CN104591188B - A kind of preparation method of nanometer molybdenum disilicide powder - Google Patents
A kind of preparation method of nanometer molybdenum disilicide powder Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of nanometer molybdenum disilicide powder, described method is liquid phase synthesizing method.The nanometer molybdenum disilicide powder product granularity uniform, controllable that the method for the present invention prepares, good dispersion, and can use as lithium ion battery negative.
Description
Technical field
The present invention relates to new high-tech material field, be specifically related to the preparation side of a kind of nanometer molybdenum disilicide powder
Method.
Background technology
Molybdenum disilicide (MoSi2) there is the high-temperature oxidation resistance of excellence, high elastic modulus, low-thermal-expansion
The advantages such as coefficient, higher intensity, resistance to chemical attack, good thermal shock resistance and high-melting-point, are to have skill
The function ceramics of art market prospects and structural ceramics, it is as high temperature exothermic body member material, high temperature antioxygen
Change coating and obtain extensively application it is considered to be the most potential high temperature structural material.Along with
The development of new and high technology, many emerging fields are in the urgent need to high performance MoSi2Sill.
Hinder MoSi2The main cause that sill is applied in high-end field is that its low-temperature flexibility is poor, high
The temperature low and easy generation of intensity " Pesting ".The regulation and control that become more meticulous of microstructure can be effectively improved material
Performance, it is critical only that and obtain the molybdenum disilicide powder that particle diameter is tiny, particularly nano-powder.
But, in existing research, molybdenum silicide based material is the most all that the method by synthesis in solid state obtains
, the most this kind of method is difficult to obtain particle diameter, the powder of composition high uniformity, for sintered body
Then it is easily caused stress raisers, thus affects the overall performance of material；On the other hand by this kind of side
Method is difficult to obtain the nanocrystalline M oSi of polymolecularity2Sill, although using Mechanic Alloying Technology to obtain
To nano-powder, but easily reunite, it is impossible in the thermal expansion fundamentally solving enhancing and matrix phase
Difference of coefficients problem, it is impossible to make material property obtain more efficiently lifting, cause MoSi2Based structures material
The practicalization stagnation of material.Therefore, it is necessary to the liquid phase synthesis route exploring novelty obtains and receives
The brilliant MoSi of rice2Sill.
Summary of the invention
It is an object of the invention to, it is provided that the nanometer molybdenum disilicide powder of the polymolecularity of a kind of controlled preparation
Method, the method prepare product granularity uniform, controllable, good dispersion.
For achieving the above object, technical scheme is as follows:
The preparation method of a kind of nanometer molybdenum disilicide powder, described method is liquid phase synthesizing method.
Preferably, the present invention prepares the method for nanometer molybdenum disilicide powder and includes procedure below:
(1) mixed aqueous solution of ammonium molybdate and sucrose is prepared；
(2) aqueous isopropanol of tetraethyl orthosilicate is prepared；
(3) mixed aqueous solution of preparation in step (1) is slowly added in the solution of step (2)；
(4) mixed solution that step (3) prepares is prepared as wet gel；
(5) wet gel in step (4) is prepared as xerogel；
(6) xerogel in step (5) is prepared as dried powder；
(7) dried powder in step (6) is prepared as nanometer molybdenum disilicide powder.
Preferably, in step (1), the mixed aqueous solution deionization of described ammonium molybdate and sucrose
Water is formulated, and wherein, the concentration of described ammonium molybdate is 0.019～0.152mol/L, is preferably
0.076mol/L；The concentration of described sucrose is 0.067～0.760mol/L, preferably 0.31mol/L.
Preferably, in step (2), the aqueous isopropanol of described tetraethyl orthosilicate is by 76 volumes
Part tetraethyl orthosilicate dissolve in the isopropanol of 100 parts by volume and be prepared from.
