CN110203972A - The preparation method of phase-M vanadium dioxide nanometre powder - Google Patents
The preparation method of phase-M vanadium dioxide nanometre powder Download PDFInfo
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- CN110203972A CN110203972A CN201910514224.7A CN201910514224A CN110203972A CN 110203972 A CN110203972 A CN 110203972A CN 201910514224 A CN201910514224 A CN 201910514224A CN 110203972 A CN110203972 A CN 110203972A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
This application involves a kind of preparation methods of phase-M vanadium dioxide nanometre powder, belong to inorganic functional material technical field.A kind of preparation method of phase-M vanadium dioxide nanometre powder, comprising: sequentially add acid reagent and hydrazine hydrochloride aqueous solution into the aqueous solution of pentavalent vanadium-containing compound, be configured to mixed solution.Mixed solution and alkaline reagent are mixed to get suspension.Suspension is separated by solid-liquid separation to obtain solid product, hydro-thermal reaction is carried out to the aqueous solution of solid product.The aqueous solution of solid product is directly used into the available phase-M vanadium dioxide nanometre powder of hydro-thermal method, does not need subsequent high temperature annealing, product has purer object phase, and preferable crystallinity, diameter of particle is small and particle diameter distribution is uniform.The hydrothermal crystallization process of the application does not have gas generation, and safety is good, not high to equipment, reaction temperature and time requirement, is suitble to industrialization large-scale production, and the preparation method has the features such as easy to operate, low in cost.
Description
Technical field
This application involves inorganic functional material technical fields, and in particular to a kind of system of phase-M vanadium dioxide nanometre powder
Preparation Method.
Background technique
Vanadium dioxide has up to more than 10 crystal phases, wherein only M/R phase has thermochromic properties.It has reported at present a variety of
The method for preparing vanadium dioxide powder, but it is difficult the M-phase vanadium dioxide powder that step preparation has excellent thermotropic phase transition performance, Gu
Phase method (as thermally decomposed) need to be to the high-temperature calcination of presoma containing vanadium, and energy consumption is high and the big distribution of particle size is wide.Liquid phase method is often prepared
Out be metastable state hypovanadic oxide powder, although high annealing can be transformed into M phase hypovanadic oxide, meeting in annealing process
Particle is caused to be sintered and reunite, prepared vanadium dioxide is also usually micron order.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the embodiment of the present application includes providing a kind of phase-M vanadium dioxide nanometre powder
Preparation method, improve that preparation process is complicated, and M-phase vanadium dioxide powder particle is big, the technical issues of being unevenly distributed.
In a first aspect, the embodiment of the present application proposes a kind of preparation method of phase-M vanadium dioxide nanometre powder, comprising: to
Acid reagent and hydrazine hydrochloride aqueous solution are sequentially added in the aqueous solution of pentavalent vanadium-containing compound, are configured to mixed solution.It will mix
It closes solution and alkaline reagent is mixed to get suspension.Suspension is separated by solid-liquid separation to obtain solid product, to solid product
Aqueous solution carries out hydro-thermal reaction.
The aqueous solution of solid product made from the embodiment of the present application is precursor liquid, precursor liquid is directly used hydro-thermal method can be with
Phase-M vanadium dioxide nanometre powder is obtained, does not need subsequent high temperature annealing, product has purer object phase, preferable to crystallize
Degree, diameter of particle is small and particle diameter distribution is uniform.The hydrothermal crystallization process of the application does not have gas generation, and safety is good, to equipment,
Reaction temperature and time requirement is not high, be suitble to industrialization large-scale production, and the preparation method have it is easy to operate, it is low in cost
The features such as.
In the section Example of the application, hydrazine hydrochloride and the molar ratio of vanadium in pentavalent vanadium-containing compound are
(0.05-1):1。
In the ratio range, hydrazine hydrochloride and reacting for pentavalent vanadium are more abundant, and product is more pure.
In the section Example of the application, the hydrazine hydrochloride in hydrazine hydrochloride aqueous solution includes hydrazine mono-hydrochloric salts and hydrazine two
Any one in hydrochloride or two kinds.
Hydrazine hydrochloride is reduced to tetravalence vanadium as reducing agent, by the pentavalent vanadium in solution.
