CN107916066B - Vanadium dioxide composite powder of containing graphene and the preparation method and application thereof - Google Patents
Vanadium dioxide composite powder of containing graphene and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to Vanadium dioxide composite powders of a kind of containing graphene and the preparation method and application thereof.A kind of Vanadium dioxide composite powder of containing graphene, including core-shell particles and the graphene being scattered between the core-shell particles, the core-shell particles include vanadium dioxide particle and metal, the metallic cover forms metal shell in the vanadium dioxide particle surface, and the mass ratio of the vanadium dioxide particle, the metal and the graphene is 70~98:1~20:1~10.The high conduction performance of the Vanadium dioxide composite powder of containing graphene may be implemented by the synergistic effect of metal shell and graphene for the Vanadium dioxide composite powder of above-mentioned containing graphene, and improve the electron transport ability of the Vanadium dioxide composite powder of containing graphene and the transflector ability to infrared ray.When the temperature increases, plasma resonance is formed inside vanadium dioxide particle, the conductive network that vanadium dioxide particle, metal shell and graphene are formed realizes the total reflection to infrared light, the transmission and absorption of infrared ray can be greatly reduced at this time, to reduce temperature rise, energy-efficient purpose is realized.
Description
Technical field
The present invention relates to technical field of material, more particularly to the Vanadium dioxide composite powder and its system of containing graphene
Preparation Method and application.
Background technique
Increasingly depleted due to global resources, energy-saving and emission-reduction have become the current top priority in various countries.It is estimated that building
Energy consumption accounts for 1/3 or more of social total energy consumption.Therefore, building energy conservation is the key that reduce energy consumption.Due to portion very big in building energy consumption
Divide and is used for air-conditioning, and more than half in air conditioning energy consumption is the energy loss generated by window and extraneous heat exchange, therefore is led to
Propulsion building energy-saving is crossed, energy-saving glass is developed, is expected to that greenhouse gas emission and energy consumption is greatly lowered, is finally reached energy-saving ring
The purpose of guarantor.
Existing energy-saving glass, for representative, has to visible with the low emissivity glass (Low-E glass) of commercial type
Light high transmission and characteristic to mid and far infrared high reflection, the hollow structure pair glass window and door thermal and insulating performance prepared with it
It is good, but its price is higher and cannot carry out real-time monitoring to sunlight with the variation of ambient temperature, belongs to " by dynamic response "
Type, it is difficult to adapt to the most of climatic environments cold in winter and hot in summer in China.Other " active response " type energy-saving glass, such as electroluminescent change
Color glass, gas-discoloration glass, its structure is complicated, involves great expense, and is difficult to popularize in a short time.
Vanadium dioxide (VO2) it is a kind of typical thermal induced phase transition compound.Vanadium dioxide has several isomerism crystalline forms,
Middle R phase is the stable crystalline phase of vanadium dioxide, because identical as rutile titanium dioxide crystal structure, so also known as rutile
Phase.Rutile phase hypovanadic oxide crystal has special thermochromic properties: occurring at 68 DEG C by low temperature monoclinic phase (M phase) to height
The reversible metal semiconductor phase transition of warm Rutile Type (R phase), rear its sends out the transmitance of infrared part in sunlight before phase change
The raw change dramatically by high transmission to high reflection, and along with phase transformation, many light such as resistivity, magnetic susceptibility, the transmitance of light
Reversible mutation can occur for electrical characteristics, these brilliant performances make film in smart window, energy-saving coatings, optoelectronic switch, laser
There is high application value in the fields such as protection, optical storage.
The prior art, which has been realized, is coated in the coating that vanadium dioxide is principal component on glass and exterior wall, meets mill construction
Production energy-saving requirement also may be implemented to carry out reducing energy consumption to existing simple glass.However, existing vanadium dioxide coating is although right
Visible light has preferable assimilation effect, but unsatisfactory to the absorption or reflecting effect of infrared ray, and infrared ray is also extraneous
The main source of Environmental Heat Source.Therefore, it is necessary to improve to existing hypovanadic oxide powder and coating.
Summary of the invention
Based on this, it is necessary to for the current vanadium dioxide coating problem bad to the absorption of infrared ray or reflecting effect,
A kind of Vanadium dioxide composite powder and the preparation method and application thereof of containing graphene is provided.
