CN115255379A - Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition - Google Patents
Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition Download PDFInfo
- Publication number
- CN115255379A CN115255379A CN202211165156.6A CN202211165156A CN115255379A CN 115255379 A CN115255379 A CN 115255379A CN 202211165156 A CN202211165156 A CN 202211165156A CN 115255379 A CN115255379 A CN 115255379A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- powder
- dispersion
- amorphous
- vapor deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
Abstract
The invention discloses a method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition, which comprises the following steps: 1. adjusting and modifying the active particle size of the amorphous cracked carbon particles; 2. performing low-energy ball milling after ultrasonic dispersion with molybdenum trioxide; 3. drying; 4. carrying out segmented heat treatment; 5. reducing with hydrogen to obtain superfine MoO 2 A powder; 6. and continuously reducing the molybdenum powder by hydrogen to obtain the ultrafine molybdenum powder. The invention is based on multi-step chemical vapor deposition, adopts high-activity-site amorphous cracked carbon obtained after active particle size adjustment and modification treatment as precursor powder for constructing a core-shell structure to provide a large number of heterogeneous nucleation points, and combines ultrahigh-speed stirring to adjust a pore structureAnd the dispersibility provides a foundation for the dispersibility and gas phase transmission regulation and control of products in the heat treatment and two-step hydrogen reduction treatment processes, the effective control of the particle sizes of the superfine molybdenum dioxide and the molybdenum powder is realized, and meanwhile, the method has the advantages of wide raw material source, low cost, simple method and easy engineering application.
Description
Technical Field
The invention belongs to the technical field of preparation of nano powder materials, and particularly relates to a method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition.
Background
Molybdenum is one of the most widely used refractory metals at present, and has important application in the fields of aviation, aerospace, military, chemistry, nuclear energy, metallurgy and the like. China is the world with the largest molybdenum resource, production and consumption countries, and by 2018, the molybdenum reserve in China is 830 ten thousand tons, which accounts for about 49.3 percent of the world; the yield and consumption of the molybdenum respectively reach 9.3 ten thousand tons and 8.9 ten thousand tons. The molybdenum powder is a key basic raw material for preparing molybdenum and alloy materials thereof, and the characteristics (particularly the granularity) of the molybdenum powder have great influence on the preparation process, the tissue structure and the performance of subsequent molybdenum products.
The traditional molybdenum powder has the problems of large granularity, low sintering activity, high sintering temperature and the like, so that the granularity of the prepared molybdenum material reaches 10 micrometers, and the further improvement of the performance of the molybdenum material is restricted. Many researches show that the reduction of the granularity of the molybdenum powder is one of the most effective modes for improving the sintering activity, reducing the sintering temperature and preparing the high-performance micro-nano structure material. In recent years, many researchers at home and abroad use ultrafine molybdenum powder as a raw material to prepare a series of high-performance molybdenum alloys.
The ultrafine molybdenum dioxide is a key raw material for preparing ultrafine molybdenum powder, and the granularity of the ultrafine molybdenum dioxide has great influence on the granularity and the dispersity of the molybdenum powder. Hydrogen reduction is the main process for preparing molybdenum dioxide and molybdenum powder at present, but the method is difficult to prepare superfine molybdenum dioxide and then superfine molybdenum powder. Although many researchers regulate and control the reduction of the molybdenum oxide by hydrogen through a plurality of methods, such as changing the temperature, the dew point of the hydrogen, the thickness of a material layer and the like, the effect is not ideal. At present, how to reduce the molybdenum trioxide with large particle size into the ultrafine molybdenum dioxide is still a challenge.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition, aiming at the defects of the prior art. Based on multi-step chemical vapor deposition, the invention provides a large amount of heterogeneous nucleation points by using high-activity-site amorphous cracked carbon obtained after active particle size adjustment and modification treatment as precursor powder for constructing a core-shell structure, and provides a foundation for product dispersibility and gas phase transmission adjustment in the heat treatment and two-step hydrogen reduction treatment processes by combining ultrahigh-speed stirring to adjust the pore structure and the dispersibility, thereby realizing effective control of the particle sizes of the superfine molybdenum dioxide and the molybdenum powder.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on the chemical vapor deposition is characterized by comprising the following steps of:
step one, carrying out active particle size adjustment and modification treatment on amorphous cracked carbon particles to obtain high-activity-site amorphous cracked carbon;
step two, carrying out ultrasonic stirring and dispersion on molybdenum trioxide and the high-activity-site amorphous cracked carbon obtained in the step one under the assistance of a dispersing agent, and then putting the mixture into a ball-milling tank for low-energy ball-milling mixing to obtain uniformly mixed slurry;
step three, drying the slurry obtained in the step two, then placing the dried slurry into an ultrahigh-speed stirrer to stir for agglomeration and crushing and adjusting the porosity, and obtaining a high-dispersion low-apparent-density amorphous cracked carbon uniformly-coated molybdenum trioxide nano mixture;
step four, uniformly coating the amorphous cracked carbon with high dispersion and low apparent density obtained in the step three with the molybdenum trioxide nano mixture for segmented heat treatment to obtain the core-shell structure nano molybdenum dioxide coated micron Mo with high dispersion and high porosity 4 O 11 Compounding powder;
step five, coating the core-shell structure nano molybdenum dioxide with high dispersion and high porosity obtained in the step four with micron Mo 4 O 11 Hydrogen generation from composite powderGas reduction treatment is carried out, so that nano molybdenum dioxide grows at the shell of the core-shell structure through vapor deposition, and the superfine MoO with high dispersion and high porosity is obtained 2 A powder;
step six, the superfine MoO with high dispersion and high porosity obtained in the step five 2 And carrying out hydrogen reduction treatment on the powder to obtain the ultrafine molybdenum powder with high dispersion and high porosity.
The invention is based on a multi-step chemical vapor deposition growth method, adopts high-activity-site amorphous cracking carbon obtained after active particle size adjustment and modification treatment as precursor powder for constructing a core-shell structure, provides a large amount of heterogeneous nucleation sites, then combines ultrahigh-speed stirring treatment to adjust and optimize the pore structure and the dispersibility of the amorphous cracking carbon uniformly coated molybdenum trioxide nano mixture, provides a foundation for product dispersibility and gas phase transmission regulation and control in the subsequent heat treatment and reduction treatment processes, and constructs a core-shell structure through segmented heat treatment, wherein the nano molybdenum dioxide is coated with micron Mo 4 O 11 The composite powder is subjected to hydrogen reduction treatment to obtain large-particle Mo 4 O 11 The composite powder is dissolved into gas phase and transferred to the molybdenum dioxide at the shell for deposition growth to prepare the ultrafine MoO with high dispersion and high porosity 2 And (3) continuously carrying out hydrogen reduction treatment on the powder to obtain the ultrafine molybdenum powder with high dispersion and high porosity, thereby realizing effective control on the particle sizes of the molybdenum dioxide and the molybdenum powder.
The method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition is characterized in that in the step one, the amorphous cracked carbon particles are high-activity amorphous cracked carbon obtained by cracking a gas-phase, liquid-phase or solid-phase carbon source, and the method for adjusting and modifying the activity particle size comprises ultrasonic treatment, friction treatment, plasma treatment or microwave treatment.
The method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on the chemical vapor deposition is characterized in that in the second step, the mass purity of the molybdenum trioxide is more than 99.5%, and the mass of the high-activity-site amorphous cracking carbon is less than 3% of the mass of the molybdenum trioxide. The preferred high active site amorphous carbon cleavage addition provides a more dispersed nucleation site for the product,and in Mo 4 O 11 The nano molybdenum dioxide with proper quantity and granularity is constructed around the hydrogen reduction treatment device, so that excellent conditions are created for the directional gas phase transmission growth of the molybdenum dioxide in the subsequent hydrogen reduction treatment process.
In the method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition, the dispersing agents in the second step are PEG and PVP, and the mass of the dispersing agent is less than 0.5% of that of the molybdenum trioxide. The preferred dispersant type and quality promotes adequate dispersion of the molybdenum trioxide with the highly active site amorphous cracked carbon.