In the section Example of the application, the concentration of vanadium ion is 0.05- in the aqueous solution of pentavalent vanadium-containing compound
0.5mol/L。
In the ratio range, hydrazine hydrochloride and reacting for pentavalent vanadium are more abundant, and product is more pure.
In the section Example of the application, pentavalent vanadium-containing compound includes vanadic anhydride, ammonium metavanadate, metavanadic acid
In sodium, potassium metavanadate, sodium vanadate and potassium vanadate any one or at least two composition.
Above-mentioned substance can be used as reaction raw materials preparation phase-M vanadium dioxide nanometre powder.
In the section Example of the application, the pH value of mixed solution is 1-2.
Acid reagent adjusts the pH value of pentavalent vanadium-containing compound aqueous solution, and the mixed solution of the pH condition can to restore
Reaction carries out more complete.
In the section Example of the application, the pH value of suspension is 6-10, and optionally, the pH value of suspension is 7-8.
The suspension of the pH value can make tetravalence vanadium sufficiently react to obtain suspension with alkali, and tetravalence vanadium is passed through solid-liquid point
It is separated from from solution.
In the section Example of the application, before carrying out hydro-thermal reaction, doping is added in the aqueous solution of solid product
Agent, the molar ratio of vanadium is (0.005-0.1) in the doped chemical and pentavalent vanadium-containing compound in dopant: 1.
In the section Example of the application, dopant includes the soluble-salt of tungsten, molybdenum, aluminium, magnesium, niobium, osmium, fluorine and ruthenium
Any one of or two kinds of composition.
Dopant can regulate and control the phase transition temperature of gained hypovanadic oxide powder, in the range of above-mentioned amount ratio, dopant
Effect it is more obvious.
In the section Example of the application, the aqueous solution of solid product carries out hydro-thermal reaction, reaction temperature in a kettle
Degree is 220-260 DEG C, reaction time 12-72h.
Phase-M vanadium dioxide nanometre powder can be made in the reaction temperature and reaction time, and under the reaction temperature into
Row hydro-thermal reaction can shorten the reaction time, shorten the production cycle.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the X-ray diffractogram for the hypovanadic oxide powder that the embodiment of the present application 1 provides；
Fig. 2 is the scanning electron microscope diagram for the hypovanadic oxide powder that the embodiment of the present application 1 provides；
Fig. 3 is the particle diameter distribution statistic histogram for the hypovanadic oxide powder that the embodiment of the present application 1 provides；
Fig. 4 is the differential scanning amount thermal analysis curve for the hypovanadic oxide powder that the embodiment of the present application 1 provides；
Fig. 5 is the high/low temperature transmitance map after the hypovanadic oxide powder film that the embodiment of the present application 1 provides；
Fig. 6 is the scanning electron microscope diagram for the hypovanadic oxide powder that the embodiment of the present application 2 provides；
Fig. 7 is the particle diameter distribution statistic histogram for the hypovanadic oxide powder that the embodiment of the present application 2 provides；
Fig. 8 is the X-ray diffractogram for the hypovanadic oxide powder that the embodiment of the present application 3 provides；
Fig. 9 is the scanning electron microscope diagram for the hypovanadic oxide powder that the embodiment of the present application 4 provides；
Figure 10 is the particle diameter distribution statistic histogram for the hypovanadic oxide powder that the embodiment of the present application 4 provides；
Figure 11 is the X-ray diffractogram for the hypovanadic oxide powder that the embodiment of the present application 5 provides；
Figure 12 is the scanning electron microscope diagram for the hypovanadic oxide powder that the embodiment of the present application 6 provides；
Figure 13 is the differential scanning amount thermal analysis curve for the hypovanadic oxide powder that the embodiment of the present application 7 provides.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
There is research disclose a kind of utilization alcohols at present to make solvent and directly synthesize M phase VO2The method of powder, but the powder granule
Three-dimensional dimension is all larger than 100nm, and biggish size and poor dispersibility limit the application of the powder, and in production process
A large amount of alcohol organic solvents need to be consumed, pollution is big.Separately there is research to disclose a kind of preparation method of vanadium dioxide nano powder, it should
Powder is the spherical shape or spherical particle of 20~60nm of size, but this method need to react in the village Shuan Nei that can provide oxidizing atmosphere
It is carried out in kettle, complicated reaction kettle structure and uncontrollable oxidizing gas concentration limit its large-scale production and actually answer
With.There is research to disclose a kind of VO with pencil nanostructure2Phase-change material and preparation method thereof, gained powder length are
18-25 microns, diameter is 3-5 microns, this method need under the conditions of 240~300 DEG C hydro-thermal reaction, then in a nitrogen atmosphere 500
~700 DEG C of high-temperature calcinations, the preparation process is complicated and energy consumption is high.Present inventor on the basis of existing technology, provides
A kind of preparation method of phase-M vanadium dioxide nanometre powder, to improve prior art preparation complex process, M-phase vanadium dioxide powder
Particle is big, is unevenly distributed, and energy consumption is high, needs the technical issues of subsequent heat treatment.