A kind of Vanadium dioxide composite powder of containing graphene including core-shell particles and is scattered between the core-shell particles
Graphene, the core-shell particles include vanadium dioxide particle and metal, and the metallic cover is in the vanadium dioxide particle surface
Form metal shell, the mass ratio of the vanadium dioxide particle, the metal and the graphene be 70~98:1~20:1~
10。
In a wherein embodiment, the vanadium dioxide particle is spheric granules；The grain of the vanadium dioxide particle
Diameter is 10nm~1000nm.
In a wherein embodiment, the metal is selected from least one of Au, Ag, Pt, Cu and Al.
In a wherein embodiment, the metal shell with a thickness of 1nm~100nm.
In a wherein embodiment, the face of the graphene is having a size of 1 μm~100 μm；The thickness of the graphene
For 0.5nm~50nm；The specific surface area of the graphene is 10m2/ g~1000m2/g。
The Vanadium dioxide composite powder of above-mentioned containing graphene is in vanadium dioxide composite mortar and in the compound patch of vanadium dioxide
Application in film.
The preparation method of the Vanadium dioxide composite powder of above-mentioned containing graphene, comprising the following steps:
It disperses graphene in metal salt solution；
It again disperses vanadium dioxide particle in metal salt solution and obtains mixed liquor；
PH adjusting agent, stabilizer, complexing agent and reducing agent are sequentially added into the mixture to react to obtain reaction solution, are made
It obtains the metal salt and reduction reaction occurs in vanadium dioxide particle surface formation metal shell；
The reaction solution is centrifuged, is washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.
In a wherein embodiment, further include the steps that preparing the vanadium dioxide particle: to tetravalent vanadium ion water
Alkaline reagent is added in solution and obtains presoma containing vanadium；And hydro-thermal process is carried out to the presoma containing vanadium and obtains vanadium dioxide
Grain.
In a wherein embodiment, the metal salt solution is selected from AuCl3、AgNO3、AgCl、PtCl4、PtCl2、
CuSO4、CuCl2、Al(NO3)3And AlCl3At least one of.
In a wherein embodiment, the pH adjusting agent is selected from sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate
At least one of with boric acid；
And/or the stabilizer is selected from methanol and 2, at least one of 2- bipyridyl；
And/or the complexing agent is selected from least one of sodium citrate and triethanolamine；
And/or the reducing agent is selected from least one of formaldehyde and sodium phosphite.
In the Vanadium dioxide composite powder of above-mentioned containing graphene, using vanadium dioxide particle as substrate, in vanadium dioxide particle
Surface clad shell, and formed and bridged by graphene.Vanadium dioxide is a kind of phase-change material, with changing for ambient temperature
Become the reversible transition that may be implemented between metal phase and semiconductor phase, the transflection to infrared ray can be brought while phase transition
Penetrate the change of performance；In the surface clad shell of vanadium dioxide particle, the core-shell particles with core-shell structure, metal are formed
Shell can significantly improve the electric conductivity of vanadium dioxide particle；Meanwhile graphene forms bridge joint between core-shell particles, so that core
It is connected with each other between shell particles, and forms conductive network.It may be implemented by the synergistic effect of metal shell and graphene containing stone
The high conduction performance of the Vanadium dioxide composite powder of black alkene, and improve the electron-transport of the Vanadium dioxide composite powder of containing graphene
Ability and transflector ability to infrared ray.When the temperature increases, plasma resonance, titanium dioxide are formed inside vanadium dioxide particle
Total reflection of the conductive network realization that vanadium particle, metal shell and graphene are formed to infrared light, rather than conventional diffusing reflection,
The transmission and absorption of infrared ray can be greatly reduced at this time, to reduce temperature rise, realize energy-efficient purpose.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the Vanadium dioxide composite powder of the containing graphene of an embodiment；
Fig. 2 is the flow chart of the preparation method of the Vanadium dioxide composite powder of the containing graphene of an embodiment.
Specific embodiment
Below in conjunction with specific embodiment and attached drawing to the Vanadium dioxide composite powder and preparation method thereof of containing graphene
It is described in further detail with application.
Referring to Fig. 1, the Vanadium dioxide composite powder 100 of the containing graphene of an embodiment include core-shell particles 110 and
The graphene 120 being scattered between core-shell particles 110.
In a wherein embodiment, core-shell particles 110 include vanadium dioxide particle 111 and metal.Metallic cover exists
The surface of vanadium dioxide particle 111 forms metal shell 113.
In a wherein embodiment, vanadium dioxide particle 111 is spheric granules, the partial size of vanadium dioxide particle 111
For 10nm~1000nm.Preferably, the partial size of vanadium dioxide particle is 10nm~100nm.
