic and excellent moisture-proof, and also be directed to use with niobium powder and sintered body capacitor and niobium powder, The manufacture method of sintered body and capacitor.

Background technology

There is small size and high capacitance for the capacitor requirement in electronic machine such as portable phone and PC. In these capacitors, tantalum capacitor is preferably as relative to its size, capacitance is big and performance is good.

Additionally, in recent years, it is desirable to which electronic device is operated under low-voltage and altofrequency, and with low noise, and for Solid electrolyte capacitators, also require relatively low equivalent parallel resistance (ESR).

In this tantalum capacitor, the sintered body of tantalum powder is typically used for anode part.By this powder forming, then Sintering, so that the powder integration and making the electrode for being referred to as sintered body.By electricity each other inside this sintered body Structure with the powder particle being mechanically linked forms 3 D complex, in the sintered body surface on internal void surface is included, is formed Dielectric film layers, impregnate as the material to electrode, so as to prepare a kind of capacitor.As long as Dielectric film layers are uniformly incorporated to institute The inner surface or outer surface of sintered body are stated, the capacitance of manufactured capacitor is just depended primarily on to electrode material on microcosmic With the contact condition of Dielectric film layers.

In order to improve the capacitance of tantalum capacitor, it is necessary to which the quality or use for improving sintered body is increased by broken tantalum powder The big sintered body of surface area.

The method for improving Sintered Quality necessarily refers to the expansion of capacitor shape, and can not meet the requirement of miniaturization. On the other hand, in broken tantalum powder so that in the method for increasing specific surface area, the aperture of tantalum sintered object reduces or in sintering stage envelope The hole for closing increases, as a result, the dipping of negative electrode reagent becomes difficult in subsequent step.

For example it is assumed that when using phosphate aqueous solution as to electrode material, contact of the solution with Dielectric film layers State be completely, and capacitance now it is apparent than (also referred to as negative electrode reagent-impregnated ratio) be 100%, using have height Viscosity to electrode material, particularly Solid electrode materials in the case of, the 100% apparent ratio of capacitance can hardly be obtained.It is special Not, when the particle mean size of tantalum powder is little or by tantalum powder manufacture sintered body there is big shape when, difficulty increase and Under extreme case, the apparent ratio of capacitance is not even likely to be breached 50%.With the apparent ratio of such low-voltage capacity, manufactured electricity Container can not possibly have sufficiently high moisture-proof.

In the case where the tantalum powder of production tantalum sintered object has small-bore, it causes the small-bore of tantalum sintered object and low substantially The apparent ratio of capacitance.Therefore, the irreducible problems of ESR are produced.

As one of measure for solving these problems, it may be considered that using sintered body as the capacitor of an electrode, be somebody's turn to do Sintered body is produced using the dielectric material for being more than tantalum with dielectric constant, and provides the apparent ratio of high-capacitance.

As this kind of electrode material that can industrially supply, it is known that the dielectric constant of niobium is more than tantalum, and with big Storage capacity.

JP-A-55-157226 (term " JP-A " used herein refers to " unexamined publication Japanese patent application ") is disclosed A kind of sintering device for producing capacitor, wherein, the valve action metal powder of the reunion that granularity is 2.0 microns or less is added Pressing formation, then sinters, and formed thereby and sintering base substrate is cut into into tiny piece, and conductor part is linked with it, and again Sinter these.But, the details of manufacture method and the property of niobium capacitor are not described in the patent is disclosed.

United States Patent (USP) 4,084,965 discloses the capacitor of the sintered body using the niobium powder that particle mean size is 5.1 microns, institute State niobium powder to obtain by hydrogenating and crushing niobium ingot.But, disclosed capacitor has gross leak electric current (hereinafter sometimes simply referred to as " LC ") value, and the practical use with very little.

JP-A-10-242004 (WO98/38660) discloses a kind of partial nitridation niobium powder and therefore improves the technology of LC values.

For the niobium powder of capacitor tap density be niobium powder shaping operation key factor.The tap density of traditional niobium powder It is 2.5g/ml or bigger, concrete about 4g/ml, this is inadequate for shaping.

That is, if shaping and sintering such niobium powder to prepare sintered body, niobium powder is indigently from the hopper stream of forming machine In moving metal die, and the niobium powder of the constant basis that is difficult to weigh and it is set to flow in metal die.As a result, it is produced The dimensionally stable of problem, such as molded article is not enough, and the intensity of molded article and sintered body is not enough, and Jing often productions are with inferior The capacitor of LC.If using can also process the special former with inferior mobility, shaping cost too increases, and And this is unpractical.

So, the conventionally known niobium powder for capacitor has the powder can not completely adapt to progressive forming and capacitor The low problem of productivity ratio.

Disclosure of the invention

It is an object of the invention to provide the capacitor that a kind of unit mass capacitance is big, leakage current is little and moisture-proof is high； A kind of electrode material that can serve as the capacitor and it is obtained in that the sintered body of the apparent ratio of high-capacitance；One kind is used as the sintering The material of body preferably, in shaping operation shows good fluidity, promotion progressive forming and energy steady production capacitor Niobium powder；With the manufacture method of the capacitor, the sintered body and the niobium powder.

As the widely studied result for solving the above problems, it has been found by the present inventors that work as that there is specific pore size distribution, It is preferred that when having the niobium powder of multiple aperture peaks in pore-size distribution for electrode for capacitors, it is possible to obtain the apparent ratio of high-capacitance, And the capacitor that leakage current is little and moisture-proof is good can be produced.The present inventors have additionally discovered that, preferably with 0.5-2.5g/ml's Tap density, more preferably particle mean size are 10～1,000 micron of niobium powder, show good mobility, can be continuous Shaping and be preferred as the material of above-mentioned sintered body, when using the niobium powder, can stably produce leakage current little Capacitor.It has been found by the present inventors that it is further preferred that using wide by pore size distribution range and multiple aperture peaks are all 0.5 micron Or the capacitor as electrode of the niobium sintered body of bigger niobium powder production, can obtain simultaneously high-capacitance it is apparent than and it is low ESR.Based on these inventions, the present invention is completed.

It is more particularly related to following niobium powder, niobium sintered body and the capacitor using it, and it is related to niobium The manufacture method of powder, niobium sintered body and capacitor.

(1) a kind of niobium powder for capacitor, is 0.5～2.5g/ml with tap density.

(2) the niobium powder as described in above-mentioned 1, wherein, particle mean size is 10～1,000 micron.

(3) the niobium powder as described in above-mentioned 1 or 2, wherein, angle of repose is 10 °～60 °.

(4) as above-mentioned 1～3 any one described in niobium powder, wherein, BET specific surface area be 0.5～40m²/g。

(5) as above-mentioned 1～4 any one described in niobium powder, with aperture peak in 0.01～500 micrometer range Pore-size distribution.

(6) the niobium powder as described in above-mentioned 5, wherein, pore-size distribution has multiple aperture peaks.

(7) the niobium powder as described in above-mentioned 5 or 6, wherein, any one of aperture peak is in 0.5～100 micrometer range.

(8) as above-mentioned 1～7 any one described in niobium powder, wherein, selected from least one of nitrogen, carbon, boron and element sulphur The content of element is 200,000 mass ppm or less.

(9) a kind of sintered body, it uses the niobium powder described in any one such as above-mentioned 1～8.

(10) sintered body as described in above-mentioned 9, it has pore-size distribution of the aperture peak at 0.01～500 micron.

(11) a kind of niobium sintered body for electrode for capacitors, wherein, the pore-size distribution of niobium sintered body has multiple apertures Peak value.

(12) niobium sintered body as described in above-mentioned 11, wherein, pore-size distribution has two aperture peaks.

(13) niobium sintered body as described in above-mentioned 11 or 12, wherein, it is relatively strong with highest in multiple aperture peaks The peak value at two peaks of degree is respectively present in 0.2～0.7 micrometer range and in 0.7～3 micrometer range.

(14) as above-mentioned 11～13 any one described in niobium sintered body, wherein, in multiple aperture peaks, with most The peak value at the peak of high relative intensity is present in than with time side of the peak value larger diameter at the peak of highest relative intensity.

(15) as above-mentioned 9～14 any one described in niobium sintered body, wherein, the volume of sintered body is 10mm³Or more Greatly, including hole volume.

(16) as above-mentioned 9～15 any one described in niobium sintered body, wherein, the specific surface area of sintered body is 0.2～ 7m²/g。

(17) as above-mentioned 9～16 any one described in niobium sintered body, wherein, a part of sintered body is nitrogenized.

(18) as above-mentioned 12～17 any one described in niobium sintered body, wherein, the sintered body be by a kind of niobium into The sintered body that body is obtained, it is 40,000～200,000 μ FV/g that the niobium formed body produces a kind of CV values in 1300 DEG C of sintering Sintered body.

(19) a kind of capacitor, an electrode comprising the niobium sintered body described in any one used such as above-mentioned 9～18, One to electrode and intervenient dielectric material.

(20) capacitor as described in above-mentioned 19, wherein, dielectric material mainly includes niobium oxide.

(21) capacitor as described in above-mentioned 19, wherein, it is that at least one is selected from electrolyte solution, You Jiban to electrode The material of conductor and inorganic semiconductor.

(22) capacitor as described in above-mentioned 21, wherein, it is organic semiconductor to electrode, and organic semiconductor is choosing The organic semiconductor of self-contained benzopyrrole quinoline tetramer and chloranil, main organic semiconductor, master comprising four thio naphthacene To include the organic semiconductor of four cyano quinone bismethane and at least one material of electric conductive polymer.

(23) capacitor as described in above-mentioned 22, wherein, electric conductive polymer is at least one selected from polypyrrole, poly- thiophene The composition of fen, polyaniline and its substitutive derivative.

(24) capacitor as described in above-mentioned 22, wherein, electric conductive polymer is by containing following formula (1) or (2) The electric conductive polymer that dopant is obtained is mixed in the polymer of the repetitives of expression：

(wherein, R¹～R⁴Represent independently of one another selected from hydrogen atom, the straight or branched containing 1～10 carbon atom it is full And/or unsaturated alkyl, alkoxyl or alkyl ester group, halogen atom, nitro, cyano group, primary, secondary or tertiary amino, CF₃Group, The univalent perssad of phenyl and the phenyl for replacing；Every a pair of R¹And R²、R³And R⁴Bivalence chain can be at an arbitrary position combined to form, is used In with by R¹And R²Or by R³And R⁴Substituted carbon atom forms together at least one 3-, 4-, 5-, 6- or 7- unit's saturations or insatiable hunger With hydrocarbon ring structure；The chain that ring-type is combined can at an arbitrary position contain carbonyl, ether, ester, amide, thioether, sulfinyl, sulfonyl Or imino group；X represents oxygen atom, sulphur atom or nitrogen-atoms；R⁵Just exist only when X is nitrogen-atoms, and independently represent hydrogen Atom or straight or branched, saturation or unsaturated alkyl containing 1～10 carbon atom).

