WO2016070303A1 - 钽粉及其制造方法和由其制成的烧结阳极 - Google Patents

钽粉及其制造方法和由其制成的烧结阳极 Download PDF

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Publication number
WO2016070303A1
WO2016070303A1 PCT/CN2014/090151 CN2014090151W WO2016070303A1 WO 2016070303 A1 WO2016070303 A1 WO 2016070303A1 CN 2014090151 W CN2014090151 W CN 2014090151W WO 2016070303 A1 WO2016070303 A1 WO 2016070303A1
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Prior art keywords
powder
tantalum powder
potassium
ppm
tantalum
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PCT/CN2014/090151
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English (en)
French (fr)
Inventor
程越伟
林辅坤
张学清
雒国清
马海燕
马应会
王彦杰
王轩宇
张东杰
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宁夏东方钽业股份有限公司
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Priority to CN201480073270.3A priority Critical patent/CN105916616B/zh
Priority to CZ2017250A priority patent/CZ309286B6/cs
Priority to GB1615614.3A priority patent/GB2538211B/en
Priority to PCT/CN2014/090151 priority patent/WO2016070303A1/zh
Priority to US15/125,803 priority patent/US10513769B2/en
Priority to JP2016570847A priority patent/JP6561074B2/ja
Priority to KR1020167031539A priority patent/KR102251986B1/ko
Publication of WO2016070303A1 publication Critical patent/WO2016070303A1/zh
Priority to IL248759A priority patent/IL248759B/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • 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
    • 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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • 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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G2009/05—Electrodes or formation of dielectric layers thereon characterised by their structure consisting of tantalum, niobium, or sintered material; Combinations of such electrodes with solid semiconductive electrolytes, e.g. manganese dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes

Definitions

  • the invention belongs to the field of rare metal smelting, and particularly relates to a tantalum powder for manufacturing capacitors, a manufacturing method thereof and a sintered anode made thereof.
  • Tantalum powder is mainly used to make tantalum capacitors. With the miniaturization of electronic devices and electronic circuits and the competition between multilayer ceramic capacitors (MLCC) and aluminum capacitors in traditional applications and tantalum capacitors, the market demands to provide more. High specific capacity and better pressure resistance and sintering resistance.
  • the commercial application of tantalum powder has a specific capacity of 8,000 to 200,000 ⁇ FV/g, the maximum amount is 30,000 to 100,000 ⁇ FV/g, and the amount of tantalum powder of 120,000 to 200,000 ⁇ FV/g is smaller. It is also reported in the literature that the specific capacity exceeds 200,000 ⁇ F. /g powder, but not yet seen in commercial applications.
  • the general practice is to increase the sintering temperature, prolong the sintering time, and increase the energizing voltage.
  • increasing the sintering temperature and prolonging the sintering time will result in a loss of specific capacitance and an increase in the enabling voltage. Increase residual current.
  • the usual method of making tantalum powder is to reduce potassium fluoroantimonate (K 2 TaF 7 ) with sodium.
  • the particle size or specific surface area of the tantalum powder is controlled by the addition of a diluent salt such as KCl, NaCl, KF.
  • a diluent salt such as KCl, NaCl, KF.
  • KCl, NaCl, KF a diluent salt
  • Increasing the proportion of the diluted salt causes the obtained niobium powder to be thinner, that is, to increase the surface area of the formed powder.
  • the production capacity of the meal during the reduction process decreases as the proportion of the diluted salt increases.
  • the sodium reduction of potassium fluoroantimonate (K 2 TaF 7 ) method which is industrially carried out is more economical than a capacitor powder having a capacity of 18,000 to 70,000 ⁇ FV/g.
  • K 2 TaF 7 potassium fluoroantimonate
  • tantalum powder is mainly produced by sodium reduction of potassium fluoroantimonate method and magnesium reduction of ruthenium oxide method.
  • the sodium reduction fluoroantimonate method is a traditional production process of glutinous rice powder, the process is mature, and the market occupies a large amount; the magnesium reduction cerium oxide method is an emerging production process, and the produced glutinous rice powder also occupies a certain market share.
  • Other literatures have also been reported in the literature, such as TaCl 5 and alkali metal, alkaline earth metal reaction, rare earth metal and/or hydride reduction of lanthanum oxide, etc., but the tantalum powder produced by these methods is on the market. Not available yet.
  • Chinese patent ZL98802473.X family patent US6193779 discloses an alkali-free metal and fluorine-free tantalum powder having an initial particle size of 50 to 300 nm and a secondary particle size of 10 ⁇ m or more according to a D-50 value (ASTM-B-288).
  • the specific capacitance of the capacitor obtained by sintering at 1100-1300 ° C for 10 minutes and then with 16 V is between 120,000 and 180,000 ⁇ FV/g, and the residual current is less than 2 nA/ ⁇ FV.
  • the patent also discloses a method for preparing the tantalum powder by reacting TaCl 5 with an alkali metal or an alkaline earth metal in an inert atmosphere.
  • Chinese patent ZL98802572.8 (family patent US6238456) discloses an alkali-free metal and fluorine-free tantalum powder having an initial particle size of 150 to 300 nm and a secondary particle size of 5 ⁇ m or more obtained by sintering.
  • the specific capacitance of the capacitor obtained by sintering at 10 C for 10 minutes and then with 16 V is between 80,000 and 120,000 ⁇ FV/g, and the residual current is less than 5 nA/ ⁇ FV.
  • the patent also discloses a method for producing the tantalum powder by reducing sodium fluoroantimonate with sodium metal. method.
  • Japanese Patent No. JP 4828016 discloses a method for producing tantalum powder by reducing potassium fluoroantimonate with sodium metal, which has a specific capacitance of tantalum powder of 80000-250000 ⁇ FV/g. .
  • World Patent WO 2010/148627 A1 discloses a method for preparing tantalum powder for a high specific volume capacitor by a three-step reduction method, which uses a hydride of a rare earth metal and/or a rare earth metal to reduce cerium oxide. This method can prepare a tantalum powder having a specific capacitance of 100,000 to 400,000 ⁇ FV/g.
  • the Chinese patent ZL98802473.X (the same family patent US6193779) has a smaller particle size, a poor sinter resistance and a low enabling voltage.