In a wherein embodiment, the material of metal shell 113 is selected from least one of Au, Ag, Pt, Cu and Al.
The conductivity of metal shell 113 is 100S/m~10000S/m.
Above-mentioned metal material all has higher conductivity, can promote the electric conductivity of hypovanadic oxide powder to realize two
The phase transition ability of vanadium oxide particle and albedo to infrared ray.Wherein, Au, Ag and Pt have more excellent electric conductivity
Can, but above-mentioned metal belongs to noble metal, is substantially more expensive.In other embodiments, use Cu and Al as metal shell
113 material not only has preferable electric conductivity, but also can substantially reduce cost.
In a wherein embodiment, the specific surface area of the core-shell particles 110 formed after the cladding of metal shell 113
For 10m2/ g~200m2/g。
In a wherein embodiment, metal shell 113 with a thickness of 1nm~100nm.Preferably, metal shell 113
With a thickness of 1nm~10nm.
In a wherein embodiment, graphene 120 be scattered between core-shell particles 110 and core-shell particles 110 it
Between formed bridge joint.
In a wherein embodiment, the face of graphene 120 is having a size of 1 μm~100 μm.Graphene 120 with a thickness of
0.5nm~50nm.The specific surface area of graphene is 10m2/ g~1000m2/g。
In a wherein embodiment, the conductivity of graphene 120 is 500S/m~5000S/m；The heat of graphene 120
Conductance is 200W/ (mK)~2000W/ (mK).
In a wherein embodiment, the mass ratio of vanadium dioxide particle 111, metal 113 and graphene 120 is 70~
98:1~20:1~10.
In the Vanadium dioxide composite powder of above-mentioned containing graphene, using vanadium dioxide particle as substrate, in vanadium dioxide particle
Surface clad shell, and formed and bridged by graphene.Vanadium dioxide is a kind of phase-change material, with changing for ambient temperature
Become the reversible transition that may be implemented between metal phase and semiconductor phase, the transflection to infrared ray can be brought while phase transition
Penetrate the change of performance.But the electric conductivity of vanadium dioxide and thermal conductivity are limited, cause it limited to the obstructing capacity of infrared ray,
In the surface clad shell of vanadium dioxide particle, the core-shell particles with core-shell structure are formed, metal shell can be significant
Improve the electric conductivity of vanadium dioxide particle.Meanwhile graphene forms bridge joint between core-shell particles, so that phase between core-shell particles
It connects, and forms conductive network.The titanium dioxide of containing graphene may be implemented by the synergistic effect of metal shell and graphene
The high conduction performance of vanadium composite granule, and improve the electron transport ability of the Vanadium dioxide composite powder of containing graphene and to infrared
The transflector ability of line.When the temperature increases, plasma resonance, vanadium dioxide particle, metal are formed inside vanadium dioxide particle
Total reflection of the conductive network realization that shell and graphene are formed to infrared light, rather than conventional diffusing reflection, at this time can be big
The transmission and absorption that width reduces infrared ray realize energy-efficient purpose to reduce temperature rise.
The Vanadium dioxide composite powder of above-mentioned containing graphene is in the vanadium dioxide composite mortar of containing graphene and in graphitiferous
Application in the vanadium dioxide composite film-stuck of alkene.
In a wherein embodiment, the Vanadium dioxide composite powder of above-mentioned containing graphene can be used for being prepared and contain
The vanadium dioxide composite mortar of graphene.The vanadium dioxide composite mortar of above-mentioned containing graphene is intelligent temperature control slurry.
In a wherein embodiment, the method for preparing the vanadium dioxide composite mortar of containing graphene includes following step
It is rapid: according to the mass fraction, by 40 parts~60 parts of transparent film-forming resin, 20 parts~50 parts of solvent, 1 part~10 parts of graphitiferous
The Vanadium dioxide composite powder of alkene and 1 part~10 parts of auxiliary agent, which are uniformly mixed, obtains the vanadium dioxide composite mortar of containing graphene.
In a wherein embodiment, transparent film-forming resin be selected from organic siliconresin, acrylic resin, polyester resin,
At least one of polyurethane resin, alkyd resin and epoxy resin.
In a wherein embodiment, solvent be selected from water, ethyl alcohol, propyl alcohol, isopropanol, butanol, ethyl acetate, toluene,
At least one of dimethylbenzene, chloroform, dimethylformamide.
In a wherein embodiment, auxiliary agent in film forming agent, wetting agent, defoaming agent and levelling agent at least one
Kind.
