CN115229180B - Preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity - Google Patents
Preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity Download PDFInfo
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Abstract
The invention discloses a preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity, which comprises the following steps: 1. modifying amorphous cracked carbon, and crushing molybdenum trioxide; 2. mixing molybdenum trioxide particles, amorphous cracked carbon particles, an activating agent, ethanol and deionized water; 3. drying the slurry and stirring at a super high speed; 4. carrying out sectional heat treatment and ultrahigh-speed stirring on the nano composite powder; 5. heating the nano mixed powder, adding an ammonium metatungstate solution, and stirring at a high speed; 6. and thermally reducing the nano composite powder to obtain the molybdenum-tungsten nano composite powder with high dispersion and high porosity. The method adopts a method of combining liquid phase premixing with ultrahigh speed stirring and mixing to uniformly mix raw materials, obtains nano composite powder by heating and mixing while stirring, and finally carries out multi-stage hydrogen reduction to reduce ammonium tungstate nano particles into tungsten nano particles and reduce molybdenum oxide into molybdenum to obtain the highly dispersed and highly porous molybdenum-tungsten nano composite powder.
Description
Technical Field
The invention belongs to the technical field of preparation of nano powder materials, and particularly relates to a preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity.
Background
Molybdenum metal has many excellent characteristics, such as: the high-temperature-resistant copper-nickel alloy has the characteristics of very high melting point, high-temperature strength, elastic modulus, electric conductivity, thermal conductivity and corrosion resistance, small expansion coefficient, small vapor pressure, small evaporation rate, high sputtering threshold value and the like. By virtue of these excellent characteristics, molybdenum and its alloy materials have very critical applications in many fields such as nuclear industry, military industry, electronics and electrical industry, chemical industry and metallurgical industry. With the development of technology, the demand for improving the performance of molybdenum in these fields is increasing. Many researchers have proposed a series of methods for improving the properties of molybdenum materials, such as: solid solution strengthening, grain refining, dispersion strengthening, deformation strengthening and the like. At present, the powder metallurgy method is the main method for preparing molybdenum and alloy materials thereof, and the characteristics (such as particle size) and components of molybdenum powder have a decisive influence on the sintering, the structure and the performance of the molybdenum. Therefore, molybdenum powder particle size and composition regulation are the basis of all strengthening measures.
Tungsten and molybdenum belong to the same group elements and have similar characteristics and crystal structures, and tungsten and molybdenum can be dissolved at any ratio on one hand, and on the other hand, a coherent structure with strong binding force can be formed. Therefore, the addition of tungsten in molybdenum alloys as a solid solution or coherent dispersion is one of the ways to optimize the molybdenum structure and improve performance. At present, the main methods for preparing molybdenum-tungsten composite powder include a molybdenum-tungsten powder mixing method, a mixed molybdenum oxide and tungsten oxide reduction method, and the like. However, currently, the prepared tungsten-molybdenum composite powder can only reach the size of micron level, and the mixing of tungsten and molybdenum can only reach the mixing of micron level, so that the advantage of doped tungsten cannot be fully exerted. In addition, because the molybdenum-tungsten powder product has large granularity, uneven mixing and low sintering activity, a compact sample can be obtained only by sintering for a long time at a high sintering temperature of about 2000 ℃, and the requirement for preparing a high-performance micro-nano structure molybdenum-tungsten alloy material is difficult to meet.