A kind of preparation method of phase-M vanadium dioxide nanometre powder of the embodiment of the present application is specifically described below.
The embodiment of the present application proposes a kind of preparation method of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
The application uses pentavalent vanadium-containing compound for raw material, disperses pentavalent vanadium-containing compound in deionized water, successively
Acid reagent and hydrazine hydrochloride aqueous solution is added, is configured to mixed solution.In this application, acid reagent adjusts pentavalent containing vanadium
The pH value for closing object aqueous solution reacts with pentavalent vanadium-containing compound to hydrazine hydrochloride and provides acidic environment.Add hydrazine hydrochloride water
Solution, hydrazine hydrochloride are reacted with pentavalent vanadium-containing compound, and pentavalent vanadium is reduced to tetravalence vanadium, obtains mixed solution, the mixing is molten
Liquid is clarification blue solution.In the section Example of the application, the pH value of the research through present inventor, mixed solution is
1-2, it is complete which carry out reduction reaction.
In order to enable hydrazine hydrochloride is sufficiently reacted with pentavalent vanadium, hydrazine hydrochloride aqueous solution is slowly added to, and is such as added dropwise.In this Shen
In section Example please, the hydrazine hydrochloride in hydrazine hydrochloride aqueous solution includes any in hydrazine mono-hydrochloric salts and hydrazine dihydrochloride
It is one or two kinds of.
In the section Example of the application, in order to guarantee sufficiently reacting for hydrazine hydrochloride and pentavalent vanadium, hydrazine hydrochloride with
The molar ratio of vanadium is (0.05-1) in pentavalent vanadium-containing compound: 1.Vanadium ion is dense in the aqueous solution of pentavalent vanadium-containing compound
Degree is 0.05-0.5mol/L.Wherein, in hydrazine hydrochloride and pentavalent vanadium-containing compound vanadium molar ratio can for 0.1:1,
0.25:1,0.5:1,0.7:1.The concentration of vanadium ion can be 0.1mol/L, 0.2mol/ in the aqueous solution of pentavalent vanadium-containing compound
L、0.3mol/L、0.4mol/L。
In the section Example of the application, pentavalent vanadium-containing compound includes vanadic anhydride, ammonium metavanadate, metavanadic acid
In sodium, potassium metavanadate, sodium vanadate and potassium vanadate any one or at least two composition.
Alkaline reagent is added into obtained mixed solution, adjusts the pH value of solution to 6-10, so that tetravalence vanadium and alkali are anti-
Precipitating should be generated and obtain suspension.In the section Example of the application, the pH value of suspension is 7-8.
Suspension is separated by solid-liquid separation, so that tetravalence vanadium is separated from solution.In the section Example of the application
In, using the method for centrifugation or filtering.Specifically, being centrifuged using centrifuge to suspension, centrifugal rotational speed 5000-
The solid that centrifugation obtains is washed with deionized in 11000rpm, then by solid ultrasonic disperse in deionized water, ultrasonic time
For 15-45min, precursor liquid is obtained.