In a wherein embodiment, film forming agent is selected from ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether
At least one of ether ester, glycol propyl ether, dipropyl ether, propylene glycol phenylate, benzyl alcohol and Lauryl Alcohol ester.
In a wherein embodiment, wetting agent is selected from lauryl sulfate, dodecane sulfonate, polyethylene
At least one of alcohol, polyvinylpyrrolidone, organo-silicon compound and organofluorine compound.
In a wherein embodiment, defoaming agent is selected from dimethicone, ether ester compound, modified mineral oil, polyoxy
At least one of ethyl glycerin ether, small molecule metallorganic and silicon modified organic polymer.
In a wherein embodiment, levelling agent is selected from butyl glycol ether, cellaburate, polyacrylate, silicon
At least one of oil, hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane and modified organic silicon compound.
By being coated with above-mentioned slurry on glass, lower infrared light transmission at high temperature may be implemented, reduce indoor
The raising of temperature, the infrared light transmission with higher in low temperature improve room temperature, achieve the effect that cool in summer and warm in winter.
In a wherein embodiment, the Vanadium dioxide composite powder of above-mentioned containing graphene can be used for being prepared and contain
The vanadium dioxide composite film-stuck of graphene.The vanadium dioxide composite film-stuck of above-mentioned containing graphene is intelligent temperature control pad pasting.
In a wherein embodiment, the method for preparing the vanadium dioxide composite film-stuck of containing graphene includes following step
It is rapid: the vanadium dioxide composite mortar of containing graphene being prepared using the Vanadium dioxide composite powder of containing graphene；Contain above-mentioned
The vanadium dioxide composite paste of graphene is over the transparent substrate；And to the vanadium dioxide composite pulp for being coated with containing graphene
The transparent substrate of material is dried to obtain the vanadium dioxide composite film-stuck of containing graphene.
In a wherein embodiment, transparent substrate is selected from least one of PP, PE, PA, PVC, PET and PMMA.
In a wherein embodiment, by the way of spraying, blade coating, brushing, showering or roller coating over the transparent substrate
It is coated with the vanadium dioxide composite mortar of containing graphene.
In a wherein embodiment, the temperature of drying process is 70 DEG C~90 DEG C；The time of drying process is 1min
~5min.
Referring to Fig. 2, the preparation method of the Vanadium dioxide composite powder of the containing graphene of an embodiment, including following step
It is rapid:
S110, vanadium dioxide particle is prepared.
In a wherein embodiment, the step of preparing vanadium dioxide particle, is specifically included:
S111, into tetravalent vanadium ion aqueous solution, addition alkaline reagent obtains presoma containing vanadium.
In a wherein embodiment, anion is SO in tetravalent vanadium ion aqueous solution4 2-、Cl-And C2O4 2-In at least
It is a kind of.
In a wherein embodiment, alkaline reagent is selected from least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide.
Preferably, alkaline reagent aqueous solution is configured to be then added in tetravalent vanadium ion aqueous solution.
In a wherein embodiment, in tetravalent vanadium ion aqueous solution the concentration of tetravalent vanadium ion be 0.01mol/L~
1mol/L。
In a wherein embodiment, the molar ratio of alkaline reagent and tetravalent vanadium ion is 1:10~10:1.
S113, vanadium dioxide particle is obtained to the progress of presoma containing vanadium hydro-thermal process.
In a wherein embodiment, carrying out hydro-thermal process is to carry out in a high pressure reaction kettle.The temperature of hydro-thermal process
It is 150 DEG C~300 DEG C.The time of hydro-thermal process is 4h~20h.
In a wherein embodiment, pressure when carrying out hydro-thermal process is 1MPa~10MPa.
S120, it disperses graphene in metal salt solution.
In a wherein embodiment, metal salt solution is selected from AuCl3、AgNO3、AgCl、PtCl4、PtCl2、CuSO4、
CuCl2、Al(NO3)3And AlCl3At least one of.
In a wherein embodiment, the concentration of metal salt solution is 0.001~0.1mol/L.
In a wherein embodiment, the molar ratio of graphene and metal salt is 1:10~10:1.
In a wherein embodiment, passes through ultrasound and dispersed graphene in metal salt solution by way of stirring.
The power of ultrasonic disperse is 20Hz~50Hz.The revolving speed of stirring is 200r/min~2000r/min.Ultrasonic disperse and stirring when
Between be 10min~120min.