The method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on the chemical vapor deposition is characterized in that in the third step, the stirring speed is more than 5000 revolutions per minute, the stirring time is more than 60 seconds, and the amorphous cracked carbon uniformly coats the molybdenum trioxide nano mixture and has the apparent density of less than 1.0g/cm 3 。
The method for preparing the high-dispersion superfine molybdenum dioxide and molybdenum powder based on the chemical vapor deposition is characterized in that the temperature of the segmented heat treatment in the fourth step is 400-650 ℃, the heating rate is less than 15 ℃/min, the treatment time is more than 30min, and the atmosphere is vacuum or inert gas; the core-shell structure nanometer molybdenum dioxide coats micron Mo 4 O 11 The phase composition of the composite powder is micron-sized MoO 3 /Mo 4 O 11 And nano MoO 2 And the core-shell structure nanometer molybdenum dioxide coats the micron Mo 4 O 11 The bulk density of the composite powder is less than 1.0g/cm 3 The porosity is greater than 80%. By adopting the sectional heat treatment process parameters, on one hand, the heat treatment speed is controlled, and then the high-dispersion and high-porosity core-shell structure nano molybdenum dioxide coated micron Mo is controlled 4 O 11 The generation speed of the composite powder is high, and on the other hand, the high-dispersion and high-porosity core-shell structure nano molybdenum dioxide coated micron Mo is realized 4 O 11 The control of the granularity of the composite powder avoids the generation of a byproduct and coarsening of the granularity of the product due to overhigh concentration of carbon dioxide caused by overhigh reaction speed.
The preparation of the high-dispersion superfine titanium dioxide based on the chemical vapor depositionThe method for oxidizing molybdenum and molybdenum powder is characterized in that in the fifth step, the temperature of hydrogen reduction treatment is 450-650 ℃, the treatment time is more than 30min, and the superfine MoO is obtained 2 The powder has an average particle size of less than 500nm and a bulk density of less than 1.0g/cm 3 The porosity is greater than 90%. The optimized technological parameters of the hydrogen reduction treatment effectively control the generation of molybdenum-containing gas phase hydrate and the gas phase migration of molybdenum, thereby realizing the directional transmission and the deposition growth of large-particle raw material phase superfine molybdenum dioxide in the hydrogen reduction treatment process.
The method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition is characterized in that in the sixth step, the hydrogen reduction treatment temperature is 700-1000 ℃, the treatment time is more than 30min, the average particle size of the ultrafine molybdenum powder is less than 500nm, and the apparent density is less than 1.0g/cm 3 The porosity is greater than 90%. The optimized technological parameters of the hydrogen reduction treatment promote the molybdenum dioxide to be reduced into molybdenum powder, and meanwhile, the abnormal coarsening of the granularity of the molybdenum powder is avoided, and the superfine molybdenum powder is ensured to be obtained.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of carrying out active particle size adjustment and modification treatment on amorphous cracking carbon particles to obtain high-activity-site amorphous cracking carbon with high dispersibility, taking the amorphous cracking carbon as precursor powder for constructing a core-shell structure, uniformly stirring the precursor powder and molybdenum trioxide through a liquid-phase machine, then carrying out ultrahigh-speed stirring to obtain a high-dispersion low-apparent-density amorphous cracking carbon uniformly-coated molybdenum trioxide nano mixture, and carrying out subsequent high-dispersion high-porosity core-shell-structure nano molybdenum dioxide-coated micron Mo-coated nano-mixture 4 O 11 The composite powder provides conditions.
2. The invention adopts ultra-high speed stirring to adjust the core-shell structure nanometer molybdenum dioxide to coat micron Mo 4 O 11 The dispersibility and the pore structure of the composite powder are adopted to obtain the amorphous cracked carbon with high dispersion and low apparent density and uniformly coated with the molybdenum trioxide nano mixture, so that the core-shell structure nano molybdenum dioxide coated with the micron Mo is obtained subsequently 4 O 11 Composite powder and ultrafine MoO 2 The powder provides the conditions.
3. The invention constructs the core-shell structure nano molybdenum dioxide coated micron Mo with high dispersion and high porosity 4 O 11 Composite powder, which is favorable for large-grained Mo in the shell during hydrogen reduction treatment 4 O 11 The deposition growth is carried out on the dispersed molybdenum dioxide after the gas phase dissolution, diffusion and reduction, thereby realizing the large-particle Mo 4 O 11 To ultra-fine MoO 2 Conversion of the powder to obtain ultra-fine MoO with extremely high dispersibility, porosity and particle size uniformity 2 And the effective control of the granularity of the molybdenum dioxide is realized by the powder.
