CN107398556B - Heat-insulating and energy-saving composite granule of containing graphene and the preparation method and application thereof - Google Patents
Heat-insulating and energy-saving composite granule of containing graphene and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to heat-insulating and energy-saving composite granules of a kind of containing graphene and the preparation method and application thereof.A kind of heat-insulating and energy-saving composite granule of containing graphene, including core-shell particles and the graphene being scattered between the core-shell particles, the core-shell particles include infrared high reflection particle and metal, the metallic cover forms metal shell in the infrared high reflection particle surface, and the mass ratio of the infrared high reflection particle, the metal and the graphene is 70~98:1~20:1~10.The high conduction performance of the heat-insulating and energy-saving composite granule of containing graphene may be implemented in the heat-insulating and energy-saving composite granule of above-mentioned containing graphene, and improves the electron transport ability of composite granule and the albedo to infrared ray.The conductive network that infrared high reflection particle, metal shell and graphene are formed may be implemented the total reflection to infrared light, rather than conventional diffusing reflection, and absorption and transmission of the substrate to infrared ray can be greatly reduced at this time to reduce temperature rise and realize energy-efficient purpose.
Description
Technical field
The present invention relates to technical field of material, more particularly to the heat-insulating and energy-saving composite granule 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.
Having realized at present will be coated on glass and exterior wall with heat-insulating and energy-saving powder coating as main component, meet factory
Building energy conservation production requirement also may be implemented to carry out reducing energy consumption to existing simple glass.However, existing heat-insulating and energy-saving powder
It is unsatisfactory to the absorption or reflecting effect of infrared ray, and infrared ray is also the main source of external environment heat source.Therefore, it is necessary to
Existing heat-insulating and energy-saving powder, coating and pad pasting are improved.
Summary of the invention
Based on this, it is necessary to for the current heat-insulating and energy-saving powder problem bad to the absorption of infrared ray or reflecting effect,
A kind of heat-insulating and energy-saving composite granule and the preparation method and application thereof of containing graphene is provided.
A kind of heat-insulating and energy-saving composite granule of containing graphene, including core-shell particles and is scattered between the core-shell particles
Graphene, the core-shell particles include infrared high reflection particle and metal, and the metallic cover is in the infrared high reflection particle
Surface forms metal shell, the mass ratio of the infrared high reflection particle, the metal and the graphene be 70~98:1~
20:1~10.
In a wherein embodiment, the material of the infrared high reflection particle be selected from ITO, ATO, FTO, AZO, AGO,
TiO2, BiOCl, at least one of potassium hexatitanate and wolframic acid caesium.
In a wherein embodiment, the infrared high reflection particle is spheric granules；The infrared high reflection particle
Partial size be 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 heat-insulating and energy-saving composite granule of above-mentioned containing graphene is in heat-insulating and energy-saving composite mortar and in the compound patch of heat-insulating and energy-saving
Application in film.
The preparation method of the heat-insulating and energy-saving composite granule of above-mentioned containing graphene, comprising the following steps:
It disperses graphene in metal salt solution；
It again disperses infrared high reflection 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 the infrared high reflection particle surface formation metal shell；
The reaction solution is separated by solid-liquid separation to obtain the heat-insulating and energy-saving composite granule of containing graphene.
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 heat-insulating and energy-saving composite granule of above-mentioned containing graphene, using infrared high reflection particle as substrate, in infrared high reflection
Particle surface coats metal shell, and is formed and bridged by graphene.Infrared high reflection particle has infrared ray good anti-
Characteristic is penetrated, in the surface clad shell of infrared high reflection particle, forms the core-shell particles with core-shell structure, metal shell
The electric conductivity of infrared high reflection particle can be significantly improved；Meanwhile graphene forms bridge joint between core-shell particles, so that nucleocapsid
It is connected with each other between particle, and forms conductive network.Graphitiferous may be implemented by the synergistic effect of metal shell and graphene
The high conduction performance of the heat-insulating and energy-saving composite granule of alkene, and improve the electron-transport energy of the heat-insulating and energy-saving composite granule of containing graphene
Power and albedo to infrared ray.The conductive network that infrared high reflection particle, metal shell and graphene are formed may be implemented
Total reflection to infrared light, rather than conventional diffusing reflection, can be greatly reduced absorption and transmission of the substrate to infrared ray at this time,
To reduce temperature rise, energy-efficient purpose is realized.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the heat-insulating and energy-saving composite granule of the containing graphene of an embodiment；
Fig. 2 is the flow chart of the preparation method of the heat-insulating and energy-saving composite granule of the containing graphene of an embodiment.
