CN105665731B - A kind of tantalum powder preparation method - Google Patents
A kind of tantalum powder preparation method Download PDFInfo
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- CN105665731B CN105665731B CN201610236819.7A CN201610236819A CN105665731B CN 105665731 B CN105665731 B CN 105665731B CN 201610236819 A CN201610236819 A CN 201610236819A CN 105665731 B CN105665731 B CN 105665731B
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000843 powder Substances 0.000 claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001291 vacuum drying Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 206010058490 Hyperoxia Diseases 0.000 claims abstract description 15
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 230000000222 hyperoxic effect Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 240000000111 Saccharum officinarum Species 0.000 claims 1
- 235000007201 Saccharum officinarum Nutrition 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 abstract description 45
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000006392 deoxygenation reaction Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 9
- 229930006000 Sucrose Natural products 0.000 description 9
- 239000005720 sucrose Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000428 dust Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 238000011026 diafiltration Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QACCSKHOINSZEL-UHFFFAOYSA-M [C+4].[O-2].[O-2].[O-2].[O-2].[OH-].[Ta+5] Chemical compound [C+4].[O-2].[O-2].[O-2].[O-2].[OH-].[Ta+5] QACCSKHOINSZEL-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910003070 TaOx Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- -1 mobility Chemical compound 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a kind of method for preparing high specific capacitance tantalum powder, this method comprises the following steps：（1）Take tantalum pentoxide and carbonaceous reducing agent that they are dissolved in into deionized water by weight, and stir, mixed liquor is made；Above-mentioned obtained mixed liquor is put into filter press, pressurization carries out press filtration, obtains filter cake；By filter cake heat drying, then crush, sieve, finally obtain the precursor powder containing tantalum oxide and carbon source；(2) precursor powder in step (1) is placed in vacuum drying oven, carbon reduction treatment is carried out under vacuo, the oxidation tantalum powder of low oxygen content is obtained；（3）The low-oxidation-state powder of tantalum is mixed with metal magnesium powder, and reduction reaction is then carried out in inert gas or vacuum atmosphere, obtains hyperoxia tantalum powder；（4）Hyperoxia tantalum powder is mixed with magnesium powder, second of deoxidation, obtains being adapted to the tantalum metal powder of capacitor；Wherein after with magnesium to tantalum powder deoxygenation step, the magnesium metal of magnesia and residual is removed from reaction product.
Description
Technical field
The present invention relates to rare metal field of smelting is belonged to, being related to the process technology of tantalum powder powder, there is provided a kind of capacitor
With the preparation method of tantalum powder, tantalum powder presoma more particularly to is produced with carbon thermal reduction tantalum pentoxide, is made by doping, deoxidation
It is suitable for the tantalum powder of capacitor anode block.
Background technology
Metal tantalum is a kind of valve metal, and it can have the property of unilateal conduction in one layer of fine and close oxide-film of Surface Creation
Matter.The anode film stable chemical performance of its made tantalum capacitor, resistivity height, dielectric constant are big, leakage current is small.Other tantalum electricity
Container also has the advantages that operating temperature range is wide, reliability is high, antidetonation and service life are long.Therefore, it be make small volume,
The ideal material of the high capacitor of reliability.
When tantalum powder is as electrolytic condenser anode material, powder is thinner, then specific surface area is bigger, and specific capacitance is bigger.
Want to reach higher capacity in given volume, it is common practice to develop the tantalum powder with more high-specific surface area.Sodium
The technique for reducing the manufacture of potassium floutaramite method is that the current world is most widely used, a kind of technological development most ripe tantalum powder production technology.
With existing tantalum powder production technology level, specific surface area can reach 4.5m2/g.This reducing process can be by using higher
Diluting salt and sintering delayer realize, so as to produce and maintain high specific surface area.Economically to be given birth to using this technique
Output specific surface area is more than 4.5m2The tantalum powder of/g high-quality is highly difficult.
There are many specific requirements for preparing the tantalum powder of solid electrolytic capacitor, these powder there must be 0.4m2/g
~10m2/ g surface area；Need good shaping and dipping characteristic；Suitable particle and pore size distribution.It is solid in order to eliminate
Loss (aftercurrent) in body electrolytic capacitor, it needs high-purity and accurately control impurity and dopant；Tantalum powder also needs tool
There are good mobility and suppression performance.