4. The high-dispersion and high-porosity ultrafine MoO prepared by the invention 2 The powder has extremely fine granularity and higher reaction activity, and provides a large number of nucleation sites for molybdenum nucleation in the hydrogen reduction treatment process, so that the highly dispersed ultra-fine molybdenum powder is obtained, and the effective control of the granularity of the molybdenum powder is realized.
5. The invention takes the micron-sized molybdenum trioxide which is easily obtained commercially as the raw material and the hydrogen as the reducing agent, the raw material has wide source and low cost, and the preparation method of the invention is simple and is easy for engineering application.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is an SEM image of a molybdenum trioxide nano-mixture uniformly coated with amorphous carbon soot prepared in example 1 of the present invention.
FIG. 2 shows that the core-shell structure nano-molybdenum dioxide coated with micro-Mo prepared in example 1 of the present invention 4 O 11 SEM image of composite powder.
FIG. 3 shows an ultrafine MoO prepared in example 1 of the present invention 2 SEM image of the powder.
FIG. 4 shows an ultrafine MoO prepared in example 2 of the present invention 2 SEM image of the powder.
Detailed Description
Example 1
The embodiment comprises the following steps:
firstly, carrying out ultrasonic irradiation treatment on amorphous cracked carbon particles obtained by cracking gas-phase carbon source methane for 3 hours to carry out active particle size adjustment and modification treatment to obtain high-activity site amorphous cracked carbon;
secondly, performing ultrasonic stirring and dispersion on molybdenum trioxide with the mass purity of 99.95% and the high-activity-site amorphous cracked carbon obtained in the first step under the assistance of PEG (polyethylene glycol) and PVP (polyvinyl pyrrolidone) as dispersing agents, and then putting the mixture into a ball-milling tank to perform low-energy ball-milling mixing at the rotating speed of 200 revolutions per minute to obtain uniformly mixed slurry; the mass of the high-activity-site amorphous pyrolysis carbon is 2.5% of that of the molybdenum trioxide, and the mass of the dispersing agents PEG and PVP is 0.3% of that of the molybdenum trioxide;
step three, drying the slurry obtained in the step two at the temperature of more than 60 ℃ for 6h, then placing the slurry into an ultra-high speed stirrer to stir at the rotating speed of 20000 revolutions per minute for 160 seconds to perform agglomeration and crushing and adjust the porosity, so as to obtain a high-dispersion low-apparent-density amorphous cracked carbon uniformly-coated molybdenum trioxide nano mixture, as shown in figure 1; the loose packed density of the amorphous cracked carbon uniformly coated molybdenum trioxide nano mixture is 0.6g/cm 3 ；
Step four, carrying out segmented heat treatment on the amorphous cracked carbon uniformly coated with the molybdenum trioxide nano mixture with high dispersion and low apparent density obtained in the step three at 400-500 ℃ and 550-600 ℃ respectively, wherein the heating rate is 10 ℃/min, the treatment time is 120min, and the atmosphere is argon atmosphere, so as to obtain the core-shell structure nano molybdenum dioxide coated micron Mo with high dispersion and high porosity 4 O 11 Compounding powder; the core-shell structure nanometer molybdenum dioxide coats micron Mo 4 O 11 The phase composition of the composite powder is micron-sized MoO 3 /Mo 4 O 11 And nano MoO 2 As shown in FIG. 2, and the core-shell structure nanometer molybdenum dioxide coats the micrometer Mo 4 O 11 The bulk density of the composite powder was 0.5g/cm 3 Porosity of 88%;
step five, coating the core-shell structure nano molybdenum dioxide with high dispersion and high porosity obtained in the step four with micron Mo 4 O 11 Performing hydrogen reduction treatment on the composite powder at 450-650 ℃ for 120min to grow the nano molybdenum dioxide on the shell of the core-shell structure by vapor deposition to obtain high dispersion and high purityPorous ultrafine MoO 2 Powder, as shown in FIG. 3, the ultrafine MoO 2 The powder has an average particle size of less than 300nm and a bulk density of 0.5g/cm 3 Porosity 94%;
step six, the superfine MoO with high dispersion and high porosity obtained in the step five 2 Performing hydrogen reduction treatment on the powder at 700-900 ℃ for 120min to obtain high-dispersion and high-porosity ultrafine molybdenum powder; the average particle size of the ultrafine molybdenum powder is 300nm, and the apparent density is 0.7g/cm 3 The porosity was 93%.
