CN107461948A - A kind of solar selectively absorbing coating, its preparation method and photothermal conversion device - Google Patents
A kind of solar selectively absorbing coating, its preparation method and photothermal conversion device Download PDFInfo
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- CN107461948A CN107461948A CN201710656018.0A CN201710656018A CN107461948A CN 107461948 A CN107461948 A CN 107461948A CN 201710656018 A CN201710656018 A CN 201710656018A CN 107461948 A CN107461948 A CN 107461948A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Abstract
The invention provides a kind of solar selectively absorbing coating, its preparation method and photothermal conversion device, preparation method comprises the following steps：(1) infrared reflecting layer is prepared on matrix；(2) spin coating liquid is spun to the infrared external reflection layer surface, be absorbed layer；Wherein, the spin coating liquid is mainly mixed to get by polyvinyl alcohol water solution and/or phenolic resin ethanol solution and grapheme material；(3) anti-reflection layer is prepared on the absorbed layer, obtains the solar selectively absorbing coating.In the solar selectively absorbing coating that the preparation method obtains the adhesive force of grapheme material layer significantly improve, the adhesion between each layer it is strong, preparation technology is simple, it is easily controllable, rate of film build is fast, dense uniform is good, low to the absorptivity height and emissivity of solar energy, and heat endurance is good, heat transfer efficiency is high, suitable large-scale application.
Description
Technical field
The invention belongs to solar selectively absorbing coating technical field, be related to a kind of solar selectively absorbing coating and
Its preparation method and application, more particularly to the solar selectively absorbing coating of a kind of high-absorbility, low-launch-rate, its preparation side
Method and photothermal conversion device.
Background technology
With the shortage of traditional fossil energy, the getting worse of environmental pollution and greenhouse effects, people are to clean energy resource
Demand is more and more urgent.Solar energy rich reserves, clean environment firendly, it is as new green power just increasingly by the weight of people
Depending on.
In world today's energy consumption structure, heat energy is main and most common form.Using photothermal conversion technology,
Solar radiant energy is converted into heat energy, for industrial production and daily life, for promoting the sustainable of human society
Develop significant.
The key device for realizing solar energy thermal transition is solar thermal collector, and the core of solar thermal collector is the sun
Can coating for selective absorption.High-quality solar selectively absorbing coating, photothermal conversion efficiency can be effectively improved, to greatest extent
Utilize solar energy, just as people research focus.
The solar radiation that earth surface receives is mainly distributed on 300nm-2500nm or so SPECTRAL REGION, i.e., in visible ray
Area and near-infrared region.This portion of energy adds part ultraviolet region energy, accounts for the 98% of total solar radiation energy.Solar energy selects
Property absorber coatings must are fulfilled for two conditions, i.e.,：(1) coating material will have higher absorptivity α in solar spectrum；(2) apply
Layer material has relatively low emissivity ε in itself radiated wavelength range.At present, provided in China's solar water heater standard, too
The absorptivity α ＞ 0.9, emissivity ε ＜ 0.1 of positive energy coating for selective absorption.
Researcher is according to effective media theory, it is proposed that a variety of solar selectively absorbing coating types, such as interference of light
Type coating, multilayer sequential model coating, Intrinsic Gettering coating, cermet composite coating, optical trap coating etc..It is mostly several classes of
The coating of type, be scattered here and there in medium many metallics, and in absorbed layer, from top to bottom, the content of metallic gradually decreases.Too
Sunlight produces multiple reflections and scattering in the presence of metallic, absorbs solar radiant energy.Using this photothermal conversion principle
Solar selectively absorbing coating, its absorbed layer forms by two layers mostly, i.e., positioned at lower floor high metal absorbed layer and be located at
The low metal absorbed layer on upper strata.Such as the refractory metal ceramic solar coating for selective absorption that CN 103528251A are proposed, inhale
Layer is received by silver-colored aluminium or silver-colored titanium alloy particle and Al2O3It is combined, is absorbed in structure by the thickness high metal different with tenor
Layer and low metal absorbed layer are formed；One kind that CN 102689467A are proposed has Si3N4With the double ceramic structure high temperature solars of AlN
Coating for selective absorption, its absorbed layer include two sublayer structures, are Si3N4And AlN film；The one of CN 203063207U propositions
Kind high temperature solar selectively absorbing coating, for its absorbed layer by two layers, high metal fill factor, curve factor absorbed layer is the first Ti-AlN
Film, low metal fill factor, curve factor absorbed layer are the 2nd Ti-AlN films.
The solar selectively absorbing coating of said structure, complicated, each layer metallic content requirement of absorbed layer is tight
Lattice, operating condition requires high in preparation process, limits the production and application of coating.
CN 106556173A disclose a kind of graphene solar absorption agent applied to solar water heater, by medium
Water, pH adjusting agent, nanometer powder and dispersant are formulated；CN 106524525A disclose one kind and are applied to solar water
The carbon black of device-graphene nano solar absorption agent, is formulated by WATER AS FLOW MEDIUM, pH adjusting agent, nanometer powder and dispersant.But
Be, above-mentioned solar absorption agent because the thermal conductivity factor of graphene is high, its radiate it is very fast, to the utilization ratio of solar energy not
It is high.
Therefore, exploitation is a kind of simple in construction, photo-thermal conversion efficiency is high, the easily operated new type solar energy selection of preparation technology
Property absorber coatings are imperative.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of solar selectively absorbing coating,
Its preparation method and photothermal conversion device, the adhesive force of grapheme material layer significantly carries in the solar selectively absorbing coating
Height, the adhesion between each layer is strong, and rate of film build is fast, and dense uniform is good, easily controllable, high to the absorptivity of solar energy and send out
It is low to penetrate rate, heat endurance is good, and heat transfer efficiency is high, suitable large-scale application.
High-absorbility of the present invention, the solar selectively absorbing coating of low-launch-rate refer to the solar energy selection
Property absorber coatings absorptivity be more than 0.94, emissivity be less than 0.08.