(25) capacitor as described in above-mentioned 24, wherein, electric conductive polymer is containing the repetition represented by following formula (3) The electric conductive polymer of unit：

(wherein, R⁶And R⁷Independently of one another represent hydrogen atom, the saturation of the straight or branched containing 1～6 carbon atom or Unsaturated alkyl, or a substituent group, for being formed by the alkyl acquisition that be combined with each other at an arbitrary position containing two oxygen originals At least one 5-, 6- or 7- units saturated hydrocarbons ring structure of son；And circulus include have can be substituted ethenylidene key, The structure of the phenylene structure that can be substituted).

(26) capacitor as described in above-mentioned 22, wherein, electric conductive polymer is by poly- (3,4- ethylidene dioxies Thiophene) the middle electric conductive polymer for mixing dopant acquisition.

(27) capacitor as described in above-mentioned 19, wherein, to electrode by the material system at least partly with layer structure Into.

(28) capacitor as described in above-mentioned 19, wherein, organic sulfonic acid root anion conduct is contained to the material of electrode Dopant.

(29) a kind of method for producing the niobium powder described in above-mentioned 1～8 any one, it includes the work of niobium or niobium compound Change is processed.

(30) method of the production niobium powder as described in above-mentioned 29, wherein, the activation processing of niobium or niobium compound is to pass through At least one is carried out selected from sintering step and the step of destruction step.

(31) method of the production niobium powder as described in above-mentioned 29 or 30, wherein, using niobium or niobium compound and activator Mixture carry out the activation processing of niobium or niobium compound.

(32) as above-mentioned 29～31 any one described in production niobium powder method, wherein, carry out activation processing processing Niobium or niobium compound particle mean size be 0.01～10 micron.

(33) as above-mentioned 29～32 any one described in production niobium powder method, wherein, the niobium or niobium compound Containing at least one element selected from nitrogen, carbon, boron and sulfur, its content is 200,000ppm or less.

(34) as above-mentioned 29～33 any one described in production niobium powder method, wherein, niobium compound is selected from hydrogen Change at least one of niobium, niobium alloy and hydrogenation niobium alloy.

(35) method of the production niobium powder as described in above-mentioned 34, wherein, it is contained in niobium alloy or hydrogenation niobium alloy to remove Composition beyond niobium is at least one element selected from the element that atomic number is 88 or less, but not including that hydrogen, nitrogen, oxygen, Fluorine, chlorine, bromine, iodine, niobium, helium, neon, argon, krypton, xenon and radon.

(36) method of the production niobium powder as described in above-mentioned 31, wherein, it is mixed with activator containing niobium or niobium compound Compound mixes these compositions and obtains by using solvent.

(37) method of the production niobium powder as described in above-mentioned 36, wherein, the solvent be it is at least one selected from water, alcohol, The solvent of ether, cellosolve, ketone, aliphatic hydrocarbon, aromatic hydrocarbon and halogenated hydrocarbons.

(38) method of the production niobium powder as described in above-mentioned 31, wherein, based on the total amount of niobium or niobium compound, activator Consumption be 1～40 mass %.

(39) method of the production niobium powder as described in above-mentioned 31 or 38, wherein, the particle mean size of activator is 0.01～ 500 microns.

(40) as above-mentioned 31,38 and 39 any one described in production niobium powder method, wherein, activator has multiple grains Degree peak value.

(41) such as the method for the production niobium powder described in the above-mentioned 31, any one of 38-40, wherein, activator is that one kind exists 2,000 DEG C or temperature below removed material in gaseous form.

(42) method of the production niobium powder as described in above-mentioned 41, wherein, activator is selected from naphthalene, anthracene, quinone, Camphora, poly- Acrylic acid, polyacrylate, polyacrylamide, polymethylacrylic acid, polymethacrylates, PMAm, poly- second Enol, NH₄Cl、ZnO、WO₂、SnO₂And MnO₃At least one.

(43) such as the method for the production niobium powder described in the above-mentioned 31, any one of 38-40, wherein, activator is selected from water Soluble substance, organic solvent-soluble material, acid solution solable matter, aqueous slkali solable matter forms complex and becomes Into the material of the material for being dissolved in water, organic solvent, acid solution or aqueous slkali, become to be dissolved under 2000 DEG C or lower temperature At least one in the material of the material of water, organic solvent, acid solution or aqueous slkali.

(44) method of the production niobium powder as described in above-mentioned 43, wherein, activator be selected from metal and carbonic acid, sulphuric acid, The compound of sulfurous acid, halogen, perhalogeno acid, hypohalogenous acids, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, metal, metal At least one of hydroxide and metal-oxide.

(45) as described in above-mentioned 43 production niobium powder method, wherein, activator be selected from lithium, sodium, potassium, rubidium, caesium, Francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, cerium, neodymium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, Iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, boron, aluminum, gallium, indium, thallium, silicon, germanium, stannum, lead, arsenic, antimony, bismuth selenium tellurium, polonium and its chemical combination At least one of thing.

(46) as above-mentioned 29～40 and 43～45 any one described in production niobium powder method, wherein, activation processing It is the process for removing activator before sintering step or in sintering step by heating and/or under reduced pressure.

(47) as above-mentioned 29～40 and 43～45 any one described in production niobium powder method, wherein, the activation Process is after a sintering step and is contacted with sintering or broken product by making solvent in shattering process or after shattering process To remove the process of activator component.

(48) method of the production niobium powder as described in above-mentioned 47, wherein, the solvent is selected from water, organic solvent, acid At least one in solution, aqueous slkali and the solution containing the part for forming soluble complexes.

(49) method of the production niobium powder as described in above-mentioned 48, wherein, acid solution is selected from nitric acid, sulphuric acid, Fluohydric acid. With at least one solution in hydrochloric acid.

(50) method of the production niobium powder as described in above-mentioned 48, wherein, aqueous slkali contains selected from alkali metal hydroxide With at least one composition of ammonia.

(51) method of the production niobium powder as described in above-mentioned 48, wherein, the part is selected from ammonia, glycine and second two At least one of amine tetraacethyl.

(52) method of the production niobium powder as described in above-mentioned 48, wherein, the organic solvent is methyl iso-butyl ketone (MIBK).

(53) a kind of method for producing nitrogenous niobium powder, it is included with selected from bath nitriding, ionic nitriding and gas nitriding At least one method processes the niobium powder described in above-mentioned 1～7 any one.

(54) a kind of method for producing carbon containing niobium powder, it is included with selected from least one side of solid phase carbonization and liquid phase carbonation Niobium powder of the method process described in above-mentioned 1～7 any one.

(55) a kind of method for producing boracic niobium powder, it is included with selected from least one side of gas phase boronation and solid phase boronation Niobium powder of the method process described in above-mentioned 1～7 any one.

(56) a kind of method for producing sulfur-bearing niobium powder, it is included with selected from gas-phase presulfiding, ion sulfuration and solid phase vulcanizing At least one method processes the niobium powder described in above-mentioned 1～7 any one.

(57) the niobium powder that the manufacture method described in a kind of any one with above-mentioned 29～56 is obtained.

(58) a kind of production method of niobium sintered body, the niobium powder described in any one using above-mentioned 1～8 and 57.

(59) a kind of method for producing capacitor, the capacitor uses the electrode of niobium sintered body, is sintering comprising one On body surface face formed dielectric material and provide on the dielectric material to electrode, wherein, niobium sintered body be by being sintered on State what the niobium powder described in 1～8 and 57 any one was obtained.

(60) method of the production capacitor as described in above-mentioned 59, wherein, dielectric material is formed by electrolytic oxidation 's.

(61) a kind of method for producing capacitor, the capacitor comprising one using niobium sintered body electrode, described On sintered body surface formed dielectric material and on the dielectric material provide to electrode, wherein, the niobium sintered body is Niobium sintered body described in above-mentioned 9～18 any one.

(62) electronic circuit of the capacitor described in a kind of any one using above-mentioned 19～28.

(63) electronic machine of the capacitor described in a kind of any one using above-mentioned 19～28.

The brief description of accompanying drawing

Fig. 1 is the enlarged drawing of the schematically illustrate niobium powder of the present invention with two or more aperture peaks.

Fig. 2 is the sketch map of the pore-size distribution of the niobium powder measured by mercury injection method.

Implement the mode of the present invention

Below description has the capacitor of good leak current characteristic and excellent moisture-proof, can be allowed to have these performances And be given the apparent ratio of high-capacitance niobium sintered body, preferably as the sintered material and have good fluidity and can continuously into The niobium powder of shape and the manufacture method of the capacitor, niobium sintered body and niobium powder.

In the present invention, tap density is the capacitor niobium powder (sometimes referred to simply as " niobium powder ") of 0.5～2.5g/ml as full The above-mentioned performance of sufficient capacitor simultaneously improves the niobium powder of productivity ratio in capacitor production.

Niobium powder for capacitor used herein refers to that the main niobium that includes simultaneously can be used as the niobium powder of production capacitor material.The niobium Powder can contain, and for example, the composition of alloy, i.e., the composition in addition to niobium, such as nitrogen and/or oxygen can be formed with niobium.

By using following methods shape and sinter niobium powder for capacitor with obtain for capacitor niobium sintered body (sometimes Referred to as niobium sintered body), then it is formed on dielectric layer and to electrode layer, capacitor can be produced.

Niobium powder for capacitor is added to by the way that binding agent described below is dissolved in into organic solvent such as toluene or methanol In and be sufficiently mixed in obtained solution using shaking mixer or v-shaped mixer.Then, it is dry using exsiccator such as circular cone Dry device distills out under reduced pressure organic solvent to prepare the niobium mixed-powder containing binding agent.This mixed-powder is put into certainly In the hopper of dynamic forming machine, weigh and make niobium powder to flow through the feed pipe in the metal die for reaching metal forming machine from hopper, make It automatically falls into metal die, and shapes together with wire.Remove binding agent after, the molded article 500～2,000 DEG C The lower sintering of decompression, to manufacture niobium sintered body.

The niobium sintered body is formed through electrochemical treatments, such as in the electrolysis of the phosphoric acid and adipic acid that concentration is 0.1 mass % In matter solvent, at 30～90 DEG C, under the voltage of 20～60V, process 1～30 hour, to form the main dielectric comprising niobium oxide Layer.Formed on the dielectric layer solid electrolyte layer such as manganese dioxide, Lead oxide brown and electric conductive polymer and graphite linings and Silver paste layer.After by soldering cathode leg is connected thereto, with resin seal preparing solid electrolyte capacitators.

In shaping, in the case of the mixed-powder without proper flow or angle of repose, the powder can not be from hopper stream Freely flow in metal die, and can not stably form.Especially, due to being conveyed from hopper using such as vibration method The mixed-powder, the excessive or too small tap density of mixed-powder or particle mean size cause molded article quality or sintered body Intensity or shape dispersibility are big, and in some cases, cause to produce breach (chipping) or cracking, cause leakage current Value difference.Therefore, the tap density of mixed-powder, particle mean size, mobility and angle of repose are the good sintered body of production and good electricity The key factor of container.