The method of metallic sodium fused salt thermal reduction potassium floutaramite disclosed in United States Patent (USP) US3012877, is preparing ultra-fine tantalum
Substantial amounts of halide diluent is added during powder, except being readily incorporated in addition to excessive impurity, also resulting in productivity ratio seriously reduces.Its
Shortcoming includes cost height, and pollution is big, it is impossible to continuous production etc..
The application for reducing manufacture tantalum powder with tantalum pentoxide is also in increased trend.For many years, the tantalum powder producer is to by tantalum
Oxide directly prepares tantalum powder and has carried out a series of research, it is desirable to obtains the tantalum powder that cost is low, the small, performance of pollution is excellent and prepares work
Skill.
Chinese patent CN101574741 develops a kind of rare earth metal or high ratio is produced in the reduction of rare earth metal hydride multistep
The method of capacitance tantalum powder.This method uses three stage reduction methods, it is to avoid reducing agent adds people excessive during one-step and two-step method, heat release
Amount is big, and the high phenomenon of reduction temperature has prepared the tantalum powder of Fabrication of High Specific Capacitance.To obtain the tantalum powder of good fluidity, it is necessary in the first step also
Dough and doping treatment are carried out to oxidation tantalum powder before original reaction.This method is directly connect with tantalum pentoxide with rare earth metal
Touch, the reaction time is very short, thermal discharge is big, is uncontrollable reaction.The particle diameter of tantalum powder determines by reduction temperature, due to can not
Complete controlling reaction temperature, is difficult to repeatability and obtains the powder with the particle diameter for being adapted to manufacture capacitor.
United States Patent (USP) US6136062 A are disclosed prepares ta powder using alkaline-earth metal or rare earth metal reduction-oxidation tantalum.
Its process is that then x=0.5~1.5 are carried out again with TaOx through pickling, is obtained after magnesium-reduced tantalum oxide at 750~950 DEG C
Magnesium-reduced, pickling obtains tantalum powder.Tantalum powder oxygen content prepared by this method, content of magnesium are high, other metal impurities, such as iron, nickel,
Chromium etc. is lower than the tantalum powder of sodium reduction potassium floutaramite.This method reaction speed is fast, produces substantial amounts of heat, thus cannot get fine gold
Belong to powder.
United States Patent (USP) US6171363 B1 produce after fine tantalum powder, reduction product through diluted acid using gaseous magnesium reduction-oxidation tantalum
Washing, further deoxidation, dough processing, can be made than surface up to 5~13m2/ g Ta powder used in capacitor.It is used as capacitor tantalum
Powder this method has certain industrial prospect.This method weak point is higher to reduction apparatus requirement, and equipment complexity is, it is necessary to enter
One step research reduction effect is good, not polluted product reduction apparatus.
Sun Peimei, Li Honggui (Central-South China Institute of Mining and Metallurgy journal No:4 (Sum 34) Dec.1982) in research tantalum pentoxide carbon
The mechanism of reduction process is found：
Carbon reduces Ta2O5Production metal tantalum net reaction be:
Ta2O5+ 5C=2Ta+5CO ↑
In fact, the reduction process may pass through a series of intermediate reaction.
Ta2O5+ 7C=2TaC+5CO ↑
Ta2O5+ 12TaC=7Ta2C+5CO↑
Ta2O5+5Ta2C=12Ta+5CO ↑
It can be seen that, reduce Ta in carbon205During, by the various carbide of preferential generation tantalum, and metal tantalum is generated, then relied on
Carbide and Ta205Between further reaction.
The B of Chinese patent CN 1018736 develop a kind of method that reduction with carbon tantalum pentoxide legal system takes tantalum powder.The party
The direct two sections of carbon reduction tantalum pentoxide of method obtains tantalum bar, then hydrogenates powder processed, develops the high and low specific volume capacitor level of operating voltage
Tantalum powder.
Restelli US-A3647420 develop it is a kind of reduce corresponding oxide in a vacuum using carbon manufacture niobium with
The method of tantalum powder.The reaction needs high temperature, and there occurs the sintering of particle, thereby reduces the surface area of powder.Refer to
Another obvious defect of the technology is that carbon pollutes metal dust, so as to it is difficult to use it for the system of capacitor.