S130, it disperses vanadium dioxide particle in metal salt solution obtain mixed liquor again.
In a wherein embodiment, stir and ultrasound by way of by vanadium dioxide particle to disperse metal salt molten
In liquid.The power of ultrasonic disperse is 20Hz~50Hz.The revolving speed of stirring is 200r/min~2000r/min.It ultrasonic disperse and stirs
The time mixed is 10min~120min.
In a wherein embodiment, the molar ratio of vanadium dioxide particle and metal salt is 10:1~100:1.
S140, pH adjusting agent, stabilizer, complexing agent and reducing agent are sequentially added into mixed liquor react to obtain reaction solution.
In a wherein embodiment, pH adjusting agent, stabilizer, complexing agent and reducing agent are sequentially added into mixed liquor
Reaction forms metal shell in vanadium dioxide particle surface so that reduction reaction occurs for metal salt.
In a wherein embodiment, pH adjusting agent is selected from sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and boron
At least one of acid.PH adjusting agent and the molar ratio of metal salt are 1:10~10:1.
In a wherein embodiment, stabilizer is selected from methanol and 2, at least one of 2- bipyridyl.Stabilizer with
The molar ratio of metal salt is 1:10~10:1.
In a wherein embodiment, complexing agent is selected from least one of sodium citrate and triethanolamine.Complexing agent
Molar ratio with metal salt is 1:100~1:1.
In a wherein embodiment, reducing agent is selected from least one of formaldehyde and sodium phosphite.Reducing agent and gold
The molar ratio for belonging to salt is 1:10~1:1.
In a wherein embodiment, pH adjusting agent, stabilizer, complexing agent and reducing agent are sequentially added into mixed liquor
The temperature of reaction is -20 DEG C~100 DEG C；The time of reaction is 0.5h~2h.
S150, reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.
In a wherein embodiment, the revolving speed being centrifuged when reaction solution is centrifuged is 2000r/min~20000r/
min。
In a wherein embodiment, centrifugation product is washed with water.Time for being preferably centrifuged and being washed
Number is 1~5 time.
In a wherein embodiment, withering temperature is 20 DEG C~100 DEG C, when withering
Between be 10min~120min.
The preparation method of the Vanadium dioxide composite powder of above-mentioned containing graphene is simple, is easy to realize industrial production.
It should be noted that in other embodiments, step S110 also can be omitted, when omitting step S110, directly
The mode for connecting outsourcing obtains vanadium dioxide particle.In other embodiments, the sequence of step S120 and step S130 can
To exchange, certainly, step S120 and step 130 can also merge.
Here is the explanation of specific embodiment, and following embodiment is unless otherwise specified, then inevitably miscellaneous without containing removing
The component pointed out is not known in other other than matter.
Embodiment 1
(1) the tetravalent vanadium ion aqueous solution of 10g is weighed, wherein the concentration of tetravalent vanadium ion is 0.8mol/L；Again thereto
Alkaline reagent of the addition containing 10g sodium hydroxide, which is uniformly mixed, obtains presoma containing vanadium；Above-mentioned presoma containing vanadium is placed in high pressure
In reaction kettle, 150 DEG C, pressure be 1MPa under conditions of react 20h；Product is filtered again, wash and is dried
To vanadium dioxide particle.The partial size for the vanadium dioxide particle being prepared is 100nm.
(2) AuCl of 4L is weighed3Solution, wherein AuCl3Concentration be 0.01mol/L；The graphene of 5g is added thereto,
Pass through ultrasound and keeps graphene dispersion uniform by way of stirring.Wherein, the face of graphene is having a size of 1 μm, the thickness of graphene
For 0.5nm, the specific surface area of graphene is 10m2/g.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 200r/min, is surpassed
The time of sound dispersion and stirring is 60min.
(3) the vanadium dioxide particle for adding 90g passes through ultrasound and so that vanadium dioxide particle is uniformly dispersed by way of stirring
Obtain mixed liquor.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 200r/min, and the time of ultrasonic disperse and stirring is
60min。
(4) sequentially added into mixed liquor the sodium hydroxide of 0.25g, the methanol of 0.25g, 0.25g sodium citrate and
The sodium phosphite of 0.25g, and react 1h at -20 DEG C and obtain reaction solution.
(5) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles, graphene forms bridge joint between core-shell particles.The metal shell of formation with a thickness of 2nm；Vanadium dioxide
The mass ratio of grain, metal shell and graphene is 90:5:5.