In the section Example of the application, when preparing precursor liquid, dopant is added into the aqueous solution of solid product,
To regulate and control the phase transition temperature of gained hypovanadic oxide powder, the molar ratio of doped chemical and vanadium in pentavalent vanadium-containing compound is
(0.005-0.1):1.Dopant includes any one of soluble-salt of tungsten, molybdenum, aluminium, magnesium, niobium, osmium, fluorine and ruthenium or two kinds
Composition.Optionally, the molar ratio of doped chemical and vanadium in pentavalent vanadium-containing compound is 0.01:1,0.03:1,0.05:
1、0.08:1。
Hydro-thermal reaction.
The aqueous solution of solid product is transferred in reaction kettle, carries out hydro-thermal reaction in a kettle, reaction temperature is
220-260 DEG C, reaction time 12-72h.In order to which reaction is under the conditions of 220-260 DEG C of temperature to shorten the reaction time, reaction kettle
Liner is polytetrafluoro liner or PPL (polyparaphenylene phenol) liner, and water heating kettle packing ratio is 40-70%.After the reaction was completed, by product
Using alternately washing 2-3 times of deionized water and dehydrated alcohol, vacuum drying.
The application prepares precursor liquid and phase-M vanadium dioxide nanometre powder is made using hydro-thermal method, does not need subsequent high temperature annealing
Processing, product have purer object phase, and thermal induced phase transition point can be adjusted to 0~70 DEG C by doping, powder by preferable crystallinity
Body partial size is small and particle diameter distribution is uniform.By the powder ultrasonic disperse in water or other solvents, then it is added organic polymer-based
Matter can be configured to the vanadium dioxide coating slurry of good dispersion property.
The hydrothermal crystallization process of the application does not have gas generation, and safety is good, not to equipment, reaction temperature and time requirement
Height is suitble to industrialization large-scale production, and the preparation method has the features such as easy to operate, low in cost.
The feature of the application and performance are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 1.82g vanadic anhydride, be added in 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, successively slow drop
Add the hydrochloric acid that 3.12ml mass fraction is 38% and the hydrazine mono-hydrochloric salts solution that 5ml concentration is 1M, continues stirring 30 minutes, obtain
Clarify blue solution.Then the ammonium hydroxide that mass fraction is 28~30% is slowly added dropwise into blue solution under agitation, this
When gradually generate khaki precipitating, adjust solution PH=7 taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound is scattered in 40ml deionized water for 30 minutes,
Gained dispersion liquid is transferred in 100mlPPL liner, stainless steel cauldron is put into, 240 DEG C of hydro-thermal process in electric heating bellows
12h after the completion of hydrothermal crystallizing, is centrifuged 15min, isolated product, with deionized water and anhydrous second with the revolving speed of 11000rpm
Alcohol alternately washing 2~3 times, in 80 DEG C of vacuum drying 10h, can be obtained M-phase vanadium dioxide powder.
Embodiment 2
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 0.91g vanadic anhydride, be added 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, be successively slowly added dropwise
The hydrochloric acid that 1.56ml mass fraction is 38%, 2.5ml concentration are the hydrazine dihydrochloride solution of 1M, continue stirring 30 minutes, obtain
Blue solution is clarified, the sodium hydroxide solution that concentration is 1mol/L is then slowly added dropwise into blue solution under agitation,
Khaki precipitating is gradually generated at this time, is adjusted solution PH=8 and is obtained taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound is scattered in 50ml deionized water for 30 minutes,
Gained dispersion liquid is transferred in 100mlPPL liner, stainless steel cauldron is put into, 240 DEG C of hydro-thermal process in electric heating bellows
For 24 hours, after the completion of hydrothermal crystallizing, 10min, isolated product, with deionized water and anhydrous second are centrifuged with the revolving speed of 10000rpm
Alcohol alternately washing 2~3 times, in 80 DEG C of vacuum drying 10h, can be obtained M-phase vanadium dioxide powder.
Embodiment 3
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 1.82g vanadic anhydride, be added 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, be successively slowly added dropwise
4ml concentration is the sulfuric acid of 5mol/L, and 5ml concentration is the hydrazine dihydrochloride solution of 1M, continues stirring 30 minutes, obtains clarification blue
Then solution is slowly added dropwise the ammonium hydroxide that mass fraction is 28~30% into blue solution under agitation, gradually produces at this time
Raw-soil yellow mercury oxide adjusts solution PH=9 and obtains taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound is scattered in 40ml deionized water for 30 minutes,
Gained dispersion liquid is transferred in 100mlPPL liner, stainless steel cauldron is put into, 260 DEG C of hydro-thermal process in electric heating bellows
18h after the completion of hydrothermal crystallizing, is centrifuged 15min, isolated product, with deionized water and anhydrous second with the revolving speed of 11000rpm
Alcohol alternately washing 2~3 times, in 80 DEG C of vacuum drying 10h, can be obtained M-phase vanadium dioxide powder.