In conclusion, the nanoscale molybdenum-tungsten composite powder has great technical problems in particle size, dispersibility, porosity regulation and control and mixing uniformity control.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a molybdenum-tungsten nano composite powder with high dispersion and high porosity, aiming at the defects of the prior art. The method comprises the steps of taking amorphous cracked carbon and molybdenum trioxide as raw materials, uniformly mixing the raw materials by adopting a liquid-phase premixing and ultrahigh-speed stirring mixing method, carrying out segmented heat treatment to obtain molybdenum @ molybdenum dioxide nano mixed powder, carrying out heating treatment and mixing while stirring to obtain mixed ammonium metatungstate, molybdenum dioxide and molybdenum nano composite powder, finally carrying out multi-segment hydrogen reduction to reduce ammonium tungstate nano particles into tungsten nano particles, and reducing molybdenum oxide into molybdenum to obtain high-dispersion and high-porosity molybdenum-tungsten nano composite powder.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized by comprising the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and crushing molybdenum trioxide to obtain molybdenum trioxide particles;
step two, mixing the molybdenum trioxide particles obtained in the step one, the amorphous cracked carbon particles obtained in the step one, an activating agent, ethanol and deionized water to obtain slurry;
step three, drying the slurry obtained in the step two, and then stirring at a super high speed to obtain amorphous cracked carbon particle @ molybdenum trioxide nano composite powder;
step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then stirring at a super high speed to obtain nano mixed powder of molybdenum @ molybdenum dioxide of a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 400-600 ℃, then preserving heat, and then heating to 800-1000 ℃ and preserving heat;
step five, heating the nano mixed powder obtained in the step four, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then carrying out ultrahigh-speed stirring to obtain the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum with the multistage core-shell structure;
and step six, carrying out thermal reduction on the nanometer composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain the high-dispersion and high-porosity molybdenum-tungsten nanometer composite powder.
The invention takes amorphous cracked carbon and molybdenum trioxide as raw materials, and obtains amorphous cracked carbon particles with high defect, high reaction activity, fine granularity and high dispersity by adjusting the activity, the dispersity and the granularity of the amorphous cracked carbon particles; the method adopts a method of liquid phase premixing combined with ultrahigh speed stirring mixing to uniformly mix the raw materials, the amorphous cracked carbon particles with high activity and molybdenum trioxide can be mixed to be close to nano-scale under the action of ultrahigh speed stirring, and the amorphous cracked carbon particles and the molybdenum trioxide can be crushed and agglomerated, so that the porosity of the raw materials is greatly improved, good conditions are created for the discharge of subsequent generated gas and the prevention of the coalescence growth of product nano particles, and the granularity, the porosity and the dispersibility of the product are further remarkably improved; the method comprises the steps of carrying out segmented heat treatment on a mixture of high-dispersion and high-porosity molybdenum trioxide and high-activity amorphous cracked carbon particles to obtain a mixture of high-dispersion and high-porosity nano molybdenum dioxide and molybdenum, then heating the mixture, adding ammonium molybdate solution droplets into the mixture while stirring, and drying to separate out ammonium tungstate nano particles; moreover, as the precursor is heated to a certain temperature, the ammonium tungstate liquid drops can be quickly dried and separated out after being contacted with the hot material, thereby effectively avoiding the agglomeration of the material and improving the dispersibility of the product; the invention reduces the ammonium metatungstate, molybdenum dioxide and molybdenum nano composite powder with high dispersion and high porosity into tungsten nano particles by hydrogen, and reduces the molybdenum oxide into molybdenum, wherein, because of the very high porosity, on one hand, hydrogen is easy to diffuse into the material layer for reaction, on the other hand, generated steam is easy to diffuse out, thereby reducing the steam concentration in the material layer, avoiding the reaction of the tungsten and molybdenum nano particles with the steam, in addition, the existing tungsten and molybdenum nano particles can be used as the substrate of molybdenum chemical vapor deposition in the reduction process, thereby achieving the purposes of reducing the molybdenum particle size and improving the dispersibility, and obtaining the molybdenum-tungsten nano composite powder with high dispersion and high porosity.