The amorphous cracked carbon particles in the first step of this embodiment may also be high-activity amorphous cracked carbon obtained by cracking a solid or liquid carbon source, and the methods of activity adjustment, modification and dispersion treatment may also be replaced by friction treatment, plasma treatment or microwave treatment.
Example 2
Step one, carrying out ultrasonic irradiation treatment on amorphous cracked carbon particles obtained by cracking gas-phase carbon source methane for 3 hours to carry out active particle size adjustment and modification treatment to obtain high-activity site amorphous cracked carbon;
secondly, performing ultrasonic stirring and dispersion on molybdenum trioxide with the mass purity of 99.9% and the high-activity-site amorphous cracked carbon obtained in the first step under the assistance of PEG (polyethylene glycol) and PVP (polyvinyl pyrrolidone) dispersants, and then putting the mixture into a ball-milling tank to perform low-energy ball-milling mixing at the rotating speed of 200 revolutions per minute to obtain uniformly mixed slurry; the mass of the high-activity-site amorphous pyrolysis carbon is 1.25% of that of the molybdenum trioxide, and the mass of the dispersing agents PEG and PVP is 0.3% of that of the molybdenum trioxide;
step three, drying the slurry obtained in the step two at the temperature of 70 ℃ for 6h, then putting the slurry into an ultrahigh-speed stirrer, stirring the slurry for 240 seconds at the rotating speed of 15000 r/min, performing agglomeration crushing and porosity adjustment to obtain a high-dispersion low-apparent-density amorphous cracked carbon uniformly-coated molybdenum trioxide nano mixture; the loose packed density of the amorphous cracked carbon uniformly coated molybdenum trioxide nano mixture is 0.7g/cm 3 ；
Step four, uniformly coating the amorphous cracked carbon with high dispersion and low apparent density obtained in the step three with a molybdenum trioxide nano mixture at 500-56 ℃ respectivelyCarrying out heat treatment at 0 ℃ and 600-650 ℃, wherein the heating rate is 5 ℃/min, the treatment time is 120min, the adopted atmosphere is vacuum atmosphere, the vacuum degree is 1Pa, and the high-dispersion and high-porosity core-shell structure nano molybdenum dioxide coated micron Mo is obtained 4 O 11 Compounding powder; the core-shell structure nanometer molybdenum dioxide coats micron Mo 4 O 11 The phase composition of the composite powder is micron-sized MoO 3 /Mo 4 O 11 And nano MoO 2 And the core-shell structure nanometer molybdenum dioxide coats the micron Mo 4 O 11 The bulk density of the composite powder was 0.6g/cm 3 Porosity of 85%;
step five, coating the core-shell structure nano molybdenum dioxide with high dispersion and high porosity obtained in the step four with micron Mo 4 O 11 Performing hydrogen reduction treatment on the composite powder at 500-600 ℃ for 90min to grow nano molybdenum dioxide on the shell of the core-shell structure through vapor deposition to obtain highly dispersed and highly porous superfine MoO 2 Powder, as shown in FIG. 4, the ultrafine MoO 2 The powder had an average particle size of 400nm and a bulk density of 0.6g/cm 3 Porosity 91%;
step six, the superfine MoO with high dispersion and high porosity obtained in the step five 2 Carrying out hydrogen reduction treatment on the powder at 800-1000 ℃ for 6min to obtain high-dispersion and high-porosity ultrafine molybdenum powder; the average particle size of the ultrafine molybdenum powder is 480nm, and the apparent density is 0.9g/cm 3 The porosity was 91%.