Specific embodiment
Below in conjunction with specific embodiment and attached drawing to the heat-insulating and energy-saving composite granule and preparation method thereof of containing graphene
It is described in further detail with application.
Referring to Fig. 1, the heat-insulating and energy-saving composite granule 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 infrared high reflection particle 111 and metal.Metallic cover
Metal shell 113 is formed on the surface of infrared high reflection particle 111.
In a wherein embodiment, the material of infrared high reflection particle is selected from indium tin oxide (ITO), antimony tin aoxidizes
Object (ATO), fluorine tin-oxide (FTO), Zinc-aluminium (AZO), gallium aluminum oxide (AGO), titanium dioxide (TiO2), oxychloride
At least one of bismuth (BiOCl), potassium hexatitanate and wolframic acid caesium.
In a wherein embodiment, infrared high reflection particle 111 is spheric granules, infrared high reflection particle 111
Partial size is 10nm~1000nm.Preferably, the partial size of infrared high reflection 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 infrared high reflection particle to improve
Albedo of the infrared high reflection particle to infrared ray.Wherein, Au, Ag and Pt have more excellent electric conductivity, but above-mentioned
Metal belongs to noble metal, is substantially more expensive.In other embodiments, use Cu and Al as the material of metal shell 113,
Not only there is preferable electric conductivity, but also cost can be substantially reduced.
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 infrared high reflection particle 111, metal 113 and graphene 120 is 70
~98:1~20:1~10.
In the heat-insulating and energy-saving composite granule of above-mentioned containing graphene, using infrared high reflection particle as substrate, in infrared high reflection
Particle surface coats metal shell, and is formed and bridged by graphene.Infrared high reflection particle has infrared ray good anti-
Characteristic is penetrated, in the surface clad shell of infrared high reflection particle, forms the core-shell particles with core-shell structure, metal shell
The electric conductivity of infrared high reflection particle can be significantly improved；Meanwhile graphene forms bridge joint between core-shell particles, so that nucleocapsid
It is connected with each other between particle, and forms conductive network.Graphitiferous may be implemented by the synergistic effect of metal shell and graphene
The high conduction performance of the heat-insulating and energy-saving composite granule of alkene, and improve the electron-transport energy of the heat-insulating and energy-saving composite granule of containing graphene
Power and albedo to infrared ray.The conductive network that infrared high reflection particle, metal shell and graphene are formed may be implemented
Total reflection to infrared light, rather than conventional diffusing reflection, can be greatly reduced absorption and transmission of the substrate to infrared ray at this time,
To reduce temperature rise, energy-efficient purpose is realized.
The heat-insulating and energy-saving composite granule of above-mentioned containing graphene is in the heat-insulating and energy-saving composite mortar of containing graphene and in graphitiferous
Application in the heat-insulating and energy-saving composite film-stuck of alkene.
In a wherein embodiment, the heat-insulating and energy-saving composite granule of above-mentioned containing graphene, which can be used for being prepared, to be contained
The heat-insulating and energy-saving composite mortar of graphene.The heat-insulating and energy-saving composite mortar of above-mentioned containing graphene is effectively insulating energy conservation slurry.
In a wherein embodiment, the method for preparing the heat-insulating and energy-saving 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 heat-insulating and energy-saving composite granule of alkene and 1 part~10 parts of auxiliary agent, which are uniformly mixed, obtains the heat-insulating and energy-saving 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, absorption and transmission of the substrate to infrared ray can be greatly reduced, reduce room
The raising of interior temperature, to have the energy-efficient effect of effectively insulating.
In a wherein embodiment, the heat-insulating and energy-saving composite granule of above-mentioned containing graphene, which can be used for being prepared, to be contained
The heat-insulating and energy-saving composite film-stuck of graphene.The heat-insulating and energy-saving composite film-stuck of above-mentioned containing graphene is effectively insulating energy conservation pad pasting.