These physical propertys of mixed-powder seldom change before and after mixing with binding agent, but are used by capacitor used What the physical property of niobium powder was determined.It is therefore important that the tap density of niobium powder used, particle mean size, mobility and angle of repose. Tap density or average particle size influences are mainly received the mobility of niobium powder and angle of repose, therefore, tap density and particle mean size become Important factor.

In the present invention, in order to improve the productivity ratio and intensity of sintered body, and improve mobility or angle of repose, so as to obtain Reduce the effect of leakage current, tap density preferably 0.5～2.5g/ml, more preferably 0.8～1.9g/ml.The niobium powder of the present invention Particle mean size preferably 10～1,000 micron, more preferably 50～200 microns.

In order that niobium powder freely can be fallen in the metal die of forming machine under hopper, the angle of repose of niobium powder of the present invention is excellent Select 10 °～60 °, more preferably 10 °～50 °.

By carrying out at least one sintering step and destruction step successively, use containing niobium powder or niobium compound powder (hereafter Referred to as " raw material niobium powder ") and activator (also referred to as " hole formation material ", and hereinafter sometimes referred to " additive ") mixture (hereinafter referred to as " raw mixture ") can produce the niobium powder with above-mentioned physical property.

During the niobium powder for producing the present invention from raw mixture, in sintering step or destruction step deactivator is removed. The removal of activator is also independent from the sintering step or destruction step to be carried out.

According to the chemical property of activator, can arbitrarily using except the various methods of deactivator.Can be using energy easily Ground removes a method of activator or various these methods is used in combination.

Except the example of the method for deactivator includes evaporation, distillation or thermal decomposition activation agent and the side for removing in gaseous form Method, and by dissolving it in solvent in remove activator method.

In the case where activator is removed in gaseous form, can be removed in sintering step, or before sintering The step of setting one removes deactivator under heating and/or decompression.

Dissolve it in be removed in solvent after sintering by raw mixture or in shattering process or after shattering process and live In the case of agent, the solvent for making described below is contacted with sintered product or breakdown products, so as to dissolve and removes activator.

Nitridation, boronation, carbonization can be set in any stage during the niobium powder that the present invention is produced by raw mixture Or the step of sulfuration a part of niobium powder.

The method of the niobium powder of the production present invention described in detail below.

Raw material niobium powder can be at least one powder in niobium, hydrogenated niobium, niobium alloy and hydrogenation niobium alloy.A part Powder can be nitrogenized, vulcanized, being carbonized or boronation." alloy " used includes the solid solution with other alloying components in the present invention Body.

The particle mean size of raw material niobium powder is preferably 0.01～10 micron, more preferably 0.02～5 micron, more preferably 0.05～2 micron.

Obtaining the example of the method for the niobium as raw material niobium powder includes hydrogenation, broken and dehydrogenation niobium ingot, niobium granule or niobium powder Method, the method for reducing potassium niobate fluoride and broken reduzate with sodium etc., at least one using hydrogen, carbon, magnesium and aluminum reduce The method of niobium oxide and broken reduzate, and the method for hydrogen reduction halogenation niobium.

Obtaining the example of the method for the hydrogenated niobium as raw material niobium powder includes hydrogenating and crushing niobium ingot, niobium granule or niobium powder Method.

Obtain the example of the method for the hydrogenation niobium alloy as raw material niobium powder include broken niobium alloy ingot, niobium alloy granule or The method of the hydride of niobium alloy powder.Obtain the hydrogen that the example of the method for the niobium alloy as raw material niobium powder includes making to be obtained as described above The method for changing niobium alloy dehydrogenation.

As the alloying component in addition to niobium, niobium alloy or hydrogenation niobium alloy contain selected from atomic number be 88 or less Element at least one element, not including hydrogen, nitrogen, oxygen, fluorine, chlorine, bromine, iodine, niobium, helium, neon, argon, krypton, xenon and radon.

Activator can be the material that any step during niobium powder of the present invention is produced by raw mixture is removed. In the niobium powder of the present invention, generally hole is formed in the part except deactivator.

The aperture of the particle size influences niobium powder of the present invention of activator, the aperture of the pore size influences niobium sintered body of niobium powder, and niobium The impregnability of negative electrode agent in the capacitance and capacitor production stage of the pore size influences capacitor of sintered body.

The impregnability of negative electrode agent has a significant impact in the capacitor of production high power capacity and low ESR.By decompression During lower shaping niobium powder production sintered body, the aperture of niobium sintered body is naturally less than the aperture of niobium powder.Due to being difficult to little by aperture Impregnated cathode agent in the niobium sintered body of niobium powder production, therefore, the average pore size of niobium powder is preferably 0.5 micron or bigger, more preferably For 1 micron or bigger.

The average pore size of niobium powder is preferably 0.01～500 micron, more preferably 0.03～300 micron, more preferably 0.1～200 micron.In order to the particle mean size with aperture within the range, activator is preferably 0.01～500 micron, more Preferably 0.03～300 micron, more preferably 0.1～200 micron.

The average pore size of niobium powder is most preferably 0.5～100 micron, and the particle mean size of activator be most preferably 0.5～ 100 microns.

Can reduce aperture diameter using the activator of small grain size, and the activator using big granularity can increase hole Footpath.

By the particle size distribution for adjusting activator, can be distributed with adjustment aperture.

It is related to the capacitor of problem with enough high capacitances and without negative electrode agent impregnability aspect to obtain, it is excellent Choosing suitably provides sufficiently small hole to produce desired capacitance according to the physical property of negative electrode agent in niobium sintered body, suitably There is provided sufficiently large hole to ensure the satisfied dipping of negative electrode agent.

In order to adjust the pore-size distribution of niobium powder or niobium sintered body, for example, by using the grain with two or more peak values The activator (powder) of degree distribution, can make niobium powder have the pore-size distribution of two or more peak values.By sintering this niobium powder, The niobium sintered body in the equal aperture with two or more peak values in pore-size distribution can be obtained.In this case, it is described Aperture peak is preferably in 0.01～500 micrometer range, more preferably 0.03～300 micron, and further preferred 0.1～200 Micron, particularly preferred 0.1～30 micron, most preferably 0.2～3 micron.

The niobium powder of production above niobium sintered body has two or more peak values in particle size distribution.Described two or multiple peaks Any one preferably 0.5 micron or bigger of value.For example, there are two peak values 0.7 and 3 microns of niobium in particle size distribution to produce Sintered body, two peak values of niobium powder can be adjusted to about 1.5 and about 2.5 microns.In order to obtain with 1.5 microns of small-bore and With 25 microns of wide-aperture niobium powder, need respectively using the activator that average pore size is 1.5 microns and 25 microns.It is general next Say, when the hole of the hole and major diameter that there is minor diameter in niobium powder, during press molding, the hole of major diameter becomes It is little.So, the peak value of major diameter is preferably 20 microns or bigger.30 volumes % of further preferably whole pore volumes more have 20 microns or bigger aperture, more preferably 40 volumes % or more.

Above example is described in detail below based on accompanying drawing.Fig. 1 is the enlarged drawing of schematically illustrate niobium powder of the present invention.In Fig. 1 Niobium powder be pelletizing, it is included with the starting powder of special pore size distribution formed by activator.Respectively using average diameter about 1.5 microns and about 25 microns of activator forms hole (A) and (B).As such, it is possible to efficiently make starting powder mutually condense. Fig. 2 is the sketch map of the niobium powder pore-size distribution determined by mercury injection method.Peak (A) is corresponded to by the work of about 1.5 microns of average diameter The hole (A) that agent is formed, peak (B) is corresponding to the hole (B) formed by the activator of about 25 microns of average diameter.Compare at peak (B) Peak (A) is high, and all the 44% of pore volume has 20 microns or bigger aperture.

For example, by being blended in particle size distribution in there are two or more activators of different peak values, it is possible to obtain granularity Activator with two or more peak values in distribution.

Sintering temperature or the following material for becoming gas are included in as the example of the material of activator and at least in sintering The material in solvent is dissolved in afterwards.

Include becoming gas by evaporation, distillation or thermal decomposition in the example of sintering temperature or the following material for becoming gas Material.It is preferred that even can also easily become gas and not leave the cheap material of residue at low temperature.The example Including aromatic compound such as naphthalene, anthracene and quinone, Camphora, NH₄Cl、ZnO、WO₂、SnO₂、MnO₃And organic polymer.

The example of organic polymer includes polyacrylic acid, polyacrylate, polyacrylamide, polymethylacrylic acid, poly- first Base acrylate, PMAm and polyvinyl alcohol.

At least solvable after sintering material is the material that the residue of activator or its thermal decomposition product are dissolved in solvent. The material that can be readily dissolved in solvent described below after sintering or in shattering process or after broken is special Preferably.Such material can be selected from many materials according to the combination of solvent.

The example include metal and carbonic acid, sulphuric acid, sulfurous acid, halogen, perhalogeno acid, hypohalogenous acids, nitric acid, nitrous acid, phosphoric acid, The compound of acetic acid, oxalic acid or boric acid, metal-oxide, metal hydroxidess and metal.

Wherein, the big compound of dissolubility preferably in solvent described below such as acid, alkali or ammonium salt solution.Example bag Include containing selected from lithium, sodium, potassium, rubidium, caesium, 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, aluminum, gallium, indium, thallium, germanium, stannum, lead, antimony, The compound of at least one composition of bismuth selenium tellurium, polonium, boron, silicon and arsenic.Wherein, preferred slaine, more preferably such as Barium monoxide, Manganese nitrate (II) and Calcium Carbonate.

These activators can be used alone or its combination of two or more is used.

In order to be effectively formed special pore size distribution, the material for existing in solid form at a sintering temperature is as activator material Preferably.Reason is the undue agglomeration that the activator for existing with solid-state at a sintering temperature hinders original niobium powder so that niobium powder is only Can mutually fuse at contact point.If activator exists at a sintering temperature with liquid or gas form, it is to hindering The effect of this reunion is little and be likely to form than desired less hole.Therefore, with comprising more high-melting-point substances such as oxidation The activator ratio of barium, Calcium Carbonate, aluminium oxide and magnesium oxide includes low melting point such as aluminum metal, magnesium metal, magnesium hydride and calcium gold The activator of category can make aperture become more stable.

If adding activator on a small quantity, tap density and angle of repose become greatly, and if a large amount of add, then tap density becomes It is little, and increase in sintering stage hole of remaining silent.In order to obtain 60 ° or less of angle of repose and the vibration density of 0.5～2.5g/ml The problem of the hole of remaining silent without sintering stage is spent, the addition of activator is generally 1～40 mass % or less (unless another External declaration, quality % is hereinafter referred to as %), preferably 5～25%, more preferably 10～20%, based on raw material niobium, but, this Can be changed according to the particle mean size of activator.

The activator and niobium raw material of powder type is respectively by not using solvent mixing or by using suitable solvent Hybrid activator and niobium raw material are simultaneously dried the mixture, it is possible to obtain raw mixture.

The example of the solvent that can be used includes water, alcohol, ether, cellosolve, ketone, aliphatic hydrocarbon, aromatic hydrocarbon and halogenated hydrocarbons.