  • the Chinese patent ZL98802572.8 (the same family patent US6238456) has a lower specific capacitance and a larger residual current.
  • Japanese Patent JP4828016 family patent PCT/JP01/06768, WO02/11932 adds 40-1000 times the amount of diluted salt before sodium addition to potassium fluoroantimonate (K 2 TaF 7 ), which is uneconomical; The residual current of the tantalum powder is not disclosed.
  • the method for preparing tantalum powder by the world patent WO 2010/148627 A1 has high requirements for the raw material cerium oxide, and the obtained properties are subject to cerium oxide, and the process is more complicated than the sodium reducing potassium fluoroantimonate method.
  • an object of the present invention to provide a high specific volume tantalum powder which is resistant to sintering and has a high energizing voltage (20 V); another object of the present invention is to provide an economical method for producing the tantalum powder, which has a diluted salt amount. It is 4-10 times that of potassium fluoroantimonate; a further object of the present invention is to reduce the leakage current of the sintered anode made of the tantalum powder by providing an improved tantalum powder.
  • the invention also relates to a method of providing the above powder.
  • the present invention provides a FSSS having a particle size of 1.2-3.0 ⁇ m, preferably 1.5-2.0 ⁇ m, and a standard sieve size of more than 75% (preferably more than 80%) of +325 mesh and a preparation method thereof. One or more.
  • the tantalum powder provided by the present invention has a particle size distribution D50 value of 60 ⁇ m or more.
  • the capacitor anode obtained by sintering the tantalum powder of the present invention at 1200 ° C for 20 minutes and then with 20 V is capable of having a specific capacitance of 140,000 to 180,000 ⁇ FV/g and a residual current of less than 1.0 nA/ ⁇ FV.
  • the oxygen content is from 7,000 to 12,000 ppm, preferably from 9,000 to 11,000 ppm.
  • the niobium powder has a nitrogen content of from 1500 to 2500 ppm, preferably from 2000 to 2200 ppm.
  • the niobium powder has a phosphorus content of from 110 to 180 ppm, preferably from 140 to 160 ppm.
  • the niobium powder has an alkaline earth metal content of less than 15 ppm, preferably less than 12 ppm.
  • the invention also provides a method of manufacturing tantalum powder, comprising the steps of:
  • the initial powder is prepared in step 1) by reducing potassium fluoroantimonate (K 2 TaF 7 ) with sodium metal as a dilute salt alkali metal halide.
  • K 2 TaF 7 potassium fluoroantimonate
  • the diluted salt is usually added in one portion, but the number of additions is not limited.
  • a mixture of potassium fluoroantimonate (K 2 TaF 7 ) and potassium iodide (KI) is added to the reaction vessel containing the alkali metal halide molten salt several times, each time adding fluoroquinone
  • the corresponding stoichiometric amount of sodium metal that is, the stoichiometric metal Na here is calculated based on the potassium fluoroantimonate just added
  • the resulting initial powder is washed with an aqueous mineral acid solution having a pH of 3-5, then washed with deionized water and dried.
  • the alkali metal halide is potassium chloride (KCl), sodium chloride (NaCl), potassium fluoride (KF) or a mixture thereof;
  • the inorganic acid is hydrochloric acid and/or sulfuric acid, preferably hydrochloric acid.
  • step 1) the particle size of the initial powder can be adjusted by adjusting the amount of potassium fluoroantimonate added each time, and the method of adding potassium fluoroantimonate and sodium metal in multiple times can maintain the consumption of the diluted salt. More economical.
  • the mass ratio of the cumulatively added potassium fluoroantimonate and the alkali metal halide is controlled to 1: (4 to 10), wherein the alkali metal halide refers to an alkali metal halide as a diluent salt, Includes potassium iodide.
  • potassium fluoroantimonate and potassium iodide are mixed in a mass ratio (10 to 20):1 while being mixed with the grain refining agent potassium sulfate (K 2 SO 4 ) and/or phosphoric acid Ammonium hydroxide (NH 4 H 2 PO 4 ). This can effectively avoid the initial particle agglomeration just formed by the reaction.
  • the agglomeration treatment is carried out in step 2) at a temperature in the range from 800 to 1200 ° C, in particular from 900 to 1050 ° C.
  • step 2) water is used as a binder during the pre-agglomeration process.
  • the "ultrafine tantalum powder” as referred to herein means a tantalum powder having a particle diameter of ⁇ 0.05 ⁇ m.
  • the sintered agglomerated tantalum powder can be deoxidized with metallic magnesium chips or magnesium alloy scraps.
  • ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) is added during the deoxidation treatment to prevent excessive sintering between the particles during the deoxidation treatment, maintaining the effective surface of the tantalum powder particles.
  • ammonium dihydrogen phosphate decomposes when heated, and the phosphorus element actually acts. Therefore, the amount of ammonium dihydrogen phosphate added in the examples means an effective phosphorus equivalent, that is, phosphorus contained in ammonium dihydrogen phosphate. The amount of the element.
  • the N-doping treatment in the step 3) can be carried out, for example, according to the method of Chinese Patent ZL200810002930.5.
  • the air is passivated intermittently for a plurality of times during the cooling to the room temperature, because the surface of the tantalum powder is oxidized and exothermed when the air is filled, and the intermittent inflation can be controlled.
  • the cerium powder obtained in step 3) is washed with a mixed aqueous solution of a mineral acid and hydrogen peroxide in step 4) to remove residual magnesium metal and reaction by-product magnesium oxide.
  • the mineral acid used is hydrochloric acid, nitric acid or a mixture of hydrochloric acid and nitric acid.
  • the tantalum powder obtained in step 4) is also subjected to hydraulic classification to remove fine tantalum powder having a particle size of less than 5 ⁇ m.
  • the hydraulic classification is by rinsing with water (preferably deionized water) or by commercial hydraulic classification equipment.
  • the hydraulic fractionation of the fine tantalum powder is as thorough as possible to avoid excessive residual fine tantalum powder in the tantalum powder product affecting the residual residual current of the anode made of tantalum powder.
  • rinse with deionized water to a conductivity of ⁇ 50 ⁇ s/cm.