To use following technical scheme up to this purpose, the present invention：
An object of the present invention is to provide a kind of preparation method of solar selectively absorbing coating, the preparation side
Method comprises the following steps：
(1) infrared reflecting layer is prepared on matrix；
(2) spin coating liquid is spun to the infrared external reflection layer surface, be absorbed layer；Wherein, the spin coating liquid mainly by
Polyvinyl alcohol water solution and/or phenolic resin ethanol solution and grapheme material are mixed to get；
(3) anti-reflection layer is prepared on the absorbed layer, obtains the solar selectively absorbing coating.
Solar selectively absorbing coating of the present invention includes infrared reflecting layer, absorbed layer and anti-reflection successively from the bottom to top
Layer, and the absorbed layer is grapheme material layer prepared by spin-coating method.Polyvinyl alcohol water solution and/or phenolic aldehyde in the spin-coating method
The selection of resin ethanol solution is most important, is replaced with other materials, then the adhesive force of grapheme material layer can be caused to become
It is weak, and influence the combination between grapheme material layer and infrared reflecting layer and anti-reflection layer.
The material of step (1) described matrix is selected from glass material or metal material, preferably sheet glass, glass tube, steel pipe,
Any one in steel plate, aluminium sheet or aluminum pipe.
Preferably, step (1) first cleans matrix, then infrared reflecting layer is prepared on matrix, and the cleaning matrix includes：Will
Matrix is cleaned by ultrasonic in acetone soln, uses deionized water rinsing；Matrix is put into absolute ethyl alcohol again and is cleaned by ultrasonic, spend from
Sub- water rinses；Finally matrix is put into absolute ethyl alcohol, takes out, uses N2Drying.
Step (1) prepares infrared reflecting layer, the direct current or radio frequency using direct current or radio-frequency magnetron sputter method on matrix
Magnetron sputtering method includes：Using high pure metal as target, using argon gas as sputter gas, by control sputtering voltage, sputtering current and
Sputtering time, obtain infrared reflecting layer.
Unless otherwise specified, the purity each means the purity of weight/mass percentage composition to the present invention.
The high pure metal refers to that purity is more than 99% (such as 99.1%, 99.3%, 99.5%, 99.7% or 99.9%
Deng) metal.
Infrared reflecting layer is prepared on matrix using direct current or radio-frequency magnetron sputter method to have the following advantages that：Using above-mentioned side
Infrared reflecting layer prepared by method, can be such that matrix is combined with infrared reflecting layer firm, coating quality is good, and makes infrared reflecting layer and stone
Good combination is formed between black alkene material layer, prevents coming off for grapheme material layer.
Preferably, the high pure metal is high purity copper or high purity silver.
Preferably, the thickness of step (1) described infrared reflecting layer is 40-300nm, as 45nm, 50nm, 80nm, 100nm,
130nm, 150nm, 180nm, 200nm, 230nm, 250nm or 280nm etc..Grapheme material in step (2) the spin coating liquid
Concentration is 0.5-10g/L, such as 0.6g/L, 0.8g/L, 1.0g/L, 2.0g/L, 3.0g/L, 5.0g/L, 7.0g/L or 9.0g/L,
The grapheme material in graphene, graphene oxide or Graphene derivative any one or at least two group
Close, typical but non-limiting combination such as graphene and graphene oxide, graphene and Graphene derivative, graphene, oxidation
The graphene that graphene and Graphene derivative, preferably graphene, more preferably pyrolysis method are prepared.The stone
Black alkene is alternatively graphite and is prepared through mechanical stripping method.Specifically refer to：Graphene alliance standard T/CGIA 001-2017
" term, definition and the code name of grapheme material ".
Preferably, step (2) first by grapheme material be distributed in ethanol again with polyvinyl alcohol water solution and/or phenolic aldehyde tree
Fat ethanol solution mixes.
Preferably, step (2) described polyvinyl alcohol water solution is 0.1 by the mass ratio of polyvinyl alcohol and water:100-10:
100 prepare, and such as 0.5:100、0.8:100、1:100、3:100、5:100、7:100、8:100 or 9:100 etc..
Preferably, step (2) the phenolic resin ethanol solution is 100 by the mass ratio of phenolic resin and ethanol:10-
100:400 prepare, and such as 100:15、100:20、100:30、100:40、100:50、100:60、100:70、100:80、100:90、
100:100、100:150、100:200、100:250、100:300、100:350 or 100:380 etc..
The concentration of step (2) polyvinyl alcohol water solution and/or phenolic resin ethanol solution is favourable in particular range
In the adhesive force for improving grapheme material layer.
Preferably, spin coating liquid is spun to infrared external reflection layer surface by step (2) using sol evenning machine.
Preferably, the spin coating rotating speed of the sol evenning machine is 450-5000r/min, such as 500r/min, 600r/min, 800r/
min、1000r/min、1500r/min、1800r/min、2000r/min、2300r/min、2500r/min、2800r/min、
3500r/min, 4000r/min or 4500r/min etc..
Preferably, the spin coating time of the sol evenning machine is 20-60s, such as 25s, 30s, 35s, 45s, 55s or 58s.
Preferably, the number of step (2) described spin coating is 1-10 times, such as 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9
It is inferior.
Preferably, the interval time of each spin coating is 2-60min, as 3min, 5min, 10min, 20min, 30min,
40min, 45min, 55min or 58min etc..
Preferably, the spin coating liquid measure of each spin coating is 0.02-0.2mL, as 0.05mL, 0.08mL, 0.10mL, 0.13mL,
0.15mL or 0.18mL etc..
In spin-coating method operating process, between spin coating machine speed, spin coating time, spin coating liquid measure, spin coating number and each spin coating
Had a major impact every to grapheme material thickness degree and quality.Each technological parameter within the above range, the matter of grapheme material layer
Measure optimal.