Can be mixed using mixer.With regard to mixer, it is possible to use common equipment such as shaking mixer, V-type Mixer and Nauter mixers are without any problem.Temperature during mixing is limited by the boiling point and freezing point of solvent, but Generally -50～120 DEG C, preferably -50～50 DEG C, more preferably -10～30 DEG C.The mixing time used is not particularly limited, only Will its be 10 minutes or more, but, mixing preferably carries out 1 in the oxygen-free atmosphere using noble gases such as nitrogen or argon～ 6 hours.

In the case of using solvent, less than 80 DEG C, preferably shorter than 50 DEG C, using circular cone exsiccator or chamber dryer Mixture obtained by drying.If the drying mixture at 80 DEG C or higher of temperature, in niobium or hydrided niobium powder Contained oxygen adversely increases.

Activator sintering temperature or it is following become gas in the case of, activator can sintering when remove, but The condition for being set as the condition of such as temperature, pressure and time to promote to remove by the chemical property according to activator, can be with The step of making activator form gas and remove is independently positioned at before sintering.In this case, activator is 100～800 Evaporate within a few hours DEG C under reduced pressure.

In the case of using hydrogenated niobium or hydrogenation niobium alloy as raw material niobium, can realize taking off by carrying out above-mentioned steps Hydrogen, and it is unrelated with the species of activator.

500～2,000 DEG C, preferably 800～1,500 DEG C, more preferably 1,000～1300 DEG C, under reduced pressure or also Step is sintered in Primordial Qi atmosphere such as argon.After the completion of sintering, sintered product is preferably cooled to the temperature of niobium (sometimes referred to simply as " product temperatur ") become 30 DEG C or lower, it is gradually added into containing 0.01～10 volume %, preferably 0.1～1 volume % oxygen is lazy Property gas such as nitrogen or argon so that product temperatur be less than 30 DEG C, and stand 8 hours or more after, take out sintering produce Thing, obtains sintering agglomerate.

In destruction step, agglomerates will be sintered to suitable granularity using disintegrating machine such as roll-type granulation machine.

In the case where activator at least dissolves in solvent after a sintering step, suitable solvent is made with sintering agglomerate or burning After knot and before breaking, the broken powder contact among or afterwards or in multiple these steps, so as to the activator It is dissolved and removes.Easy due to removing, activator component dissolves and removes in the broken powder preferably from after crushing.

It is the activator to be dissolved solvent with enough high-dissolvabilities wherein used herein of solvent.Cheaply and almost The solvent not remained is preferred.For example, in the case of water soluble activating agent, it is possible to use water；In organic solvent-soluble In the case of activator, it is possible to use the organic solvent such as methylisobutylketone, ethanol or dimethyl sulfoxide (DMSO)；Acid-soluble In the case of activator, it is possible to use such as nitric acid, sulphuric acid, phosphoric acid, boric acid, carbonic acid, Fluohydric acid., hydrochloric acid, hydrobromic acid, hydroiodic acid Or the acid solution such as organic acid；In the case of alkali solubility activator, it is possible to use such as alkali metal hydroxide, alkaline-earth metal hydrogen The aqueous slkali such as oxide or ammonia；In the case where the activator of soluble complexes is formed, it is possible to use become complex ligands Ammonia or the polyphosphoric acid such as aminoacid, the sodium tripolyphosphate such as amine aqueous solution, the glycine such as ethylenediamine, crown ether, such as The chelating agen such as thiosulfate or ethylenediaminetetraacetic acid such as sodium thiosulfate.

Can also be suitably used the ammonium salt solutions such as ammonium chloride, ammonium nitrate and ammonium sulfate, cation exchange resin and Anion exchange resin.It is preferred that dissolving and removing activator at a lower temperature.If activator dissolves at high temperature and removes, Then the surface of niobium is oxidized, because niobium is high with the affinity of oxygen.Therefore, the temperature for dissolving and removing is preferably 50 DEG C or lower, More preferably -10 DEG C -40 DEG C, more preferably 0 DEG C -30 DEG C.According to above reason, preferably select in dissolving and removal process The middle method for producing little heat.For example, when using metal-oxide or metal as activator, the dissolving that carried out with acid and Removal typically produces the high heat of neutralization.It is preferred, therefore, that selecting a kind of method for producing little heat, for example, it is dissolved in water and organic In solvent, soluble complexes are formed by using the solvent of ammonium salt and edetate and is dissolved in containing ion In the solvent of exchanger resin.

The instantiation of the combination of activator and solvent includes Barium monoxide and water, calcium oxalate and hydrochloric acid, aluminium oxide and hydrogen-oxygen Change sodium water solution, hafnium oxide and methylisobutylketone and magnesium carbonate and tetrasodium ethylenediamine tetraacetate aqueous solution.

After dissolving and removing activator, residue is fully washed and is dried.For example, barytic situation is being removed with water Under, residue is fully washed using ion exchanged soln until the electrical conductivity of washing liquid is reduced to 5 μ S/cm or less.Subsequently, at 50 DEG C Or lower product temperature is dried under reduced pressure the product.Here, the amount of remaining activator or solvent composition is usually 100ppm or less, but this changes with wash conditions.

In order to improve LC values, niobium powder, the sintering group for so obtaining is soon and niobium raw material powder can be through a part of niobium powder Nitridation, boronation, carbonization or sulfuration, or various these process.

The present invention niobium powder can contain obtained niobium nitride, niobium (Nb) boride, niobium carbide or sulfuration niobium or it is various these Material.The total amount of nitrogen, boron, carbon and sulfur each element changes with the shape of niobium powder, but it is 0～200,000ppm, excellent Elect 50～100,000ppm, more preferably 200～20,000ppm as.If total content is more than 200,000ppm, the electricity for being produced Container capacity characteristic deteriorates, and is not suitable for capacitor.

The nitridation of niobium powder can pass through liquid phase nitrogenize, ionic nitriding and Gaseous Nitriding any one or by its combine into OK.Wherein, the Gaseous Nitriding in blanket of nitrogen is preferably as its equipment is simple and processing ease.For example, it is above-mentioned by making Niobium powder stands in blanket of nitrogen and can realize the Gaseous Nitriding in blanket of nitrogen.With 2,000 DEG C or less of nitriding atmosphere temperature With 100 hours or shorter time of repose, it is possible to obtain the niobium powder with target nitridation amount.Carrying out process in higher temperature can be with Shorten process time.

The boronation of niobium powder can be gas phase boronation or solid phase boronation.For example, can by making it with boron source such as boron particles or Halogenation boron (such as boron trifluoride) stands under reduced pressure 1 minute～100 hours in 2,000 DEG C or less of temperature, makes niobium powder boron Change.

The carbonization of niobium powder can be any one of gas carburization, solid phase carbonization and liquid phase carbonation.For example, can be by making it Together with the organic materials (such as methane) of carbon source such as material with carbon element or carbon containing 2,000 DEG C or less temperature stand 1 minute～ Niobium powder is set within 100 hours to be carbonized under reduced pressure.

The sulfuration of niobium powder can be any one of gas-phase presulfiding, ion sulfuration and solid phase vulcanizing.For example, existed by making niobium powder Standing in sulfur atmosphere can realize the gas-phase presulfiding in sulfur atmosphere.Vulcanized gas temperature and 100 with 2,000 DEG C or less is little When or shorter time of repose, it is possible to obtain the niobium powder with target sulfuration amount.Can be with by carrying out process at a higher temperature Shorten process time.

The BET specific surface area of the niobium powder of the invention for so obtaining is usually 0.5～40m²/ g, preferably 0.7～10m²/ g, More preferably 0.9～2m²/g。

The niobium powder of the present invention can be tap density, granularity, angle of repose, BET specific surface area, pore-size distribution and by nitrogen The mixture for processing different niobium powder of change, boronation, carbonization or sulfuration.

The sintered body of the present invention of electrode for capacitors be can serve as preferably for example, by the above-mentioned niobium powder next life of the sintering present invention Produce.For example, by the way that niobium powder is compressed and molded into into reservation shape, then at 500 DEG C～2,000 DEG C, preferably 800 DEG C～1,500 DEG C, More preferably 1,000 DEG C～1300 DEG C 10^-5～10²Pa makes its heating 1 minute～10 hours.

The pore-size distribution of the sintered body obtained by the niobium powder of the present invention generally has aperture peak in 0.01～500 micrometer range Value.

By the way that impressed pressure during shaping is adjusted to into specific pressure value, the sintered body can have bigger than niobium powder Aperture peak number.The external pressurized force value is with press molding the condition such as physical property of niobium powder, the shape of molded article and shaping Machine etc. changes, but can be in the pressure limit that is not closed to sintered body hole of pressure of press molding.By preliminary experiment The conditions such as the physical property according to niobium powder to be formed determine preferred pressure value to make it have multiple aperture peaks.Example Such as, the forming machine load for being applied to molded article by control can control external pressurized force value.

The pore-size distribution of sintered body preferably have at least two aperture peaks, so as to contain it is sufficiently small with obtain wish electric capacity The sufficiently large hole to obtain the satisfied dipping of negative electrode agent of the hole of amount and the physical property according to negative electrode agent.By in aperture point There is this sintered body of multiple peak values in cloth, can produce with the apparent ratio of excellent impregnability and high-capacitance to electrode Capacitor.

When in multiple pore-size distribution peak values, respectively in 0.2～0.7 micrometer range and in 0.7～3 micrometer range, It is preferred that when there is the peak value at two peaks with highest relative intensity in 0.2～0.7 micron and 0.9～3 micrometer range respectively, The capacitor produced by the sintered body can have good moisture-proof.It is relative with highest in multiple pore-size distribution peak values The peak value at the peak of intensity is preferably in the side of the peak value larger diameter at the peak than secondary highest relative intensity, because capacitor can With with more excellent moisture-proof.

The specific surface area of so sintered body of production is generally 0.2～7m²/g。

Generally, the shape of sintered body is bigger, more difficult to the dipping of electrode.For example, there is 10mm in sintered body³Or it is bigger Size in the case of, can particularly effectively use in pore-size distribution with multiple peak values sintered body of the present invention.

The sintered body of the present invention can be with partial nitridation.With regard to nitriding method, it is possible to use with regard to niobium powder said method and Reaction condition.A part of nitrogen powder can also be in advance nitrogenized, is burnt by a part for the niobium powder production for producing sintered body and nitridation Knot body.

Such sintered body usually contains the oxygen of 500～70,000 mass ppm, because deposit containing in niobium powder before sintering Autoxidation oxygen and after sintering by autoxidation add oxygen.In the sintered body of the present invention, except niobium, alloy shape The content of the element into beyond element, oxygen and nitrogen is usually 400 mass ppm or less.

Used as an example, when the sintered body of the present invention is when sintering for 1300 DEG C, CV values are (at 80 DEG C in 0.1 mass % phosphoric acid In solution the electrochemical shaping electrochemical shaping voltage of 120 minutes and 120Hz capacitance product) be 4,000～200, 000μFV/g。

The production of capacitor devices is below described.