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the step one, the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase carbon source and has an amorphous structure, and the specific surface area is more than 150g/cm 3 (ii) a The particle size and active site adjustment and modification is ultrasonic treatment, friction treatment, plasma treatment or microwave treatment. The amorphous cracked carbon generated by cracking the gas-phase or solid-phase carbon source is adopted, and the activity, the dispersity and the granularity are adjusted to obtain the amorphous cracked carbon particles with high defects, high reaction activity, fine granularity and high dispersity, the treated carbon has very remarkable advantages in nucleation, granularity and uniformity regulation, and the reaction temperature and the reaction time can be remarkably reduced, the heterogeneous nucleation rate is improved, and the granularity of molybdenum dioxide and molybdenum can be reduced.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the first step, the mass purity of the molybdenum trioxide is more than 99.9%, the crushing is ultrasonic treatment or ball milling treatment, and the apparent density of the molybdenum trioxide particles is less than 1g/cm 3 . The invention ensures that impurities are not introduced by controlling the quality purity of the molybdenum trioxideThe molybdenum trioxide is subjected to dispersity and granularity adjustment by crushing, the transmission efficiency and the product uniformity in the reaction process are further improved, the loose packing density of the molybdenum trioxide particles is controlled, the crushed molybdenum trioxide particles are guaranteed to have higher dispersity, and high dispersity is realized.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the second step, the mass of the amorphous cracked carbon particles in the slurry is 7% -13% of the mass of the molybdenum trioxide particles, and the mass of the activating agent in the slurry is 0.2% -0.5% of the mass of the molybdenum trioxide particles. The invention ensures that the molybdenum @ molybdenum dioxide nano mixed powder with excellent dispersibility and porosity can be obtained by controlling the proportion of the components in the slurry.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the second step, the activating agent is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1. The addition of the activating agent in the invention is mainly to further carry out surface modification treatment on the raw materials so as to improve the dispersibility of the raw materials and subsequently improve the porosity, and the polyethylene glycol and the polyvinyl alcohol are removed before the heat treatment temperature is reached by adopting the activating agent, so that the subsequent reaction is not influenced.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that the loose packed density of the nano composite powder in the step III is less than 0.7g/cm 3 . The preferred apparent density represents a higher porosity of the nanocomposite powder, providing excellent conditions for subsequent ammonium metatungstate doping.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that the stirring speed of ultrahigh-speed stirring in the third step, the fourth step and the fifth step is greater than 5000r/min, and the stirring time is not less than 30s. According to the invention, the high-activity amorphous cracked carbon particles and molybdenum trioxide can be mixed to be close to a nanometer level by controlling the parameter of ultrahigh-speed stirring, the raw materials are crushed and agglomerated, the porosity of the raw materials is greatly improved, good conditions are created for the discharge of subsequent generated gas and the prevention of the agglomeration growth of product nanoparticles, the particle size, the porosity and the dispersibility of the product are further remarkably improved, and the preferable rotating speed and time can obtain excellent porosity and apparent density.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the step four, the heat preservation time of each section in the sectional heat treatment is more than 1h, the temperature rise rate is less than 30 ℃/min, and the atmosphere is vacuum or inert gas; the apparent density of the nano mixed powder is less than 0.55g/cm 3 The porosity is greater than 85%. According to the invention, by controlling parameters of the segmented heat treatment, the reduction efficiency, the granularity of the reduction product and the component quality are taken into consideration, the reaction between the carbon dioxide product and the molybdenum dioxide and molybdenum is effectively avoided, and the problems of agglomeration and poor dispersibility of the product are further avoided.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that in the fifth step, the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is more than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is less than 0.2g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 mu m; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.6g/cm 3 The porosity is greater than 85%. According to the invention, nanometer mixed powder is heated, ammonium metatungstate solution droplets are dropwise added into the nanometer mixed powder while stirring, ammonium tungstate nanoparticles are separated out after drying, and the obtained mixture of nanometer molybdenum dioxide and molybdenum has very high porosity, dispersibility and specific surface area, so that the ultrafine ammonium tungstate droplets are easy to migrate and disperse to obtain a nanometer mixed composite precursor which is high-dispersion and high-porosity nanometer molybdenum-tungsten composite powder; and because the precursor is heated to a certain temperature, the ammonium tungstate is drippedCan be quickly dried and separated out after being contacted with hot materials, effectively avoids the agglomeration of the materials and improves the dispersibility of the product.