In a wherein embodiment, the method for preparing the heat-insulating and energy-saving composite film-stuck of containing graphene includes following step
It is rapid: the heat-insulating and energy-saving composite mortar of containing graphene being prepared using the heat-insulating and energy-saving composite granule of containing graphene；Contain above-mentioned
The heat-insulating and energy-saving composite paste of graphene is over the transparent substrate；And to the heat-insulating and energy-saving composite pulp for being coated with containing graphene
The transparent substrate of material is dried to obtain the heat-insulating and energy-saving 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 heat-insulating and energy-saving 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 heat-insulating and energy-saving composite granule of the containing graphene of an embodiment, including following step
It is rapid:
S110, 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.
S120, it disperses infrared high reflection particle in metal salt solution obtain mixed liquor again.
In a wherein embodiment, metal salt is dispersed by infrared high reflection particle by way of stirring and is ultrasonic
In solution.The power of ultrasonic disperse is 20Hz~50Hz.The revolving speed of stirring is 200r/min~2000r/min.Ultrasonic disperse and
The time of stirring is 10min~120min.
In a wherein embodiment, the molar ratio of infrared high reflection particle and metal salt is 10:1~100:1.
S130, 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 infrared high reflection 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.
S140, reaction solution is separated by solid-liquid separation to obtain the heat-insulating and energy-saving composite granule of containing graphene.
In a wherein embodiment, solid-liquid separation treatment includes being centrifuged, washed and being dried to reaction solution.
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 heat-insulating and energy-saving composite granule of above-mentioned containing graphene is simple, is easy to realize industrial production.
It should be noted that in other embodiments, the sequence of step S120 and step S130 can be interchanged, 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) 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.
(2) the infrared high reflection particle ITO for adding 90g passes through ultrasound and makes infrared high reflection particle by way of stirring
It is uniformly dispersed to obtain mixed liquor.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 200r/min, ultrasonic disperse and stirring
Time is 60min.
(3) 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.
(4) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in the heat-insulating and energy-saving composite granule of containing graphene, which is formed, has nucleocapsid knot
The core-shell particles of structure, graphene form bridge joint between core-shell particles.The metal shell of formation with a thickness of 2nm；It is infrared high anti-
The mass ratio for penetrating particle, metal shell and graphene is 90:5:5.
Embodiment 2
(1) 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.
(2) the infrared high reflection particle ATO for adding 80g passes through ultrasound and makes infrared high reflection particle by way of stirring
It is uniformly dispersed to obtain mixed liquor.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 2000r/min, ultrasonic disperse and stirring
Time be 90min.
(3) 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.
(4) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in the heat-insulating and energy-saving composite granule of containing graphene, which is formed, has nucleocapsid knot
The core-shell particles of structure, graphene form bridge joint between core-shell particles.The metal shell of formation with a thickness of 50nm；It is infrared high anti-
The mass ratio for penetrating particle, metal shell and graphene is 80:10:10.
Embodiment 3
(1) 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.
(2) the infrared high reflection particle FTO for adding 70g passes through ultrasound and makes infrared high reflection particle by way of stirring
It is uniformly dispersed to obtain mixed liquor.The power of ultrasonic disperse is 20Hz, and the revolving speed of stirring is 200r/min, ultrasonic disperse and stirring
Time is 120min.
(3) 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.
(4) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in the heat-insulating and energy-saving composite granule of containing graphene, which is formed, has nucleocapsid knot
The core-shell particles of structure, graphene form bridge joint between core-shell particles.The metal shell of formation with a thickness of 5nm；It is infrared high anti-
The mass ratio for penetrating particle, metal shell and graphene is 70:20:10.
Embodiment 4
(1) 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.
(2) the infrared high reflection particle AZO for adding 88g passes through ultrasound and makes infrared high reflection particle by way of stirring
It is uniformly dispersed to obtain mixed liquor.The power of ultrasonic disperse is 50Hz, and the revolving speed of stirring is 2000r/min, ultrasonic disperse and stirring
Time be 10min.
(3) 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.
(4) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in the heat-insulating and energy-saving composite granule of containing graphene, which is formed, has nucleocapsid knot
The core-shell particles of structure, graphene form bridge joint between core-shell particles.The metal shell of formation with a thickness of 100nm；Infrared height
The mass ratio of reflection grain, metal shell and graphene is 88:10:2.
Embodiment 5
(1) 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.