  • the tantalum powder provided by the present invention is particularly suitable for use in the manufacture of an anode in an electrolytic capacitor having a specific capacitance of 140,000 to 0000 ⁇ FV/g and a residual current of less than 1 nA/ ⁇ FV.
  • the capacitor anode is produced by sintering the tantalum powder provided by the present invention at a temperature of 1200 ° C for 20 minutes and energizing with an energization voltage of 20V.
  • a sintered anode made of the tantalum powder of the present invention has a high specific capacitance and a small residual current.
  • the preparation method of the invention has mature process, and the mass ratio of potassium fluoroantimonate and alkali metal halide is small, and the production economy is high.
  • the "+” or “-” sign before the mesh means a screen which "passes” or “passes” the mesh, respectively.
  • "-60 mesh” means passing through a 60-mesh screen
  • "+200 mesh” means passing through a 200-mesh screen.
  • the analysis of the impurity content in the tantalum powder is carried out according to the Chinese standard GB/T15076.1 ⁇ 15076.15, and the physical properties are carried out according to the industry standard YS/T573-2007.
  • the test of leakage current and capacitance in tantalum powder is carried out in accordance with the Chinese standard GB/T3137.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 850 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • the initial powder obtained in the step 1) was subjected to a pre-agglomeration treatment using deionized water as a binder.
  • the pre-agglomerated tantalum powder is placed in a crucible, and then placed in a vacuum heat treatment furnace, and subjected to a 5-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept for 1 hour. After heating to 1050 ° C, the temperature was kept for 30 minutes, and then the temperature was raised to 1100 ° C, and then kept for 30 minutes, and then heated to 1180 ° C and then kept for 20 minutes. After the sinter agglomeration, it was cooled to room temperature, the cerium powder was taken out, and it was crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.0% of magnesium turnings and a phosphorus equivalent weight of 120 ppm of ammonium dihydrogen phosphate were added and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.15 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, the mixture was cooled to room temperature and intermittently filled with air for passivation treatment, and then the tantalum powder was taken out.
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 850 ° C to start stirring, and the temperature was kept for 30 minutes. Then, a mixture consisting of 5 kg of potassium fluoroantimonate, 250 g of potassium iodide and 500 g of potassium sulfate (K 2 SO 4 ) and 0.4 g of ammonium dihydrogen phosphate was added.
  • the initial tantalum powder obtained in the step 1) is pre-agglomerated with deionized water as a binder. Then, the pre-agglomerated tantalum powder is charged into the crucible, and then the crucible is placed in a vacuum heat treatment furnace to carry out a 5-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C. After heat preservation for 1 hour, the temperature was raised to 1050 ° C and then kept for 30 minutes. After heating to 1100 ° C, the temperature was kept for 30 minutes, and then the temperature was raised to 1180 ° C and then kept for 20 minutes. After the completion of the agglomeration, the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed through a 60 mesh sieve.
  • a 5-stage sintering agglomeration treatment that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 °
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.0% of magnesium turnings, ammonium dihydrogen phosphate (phosphorus equivalent weight: 80 ppm) was added to the tantalum powder, and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.15 MPa. The temperature was controlled at 180 ° C ⁇ 5 ° C for 8 hours. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • ammonium dihydrogen phosphate phosphorus equivalent weight: 80 ppm
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 830 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • the initial powder obtained in the step 1) was subjected to a pre-agglomeration treatment using deionized water as a binder.
  • the pre-agglomerated tantalum powder is placed in a crucible, and then placed in a vacuum heat treatment furnace, and subjected to a 5-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept for 1 hour. After heating to 1050 ° C, the temperature was kept for 30 minutes, and then the temperature was raised to 1100 ° C, and then kept for 30 minutes, and then heated to 1180 ° C and then kept for 20 minutes. After the sinter agglomeration, it was cooled to room temperature, the cerium powder was taken out, and it was crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.5% of magnesium turnings and a phosphorus equivalent weight of 140 ppm of ammonium dihydrogen phosphate were added and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.18 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 830 ° C to start stirring, and the temperature was kept for 30 minutes. Then a mixture of 5 kg of potassium fluoroantimonate, 250 g of potassium iodide and 50 g of potassium sulphate (K 2 SO 4 ) and 0.5 g of ammonium dihydrogen phosphate was added.
  • K 2 SO 4 potassium sulphate
  • the initial powder obtained in the step 1) was subjected to a pre-agglomeration treatment using deionized water as a binder.
  • the pre-agglomerated tantalum powder is placed in a crucible, and then placed in a vacuum heat treatment furnace, and subjected to a 5-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept for 1 hour. After heating to 1050 ° C, the temperature was kept for 30 minutes, and then the temperature was raised to 1100 ° C, and then kept for 30 minutes, and then heated to 1180 ° C and then kept for 20 minutes. After the sinter agglomeration, it was cooled to room temperature, the cerium powder was taken out, and it was crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.5% of magnesium turnings and a phosphorus equivalent of 100 ppm of ammonium dihydrogen phosphate in a mass ratio of tantalum powder were added and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.18 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • the cerium powder obtained in the step 3) is added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, The mixture was stirred for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 830 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • the analytical data of the obtained initial tantalum powder are as follows:
  • Step 1) The obtained initial powder was pre-agglomerated with deionized water as a binder.
  • the pre-agglomerated tantalum powder is placed in a crucible, and then the crucible is placed in a vacuum heat treatment furnace for 4 stages.
  • the sinter agglomeration treatment that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C for 1 hour, then heated to 1050 ° C for 30 minutes, and then heated to 1120 ° C for 20 minutes.
  • the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.8% of magnesium turnings, ammonium dihydrogen phosphate (phosphorus equivalent of 150 ppm by mass of the tantalum powder) were added to the tantalum powder, and mixed, and then placed in a covered pot. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.18 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • ammonium dihydrogen phosphate phosphorus equivalent of 150 ppm by mass of the tantalum powder
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 830 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • the analytical data of the obtained initial tantalum powder are as follows:
  • Step 1) The obtained initial powder was pre-agglomerated with deionized water as a binder.