Preferably, the mixed aqueous solution of preparation in step (1) is being slowly added to the solution of step (2)
Before, acid adding in the mixed aqueous solution of preparation in step (1), until this solution becomes from clear, colorless
For blackish green；Preferably, the mixed aqueous solution of preparation in step (1) is being slowly added to step (2)
Solution before, the mixed aqueous solution prepared to step (1) is in 50 DEG C of waters bath with thermostatic control intensively stirred
Under the conditions of drip the hydrochloric acid of 10mol/L, until this solution becomes blackish green from clear, colorless.
Preferably, step (3) is to carry out under conditions of 50 DEG C of waters bath with thermostatic control strong agitation.
Preferably, ammonium molybdate, sucrose and positive silicic acid second in the final mixed solution prepared in step (3)
The mol ratio of ester is 1:(3.5～5): 14, preferably 1:4.08:14.
Preferably, the wet gel described in step (4) is to be existed by the mixed solution obtained in step (3)
Under the conditions of 50 DEG C of waters bath with thermostatic control, strong agitation is after 1 hour, is added dropwise over ammonia after room temperature is aged 18 hours
Water is prepared from.
Preferably, the xerogel described in step (5) is by 200 DEG C of vacuum in electric vacunm drying case
Being dried 6 hours under environment and obtain, the xerogel obtained is grey black.
Preferably, the dried powder described in step (6) is to be ground by the xerogel of gained in step (5)
Broken, wash, dry and be prepared from；Preferably, the dried powder described in step (6) is by step
(5) in, the xerogel mortar of gained is ground into powder, is washed with deionized twice, then uses anhydrous second
Alcohol washed once, and dries and obtain under 90 DEG C of vacuum environments.
Preferably, nanometer molybdenum disilicide powder described in step (7) is dry by obtain in step (6)
The heating of dry powder obtains；Preferably, described in step (7), nanometer molybdenum disilicide powder is by step
(6) dried powder obtained in is put in vacuum molybdenum wire furnace through heating technique acquisition.Preferably,
Described heating technique is: be first heated to 300 DEG C from room temperature in 30 minutes, then 300 DEG C of insulations
1 hour, then in 50 minutes, it is heated to 800 DEG C, it is incubated 30 minutes at 800 DEG C, then 30～40
It is heated in minute 1100～1200 DEG C (preferably 1100 DEG C), at 1100～1200 DEG C (preferably
1100 DEG C) it is incubated 2 hours, finally lower the temperature with stove.
In a specific embodiment, the preparation method of the nanometer molybdenum disilicide powder of the present invention include with
Lower step:
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
The concentration of acid ammonium is 0.076mol/L, and the concentration of described sucrose is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added in the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes finally to mix
The molar ratio of Molybdenum in Solution acid ammonium, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein, directly
Wet gel is become to solution；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30～40 minutes, is heated to 1100～1200 DEG C (preferably
1100 DEG C), it is incubated 2 hours at 1100～1200 DEG C (preferably 1100 DEG C), finally lowers the temperature with stove.
Compared to prior art, present invention have the advantage that
(1) the product granularity uniform, controllable that prepared by the present invention, good dispersion.
(2) product prepared by the present invention can use as lithium ion battery negative, filling at 100mA/g
Under discharging condition, discharge capacity is 355-488mAh/g first, stably puts after 20 charge and discharge cycles
Capacitance is 140-160mAh/g.This capacity is significantly better than document (Journal of Power Sources 202
(2012) 269 275) numerical value of report in.
Detailed description of the invention
Technical scheme will be illustrated below by way of example, but following example will be not
Limit the scope of the present invention.
The preparation method of the nanometer molybdenum disilicide powder of embodiment 1 present invention
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours at 1100 DEG C,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
91.5%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 150-300nm.
The preparation method of the nanometer molybdenum disilicide powder of embodiment 2 present invention
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
The concentration of acid ammonium is 0.076mol/L, and the concentration of sucrose is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes finally to mix molten
In liquid, the molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 40 minutes, is heated to 1200 DEG C, be incubated 2 hours at 1200 DEG C,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
81.5%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 200-400nm.