Preferably, the thickness of step (2) described absorbed layer is 30-300nm, as 35nm, 40nm, 50nm, 80nm, 100nm,
120nm, 150nm, 180nm, 210nm, 250nm, 280nm or 290nm etc..
Step (3) described anti-reflection layer is SiO2Layer, the SiO2Layer is prepared using direct current or radio-frequency magnetron sputter method, described
Direct current or radio-frequency magnetron sputter method, which prepare anti-reflection layer, to be included：Using high-purity Si as target, argon gas is sputter gas, and oxygen is reaction gas
Body, by adjusting gas flow, sputtering voltage, electric current and sputtering time, obtain SiO2Anti-reflection layer；Or,
With high-purity Si O2For target, argon gas is sputter gas, by adjusting sputtering voltage, electric current and sputtering time, is obtained
SiO2Anti-reflection layer.
High-purity Si and the high-purity Si O2Refer to respectively purity not less than 99% (such as 99.1%, 99.3%, 99.5%,
99.7% or 99.9% etc.) Si and SiO2。
Anti-reflection layer is prepared using the above method to have the following advantages that：Using anti-reflection layer prepared by the above method and graphene material
Contacted closely between the bed of material, adhesion is strong, difficult for drop-off, and anti-reflection layer film forming is uniform, and quality is preferable.
Preferably, the SiO2Layer thickness be 30-120nm, as 35nm, 40nm, 50nm, 60nm, 80nm, 90nm,
100nm or 110nm etc..
As preferable technical scheme, the preparation method of the solar selectively absorbing coating comprises the following steps：
(1) using high-purity Cu or high-purity Ag as target, using argon gas as sputter gas, by controlling sputtering voltage, sputtering current
And sputtering time, it is 40-300nm infrared reflecting layers to obtain thickness on matrix after cleaning；
(2) grapheme material is added in polyvinyl alcohol water solution and/or phenolic resin ethanol solution, polyvinyl alcohol water
Solution is 0.1 by the mass ratio of polyvinyl alcohol and water:100-10:100 prepare, and phenolic resin ethanol solution presses phenolic resin and second
The mass ratio of alcohol is 100:10-100:400 prepare, and obtain spin coating liquid, are spun to spin coating liquid using sol evenning machine described infrared anti-
Layer surface is penetrated, the spin coating rotating speed of sol evenning machine is 450-5000r/min, and spin coating time 20-60s, the number of the spin coating is 1-
10 times, the interval time of each spin coating is 2-60min, and the spin coating liquid measure of each spin coating is 0.02-0.2mL, and it is 30- to obtain thickness
300nm grapheme material layer, i.e. absorbed layer；
(3) using high-purity Si as target, argon gas is sputter gas, and oxygen is reacting gas, passes through adjusting gas flow, sputtering
Voltage, electric current and sputtering time, the thickness obtained positioned at absorption layer surface are 30-120nm SiO2Anti-reflection layer；Or,
With high-purity Si O2For target, argon gas is sputter gas, by adjusting sputtering voltage, electric current and sputtering time, is obtained
The SiO that thickness positioned at absorption layer surface is 30-120nm2Anti-reflection layer, so as to obtain the solar selectively absorbing coating.
The second object of the present invention is that providing the solar selectively that preparation method obtains a kind of as described above absorbs painting
Layer, the solar selectively absorbing coating include infrared reflecting layer, absorbed layer and anti-reflection layer, the absorption successively from the bottom to top
Layer is grapheme material layer.
The solar selectively absorbing coating is high to the absorptivity of solar energy, and emissivity is low.Because its absorbed layer uses
Grapheme material, and grapheme material heat absorption capacity is strong, thermal conductivity factor is high, and specific surface area is big, and mechanical strength and stability are good, makes
It is good to obtain the heat endurance of the solar selectively absorbing coating, heat transfer efficiency is high.Cooperated between three layers so that it is described too
The absorptivity of positive energy coating for selective absorption is more than 0.94, and emissivity is less than 0.08.
The thickness of the infrared reflecting layer is 40-300nm, as 45nm, 50nm, 80nm, 100nm, 130nm, 150nm,
180nm, 200nm, 230nm, 250nm or 280nm etc., the thickness of the absorbed layer is 30-300nm, as 35nm, 40nm, 50nm,
80nm, 100nm, 120nm, 150nm, 180nm, 210nm, 250nm, 280nm or 290nm etc., the thickness of the anti-reflection layer is 30-
120nm, such as 35nm, 40nm, 50nm, 60nm, 80nm, 90nm, 100nm or 110nm.
The thickness of the infrared reflecting layer, absorbed layer and anti-reflection layer has the following advantages that within the above range：Above-mentioned thickness
In the range of infrared reflecting layer, grapheme material layer and anti-reflection layer it is higher to the selective absorbing rate of sunshine, emissivity is lower.
In addition, preparing the infrared reflecting layer of above-mentioned thickness using direct current or radio-frequency magnetron sputter method, prepared using above-mentioned spin-coating method above-mentioned
The absorbed layer of thickness, and use direct current or radio-frequency magnetron sputter method to prepare the anti-reflection layer of above-mentioned thickness, obtained solar energy choosing
Selecting property absorber coatings, its absorptivity highest, can reach 0.986, and emissivity is minimum, can as little as 0.053.
The grapheme material layer is including any one in graphene, graphene oxide or Graphene derivative or at least
Two kinds of combination, typical but non-limiting combination such as graphene and graphene oxide, graphene and Graphene derivative, graphite
The graphite that alkene, graphene oxide and Graphene derivative, preferably graphene, more preferably pyrolysis method are prepared
Alkene.The graphene is alternatively the product that graphite obtains through mechanical stripping.
Preferably, the infrared reflecting layer is selected from metal level, preferably Cu layers and/or Ag layers.
Preferably, the anti-reflection layer is selected from SiO2Layer.
The third object of the present invention is to provide a kind of application of solar selectively absorbing coating as described above, i.e., and one
Kind photothermal conversion device, the photothermal conversion device bag solar selectively absorbing coating as described above.The photothermal deformation
Device such as solar thermal collector.