  • the pre-agglomerated tantalum powder is charged into the crucible, and then the crucible is placed in a vacuum heat treatment furnace for four-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept warm. After an hour, the temperature was raised to 1050 ° C and then kept for 30 minutes, and then heated to 1120 ° C and then kept for 20 minutes. After the completion of the agglomeration, the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.8% of magnesium powder, ammonium dihydrogen phosphate (phosphorus equivalent weight of 120 ppm of the tantalum powder) was added to the tantalum powder, and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.18 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • ammonium dihydrogen phosphate phosphorus equivalent weight of 120 ppm of the tantalum powder
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, will ⁇ The powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 800 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • Step 1) The obtained initial powder was pre-agglomerated with deionized water as a binder.
  • the pre-agglomerated tantalum powder is charged into the crucible, and then the crucible is placed in a vacuum heat treatment furnace for four-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept warm. After an hour, the temperature was raised to 1050 ° C and then kept for 30 minutes, and then heated to 1100 ° C and then kept for 20 minutes. After the sintering is completed, it is cooled to room temperature, and the powder is taken out and broken into 60 mesh. screen.
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% hydrochloric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 800 ° C to start stirring, and the temperature was kept for 30 minutes. Then a mixture of 2.5 kg of potassium fluoroantimonate, 250 g of potassium iodide and 50 g of potassium sulphate (K 2 SO 4 ) and 0.5 g of ammonium dihydrogen phosphate was added.
  • K 2 SO 4 potassium sulphate
  • Step 1) The obtained initial powder was pre-agglomerated with deionized water as a binder.
  • the pre-agglomerated tantalum powder is charged into the crucible, and then the crucible is placed in a vacuum heat treatment furnace for four-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1000 ° C and then kept warm. After an hour, the temperature was raised to 1050 ° C and then kept for 30 minutes, and then heated to 1100 ° C and then kept for 20 minutes. After the completion of the agglomeration, the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.5% of magnesium turnings, ammonium dihydrogen phosphate (phosphorus equivalent of 140 ppm by mass of the tantalum powder) was added to the tantalum powder, and mixed, and then placed in a covered pot. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.18 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • ammonium dihydrogen phosphate phosphorus equivalent of 140 ppm by mass of the tantalum powder
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% hydrochloric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 850 ° C to start stirring, and the temperature was kept for 30 minutes.
  • KCl potassium chloride
  • KF potassium fluoride
  • the initial powder obtained in the step 1) was subjected to a pre-agglomeration treatment using deionized water as a binder. Then, the pre-agglomerated tantalum powder is placed in a crucible and placed in a vacuum heat treatment furnace for three-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C and then kept for 1 hour, and then heated to 1050 ° C and then kept for 30 minutes. After heating to 1180 ° C, the temperature was kept for 20 minutes. After the completion of the agglomeration, the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed through a 60 mesh sieve.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.0% of magnesium turnings, ammonium dihydrogen phosphate (phosphorus equivalent of 120 ppm by mass of the tantalum powder) was added to the tantalum powder, and mixed, and then placed in a covered pot.
  • the crucible was placed in an argon-protected reaction vessel and kept at 840 ° C for 2 hours, followed by cooling. However, it was kept at 180 ° C, and after the temperature was stabilized, nitrogen gas was charged to make the pressure in the reaction vessel reach 0.15 MPa, and the temperature was controlled at 180 ° C ⁇ 5 ° C for 8 hours. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the reaction vessel was evacuated and then replaced with argon. Next, 100 kg of potassium chloride (KCl), 100 kg of potassium fluoride (KF), 1 kg of fine powder of FSSS particle size ⁇ 0.5 ⁇ m were weighed and mixed, and then the mixture was charged into a reaction vessel. Then, the reaction vessel was placed in a heating furnace and heated, and the temperature was raised to 850 ° C to start stirring, and the temperature was kept for 30 minutes. Then, a mixture consisting of 5 kg of potassium fluoroantimonate, 250 g of potassium iodide and 500 g of potassium sulfate (K 2 SO 4 ) and 0.4 g of ammonium dihydrogen phosphate was added.
  • the initial tantalum powder obtained in the step 1) is pre-agglomerated with deionized water as a binder. Then, the pre-agglomerated tantalum powder is charged into the crucible, and the crucible is placed in a vacuum heat treatment furnace for three-stage sintering agglomeration treatment, that is, the vacuum is heated to 800 ° C, and then kept for 1 hour, and then heated to 1050 ° C. After holding for 30 minutes, the temperature was raised to 1180 ° C and then kept for 20 minutes. After the completion of the agglomeration, the mixture was cooled to room temperature, and the tantalum powder was taken out and crushed and sieved.
  • the tantalum powder obtained in the step 2) To the tantalum powder obtained in the step 2), 3.0% of magnesium turnings, ammonium dihydrogen phosphate (phosphorus equivalent weight: 80 ppm) was added to the tantalum powder, and mixed, and then placed in a covered crucible. Next, the crucible is placed in an argon-protected reaction vessel and then incubated at 840 ° C for 2 hours, and cooled to 180 ° C. After the temperature is stabilized, nitrogen gas is charged to bring the pressure in the reaction vessel to 0.15 MPa, and the control temperature is 180 ° C ⁇ 5 Incubate for 8 hours at °C. After the end of the heat preservation, it is cooled to room temperature and repeatedly filled with air for passivation treatment, and then the tantalum powder is taken out.
  • ammonium dihydrogen phosphate phosphorus equivalent weight: 80 ppm
  • the tantalum powder obtained in the step 3) was added to a mixed aqueous solution of 10% nitric acid and 0.5% hydrogen peroxide, and washed with stirring for 2 hours to remove residual magnesium metal and reaction by-product magnesium oxide. Then, the acid solution was decanted, followed by stirring with deionized water for 1 minute, and after standing for 5 minutes, the aqueous solution containing the fine cerium powder was rinsed off, and the operation was repeated until the conductivity was ⁇ 50 ⁇ s/cm. Then, the tantalum powder was transferred to a filter tank for filtration, washed with deionized water to a conductivity of less than 5 ⁇ s/cm, and filtered. The product was then dried through an 80 mesh screen to obtain a product powder.
  • the finished tantalum powder obtained in Examples 1-10 was also pressed, sintered, and energized to obtain a sintered anode to detect its specific capacity and residual current.