The preparation method of the nanometer molybdenum disilicide powder of embodiment 3 present invention
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
Acid ammonium concentration is 0.038mol/L, and described sucrose concentration is 0.155mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation one under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained is little
Time, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours at 1100 DEG C,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
83.2%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 100-200nm.
The preparation method of the nanometer molybdenum disilicide powder of embodiment 4 present invention
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.266mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:3.5:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours 1100,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
65.5%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 150-300nm.
The preparation method of the nanometer molybdenum disilicide powder of embodiment 5 present invention
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.38mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:5:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours at 1100 DEG C,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
56.3%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 150-300nm.
Comparative example 1
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.155mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:2.04:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours at 1100 DEG C,
Finally lower the temperature with stove.
Performance parameter: the powder of acquisition is through XRD test display Mo4.8Si3C0.6For principal crystalline phase, contain simultaneously
There is a small amount of MoSi2And Mo5Si3, particle diameter is at 150-300nm.
Comparative example 2
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.443mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:5.83:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30 minutes, is heated to 1100 DEG C, be incubated 2 hours at 1100 DEG C,
Finally lower the temperature with stove.
Performance parameter: the powder of acquisition is through XRD test display Mo4.8Si3C0.6For principal crystalline phase, contain simultaneously
There is a small amount of MoSi2, particle diameter is at 150-300nm.
Comparative example 3
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
The concentration of acid ammonium is 0.076mol/L, and the concentration of sucrose is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes finally to mix molten
In liquid, the molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 25 minutes, is heated to 1050 DEG C, be incubated 2 hours at 1050 DEG C,
Finally lower the temperature with stove.
Performance parameter: the powder of acquisition is through XRD test display Mo4.8Si3C0.6For principal crystalline phase, contain simultaneously
There is a small amount of MoSi2And Mo5Si3, particle diameter is at 150-300nm.
Comparative example 4
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 45 minutes, is heated to 1250 DEG C, be incubated 2 hours at 1250 DEG C,
Finally lower the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
39.5%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 200-500nm.
Comparative example 5
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, ammonium molybdate
Concentration is 0.076mol/L, and sucrose concentration is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added to the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes in mixed solution
The molar ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the mixed solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein,
Until solution becomes wet gel；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, added in 110 minutes
Heat, to 1100 DEG C, is incubated 2 hours at 1100 DEG C, finally lowers the temperature with stove.
Performance parameter: the molybdenum disilicide powder of acquisition is through XRD test display MoSi2Powder content is
41.6%, remaining is Mo5Si3And Mo4.8Si3C0.6, particle diameter is at 100-300nm.
It should be appreciated that invention described herein is not limited to specific methodology, experimental program or reagent,
Because these can change.Discussion provided in this article and example are merely to describe specific enforcement
Scheme presents and is not intended to limit the scope of the present invention, and the scope of the present invention is only limited by claim
Fixed.
Claims (19)
1. the preparation method of a nanometer molybdenum disilicide powder, it is characterised in that described method is liquid phase
Synthetic method, wherein, described liquid phase synthesizing method includes procedure below:
(1) mixed aqueous solution of ammonium molybdate and sucrose is prepared；
(2) aqueous isopropanol of tetraethyl orthosilicate is prepared；
(3) mixed aqueous solution of preparation in step (1) is slowly added in the solution of step (2)；
(4) mixed solution that step (3) prepares is prepared as wet gel；
(5) wet gel in step (4) is prepared as xerogel；
(6) xerogel in step (5) is prepared as dried powder；
(7) dried powder in step (6) is prepared as nanometer molybdenum disilicide powder.
2. according to the method described in claim 1, it is characterised in that in step (1), described
Ammonium molybdate and the mixed aqueous solution deionized water of sucrose formulated, wherein, described ammonium molybdate dense
Degree is 0.019～0.152mol/L；The concentration of described sucrose is 0.067～0.760mol/L.