Number range of the present invention not only includes the above-mentioned point value enumerated, in addition to the above-mentioned numerical value not included
Arbitrary point value between scope, as space is limited and the consideration for simplicity, no longer scope described in exclusive list of the invention include
Specific point value.
Compared with prior art, beneficial effects of the present invention are：
Solar selectively absorbing coating provided by the invention prepares absorbed layer using spin-coating method, and technique is simple, is easy to control
System, film forming speed is fast, and selects (polyvinyl alcohol water solution and/or phenolic resin ethanol solution) by specific material, obtains
Grapheme material layer compactness it is good, grapheme material is evenly distributed, and adhesive force is strong, and its adhesive force is one-level；
Solar selectively absorbing coating provided by the invention prepares infrared reflecting layer and anti-reflection layer using magnetron sputtering method,
The absorbed layer that can be prepared with spin-coating method cooperates, the combination of obtained infrared reflecting layer and anti-reflection layer and grapheme material layer
Power is strong, difficult for drop-off, and adhesive force is one-level；
The absorptivity of solar selectively absorbing coating provided by the invention is more than 0.94, and emissivity is less than 0.08, photo-thermal
High conversion efficiency, mechanical strength, stablize, and weatherability is strong；
Solar selectively absorbing coating provided by the invention is suitable for solar energy optical-thermal conversion art, and it can be more preferable
Ground utilizes solar energy.
Brief description of the drawings
Fig. 1 is the structural representation for the grapheme material solar selectively absorbing coating that one embodiment of the present invention provides
Figure.
Wherein：1, infrared reflecting layer；2, absorbed layer；3, anti-reflection layer；4, matrix.
Fig. 2 is the preparation technology for the grapheme material solar selectively absorbing coating that one embodiment of the present invention provides
Flow chart.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
A kind of grapheme material solar selectively absorbing coating, as shown in figure 1, including infrared external reflection successively from the bottom to top
Layer 1, absorbed layer 2 and anti-reflection layer 3, the absorbed layer 2 are grapheme material layer, and the grapheme material solar selectively absorbs
Coating is located on matrix 4.
The grapheme material layer is including any one in graphene, graphene oxide or Graphene derivative or at least
Two kinds of combination, typical but non-limiting combination such as graphene and graphene oxide, graphene and Graphene derivative, graphite
The graphite that alkene, graphene oxide and Graphene derivative, preferably graphene, more preferably pyrolysis method are prepared
Alkene.
The preparation method of the grapheme material solar selectively absorbing coating, as shown in Fig. 2 comprising the following steps：
(1) matrix is cleaned；
(2) infrared reflecting layer is prepared：Using high-purity Cu or high-purity Ag as target, using argon gas as sputter gas, splashed by control
Radio pressure, sputtering current and sputtering time, infrared reflecting layer is obtained on matrix after cleaning；
(3) grapheme material layer is prepared on infrared reflecting layer：By grapheme material be added to polyvinyl alcohol water solution and/
Or in phenolic resin ethanol solution, spin coating liquid is obtained, spin coating liquid is spun to the infrared external reflection layer surface using sol evenning machine, obtained
To grapheme material layer, i.e. absorbed layer；
(4) anti-reflection layer is prepared on absorbed layer：Using high-purity Si as target, argon gas is sputter gas, and oxygen is reacting gas,
By adjusting gas flow, sputtering voltage, electric current and sputtering time, SiO is obtained2Anti-reflection layer；Or,
With high-purity Si O2For target, argon gas is sputter gas, by adjusting sputtering voltage, electric current and sputtering time, is obtained
SiO2Anti-reflection layer；And then obtain the solar selectively absorbing coating.
Embodiment 1-5 uses the graphene arrived prepared by pyrolysis method, and it is " fine that preparation process may be referred to CN104724699A
Embodiment 1 in the method that dimension element prepares biomass graphene for raw material ".
Embodiment 1
A kind of high-absorbility graphene solar selectively absorbing coating, from down to up successively by infrared reflecting layer, absorption
Layer and anti-reflection layer are formed；Infrared reflecting layer is Cu, thickness 160nm；Absorbed layer is graphene, thickness 200nm；Anti-reflection layer is
SiO2, thickness 100nm.
The high-absorbility graphene solar selectively absorbing coating making step is as follows：
Step 1：Infrared reflecting layer is prepared on matrix.
The cleaning process of matrix is as follows：(1) matrix is cleaned by ultrasonic 10min in acetone soln, uses deionized water rinsing；
(2) matrix is put into absolute ethyl alcohol and is cleaned by ultrasonic 10min, use deionized water rinsing；(3) matrix is put into absolute ethyl alcohol,
Take out, use N2Dry up standby.
Infrared reflecting layer is prepared using direct current magnetron sputtering process：Using high-purity Cu as target, with argon gas (Ar) for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 4 × 10 before sputtering-3Pa, adjustment sputtering distance is 130mm, is passed through Ar, adjusts sputtering pressure
For 0.4Pa, regulation sputtering voltage is 380V, sputtering current 8A, prepares the Cu films that thickness is 160nm.
Step 2：Absorbed layer is prepared on infrared reflecting layer.
Graphene absorbed layer is prepared using spin-coating method：Using graphene as raw material, poly-vinyl alcohol solution is adhesive, and ethanol is
Dispersant, prepared using sol evenning machine.Polyvinyl alcohol is added in appropriate amount of deionized water, 20min, poly- second are stirred after being heated to 60 DEG C
Filtered after enol dissolving, obtain the poly-vinyl alcohol solution that polyvinyl alcohol concentration is 4g/L；Added in poly-vinyl alcohol solution appropriate
Ethanol and graphene, stir, and obtain the graphene poly-vinyl alcohol solution that graphene concentration is 2g/L；The spin coating of sol evenning machine turns
Speed is 3000r/min, and spin coating time 20s, the number of the spin coating is 5 times, and the interval time of each spin coating is 60min, often
The spin coating liquid measure of secondary spin coating is 0.2mL, obtains the absorbed layer that thickness is 200nm.