  • the conditions for manufacturing the anode and the electrical property data obtained by the test are shown in Table 3.
  • the particle size distribution data was determined by a Coulter Laser Particle Size Distribution Apparatus LS230.

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Abstract

本发明属于稀有金属冶炼领域，具体涉及制作电容器用的一种钽粉及其制造方法和由其制成的烧结阳极，其初始粉末的BET为3.0-4.5m2/g，二次团化颗粒粒度大，FSSS粒径为1.2-3.0μm，以标准筛筛目度量75%大于325目，粒度分布D50值为60μm以上，其二次粒度大，用这种钽粉在1200ºC烧结20分钟再用20V赋能获得的电容器的比电容量在140000到180000μFV/g，残余电流小于1.0nA/μFV。本发明同时提供了一种经济制造该钽粉的方法。

Description

钽粉及其制造方法和由其制成的烧结阳极 技术领域
本发明属于稀有金属冶炼领域，具体涉及制作电容器用的一种钽粉及其制造方法和由其制成的烧结阳极。
背景技术
钽粉主要是用于制作钽电容器，随着电子装置和电子线路小型化的要求以及应对多层陶瓷电容器(MLCC)和铝电容器在传统的应用领域中和钽电容器进行的竞争，市场要求提供更高比电容量和更好耐压性能、耐烧结性能的钽粉。商业应用钽粉的比电容量为8000到200000μFV/g，用量最大的范围是30000到100000μFV/g，120000到200000μFV/g比电容量的钽粉用量还较小，也有文献报道比电容量超过200000μFV/g的钽粉，但还未见商业应用。为了提高钽粉的耐压性能、耐烧结性能，一般的做法是提高烧结温度、延长烧结时间、提高赋能电压，但提高烧结温度、延长烧结时间会使比电容量损失，提高赋能电压会增加残余电流。
制造钽粉通常使用的方法是用钠将氟钽酸钾(K2TaF7)还原。钽粉的粒径或比表面积是通过加入稀释盐如KCl、NaCl、KF来进行控制。增大稀释盐的比例时会使获得的钽粉变细，即增大形成的粉末表面积。但是还原过程中钽粉的生产能力随着稀释盐比例的增加而相应降低。一般认为在工业上进行的钠还原氟钽酸钾(K2TaF7)法制成比电容量为18000到70000μFV/g的电容器粉末是比较经济的。如果要求制成高比电容量的电容器，就要求初始粒度更细的钽粉，这就需要使氟钽酸钾(K2TaF7)在更高比例的稀释(KCl、NaCl、KF的稀释盐)条件下进行钠还原。
目前钽粉主要是由钠还原氟钽酸钾法和镁还原氧化钽法生产的。钠还原氟钽酸钾法是钽粉的传统生产工艺，工艺成熟，市场占有量大；镁还原氧化钽法是新兴的一种生产工艺，所生产钽粉也占有一定市场份额。文献也报道过其他一些钽粉的生产方法，如TaCl5与碱金属、碱土金属反应法、稀土金属和/或稀土金属的氢化物还原氧化钽法等，但这些方法生产的钽粉在市面上尚未有售。
中国专利ZL98802473.X(同族专利US6193779)公开了一种无碱金属和无氟的钽粉，其初始粒度为50到300nm，二次粒度按照D-50值(ASTM-B-288)为10μm以上，经过在1100-1300℃烧结10分钟再用16V赋能获得的电容器的比电容量在120000到180000μFV/g，残余电流小于2nA/μFV。该专利同时公开了一种用TaCl5与碱金属、碱土金属在惰性气氛中反应制取该钽粉的方法。
中国专利ZL98802572.8(同族专利US6238456)公开了一种无碱金属和无氟的钽粉，其初始粒度为150到300nm，烧结得到的二次颗粒粒度为5μm以上，用这种钽粉在1200℃烧结10分钟再用16V赋能获得的电容器的比电容量在80000到120000μFV/g，残余电流小于5nA/μFV；该专利同时公开了一种用金属钠还原氟钽酸钾制造该钽粉的方法。
日本专利JP4828016(同族专利PCT/JP01/06768、WO 02/11932)公开了一种用金属钠还原氟钽酸钾制造钽粉的方法，该专利方法制造的钽粉比电容为80000-250000μFV/g。
世界专利WO 2010/148627A1(PCT/CN2010/000414)公开了一种通过三步还原法制备高比容电容器用钽粉的方法，该方法用稀土金属和/或稀土金属的氢化物还原氧化钽，该方法可制备比电容为100000-400000μFV/g的钽粉。
上述专利分别具有以下的缺点并且因此在实际应用中具有一定的局限性。
中国专利ZL98802473.X(同族专利US6193779)制造的钽粉粒度较小，耐烧结性差和赋能电压低。
中国专利ZL98802572.8(同族专利US6238456)制造的钽粉比电容低，残余电流大。
日本专利JP4828016(同族专利PCT/JP01/06768、WO02/11932)的方法添加钠前稀释盐量是氟钽酸钾(K2TaF7)的40-1000倍，不经济；另外该专利只公开了所制造钽粉的比电容，未公开钽粉的残余电流。
世界专利WO 2010/148627A1(PCT/CN2010/000414)制备钽粉的方法对原料氧化钽要求较高，所得性能受制于氧化钽，工艺较钠还原氟钽酸钾法复杂。
发明内容
鉴于上述缺点，本发明的目的是提供一种耐烧结并且赋能电压高(20V)的高比容钽粉；本发明的另一目的是提供一种制造此钽粉的经济方法，稀释盐量是氟钽酸钾的4-10倍；本发明的再一目的是通过提供一种改善的钽粉使得由该钽粉制成的烧结阳极的漏电流降低。
本发明还涉及提供生产上述粉末的方法。
本发明提供一种FSSS粒径为1.2-3.0μm，优选1.5-2.0μm，以标准筛筛目度量大于75％(优选大于80％)为+325目的钽粉及其制备方法实现上述目的中的一种或多种。
优选地，本发明提供的钽粉的粒度分布D50值为60μm以上。
优选地，用本发明的钽粉在1200℃烧结20分钟再用20V赋能获得的电容器阳极的比电容量在140000到180000μFV/g，残余电流小于1.0nA/μFV。
在本发明提供的钽粉的一个优选实施方案中，其氧含量为7000-12000ppm，优选9000-11000ppm。在一个实施方案中，所述钽粉的氮含量为1500-2500ppm，优选2000-2200ppm。在又一个实施方案中，所述钽粉磷含量为110-180ppm，优选140-160ppm。在更优选的实施方案中，所述钽粉的碱土金属含量小于15ppm，优选小于12ppm。
本发明还提供了一种制造钽粉的方法，包括以下步骤：
1)提供BET为3.0-4.5m2/g的初始粉末；
2)将步骤1)获得的初始粉末进行预团化处理，然后再进入真空热处理炉中进行3-5段烧结团化处理；
3)对经烧结团化处理的钽粉进行脱氧掺氮处理；和
4)对脱氧掺氮的钽粉进行洗涤和干燥，得到产品钽粉。
优选地，在步骤1)中通过使在作为稀释盐碱金属卤化物中用金属钠还原氟钽酸钾(K2TaF7)制成初始粉末。该稀释盐通常一次性加入，但对其 加入次数不加限制。更优选地，在钠还原过程中，将氟钽酸钾(K2TaF7)和碘化钾(KI)的混合物分多次加入装有碱金属卤化物熔盐的反应容器中，每次加入氟钽酸钾后再加入相应化学计量比的金属钠(即此处的化学计量的金属Na是根据刚刚加入的氟钽酸钾所计算出的)，在氩气的气氛中在800-860℃下还原，分离副产物，得到初始粉末。最优选地，在步骤1)中还包括用pH值为3-5的无机酸水溶液洗涤所得初始粉末，然后用去离子水洗涤并干燥。
优选地，所述碱金属卤化物为氯化钾(KCl)、氯化钠(NaCl)、氟化钾(KF)或它们的混合物；无机酸为盐酸和/或硫酸，优选盐酸。
如本领域中公知的那样，加入的氟钽酸钾的量越大，所得到的初始粉末粒度越大；加入的氟钽酸钾的量越小，所得到的初始粉末粒度越小。因此，在步骤1)中，可以通过调整每次加入的氟钽酸钾的量来调整初始粉末的粒度，同时分多次加入氟钽酸钾和金属钠的方法可以使稀释盐的消耗保持一个比较经济的水平。在本发明中，累计加入的氟钽酸钾和碱金属卤化物的质量比控制在1∶(4～10)，其中所述的碱金属卤化物是指作为稀释盐的碱金属卤化物，不包括碘化钾。
在步骤1)中，优选地，将氟钽酸钾和碘化钾按质量比(10～20)∶1的比例混合，同时混入晶粒细化剂硫酸钾(K2SO4)和/或磷酸二氢铵(NH4H2PO4)。这样做可以有效地避免反应刚生成的初始颗粒凝聚。