Embodiment 4
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 2.34g ammonium metavanadate, be added 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, be successively slowly added dropwise
The hydrochloric acid that 3.12ml mass fraction is 38%, 5ml concentration are the hydrazine dihydrochloride solution of 1M, continue stirring 30 minutes, obtain clear
Then the ammonium hydroxide that mass fraction is 28~30% is slowly added dropwise, at this time in clear blue solution into blue solution under agitation
Khaki precipitating is gradually generated, solution PH=8 is adjusted and obtains taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound is scattered in 50ml deionized water for 30 minutes,
Gained dispersion liquid is transferred in 100mlPPL liner, stainless steel cauldron is put into, 240 DEG C of hydro-thermal process in electric heating bellows
For 24 hours, after the completion of hydrothermal crystallizing, 15min, isolated product, with deionized water and anhydrous second are centrifuged with the revolving speed of 10000rpm
Alcohol alternately washing 2~3 times, in 80 DEG C of vacuum drying 10h, can be obtained M-phase vanadium dioxide powder.
Embodiment 5
The present embodiment provides a kind of preparation method of phase-M vanadium dioxide nanometre powder, the difference with embodiment 4 is:
The temperature of hydro-thermal reaction be 260 DEG C, the reaction time be for 24 hours, after the completion of hydrothermal crystallizing, with the revolving speed of 10000rpm from
Heart 10min, isolated product replace washing 2~3 times with deionized water and dehydrated alcohol, in 80 DEG C of vacuum drying 10h, i.e.,
It can get M-phase vanadium dioxide powder.
Embodiment 6
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 1.82g vanadic anhydride, be added 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, be successively slowly added dropwise
The hydrochloric acid that 3.12ml mass fraction is 38%, 5ml concentration are the hydrazine mono-hydrochloric salts solution of 1M, continue stirring 30 minutes, obtain clear
Then the potassium hydroxide solution that concentration is 1mol/L is slowly added dropwise in clear blue solution into blue solution under agitation, this
When gradually generate khaki precipitating, adjust solution PH=10 taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound is scattered in 70ml deionized water for 30 minutes,
Gained dispersion liquid is transferred in 100mlPPL liner, stainless steel cauldron is put into, 220 DEG C of hydro-thermal process in electric heating bellows
72h after the completion of hydrothermal crystallizing, is centrifuged 10min, isolated product, with deionized water and anhydrous second with the revolving speed of 10000rpm
Alcohol alternately washing 2~3 times, in 80 DEG C of vacuum drying 10h, can be obtained M-phase vanadium dioxide powder.
Embodiment 7
The present embodiment provides a kind of preparation methods of phase-M vanadium dioxide nanometre powder, comprising:
Prepare precursor liquid.
Weigh 1.82g vanadic anhydride, be added 50ml deionized water, 60 DEG C magnetic agitation 30 minutes, be successively slowly added dropwise
The hydrochloric acid that 3.12ml mass fraction is 38%, 5ml concentration are the hydrazine mono-hydrochloric salts solution of 1M, continue stirring 30 minutes, obtain clear
Then the ammonium hydroxide that mass fraction is 28~30% is slowly added dropwise, at this time in clear blue solution into blue solution under agitation
Khaki precipitating is gradually generated, solution PH=7 is adjusted and obtains taupe suspension.
Hydro-thermal reaction.
Suspension is centrifuged and is spent ion-cleaning 1 time, gained precipitating ultrasound 30 minutes, is scattered in 40ml deionization again
In water, and 0.0837g ammonium tungstate is added, gained dispersion liquid is transferred in 100mlPPL liner after mixing evenly, is put into stainless
Steel reaction kettle, 240 DEG C of hydro-thermal process for 24 hours, after the completion of hydrothermal crystallizing, are centrifuged in electric heating bellows with the revolving speed of 11000rpm
15min, isolated product are alternately washed 2~3 times with deionized water and dehydrated alcohol, in 80 DEG C of vacuum drying 10h
Obtain witch culture M-phase vanadium dioxide powder.