The content of the invention
It is an object of the invention to overcome defect present in prior art, there is provided the tantalum powder that a kind of cost is low, specific volume is high
Preparation method.
The technical scheme is that：A kind of tantalum powder preparation method, its step：(1), take that powdery is ultra-fine, ball by weight
Shape tantalum pentoxide 300g~500g and carbonaceous reducing agent 95g~165g, they are dissolved in deionized water or distilled water, and stirs
Mix uniform, obtained solution or mixed liquor；(2), above-mentioned obtained solution or mixed liquor are put into filter press, plus 0.1MP~0.2MP
Pressure carry out press filtration, obtain filter cake；(3), filter cake is heated 1~2 hour under the conditions of 100~200 DEG C, at 50~100 DEG C
Under the conditions of dry 2~5 hours, then crush, cross 70 mesh sieves.Finally obtain the precursor powder containing tantalum oxide and carbon source；
(4), precursor powder is placed in vacuum drying oven, 1450 DEG C are incubated 1 hour under vacuo, is warming up to 1700 DEG C and is incubated 10~30 points
Clock carries out carbon reduction treatment.During cooling, introduce a small amount of air and be passivated processing, then come out of the stove, crush and cross 70 mesh sieves, obtain
To the oxidation tantalum powder of low oxygen content.Now the oxygen content of powder is 5wt%~10wt%；(5), the oxidation tantalum powder of low oxygen content
End is mixed with 0.8~1.5Wt% magnesium powders relative to oxygen content in power stoichiometry, is put into progress first time deoxidation in reactor
Processing, 780 DEG C~860 DEG C of temperature is incubated 4~8 hours；It is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated
Processing；(6) after, deoxidation is come out of the stove, wash unnecessary magnesium and magnesia with 10%~15%Wt nitric acid, and be washed with deionized to
It is neutral.Vacuum drying powder, temperature 60 C, 12 hours time, and 70 mesh sieves are crossed, hyperoxia tantalum powder is obtained, now powder is oxygen-containing
Measure as 1.5wt%~4wt%；(7), the NH of the phosphorus content equivalent to 150ppm needed for tantalum powder4H2PO4Solution was mixed into complete
The hyperoxia tantalum powder of sieve, is then placed in vacuum drying chamber, temperature 60 C, the drying of 12 hours time；(8) powder and phase after, drying
1~1.5Wt% magnesium powders for oxygen content in power stoichiometric amount are mixed, second of deoxidation treatment of progress, and 780 DEG C of temperature~
860 DEG C of 3~5 hours times, when deoxidation cools to 170 DEG C~300 DEG C, Nitrizing Treatment is carried out, environment temperature is cooled to
Afterwards, a small amount of air is introduced step by step be passivated processing；(9) after, deoxidation is come out of the stove, unnecessary magnesium is washed with 10%~15Wt% nitric acid
And magnesia, and with deionized water filtration washing to neutrality；(10), vacuum drying powder, temperature 60 C, 12 hours time, and
70 mesh sieves are crossed, Ta powder used in capacitor is obtained.
Heretofore described carbonaceous reducing agent is any one in glucose or sucrose.
Heretofore described method of deoxidation is the method known in the art that oxygen in tantalum powder is sloughed with metal magnesium powder.
Heretofore described Nitrizing Treatment method is passed through high pure nitrogen to be known in the art to reactor, in tantalum powder particle table
The method that face generates TaN film.
In the solution of the present invention, according to the fluidity testing situation of powder, before last time deoxidation, with known in the art
Method, increase powder the granulation of pelletizingization to improve the mobility of powder.
In another program of the present invention, low-oxide Ta powder is directly obtained with carbothermic method, electricity is obtained by a deoxidation
Container is Ta powder used.Because the reducing agent of addition is more, cause finished powder carbon content high；The recovery time is long simultaneously, causes powder sintered,
The specific surface area of powder declines, and specific volume is relatively low.