Step 3：Anti-reflection layer is prepared on absorbed layer.
Anti-reflection layer is prepared using radio-frequency magnetron sputter method：With high-purity Si O2For target, argon gas (Ar) is prepared for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 4 × 10 before sputtering-3Pa, adjustment sputtering distance is 140mm, is passed through Ar, adjusts sputtering pressure
For 0.4Pa；Regulation sputtering voltage is 600V, sputtering current 8A, and the SiO that thickness is 100nm is made2Anti-reflection layer.
Graphene solar selectively absorbing coating prepared by this example, under the conditions of air quality factors A M1.5, absorb
Rate is 0.974, emissivity 0.068；And graphene layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
In addition, the concentration of graphene in step 2 is adjusted to 0.5g/L, the selection of its graphene solar energy finally given
The performance of property absorber coatings is identical with the performance of graphene solar selectively absorbing coating described in embodiment 1.
Embodiment 2
A kind of high-absorbility graphene solar selectively absorbing coating, from down to up successively by infrared reflecting layer, absorption
Layer and anti-reflection layer are formed；Infrared reflecting layer is Cu, thickness 100nm；Absorbed layer is graphene, thickness 150nm；Anti-reflection layer is
SiO2, thickness 110nm.
The making step of the high-absorbility graphene solar selectively absorbing coating is as follows：
Step 1：Infrared reflecting layer is prepared on matrix.
The cleaning process of matrix is as follows：(1) matrix is cleaned by ultrasonic 12min in acetone soln, uses deionized water rinsing；
(2) matrix is put into absolute ethyl alcohol and is cleaned by ultrasonic 15min, use deionized water rinsing；(3) matrix is put into absolute ethyl alcohol,
Take out, use N2Dry up standby.
Infrared reflecting layer is prepared using direct current magnetron sputtering process：Using high-purity Cu as target, with argon gas (Ar) for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 4.5 × 10 before sputtering-3Pa, adjustment sputtering distance is 140mm, is passed through Ar, regulation sputtering gas
Press as 0.5Pa；Regulation sputtering voltage is 400V, sputtering current 10A, prepares the Cu films that thickness is 100nm.
Step 2：Absorbed layer is prepared on infrared reflecting layer.
Graphene absorbed layer is prepared using spin-coating method：Using graphene as raw material, poly-vinyl alcohol solution is adhesive, and ethanol is
Dispersant, prepared using sol evenning machine.Polyvinyl alcohol is added in appropriate amount of deionized water, 25min, poly- second are stirred after being heated to 50 DEG C
Filtered after enol dissolving, obtain the poly-vinyl alcohol solution that polyvinyl alcohol concentration is 6g/L；Added in poly-vinyl alcohol solution appropriate
Ethanol and graphene, stir, and obtain the graphene poly-vinyl alcohol solution that graphene concentration is 3g/L；The spin coating of sol evenning machine turns
Speed is 5000r/min, and spin coating time 60s, the number of the spin coating is 3 times, and the interval time of each spin coating is 50min, often
The spin coating liquid measure of secondary spin coating is 0.1mL, obtains the absorbed layer that thickness is 150nm.
Step 3：Anti-reflection layer is prepared on absorbed layer.
Anti-reflection layer is prepared using direct current magnetron sputtering process：Using high-purity Si as target, argon gas (Ar) is sputter gas, oxygen
(O2) prepared for reacting gas.Vacuum chamber is taken out to base vacuum in advance to 5 × 10 before sputtering-3Pa, adjustment sputtering distance is 145mm,
It is passed through Ar and O2, O2Flow be 30sccm, Ar and O2Flow-rate ratio be 3, regulation sputtering pressure is 0.35Pa.Regulation sputtering electricity
Press as 700V, sputtering current 9A, the SiO that obtained thickness is 80nm2Anti-reflection layer.
Graphene solar selectively absorbing coating prepared by this example, under the conditions of air quality factors A M1.5, absorb
Rate is 0.965, emissivity 0.064；And graphene layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
Embodiment 3
A kind of high-absorbility graphene solar selectively absorbing coating, from the bottom to top successively by infrared reflecting layer, absorption
Layer and anti-reflection layer are formed；Infrared reflecting layer is Ag, thickness 70nm；Absorbed layer is graphene, thickness 250nm；Anti-reflection layer is
SiO2, thickness 60nm.
The making step of the high-absorbility graphene solar selectively absorbing coating is as follows：
Step 1：Infrared reflecting layer is prepared on matrix.
The cleaning process of matrix is as follows：(1) matrix is cleaned by ultrasonic 15min in acetone soln, uses deionized water rinsing；
(2) matrix is put into absolute ethyl alcohol and is cleaned by ultrasonic 15min, use deionized water rinsing；(3) matrix is put into absolute ethyl alcohol,
Take out, use N2Dry up standby.
Infrared reflecting layer is prepared using direct current magnetron sputtering process：Using high-purity Ag as target, with argon gas (Ar) for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 3.5 × 10 before sputtering-3Pa, adjustment sputtering distance is 130mm, is passed through Ar, regulation sputtering gas
Press as 0.35Pa.Regulation sputtering voltage is 430V, sputtering current 10A, prepares the Ag films that thickness is 70nm.
Step 2：Absorbed layer is prepared on infrared reflecting layer.
Graphene absorbed layer is prepared using spin-coating method：Using graphene as raw material, poly-vinyl alcohol solution is adhesive, and ethanol is
Dispersant, prepared using sol evenning machine.Polyvinyl alcohol is added in appropriate amount of deionized water, 25min, poly- second are stirred after being heated to 80 DEG C
Filtered after enol dissolving, obtain the poly-vinyl alcohol solution that polyvinyl alcohol concentration is 7g/L.Added in poly-vinyl alcohol solution appropriate
Ethanol and graphene, stir, and obtain the graphene poly-vinyl alcohol solution that graphene concentration is 4g/L；The spin coating of sol evenning machine turns
Speed is 4000r/min, and spin coating time 60s, the number of the spin coating is 6 times, and the interval time of each spin coating is 10min, often
The spin coating liquid measure of secondary spin coating is 0.2mL, obtains the absorbed layer that thickness is 250nm.