For example, metal such as niobium or tantalum comprising rectified action are prepared and there is the wire of suitable shape and length, in niobium powder Press molding when by the wire integral forming so that a part of wire inserts the inside of molded article, so that wire can Using the lead-out wire as sintered body.Or shaping and sintered niobium powder without using lead, then, by welding etc. will individually make Standby lead is coupled.

Using this sintered body as an electrode, by the electrode and to inserting a kind of dielectric material between electrode, Capacitor can be produced.For example, by using niobium sintered body as an electrode, on the sintered body surface (including in hole Surface) on form dielectric material and provide to electrode on the dielectric material, prepare capacitor.

Dielectric material for the capacitor preferably mainly includes the dielectric material of niobium oxide, more preferably mainly includes five oxygen Change the dielectric material of two niobiums.For example, can be obtained mainly containing five oxidations as the niobium sintered body of an electrode by electrolytic oxidation The dielectric material of two niobiums.For niobium electrode described in electrolytic oxidation in the electrolytic solution, protonic acid aqueous solution is generally used, such as 0.1% Phosphate aqueous solution, aqueous sulfuric acid, 1% acetic acid aqueous solution or adipic acid aqueous solution.So by electrification in the electrolytic solution In the case of studying shape niobium electrode acquisition niobium oxide dielectric material, the capacitor of the present invention is a kind of electrolysis condenser and niobium electricity Pole is used as anode.

In the capacitor of the present invention, to being not particularly limited to electrode for the niobium sintered body, for example, can use in aluminum Known at least one material (chemical combination selected from electrolyte, organic semiconductor and inorganic semiconductor in electrolysis condenser technology Thing).

The instantiation of electrolyte includes wherein dissolving the diformazan of 5 mass % isobutyl group tripropyl ammonium tetrafluoroborate electrolyte Base Methanamide-ethylene glycol mixed solution and wherein dissolve 7 mass % tetraethyl ammonium tetrafluoroborates propylene carbonate-ethylene glycol mix Close solution.

Organic semi-conductor instantiation includes, the organic semiconductor comprising benzene pyrrolin tetramer and chloranil, mainly contains The organic semiconductor that has four thio naphthacene, the organic semiconductor for mainly containing four cyano quinone bismethane and containing by following formula (1) Or the electric conductive polymer of the repetitives of (2) expression：

Wherein, R¹～R⁴Represent independently of one another selected from hydrogen atom, the straight or branched containing 1～10 carbon atom it is full And/or unsaturated alkyl, alkoxyl or alkyl group, halogen atom, nitro, cyano group, primary, secondary or tertiary amino, CF₃Group, benzene The univalent perssad of base and the phenyl for replacing；Every a pair of R¹And R²、R³And R⁴Bivalence chain can be at an arbitrary position combined to form, is used for With by R¹And R²Or by R³And R⁴Substituted carbon atom forms together at least one 3-, 4-, 5-, 6- or 7- unit's saturations or unsaturation Hydrocarbon ring structure；Annular combine chain can contain at an arbitrary position carbonyl, ether, ester, amide, thioether, sulfinyl, sulfonyl or Imino group；X represents oxygen atom, sulphur atom or nitrogen-atoms；R⁵Just exist only when X is nitrogen-atoms, and independently represent that hydrogen is former Son or straight or branched, saturation or unsaturated alkyl containing 1～10 carbon atom.

In the present invention, the R in formula (1) or (2)¹～R⁴Hydrogen atom is preferably represented independently of one another or containing 1～6 The straight or branched of carbon atom, saturation or undersaturated alkyl or alkoxyl, and each pair R¹And R²、R³And R⁴Can combine Form ring.

In the present invention, the electric conductive polymer containing the repetitives represented by formula (1) is preferably comprised by following formula (3) table Electric conductive polymer of the construction unit for showing as repetitives：

Wherein, R⁶And R⁷Hydrogen atom, the saturation of the straight or branched containing 1～6 carbon atom or not are represented independently of one another Saturated alkyl, or a substituent group, for being formed by the alkyl acquisition be combineding with each other at an arbitrary position containing two oxygen originals At least one 5-, 6- or 7- units saturated hydrocarbons ring structure of son；And circulus include have can be substituted ethenylidene key, The structure of the phenylene structure that can be substituted.

A kind of dopant of electric conductive polymer containing such chemical constitution doping, and for the dopant, can With using known dopant without limit.

The instantiation of inorganic semiconductor includes the main inorganic semiconductor comprising Lead oxide brown or manganese dioxide, and includes The inorganic semiconductor of ferroso-ferric oxide.These quasiconductors can be used alone, or its combination of two or more is used.

The example of the polymer of the repetitives represented containing formula (1) or (2) include polyaniline, polyphenylene oxide, polyphenylene sulfide, Polythiophene, poly- furan, polypyrrole, poly-methyl pyrrole, and its substitutive derivative and copolymer.Wherein, preferred polypyrrole, polythiophene And its substitutive derivative (such as poly- (3,4- ethyldioxythiophenes)).

When the electrical conductivity of organic or inorganic quasiconductor used is 10^-2S/cm～10³During S/cm, the capacitor for being produced can There is less resistance value and high-frequency electrical capacity can be increased.

For example, can by polymerization under the oxidant effect of the oxidation reaction aoxidized in two electronics that can satisfactorily carry out dehydrogenation The method of polymerizable compound such as aniline, thiophene, furan, pyrroles, methylpyrrole or their substitutive derivative, can produce electric conductivity Polymer.The example of the polyreaction of polymerizable compound (monomer) includes gas-phase polymerization and polymerisation in solution.Electric conductive polymer Layer has thereon formation on the niobium sintered body surface of the niobium sintered body of dielectric material.Being in electric conductive polymer being capable of solution coating Organic solvent-soluble polymer in the case of, form conductive poly using the coated polymeric on the sintered body surface The method of compound layer.

A use of preferred example of the manufacture method of polymerisation in solution is a kind of will to be formed on dielectric layer Niobium sintered body is immersed in the solution containing oxidant (solution 1), and subsequently the sintered body is immersed in containing monomer and dopant In solution (solution 2), so as to be polymerized, to form conductive polymer layer on the sintered body surface.Can also be at it After being immersed in solution 2, then the sintered body is immersed in solution 1.The solution 2 for using in the above-mentioned methods, can be free from doping The monomer solution of agent.In the case of using dopant, the dopant can be made to exist together with the solution containing oxidant.

The operation for carrying out these polymerization procedures by the sintered body for having dielectric material thereon is repeated one or more times, preferably 3～ 20 times, such that it is able to the conductive polymer layer for being readily formed densification and be layered.

In the manufacture method of the capacitor of the present invention, it is possible to use any oxidant, as long as it can not adversely affect The reducing agent of capacitor performance and oxidant can become dopant and improve the electric conductivity of electric conductive polymer.In production The industrial cheap compound of easy to handle is preferred.

The instantiation of oxidant includes Fe (III) based compound such as FeCl₃、FeClO₄With Fe (organic anion) salt； Anhydrous Aluminum chloride/Cu-lyt.；Alkali metal persulphate；Ammonium persulfate.；Peroxide；Manganese class such as potassium permanganate；Quinone such as 2, The chloro- 5,6- dicyanos -1,4- benzoquinone (DDQ) of 3- bis-, four chloro- 1,4- benzoquinone and four cyano -1,4- benzoquinone；Halogen such as iodine and bromine； Peracid；Sulfonic acid such as sulphuric acid, oleum, sulfur trioxide, chlorosulfonic acid, fluosulfonic acid and sulfamic acid；Ozone；With various these oxidations The mixture of agent.

Forming the example of the basic compound of the organic anion of above-mentioned Fe (organic anion) salt includes organic sulphur Acid, organic carboxyl acid, organic phosphoric acid and organic boronic.The instantiation of organic sulfonic acid includes benzenesulfonic acid, p-methyl benzenesulfonic acid, first sulphur (example of alkyl includes butyl, triisopropyl for acid, ethyl sulfonic acid, alpha-sulfo naphthalene, β-sulfo group naphthalene, naphthalenedisulfonic acid and alkyl naphthalene sulfonic acid And di-t-butyl).

The instantiation of organic carboxyl acid includes acetic acid, propanoic acid, benzoic acid and oxalic acid.Additionally, can also make in the present invention With polymer dielectric anion such as polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, poly- α-first Base sulfonic acid, polyvinyl sulfuric acid and polyvinyl sulfonic acid and polyphosphoric acid.These organic sulphuric acid and organic carboxyl acid are only example, and this Invention is not limited to these.The example of the counter cation of above-mentioned anion includes alkali metal ion such as H⁺、Na⁺And K⁺, and by hydrogen The ammonium ion that atom, tetramethyl, tetraethyl, the tetrabutyl or tetraphenyl replace, but, the invention is not restricted to these.In these oxygen In agent, trivalent Fe- based compound, Cu-lyt., alkali metal persulphate, Ammonium persulfate. or quinone are preferably comprised.

For the polymer composition of electric conductive polymer production in, can exist together as needed with doping The anion (anion in addition to the reducing agent anion of oxidant) of agent ability, it is possible to use produced by above-mentioned oxidant It is cloudy as the electrolytic anion of counter anion or other electrolyte containing oxidant anion (reducing agent of oxidant) Ion.Its instantiation includes proton acid anion, including the halide anions such as PF of 5B races element₆ ^-、SbF₆ ^-And AsF₆ ^-； The halide anions such as BF of 3B constituent elements element₄ ^-；Halide anion such as I^-(I₃ ^-)、Br^-And Cl^-；Full halate ion such as ClO₄ ^-；Road Lewis acid anion such as AlCl₄ ^-、FeCl₄ ^-And SnCl₅ ^-；Inorganic anion such as NO₃ ^-And SO₄ ^2-；Sulfonic acid anion is such as to toluene Sulfonic acid, LOMAR PWA EINECS 246-676-2 and the alkyl-substituted LOMAR PWA EINECS 246-676-2 (hereinafter referred to as " Cl-5 ") containing 1～5 carbon atom；Organic sulfonic acid root Anion such as CF₃SO₃ ^-And CH₃SO₃ ^-；With carboxylate anion such as CH₃COO^-And C₆H₅COO^-。

Other examples include polymer dielectric anion such as polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, gather Vinyl sulfonic acid, polyvinyl sulfuric acid, poly- Alpha-Methyl sulfonic acid, polyvinyl sulfonic acid and polyphosphoric acid.However, the invention is not restricted to this A bit.In these aniones, preferred macromolecule or low molecule organic sulfonic acid compound or polyphosphoric acid compound.It is preferred that, aromatics sulphur Acid compound (such as dodecylbenzene sodium sulfonate, sodium naphthalene sulfonate) is used as anion supplying compound.

In organic sulfonic acid root anion, more effective dopant is to contain one or more sulfonate anions in intramolecular Group (- SO₃ ^-) and the sulfo group naphtoquinone compounds with quinone structure, and rylnthracene sulfonin root anion.