优选地，在步骤2)在800-1200℃，特别是900-1050℃范围内进行烧结团化处理。
在步骤2)中，在预团化处理过程中，采用水作粘结剂。申请人意外地发现，通过本发明所述的烧结团化处理可以有效地消除有害的超微细钽粉末。这里所述的“超微细钽粉末”是指粒径≤0.05μm的钽粉末。
例如，在步骤3)中可以用金属镁屑或镁合金屑对经烧结团化处理的钽粉进行脱氧。优选地，脱氧处理时加入磷酸二氢铵(NH4H2PO4)，从而防止脱氧处理时颗粒间的过度烧结，保持钽粉颗粒的有效表面。应理解，磷酸二氢铵在受热时分解，真正起作用的是磷元素，因此在实施例中添加的磷酸二氢铵的量是指有效的磷当量，即磷酸二氢铵中所含有的磷元素的量。
在步骤3)中的掺N处理可以例如按中国专利ZL200810002930.5的方法进行。
优选地，待保温结束后，在冷却到室温的过程中多次间歇性充入空气进行钝化处理，这是因为在充入空气时，钽粉表面会氧化放热，而间歇性充气可以控制放热量。在本发明的一个优选实施方案中，在步骤4)中用无机酸和双氧水的混合水溶液洗涤步骤3)中获得的钽粉去除残余金属镁及反应副产物氧化镁。优选地，所使用的无机酸为盐酸、硝酸或盐酸和硝酸的混合物。
在本发明的另一个优选实施方案中，在步骤4)中获得的钽粉还经水力分级去除粒径小于5μm的微细钽粉。优选地，水力分级是采用水(优选去离子水)漂洗或采用市售水力分级设备进行分级。
优选地，水力分级分离微细钽粉末要尽可能彻底，以避免钽粉产品中残留过多微细钽粉末影响由钽粉制成的阳极残余电流。一般来说，用去离子水漂洗至电导率＜50μs/cm即可。
本发明提供的钽粉尤其适合于用来制造比电容量为140000-180000μFV/g，残余电流小于1nA/μFV的电解质电容器中的阳极。例如，通过在温度为1200℃下20分钟烧结本发明提供的钽粉，并以20V的赋能电压进行赋能制造该电容器阳极。
本发明的有益效果主要体现在以下两方面：
1、由本发明的钽粉制成的烧结阳极的比电容量高且残余电流小。
2、本发明的制备方法工艺成熟，氟钽酸钾和碱金属卤化物的质量比小，生产经济性高。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明优选的实施方式进行描述，可以明显地看出本发明的目的、特征和优点。但这些描述只是为了进一步说明本发明的特征和优点，而不是对本发明的限制。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
出于本说明书的目的，在说明书和权利要求书中所有表示成分的量、反应条件等的数字在所有的情况下应被理解为由术语“约”修饰，除非另有指定。相应地，以下的说明书和所附权利要求书中给出的数值参数是近似值，其可根据本发明试图得到的所希望的性质而变化，除非有相反的指示。至少，且不打算限制等同原则在权利要求范围上的应用，每个数值参数应该至少按照所报道的有效数字的位数并按照通常的四舍五入技术来解释。
在本发明中，当用目数表示粉末的粒度时，在目数之前的“+”或“-”号分别表示“通不过”或“通过”所述目数的筛网。例如，“-60目”表示通过60目的筛网，而“+200目”表示通不过200目的筛网。
钽粉中杂质含量的分析按中国标准GB/T15076.1～15076.15，物理性能按行业标准YS/T573-2007中规定进行。钽粉中漏电流、电容量的测试按中国标准GB/T3137的规定进行。
实施例1
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至850℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)组成的混合物，待温度重新升到850℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到850℃后加入化学计量比的金属钠，将此加料过程再重复9次。反应结束后在830℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为3的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000001
Figure PCTCN2014090151-appb-000002
步骤2)
用去离子水作为粘结剂将步骤1)所得初始粉末进行预团化处理。将预团化后的钽粉装入坩埚中，再放入真空热处理炉中，进行5段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温30分钟，再升温到1180℃后保温20分钟。烧结团化结束后冷却到室温，将钽粉取出，并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.0％的镁屑、磷当量为钽质量120ppm的磷酸二氢铵，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.15MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温多次间歇性充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例2
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加 热，升温至850℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、250g碘化钾和500g硫酸钾(K2SO4)、0.4g磷酸二氢铵组成的混合物，待温度重新升到850℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到850℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在830℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为3的盐酸水溶液洗涤提纯所得初始粉末，再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000003
步骤2)
用去离子水作为粘结剂将步骤1)所得初始钽粉进行预团化处理。然后，将预团化后的钽粉装入坩埚中，再将坩埚放入真空热处理炉中进行5段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温30分钟，再升温到1180℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.0％的镁屑、磷酸二氢铵(磷当量为钽质量的80ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.15MPa， 控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例3
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至830℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、350g碘化钾和50g硫酸钾(K2SO4)组成的混合物，待温度重新升到830℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到830℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在820℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为3的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000004
Figure PCTCN2014090151-appb-000005
步骤2)
用去离子水作为粘结剂将步骤1)所得初始粉末进行预团化处理。将预团化后的钽粉装入坩埚中，再放入真空热处理炉中，进行5段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温30分钟，再升温到1180℃后保温20分钟。烧结团化结束后冷却到室温，将钽粉取出，并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.5％的镁屑、磷当量为钽质量140ppm的磷酸二氢铵，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例4
