CN102176103A - Variable-emissivity variable-reflectivity electrochromic intelligent thermal control coating and preparation method thereof - Google Patents
Variable-emissivity variable-reflectivity electrochromic intelligent thermal control coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a variable-emissivity variable-reflectivity electrochromic intelligent thermal control coating and a preparation method thereof. In the method, a conductive macromolecule predoping control and multi-layer compound photoelectricity matching mode is adopted, thus the electrochromism initial voltage is effectively reduced, and the change range of the reflectivity and emissivity of an electrochromic active layer is improved. The manufactured electrochromic coating is driven by the direct current, the driving voltage is less than 2V, the reflectivity change is more than 0.4, and the emissivity change is more than 0.25; and the reflectivity change and emissivity change of the coating further meet the indexes after 100 times of positive-negative temperature exchange at 100 DEG C, thereby basically meeting the intelligent thermal control requirement of an aero spacecraft.
Description
Technical field
The present invention relates to a kind of change emissivity, reflectivity-variable electrochromic conducting macromolecule thermal control coating and preparation method, belong to intelligent thermal control coating preparing technical field.
Background technology
Thermal Control Coating Material is to realize that the spacecraft long term exposure at sunshine or in the safe operation in the cosmic space that sunshine can not arrive, guarantees the critical material of effective regulation and control of temperature in the cabin.The solar spectrum reflection characteristic or the infrared emission characteristic of traditional hot control coating layer are fixed, and can't follow variation of ambient temperature and change, and are difficult to satisfy the self-adaptation temperature control demand of spacecraft at sun front and back.The reflectivity emissivity is adjustable, and the electrochromism Thermal Control Coating Material just in time remedies the above-mentioned shortcoming of traditional hot control coating layer, this coating material can be regulated self emissivity or reflectance value according to changes in environmental conditions under voltage or electric current regulation and control energy, function with self-adapting intelligent thermal control, significant to improving spacecraft thermal control system autonomous management ability; Can be widely used in military spacecraft thermal control fields such as military communication, navigation, scouting and moonlet.Development along with space technology, novel spacecraft progressively develops to directions such as structure complicated, volume miniaturization, functional diversities, electric power maximizations, also more and more stronger than the demand of the intelligent heat control material of strong adaptability to having, the application of electrochromism intelligence Thermal Control Coating Material also will constantly enlarge.
Since the nineties, along with the appearance of conducting polymer, electrochromic material and device have caused people's very big concern from eighties of last century.J.R. Reynolds waits people (PCT/US2002/037524) to adopt two kinds of complementary polymkeric substance such as polythiophene, N replacement polypyrrole, Fc/Fc now
+As electrolyte, prepared the multiple layer polymer electrochromic device through overmatching, this device brightness can be reduced to 55% by 100%, and color and environmental stability to electrochromic are studied.Chen Wenyi (ZL200410046246.9) has prepared dipyridine tetrafluoroborate/polymethylmethacrylate/Ferrocence electricity and has caused the reduction off-color material, adopts two-layer transparent base to prepare and can be applicable to automatic glareproof mirror of automobile and automatic shadow shield.Wang Cong, Wang Tianmin etc. (ZL200710179549.1) adopt the method for magnetron sputtering film forming to prepare all solid state inorganic electrochromic element of electro-conductive glass/tungsten oxide/lithium metaborate (lithium sulfate)/nickel oxide/tin-doped indium oxide multilayer film, and this device is about 25% in the variation of visible light 400-800nm transmitance.Zhang Cheng, Hua Cheng etc. (in please number 200910100226.8) wait employing electrochemically oxidative polymerization method, have prepared the polythiophene electrochromic copolymer, realized-0.8v～1.4v changes from redgreenblue.Jin Litong, Pang Yuehong etc. (application number 200710171097.2) adopt Nano Silver and tungstic acid titania composite methods to prepare the electrochromism compound substance, and its transmitance variation is about 20%.Above-mentioned research adopts the method preparation of electrochemically oxidative polymerization or vacuum coating to be applicable to the off-color material that motor vehicles for civilian use are anti-dazzle mostly, mainly lay particular emphasis on material preparation process, material color and transmitance and change research, it is then relative less to change research at the necessary reflectivity of intelligent thermal control coating and emissivity, and the spraying coating process that especially be applicable to large tracts of land, flexibility, has more application prospect is still not mentioned.