The example of the basic framework of the sulfo group quinone anion of above-mentioned sulfo group naphtoquinone compounds includes 1,4-benzoquinone, adjacent benzoquinone, 1,2- Naphthoquinone, 1,4- naphthoquinone, 2,6- naphthoquinone, 9,10- anthraquinones, 1,4- anthraquinones, 1,2- anthraquinones, 1,4- bend quinone, 5,6- quinone in the wrong, 6,12- and bend Quinone, acenaphthenequinone, acenaphthene quinone, camphorquinone, 2,3- camphane diketone, 9,10- phenanthrenequione and 2,7- pyrene quinones.

In the case where being solid to electrode, conductive layer can be set thereon, it is outer with what is used on demand to obtain The good electrical contact of wire (such as lead frame).

For example heat-resisting conductive resin membrane is pasted, electroplates, metallizes or formed by curing conductive, conductive layer can be formed. The preferred embodiment of electroconductive paste includes silver paste, copper paste, aluminum paste, carbon paste and nickel paste；These can be used alone or its two kinds or many Plant and be applied in combination.In the case of using two or more pastes, these pastes can mix or can be mutual in independent stratum form Overlap.The example of plating includes nickel plating, copper plating, silver plating and aluminum plating.The example of the metal of vapor deposition includes aluminum, nickel, copper and silver.

More specifically, for example, carbon paste and silver paste are stacked on second electrode successively, and these is used into such as asphalt mixtures modified by epoxy resin The material forming of fat, so as to prepare a kind of capacitor.The capacitor can have with niobium sintered body integral sintering and shape or The niobium for welding later or tantalum lead.

For example using the thin film of resin die, resin enclosure, metal shell, the dipping of resin or stacking come to thus prepared Capacitor of the invention add casing, then as capacitor product be used for various uses.

In the case where being liquid to electrode, for example, by comprising the electricity prepared by above-mentioned two electrode and dielectric material Container be mounted in one with the shell electrically connected to electrode, to complete the capacitor.In this case, the electrode of niobium sintered body Outside is guided in side by above-mentioned niobium or tantalum lead, while using electro-insulating rubber etc. and the casing insulation.

Burning for capacitor is produced in the niobium powder that previously described embodiment of the present invention is produced by using basis Knot body and from the sintered body produce capacitor, it is possible to obtain the capacitor with Small leak electric current and good reliability.

The capacitor of the present invention has bigger volume static capacity than traditional tantalum capacitor, it is possible to obtain less The capacitor product of type.

Capacitor of the present invention with such property can apply to, for example, as being generally used for analog circuit and numeral Bypass capacitor or coupled capacitor device in circuit, and can be additionally used in traditional tantalum capacitor.

In general, such capacitor is generally used in electronic circuit, and in the capacitor using the present invention, electricity Restriction in terms of subassembly arrangement or the discharge of heat is reduced, therefore, the electronic circuit with high reliability can be arranged in than passing In narrower space needed for system electronic circuit.

Additionally, when the capacitor using the present invention, it is possible to obtain there is smaller szie and more than traditional electronic machine The electronic machine of high reliability, such as computer, computer peripheral (such as PC cards), mobile device (such as portable electric Words), housed device, equipment on a vehicle, artificial satellite and communication apparatus are installed.

Preferred embodiment of the present invention

The present invention is described in detail below with reference to embodiment and comparative example, but, the invention is not restricted to these examples.

In each example, the capacitance of the tap density of niobium powder, angle of repose, granularity and aperture and capacitor, let out The ESR values of the apparent ratio of leakage current, capacitance, moisture-proof and capacitor are all determined by the following method.

(1) measure of tap density

Tap density is according to JIS（Japanese Industrial Standards' version in 2000）Industrial monohydrate specified in K1201-1 The method of compaction device and determining instrument are determined used in apparent specific gravity algoscopy.

(2) measure of angle of repose

Angle of repose is to use JIS（Japanese Industrial Standards' version in 2000）Fluidity determining instrument and sample specified in Z2504 It is fixed that product are measured.More specifically, the hopper from hopper lower height with respect to the horizontal plane for 6cm makes niobium monoxide powder to water Plane falls, using the inclined-plane on the summit of generated circular cone to horizontal plane angle with respect to the horizontal plane as angle of repose.

(3) measure of granularity

The equipment manufactured using Microtrack (HRA9320-X100), by laser diffraction and scattering method granularity point is determined Cloth.Cumulative volume % equivalent to 50 volumes % granularity (D₅₀；Micron) it is designated as particle mean size.

(4) measure in aperture

Using the Poresizer9320 manufactured by Micromeritics, pore-size distribution is determined by mercury injection method.

In the present invention, determined maximum and led to by the rate of change of press-in cooperation amount (press-fitted amount) Cross and aperture shown in maximum be defined as into peak value, using maximum as the relative intensity at the affiliated peak of the peak value size.

(5) measure of condenser capacity

In room temperature, the LCR determinators of Hewlett-Packard manufactures are connected between the terminal of made piece, will be Solid measure value during 120Hz is used as the electric capacity for processing sheet of capacitor.

(6) measure of capacitor leakage electric current

At room temperature, the current value determined after 6.3V DC voltages being applied between the terminal of made piece 1 minute is made To process the leakage current values of sheet of capacitor.

(7) the apparent ratio of the capacitance of capacitor

It is assumed that determining under conditions of 80 DEG C and 20V the electrochemical shaping 1,000 in 0.1% phosphoric acid solution in 30% sulphuric acid Minute sintered body when capacitance be 100%, then capacitance it is apparent than with production capacitor after capacitance ratio table Show.

(8) the moisture-proof value of capacitor

Capacitance after being stood 500 hours under 60 DEG C and 95% relative humidity by the capacitor for being produced is less than initial value 110% or the number less than 120% represent moisture-proof value.Number less than 110% is more, illustrates that moisture-proof value is better.

(9) measure of the ESR values of capacitor

In room temperature, the LCR determinators of Hewlett-Packard manufactures are connected between the terminal of made piece, will be ESR of the ESR measured values under 100kHz, 1.5VDC and 0.5Vrms as capacitor.

Embodiment 1

It is fluoro niobic acid to load 5,000 grams in nickel crucible in 80 DEG C of abundant vacuum drying fluoro potassium niobates and mole The sodium that 10 times of potassium, and make the reduction reaction that it carries out under an argon 20 hours at 1,000 DEG C.Upon reaction completion, will reduce Product is cooled down, and is washed with water successively, with 95% sulfuric acid scrubbing, is then washed with water, is vacuum dried and using containing titanium dioxide silica The oxidation aluminium pot ball mill for changing aluminium ball is crushed 40 hours.By crushed products the 3 of 50% nitric acid and 10% aqueous hydrogen peroxide solution:2 (by mass) impregnate and stir in mixed solution.Then, crushed products water is fully washed, until pH value reaches 7, to go The removal of impurity, is then vacuum dried.The particle mean size of raw material niobium powder is 1.2 microns.

In niobium tank, place 500 grams of this raw material niobium powder and be added thereto to 50 grams of polybutyl methacrylates and 1 liter of first Benzene.Additionally, adding zirconia ball and being mixed content 1 hour using shaking mixer.After zirconia ball is removed, this is mixed Compound is placed in circular cone exsiccator and 1 × 10²It is vacuum dried under conditions of Pa and 80 DEG C.

Subsequently, by the niobium powder at 250-400 DEG C 1 × 10^-2Pa is heated 12 hours, to decompose and removes polymethylacrylic acid Butyl ester, then 4 × 10^-3Sinter 2 hours at 1,150 DEG C under the decompression of Pa.By the cooling of niobium powder sintering agglomerate until product temperatur 30 DEG C or lower are reduced to, it is then broken using roll pelletizer, to obtain the broken powder of niobium that particle mean size is 100 microns.

The broken powder of this niobium is obtained about by being passed through nitrogen under elevated pressure through the nitrogen treatment in 300 DEG C, 2 hours 450 grams of niobium powder.Nitrogen content is 0.22%.

The physical property of this niobium powder such as tap density, particle mean size, angle of repose, BET specific surface area and aperture peak exist Represent in table 1.

By such niobium powder for obtaining, (about 0.1 gram) loads tantalum device automatic forming machine (TAP-2R is manufactured by Seiken) In hopper, and together with the niobium silk of 0.3mm φ automatic forming come manufacture size be about 0.3cm × 0.18cm × 0.45cm into Shape product.Outward appearance and the qualitative dispersibility of molded article are represented in table 1.

The molded article is 4 × 10^-31 in the vacuum of Pa, 250 DEG C stand 30 minutes, to obtain sintered body.Prepare 100 The individual sintered body, and each use 0.1% phosphate aqueous solution electrochemical shaping 200 minutes under 20V voltages, so as to Oxide dielectric thin film is formed on surface.

Subsequently, repeat that the sintered body is immersed in 60% manganese nitrate aqueous solution and then make it heat 30 minutes at 220 DEG C Operation, so that manganese dioxide layer is formed on oxide dielectric thin film as to electrode layer.On this pair of electrode layer, layer successively Folded carbon-coating and silver paste layer.After mounted thereon lead frame, shaped the device as entirety with epoxy resin, to manufacture chip Capacitor.The apparent average capacitance amount and average leakage current than with chip capacitor (n=100) of capacitance of the capacitor (hereinafter referred to as " LC ") is represented in table 1.LC values are the 1 minute values in room temperature measuring of voltage by applying 6.3V.

Embodiment 2

In the reactor of SUS304,1,000 gram of niobium ingot is put into, and it is little to be continuously passed through hydrogen 10 thereto at 400 DEG C When.After the cooling period, the niobium ingot of hydrogenation is placed in the SUS304 tanks containing zirconia ball and is crushed 10 hours.Then, this is made Hydride forms the slurry of 20 volumes % with water, spike mill is loaded together with zirconia ball and under 40 DEG C or lower temperature Waterproof pulverization 7 hours, to obtain the hydrogenated niobium slurry of crushing.The particle mean size of this raw material hydrided niobium powder is 0.9 micron.

In SUS tanks, it is 1 to load this slurry (slurry concentration is 98%) and be added thereto to 200 grams of particle mean size The Barium monoxide of micron.Additionally, adding zirconia ball and being mixed content 1 hour using shaking mixer.Except deoxidation After zirconium ball, the mixture is placed in the bucket of niobium, and 1 × 10²It is vacuum dried under conditions of Pa and 50 DEG C.

Subsequently, 1 × 10^-2The mixture of gained are heated into 4 hours at 400 DEG C under Pa, to make hydrogenated niobium dehydrogenation, then 4 × 10^-3Sinter 2 hours at 1,100 DEG C under the decompression of Pa.By gained be mixed with the sintering agglomerate cooling of barytic niobium until Product temperatur is reduced to 30 DEG C or lower, then broken using roll pelletizer, to obtain the mixing that particle mean size is 95 microns The broken powder of barytic niobium.