The preparation method of the molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized in that the thermal reduction process in the sixth step is as follows: firstly heating to 500-700 ℃, then preserving heat for more than 30min, then heating to 720-950 ℃, and preserving heat for more than 30 min; the apparent density of the molybdenum-tungsten nano composite powder is less than 0.5g/cm 3 The porosity is greater than 95%. The thermal reduction is multi-stage hydrogen reduction, ammonium tungstate nano particles are reduced into tungsten nano particles before the heating is carried out to 500-700 ℃, molybdenum oxide is reduced into molybdenum after the heating is carried out to 720-950 ℃, wherein due to very high porosity, on one hand, hydrogen is easy to diffuse into a material layer for reaction, on the other hand, generated steam is easy to diffuse out, the concentration of the steam in the material layer is reduced, the tungsten and molybdenum nano particles are prevented from reacting with the steam, in addition, the existing tungsten and molybdenum nano particles can be used as a substrate for molybdenum chemical vapor deposition in the reduction process, the purposes of reducing the granularity of the molybdenum and improving the dispersity can be achieved, the final formation of molybdenum-tungsten nano composite powder is ensured, and the loose packing density of the molybdenum-tungsten nano composite powder is controlled to be less than 0.5g/cm 3 Namely, the molybdenum-tungsten nano composite powder has high dispersion property, and the molybdenum-tungsten nano composite powder has high porosity by controlling the porosity of the molybdenum-tungsten nano composite powder to be more than 95 percent.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of carrying out segmented heat treatment on a mixture of high-dispersion and high-porosity molybdenum trioxide and high-activity amorphous cracked carbon particles to obtain a mixture of high-dispersion and high-porosity nano molybdenum dioxide and molybdenum, then heating the mixture, then doping ammonium molybdate solution droplets into the mixture while stirring, and separating out ammonium tungstate nanoparticles after drying; and because the precursor is heated to a certain temperature, the ammonium tungstate liquid drops can be quickly dried and separated out after being contacted with the hot material, so that the agglomeration of the material can be effectively avoided, and the dispersibility of the product is improved.
2. The invention carries out multistage hydrogen reduction on the high-dispersion and high-porosity ammonium metatungstate, molybdenum dioxide and molybdenum nano composite powder, reduces the ammonium tungstate nano particles into tungsten nano particles before 500-700 ℃, and reduces the molybdenum oxide into molybdenum at 720-950 ℃, wherein due to the very high porosity, on one hand, hydrogen is easy to diffuse into a material layer for reaction, on the other hand, generated water vapor is easy to diffuse out, the water vapor concentration in the material layer is reduced, the tungsten and molybdenum nano particles are prevented from reacting with the water vapor, and in addition, the existing tungsten and molybdenum nano particles can be used as a substrate for molybdenum chemical vapor deposition in the reduction process, thereby achieving the purposes of reducing the molybdenum particle size and improving the dispersibility.
3. The invention takes amorphous cracked carbon and molybdenum trioxide as raw materials, and obtains amorphous cracked carbon particles with high defect, high reaction activity, fine granularity and high dispersity by adjusting the activity, the dispersity and the granularity of the amorphous cracked carbon and the molybdenum trioxide.
4. The method adopts a method of liquid phase premixing combined with ultrahigh speed stirring mixing to uniformly mix the raw materials, the amorphous cracked carbon particles with high activity and molybdenum trioxide can be mixed to be close to nano-scale under the action of ultrahigh speed stirring, and the amorphous cracked carbon particles and the molybdenum trioxide can be crushed and agglomerated, so that the porosity of the raw materials is greatly improved, good conditions are created for the discharge of subsequent generated gas and the prevention of the coalescence growth of product nano particles, and the granularity, the porosity and the dispersibility of the product are further remarkably improved.