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至830℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)、0.5g磷酸二氢铵组成的混合物，待温度重新升到830℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计 量比的金属钠；之后加入相同份量混合物料，待温度重新升到830℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在820℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为4的盐酸水溶液洗涤提纯所得初始粉末，再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000006
步骤2)
用去离子水作为粘结剂将步骤1)所得初始粉末进行预团化处理。将预团化后的钽粉装入坩埚中，再放入真空热处理炉中，进行5段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温30分钟，再升温到1180℃后保温20分钟。烧结团化结束后冷却到室温，将钽粉取出，并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.5％的镁屑、磷当量为钽粉质量的100ppm的磷酸二氢铵，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中， 搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例5
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至830℃开始搅拌，保温30分钟。之后加入由3kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)组成的混合物，待温度重新升到830℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到830℃后加入化学计量比的金属钠，此过程重复11次。反应结束后在820℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为4的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始钽粉的分析数据如下：
Figure PCTCN2014090151-appb-000007
步骤2)
步骤1)所得初始粉末用去离子水作为粘结剂进行预团化处理。将预团化后的钽粉装入坩埚中，然后将坩埚放入真空热处理炉中进行4段 烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1120℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.8％的镁屑、磷酸二氢铵(磷当量为钽粉质量的150ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例6
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至830℃开始搅拌，保温30分钟。之后加入由3kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)、0.5g磷酸二氢铵组成的混合物，待温度重新升到830℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到850℃后加入化学计量比的金属钠，此过程重复11次。反应结束后在820℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为4的盐酸水溶液洗涤提纯所得初始粉末，再用去离子水洗涤并干燥。
所得初始钽粉的分析数据如下：
Figure PCTCN2014090151-appb-000008
步骤2)
步骤1)所得初始粉末用去离子水作为粘结剂进行预团化处理。将预团化后的钽粉装入坩埚中，然后将坩埚放入真空热处理炉中进行4段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1120℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.8％的镁屑、磷酸二氢铵(磷当量为钽粉质量的120ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽 粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例7
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至800℃开始搅拌，保温30分钟。之后加入由2.5kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)组成的混合物，待温度重新升到800℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到800℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在800℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为5的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000009
步骤2)
步骤1)所得初始粉末用去离子水作为粘结剂进行预团化处理。将预团化后的钽粉装入坩埚中，然后将坩埚放入真空热处理炉中进行4段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目 筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.8％的镁屑、磷酸二氢铵(磷当量为钽粉质量的180ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在820℃后保温2小时，冷却到150℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％盐酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例8
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至800℃开始搅拌，保温30分钟。之后加入由2.5kg氟钽酸钾、250g碘化钾和50g硫酸钾(K2SO4)、0.5g磷酸二氢铵组成的混合物，待温度重新升到800℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到800℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在800℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为5的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000010
步骤2)
步骤1)所得初始粉末用去离子水作为粘结剂进行预团化处理。将预团化后的钽粉装入坩埚中，然后将坩埚放入真空热处理炉中进行4段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1000℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1100℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.5％的镁屑、磷酸二氢铵(磷当量为钽粉质量的140ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.18MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％盐酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例9