Load this of 500 grams in polytetrafluoroethylcontainer container and be mixed with the broken powder of barytic niobium and 1,000 gram ions Exchanged water is simultaneously cooled to 15 DEG C or lower.It is manufactured separately by 600 gram of 60% nitric acid of mixing, 150 gram of 30% hydrogen peroxide and 750 grams Ion exchange water is simultaneously cooled to 15 DEG C or lower obtained aqueous solution.Then suspended thereto under agitation mixing Aqueous solution of 500 grams of Deca in the aqueous solution of the broken powder of barytic niobium, and it is careful not to make water temperature more than 20 DEG C. After being added dropwise to complete, by solution continuous stirring 1 hour again, 30 minutes are stood, be then decanted.It is added thereto to 2,000 gram ions Exchanged water, and by the solution stirring 30 minutes of gained, 30 minutes are stood, then it is decanted.The operation is repeated 5 times.Then, niobium is broken Comminuted powder is fitted in polytetrafluoroethylene post, and washes with water 4 hours while making deionized water flow.Now, electrical conductivity of water is washed For 0.9 μ S/cm.

After the completion of washing, the broken powder of niobium is dried under reduced pressure at 50 DEG C, and by passing through nitrogen Jing under elevated pressure Cross the nitrogen treatment 3 hours at 300 DEG C, as a result, obtain about 350 grams of niobium powder.Nitrogen content is 0.28%.

The physical property of this niobium powder such as tap density, particle mean size, angle of repose, BET specific surface area and aperture peak exist Represent in table 1.

By such niobium powder for obtaining, (about 0.1 gram) loads tantalum device automatic forming machine (TAP-2R is manufactured by Seiken) In hopper, and together with the niobium silk of 0.3mm φ automatic forming come manufacture size be about 0.3cm × 0.18cm × 0.45cm into Shape product.Outward appearance and the qualitative dispersibility of molded article are represented in table 1.

The molded article is 4 × 10^-31 in the vacuum of Pa, 250 DEG C stand 30 minutes, to obtain sintered body.Prepare 100 The individual sintered body, and each use 0.1% phosphate aqueous solution electrochemical shaping 200 minutes under 20V voltages, so as to Oxide dielectric thin film is formed on surface.

Subsequently, the equivalent for making oxide dielectric thin film and 10% ammonium persulfate aqueous solution and 0.5% anthraquinone sulfonic acid solution is mixed Solution contact is closed, the operation for then contacting with pyrroles's steam repeats at least 5 times, to form bag on oxide dielectric thin film Containing polypyrrole to electrode.

On this pair of electrode layer, carbon-coating and silver paste layer are stacked gradually.After mounted thereon lead frame, using the device as Overall epoxy resin shapes, to manufacture chip capacitor.The apparent ratio of capacitance of the capacitor and chip capacitor (n=100 It is individual) average capacitance amount and average LC values represent in table 1.LC values are by applying the voltage 1 minute of 6.3V in room temperature measuring Value.

Embodiment 3～10

Niobium powder, its molded article, sintered body and capacitor are produced with method same as Example 1, but changes average The addition of granularity and polybutyl methacrylate, or produced with method same as Example 2, but change particle mean size With barytic addition.The physical property and outward appearance of niobium powder and the dispersibility of molded article quality, and the electric capacity of capacitor Amount and LC are represented in table 1.

Embodiment 11～22

With the niobium powder of method production example 11～14 and 16～18 same as Example 1, molded article and sintered body, With the niobium powder of method production example 15 and 19～22 same as Example 2, molded article and sintered body, but in every kind of feelings The activator made using table 1 under condition replaces polybutyl methacrylate or Barium monoxide.The physical property and outward appearance of niobium powder and into The dispersibility of shape quality of item, and the capacitance and LC of capacitor represent in table 1.

These molded articles are then at 1,250 DEG C 4 × 10^-330 minutes are stood under the decompression of Pa, to obtain sintered body.System Every kind of sintered body of standby 100, and using 0.1% phosphate aqueous solution under 20V voltages electrochemical shaping 200 minutes, so as to Oxide dielectric thin film is formed on surface.

Subsequently, every kind of sintered body that oxide dielectric thin film has been formed thereon is immersed in into the mistake containing 25 mass % In the aqueous solution (solution 1) of ammonium sulfate, pull out, in 80 DEG C of dryings 30 minutes, be immersed in 3, the 4- ethylenes containing 18 mass % In the aqueous isopropanol (solution 2) of oxygen thiophene, pull out, then stand 10 minutes in 60 DEG C of air, it is poly- so as to carry out oxidation Close.The sintered body is immersed in again in solution 1, then with the above identical method process.From impregnating until oxygen in solution 1 The operation for changing polymerization is repeated 8 times.Then, sintered body is washed 10 minutes with 50 DEG C of warm water, and in 100 DEG C of dryings 30 minutes, So as to be formed comprising conductive poly (3,4- ethyldioxythiophenes) to electrode.

On this pair of electrode, carbon-coating and silver paste layer are stacked gradually.After mounted thereon lead frame, using the device as whole Body is shaped with epoxy resin, to manufacture chip capacitor.The apparent ratio of capacitance and chip capacitor (n=100) of the capacitor Average capacitance amount and average LC values represent in table 1.LC values are by applying the voltage 1 minute of 6.3V in room temperature measuring Value.

Embodiment 23～25

Niobium powder, sintered body and capacitor are produced with method same as Example 2, but as raw material, in embodiment 23 Used in niobium-tin alloy powder, the hydrogenated niobium used in embodiment 24-rhenium alloys powder, the hydrogenated niobium used in embodiment 25- Yttrium-boron alloy powder.The physical property of capacitor, capacity and LC are represented in table 1.

Comparative example 1～3

It is potassium niobate fluoride 10 to load 2,000 grams in nickel crucible in 80 DEG C of abundant vacuum drying potassium niobate fluorides and mole Times sodium, and make the reduction reaction that it carries out under an argon 20 hours at 1,000 DEG C.Upon reaction completion, by reduzate Cooling, washes in order, with 95% sulfuric acid scrubbing, then washes with water, vacuum drying and using containing silica-zirconia The oxidation aluminium pot ball mill of aluminium ball is crushed, and changes grinding time.By crushed products in 50% nitric acid and 10% aqueous hydrogen peroxide solution 3:Impregnate and stir in 2 (by mass) mixed solutions.Then, every kind of crushed products water is fully washed, until pH value 7 are reached, to go the removal of impurity, is then vacuum dried.The particle mean size of the niobium powder for being produced is 1.3 microns～10 microns.

Subsequently the niobium powder of 50 grams of gained is placed in SUS304 reactors, and continuously nitrogen 2 is passed through thereto at 300 DEG C ～4 hours, to obtain niobium nitride.

The physical property of every kind of niobium powder such as tap density, particle mean size, angle of repose, BET specific surface area and aperture peak exist Represent in table 1.

By such niobium powder for obtaining, (about 0.1 gram) loads tantalum device automatic forming machine (TAP-2R is manufactured by Seiken) In hopper, and attempt the automatic forming together with the niobium silk of 0.3mm φ.Acquired results are represented in table 1.

Comparative example 4～9

Still change the barytic addition that particle mean size is 1 micron with method same as Example 2, shaken Real density is 0.2～0.4g/ml or the niobium powder of 2.6～3.3g/ml.Its physical property is represented in table 1.

By such niobium powder for obtaining, (about 0.1 gram) loads tantalum device automatic forming machine (TAP-2R is manufactured by Seiken) In hopper, and together with the niobium silk of 0.3mm φ automatic forming come manufacture size be about 0.3cm × 0.18cm × 0.45cm into Shape product.Outward appearance and the qualitative dispersibility of molded article are represented in table 1.

These molded articles are 4 × 10^-31 in the vacuum of Pa, 250 DEG C stand 30 minutes, to obtain sintered body.Prepare Every kind of sintered body of 100, and using 0.1% phosphate aqueous solution under 20V voltages electrochemical shaping 200 minutes, so as in table Oxide dielectric thin film is formed on face.

Subsequently, the equivalent for making oxide dielectric thin film and 10% ammonium persulfate aqueous solution and 0.5% anthraquinone sulfonic acid solution is mixed Close solution contact and and then the operation that contact with pyrroles's steam repeatedly at least 5 times, so as to the shape on oxide dielectric thin film Into comprising polypyrrole to electrode.

On this pair of electrode, carbon-coating and silver paste layer are stacked gradually.After mounted thereon lead frame, using the device as whole Body is shaped with epoxy resin, to manufacture chip capacitor.The apparent ratio of capacitance and chip capacitor (n=100) of the capacitor Average capacitance amount and average LC values represent in table 1.LC values are by applying the voltage 1 minute of 6.3V in room temperature measuring Value.

Embodiment 26～31

The hydride of niobium ingot is crushed and dehydrogenation is to obtain the primary granule that particle mean size is 0.8 micron.By the original of gained Beginning granule is sintered and crushed, to obtain niobium prilling powder.Then, by the 0.1 gram prilling powder and the long 10mm being manufactured separately, The niobium silk of thick 0.3mm is mounted in together in metal die (4.0mm × 3.5mm × 1.8mm), and using tantalum device automatic forming machine (TAP-2R is manufactured by Seiken) applies load as shown in table 2 to it, to produce molded article.Then each is shaped Product is sintered 30 minutes at 1300 DEG C, to obtain target sintered body.By controlling the load that forming machine applies, produce with table The sintered body of the pore-size distribution shown in 2.The size of the sintered body of embodiment 26, specific surface area and CV values are respectively 24.7mm³、 1.1m²/ g and 85,000 μ FV/g.In other embodiments, each value is in the range of ± the 2% of embodiment 26.

Embodiment 32～34

Sintered body is obtained with the identical method of embodiment 26～28, but by making primary granule classification average to change Granularity is 0.5 micron.The size of the sintered body of embodiment 32, specific surface area and CV values are respectively 24.9mm³、1.5m²/ g and 125, 000μFV/g.In other embodiments, each value is in the range of ± the 1% of embodiment 32.The hole of each sintered body for being produced Footpath is distributed in table 2 and represents.

Embodiment 35

Sintered body is obtained with the identical method of embodiment 31, but using method acquisition in the same manner as in Example 4 Niobium powder replaces the pelletizing.The size of the sintered body of embodiment 35, specific surface area and CV values are respectively 24.8mm³、1.2m²/g With 78,000 μ FV/g.The pore-size distribution of the sintered body for being produced is represented in table 2.

Comparative example 10～12

Sintered body is produced with the identical method of embodiment 26～28, but is used in 1,100 DEG C of heat treatment magnesium-reduceds Niobium powder prepared by niobium chloride replaces niobium pelletizing used in embodiment 26～28.The size of the sintered body of comparative example 10, ratio Surface area and CV values are respectively 24.3mm³、0.8m²/ g and 84,000 μ FV/g.In other comparative examples, each value is in comparative example In the range of ± the 2% of 10.The pore-size distribution of each sintered body for being produced is represented in table 2.

Embodiment 36

With the various sintered bodies 60 produced with embodiment 21 and the identical method of embodiment 26～35, each is at 80 DEG C In 0.1% phosphate aqueous solution and 20V electrochemical shapings 1,000 minute, to form oxide dielectric on sintered body surface Thin film.Sintered body after these electrochemical shapings is grouped, is constituted by 30 per group.By 30 sintered body tables 3 in per group Shown in two kinds of negative electrode agent A and B dipping.Carbon paste and silver paste are stacked gradually thereon, and the device is shaped with epoxy resin, To prepare chip capacitor.The capacitance of each manufactured capacitor is apparent than representing in table 4 with moisture-proof value.