In the embodiment of the present invention, the mobility of particle is tested by Hall flowmeter, and the measurement of mean particle size is by taking
Family name's method (Fsss) is determined, and measurement oxygen content, carbon content use oxygen, the carbon analyzer of infrared ray absorbing, and the measurement of specific surface area is used
BET method.Apparent density (SBD) uses SOTT methods.
Electric property is detected, is, by 150mg tantalum powders, to be pressed into density for 5.0g/m3, a diameter of 3.0mm briquet, true
1000~1500 DEG C sinter 20~30 minutes in empty stove, then agglomerate applies in 80 DEG C, 0.1% phosphoric acid solution to 10~
20V voltage, forms anode, then tests the capacity and leakage current of anode block.
The advantage of the invention is that：The present invention is as high activity carbon source reduction-oxidation tantalum system using glucose or sucrose
For tantalum powder, its feature is：Glucose or sucrose wrap up tantalum oxide powder to form isolated micron-sized tantalum oxide
Grain, glucose or sucrose are carbonized to form activity very high porous high-activity carbon when the temperature increases so that tantalum oxide reacts with carbon
Start temperature significantly declined, the micro channel of the porous high-activity carbon of acquisition can be successfully anti-with carbon by tantalum oxide
The carbon monoxide discharge that should be generated；The porous high-activity carbon formed after glucose or sucrose carbonization has wrapped up tantalum oxide particles,
The growth of powder grain is inhibited in course of reaction, the oxidation tantalum powder of the low oxygen content of even grain size can be obtained；In carbon
After reduction step, obtain low oxygen content oxidation tantalum powder, its oxygen content scope represented with percetage by weight should 5wt%~
Between 10wt%.The oxidation tantalum powder of above-mentioned low oxygen content is further reduced in two times with metal magnesium powder again, so as to obtain superelevation
Compare capacitance tantalum powder.Press filtration, sieving before being reduced by carbon obtain initial dough particle, and are maintained in subsequent reduction process,
Improve the physical property of tantalum powder, such as mobility, suppression performance, porosity.Resulting tantalum powder has the first of 20nm~8 μm
Grade particles particle diameter and 2m2/ g~10m2/ g BET specific surface area.When electrolytic capacitor anode is made, the anode has about 100,
000 to 400,000uFV/g specific volume.
Embodiment
Embodiment 1
Take sucrose 130g (equivalent to 0.8 times of reducing agent stoichiometry needed for the oxygen content removed in oxidation tantalum powder) and
630mL deionized water is well mixed.500g is taken to cross tantalum pentoxide powder (the Fsss average grain diameters of 60 mesh sieves：0.6μm,SBD
Apparent density:0.71g/m3) add above-mentioned sucrose solution to stir, mixed liquor is made.Mixed liquor is positioned in filter press,
Plus 0.15MP pressure carries out press filtration, filter cake enters hot air drier, to rise 5 DEG C per hour, is raised to 110 DEG C, is incubated 30 minutes, with
After cool to 90 DEG C, be incubated 4 hours and dry.After drying materials, crush and cross 70 mesh sieves.Gained powder is positioned over tantalum crucible
In, then it is put in vacuum drying oven, is warming up to 1450 DEG C after vacuumizing, is incubated 1 hour, then it is warming up to 1700 DEG C, 10 minutes are incubated,
It is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated processing.By the powder in tantalum crucible take out and crush, cross 70
Mesh sieve.The oxidation tantalum powder of low oxygen content is obtained, its oxygen content is 7.6wt% after testing, and carbon content is 38ppm.
The oxidation tantalum powder of resulting low oxygen content, adds the oxygen content institute aoxidized equivalent to low oxygen content in tantalum powder
The magnesium dust of 0.9 times of mesh sieve of mistake 20 of reducing agent stoichiometry is needed, after being well mixed, is positioned in tantalum crucible, then will be equipped with
The tantalum crucible of material is put in closed reactor, and argon gas is filled with after vacuumizing, and under argon gas protection, 5 hours are incubated at 780 DEG C.
It is cooled to after room temperature and carries out Passivation Treatment, the tantalum powder in tantalum crucible is taken out and is soaked in 15wt% nitric acid and dissolves removal
Magnesia and remaining magnesium metal, then dry powder with after deionized water diafiltration to neutrality, obtain hyperoxia tantalum powder.
