CN101263086A - Organic compound - Google Patents
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- CN101263086A CN101263086A CNA2006800195198A CN200680019519A CN101263086A CN 101263086 A CN101263086 A CN 101263086A CN A2006800195198 A CNA2006800195198 A CN A2006800195198A CN 200680019519 A CN200680019519 A CN 200680019519A CN 101263086 A CN101263086 A CN 101263086A
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- Prior art keywords
- niobium
- powder
- niobium suboxide
- suboxide powder
- nbo
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- 150000002894 organic compounds Chemical class 0.000 title 1
- 239000010955 niobium Substances 0.000 claims abstract description 108
- 239000000843 powder Substances 0.000 claims abstract description 78
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 72
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 230000000802 nitrating effect Effects 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000007323 disproportionation reaction Methods 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 metal oxide compound Chemical class 0.000 description 3
- 150000002821 niobium Chemical class 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000009183 running Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed is a niobium suboxide powder for the manufacture of capacitors with higher break down voltages, higher temperatures of operation and elongated lifetimes. The powder is doped with nitrogen which is at least partly present in the form homogeneously distributed, x-ray detectable Nb2N-crystal domains.
Description
Technical field
The present invention relates to can be used for making the niobium suboxide powder of solid electrolyte capacitators, particularly nitrogenous niobium suboxide powder.
Background technology
The solid electrolyte capacitators that can be used for mobile communication equipment generally includes the conductive carrier of high-ratio surface, this carrier is covered by non-conductive niobium or tantalum pentoxide layer, this layer has utilized the high stability and the high-k of valve-use metal oxide compound (valvemetal oxide), and the pentoxide layer that wherein insulate can be by electrolytic oxidation with very constant thickness generation.Conduction suboxide (suboxide, the NbO of valve-use metal or valve-use metal
x) as solid support material.The carrier that forms one of the electrode (anode) of electrical condenser has the highly porous spongy structure usually, and normally sintering produces this structure by very fine primary structure or spongy secondary structure are carried out.The surface of conductive carrier structure is through electrolytic oxidation (" be shaped (forming) "), thereby determines the thickness of insulation pentoxide layer by the peak voltage (" shaping voltage ") of electrolytic oxidation.Make the structure of spongy surface appearance oxidation soak manganous nitrate, the manganous nitrate thermal transition is a Manganse Dioxide, perhaps soaks Liquid precursor and its polymerisate of polymer dielectric (for example PEDT, polypyrrole (polypyrole)), thereby produces counter electrode.Electric terminals is tantalum or niobium metal line, and itself and the spongy structure of anode one side and the metal shell sintering with metal wire insulating electrical condenser of negative electrode one side are in the same place.
Capacitor C according to following formula calculable capacitor:
C＝(F·ε)/(d·V
F)
Wherein F is the effective surface of electrical condenser, and ε is the specific inductivity of pentoxide layer, and d is the thickness for the insulation pentoxide layer of every volt shaping voltage, V
FBe shaping voltage.Although the ε value of tantalum pentoxide and Columbium pentoxide (being respectively 27.6 and 41) and d value (be respectively 16.6 with 25A/V) are obviously different, their ε/d is than almost equal (being respectively 1.64 and 1.69).Therefore, the electrical condenser with identical geometry based on these two kinds of pentoxides has identical electric capacity.Because Nb, NbO
xHave nothing in common with each other with the density of Ta, thus unit weight than electric capacity difference.Therefore, Nb or NbO
xCarrier (anode) structure when being used for mobile telephone, have the advantage of weight reduction really, and weight reduction is one of target of the sector.Consider cost, NbO
xMore practical than Nb, a part of volume of anode construction is occupied by oxygen.
Important quality standard is the work-ing life of electrical condenser, and this performance depends on the operating voltage of electrical condenser, and reduces along with the rising of voltage.In order to obtain wideer range of application, the work-ing life when special hope prolongs high working voltage.
In addition, hope can improve working temperature.At present, the working temperature based on the electrical condenser of NbO is limited in about 125 ℃.Can allow higher working temperature will widen the application of electrical condenser in automotive industry based on NbO.
In addition,, wish to improve voltage breakdown, the rate of combustion that slows down, the generation heat of minimizing powder, agglomerating anode construction and electrical condenser igniting afterfire process about secure context.