Step 3：Anti-reflection layer is prepared on absorbed layer.
Anti-reflection layer is prepared using radio-frequency magnetron sputter method：With high-purity Si O2For target, argon gas (Ar) is prepared for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 3.5 × 10 before sputtering-3Pa, adjustment sputtering distance is 130mm, is passed through Ar, regulation sputtering gas
Press as 0.35Pa.Regulation sputtering voltage is 700V, sputtering current 8A, and the SiO that thickness is 60nm is made2Anti-reflection layer.
Graphene solar selectively absorbing coating prepared by this example, under the conditions of air quality factors A M1.5, absorb
Rate is 0.982, emissivity 0.071；And graphene layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
Embodiment 4
A kind of high-absorbility graphene solar selectively absorbing coating, from the bottom to top successively by infrared reflecting layer, absorption
Layer and anti-reflection layer are formed；Infrared reflecting layer is Ag, thickness 40nm；Absorbed layer is graphene, thickness 300nm；Anti-reflection layer is
SiO2, thickness 30nm.
The making step of the high-absorbility graphene solar selectively absorbing coating is as follows：
Step 1：Infrared reflecting layer is prepared on matrix.
The cleaning process of matrix is as follows：(1) matrix is cleaned by ultrasonic 12min in acetone soln, uses deionized water rinsing；
(2) matrix is put into absolute ethyl alcohol and is cleaned by ultrasonic 10min, use deionized water rinsing；(3) matrix is put into absolute ethyl alcohol,
Take out, use N2Dry up standby.
Infrared reflecting layer is prepared using direct current magnetron sputtering process：Using high-purity Ag as target, with argon gas (Ar) for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 4.0 × 10 before sputtering-3Pa, adjustment sputtering distance is 140mm, is passed through Ar, regulation sputtering gas
Press as 0.35Pa.Regulation sputtering voltage is 400V, sputtering current 10A, prepares the Ag films that thickness is 40nm.
Step 2：Absorbed layer is prepared on infrared reflecting layer.
Graphene absorbed layer is prepared using spin-coating method：Using graphene as raw material, poly-vinyl alcohol solution is adhesive, and ethanol is
Dispersant, prepared using sol evenning machine.Polyvinyl alcohol is added in appropriate amount of deionized water, 25min, poly- second are stirred after being heated to 80 DEG C
Filtered after enol dissolving, obtain the poly-vinyl alcohol solution that polyvinyl alcohol concentration is 8g/L.Added in poly-vinyl alcohol solution appropriate
Ethanol and graphene, stir, and obtain the graphene poly-vinyl alcohol solution that graphene concentration is 10g/L；The spin coating of sol evenning machine
Rotating speed is 450r/min, and spin coating time 60s, the number of the spin coating is 10 times, and the interval time of each spin coating is 2min, often
The spin coating liquid measure of secondary spin coating is 0.02mL, obtains the absorbed layer that thickness is 300nm.
Step 3：Anti-reflection layer is prepared on absorbed layer.
Anti-reflection layer is prepared using radio-frequency magnetron sputter method：With high-purity Si O2For target, argon gas (Ar) is prepared for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 4.0 × 10 before sputtering-3Pa, adjustment sputtering distance is 150mm, is passed through Ar, regulation sputtering gas
Press as 0.35Pa.Regulation sputtering voltage is 650V, sputtering current 6A, and the SiO that thickness is 30nm is made2Anti-reflection layer.
Graphene solar selectively absorbing coating prepared by this example, under the conditions of air quality factors A M1.5, absorb
Rate is 0.986, emissivity 0.075；And graphene and Ag layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
In addition, the Ag layers in the solar selectively absorbing coating are replaced with into Cu layers, the graphene solar energy of preparation
Coating for selective absorption, under the conditions of air quality factors A M1.5, absorptivity 0.984, emissivity 0.077；And graphene
Layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
Embodiment 5
A kind of high-absorbility graphene solar selectively absorbing coating, from the bottom to top successively by infrared reflecting layer, absorption
Layer and anti-reflection layer are formed；Infrared reflecting layer is Ag, thickness 300nm；Absorbed layer is graphene, thickness 30nm；Anti-reflection layer is
SiO2, thickness 120nm.
The making step of the high-absorbility graphene solar selectively absorbing coating is as follows：
Step 1：Infrared reflecting layer is prepared on matrix.
The cleaning process of matrix is as follows：(1) matrix is cleaned by ultrasonic 15min in acetone soln, uses deionized water rinsing；
(2) matrix is put into absolute ethyl alcohol and is cleaned by ultrasonic 15min, use deionized water rinsing；(3) matrix is put into absolute ethyl alcohol,
Take out, use N2Dry up standby.
Infrared reflecting layer is prepared using direct current magnetron sputtering process：Using high-purity Ag as target, with argon gas (Ar) for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 3.5 × 10 before sputtering-3Pa, adjustment sputtering distance is 120mm, is passed through Ar, regulation sputtering gas
Press as 0.40Pa.Regulation sputtering voltage is 450V, sputtering current 10A, prepares the Ag films that thickness is 300nm.
Step 2：Absorbed layer is prepared on infrared reflecting layer.