5. According to the invention, the porosity and active sites are improved by stirring the composite powder at ultrahigh speed for multiple times, ethanol and an aqueous solution are more easily volatilized after heating, the material porosity is increased while the nano-particles are prevented from agglomerating, the material nucleation rate is improved, and the product granularity is refined; the method has the advantages of simple equipment requirement, easy operation and the like, and solves the difficult problems of the preparation technology of the nano molybdenum-tungsten with controllable granularity, dispersibility, porosity and mixing uniformity.
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 the core-shell structured molybdenum @ molybdenum dioxide nano mixed powder prepared in example 1 of the present invention.
FIG. 2 is an SEM image of the Mo-W nanocomposite powder prepared in example 1 of this invention.
FIG. 3 is an EDS diagram of Mo in the Mo-W nanocomposite powder prepared in example 1 of this invention.
FIG. 4 is an EDS diagram of W in the molybdenum-tungsten nano-composite powder prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and crushing molybdenum trioxide to obtain molybdenum trioxide particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase carbon source, has an amorphous structure and a specific surface area of more than 150g/cm 3 (ii) a The particle size and the active site are adjusted and modified by ultrasonic treatment, friction treatment, plasma treatment or microwave treatment for 2 hours; the mass purity of the molybdenum trioxide is more than 99.9 percent; the crushing is performed for 6h by ball milling at the ball material ratio of 6; the loose density of the molybdenum trioxide particles is less than 1g/cm 3 ；
Step two, dispersing 100g of the molybdenum trioxide particles obtained in the step one, 13g of the amorphous cracked carbon particles obtained in the step one and 0.3g of an active agent in 100mL of a solvent consisting of ethanol and deionized water to obtain slurry; the activating agent is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1;
step three, drying the slurry obtained in the step two at 90 ℃ for 4 hours, and then stirring at ultrahigh speed to obtain amorphous cracked carbon particle @ molybdenum trioxide nano composite powder; the stirring speed of the ultra-high speed stirring is 30000r/min, and the stirring time is 200s; the apparent density of the nano composite powder is less than 0.7g/cm 3 ；
Step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain nano mixed powder of molybdenum @ molybdenum dioxide with a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 460 ℃ at a heating rate of 2.5 ℃/min, then preserving heat for 1.5h, then heating to 830 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3h; the atmosphere in the segmented heat treatment is Ar gas; the apparent density of the nano mixed powder is less than 0.55g/cm 3 Porosity is greater than 85%; the thickness of the nano composite powder in the segmented heat treatment is 12mm; the stirring speed of the ultra-high speed stirring is 20000r/min, and the stirring time is 300s;
step five, heating the nano mixed powder obtained in the step four to 80 ℃, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then carrying out ultrahigh-speed stirring to obtain the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum with the multistage core-shell structure; the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is more than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is 0.5g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 mu m; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.5g/cm 3 Porosity greater than 95%; the stirring speed of the ultra-high speed stirring is 20000r/min, and the stirring time is 300s;
step six, carrying out thermal reduction on the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-tungsten nano composite powder; the thermal reduction process comprises the following steps: firstly heating to 600 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 2h, then heating to 850 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 1h; the thickness of the nano composite powder mixed with ammonium metatungstate, molybdenum dioxide and molybdenum in the thermal reduction is 12mm.
Through detection, the apparent density of the molybdenum-tungsten nano composite powder prepared by the embodiment is 0.4g/cm 3 The porosity was 95%.
Fig. 1 is an SEM image of the nano mixed powder of molybdenum @ molybdenum dioxide having a core-shell structure prepared in this example, and it can be seen from fig. 1 that particles with the smallest particle size are the generated nano molybdenum powder.
Fig. 2 is an SEM image of the molybdenum-tungsten nanocomposite powder prepared in this example, fig. 3 is an EDS image of Mo in the molybdenum-tungsten nanocomposite powder prepared in this example, fig. 4 is an EDS image of W in the molybdenum-tungsten nanocomposite powder prepared in this example, and it can be seen from fig. 2 to fig. 4 that the molybdenum-tungsten nanocomposite powder has uniform components, fine particle size, and high dispersibility.