3. according to the method described in claim 1 or 2, it is characterised in that in step (1),
The mixed aqueous solution deionized water of described ammonium molybdate and sucrose is formulated, wherein, and described ammonium molybdate
Concentration be 0.076mol/L；The concentration of described sucrose is 0.31mol/L.
4. according to the method described in claim 1 or 2, it is characterised in that in step (2),
The aqueous isopropanol of described tetraethyl orthosilicate is that the tetraethyl orthosilicate of 76 parts by volume is dissolved in 100 volumes
The isopropanol of part is prepared from.
5. according to the method described in claim 1 or 2, it is characterised in that by step (1)
Before the mixed aqueous solution of preparation is slowly added to the solution of step (2), in step (1), preparation is mixed
Acid adding in Heshui solution, until this solution becomes blackish green from clear, colorless.
6. according to the method described in claim 5, it is characterised in that by preparation in step (1)
Mixed aqueous solution be slowly added to step (2) solution before, the mixing prepared to step (1) is water-soluble
Liquid drips the hydrochloric acid of 10mol/L under conditions of 50 DEG C of waters bath with thermostatic control strong agitation, until this solution from
Clear, colorless becomes blackish green.
7. according to the method described in claim 1 or 2, it is characterised in that step (3) is at 50 DEG C
Carry out under conditions of water bath with thermostatic control strong agitation.
8. according to the method described in claim 1 or 2, it is characterised in that step (3) prepares
Final mixed solution in ammonium molybdate, the mol ratio of sucrose and tetraethyl orthosilicate be 1:(3.5～5): 14.
Method described in the most according to Claim 8, it is characterised in that prepare in step (3)
In whole mixed solution, the mol ratio of ammonium molybdate, sucrose and tetraethyl orthosilicate is 1:4.08:14.
10. according to the method described in claim 1 or 2, it is characterised in that institute in step (4)
The wet gel stated is strongly to be stirred under the conditions of 50 DEG C of waters bath with thermostatic control by the mixed solution obtained in step (3)
After mixing 1 hour, after room temperature is aged 18 hours, it is added dropwise over ammoniacal liquor is prepared from.
11. according to the method described in claim 1 or 2, it is characterised in that institute in step (5)
The xerogel stated obtains by being dried 6 hours under 200 DEG C of vacuum environments in electric vacunm drying case,
To xerogel be grey black.
12. according to the method described in claim 1 or 2, it is characterised in that institute in step (6)
The dried powder stated is to be ground by the xerogel of gained in step (5), wash, dry and be prepared from.
13. according to the method described in claim 12, it is characterised in that described in step (6)
Dried powder, for the xerogel mortar of gained in step (5) is ground into powder, is washed with deionized
Twice, then with absolute ethanol washing once, dry under 90 DEG C of vacuum environments and obtain.
14. according to the method described in claim 1 or 2, it is characterised in that institute in step (7)
Stating nanometer molybdenum disilicide powder is the dried powder heating obtained in step (6) to be obtained.
15. according to the method described in claim 14, it is characterised in that step is received described in (7)
Rice molybdenum disilicide powder is to be put in vacuum molybdenum wire furnace the dried powder obtained in step (6) through adding
Thermal process obtains.
16. methods according to claim 15, it is characterised in that described heating technique is: first
First in 30 minutes, it is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then at 50 points
It is heated to 800 DEG C in clock, is incubated 30 minutes at 800 DEG C, then was heated in 30～40 minutes
1100～1200 DEG C, it is incubated 2 hours at 1100～1200 DEG C, finally lowers the temperature with stove.
17. methods according to claim 16, it is characterised in that described heating technique is: first
First in 30 minutes, it is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then at 50 points
It is heated to 800 DEG C in clock, is incubated 30 minutes at 800 DEG C, then in 30～40 minutes, is heated to 1100 DEG C,
It is incubated 2 hours at 1100 DEG C, finally lowers the temperature with stove.