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至850℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、250g碘化钾和500g硫酸钾(K2SO4)组成的混合物，待温度重新升到830℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到850℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在830℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为3的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000011
步骤2)
用去离子水作为粘结剂将步骤1)所得初始粉末进行预团化处理。然后，将预团化后的钽粉装入坩埚中放入真空热处理炉中进行3段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1180℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过60目筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.0％的镁屑、磷酸二氢铵(磷当量为钽粉质量的120ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷 却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.15MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
实施例10
步骤1)
将反应容器抽真空然后用氩气置换。接着，称取100kg氯化钾(KCl)、100kg氟化钾(KF)、1kg FSSS粒径≤0.5μm的微细钽粉，并将其混合，然后将混合物装入反应容器中。继而，将反应容器放入加热炉中加热，升温至850℃开始搅拌，保温30分钟。之后加入由5kg氟钽酸钾、250g碘化钾和500g硫酸钾(K2SO4)、0.4g磷酸二氢铵组成的混合物，待温度重新升到850℃后按化学反应K2TaF7+5Na＝Ta+5NaF+2KF计算并加入化学计量比的金属钠；之后加入相同份量混合物料，待温度重新升到850℃后加入化学计量比的金属钠，此过程重复9次。反应结束后在830℃保温10分钟，之后停搅拌并冷却至室温。
取出反应产物后分离副产物，用pH值为3的盐酸水溶液洗涤提纯所得初始粉末再用去离子水洗涤并干燥。
所得初始粉末的分析数据如下：
Figure PCTCN2014090151-appb-000012
Figure PCTCN2014090151-appb-000013
步骤2)
用去离子水作为粘结剂将步骤1)所得初始钽粉进行预团化处理。然后，将预团化后的钽粉装入坩埚中，并将坩埚放入真空热处理炉中进行3段烧结团化处理，即抽真空升温到800℃后保温1小时，再升温到1050℃后保温30分钟，再升温到1180℃后保温20分钟。待烧结团化结束后冷却到室温，将钽粉取出并破碎过筛。
步骤3)
向步骤2)所得钽粉加入按钽粉质量比计3.0％的镁屑、磷酸二氢铵(磷当量为钽质量的80ppm)，并混匀，然后放在有盖的钽坩埚中。接着，将该坩埚放入氩气保护的反应容器中在840℃后保温2小时，冷却到180℃，待温度稳定后充入氮气，使反应容器内压力达到0.15MPa，控制温度180℃±5℃保温8小时。待保温结束后，冷却到室温反复充入空气进行钝化处理，然后取出钽粉。
步骤4)
将步骤3)所得钽粉加入10％硝酸和0.5％双氧水的混合水溶液中，搅拌洗涤2小时，以去除残余金属镁及反应副产物氧化镁。然后，倾析去除酸液，接着加入去离子水搅拌1分钟，静置5分钟后漂去上部含微细钽粉末的水溶液，反复操作直至电导率＜50μs/cm为止。然后，将钽粉转至滤洗槽中过滤，用去离子水洗涤至电导率低于5μs/cm，过滤。然后干燥过80目筛得到产品钽粉。
对实施例1-10获得的成品钽粉进行测试，测得其中的化学杂质如表1所示，物理性能如表2所示。
还将实施例1-10获得的成品钽粉进行压制、烧结、赋能得到烧结阳极，以检测其比电容量和残余电流。制造阳极的条件及检测得到的电性能数据如表3所示。
表1 成品钽粉化学杂质
Figure PCTCN2014090151-appb-000014
表2 成品钽粉物理性能
Figure PCTCN2014090151-appb-000015
粒度分布数据由库尔特激光粒度分布仪LS230测定。
表3 成品钽粉电性能数据
Figure PCTCN2014090151-appb-000016

Claims (12)

  1. 一种钽粉，其FSSS粒径为1.2-3.0μm，优选1.5-2.0μm，以标准筛筛目度量大于75％(优选大于80％)的钽粉为+325目。
  2. 权利要求1的钽粉，其D50值为60μm以上。
  3. 权利要求1或2的钽粉，该钽粉具有：
    氧含量7000-12000ppm，优选9000-11000ppm，
    任选地，氮含量1500-2500ppm，例如2000-2200ppm；
    任选地，磷含量110-180ppm，例如140-160ppm；和/或
    任选地，碱土金属含量＜15ppm，例如小于12ppm。
  4. 权利要求1、2或3的钽粉，其中用本发明的钽粉在1200℃烧结20分钟再用20V赋能获得的电容器阳极的比电容量在140000到180000μFV/g，和/或残余电流小于1.0nA/μFV。
  5. 权利要求1-4中任一项的钽粉，该钽粉为团化的钽粉，其初始粉末的BET为3.0-4.5m2/g，优选3.5-4.2m2/g。
  6. 制造钽粉的方法，包括以下步骤：
    1)提供BET为3.0-4.5m2/g的初始粉末，例如通过在碱金属卤化物中用金属钠还原氟钽酸钾(K2TaF7)制成初始粉末，并任选用无机酸(优选地无机酸为盐酸和/或硫酸，优选盐酸，例如pH值为3-5的水溶液)洗涤所得初始粉末并干燥；
    2)将步骤1)获得的初始粉末进行预团化(例如采用水作为粘结剂)处理，然后再进入真空热处理炉中进行3-5段烧结团化处理；
    3)对经烧结团化处理的钽粉进行脱氧掺氮处理，优选用金属镁屑或镁合金屑对经烧结团化处理的钽粉进行脱氧，其中脱氧处理时任选加入以 钽粉质量计磷当量为50-150ppm优选80-120ppm的磷酸二氢铵(NH4H2PO4)和
    4)对脱氧掺氮的钽粉进行洗涤和干燥，得到产品钽粉。
  7. 权利要求6的方法，其中在步骤1)中分多次向装有碱金属卤化物(例如氯化钾(KCl)、氯化钠(NaCl)、氟化钾(KF)或它们的混合物)熔盐的反应容器中加入氟钽酸钾(K2TaF7)和碘化钾(KI)的混合物。
  8. 权利要求6或7的方法，其中将氟钽酸钾和碘化钾按质量比(10～20)∶1的比例混合，同时混入晶粒细化剂硫酸钾(K2SO4)和/或磷酸二氢铵(NH4H2PO4)。
  9. 权利要求6-8中任一项的方法，其中在步骤4)中用无机酸(例如盐酸、硝酸，或盐酸和硝酸的混合物)和双氧水的混合水溶液洗涤步骤3)中获得的钽粉，然后任选经水力分级去除微细钽粉末。
  10. 权利要求9中任一项的方法，其中用去离子水进行水力分级直至电导率＜50μs/cm即可。
  11. 通过权利要求6-10中任一项的方法获得的钽粉。
  12. 阳极，通过烧结权利要求1-5和11中任一项的钽粉获得，以及包含该阳极的电容器。
PCT/CN2014/090151 2014-11-03 2014-11-03 钽粉及其制造方法和由其制成的烧结阳极 WO2016070303A1 (zh)

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