It will be equivalent to the NH of the phosphorus content of 150ppm needed for tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving,
It is then placed in vacuum drying chamber, temperature 60 C, the drying of 8 hours time；
Above-mentioned powder is added into 1.3 times of mesh of mistake 20 equivalent to reducing agent stoichiometry needed for the oxygen content in hyperoxia tantalum powder
The magnesium dust of sieve, after being well mixed, is positioned in tantalum crucible, the tantalum crucible that then will be equipped with material is put in closed reactor,
Argon gas is filled with after vacuumizing, under argon gas protection, 3 hours are incubated at 820 DEG C.When cooling down is to 230 DEG C, High Purity Nitrogen is filled with
Gas, is incubated 30 minutes.It is cooled to after room temperature and is passivated place.Tantalum powder in tantalum crucible is taken out and 15wt% nitre is soaked in
Dissolving removes magnesia and remaining magnesium metal in acid, then dries powder with after deionized water diafiltration to neutrality, obtains
Pure tantalum powder.Oxygen content, carbon content, Fsss average grain diameters, SBD apparent densitys, BET specific surface area measurement are carried out to it, is as a result seen
Table 1.
The tantalum powder that electrical property detection is obtained using said process is pressed into density for 5.0g/m3, a diameter of 3.0mm base
Block, 1200 DEG C of sintering obtain tantalum agglomerate for 20 minutes in vacuum drying oven, then by agglomerate in 80 DEG C, 0.1wt% phosphoric acid solution
Middle application 10V voltage, energize time 120min, temperature of energizing：80 DEG C, current density 110mA/g forms tantalum anode, remaining
Detected that the specific capacitance and leakage current of anode are shown in Table 1 with reference to standard GB/T/T 3137-2007 standards.
Embodiment 2
Take glucose 136g (equivalent to 0.8 times of reducing agent stoichiometry needed for the oxygen content removed in oxidation tantalum powder)
It is well mixed with 640mL deionized water.500g is taken to cross tantalum pentoxide powder (the Fsss average grain diameters of 60 mesh sieves：0.5μm,
SBD apparent densitys:0.68g/m3) add above-mentioned glucose solution and stir, mixed liquor is made.Mixed liquor is positioned over press filtration
Add 0.1MP pressure to carry out press filtration in machine, filter cake enters hot air drier, to rise 5 DEG C per hour, be raised to 110 DEG C, be incubated 30 points
Clock, then cools to 80 DEG C, is incubated 4 hours and dries.Material after drying is crushed and 70 mesh sieves are crossed.Gained powder is positioned over
In tantalum crucible, the tantalum crucible that then will be equipped with material is put in vacuum drying oven, and 1450 DEG C are warming up to after vacuumizing, and is incubated 1 hour, then
1700 DEG C are warming up to, 10 minutes is incubated, is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated processing.By tantalum earthenware
Powder in crucible takes out and crushed, crosses 70 mesh sieves.The oxidation tantalum powder of low oxygen content is obtained, its oxygen content is after testing
7.9wt%.Carbon content is 58ppm.
The oxidation tantalum powder of resulting low oxygen content, adds the oxygen content institute aoxidized equivalent to low oxygen content in tantalum powder
The magnesium dust of 0.9 times of mesh sieve of mistake 20 of reducing agent stoichiometry is needed, after being well mixed, is positioned in tantalum crucible, then will be equipped with
The tantalum crucible of material is put in closed reactor, and argon gas is filled with after vacuumizing, and under argon gas protection, 6 hours are incubated at 780 DEG C.
It is cooled to after room temperature and carries out Passivation Treatment, the tantalum powder in tantalum crucible is taken out and is soaked in 15wt% nitric acid and dissolves removal
Magnesia and remaining magnesium metal, then dry powder with after deionized water diafiltration to neutrality, obtain hyperoxia tantalum powder.