(2) the infrared high reflection particle AGO for adding 98g passes through ultrasound and makes infrared high reflection particle by way of stirring
It is uniformly dispersed to obtain mixed liquor.The power of ultrasonic disperse is 30Hz, and the revolving speed of stirring is 1000r/min, ultrasonic disperse and stirring
Time be 120min.
(3) 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.
(4) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in the heat-insulating and energy-saving composite granule of containing graphene, which is formed, has nucleocapsid knot
The core-shell particles of structure, graphene form bridge joint between core-shell particles.The metal shell of formation with a thickness of 1nm；It is infrared high anti-
The mass ratio for penetrating particle, metal shell and graphene is 98:1:1.
Embodiment 6
(1) CuCl of 5L is weighed2Solution, wherein CuCl2Concentration be 0.05mol/L；The infrared height of 90g is added thereto
Reflection grain ITO passes through ultrasound and makes infrared high reflection particle be uniformly dispersed to obtain mixed liquor by way of stirring.Ultrasonic disperse
Power is 30Hz, and the revolving speed of stirring is 1000r/min, and the time of ultrasonic disperse and stirring is 60min.
(2) 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.
(3) reaction solution is centrifuged, washed and is dried to obtain the heat-insulating and energy-saving composite granule of containing graphene.It is above-mentioned
The surface that metal shell is coated on infrared high reflection particle in heat-insulating and energy-saving composite granule forms the nucleocapsid grain with core-shell structure
Son.The metal shell of formation with a thickness of 10nm；The mass ratio of infrared high reflection particle and metal shell is 9:1.
Heat-insulating and energy-saving is prepared in the heat-insulating and energy-saving composite granule of containing graphene prepared by 1~embodiment of embodiment 6
Composite coating.Weigh respectively 40 parts of acrylic resin, 40 parts of solvent, 10 parts of containing graphene heat-insulating and energy-saving composite granule
And 10 parts auxiliary agent be uniformly mixed obtain heat-insulating and energy-saving composite mortar；Again by heat-insulating and energy-saving composite mortar in PET transparent substrate
It is scratched, and dry 5min obtains heat-insulating and energy-saving 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.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Coating layer thickness | 3μm | 4μm | 5μm | 3μm | 4.5μm | 3μm |
| Visible light transmittance | 66% | 63% | 57% | 68% | 60% | 70% |
| Infrared light transmission | 8% | 7% | 5% | 10% | 6% | 23% |
| Ultraviolet isolating rate | 99% | 99% | 99% | 99% | 99% | 95% |
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 (10)
1. a kind of heat-insulating and energy-saving composite granule 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 infrared high reflection particle and metal, and the metallic cover is described infrared
High reflection particle surface forms metal shell, and the mass ratio of the infrared high reflection particle, the metal and the graphene is
70~98:1~20:1~10.
2. the heat-insulating and energy-saving composite granule of containing graphene according to claim 1, which is characterized in that the infrared high reflection
The material of particle is selected from ITO, ATO, FTO, AZO, AGO, TiO2, BiOCl, at least one of potassium hexatitanate and wolframic acid caesium.
3. the heat-insulating and energy-saving composite granule of containing graphene according to claim 1, which is characterized in that the infrared high reflection
Particle is spheric granules；The partial size of the infrared high reflection particle is 10nm~1000nm.
4. the heat-insulating and energy-saving composite granule 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.
5. the heat-insulating and energy-saving composite granule of containing graphene according to claim 1, which is characterized in that the metal shell
With a thickness of 1nm~100nm.
6. the heat-insulating and energy-saving composite granule 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。
7. the heat-insulating and energy-saving composite granule of the described in any item containing graphenes of claim 1~6 in heat-insulating and energy-saving composite mortar and
Application in heat-insulating and energy-saving composite film-stuck.
8. the preparation method of the heat-insulating and energy-saving composite granule of the described in any item containing graphenes of claim 1~6, feature exist
In, comprising the following steps:
It disperses graphene in metal salt solution；
It again disperses infrared high reflection 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 the infrared high reflection particle surface formation metal shell；
The reaction solution is separated by solid-liquid separation to obtain the heat-insulating and energy-saving composite granule of containing graphene.
9. the preparation method of the heat-insulating and energy-saving composite granule of containing graphene according to claim 8, 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.
10. the preparation method of the heat-insulating and energy-saving composite granule of containing graphene according to claim 8, which is characterized in that institute
It states pH adjusting agent and 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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