In a word, electrochromic conducting polymer causes off-color material and has that trigger voltage is low, energy consumption is little, good manufacturability, be fit to characteristics such as large tracts of land moulding, is with a wide range of applications in fields such as the anti-glare of motor vehicles for civilian use, shadow shields.Simultaneously also the reflection characteristic of the near-infrared band of himself change color correspondence and the radiation characteristic of thermal infrared wave band can be changed the thermal control coating field of introducing spacecrafts such as satellite, spectrum property according to Electro-Discolor Coating changes emissivity and the emissivity regulation and control that realize thermal control coating, and then realizes the environment self-adaption of thermal control coating.
Summary of the invention
Technology of the present invention is dealt with problems and is: overcome the deficiencies in the prior art, a kind of required change emissivity in spacecraft thermal control field such as satellite, reflectivity-variable electrochromism intelligence thermal control coating and preparation method of being applicable to is provided.Coating of the present invention has initial reflectance, emissivity is adjustable, and reflectivity, characteristics that emissivity is big before and after the electrochromism.
Technical solution of the present invention is: become emissivity, reflectivity-variable electrochromism intelligence thermal control coating, adopt multi-layer compound structure, multi-layer compound structure is followed successively by environment encapsulated layer, electrochromism active layer, dielectric substrate, electrode layer and substrate layer from top to bottom, a pair of auxiliary electrode is being installed between electrode layer and the dielectric substrate and between electrochromism active layer and the environment encapsulated layer
Wherein, substrate layer and environment encapsulated layer are glass, quartz, polyimide, polyester, tygon, polypropylene, polycarbonate, polyurethane or organic siliconresin, electrode layer and auxiliary electrode are gold, aluminium, silver, calcium or indium tin oxide ITO, the conductive materials of dielectric substrate is lithium perchlorate, ionic liquid, trifluoromethyl sulfonic acid lithium or sodium chloride, and the electrochromism active layer is that in polyaniline, polythiophene or the polypyrrole one or both are compound.
Described multi-layer compound structure is followed successively by environment encapsulated layer, electrode layer, electrochromism active layer, dielectric substrate and substrate layer from top to bottom, between dielectric substrate and the substrate layer and between electrode layer and the electrochromism active layer a pair of auxiliary electrode is being installed, wherein electrode layer is indium tin oxide ITO.
The thickness of described electrochromism active layer is not more than 200um.
The conductivity of described dielectric substrate is 10
-7～10
-4S/cm.
The width of described auxiliary electrode is not more than 0.1cm.
Described ionic liquid comprises [emim] BF
4, [emim] PF
6, [emim] CF
3COO or [emim] CF
3SO
3
A kind of method that becomes emissivity, reflectivity-variable electrochromism intelligence thermal control coating for preparing is characterized in that realizing by following steps:
The first step forms electrode layer with gold, aluminium, silver, calcium or indium tin oxide ITO by sputtering on the substrate layer;
Second step, the preparation dielectric substrate,
A2.1, the ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts;
A2.2, in the solution that steps A 2.1 obtains, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution;
A2.3, mixed solution is heated to is not less than 60 ℃, stir;
A2.4, the mixed solution that steps A 2.3 is obtained adopt The tape casting to obtain conductivity 10
-7～10
-4The S/cm thin layer of electrolyte is placed on thin layer of electrolyte that electrode layer that the first step obtains obtains dielectric substrate by hot pressing or mixed solution that steps A 2.3 is obtained forms conductivity 10 by the electrode layer that is sprayed on the first step and obtains
-7～10
-4The dielectric substrate of S/cm;
The 3rd step, utilize steps A 3.1～A3.2 or step B3.1～B3.2 to prepare the electrochromism active layer,
A3.1 is 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine with mol ratio, and one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M;
A3.2, to obtain in the mixed liquor adding volumetric molar concentration in steps A 3.1 be the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, electro-deposition obtains the electrochromism active layer that thickness is 0.4～100um on second dielectric substrate that obtain of step;
B3.1, in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M;
B3.2, to add volumetric molar concentration in the polymer solution that step B3.1 obtains be the adulterant of 0.01～10M, grinds the back that is uniformly dispersed and adopt spraying method, and preparation thickness is the electrochromism active layer of 0.1um～200um on the dielectric substrate that obtains in second step;
The 4th step, with second preparation that obtain of step the dielectric substrate of electrochromism active layer, electrode layer and environment encapsulated layer, auxiliary electrode and substrate layer be combined with each other by lamination, obtain becoming emissivity, reflectivity-variable electrochromism intelligence thermal control coating.