The amorphous cracked carbon particles in the first step of this embodiment may also be high-activity amorphous cracked carbon obtained by cracking a solid or liquid carbon source, and the methods of activity adjustment, modification and dispersion treatment may also be replaced by friction treatment, plasma treatment or microwave treatment.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. The method for preparing the high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition is characterized by comprising the following steps:
step one, carrying out active particle size adjustment and modification treatment on amorphous cracked carbon particles to obtain high-activity-site amorphous cracked carbon;
step two, carrying out ultrasonic stirring and dispersion on molybdenum trioxide and the high-activity-site amorphous cracked carbon obtained in the step one under the assistance of a dispersing agent, and then putting the mixture into a ball-milling tank for low-energy ball-milling mixing to obtain uniformly mixed slurry;
step three, drying the slurry obtained in the step two, then putting the dried slurry into an ultrahigh-speed stirrer to stir, carrying out agglomeration and crushing and adjusting the porosity, and obtaining a molybdenum trioxide nano mixture uniformly coated by amorphous cracked carbon with high dispersion and low apparent density;
step four, uniformly coating the amorphous cracked carbon with high dispersion and low apparent density obtained in the step three with the molybdenum trioxide nano mixture for segmented heat treatment to obtain the core-shell structure nano molybdenum dioxide coated micron Mo with high dispersion and high porosity 4 O 11 Compounding powder;
step five, coating the core-shell structure nano molybdenum dioxide with high dispersion and high porosity obtained in the step four with micron Mo 4 O 11 Hydrogen reduction treatment is carried out on the composite powder, so that nano molybdenum dioxide grows at the shell of the core-shell structure through vapor deposition, and the superfine MoO with high dispersion and high porosity is obtained 2 A powder;
step six, the superfine MoO with high dispersion and high porosity obtained in the step five 2 And carrying out hydrogen reduction treatment on the powder to obtain the ultrafine molybdenum powder with high dispersion and high porosity.
2. The method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition according to claim 1, wherein the amorphous cracked carbon particles in the first step are high-activity amorphous cracked carbon obtained by cracking a gas-phase, liquid-phase or solid-phase carbon source, and the method for adjusting and modifying the activity particle size is ultrasonic treatment, friction treatment, plasma treatment or microwave treatment.
3. The method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition according to claim 1, wherein the mass purity of the molybdenum trioxide in the second step is more than 99.5%, and the mass of the high-activity-site amorphous cracked carbon is less than 3% of the mass of the molybdenum trioxide.
4. The method for preparing ultra-fine molybdenum dioxide and molybdenum powder with high dispersibility based on chemical vapor deposition as claimed in claim 1, wherein the dispersant in the second step is PEG and PVP, and the mass of the dispersant is less than 0.5% of the mass of molybdenum trioxide.
5. The method for preparing ultra-fine highly dispersed molybdenum dioxide and molybdenum powder based on chemical vapor deposition as claimed in claim 1, wherein the rotation speed of stirring in step three is greater than 5000 r/min, the stirring time is greater than 60 s, the loose packed density of the amorphous cracked carbon uniformly coated molybdenum trioxide nano-mixture is less than 1.0g/cm 3 。
6. The method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition according to claim 1, wherein the temperature of the segmented heat treatment in the fourth step is 400 ℃ to 650 ℃, the heating rate is less than 15 ℃/min, the treatment time is more than 30min, and the atmosphere is vacuum or inert gas; the core-shell structure nanometer molybdenum dioxide coats micron Mo 4 O 11 The phase composition of the composite powder is micron-sized MoO 3 /Mo 4 O 11 And nano MoO 2 And the core-shell structure nanometer molybdenum dioxide coats the micron Mo 4 O 11 The bulk density of the composite powder is less than 1.0g/cm 3 The porosity is greater than 80%.
7. The method for preparing highly dispersed ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition as claimed in claim 1, wherein the temperature of the hydrogen reduction treatment in step five is 450 ℃ to 650 ℃, the treatment time is more than 30min, and the ultrafine molybdenum dioxide and molybdenum powder is prepared by the chemical vapor deposition methodFine MoO 2 The powder has an average particle size of less than 500nm and a bulk density of less than 1.0g/cm 3 The porosity is greater than 90%.