Test example 1
It chooses M-phase vanadium dioxide powder made from embodiment 1-7 and carries out X-ray diffraction analysis, obtained XRD spectrum shows
Powder obtained is M-phase vanadium dioxide powder.
Wherein, embodiment 1 obtain powder X-ray diffraction result as shown in Figure 1, powder made from embodiment 3 XRD
Shown in result figure 8, shown in the XRD result figure 11 of powder made from embodiment 5.Such as scheming all peaks all is M phase hypovanadic oxide
Diffraction maximum shows that sample has preferable purity without other miscellaneous phases, and peak shape is more sharp, illustrates the better crystallinity degree of product.
Test example 2
It chooses M-phase vanadium dioxide powder made from embodiment 1-7 and carries out Micro-Structure Analysis.The powder that SEM chart face obtains
Body is evenly distributed having a size of 15~40nm, diameter of particle.
Wherein, the SEM figure of embodiment 1 is Fig. 2 and particle diameter distribution result is Fig. 3, and the SEM figure of the powder of embodiment 2 is Fig. 6
It is Fig. 7 with particle diameter distribution result, the SEM figure of the powder of embodiment 4 is Fig. 9 and particle diameter distribution result is Figure 10, the powder of embodiment 6
The SEM figure of body is Figure 12.As can be seen from the results, the hypovanadic oxide powder of preparation is spherical or spherical structure, having a size of 15~
40nm, and most of grain diameters are in 20nm or so.
Test example 3
It chooses the powder that embodiment 1 and embodiment 7 obtain and carries out differential scanning thermometric analysis, as a result such as Fig. 4 and Figure 13.By
Figure it is found that 1 powder of embodiment DSC the result shows that powder temperature-rise period phase transition temperature be 54.7 DEG C, 7 powder of embodiment
DSC the result shows that powder temperature-rise period phase transition temperature be 48.5 DEG C.Illustrate the powder as made from the preparation method of the application
The phase transition temperature of body is met the requirements.
Test example 4
After slurry is made in powder made from embodiment 1 as a result film such as schemes coating progress high/low temperature transmitance detection
5.The result shows that vanadium dioxide film high/low temperature transmitance difference at 1200nm is more than 30%, it is calculated by formula thin
Film visible light transmittance (Tlum, 380-780nm) and it is 69.04%, sun regulating power (Δ Tsol, 300-2500nm) and it reaches
12.73%, show that the film has excellent thermochromic properties.Calculation formula is as follows:
Tlum/sol=f ψlum/sol(λ)T(λ)d(λ)/fψlum/sol(λ)d(λ)
ΔTsol=Tsol,s- Tsol,m
Wherein, T (λ) indicates the transmitance of af at wavelength lambda, ψlum(λ) is the relative spectral luminous efficiency curve of human eye, ψsol
(λ) indicates the solar radiation curve of spectrum.
Embodiments described above is some embodiments of the present application, instead of all the embodiments.The reality of the application
The detailed description for applying example is not intended to limit claimed scope of the present application, but is merely representative of the selected implementation of the application
Example.Based on the embodiment in the application, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall in the protection scope of this application.
Claims (10)
1. a kind of preparation method of phase-M vanadium dioxide nanometre powder characterized by comprising
Acid reagent and hydrazine hydrochloride aqueous solution are sequentially added into the aqueous solution of pentavalent vanadium-containing compound, are configured to mix molten
Liquid；
The mixed solution and alkaline reagent are mixed to get suspension；
The suspension is separated by solid-liquid separation to obtain solid product, hydro-thermal reaction is carried out to the aqueous solution of the solid product.
2. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that the hydrazonium salt acid
The molar ratio of vanadium is (0.05-1) in salt and the pentavalent vanadium-containing compound: 1.
3. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1 or 2, which is characterized in that the hydrazonium salt
Hydrazine hydrochloride in acid salt aqueous solution includes any one or two kinds in hydrazine mono-hydrochloric salts and hydrazine dihydrochloride.
4. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that the pentavalent contains
The concentration of vanadium ion is 0.05-0.5mol/L in the aqueous solution of vfanadium compound.
5. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1 or 4, which is characterized in that the pentavalent
Vanadium-containing compound includes any in vanadic anhydride, ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate and potassium vanadate
It is a kind of or at least two composition.
6. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that the mixing is molten
The pH value of liquid is 1-2.
7. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that the suspension
PH value be 6-10, optionally, the pH value of the suspension is 7-8.
8. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that described in progress
Before hydro-thermal reaction, dopant is added in the aqueous solution of Xiang Suoshu solid product, the doped chemical in the dopant with it is described
The molar ratio of vanadium is (0.005-0.1) in pentavalent vanadium-containing compound: 1.
9. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 8, which is characterized in that the dopant
Any one of soluble-salt including tungsten, molybdenum, aluminium, magnesium, niobium, osmium, fluorine and ruthenium or two kinds of composition.
10. the preparation method of phase-M vanadium dioxide nanometre powder according to claim 1, which is characterized in that the solid produces
The aqueous solution of object carries out hydro-thermal reaction in a kettle, and reaction temperature is 220-260 DEG C, reaction time 12-72h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615477A (en) * | 2019-10-24 | 2019-12-27 | 成都先进金属材料产业技术研究院有限公司 | VO (vanadium oxide) rapidly prepared by using failure vanadium battery positive electrolyte2Method (2) |
| CN110838583A (en) * | 2019-12-10 | 2020-02-25 | 华中科技大学 | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery |
| CN110923814A (en) * | 2019-11-25 | 2020-03-27 | 北京理工大学重庆创新中心 | Preparation method of nano vanadium dioxide film |
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
| CN112174205A (en) * | 2020-10-16 | 2021-01-05 | 成都先进金属材料产业技术研究院有限公司 | Vanadyl hydroxide stabilized ethanol solution dispersion system and preparation of M-phase VO by using same2Method for preparing nano powder |
| CN112209443A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method |
| CN112209440A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing M-phase vanadium dioxide nano powder |
| CN112266018A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by reverse hydrolysis precipitation |
| CN113277559A (en) * | 2021-06-04 | 2021-08-20 | 吉林大学 | Preparation method of vanadium dioxide film |
| CN113511678A (en) * | 2020-04-09 | 2021-10-19 | 北京理工大学 | M-phase vanadium dioxide nano powder and preparation method and preparation device thereof |
| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
| CN117304751A (en) * | 2023-10-29 | 2023-12-29 | 董理 | Preparation method of water-based paint |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615477A (en) * | 2019-10-24 | 2019-12-27 | 成都先进金属材料产业技术研究院有限公司 | VO (vanadium oxide) rapidly prepared by using failure vanadium battery positive electrolyte2Method (2) |
| CN110923814A (en) * | 2019-11-25 | 2020-03-27 | 北京理工大学重庆创新中心 | Preparation method of nano vanadium dioxide film |
| CN110838583A (en) * | 2019-12-10 | 2020-02-25 | 华中科技大学 | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery |
| CN110838583B (en) * | 2019-12-10 | 2020-10-16 | 华中科技大学 | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery |
| CN113511678A (en) * | 2020-04-09 | 2021-10-19 | 北京理工大学 | M-phase vanadium dioxide nano powder and preparation method and preparation device thereof |
| CN112209443A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method |
| CN112174205A (en) * | 2020-10-16 | 2021-01-05 | 成都先进金属材料产业技术研究院有限公司 | Vanadyl hydroxide stabilized ethanol solution dispersion system and preparation of M-phase VO by using same2Method for preparing nano powder |
| CN112209440A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing M-phase vanadium dioxide nano powder |
| CN112266018A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by reverse hydrolysis precipitation |
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
| CN113277559A (en) * | 2021-06-04 | 2021-08-20 | 吉林大学 | Preparation method of vanadium dioxide film |
| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
| CN117304751A (en) * | 2023-10-29 | 2023-12-29 | 董理 | Preparation method of water-based paint |
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