Comparative example 13

With the various sintered bodies 60 produced with the identical method of comparative example 9～12, each phosphoric acid water at 80 DEG C 0.1% In solution and 20V electrochemical shapings 1,000 minute, to form oxide dielectric thin film on sintered body surface.By these Sintered body packet after electrochemical shaping, is constituted per group by 30.By 30 negative electrodes of the sintered body shown in table 3 in per group Agent A impregnates.Carbon paste and silver paste are stacked gradually thereon, and the device is shaped with epoxy resin, to prepare chip capacitor.Institute The capacitance of each capacitor of manufacture is apparent than representing in table 4 with moisture-proof value.

Embodiment 37

Raw material hydrided niobium powder is crushed by method same as Example 2, slurry is obtained.The hydrogenant agent powder it is average Granularity is 0.6 micron.After pulp centrifuged sedimentation, the supernatant is removed by decantation.Being added thereto to anhydrous propanone makes slurry Concentration is 40 mass % and well suspended.After the solution centrifugal sedimentation of gained, the supernatant is removed by decantation.Thereto plus Enter anhydrous propanone, make slurry concentration for 60 mass % and well suspended.The slurry is mounted in SUS tanks, and is added respectively thereto The particle mean size of 15 mass % and 10 mass % that enter niobium quality is the Barium monoxide of 1.4 microns and 23 microns.Additionally, adding zirconium oxide Ball simultaneously mixes content 1 hour using shaking mixer.Remove zirconia ball after, by the mixture be placed in niobium bucket and 1×10²It is vacuum dried under the conditions of Pa and 50 DEG C.

Obtained with method same as Example 2 and be mixed with barytic niobium sintering agglomerate and the broken powder of niobium.

Under agitation this of 500 grams is mixed with into the broken powder of barytic niobium and is added to and be cooled to 15 DEG C or lower 1, In 000 gram ion exchanged water and it is careful not to make water temperature more than 20 DEG C.After the addition is complete, by the solution, again continuous stirring 1 is little When, 30 minutes are stood, then it is decanted.It is added thereto to 2,000 gram ion exchanged water, and by the solution stirring 30 minutes of gained, 30 minutes are stood, is then decanted.The operation is repeated 5 times.Then, the broken powder of niobium is fitted in polytetrafluoroethylene post, and is washed with water Wash 4 hours while making deionized water flow.Now, it is 0.5 μ S/cm to wash electrical conductivity of water.

After the completion of washing, the broken powder of niobium is dried under reduced pressure at 50 DEG C and passes through nitrogen under elevated pressure and is passed through 300 DEG C of nitrogen treatment 3 hours, as a result, obtain about 350 grams of niobium powder.Nitrogen content is 0.30%.

The physical property of this niobium powder such as tap density, particle mean size, angle of repose, BET specific surface area and aperture peak exist Represent in table 5.

With method manufacture molded article same as Example 2.The outward appearance and mass-dispersion of molded article table in table 5 Show.

Then thin dielectric film is formed on the surface of the sintered body of molded article with method same as Example 2.So Shape paired electrode and it is laminated carbon-coating and silver paste layer thereon successively afterwards.After mounted thereon lead frame, the device is used as overall use Epoxy resin shapes, to prepare chip capacitor.The capacitance of the capacitor is apparent than average with chip capacitor (n=100) Capacitance and average LC values are represented in table 5.

Embodiment 38～44

By the species, the average pore size of two kinds of niobium powder to be mixed and the consumption that change added activator, with reality Apply identical method in example 37 and obtain the broken powder of the niobium mixed with activator.Dissolving activator solvent selected from water, acid, alkali, Solvent containing ion exchange resin, ammonium nitrate solvent and the solution containing edetate.With with phase in embodiment 37 Same method dissolves activator to obtain niobium powder.The physical property of the niobium powder is represented in table 5.

Molded article and sintered body are manufactured with identical method in embodiment 37, to prepare chip capacitor.Shaping system The outward appearance and mass-dispersion of product and the capacitance of capacitor and average LC values are represented in table 5.

Embodiment 45～47

As raw material, the niobium used in embodiment 45-neodymium alloy powder respectively, niobium-tungsten alloy used in embodiment 46 Powder, the niobium used in embodiment 47-tantalum alloy powder obtains niobium alloy powder with identical method in embodiment 37.Niobium The physical property of alloy powder is represented in table 5.

With preparing molded article and sintered body to prepare chip capacitor with identical method in embodiment 37.Shaping system The outward appearance and mass-dispersion of product and the capacitance of capacitor and average LC values are represented in table 5.

Embodiment 48～58

Using the niobium powder obtained in embodiment 37～47, with method production niobium sintered body same as Example 2.Sintering The pore-size distribution of body is represented in table 6.

Embodiment 59～69

The every kind of sintered body 100 obtained in embodiment 48～58 is prepared, and is existed using 0.1 mass % phosphate aqueous solution 20V and 80 DEG C of electrochemical shaping 1,000 minute, to form oxide dielectric thin film on the surface.These sintered bodies table 3 Shown in negative electrode agent dipping.Carbon-coating and silver paste layer are stacked gradually thereon and overall epoxy resin shaping is to prepare chip electricity Container.The capacitance of prepared capacitor is apparent than representing in table 7 with ESR.

Comparative example 14～17

The every kind of sintered body 100 obtained in comparative example 9～12 is prepared, and is existed using 0.1 mass % phosphate aqueous solution 20V and 80 DEG C of electrochemical shaping 1,000 minute, to form oxide dielectric thin film on the surface.These sintered bodies table 3 Shown in negative electrode agent dipping.Carbon-coating and silver paste layer are stacked gradually thereon and overall epoxy resin shaping is to prepare chip electricity Container.The capacitance of prepared capacitor is apparent than representing in table 7 with ESR.

Table 2

Table 3

Table 4

Table 6

Table 7

Industrial applicibility

Tap density is 0.5～2.5g/ml, particle mean size is 10～1000 microns, angle of repose is 10～60 ° and BET ratios Surface area is 0.5～40m²The niobium powder of the present invention of/g is excellent in terms of mobility and can progressive forming.By sintering institute State that niobium powder is obtained and have aperture peak in 0.01～500 micrometer range and preferably there are multiple aperture peaks in pore-size distribution The niobium sintered body of value is used for electrode for capacitors, it is possible to obtain high-capacitance it is apparent than and can produce that leakage current is low and moisture-proof The excellent capacitor of property.

Claims (18)

1. a kind of electrode for capacitors including niobium sintered body, wherein, niobium sintered body be that niobium powder is compressed and molded into into reservation shape and Obtain, the pore-size distribution of niobium sintered body has multiple aperture peaks, and the specific surface area of the sintered body is 0.2～7m²/ g, institute Stating niobium sintered body is obtained by using the activator of the particle size distribution with multiple peak values.

2. the electrode for capacitors described in claim 1, wherein, the pore-size distribution has two aperture peaks.

3. the electrode for capacitors described in claim 1, wherein, the volume of the sintered body is 10mm³Or it is bigger, including hole Volume.

4. the electrode for capacitors described in claim 1, wherein, a part of sintered body is nitrogenized.

5. the electrode for capacitors described in claim 1, wherein, the sintered body is the sintering obtained by a kind of niobium formed body Body, the niobium formed body produces a kind of sintered body of CV values in 1300 DEG C of sintering for 40,000～200,000 μ FV/g.

6. a kind of capacitor, comprising usage right require the electrode for capacitors described in 1～5 any one an electrode, one It is individual to electrode and intervenient dielectric material.

7. the capacitor described in claim 6, wherein, the dielectric material mainly includes niobium oxide.

8. the capacitor described in claim 6, wherein, it is at least one to electrode selected from electrolyte solution, organic semiconductor With the material of inorganic semiconductor.

9. the capacitor described in claim 8, wherein, it is organic semiconductor to electrode, and organic semiconductor is selected from bag The organic semiconductor of the tetramer of quinoline containing benzopyrrole and chloranil, the main organic semiconductor comprising four thio naphthacene, main bag The organic semiconductor of the bismethane of quinone containing four cyano and at least one material of electric conductive polymer.

10. the capacitor described in claim 9, wherein, electric conductive polymer be it is at least one selected from polypyrrole, polythiophene, The composition of polyaniline and its substitutive derivative.

Capacitor described in 11. claim 9, wherein, electric conductive polymer is by containing following formula (1) or (2) expression Repetitives polymer in mix dopant obtain electric conductive polymer：

Wherein, R¹～R⁴Independently of one another represent selected from hydrogen atom, the saturation of the straight or branched containing 1～10 carbon atom or Unsaturated alkyl, alkoxyl or alkyl ester group, halogen atom, nitro, cyano group, primary, secondary or tertiary amino, CF₃Group, phenyl With the univalent perssad of the phenyl for replacing；Every a pair of R¹And R²、R³And R⁴Bivalence chain can at an arbitrary position be combined to form, for By R¹And R²Or by R³And R⁴Substituted carbon atom forms together at least one 3-, 4-, 5-, 6- or 7- unit's saturations or unsaturated hydrocarbons Ring structure；The chain that ring-type is combined optionally contains at an arbitrary position carbonyl, ether, ester, amide, thioether, sulfinyl, sulfonyl or Asia Amino；X represents oxygen atom, sulphur atom or nitrogen-atoms；R⁵Just exist only when X is nitrogen-atoms, and independently represent hydrogen atom Or straight or branched the, saturation or unsaturated alkyl containing 1～10 carbon atom.

Capacitor described in 12. claim 11, wherein, electric conductive polymer is containing the repetition list represented by following formula (3) The electric conductive polymer of unit：

Wherein, R⁶And R⁷Hydrogen atom, the saturation of the straight or branched containing 1～6 carbon atom or unsaturation are represented independently of one another Alkyl, or a substituent group, for formed by the alkyl that be combined with each other at an arbitrary position obtain containing two oxygen atoms At least one 5-, 6- or 7- units saturated hydrocarbons ring structure；And circulus include having the ethenylidene key that can be substituted, can be with The structure of substituted phenylene structure.

Capacitor described in 13. claim 9, wherein, electric conductive polymer is by poly- (3,4- ethylidene dioxy thiophenes Fen) the middle electric conductive polymer for mixing dopant acquisition.

Capacitor described in 14. claim 6, wherein, electrode is made up of the material at least partly having layer structure.

Capacitor described in 15. claim 6, wherein, organic sulfonic acid root anion is contained as doping to the material of electrode Agent.

A kind of 16. methods for producing capacitor, the capacitor is comprising an electrode using niobium sintered body, in the sintered body On surface formed dielectric material and on the dielectric material provide one to electrode, wherein, the niobium sintered body be The niobium sintered body included by electrode for capacitors described in any one of Claims 1 to 5.

A kind of 17. usage rights require the electronic circuit of the capacitor described in 6～15 any one.

A kind of 18. usage rights require the electronic machine of the capacitor described in 6～15 any one.