Embodiment 2
(1) the tetravalent vanadium ion aqueous solution of 100g is weighed, wherein the concentration of tetravalent vanadium ion is 0.02mol/L；Again to it
Middle alkaline reagent of the addition containing 10g ammonium hydroxide is uniformly mixed and obtains presoma containing vanadium；It is anti-that above-mentioned presoma containing vanadium is placed in high pressure
Answer in kettle, 300 DEG C, pressure be 10MPa under conditions of react 4h；Product is filtered again, is washed and drying process obtains
Vanadium dioxide particle.The partial size for the vanadium dioxide particle being prepared is 200nm.
(2) AgNO of 3L is weighed3Solution, wherein AgNO3Concentration be 0.05mol/L；The graphene of 10g is added thereto,
Pass through ultrasound and keeps graphene dispersion uniform by way of stirring.Wherein, the face of graphene is having a size of 100 μm, the thickness of graphene
Degree is 50nm, and the specific surface area of graphene is 1000m2/g.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 2000r/
The time of min, ultrasonic disperse and stirring is 90min.
(3) the vanadium dioxide particle for adding 80g passes through ultrasound and so that vanadium dioxide particle is uniformly dispersed by way of stirring
Obtain mixed liquor.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 2000r/min, and the time of ultrasonic disperse and stirring is
90min。
(4) sequentially added into mixed liquor the sodium carbonate of 0.4g, the 2,2- bipyridyl of 0.4g, 0.04g triethanolamine and
The formaldehyde of 0.25g, and react 2h at 50 DEG C and obtain reaction solution.
(5) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles, graphene forms bridge joint between core-shell particles.The metal shell of formation with a thickness of 50nm；Vanadium dioxide
The mass ratio of grain, metal shell and graphene is 80:10:10.
Embodiment 3
(1) the tetravalent vanadium ion aqueous solution of 100g is weighed, wherein the concentration of tetravalent vanadium ion is 0.01mol/L；Again to it
Middle alkaline reagent of the addition containing 10g ammonium hydroxide is uniformly mixed and obtains presoma containing vanadium；It is anti-that above-mentioned presoma containing vanadium is placed in high pressure
Answer in kettle, 200 DEG C, pressure be 5MPa under conditions of react 15h；Product is filtered again, is washed and drying process obtains
Vanadium dioxide particle.The partial size for the vanadium dioxide particle being prepared is 10nm.
(2) PtCl of 2L is weighed4Solution, wherein PtCl4Concentration be 0.1mol/L；The graphene of 10g is added thereto,
Pass through ultrasound and keeps graphene dispersion uniform by way of stirring.Wherein, the face of graphene is having a size of 70 μm, the thickness of graphene
For 30nm, the specific surface area of graphene is 800m2/g.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 200r/min, is surpassed
The time of sound dispersion and stirring is 120min.
(3) the vanadium dioxide particle for adding 70g passes through ultrasound and so that vanadium dioxide particle is uniformly dispersed by way of stirring
Obtain mixed liquor.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 200r/min, and the time of ultrasonic disperse and stirring is
120min。
(4) sodium citrate of the potassium hydroxide of 0.5g, the 2,2- bipyridyl of 0.5g, 0.05g are sequentially added into mixed liquor
With the sodium phosphite of 0.2g, and at 0 DEG C react 1h obtain reaction solution.
(5) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles, graphene forms bridge joint between core-shell particles.The metal shell of formation with a thickness of 5nm；Vanadium dioxide
The mass ratio of grain, metal shell and graphene is 70:20:10.
Embodiment 4
(1) the tetravalent vanadium ion aqueous solution of 100g is weighed, wherein the concentration of tetravalent vanadium ion is 0.1mol/L；Again thereto
Alkaline reagent of the addition containing 10g ammonium hydroxide, which is uniformly mixed, obtains presoma containing vanadium；Above-mentioned presoma containing vanadium is placed in reaction under high pressure
In kettle, 200 DEG C, pressure be 5MPa under conditions of react 15h；Product is filtered again, is washed and drying process obtains two
Vanadium oxide particle.The partial size for the vanadium dioxide particle being prepared is 1000nm.
(2) CuSO of 5L is weighed4Solution, wherein CuSO4Concentration be 0.05mol/L；The graphene of 2g is added thereto,
Pass through ultrasound and keeps graphene dispersion uniform by way of stirring.Wherein, the face of graphene is having a size of 70 μm, the thickness of graphene
For 30nm, the specific surface area of graphene is 800m2/g.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 2000r/min,
The time of ultrasonic disperse and stirring is 10min.