The preparation method of 18. 1 kinds of nanometer molybdenum disilicide powders, it is characterised in that described method include with
Lower step:
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
The concentration of acid ammonium is 0.076mol/L, and the concentration of described sucrose is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added in the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes finally to mix
The molar ratio of Molybdenum in Solution acid ammonium, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein, directly
Wet gel is become to solution；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30～40 minutes, is heated to 1100～1200 DEG C,
1100～1200 DEG C are incubated 2 hours, finally lower the temperature with stove.
19. methods according to claim 18, it is characterised in that described method includes following step
Rapid:
(1) with deionized water dissolving ammonium molybdate and sucrose, and stirring makes molybdic acid under 50 DEG C of water bath condition
Ammonium and sucrose fully dissolve, and obtain the mixed aqueous solution of ammonium molybdate and sucrose, standby；Wherein, described molybdenum
The concentration of acid ammonium is 0.076mol/L, and the concentration of described sucrose is 0.31mol/L；
(2) take in the isopropanol that the tetraethyl orthosilicate of 76 parts by volume dissolves in 100 parts by volume, make positive silicon
The aqueous isopropanol of acetoacetic ester, standby；
(3) mixed aqueous solution in step (1) is taken, in 50 DEG C of waters bath with thermostatic control intensively stirred condition
The hydrochloric acid of lower dropping 10mol/L, until solution becomes blackish green from clear, colorless；
(4) the blackish green solution that step (3) obtains is taken, at 50 DEG C of waters bath with thermostatic control intensively stirred bar
Under part, it is slowly added in the aqueous isopropanol of the tetraethyl orthosilicate that step (2) obtains, makes finally to mix
The molar ratio of Molybdenum in Solution acid ammonium, sucrose and tetraethyl orthosilicate is 1:4.08:14；
(5) the mixed solution strong agitation 1 under the conditions of 50 DEG C of waters bath with thermostatic control step (4) obtained
Hour, then the solution obtained at room temperature is aged 18 hours, is added dropwise over ammoniacal liquor wherein, directly
Wet gel is become to solution；
(6) wet gel that step (5) obtains is put in electric vacunm drying case and be dried, baking temperature
Being 200 DEG C, drying time is 6 hours, obtains the xerogel of grey black；
(7) the xerogel mortar that step (6) obtains is ground into powder, is washed with deionized twice,
Again with absolute ethanol washing once, dry under 90 DEG C of vacuum environments, obtain dried powder；
(8) dried powder that step (7) obtains is put in vacuum molybdenum wire furnace, first in 30 minutes
It is heated to 300 DEG C from room temperature, is then incubated 1 hour at 300 DEG C, then in 50 minutes, is heated to 800 DEG C,
It is incubated 30 minutes at 800 DEG C, then in 30～40 minutes, is heated to 1100 DEG C, be incubated 2 at 1100 DEG C
Hour, finally lower the temperature with stove.
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| CN100999321A (en) * | 2007-01-04 | 2007-07-18 | 北京科技大学 | Method of preparing molybdenum silicide powder |
| CN100999020A (en) * | 2007-01-04 | 2007-07-18 | 北京科技大学 | Method of preparing tunsten and aluminium-doped molybdenum silicide powder |
| CN101445244A (en) * | 2008-12-22 | 2009-06-03 | 中南大学 | Production method of high-performance molybdenum disilicide bar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999321A (en) * | 2007-01-04 | 2007-07-18 | 北京科技大学 | Method of preparing molybdenum silicide powder |
| CN100999020A (en) * | 2007-01-04 | 2007-07-18 | 北京科技大学 | Method of preparing tunsten and aluminium-doped molybdenum silicide powder |
| CN101445244A (en) * | 2008-12-22 | 2009-06-03 | 中南大学 | Production method of high-performance molybdenum disilicide bar |
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