Summary of the invention
An object of the present invention is to provide a kind of niobium suboxide powder, this niobium suboxide powder has the character of improvement, and produces the electrical condenser that increase work-ing life thus.
Another object of the present invention provides a kind of niobium suboxide powder, and this niobium suboxide powder has the character of improvement, can be worked under higher temperature by the electrical condenser of its production.
Another object of the present invention provides a kind of niobium suboxide powder, and this niobium suboxide powder has the character of improvement, can produce the electrical condenser with higher voltage breakdown.
Another object of the present invention provides a kind of niobium suboxide powder and by the anode construction of its manufacturing, they have rate of combustion that slows down and the generation heat that reduces when igniting.
Embodiment
Realize these and other objects by the present invention.
Theme of the present invention is the niobium protoxide powder that comprises niobium protoxide particle, and its volume (bulk) contains The nitrogen amount is 500-20, and 000ppm is preferably 1000-10,000ppm. More preferably nitrogen content is 2000-8000ppm is particularly preferably 3000-5000ppm.
The form of the nitrogen that preferably, contains in the niobium protoxide powder of the present invention is Nb at least in part2N crystal or oxynitriding niobium NbOxN
vCrystal.
Well-known in the tantalum capacitor technical field, surface nitrogen has positive effect to the sintering of tantalum powder Really, and can improve the leakage current of tantalum capacitor. In contrast, an importance of the present invention is nitrogen Substantially the body that is evenly distributed in powder particle mutually in, is very little Nb at least in part preferably2The form of N domain, and the amount of nitrogen and size should be enough big, so that using CuκαWhen the x Diffraction of-radiation is observed, at 2 about 38.5 ° Θ-angle (Nb2The 101 reflection crystal faces of N) can detect the peak.
Preferably, locate Nb about 2 Θ=38.5 °2The height at N peak is less than ° locate NbO peak (NbO in 2 Θ=30 110 reflection crystal faces) height 25%, preferably less than ° locate 15% of NbO peak heights in 2 Θ=30.
More preferably powder ° locates to show Cu in 2 Θ=38.5
κ α-x ray peak, the height at this peak be ° locate in 2 Θ=30 the NbO peak height at least 2%, preferably at least 5%.
In the higher scope of nitrogen content, can detect other crystal nitride phase, for example niobium nitride or oxynitriding niobium.More specifically, can detect Nb
4N
3, NbN
0.77, Nb
0.77N
0.091, NbN
0.64, NbN
0.9, NbN
0.95, Nb
4.62N
2.14, Nb
4N
3.92, Nb
4N
5, Nb
5N
6, NbN
0.801, NbN etc. or its mixture, perhaps oxynitriding niobium, for example NbN
0.6O
0.3, NbN
0.6O
0.2, NbN
0.9O
0.1, Nb (N, O) wait or they each other mixture or with the mixture of niobium nitride.Especially can detect NbN
0.77, NbN
0.95, NbN etc. or oxynitriding niobium.
Locate (Nb about 2 Θ=38.5 °
2(101)-peak of N) Cu
κ α 1The peak width at half height at-peak is preferably 0.05 ° to 0.2 °, be preferably 0.07-0.15 °, this structure is measured by goniometer Panalytical X ' Pert MPD PW 3050, the anode of described instrument is Cu, and 50 kilovolts and 40 milliamperes, having respectively is divergent slit and the anti-scatter slit of 1/2 ° of 2 Θ, 0.2 the reception slit of millimeter, 0.04 the Suo La of rad (Soller) slit, 20 millimeters beam cover, detector charges into Xe pro rata.Scanning sequence is 0.01 ° of 2 Θ of step-length between 37.7-39.5 ° of 2 Θ, and scanning speed is 0.001 ° of 2 Θ/second.Cu
K α 2Reflect to form the band peak.
Preferably, as follows according to the particle size distribution characteristic of powder of the present invention: the D10 value is the 50-90 micron, and the D50 value is the 150-210 micron, and the D90 value is the 250-350 micron, and this numerical basis AS TM B 822 (" Mastersizer ", wetting agent Daxad 11) records.Particularly preferably be, powder is sphere or ellipsoidal particle, has good flowability, and the numerical value that records according to ASTM B 213 (" Hall flowability (Hall flow) ") restrains less than 80 seconds/25, preferably less than 60 seconds/25 grams, is more preferably less than 40 seconds/25 grams.Volume density according to powder of the present invention is preferably the 0.5-2 gram per centimeter
3, 0.9-1.2 gram per centimeter more preferably
3(14.8-19.7 gram/inch
3), this numerical basis ASTM B 329 (" scott density (Scott density) ") records.