(3) the vanadium dioxide particle for adding 88g passes through ultrasound and so that vanadium dioxide particle is uniformly dispersed by way of stirring
Obtain mixed liquor.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 2000r/min, and the time of ultrasonic disperse and stirring is
10min。
(4) sequentially added into mixed liquor the potassium carbonate of 4.5g, the 2,2- bipyridyl of 4.5g, 0.45g sodium citrate and
The sodium phosphite of 0.225g, and react 2h at 100 DEG C and obtain reaction solution.
(5) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles, graphene forms bridge joint between core-shell particles.The metal shell of formation with a thickness of 100nm；Vanadium dioxide
The mass ratio of particle, metal shell and graphene is 88:10:2.
Embodiment 5
(1) the tetravalent vanadium ion aqueous solution of 100g is weighed, wherein the concentration of tetravalent vanadium ion is 0.5mol/L；Again thereto
Alkaline reagent of the addition containing 10g ammonium hydroxide, which is uniformly mixed, obtains presoma containing vanadium；Above-mentioned presoma containing vanadium is placed in reaction under high pressure
In kettle, 200 DEG C, pressure be 5MPa under conditions of react 15h；Product is filtered again, is washed and drying process obtains two
Vanadium oxide particle.The partial size for the vanadium dioxide particle being prepared is 500nm.
(2) Al (NO of 40L is weighed3)3Solution, wherein Al (NO3)3Concentration be 0.001mol/L；It is added 1g's thereto
Graphene passes through ultrasound and keeps graphene dispersion uniform by way of stirring.Wherein, the face of graphene is having a size of 70 μm, graphite
Alkene with a thickness of 30nm, the specific surface area of graphene is 800m2/g.The power of ultrasonic disperse is 30Hz, and the revolving speed of stirring is
The time of 1000r/min, ultrasonic disperse and stirring is 120min.
(3) the vanadium dioxide particle for adding 98g passes through ultrasound and so that vanadium dioxide particle is uniformly dispersed by way of stirring
Obtain mixed liquor.The power of ultrasonic disperse is 30Hz, and the revolving speed of stirring is 1000r/min, and the time of ultrasonic disperse and stirring is
120min。
(4) boric acid of 80g, the 2,2- bipyridyl of 80g, the sodium citrate of 0.8g and 1.6g are sequentially added into mixed liquor
Sodium phosphite, and react 0.5h at -20 DEG C and obtain reaction solution.
(5) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles, graphene forms bridge joint between core-shell particles.The metal shell of formation with a thickness of 1nm；Vanadium dioxide
The mass ratio of grain, metal shell and graphene is 98:1:1.
Embodiment 6
(1) the tetravalent vanadium ion aqueous solution of 100g is weighed, wherein the concentration of tetravalent vanadium ion is 1mol/L；Add thereto again
Enter the alkaline reagent containing 10g ammonium hydroxide be uniformly mixed obtain presoma containing vanadium；Above-mentioned presoma containing vanadium is placed in autoclave
In, 200 DEG C, pressure be 3MPa under conditions of react 15h；Product is filtered again, is washed and drying process obtains dioxy
Change vanadium particle.The partial size for the vanadium dioxide particle being prepared is 50nm.
(2) CuCl of 5L is weighed2Solution, wherein CuCl2Concentration be 0.05mol/L；The titanium dioxide of 90g is added thereto
Vanadium particle passes through ultrasound and makes vanadium dioxide particle be uniformly dispersed to obtain mixed liquor by way of stirring.The power of ultrasonic disperse is
30Hz, the revolving speed of stirring are 1000r/min, and the time of ultrasonic disperse and stirring is 60min.
(3) sequentially added into mixed liquor the potassium hydroxide of 45g, the 2,2- bipyridyl of 45g, 0.45g sodium citrate and
The sodium phosphite of 0.45g, and react 2h at 20 DEG C and obtain reaction solution.
(4) reaction solution is centrifuged, washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.It is above-mentioned
The surface that metal shell is coated on vanadium dioxide particle in the Vanadium dioxide composite powder of containing graphene, which is formed, has core-shell structure
Core-shell particles.The metal shell of formation with a thickness of 10nm；The mass ratio of vanadium dioxide particle and metal shell is 9:1.