Example 2
The embodiment comprises the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and crushing molybdenum trioxide to obtain molybdenum trioxide particles; the amorphous cracked carbon is generated by cracking a gas phase or solid phase carbon source, has an amorphous structure and a specific surface area of more than 150g/cm 3 (ii) a The particle size and the active site are adjusted and modified by ultrasonic treatment, friction treatment, plasma treatment or microwave treatment for 1h; the mass purity of the molybdenum trioxide is more than 99.9 percent; the crushing is performed for 5 hours by ball milling at the ball-material ratio of 6 and the rotating speed of 300 r/min; the loose density of the molybdenum trioxide particles is less than 1g/cm 3 ；
Step two, dispersing 100g of the molybdenum trioxide particles obtained in the step one, 10g of the amorphous cracked carbon particles obtained in the step one and 0.2g of an active agent in 100mL of a solvent consisting of ethanol and deionized water to obtain slurry; the activating agent is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1;
step three, drying the slurry obtained in the step two at 85 ℃ for 5 hours, and then stirring at ultrahigh speed to obtain amorphous cracked carbon particles @ molybdenum trioxide nano composite powder;the stirring speed of the ultra-high speed stirring is 30000r/min, and the stirring time is 200s; the apparent density of the nano composite powder is less than 0.7g/cm 3 ；
Step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain nano mixed powder of molybdenum @ molybdenum dioxide with a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 450 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 1.5h, then heating to 860 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2.5h; the atmosphere in the segmented heat treatment is vacuum; the apparent density of the nano mixed powder is less than 0.55g/cm 3 Porosity greater than 85%; the thickness of the nano composite powder in the segmented heat treatment is 10mm; the stirring speed of the ultra-high speed stirring is 30000r/min, and the stirring time is 200s;
step five, heating the nano mixed powder obtained in the step four to 85 ℃, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then stirring at ultrahigh speed to obtain the nano composite powder of mixed ammonium metatungstate, molybdenum dioxide and molybdenum with a multistage core-shell structure; the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is more than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is 0.5g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 mu m; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.4g/cm 3 Porosity is greater than 96%; the stirring speed of the ultra-high speed stirring is 30000r/min, and the stirring time is 200s;
step six, carrying out thermal reduction on the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-tungsten nano composite powder; the thermal reduction process comprises the following steps: firstly heating to 620 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 2h, then heating to 800 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 1h; the thickness of the nano composite powder mixed with ammonium metatungstate, molybdenum dioxide and molybdenum in the thermal reduction is 10mm.
Through detection, the apparent density of the molybdenum-tungsten nano composite powder prepared by the embodiment is 0.4g/cm 3 The porosity was 97%.