8. The method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition according to claim 1, wherein the temperature of the hydrogen reduction treatment in the sixth step is 700 ℃ to 1000 ℃, the treatment time is more than 30min, the average particle size of the ultrafine molybdenum powder is less than 500nm, and the apparent density is less than 1.0g/cm 3 The porosity is more than 90 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211165156.6A CN115255379B (en) | 2022-09-23 | 2022-09-23 | Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211165156.6A CN115255379B (en) | 2022-09-23 | 2022-09-23 | Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115255379A true CN115255379A (en) | 2022-11-01 |
| CN115255379B CN115255379B (en) | 2022-12-23 |
Family
ID=83757374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211165156.6A Active CN115255379B (en) | 2022-09-23 | 2022-09-23 | Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115255379B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5330557A (en) * | 1990-02-12 | 1994-07-19 | Amax Inc. | Fluid bed reduction to produce flowable molybdenum metal |
| US20060165572A1 (en) * | 2004-06-29 | 2006-07-27 | Mchugh Lawrence F | Method of making MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials |
| US20110223054A1 (en) * | 2008-10-17 | 2011-09-15 | H.C. Starck Inc. | Production of molybdenum metal powder |
| CN103286317A (en) * | 2013-06-30 | 2013-09-11 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by ammonium molybdate |
| CN107262733A (en) * | 2017-08-02 | 2017-10-20 | 北京科技大学 | A kind of method that two-part reduction prepares ultrafine molybdenum powder |
| CN107706394A (en) * | 2017-10-23 | 2018-02-16 | 陕西科技大学 | A kind of MoO2/Mo4O11Mixed phase nano-electrode material and preparation method thereof |
| CN107739053A (en) * | 2017-10-23 | 2018-02-27 | 陕西科技大学 | A kind of three-phase system molybdenum oxide MoO3/Mo4O11/MoO2Nano-electrode material and preparation method thereof |
| CN108821342A (en) * | 2018-08-31 | 2018-11-16 | 厦门理工学院 | A kind of high-purity molybdenum dioxide and preparation method thereof |
| US20190071320A1 (en) * | 2017-09-04 | 2019-03-07 | University-Industry Cooperation Group Of Kyung Hee University | Method for preparing metal/molybdenum oxide nanoparticles |
| CN109494358A (en) * | 2018-09-28 | 2019-03-19 | 陕西科技大学 | A kind of Mo of carbon base body support4O11/MoO2Lithium ion battery negative material and preparation method thereof |
| CN111554893A (en) * | 2020-04-24 | 2020-08-18 | 宁波大学 | Preparation method of molybdenum oxide compound serving as negative electrode material of lithium battery |
| CN112222419A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application |
| CN114029496A (en) * | 2021-10-12 | 2022-02-11 | 南昌大学 | Preparation method of novel superfine molybdenum-rhenium alloy powder |
-
2022
- 2022-09-23 CN CN202211165156.6A patent/CN115255379B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5330557A (en) * | 1990-02-12 | 1994-07-19 | Amax Inc. | Fluid bed reduction to produce flowable molybdenum metal |
| US20060165572A1 (en) * | 2004-06-29 | 2006-07-27 | Mchugh Lawrence F | Method of making MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials |
| US20110223054A1 (en) * | 2008-10-17 | 2011-09-15 | H.C. Starck Inc. | Production of molybdenum metal powder |
| CN103286317A (en) * | 2013-06-30 | 2013-09-11 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by ammonium molybdate |
| CN107262733A (en) * | 2017-08-02 | 2017-10-20 | 北京科技大学 | A kind of method that two-part reduction prepares ultrafine molybdenum powder |
| US20190071320A1 (en) * | 2017-09-04 | 2019-03-07 | University-Industry Cooperation Group Of Kyung Hee University | Method for preparing metal/molybdenum oxide nanoparticles |
| CN107739053A (en) * | 2017-10-23 | 2018-02-27 | 陕西科技大学 | A kind of three-phase system molybdenum oxide MoO3/Mo4O11/MoO2Nano-electrode material and preparation method thereof |
| CN107706394A (en) * | 2017-10-23 | 2018-02-16 | 陕西科技大学 | A kind of MoO2/Mo4O11Mixed phase nano-electrode material and preparation method thereof |