The highly porous coacervate of the primary particles that each particulate of niobium suboxide powder or particle are preferably intensive (primary particles), the mean particle size of described primary particles are that minimum diameter of section is the 0.1-1.5 micron, are preferably the 0.3-1.0 micron.Described primary particles can be sphere, crumb form or fibrous texture.The smallest cross-sectional diameter of preferred described primary particles is the 0.4-1 micron.
Be preferably 50-70 volume %, more preferably 53-65 volume % by what mercury penetration method (mercury intrusion) measured by the powder sintered anodic porosity that forms of the present invention.Surpassing 90% pore volume is that the hole of 0.2-2 micron is formed by diameter.Wide pore distribution curve has precipitous slope in both sides, minimum value is within the double-wide of initial particle.
The specific surface area of the powder of being measured by ASTM D 3663 (" BET-surface-area ") of the present invention is preferably 0.5-12.0 rice
2/ gram is preferably 0.6-6 rice
2/ gram, more preferably 0.7-2.5 rice
2/ gram, preferred especially specific surface area is a 0.8-1.2 rice
2/ gram, perhaps 0.8-1.3 rice
2/ gram.
Ratio electric capacity by the electrical condenser of powdered preparation of the present invention is 40,000-300, and 000 μ FV/g is generally 60,000-200,000 μ FV/g.
Preferred niobium oxide powder of the present invention has as general formula NbO
xComposition, 0.7＜x＜1.3 wherein, being equivalent to oxygen level is 10.8-18.3 weight %, is preferably 1.0＜x＜1.033 especially, perhaps the oxygen level of powder is 14.5-15.1 weight %.
Usually, the impurity in the niobium suboxide powder of the present invention should be low as far as possible, particularly should be respectively less than 15ppm for the content of the deleterious impurity of electrical condenser articles for use such as Fe, Cr, Ni, Cu, Na, K and Cl.The total content of preferred these detrimental impurity is less than 35ppm.Carbon content is preferably less than 40ppm.The content of impurity that other hazardous property is lower slightly such as Al, B, Ca, Mn and Ti is preferably less than 10ppm, and Si content is less than 20ppm.The content of Mg mostly is 500ppm most.
Phosphorus is normally harmless.At niobium metal that is used for electrical condenser and tantalum metal powder, Doping Phosphorus can reduce the sintering activity of powder.The sintering activity of not wishing niobium suboxide powder of the present invention usually reduces.Therefore, the content of preferred phosphorus is lower than 10ppm.If desired, can be before sintering, handle substantially not phosphorated powder with phosphoric acid, ammonium hydrogen phosphate or ammonium phosphate solution.
As general formula (Nb, Ta) O
xShown in, tantalum can be used as the alloy compositions that substitutes niobium and exists.
Theme of the present invention also comprises the method for making nitrogenous niobium suboxide powder, this method by the niobium metal powders precursor as raw material, feature be the niobium metal precursor before being converted into niobium oxide by nitrogenize.
Various known methods can be used for making niobium metal powders to be converted into NbO.Preferred the inventive method is solid-state disproportionation (disproportionation) method: niobium metal powders is mixed with the niobium oxide of stoichiometric quantity, and this niobium oxide has been oxidized to the valence state that is higher than required product, is preferably Nb
2O
5Or NbO
2, then with mixture at nonoxidizing atmosphere, preferably be heated to the temperature that is enough to cause disproportionation reaction in reductibility inert atmosphere such as hydrogen or the argon gas/hydrogen mixed gas, normally be heated to 800-1600 ℃, the heating time enough for example heated several hours, obtained uniform oxygen distribution.Preferably, metal precursor and metal oxide precursor are approximately equal to or less than 1 micron primary particles composition by diameter (if the right and wrong sphere then is minimum cross section).