Example 3
The embodiment comprises the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and then crushing molybdenum trioxide to obtain molybdenum trioxide particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase carbon source, has an amorphous structure and a specific surface area of more than 150g/cm 3 (ii) a The particle size and the active site are adjusted and modified by ultrasonic treatment, friction treatment, plasma treatment or microwave treatment for 1h; the mass purity of the molybdenum trioxide is more than 99.9 percent; the crushing is performed for 4 hours by ball milling at the ball material ratio of 4; the loose packed density of the molybdenum trioxide particles is less than 1g/cm 3 ；
Step two, dispersing 100g of the molybdenum trioxide particles obtained in the step one, 9g of the amorphous cracked carbon particles obtained in the step one and 0.5g of an active agent in 100mL of a solvent consisting of ethanol and deionized water to obtain slurry; the activating agent is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1;
step three, drying the slurry obtained in the step two at 80 ℃ for 7 hours, and then stirring at an ultrahigh speed to obtain amorphous cracked carbon particle @ molybdenum trioxide nano composite powder; the stirring speed of the ultra-high speed stirring is 25000r/min, and the stirring time is 250s; the apparent density of the nano composite powder is less than 0.7g/cm 3 ；
Step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then stirring at a super high speed to obtain nano mixed powder of molybdenum @ molybdenum dioxide of a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 440 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 2h, then heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1.5h; the atmosphere in the segmented heat treatment is vacuum; the apparent density of the nano mixed powder is less than 0.55g/cm 3 Porosity greater than 85%; the thickness of the nano composite powder in the segmented heat treatment is 8mm; the stirring speed of the ultra-high speed stirring is 25000r/min, and the stirring time is 250s;
step five, heating the nano mixed powder obtained in the step four to 80 ℃, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then carrying out ultrahigh-speed stirring to obtain the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum with the multistage core-shell structure; the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is more than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is 0.5g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 mu m; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.4g/cm 3 Porosity greater than 96%; the stirring speed of the ultra-high speed stirring is 25000r/min, and the stirring time is 200s;
step six, carrying out thermal reduction on the nanometer composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-tungsten nanometer composite powder; the thermal reduction process comprises the following steps: firstly heating to 630 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 1.5h, then heating to 750 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 2h; the thickness of the nanometer composite powder mixed with ammonium metatungstate, molybdenum dioxide and molybdenum in the thermal reduction is 8mm.
Through detection, the apparent density of the molybdenum-tungsten nano composite powder prepared by the embodiment is 0.4g/cm 3 The porosity was 96%.
Example 4
The embodiment comprises the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and then crushing molybdenum trioxide to obtain molybdenum trioxide particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase carbon source, has an amorphous structure and a specific surface area of more than 150g/cm 3 (ii) a The particle size and the active site are adjusted and modified by ultrasonic treatment, friction treatment, plasma treatment or microwave treatment for 1h; the mass purity of the molybdenum trioxide is more than 99.9%; the crushing is performed by ball milling for 3 hours at a ball material ratio of 4; the loose density of the molybdenum trioxide particles is less than 1g/cm 3 ；
Step two, dispersing 100g of the molybdenum trioxide particles obtained in the step one, 7g of the amorphous cracked carbon particles obtained in the step one and 0.3g of an active agent in 100mL of a solvent consisting of ethanol and deionized water to obtain slurry; the activating agent is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1;
step three, drying the slurry obtained in the step two at 75 ℃ for 10 hours, and then stirring at a super high speed to obtain amorphous cracked carbon particle @ molybdenum trioxide nano composite powder; the stirring speed of the ultra-high speed stirring is 20000r/min, and the stirring time is 300s; the apparent density of the nano composite powder is less than 0.7g/cm 3 ；
Step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain nano mixed powder of molybdenum @ molybdenum dioxide with a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 420 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 2.5h, then heating to 950 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1h; the atmosphere in the segmented heat treatment is inert gas; the apparent density of the nano mixed powder is less than 0.55g/cm 3 Porosity greater than 85%; the thickness of the nano composite powder in the segmented heat treatment is 5mm; the stirring speed of the ultra-high speed stirring is 20000r/min, and the stirring time is 300s;
step five, heating the nano mixed powder obtained in the step four to 90 ℃, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then stirring at ultrahigh speed to obtain the nano composite powder of mixed ammonium metatungstate, molybdenum dioxide and molybdenum with a multistage core-shell structure; the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is more than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is 0.5g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 mu m; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.3g/cm 3 Porosity is greater than 97%; the stirring speed of the ultra-high speed stirring is 20000r/min, and the stirring time is 300s;
step six, carrying out thermal reduction on the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-tungsten nano composite powder; the thermal reduction process comprises the following steps: firstly heating to 650 ℃ at the heating rate of 2.5 ℃/min, then preserving heat for 1h, then heating to 700 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 4h; the thickness of the nanometer composite powder mixed with ammonium metatungstate, molybdenum dioxide and molybdenum in the thermal reduction is 5mm.
Through detection, the apparent density of the molybdenum-tungsten nano composite powder prepared by the embodiment is 0.3g/cm 3 The porosity was 97%.