A kind of method that becomes emissivity, reflectivity-variable electrochromism intelligence thermal control coating for preparing is characterized in that realizing by following steps:
The first step forms electrode layer with indium tin oxide ITO by sputtering on the environment encapsulated layer;
Second step, utilize steps A C2.1～C2.2 or step D2.1～D2.2 to prepare the electrochromism active layer,
C2.1 is 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine with mol ratio, and one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M;
C2.2, to obtain in the mixed liquor adding volumetric molar concentration at step C2.1 be the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, electro-deposition obtains the electrochromism active layer that thickness is 0.4～100um on the electrode layer that the first step obtains;
D2.1, in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M;
D2.2, to add volumetric molar concentration in the polymer solution that step D2.1 obtains be the adulterant of 0.01～10M, grinds the back that is uniformly dispersed and adopt spraying method, and preparation thickness is the electrochromism active layer of 0.1um～200um on the electrode layer that the first step obtains;
The 3rd step, the preparation dielectric substrate,
E3.1, the ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts;
E3.2, in the solution that step e 3.1 obtains, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution;
E3.3, mixed solution is heated to is not less than 60 ℃, stir;
E3.4, the mixed solution that step e 3.3 is obtained adopt The tape casting to obtain conductivity 10
-7～10
-4The S/cm thin layer of electrolyte is placed on the substrate layer thin layer of electrolyte by hot pressing and obtains dielectric substrate or mixed solution that step e 3.3 is obtained forms conductivity 10 by being sprayed on electrochromism active layer that second step obtained or the substrate layer
-7～10
-4The dielectric substrate of S/cm;
The 4th step, with second preparation that obtain of step the electrode layer of electrochromism active layer, dielectric substrate, environment encapsulated layer, auxiliary electrode and substrate layer be combined with each other by lamination, obtain becoming emissivity, reflectivity-variable electrochromism intelligence thermal control coating.
The conduction component also comprises ionic liquid in the described steps A 2.1.
The conduction component also comprises ionic liquid in the described step e 2.1.
Adulterant is poly-potassium sulfonate, camphorsulfonic acid, polymethyl-benzene sulfonic acid potassium salt, lithium perchlorate, sulfuric acid or hydrochloric acid among described steps A 3.2, step B3.2, step C2.2 or the step D2.2.
The present invention compared with prior art beneficial effect is:
(1) the present invention adopts the control technology of multilayer optical coupling and electricity coupling, has realized the controllable variations of the electrochromism of electrochromic device and reflectivity, emissivity by voltage-regulation;
(2) the present invention by conducting polymer pre-doping control and the application of porous electrode, the potential barrier of the carrier transport of effectively having demoted has reduced the trigger voltage of Electro-Discolor Coating;
(3) emissivity, the reflectivity modification scope of the electrochromism active layer of the present invention's preparation are big, and the corresponding time is short, electrochemical stability good, the characteristics of high-low temperature resistant alternation, satisfy spacecraft intelligence thermal control demand substantially;
(4) the electrochromism active layer emissivity of the present invention preparation can be in 0.07～0.89 scope, reflectivity can regulate and control in 0.1～0.6 scope, under the voltage-regulation of-0.8～5v, the solar spectrum reflectance varies of electrochromism thermal control coating is greater than 0.4, emissivity changes greater than 0.25, through ± 100 ℃, 100 circulations are not peeled off and are not come off, and possess above-mentioned performance after the reduction;
(5) the present invention's direct-current drive can obtain Electro-Discolor Coating of all kinds such as transparent, golden yellow, light green, dark green, blackish green, and possess different reflectivity and emissivity.
Description of drawings
Fig. 1 is a structural representation of the present invention;
Fig. 2 selects the structural representation of ITO for use for electrode layer of the present invention;
Fig. 3 is preparation technology's process flow diagram of the present invention.