For the nitrogenize (making the nitrogen that mixes in the metal) of niobium metal precursor powder, with this metal-powder and solid nitrogenous compound such as Mg (N
3)
2Or NH
4Cl mixes, and perhaps handles with the aqueous solution of nitrogenous compound, is heated to 400-750 ℃ temperature under inert atmosphere, perhaps 400-750 ℃ with nitrogenous gaseous reactant such as N
2Or NH
3Reaction.Preferably, gaseous reactant provides to inert atmosphere such as argon gas with the ratio of 15-30%.Amount by suitable selection heat treatment time and thermal treatment temp control nitrating.
According to another kind of method, ratio that nanocrystal niobium nitride can be required and niobium metal powders mixture are heat-treated at 400-900 ℃ in inert atmosphere, make the metal-powder nitrogenize.
Before nitrogenize, can mix by the oxide precursor that niobium metal powders precursor and degree of oxidation is higher, can reduce operation steps like this.In this case, after nitrogenizing reaction is finished, change atmosphere, mixture further is heated to the temperature that solid-state disproportionation reaction takes place.
The extremely pure Nb that can be used as oxide precursor of the present invention
2O
5Can obtain by the following method: to H
2NbF
7Add NH in the solution
4The OH aqueous solution obtains the niobium hydroxide precipitation, and isolating niobium hydroxide from solution is calcined.
Preferably by extremely pure Nb
2O
5Reduction obtain the niobium metal precursor.This reaction can be undertaken by thermite reduction, promptly lights Nb
2O
5/ Al mixture therefrom cleans out aluminum oxide, by electron beam heating purifying niobium metal.The niobium metal that obtains thus can become fragile by the hydrogen diffusion of known way, grinds and obtains having the granulated powders that is similar to fragment.
The method that preferably makes pentoxide be reduced to metal is the dual stage process that discloses among the WO 00/67936.According to this method, at first in hydrogen atmosphere, pentoxide roughly is reduced to columbium dioxide at about 1000-1600 ℃, in subordinate phase, in about 900-1100 ℃ processing, be reduced to niobium metal with magnesium vapor.The magnesium oxide that forms in reduction can be removed by pickling.But in the niobium metal nitrogenize be converted into NbO
xBefore, not necessarily to remove magnesium oxide.On the contrary, be converted into NbO
xProcess in exist magnesium oxide for NbO
xThe porosity of powder has active influence.
The temperature that can be undertaken by the solid-state disproportionation of suitable selection or under argon gas atmosphere product is carried out the granularity (secondary granularity) that the temperature of sintering thermal treatment and screening (screening) is regulated powder particle afterwards, described argon gas atmosphere preferably contains maximum 10% hydrogen.
Explain the present invention in more detail by following examples now:
The A precursor: use following precursor:
Al: high purity N b
2O
5, make by following steps: to H
2NbO
7Add NH in the aqueous solution
4The OH aqueous solution produces precipitation, precipitation separation, and drying 1100 ℃ of calcinings, below is an analytical data in air:
Al：1ppm
Cr：＜0.3ppm
C：＜10ppm
Fe：＜0.5ppm
K：0.6ppm
Mg：＜1ppm
Mn：＜0.1ppm
Mo：＜0.3ppm
Na：3ppm
Ni：＜0.2ppm
Si：14ppm
Scott density: 12.2 gram/inches
3
A2: NbO
2, make by following steps: precursor Al (Nb
2O
5) be placed in the molybdenum crucible, under hydrogen atmosphere,, below be analytical data 1450 ℃ of reduction:
Al：2ppm
Cr：＜2ppm
C：12ppm
Fe：＜2ppm
K：1ppm
Mo：54ppm
Na：4ppm
Ni：＜2ppm
N：＜300ppm
O：26.79％
Si：14ppm
BET:0.17 rice
2/ gram
Scott density: 23.6 gram/inches
3
A3: niobium metal: with precursor A2 (NbO
2) be placed in the reactor, place by on the thread filter screen of niobium metal.Be crucible under filter screen, interior dress magnesium, its stoichiometric quantity are made a gesture of measuring and are NbO
21.05 times of oxygen level.Argon gas is introduced continuously from reactor bottom, it is left from reactor head.Then reactor is heated to about 950 ℃.After magnesium runs out of, make reactor cooling arrive about 150 ℃, air slowly is incorporated in the reactor, make the niobium metal surface passivation, below be analytical data:
Al：2ppm
Cr：＜2ppm
C：＜10ppm
Fe：＜2ppm
K：1ppm
Mg：28.14％
Mo：41ppm
Na：2ppm
Ni：＜2ppm
N：＜300ppm
O：18.74％
Si：7ppm
A4: niobium metal makes by following steps: with sulfuric acid scrubbing precursor A3 (containing magnesian niobium metal), water cleans up to being neutral again.Below be analytical data:
Al：3ppm
Cr：＜2ppm
C：＜10ppm
Fe：＜2ppm
K：1ppm
H：344ppm
Mg：750ppm
Mo：75ppm
Na：3ppm
Ni：＜2ppm
N：＜300ppm
O：1.65％
Si：8ppm
BET:4.52 rice
2/ gram
If "＜" arranged in the analytical data, corresponding content is lower than analysis limit, the numeral analysis limit of "＜" back.
Powder production embodiment:
Embodiment 1 (comparison)
With the precursor A4 (Nb) of 53.98 weight % and the precursor Al (Nb of 46.02 weight %
2O
5) mix equably, in hydrogen atmosphere, be heated to 1400 ℃.Product characteristics is shown in Table 1.
Embodiment 2:
With precursor A4 (Nb) and the magnesium of 1.5 times of stoichiometric quantity (with respect to oxygen level) and the NH of 5.4 weight parts
4Cl (per 100 parts of Nb) mixes equably, puts into reactor.Use argon gas cleaning reaction device then, be heated to 700 ℃, kept 90 minutes.After cooling, air is slowly charged in the reactor, be used for passivation.With after sulfuric acid scrubbing and cleaning, obtain a kind of niobium metal of nitrating, it contains the nitrogen of 9600-10500ppm (average 9871ppm).Oxygen level is 6724ppm.
According to embodiment 1 described method the niobium of nitrating is converted into NbO.Product characteristics is shown in Table 1.The x ray diffraction of this powder is illustrated among Fig. 1.Obviously, can identify ° Nb that locates in 2 Θ=38.5 of arrow indication
2N (101) peak.Therefore, the doping N of at least a portion is with crystal Nb
2The form of N phase exists.
Embodiment 3:
Repeat embodiment 2, different is with NH
4The add-on of Cl is increased to 8.2 weight parts.The average nitrogen content of niobium powder is 14730ppm.Oxygen level is 6538ppm.The product characteristics of this suboxide is shown in Table 1.
Embodiment 4:
With 53.95 weight part precursor A4 (Nb) and 46.05 weight part precursor Al (Nb
2O
5) mix equably, put into reactor.With argon gas cleaning reaction device, be heated to 500 ℃.Use 80%Ar/20%N mixture cleaning reaction device 30 minutes then at every turn, clean three times.Then powdered mixture is heated to 1450 ℃ in hydrogen atmosphere.Product characteristics is shown in Table 1.The x ray diffraction of powder is illustrated among Fig. 2.Obviously, can identify ° Nb that locates in 2 Θ=38.5 of arrow indication
2N (101) peak.
Embodiment 5:
With nitrogen precursor A3 (Nb that contains MgO) is carried out nitrogenize at 630 ℃, remove magnesium oxide and remaining magnesium metal by cleaning then with 15% sulfuric acid.The oxygen level of gained niobium metal is 1.6%b.w.; Nitrogen content is 8515ppm.
Niobium metal and 43.97 weight part precursor Al (Nb with 56.03 weight part nitratings
2O
5) mix equably, in hydrogen atmosphere, be heated to 1100 ℃.Product characteristics is shown in Table 1.The x ray diffraction of powder is illustrated among Fig. 3.Obviously, can identify ° Nb that locates in 2 Θ=38.5
2N (101) peak.
Table 1:NbO
xThe character of powder
Embodiment 6:
With precursor A2 (NbO
2) be placed in the reactor, place by on the thread filter screen of niobium metal.Under filter screen, be crucible, interior dress magnesium, its stoichiometric quantity is NbO
21.05 times of oxygen level.Argon gas is introduced continuously from reactor bottom, and it is left from reactor head.Then reactor is heated to about 950 ℃.After magnesium runs out of, make reactor cooling arrive about 575 ℃, introduced nitrogen 3 hours.Cooling, passivation and remove magnesium oxide and remaining magnesium metal after, obtain the niobium metal of nitrating, this metal can be used for being converted into NbO.
The research of rate of combustion:
The powder of each 50 gram embodiment 1 (comparison), embodiment 2 and embodiment 3 array according to 150 * 30 millimeters is placed on the niobium sheet of 0.1 mm thick.At one end light the powder array, measure the required time of perfect combustion (in air):
The powder of embodiment 1 (comparison): 3 minutes and 35 seconds combustion time,
6 minutes and the 25 seconds dust-firing time of embodiment 2,
8 minutes and the 10 seconds dust-firing time of embodiment 3.
DSC/TGA research:
The sample of embodiment 1 and embodiment 2 is heated to 600 ℃ from 25 ℃ in air, measures the increase of weight by thermogravimetric analysis (TGA).
Simultaneously, the heat flux of following by the measurement of DSC method.Fig. 4 has shown each curve of the powder of embodiment 1 (comparison), and Fig. 5 has shown each curve of the powder of embodiment 2.In these figure, curve A, curve B and curve C are represented temperature (the left side internal coordinate is from 0-600 ℃), weight % respectively, and (coordinate outside the left side is 95-125%) with respect to heat flux (the right side coordinate of weight calibration, the variation of (horizontal coordinate was from 0-50 or 60 seconds) 0-120W/g) in time.More than 200 ℃, two kinds of samples all show less weight to be increased and less thermal distortion about.Up to about 450 ℃, increase of the weight of two kinds of samples and liberated heat are all very similar.More than 450 ℃, the weight of unazotized sample suddenly increases about, the thermal distortion (Fig. 5) that corresponding appearance is violent, and for nitrogenous sample, thermal distortion and weight are advanced the speed and are also being kept mitigation more than 450 ℃, do not have exothermic peak.
The anodic preparation
NbO with embodiment 1 (comparison) and embodiment 2
xIt is that 4.1 millimeters, length are in 4.2 millimeters the cylindrical pressing mold that powder is filled into diameter round the tantalum wire of axial setting respectively.It is 2.8 gram per centimeters that powder compression is become density
3Green compact.Green compact are placed on the niobium sheet, 10
-8Be heated to 1460 ℃ under the vacuum of crust, kept 20 minutes.
The research of anode breakdown voltage
With anode be immersed in that concentration is 0.1%, temperature is in 85 ℃ the phosphate aqueous solution (specific conductivity is 8600 μ S/cm), applies 150 milliamperes steady current, be used for being shaped, up to voltage descend suddenly (voltage breakdown).The anode of being made by the powder of embodiment 1 (comparison) occurs voltage decline suddenly at 96 volts, descends and occur voltage by the anode that the powder of embodiment 2 is made suddenly at 104 volts.
The research of electrical condenser
In industrial production line, by the powder of embodiment 1 (comparison) and the powder production electrical condenser of embodiment 2.At diameter is that 4.2 millimeters, length are that the tantalum wire that is provided with round the center is with 2.8 gram per centimeters in 4.1 millimeters the pressing mold
3Pressed density powder is suppressed.With green compact 10
-8Sintering under the vacuum of crust.The antianode structure is carried out anodizing, to the voltage that is shaped be 16V, MnO is provided
2Negative electrode.As mentioned below, anode is worked under constant temperature and alternating-current operating voltage.In following each test, 50 electrical condenser parallel runnings:
Fig. 6 a and 6b have shown the electrical condenser made by the powder of embodiment 1 (comparison) work leakage current and electric capacity in 5000 hours processes respectively under the operating voltage of 125 ℃ temperature and 4 volts.
Fig. 7 a and 7b have shown the electrical condenser made by the powder of embodiment 2 (nitrating) work leakage current and electric capacity in 9000 hours processes respectively under the operating voltage of 125 ℃ temperature and 4 volts.
Fig. 8 a and 8b have shown the electrical condenser made by the powder of embodiment 1 (comparison) work leakage current and electric capacity in 5000 hours processes respectively under the operating voltage of 140 ℃ temperature and 2 volts.
Fig. 9 a and 9b have shown the electrical condenser made by the powder of embodiment 2 (nitrating) work leakage current and electric capacity in 5000 hours processes respectively under the operating voltage of 140 ℃ temperature and 2 volts.
Claims (15)
1. niobium suboxide powder, it comprises niobium suboxide particle, and described particulate volume nitrogen content is 500-20000ppm.
2. niobium suboxide powder as claimed in claim 1 is characterized in that described nitrogen content is 1000-8000ppm, is preferably 3000-5000ppm.
3. niobium suboxide powder as claimed in claim 1 or 2 is characterized in that described nitrogen is at least in part with Nb
2The form of N crystal or oxynitriding niobate crystal exists.
4. niobium suboxide powder as claimed in claim 3 is characterized in that described Nb
2N crystalline granularity is enough to obtain Cu at 2 about 38.5 ° Θ-angle place
κ α-X-ray diffraction peak.
5. niobium suboxide powder as claimed in claim 4 is characterized in that, at about 2 Θ=38.5 ° of Nb that locate
2The height at N peak is the 2-25% of the height at ° NbO peak of locating in 2 Θ=30.
6. as each described niobium suboxide powder in the claim 1 to 5, it is characterized in that, at about 2 Θ=38.5 ° of Cu that locate
κ α 1The peak width at half height at-peak is 0.05-0.2 °.
7. as each described niobium suboxide powder in the claim 1 to 6, it is characterized in that it is the 50-90 micron that the size-grade distribution of the powder of measuring according to ASTM B 822 is characterized by D10 value, the D50 value is the 150-210 micron, and the D90 value is the 250-350 micron.
8. as each described niobium suboxide powder in the claim 1 to 7, it is characterized in that described niobium suboxide powder particle is that mean diameter is the 0.1-1.5 micron, is preferably the coacervate of the primary particles of 0.3-1.0 micron.
9. as each described niobium suboxide powder in the claim 1 to 8, it is characterized in that the composition of described niobium suboxide is NbO
x, 0.7＜x＜1.3 wherein.
10. niobium suboxide powder as claimed in claim 8 is characterized in that 1＜x＜1.033.
11., it is characterized in that described oxygen level is 14.5-15.1 weight % as each described niobium suboxide powder in the claim 1 to 10.
12., it is characterized in that in 50 gram niobium suboxide powder are placed on 150 * 30 millimeters zones on the niobium sheet of 0.1 mm thick, and when at one end lighting, its combustion time was above 5 minutes as each described niobium suboxide powder in the claim 1 to 11.
13. the application of each niobium suboxide in making electrolytic condenser in the claim 1 to 12.
14. one kind is made general formula by the niobium metal powders precursor is NbO
xThe method of niobium oxide powder, 0.7＜x＜1.3 wherein, described method is characterised in that, before described niobium metal precursor conversion is niobium oxide it is carried out nitrogenize.
15. method as claimed in claim 14, it is characterized in that, mix with highly oxidized niobium oxide by niobium metal, and under reducing atmosphere, be heated to certain temperature nitrogenize, keep being enough to make the time of oxygen concn homogenizing, make the niobium metal of nitrogenize be converted into NbO
x
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0511321.2 | 2005-06-03 | ||
| GB0511321A GB0511321D0 (en) | 2005-06-03 | 2005-06-03 | Inorganic compounds |
| GB0602330.3 | 2006-02-06 |
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| Publication Number | Publication Date |
|---|---|
| CN101263086A true CN101263086A (en) | 2008-09-10 |
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ID=34835073
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| CN2006800196966A Active CN101258570B (en) | 2005-06-03 | 2006-06-01 | Capacitor |
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|---|---|
| CN (2) | CN101263086A (en) |
| GB (1) | GB0511321D0 (en) |
| ZA (2) | ZA200710352B (en) |
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| CN104495929A (en) * | 2014-12-26 | 2015-04-08 | 宁夏东方钽业股份有限公司 | Low-valent niobium oxide powder and preparation method thereof |
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| US6416730B1 (en) * | 1998-09-16 | 2002-07-09 | Cabot Corporation | Methods to partially reduce a niobium metal oxide oxygen reduced niobium oxides |
| JP4521849B2 (en) * | 2000-12-01 | 2010-08-11 | 昭和電工株式会社 | Niobium powder for capacitor, sintered body using the niobium powder, and capacitor using the sintered body |
| KR100663735B1 (en) * | 2001-05-15 | 2007-01-03 | 쇼와 덴코 가부시키가이샤 | Niobium powder, niobium sintered body and capacitor using the sintered body |
| US7655214B2 (en) * | 2003-02-26 | 2010-02-02 | Cabot Corporation | Phase formation of oxygen reduced valve metal oxides and granulation methods |
-
2005
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| CN101258570A (en) | 2008-09-03 |
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