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 (10)
1. A preparation method of molybdenum-tungsten nano composite powder with high dispersion and high porosity is characterized by comprising the following steps:
step one, adjusting and modifying the particle size and the active site of amorphous cracked carbon to obtain amorphous cracked carbon particles, and crushing molybdenum trioxide to obtain molybdenum trioxide particles; the adjustment and modification of the particle size and the active sites are ultrasonic treatment, friction treatment, plasma treatment or microwave treatment;
step two, mixing the molybdenum trioxide particles obtained in the step one, the amorphous cracked carbon particles obtained in the step one, an activating agent, ethanol and deionized water to obtain slurry;
step three, drying the slurry obtained in the step two, and then stirring at a super high speed to obtain amorphous cracked carbon particle @ molybdenum trioxide nano composite powder;
step four, carrying out segmented heat treatment on the nano composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain nano mixed powder of molybdenum @ molybdenum dioxide with a core-shell structure; the process of the segmented heat treatment comprises the following steps: firstly heating to 400-600 ℃, then carrying out heat preservation, and then heating to 800-1000 ℃ and carrying out heat preservation; the heat preservation time of each section in the sectional heat treatment is more than 1h, the heating rate is less than 30 ℃/min, and the atmosphere is vacuum or inert gas;
step five, heating the nano mixed powder obtained in the step four, then dropwise adding an ammonium metatungstate solution into the nano mixed powder while stirring, and then carrying out ultrahigh-speed stirring to obtain the nano composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum with the multistage core-shell structure;
step six, carrying out thermal reduction on the nanometer composite powder of the mixed ammonium metatungstate, the molybdenum dioxide and the molybdenum obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-tungsten nanometer composite powder; the thermal reduction process comprises the following steps: heating to 500-700 ℃, then preserving heat for more than 30min, then heating to 720-950 ℃, and preserving heat for more than 30 min.
2. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase carbon source in the step one, is of an amorphous structure, and has a specific surface area of more than 150g/cm 3 。
3. The method as claimed in claim 1, wherein the molybdenum-tungsten nano composite powder has a mass purity of more than 99.9% in the step I, the crushing is ultrasonic treatment or ball milling treatment, and the loose packed density of the molybdenum trioxide particles is less than 1g/cm 3 。
4. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein in the second step, the mass of the amorphous cracked carbon particles in the slurry is 7-13% of the mass of the molybdenum trioxide particles, and the mass of the active agent in the slurry is 0.2-0.5% of the mass of the molybdenum trioxide particles.
5. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein the active agent in the second step is prepared from polyethylene glycol and polyvinyl alcohol in a mass ratio of 1.
6. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein the loose packed density of the nano composite powder in the third step is less than 0.7g/cm 3 。
7. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity according to claim 1, wherein the stirring speed of the ultra-high speed stirring in the third step, the fourth step and the fifth step is more than 5000r/min, and the stirring time is not less than 30s.
8. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein the bulk density of the nano mixed powder in the fourth step is less than 0.55g/cm 3 The porosity is greater than 85%.
9. The preparation method of the molybdenum-tungsten nano-composite powder with high dispersion and high porosity as claimed in claim 1, wherein in step five, the mass purity of ammonium metatungstate adopted by the ammonium metatungstate solution is greater than 99.95%, the concentration of ammonium metatungstate in the ammonium metatungstate solution is less than 0.5g/mL, and the average particle size of liquid drops of the ammonium metatungstate solution is less than 1 μm; the apparent density of the nano composite powder of ammonium metatungstate, molybdenum dioxide and molybdenum is less than 0.6g/cm 3 The porosity is greater than 85%.
10. The method for preparing the molybdenum-tungsten nano composite powder with high dispersion and high porosity as claimed in claim 1, wherein the loose packed density of the molybdenum-tungsten nano composite powder in the sixth step is less than 0.5g/cm 3 And the porosity is more than 95 percent.
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