Vanadium dioxide is prepared in the Vanadium dioxide composite powder of containing graphene prepared by 1~embodiment of embodiment 6
Composite coating.Weigh respectively 40 parts of organic siliconresin, 40 parts of solvent, 10 parts of containing graphene Vanadium dioxide composite powder
And 10 parts auxiliary agent be uniformly mixed obtain vanadium dioxide composite mortar；Again by vanadium dioxide composite mortar in PET transparent substrate
It is scratched, and dry 5min obtains vanadium dioxide composite coating at 70 DEG C.
The thickness of coating, visible light transmittance, infrared light transmission and ultraviolet isolating rate are tested, as a result such as table
Shown in 1.Wherein: detecting the thickness of coating according to ASTM D 6132 using QuaNix4500 Knicks calibrator.
The visible light transmittance, infrared of coating is detected according to GB/T 2680 by ultraviolet-visible-infrared spectrophotometer
Light transmission rate, ultraviolet light rejection rate.
1500nm high/low temperature difference refers to coating respectively under the conditions of 10 DEG C and 50 DEG C to the transmitance of 1500nm wavelength light
Difference, 1500nm correspond to infrared energy light placed in the middle, and it is right at different temperatures that transmitance difference can reflect coating
The transmission ability of infrared ray.
Infrared regulation rate refer to coating respectively under the conditions of 10 DEG C and 50 DEG C to the transmitance difference of entire infrared spectroscopy, it is whole
The transmitance calculation formula of body infrared spectroscopy is as follows:
Wherein: TIRFor infrared light transmittance；
T (λ) is the light penetration that wavelength is λ.
Table 1
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of Vanadium dioxide composite powder of containing graphene, which is characterized in that including core-shell particles and be scattered in the nucleocapsid
Graphene between particle, the core-shell particles include vanadium dioxide particle and metal, and the metallic cover is in the titanium dioxide
Vanadium particle surface forms metal shell, and the mass ratio of the vanadium dioxide particle, the metal and the graphene is 70~98:
1~20:1~10；The vanadium dioxide particle is spheric granules；The partial size of the vanadium dioxide particle is 10nm~1000nm.
2. the Vanadium dioxide composite powder of containing graphene according to claim 1, which is characterized in that the metal is selected from
At least one of Au, Ag, Pt, Cu and Al.
3. the Vanadium dioxide composite powder of containing graphene according to claim 1, which is characterized in that the metal shell
With a thickness of 1nm~100nm.
4. the Vanadium dioxide composite powder of containing graphene according to claim 1, which is characterized in that the thickness of the graphene
Degree is 0.5nm~50nm；The specific surface area of the graphene is 10m2/ g~1000m2/g。
5. the Vanadium dioxide composite powder of the described in any item containing graphenes of Claims 1 to 4 in vanadium dioxide composite mortar and
Application in vanadium dioxide composite film-stuck.
6. the preparation method of the Vanadium dioxide composite powder of the described in any item containing graphenes of Claims 1 to 4, feature exist
In, comprising the following steps:
It disperses graphene in metal salt solution；
It again disperses vanadium dioxide particle in metal salt solution and obtains mixed liquor；
It sequentially adds pH adjusting agent, stabilizer, complexing agent and reducing agent into the mixture to react to obtain reaction solution, so that institute
It states metal salt and reduction reaction occurs in vanadium dioxide particle surface formation metal shell；
The reaction solution is centrifuged, is washed and is dried to obtain the Vanadium dioxide composite powder of containing graphene.
7. the preparation method of the Vanadium dioxide composite powder of containing graphene according to claim 6, which is characterized in that also wrap
It includes the step of preparing the vanadium dioxide particle: alkaline reagent being added into tetravalent vanadium ion aqueous solution and obtains presoma containing vanadium；
And hydro-thermal process is carried out to the presoma containing vanadium and obtains vanadium dioxide particle.
8. the preparation method of the Vanadium dioxide composite powder of containing graphene according to claim 6, which is characterized in that described
Metal salt solution is selected from AuCl3、AgNO3、AgCl、PtCl4、PtCl2、CuSO4、CuCl2、Al(NO3)3And AlCl3In at least one
Kind.
9. the preparation method of the Vanadium dioxide composite powder of containing graphene according to claim 6, which is characterized in that described
PH adjusting agent is selected from least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and boric acid；
And/or the stabilizer is selected from methanol and 2, at least one of 2- bipyridyl；
And/or the complexing agent is selected from least one of sodium citrate and triethanolamine；
And/or the reducing agent is selected from least one of formaldehyde and sodium phosphite.
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| CN111785960B (en) * | 2020-09-03 | 2020-11-20 | 中南大学 | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof |
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