| CN108821342A (en) * | 2018-08-31 | 2018-11-16 | 厦门理工学院 | A kind of high-purity molybdenum dioxide and preparation method thereof |
| CN109494358A (en) * | 2018-09-28 | 2019-03-19 | 陕西科技大学 | A kind of Mo of carbon base body support4O11/MoO2Lithium ion battery negative material and preparation method thereof |
| CN111554893A (en) * | 2020-04-24 | 2020-08-18 | 宁波大学 | Preparation method of molybdenum oxide compound serving as negative electrode material of lithium battery |
| CN112222419A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application |
| CN114029496A (en) * | 2021-10-12 | 2022-02-11 | 南昌大学 | Preparation method of novel superfine molybdenum-rhenium alloy powder |
Non-Patent Citations (6)
| Title |
|---|
| DA-HANG WANG等: "Preparation of ultrafine Mo powders via carbothermic prereduction of molybdenum oxide and deep reduction by hydrogen", 《INTERNATIONAL JOURNAL OF REFRACTORY METALS & HARD MATERIALS》 * |
| 孙国栋: "超细/纳米钼粉可控制备及其烧结行为研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 林宇霖等: "两段碳还原MoO_3反应产物的成分研究", 《稀有金属与硬质合金》 * |
| 王沛丽等: "两段还原法生产费氏粒度小于2.8μm钼粉工艺研究", 《中国钼业》 * |
| 赵新瑞等: "氢气还原蒸发态MoO_3制取超细钼粉的探索", 《中国钼业》 * |
| 陈成等: "二氧化钼板结影响后续生产的研究", 《中国钼业》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115255379B (en) | 2022-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112723422B (en) | Aluminum-doped cobaltosic oxide core-shell material and preparation method thereof | |
| CN110038614B (en) | Cobalt nitride loaded nitrogen-doped carbon material and preparation method thereof | |
| CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
| CN113579246B (en) | Preparation method of nano high-entropy alloy powder | |
| CN102071348B (en) | Preparation method of superfine grain nano-structure oxide dispersion strengthened steel | |
| CN108031856B (en) | Preparation method of high-cobalt nano/superfine WC-Co composite powder | |
| Liu et al. | Eliminating bimodal structures of W-Y2O3 composite nanopowders synthesized by wet chemical method via controlling reaction conditions | |
| CN110496969B (en) | Nano tungsten powder and preparation method thereof | |
| CN115321537B (en) | Preparation method of high-dispersion particle size controllable nano tungsten carbide powder | |
| CN114230340A (en) | High-density high-temperature oxidation-resistant molybdenum-based composite target material and preparation method thereof | |
| CN115255379B (en) | Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition | |
| CN113798504A (en) | Preparation method of rare earth oxide dispersion-enhanced tungsten powder for 3D printing | |
| CN108907219A (en) | A kind of production method of hypoxemia small grain size molybdenum powder | |
| CN109365829B (en) | Method for preparing nano WC-Co composite powder by high-temperature spray drying and short process | |
| CN115229199B (en) | Method for preparing high-dispersion high-porosity superfine molybdenum dioxide and molybdenum powder by induced nucleation | |
| CN110102773B (en) | Preparation method of ordered mesoporous Ni nanoparticles with controllable particle size | |
| CN106810236B (en) | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder | |
| CN113441728A (en) | Preparation method of high-uniformity ultrafine/nano tungsten powder | |
| CN115229201B (en) | Preparation method of high-dispersion nano tungsten powder | |
| CN115321598B (en) | Preparation method of low-cost, high-dispersion, high-porosity and high-purity superfine molybdenum trioxide | |
| CN112079359A (en) | Preparation method of high-uniformity nano WC powder | |
| CN115233022B (en) | Ultrahigh-hardness nano-structure molybdenum-aluminum alloy and preparation method thereof | |
| CN115229181B (en) | Method for preparing superfine molybdenum dioxide and molybdenum powder based on nano-scale solid-liquid mixed deposition | |
| CN114976033B (en) | Preparation method and application of modified metal lithium negative electrode three-dimensional carbon-based current collector | |
| CN116372168A (en) | Preparation method of composite powder material with hard phase surface coated with metal binding phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |