CN105665731A - Method for preparing tantalum powder - Google Patents
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- CN105665731A CN105665731A CN201610236819.7A CN201610236819A CN105665731A CN 105665731 A CN105665731 A CN 105665731A CN 201610236819 A CN201610236819 A CN 201610236819A CN 105665731 A CN105665731 A CN 105665731A
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- 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
Abstract
The invention provides a method for preparing tantalum powder with the high specific volume. The method includes the following steps that 1, tantalum pentoxide and a carbonaceous reducing agent are taken by weight, dissolved in deionized water and stirred to be even to obtain mixed liquid; the prepared mixed liquid is put into a pressure filter and subjected to filter pressing in a pressing mode to obtain a filter cake; the filter cake is heated, dried, smashed and sieved to obtain precursor powder with tantalum oxide and carbon sources finally; 2, the precursor powder obtained in the step 1 is placed into a vacuum furnace and subjected to carbon reduction under the vacuum to obtain tantalum oxide powder with the low oxygen content; 3, low oxidation state powder of tantalum and mental magnesium powder are mixed and then subjected to a reduction reaction in the atmosphere of inert gas or vacuum to obtain high-oxygen tantalum powder; 4, the high-oxygen tantalum powder and magnesium powder are mixed and deoxidized for the second time to obtain tantalum metal powder suitable for a capacitor; after the step that the tantalum powder is deoxidized through magnesium, magnesium oxide and residual magnesium metal are removed from a reaction product.
Description
Technical field
The present invention relates to and belong to rare metal field of smelting, relate to the process technology of tantalum powder powder, the preparation method providing a kind of tantalum powder for capacitor, produces tantalum powder presoma particularly to carbon thermal reduction tantalum pentoxide, makes, by doping, deoxidation, the tantalum powder being suitable for capacitor anode block.
Background technology
Metal tantalum is a kind of valve metal, and it can have the character of unilateal conduction at the one layer fine and close oxide-film of Surface Creation. The anode film stable chemical performance of tantalum capacitor made by it, resistivity are high, dielectric constant is big, leakage current is little. Additionally tantalum capacitor also has the advantages such as operating temperature range width, reliability height, antidetonation and long service life. Therefore, it is the ideal material making the capacitor that volume is little, reliability is high.
When tantalum powder is as electrochemical capacitor anode material, powder body is more thin, then specific surface area is more big, more bigger than electric capacity. Want to reach higher capacity in given volume, it is common practice to develop the tantalum powder with more high-specific surface area. The technique of sodium reduction potassium floutaramite method manufacture is that the current world is most widely used, a kind of tantalum powder production technology that technological development is the most ripe. With existing tantalum powder production technology level, specific surface area can reach 4.5m2/ g. This reducing process can by using higher diluting salt and sintering delayer to realize, thus producing and maintain high specific surface area. This technique is utilized to produce specific surface area economically more than 4.5m2The tantalum powder of the high-quality of/g is highly difficult.
Tantalum powder for preparing solid electrolytic capacitor has a lot of specific requirement, and these powder must have 0.4m2/ g～10m2The surface area of/g; Need good shaping and dipping characteristic; Suitable granule and pore size distribution. In order to eliminate the loss (aftercurrent) in solid electrolytic capacitor, it needs high-purity and accurately controls impurity and alloy; Tantalum powder should also have good mobility and suppression performance.
The method of the metallic sodium fused salt thermal reduction potassium floutaramite disclosed in US Patent No. 3012877, to add substantial amounts of halogenide diluent, except being readily incorporated excessive impurity, also result in productivity ratio and seriously reduce when preparing superfine tantalum powder.Its shortcoming includes cost height, pollutes big, it is impossible to production etc. continuously.
The application of tantalum powder is manufactured also in the trend increased with tantalum pentoxide reduction. For many years, tantalum powder Producer has carried out a series of research to directly being prepared tantalum powder by tantalum pentoxide, it is desirable to obtain that cost is low, it is little to pollute, performance is excellent tantalum powder preparation technique.
Chinese patent CN101574741 develops a kind of rare earth metal or rare earth metal hydride multistep and reduces the method producing high specific capacitance tantalum powder. The method adopts three stage reduction methods, it is to avoid in a step and two-step method process, to add people too much for reducing agent, and thermal discharge is big, and reduction temperature high phenomenon has prepared the tantalum powder of Fabrication of High Specific Capacitance. For obtaining the tantalum powder of good fluidity, it is necessary to tantalum oxide powder to be carried out dough and doping treatment before first step reduction reaction. The method tantalum pentoxide directly contacts with rare earth metal, and the response time is very short, and thermal discharge is big, for uncontrollable reaction. The particle diameter of tantalum powder is determined by reduction temperature, owing to can not control reaction temperature completely, is difficult to repeatability and obtains having the powder being suitable for manufacturing the particle diameter of capacitor.
US Patent No. 6136062A openly adopts alkaline-earth metal or rare earth metal reduction-oxidation tantalum to prepare ta powder. Its process be 750～950 DEG C with magnesium-reduced tantalum oxide after through pickling, obtain TaOx, x=0.5～1.5, and then carry out magnesium-reduced, pickling, obtain tantalum powder. Tantalum powder oxygen content prepared by this method, content of magnesium are high, other metal impurities, as ferrum, nickel, chromium geometric ratio sodium reduction potassium floutaramite tantalum powder low. This method response speed is fast, produces substantial amounts of heat, thus can not get refining metallic powder.
US Patent No. 6171363B1 adopts gaseous magnesium reduction-oxidation tantalum to produce fine tantalum powder, and reduction afterproduct is through weak acid scrubbing, and further deoxidation, dough process, and can prepare specific surface and reach 5～13m2The Ta powder used in capacitor of/g. As tantalum powder for capacitor the method, there is certain industrial prospect. The method weak point is that reduction apparatus requirement is higher, and equipment is complicated, it is necessary to research reduction effect reduction apparatus good, not polluted product further.
Sun Peimei, Li Honggui (Central-South China Institute of Mining and Metallurgy journal No:4 (Sum34) Dec.1982) find in the mechanism of research Carbon Reduction Process of Tantalum Pentoxide:
Carbon reduction Ta2O5The net reaction producing metal tantalum is:
Ta2O5+ 5C=2Ta+5CO ↑
It practice, this reduction process is possibly through a series of intermediate reaction.
Ta2O5+ 7C=2TaC+5CO ↑
Ta2O5+ 12TaC=7Ta2C+5CO↑
Ta2O5+5Ta2C=12Ta+5CO ↑
Visible, at carbon reduction Ta205In process, will preferentially generate the various carbides of tantalum, and generate metal tantalum, then rely on carbide and Ta205Between further reaction.
Chinese patent CN1018736B develops a kind of method that reduction with carbon tantalum pentoxide legal system takes tantalum powder. The direct two-stage nitration carbon reduction tantalum pentoxide of the method obtains tantalum bar, then hydrogenates powder process, develops the high and low specific volume Ta powder used in capacitor of running voltage.
Restelli develops at US-A3647420 and a kind of utilizes carbon to reduce corresponding oxide in a vacuum to manufacture niobium and the method for tantalum powder. This reaction needed high temperature, and there occurs the sintering of granule, thereby reduce the surface area of powder. Another of this technology mentioned significantly has the drawback that carbon pollutes metal dust, thus being difficult to use it for the system of capacitor.
Summary of the invention
It is an object of the invention to overcome the defect existed in prior art, it is provided that the tantalum powder, preparation method thereof that a kind of cost is low, specific volume is high.
The technical scheme is that a kind of tantalum powder, preparation method thereof, its step: (1), take that powdery is ultra-fine, spherical tantalum pentoxide 300g～500g and carbonaceous reducing agent 95g～165g by weight, they are dissolved in deionized water or distilled water, and stir, obtained solution or mixed liquor; (2), putting in pressure filter by above-mentioned obtained solution or mixed liquor, the pressure adding 0.1MP～0.2MP carries out filter pressing, obtains filter cake; (3), filter cake is heated 1～2 hour under 100～200 DEG C of conditions, dry 2～5 hours under 50～100 DEG C of conditions, then crush, cross 70 mesh sieves. Finally obtain the precursor powder containing tantalum oxide and carbon source; (4), being placed in vacuum drying oven by precursor powder, 1450 DEG C are incubated 1 hour under vacuo, are warmed up to 1700 DEG C of insulations and carry out carbon reduction treatment in 10～30 minutes. 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 the tantalum oxide powder of low oxygen content. Now the oxygen content of powder is 5wt%～10wt%; (5), the tantalum oxide powder of low oxygen content mix with relative to the stoichiometric 0.8～1.5Wt% magnesium powder of oxygen content in power, put into and reactor carry out first time deoxidation treatment, temperature 780 DEG C～860 DEG C, be incubated 4～8 hours; After being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing; (6), after deoxidation comes out of the stove, unnecessary magnesium and magnesium oxide are washed with 10%～15%Wt nitric acid, and with deionized water wash to neutral. Vacuum drying powder, temperature 60 C, 12 hours time, and cross 70 mesh sieves, and obtain hyperoxia tantalum powder, now the oxygen content of powder is 1.5wt%～4wt%; (7) NH of the phosphorus content of required 150ppm in tantalum powder, is equivalent to4H2PO4Solution was mixed into the hyperoxia tantalum powder of complete sieve, was then placed in vacuum drying oven, temperature 60 C, and 12 hours time dried; (8) powder after, drying mixes with the 1～1.5Wt% magnesium powder relative to oxygen content in power stoichiometric amount, carry out second time deoxidation treatment, 780 DEG C～860 DEG C 3～5 hours times of temperature, when deoxidation cool 170 DEG C～300 DEG C time, carry out Nitrizing Treatment, after being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing; (9), after deoxidation comes out of the stove, unnecessary magnesium and magnesium oxide are washed with 10%～15Wt% nitric acid, and with deionized water filtration washing to neutrality; (10), vacuum drying powder, temperature 60 C, 12 hours time, and cross 70 mesh sieves, obtain Ta powder used in capacitor.
Heretofore described carbonaceous reducing agent is any one in glucose or sucrose.
Heretofore described method of deoxidation is that metal magnesium powder known in the art sloughs the method for oxygen in tantalum powder.
Heretofore described Nitrizing Treatment method is known in the art pass into high pure nitrogen to reactor, in the method for tantalum powder particles Surface Creation TaN film.
In the solution of the present invention, the fluidity testing situation according to powder, the last time before deoxidation, by methods known in the art, powder is increased a pelletizing pelletize to improve the mobility of powder.
In another program of the present invention, directly obtain low-oxide Ta powder by carbothermic method, obtain Ta powder used in capacitor by a deoxidation. Reducing agent because adding is many, causes finished product powder carbon content high; Recovery time is long simultaneously, causes powder sintered, and the specific surface area of powder declines, and specific volume is on the low side.
In the embodiment of the present invention, the mobility of granule is tested by Hall flowmeter, the measurement of mean particle size is measured by Fei Shi method (Fsss), measures oxygen content, carbon content the employing oxygen of infrared ray absorbing, carbon analyzer, the measurement BET method of specific surface area.Apparent density (SBD) adopts SOTT method.
Electric property detects, and is by 150mg tantalum powder, and being pressed into density is 5.0g/m3, diameter is the briquet of 3.0mm, and in vacuum drying oven, 1000～1500 DEG C sinter 20～30 minutes, then by agglomerate at 80 DEG C, applies the voltage of 10～20V in the phosphoric acid solution of 0.1%, forms anode, then tests capacity and the leakage current of anode block.
It is an advantage of the current invention that: the present invention adopts glucose or sucrose to prepare tantalum powder as high activity carbon source reduction-oxidation tantalum, its feature is: tantalum oxide powder body is wrapped up and forms isolated micron-sized tantalum oxide particles by glucose or sucrose, glucose or sucrose carbonization form the porous high-activity carbon that activity is significantly high when the temperature increases, the starting temperature that tantalum oxide and carbon react significantly is declined, it is thus achieved that the micro channel of porous high-activity carbon successfully tantalum oxide and carbon can be reacted the carbon monoxide generated discharge; The porous high-activity carbon formed after glucose or sucrose carbonization has wrapped up tantalum oxide particles, inhibits the growth of powder grain, can obtain the tantalum oxide powder of the low oxygen content of even grain size in course of reaction; After carbon reduction step, it is thus achieved that the tantalum oxide powder of low oxygen content, its oxygen content scope percetage by weight represents should between 5wt%～10wt%. The tantalum oxide powder that secondary reduces above-mentioned low oxygen content further is divided again, thus obtaining super high specific capacitance tantalum powder with metal magnesium powder. Filter pressing before being reduced by carbon, sieving obtains initial dough granule, and is maintained in reduction process subsequently, improves the physical property of tantalum powder, such as mobility, suppression performance, porosity etc. Obtained tantalum powder has primary particle diameter and the 2m of 20nm～8 μm2/ g～10m2The BET specific surface area of/g. When making electrolytic capacitor anode, described anode has about 100, and 000 to 400, the specific volume of 000uFV/g.
Detailed description of the invention
Embodiment 1
Take the deionized water mix homogeneously of sucrose 130g (be equivalent to remove the oxygen content in tantalum oxide powder needed for stoichiometric 0.8 times of reducing agent) and 630mL. Take 500g to cross the tantalum pentoxide powder (Fsss mean diameter: 0.6 μm, SBD apparent density: 0.71g/m3) of 60 mesh sieves and add above-mentioned sucrose solution and stir, prepare mixed liquor. Being positioned in pressure filter by mixed liquor, the pressure adding 0.15MP carries out filter pressing, and filter cake enters hot air drier, to rise 5 DEG C per hour, is raised to 110 DEG C, is incubated 30 minutes, cools to 90 DEG C subsequently, is incubated drying in 4 hours. After drying materials, crush and cross 70 mesh sieves. Being positioned in tantalum crucible by gained powder, be then put in vacuum drying oven, be warming up to 1450 DEG C after evacuation, be incubated 1 hour, then be warmed up to 1700 DEG C, be incubated 10 minutes, after being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing. Powder in tantalum crucible is taken out and crushes, crosses 70 mesh sieves. Obtaining the tantalum oxide powder of low oxygen content, its oxygen content is 7.6wt% after testing, and carbon content is 38ppm.
The tantalum oxide powder of obtained low oxygen content; add the magnesium dust of stoichiometric 0.9 times of mistake 20 mesh sieve of reducing agent needed for the oxygen content being equivalent in low oxygen content tantalum oxide powder; after mix homogeneously; it is positioned in tantalum crucible; then will be equipped with the tantalum crucible of material and be put in closed reactor; it is filled with argon after evacuation, under argon shield, is incubated 5 hours at 780 DEG C. Carry out Passivation Treatment after being cooled to room temperature, the tantalum powder in tantalum crucible is taken out and is soaked in the nitric acid of 15wt% dissolves and remove magnesium oxide and remaining magnesium metal, then by powder with dry after deionized water diafiltration to neutrality, it is thus achieved that hyperoxia tantalum powder.
Will be equivalent to the NH of the phosphorus content of required 150ppm in tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving, and is then placed in vacuum drying oven, temperature 60 C, and 8 hours time dried;
Above-mentioned powder is added the magnesium dust of stoichiometric 1.3 times of mistake 20 mesh sieves of reducing agent needed for the oxygen content being equivalent in hyperoxia tantalum powder; after mix homogeneously; it is positioned in tantalum crucible; then will be equipped with the tantalum crucible of material and be put in closed reactor; argon it is filled with after evacuation; under argon shield, it is incubated 3 hours at 820 DEG C. When cooling down is to 230 DEG C, it is filled with high pure nitrogen, is incubated 30 minutes. Place it is passivated after being cooled to room temperature. Tantalum powder in tantalum crucible is taken out and is soaked in the nitric acid of 15wt% dissolves and remove magnesium oxide and remaining magnesium metal, then by powder with dry after deionized water diafiltration to neutrality, it is thus achieved that pure tantalum powder. It is carried out oxygen content, carbon content, Fsss mean diameter, SBD apparent density, BET specific surface area measurement, and result is in Table 1.
It is 5.0g/m that electrical property detection uses the tantalum powder that said process obtains to be pressed into density3Diameter is the briquet of 3.0mm, in vacuum drying oven, 1200 DEG C of sintering obtain tantalum agglomerate for 20 minutes, then by agglomerate at 80 DEG C, apply the voltage of 10V in the phosphoric acid solution of 0.1wt%, energize time 120min, energize temperature: 80 DEG C, electric current density 110mA/g, form tantalum anode, all the other detect with reference to standard GB/T/T3137-2007 standard, and the specific capacitance of anode and leakage current are in Table 1.
Embodiment 2
Take the deionized water mix homogeneously of glucose 136g (be equivalent to remove the oxygen content in tantalum oxide powder needed for stoichiometric 0.8 times of reducing agent) and 640mL. Take 500g and cross tantalum pentoxide powder (Fsss mean diameter: 0.5 μm, SBD apparent density: the 0.68g/m of 60 mesh sieves3) add above-mentioned glucose solution and stir, prepare mixed liquor. The pressure being positioned in pressure filter by mixed liquor to add 0.1MP carries out filter pressing, and filter cake enters hot air drier, to rise 5 DEG C per hour, is raised to 110 DEG C, is incubated 30 minutes, cools to 80 DEG C subsequently, is incubated drying in 4 hours. Material after drying is crushed and crosses 70 mesh sieves. Gained powder is positioned in tantalum crucible, then will be equipped with the tantalum crucible of material and be put in vacuum drying oven, after evacuation, be warming up to 1450 DEG C, it is incubated 1 hour, then is warmed up to 1700 DEG C, be incubated 10 minutes, after being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing. Powder in tantalum crucible is taken out and crushes, crosses 70 mesh sieves. Obtaining the tantalum oxide powder of low oxygen content, its oxygen content is 7.9wt% after testing. Carbon content is 58ppm.
The tantalum oxide powder of obtained low oxygen content; add the magnesium dust of stoichiometric 0.9 times of mistake 20 mesh sieve of reducing agent needed for the oxygen content being equivalent in low oxygen content tantalum oxide powder; after mix homogeneously; it is positioned in tantalum crucible; then will be equipped with the tantalum crucible of material and be put in closed reactor; it is filled with argon after evacuation, under argon shield, is incubated 6 hours at 780 DEG C. Carry out Passivation Treatment after being cooled to room temperature, the tantalum powder in tantalum crucible is taken out and is soaked in the nitric acid of 15wt% dissolves and remove magnesium oxide and remaining magnesium metal, then by powder with dry after deionized water diafiltration to neutrality, it is thus achieved that hyperoxia tantalum powder.
Will be equivalent to the NH of the phosphorus content of required 150ppm in tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving, and is then placed in vacuum drying oven, temperature 60 C, and 8 hours time dried;
Above-mentioned powder is added the magnesium dust of stoichiometric 1.4 times of mistake 20 mesh sieves of reducing agent needed for the oxygen content being equivalent in hyperoxia tantalum powder; after mix homogeneously; it is positioned in tantalum crucible; then will be equipped with the tantalum crucible of material and be put in closed reactor; argon it is filled with after evacuation; under argon shield, it is incubated 3 hours at 820 DEG C. When cooling down is to 230 DEG C, it is filled with high pure nitrogen, is incubated 30 minutes. Place it is passivated after being cooled to room temperature. Tantalum powder in tantalum crucible is taken out and is soaked in the nitric acid of 15wt% dissolves and remove magnesium oxide and remaining magnesium metal, then by powder with dry after deionized water diafiltration to neutrality, it is thus achieved that pure tantalum powder. It is carried out oxygen content, carbon content, Fsss mean diameter, SBD apparent density, BET specific surface area measurement, and result is in Table 1.
It is 5.0g/m that electrical property detection uses the tantalum powder that said process obtains to be pressed into density3Diameter is the briquet of 3.0mm, in vacuum drying oven, 1200 DEG C of sintering obtain tantalum agglomerate for 20 minutes, then by agglomerate at 80 DEG C, apply the voltage of 10V in the phosphoric acid solution of 0.1wt%, energize time 120min, energize temperature: 80 DEG C, electric current density 110mA/g, form tantalum anode, all the other detect with reference to standard GB/T/T3137-2007 standard, and the specific capacitance of anode and leakage current are in Table 1.
Comparative example
Take the deionized water mix homogeneously of sucrose 195g (be equivalent to remove the oxygen content in tantalum oxide powder needed for stoichiometric 1.2 times of reducing agent) and 695mL. Take 500g and cross tantalum pentoxide powder (Fsss mean diameter: 0.77 μm, SBD apparent density: the 0.85g/m of 60 mesh sieves3) add above-mentioned sucrose solution and stir, prepare mixed liquor. Being positioned in pressure filter by mixed liquor, the pressure adding 0.15MP carries out filter pressing, and filter cake enters hot air drier, to rise 5 DEG C per hour, is raised to 110 DEG C, is incubated 30 minutes, cools to 90 DEG C subsequently, is incubated drying in 4 hours. After drying materials, crush and cross 70 mesh sieves. Being positioned in tantalum crucible by gained powder, be then put in vacuum drying oven, be warming up to 1450 DEG C after evacuation, be incubated 1 hour, then be warmed up to 1700 DEG C, be incubated 30 minutes, after being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing. Powder in tantalum crucible is taken out and crushes, crosses 70 mesh sieves. Obtaining hyperoxia tantalum powder, its oxygen content is 3.6wt% after testing, and carbon content is 141ppm.
Will be equivalent to the NH of the phosphorus content of required 150ppm in tantalum powder4H2PO4Solution is mixed into the hyperoxia tantalum powder after sieving, and is then placed in vacuum drying oven, temperature 60 C, and 8 hours time dried;
Above-mentioned powder is added the magnesium dust of stoichiometric 1.2 times of mistake 20 mesh sieves of reducing agent needed for the oxygen content being equivalent in hyperoxia tantalum powder; after mix homogeneously; it is positioned in tantalum crucible; then will be equipped with the tantalum crucible of material and be put in closed reactor; argon it is filled with after evacuation; under argon shield, it is incubated 3 hours at 820 DEG C. When cooling down is to 230 DEG C, it is filled with high pure nitrogen, is incubated 30 minutes. Place it is passivated after being cooled to room temperature. Tantalum powder in tantalum crucible is taken out and is soaked in the nitric acid of 15wt% dissolves and remove magnesium oxide and remaining magnesium metal, then by powder with dry after deionized water diafiltration to neutrality, it is thus achieved that pure tantalum powder. It is carried out oxygen content, carbon content, Fsss mean diameter, SBD apparent density, BET specific surface area measurement, and result is in Table 1.
It is 5.0g/m that electrical property detection uses the tantalum powder that said process obtains to be pressed into density3Diameter is the briquet of 3.0mm, in vacuum drying oven, 1300 DEG C of sintering obtain tantalum agglomerate for 20 minutes, then by agglomerate at 80 DEG C, apply the voltage of 16V in the phosphoric acid solution of 0.1%, energize time 120min, energize temperature: 80 DEG C, electric current density 110mA/g, form tantalum anode, all the other detect with reference to standard GB/T/T3137-2007 standard, and the specific capacitance of anode and leakage current are in Table 1.
Table 1
Claims (6)
1. a tantalum powder, preparation method thereof, its step: (1), take that powdery is ultra-fine, spherical tantalum pentoxide 300g～500g and carbonaceous reducing agent 95g 165g by weight, they are dissolved in deionized water or distilled water, and stir, obtained solution or mixed liquor; (2), putting in pressure filter by above-mentioned obtained solution or mixed liquor, the pressure adding 0.1MP ~ 0.2MP carries out filter pressing, obtains filter cake; (3), filter cake is heated 1～2 hour under 100 ~ 200 DEG C of conditions, dry 2～5 hours when 50～100 ° of C, then crush, cross 70 mesh sieves; Finally obtain the precursor powder containing tantalum oxide and carbon source; (4), being placed in vacuum drying oven by precursor powder, 1450 DEG C are incubated 1 hour under vacuo, are warmed up to 1700 DEG C of insulations and carry out carbon reduction treatment in 10 ~ 30 minutes; 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 the tantalum oxide powder of low oxygen content; Now the oxygen content of powder is 5wt%～10wt%; (5), the tantalum oxide powder of low oxygen content mix with relative to the stoichiometric 0.8～1.5Wt% magnesium powder of oxygen content in power, put into and reactor carry out first time deoxidation treatment, temperature 780 DEG C ~ 860 DEG C, be incubated 4 ~ 8 hours; After being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing; (6), after deoxidation comes out of the stove, unnecessary magnesium and magnesium oxide are washed with 10%～15%Wt nitric acid, and with deionized water wash to neutral; Vacuum drying powder, temperature 60 C, 12 hours time, and cross 70 mesh sieves, and obtain hyperoxia tantalum powder, now the oxygen content of powder is 1.5wt%～4wt%; (7) NH of the phosphorus content of required 150ppm in tantalum powder, is equivalent to4H2PO4Solution was mixed into the hyperoxia tantalum powder of complete sieve, was then placed in vacuum drying oven, temperature 60 C, and 12 hours time dried; (8) powder after, drying mixes with the 1～1.5Wt% magnesium powder relative to oxygen content in power stoichiometric amount, carry out second time deoxidation treatment, 780 DEG C ~ 860 DEG C 3 ~ 5 hours times of temperature, when deoxidation cool 170 DEG C ~ 300 DEG C time, carry out Nitrizing Treatment, after being cooled to ambient temperature, substep introduces a small amount of air and is passivated processing; (9), after deoxidation comes out of the stove, unnecessary magnesium and magnesium oxide are washed with 10%～15Wt% nitric acid, and with deionized water filtration washing to neutrality; (10), vacuum drying powder, temperature 60 C, 12 hours time, and cross 70 mesh sieves, obtain Ta powder used in capacitor.
2. a kind of tantalum powder, preparation method thereof according to claim 1, it is characterised in that: described ultra-fine, spherical tantalum pentoxide is: Fsss mean diameter: 0.2～0.8 μm, purity: 99.99wt%.
3. a kind of tantalum powder, preparation method thereof according to claim 1, it is characterised in that: described carbonaceous reducing agent is any one in glucose or sucrose.
4. a kind of tantalum powder, preparation method thereof according to claim 1, it is characterised in that: described method of deoxidation is that metal magnesium powder known in the art sloughs the method for oxygen in tantalum powder.
5. a kind of tantalum powder, preparation method thereof according to claim 1, it is characterised in that: described Nitrizing Treatment method is known in the art pass into high pure nitrogen to reactor, in the method for tantalum powder particles Surface Creation TaN film.
6. a kind of tantalum powder, preparation method thereof according to claim 1, it is characterised in that: the fluidity testing situation according to powder, before deoxidation, powder is increased a pelletizing pelletize to improve the mobility of powder the last time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106216695A (en) * | 2016-08-25 | 2016-12-14 | 宁波英纳特新材料有限公司 | A kind of high-voltage capacitor preparation method of spherical tantalum powder |
| TWI744397B (en) * | 2016-10-21 | 2021-11-01 | 美商環球高級金屬美國公司 | Tantalum powder, anode, and capacitor including same, and manufacturing methods thereof |
| CN114210973A (en) * | 2021-12-15 | 2022-03-22 | 宁夏东方钽业股份有限公司 | Production method of tantalum powder and tantalum powder obtained by same |
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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 |