It will be equivalent to the NH of the phosphorus content of 150ppm needed for tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving,
It is then placed in vacuum drying chamber, temperature 60 C, the drying of 8 hours time；
Above-mentioned powder is added into 1.4 times of mesh of mistake 20 equivalent to reducing agent stoichiometry needed for the oxygen content in hyperoxia tantalum powder
The magnesium dust of sieve, after being well mixed, is positioned in tantalum crucible, the tantalum crucible that then will be equipped with material is put in closed reactor,
Argon gas is filled with after vacuumizing, under argon gas protection, 3 hours are incubated at 820 DEG C.When cooling down is to 230 DEG C, High Purity Nitrogen is filled with
Gas, is incubated 30 minutes.It is cooled to after room temperature and is passivated place.Tantalum powder in tantalum crucible is taken out and 15wt% nitre is soaked in
Dissolving removes magnesia and remaining magnesium metal in acid, then dries powder with after deionized water diafiltration to neutrality, obtains
Pure tantalum powder.Oxygen content, carbon content, Fsss average grain diameters, SBD apparent densitys, BET specific surface area measurement are carried out to it, is as a result seen
Table 1.
The tantalum powder that electrical property detection is obtained using said process is pressed into density for 5.0g/m3, a diameter of 3.0mm base
Block, 1200 DEG C of sintering obtain tantalum agglomerate for 20 minutes in vacuum drying oven, then by agglomerate in 80 DEG C, 0.1wt% phosphoric acid solution
Middle application 10V voltage, energize time 120min, temperature of energizing：80 DEG C, current density 110mA/g forms tantalum anode, remaining
Detected that the specific capacitance and leakage current of anode are shown in Table 1 with reference to standard GB/T/T 3137-2007 standards.
Comparative example
Take sucrose 195g (equivalent to 1.2 times of reducing agent stoichiometry needed for the oxygen content removed in oxidation tantalum powder) and
695mL deionized water is well mixed.500g is taken to cross tantalum pentoxide powder (the Fsss average grain diameters of 60 mesh sieves：0.77μm,
SBD apparent densitys:0.85g/m3) add above-mentioned sucrose solution and stir, mixed liquor is made.Mixed liquor is positioned over filter press
In, plus 0.15MP pressure carries out press filtration, filter cake enters hot air drier, to rise 5 DEG C per hour, is raised to 110 DEG C, is incubated 30 points
Clock, then cools to 90 DEG C, is incubated 4 hours and dries.After drying materials, crush and cross 70 mesh sieves.Gained powder is positioned over tantalum
In crucible, then it is put in vacuum drying oven, 1450 DEG C is warming up to after vacuumizing, be incubated 1 hour, then is warming up to 1700 DEG C, insulation 30
Minute, it is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated processing.Powder in tantalum crucible is taken out and broken
Broken, 70 mesh sieves excessively.Hyperoxia tantalum powder is obtained, its oxygen content is 3.6wt% after testing, and carbon content is 141ppm.
It will be equivalent to the NH of the phosphorus content of 150ppm needed for tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving,
It is then placed in vacuum drying chamber, temperature 60 C, the drying of 8 hours time；
Above-mentioned powder is added into 1.2 times of mesh of mistake 20 equivalent to reducing agent stoichiometry needed for the oxygen content in hyperoxia tantalum powder
The magnesium dust of sieve, after being well mixed, is positioned in tantalum crucible, the tantalum crucible that then will be equipped with material is put in closed reactor,
Argon gas is filled with after vacuumizing, under argon gas protection, 3 hours are incubated at 820 DEG C.When cooling down is to 230 DEG C, High Purity Nitrogen is filled with
Gas, is incubated 30 minutes.It is cooled to after room temperature and is passivated place.Tantalum powder in tantalum crucible is taken out and 15wt% nitre is soaked in
Dissolving removes magnesia and remaining magnesium metal in acid, then dries powder with after deionized water diafiltration to neutrality, obtains
Pure tantalum powder.Oxygen content, carbon content, Fsss average grain diameters, SBD apparent densitys, BET specific surface area measurement are carried out to it, is as a result seen
Table 1.
The tantalum powder that electrical property detection is obtained using said process is pressed into density for 5.0g/m3, a diameter of 3.0mm base
Block, 1300 DEG C of sintering obtain tantalum agglomerate for 20 minutes in vacuum drying oven, then by agglomerate in 80 DEG C, 0.1% phosphoric acid solution
Apply 16V voltage, energize time 120min, temperature of energizing：80 DEG C, current density 110mA/g forms tantalum anode, remaining ginseng
Detected that the specific capacitance and leakage current of anode are shown in Table 1 according to standard GB/T/T 3137-2007 standards.