Graphene absorbed layer is prepared using spin-coating method：Using graphene as raw material, poly-vinyl alcohol solution is adhesive, and ethanol is
Dispersant, prepared using sol evenning machine.Polyvinyl alcohol is added in appropriate amount of deionized water, 25min, poly- second are stirred after being heated to 80 DEG C
Filtered after enol dissolving, obtain the poly-vinyl alcohol solution that polyvinyl alcohol concentration is 5g/L.Added in poly-vinyl alcohol solution appropriate
Ethanol and graphene, stir, and obtain the graphene poly-vinyl alcohol solution that graphene concentration is 3g/L；The spin coating of sol evenning machine turns
Speed is 5000r/min, and spin coating time 20s, the number of the spin coating is 1 time, and the spin coating liquid measure of spin coating is 0.02mL, obtains thickness
Spend the absorbed layer for 30nm.
Step 3：Anti-reflection layer is prepared on absorbed layer.
Anti-reflection layer is prepared using radio-frequency magnetron sputter method：With high-purity Si O2For target, argon gas (Ar) is prepared for sputter gas.
Vacuum chamber is taken out to base vacuum in advance to 3.5 × 10 before sputtering-3Pa, adjustment sputtering distance is 130mm, is passed through Ar, regulation sputtering gas
Press as 0.35Pa.Regulation sputtering voltage is 700V, sputtering current 10A, and the SiO that thickness is 120nm is made2Anti-reflection layer.
Graphene solar selectively absorbing coating prepared by this example, under the conditions of air quality factors A M1.5, absorb
Rate is 0.945, emissivity 0.053；And graphene layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
In addition, the Ag layers in the solar selectively absorbing coating are replaced with into Cu layers, the graphene solar energy of preparation
Coating for selective absorption, under the conditions of air quality factors A M1.5, absorptivity 0.942, emissivity 0.058；And graphene
Layer and Cu layers and SiO2Adhesion between anti-reflection layer is respectively one-level.
Embodiment 1-5 during absorbed layer is prepared without using ethanol, directly by graphene dispersion to polyvinyl alcohol water
In solution, the solar selectively that the performance of obtained solar selectively absorbing coating obtains with corresponding embodiment respectively absorbs
The similar nature (difference of absorptivity and emissivity is within 2%) of coating, and graphene layer and Cu layers and SiO2Anti-reflection layer
Between adhesion be respectively one-level.
The concentration of polyvinyl alcohol water solution in embodiment 1-5 is replaced with to the arbitrary value in 1g/L-100g/L, remained to
To the graphene layer of excellent performance, and obtained solar selectively absorbing coating is inhaled under the conditions of air quality factors A M1.5
Yield is 0.945-0.984, emissivity 0.053-0.077；And graphene layer and Cu layers, Ag layers or SiO2Between anti-reflection layer
Adhesion is respectively one-level.
By the polyvinyl alcohol water solution in embodiment 1-5 replace with phenolic resin ethanol solution or polyvinyl alcohol water solution with
The mixed liquor of phenolic resin ethanol solution, obtained solar selectively absorbing coating under the conditions of air quality factors A M1.5,
Absorptivity is 0.950-0.986, emissivity 0.056-0.075；And graphene layer and Cu layers, Ag layers or SiO2Between anti-reflection layer
Adhesion be respectively one-level.
The graphene that pyrolysis method in embodiment 1-5 is prepared is replaced with into the stone that graphite prepared through mechanical stripping method
In black alkene, graphene oxide or Graphene derivative any one or at least two combination, if graphite is through mechanical stripping method
The graphene graphene and graphene oxide of preparation, the graphene and Graphene derivative that graphite is prepared through mechanical stripping method, stone
Graphene, graphene oxide and the Graphene derivative that ink is prepared through mechanical stripping method.Obtained solar selectively, which absorbs, to be applied
Layer is under the conditions of air quality factors A M1.5, absorptivity 0.945-0.980, emissivity 0.058-0.073；And graphene
Material layer and Cu layers, Ag layers or SiO2Adhesion between anti-reflection layer is respectively one-level.Graphene in embodiment 1-5 can be with
Replace with other grapheme materials in addition to above-mentioned material, the performance and embodiment of obtained solar selectively absorbing coating
The similar nature for the solar selectively absorbing coating that 1-5 is obtained.
Comparative example 1
Except the polyvinyl alcohol in step 2 is replaced with into phenolic resin in the manufacturing process of solar selectively absorbing coating,
Water is replaced with outside propyl alcohol, remaining is same as Example 3.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.975, emissivity 0.083；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Comparative example 2
Except the polyvinyl alcohol water solution in step 2 in the manufacturing process of solar selectively absorbing coating replace with it is organic
Outside silica gel stick, remaining is same as Example 3.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.972, emissivity 0.087；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Comparative example 3
In addition to graphene layer is prepared using spraying method, remaining is same as Example 3.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.964, emissivity 0.089；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Comparative example 4
In addition to using process for preparing graphenes by chemical vapour deposition layer, remaining is same as Example 3.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.973, emissivity 0.088；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Comparative example 5
In addition to one kind in using evaporation, chemical vapor deposition or plating prepares infrared anti-reflection layer, remaining and the phase of embodiment 3
Together.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.971, emissivity 0.081；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Comparative example 6
In addition to one kind in using evaporation, chemical vapor deposition or plating prepares anti-reflection layer, remaining is same as Example 3.
Through testing, under the conditions of air quality factors A M1.5, absorptivity 0.975, emissivity 0.084；Graphene layer
With Cu layers and SiO2Adhesion between anti-reflection layer is respectively two level.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.
Claims (10)
1. a kind of preparation method of solar selectively absorbing coating, it is characterised in that the preparation method comprises the following steps：
(1) infrared reflecting layer is prepared on matrix；
(2) spin coating liquid is spun to the infrared external reflection layer surface, be absorbed layer；Wherein, the spin coating liquid is mainly by poly- second
The enol aqueous solution and/or phenolic resin ethanol solution and grapheme material are mixed to get；
(3) anti-reflection layer is prepared on the absorbed layer, obtains the solar selectively absorbing coating.