Table 1
Claims (5)
1. a kind of tantalum powder preparation method, its step：（1）, by weight take that powdery is ultra-fine, spherical tantalum pentoxide 300g~500g
With carbonaceous reducing agent 95g 165g, they are dissolved in deionized water or distilled water, and stirred, obtained solution or mixing
Liquid；（2）, above-mentioned obtained solution or mixed liquor be put into filter press, plus 0.1MP ~ 0.2MP pressure carries out press filtration, is filtered
Cake；（3）, filter cake heated 1~2 hour under the conditions of 100 ~ 200 DEG C, dry 2~5 hours under the conditions of 50~100 °C, then
Crush, cross 70 mesh sieves；Finally obtain the precursor powder containing tantalum oxide and carbon source；（4）, precursor powder is placed in vacuum drying oven
In, 1450 DEG C are incubated 1 hour under vacuo, are warming up to 1700 DEG C of insulations and carry out carbon reduction treatment in 10 ~ 30 minutes；During cooling, draw
Enter a small amount of air and be passivated processing, then come out of the stove, crush and cross 70 mesh sieves, obtain the oxidation tantalum powder of low oxygen content；Now
The oxygen content of powder is 5wt%~10wt%；（5）, low oxygen content oxidation tantalum powder with relative to oxygen content in power stoichiometry
The mixing of 0.8~1.5Wt% magnesium powders, be put into reactor progress first time deoxidation treatment, 780 DEG C ~ 860 DEG C of temperature, insulation 4 ~ 8
Hour；It is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated processing；（6）, after deoxidation comes out of the stove, with 10%~15%
Wt nitric acid washs unnecessary magnesium and magnesia, and is washed with deionized to neutrality；Vacuum drying powder, temperature 60 C, time
12 hours, and 70 mesh sieves are crossed, hyperoxia tantalum powder is obtained, now the oxygen content of powder is 1.5wt%~4wt%；（7）, equivalent to tantalum powder
The NH of the phosphorus content of 150ppm needed for end4H2PO4Solution was mixed into the hyperoxia tantalum powder of complete sieve, was then placed in vacuum drying chamber, temperature
60 DEG C of degree, the drying of 12 hours time；（8）, the powder after drying and 1~1.5Wt% relative to oxygen content in power stoichiometric amount
Magnesium powder mix, carry out second of deoxidation treatment, 780 DEG C ~ 860 DEG C 3 ~ 5 hours times of temperature, when deoxidation cool to 170 DEG C ~
At 300 DEG C, Nitrizing Treatment is carried out, is cooled to after environment temperature, a small amount of air is introduced step by step and is passivated processing；（9）, deoxidation goes out
After stove, unnecessary magnesium and magnesia is washed with 10%~15Wt% nitric acid, and with deionized water filtration washing to neutrality；（10）, it is true
Sky drying powder, temperature 60 C, 12 hours time, and 70 mesh sieves are crossed, obtain Ta powder used in capacitor.
2. a kind of tantalum powder preparation method according to claim 1, it is characterised in that：The ultra-fine, spherical tantalum pentoxide is：
Fsss average grain diameters：0.2~0.8 μm, purity：99.99 wt%.
3. a kind of tantalum powder preparation method according to claim 1, it is characterised in that：The carbonaceous reducing agent is glucose or sugarcane
Any one in sugar.
4. a kind of tantalum powder preparation method according to claim 1, it is characterised in that：The Nitrizing Treatment method is to reactor
High pure nitrogen is passed through, the method for generating TaN film in tantalum powder particle surface.
5. a kind of tantalum powder preparation method according to claim 1, it is characterised in that：According to the fluidity testing situation of powder,
Increase powder a pelletizingization granulation before last time deoxidation to improve the mobility of powder.
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Effective date of registration: 20210111 Address after: 412500 Xia Yang Zhen Yan Xi Cun, Yanling County, Zhuzhou City, Hunan Province Patentee after: Yanling Longxiang tantalum niobium New Material Co.,Ltd. Address before: 338000 Dongxing North Road, Xinyu hi tech Development Zone, Jiangxi Patentee before: Chen Shangjun |