2. preparation method according to claim 1, it is characterised in that the material of step (1) described matrix is selected from glass material
Any one in matter or metal material, preferably sheet glass, glass tube, steel pipe, steel plate, aluminium sheet or aluminum pipe；
Preferably, step (1) first cleans matrix, then infrared reflecting layer is prepared on matrix, and the cleaning matrix includes：By matrix
It is cleaned by ultrasonic in acetone soln, uses deionized water rinsing；Matrix is put into absolute ethyl alcohol again and is cleaned by ultrasonic, uses deionized water
Rinse；Finally matrix is put into absolute ethyl alcohol, takes out, uses N2Drying.
3. preparation method according to claim 1 or 2, it is characterised in that step (1) uses direct current or rf magnetron sputtering
Method prepares infrared reflecting layer on matrix, and the direct current or radio-frequency magnetron sputter method include：Using high pure metal as target, with argon gas
For sputter gas, by controlling sputtering voltage, sputtering current and sputtering time, infrared reflecting layer is obtained；
Preferably, the high pure metal is high purity copper or high purity silver；
Preferably, the thickness of step (1) described infrared reflecting layer is 40-300nm.
4. according to the preparation method described in one of claim 1-3, it is characterised in that graphene in step (2) the spin coating liquid
The concentration of material is 0.5-10g/L, the grapheme material appointing in graphene, graphene oxide or Graphene derivative
Anticipate a kind of or at least two combinations, preferably graphene, the graphene that more preferably pyrolysis method is prepared；
Preferably, step (2) first by grapheme material be distributed in ethanol again with polyvinyl alcohol water solution and/or phenolic resin second
Alcoholic solution mixes；
Preferably, step (2) described polyvinyl alcohol water solution is 0.1 by the mass ratio of polyvinyl alcohol and water:100-10:100 match somebody with somebody
System；
Preferably, step (2) the phenolic resin ethanol solution is 100 by the mass ratio of phenolic resin and ethanol:10-100:
400 prepare；
Preferably, spin coating liquid is spun to infrared external reflection layer surface by step (2) using sol evenning machine；
Preferably, the spin coating rotating speed of the sol evenning machine is 450-5000r/min；
Preferably, the spin coating time of the sol evenning machine is 20-60s；
Preferably, the number of step (2) described spin coating is 1-10 times；
Preferably, the interval time of each spin coating is 2-60min；
Preferably, the spin coating liquid measure of each spin coating is 0.02-0.2mL；
Preferably, the thickness of the absorbed layer is 30-300nm.
5. according to the preparation method described in one of claim 1-4, it is characterised in that step (3) described anti-reflection layer is SiO2Layer,
The SiO2Layer is prepared using direct current or radio-frequency magnetron sputter method, and the direct current or radio-frequency magnetron sputter method prepare anti-reflection layer bag
Include：Using high-purity Si as target, argon gas is sputter gas, and oxygen is reacting gas, passes through adjusting gas flow, sputtering voltage, electricity
Stream and sputtering time, obtain SiO2Anti-reflection layer；Or,
With high-purity Si O2For target, argon gas is sputter gas, by adjusting sputtering voltage, electric current and sputtering time, obtains SiO2Subtract
Anti- layer；
Preferably, the SiO2The thickness of layer is 30-120nm.
6. according to the preparation method described in one of claim 1-5, it is characterised in that the preparation method comprises the following steps：
(1) using high-purity Cu or high-purity Ag as target, using argon gas as sputter gas, by controlling sputtering voltage, sputtering current and splashing
Penetrate the time, it is 40-300nm infrared reflecting layers that thickness is obtained on matrix after cleaning；
(2) grapheme material is added in polyvinyl alcohol water solution and/or phenolic resin ethanol solution, polyvinyl alcohol water solution
It is 0.1 by the mass ratio of polyvinyl alcohol and water:100-10:100 prepare, and phenolic resin ethanol solution is by phenolic resin and ethanol
Mass ratio is 100:10-100:400 prepare, and obtain spin coating liquid, spin coating liquid is spun into the infrared reflecting layer using sol evenning machine
Surface, the spin coating rotating speed of sol evenning machine is 450-5000r/min, and spin coating time 20-60s, the number of the spin coating is 1-10 times,
The interval time of each spin coating is 2-60min, and the spin coating liquid measure of each spin coating is 0.02-0.2mL, and it is 30-300nm to obtain thickness
Grapheme material layer, i.e. absorbed layer；
(3) using high-purity Si as target, argon gas is sputter gas, and oxygen is reacting gas, passes through adjusting gas flow, sputtering electricity
Pressure, electric current and sputtering time, the thickness obtained positioned at absorption layer surface are 30-120nm SiO2Anti-reflection layer；Or,
With high-purity Si O2For target, argon gas is sputter gas, by adjusting sputtering voltage, electric current and sputtering time, is obtained positioned at suction
The thickness for receiving layer surface is 30-120nm SiO2Anti-reflection layer, so as to obtain the solar selectively absorbing coating.
7. the solar selectively absorbing coating that a kind of preparation method according to one of claim 1-6 is prepared, its
It is characterised by, the solar selectively absorbing coating includes infrared reflecting layer, absorbed layer and anti-reflection layer, institute successively from the bottom to top
It is grapheme material layer to state absorbed layer.
8. solar selectively absorbing coating according to claim 7, it is characterised in that the thickness of the infrared reflecting layer
For 40-300nm, the thickness of the absorbed layer is 30-300nm, and the thickness of the anti-reflection layer is 30-120nm.
9. the solar selectively absorbing coating according to claim 7 or 8, it is characterised in that the grapheme material layer
Combination including any one in graphene, graphene oxide or Graphene derivative or at least two, preferably graphene,
The graphene that more preferably pyrolysis method is prepared；
Preferably, the infrared reflecting layer is selected from metal level, preferably Cu layers and/or Ag layers；
Preferably, the anti-reflection layer is selected from SiO2Layer.
10. a kind of photothermal conversion device, the photothermal conversion device includes the solar selectively described in one of claim 7-9
Absorber coatings.
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Application publication date: 20171212 |