Embodiment
The present invention as shown in Figure 1, adopt multi-layer compound structure, multi-layer compound structure is followed successively by environment encapsulated layer 6, electrochromism active layer 5, dielectric substrate 3, electrode layer 2 and substrate layer 1 from top to bottom, and a pair of auxiliary electrode 7 is being installed between electrode layer 2 and the dielectric substrate 3 and between electrochromism active layer 5 and the environment encapsulated layer 6.
Substrate layer 1 and environment encapsulated layer 6 materials are glass, quartz, polyimide, polyester, tygon, polypropylene, polycarbonate, polyurethane or organic siliconresin, and substrate layer 1 and environment encapsulated layer 6 materials can be selected a kind ofly also can select variety classes.
If electrode layer 2 is selected transparent indium tin oxide ITO, then the present invention also can be changed into multi-layer compound structure as shown in Figure 2, multi-layer compound structure is followed successively by environment encapsulated layer 6, electrode layer 2, electrochromism active layer 5, dielectric substrate 3 and substrate layer 1 from top to bottom, and a pair of auxiliary electrode 7 is being installed between dielectric substrate 3 and the substrate layer 1 and between electrode layer 2 and the electrochromism active layer 5.
The conductive materials of dielectric substrate 3 is lithium perchlorate, ionic liquid, trifluoromethyl sulfonic acid lithium or sodium chloride, and the conductivity of dielectric substrate 3 is 10
-7～10
-4S/cm.Ionic liquid comprises [emim] BF
4, [emim] PF
6, [emim] CF
3COO or [emim] CF
3SO
3
Electrochromism active layer 5 is that in polyaniline, polythiophene or the polypyrrole one or both are compound.Electrochromism active layer 5 thickness are not more than 200um.
Preparation technology of the present invention obtains by following steps as shown in Figure 3:
1, preparation electrode layer 2
Gold, aluminium, silver, calcium or indium tin oxide ITO are formed electrode layer 2 by sputtering on the substrate layer 1.
2, preparation dielectric substrate 3
The ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts; In solution, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution; Mixed solution is heated to is not less than 60 ℃, stir; Adopt The tape casting to obtain conductivity the step mixed solution 10
-7～10
-4The S/cm thin layer of electrolyte is placed on electrode layer 2 with thin layer of electrolyte and obtains dielectric substrate 3 or mixed solution is formed conductivity 10 by being sprayed on the electrode layer 2 by hot pressing
-7～10
-4The dielectric substrate 3 of S/cm.
3, preparation electrochromism active layer 5
Following two kinds of preparation methods are provided:
1) with mol ratio be 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine, one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M; Adding volumetric molar concentration in mixed liquor is the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, electro-deposition obtains the electrochromism active layer 5 that thickness is 0.4～100um on second dielectric substrate 3 that obtain of step.
2) in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M; Adding volumetric molar concentration in polymer solution is the adulterant of 0.01～10M, grinds the back that is uniformly dispersed and adopts spraying method, and preparation thickness is the electrochromism active layer 5 of 0.1um～200um on dielectric substrate 3.
4, will prepare dielectric substrate 3, electrode layer 2 and environment encapsulated layer 6, the auxiliary electrode 7 of electrochromism active layer 5 and substrate layer 1 and be combined with each other, obtain becoming emissivity, reflectivity-variable electrochromism intelligence thermal control coating by lamination.
If structure shown in Figure 2 prepares by following steps:
1, indium tin oxide ITO is formed electrode layer 2 by sputtering on the environment encapsulated layer 6.
2, preparation electrochromism active layer 5
Following two kinds of preparation methods are provided:
1) with mol ratio be 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine, one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M; Adding volumetric molar concentration in mixed liquor is the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, electro-deposition obtains the electrochromism active layer 5 that thickness is 0.4～100um on electrode layer 2.
2) in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M; Adding volumetric molar concentration in polymer solution is the adulterant of 0.01～10M, grinds the back that is uniformly dispersed and adopts spraying method, and preparation thickness is the electrochromism active layer 5 of 0.1um～200um on electrode layer 2.
3, preparation dielectric substrate 3
The ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts; In solution, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution; Mixed solution is heated to is not less than 60 ℃, stir; Adopt The tape casting to obtain conductivity mixed solution 10
-7～10
-4The S/cm thin layer of electrolyte, with thin layer of electrolyte be placed on the substrate layer 1 by hot pressing obtain dielectric substrate 3 or with mixed solution by being sprayed on electrochromism active layer 5 or substrate layer 1 forms conductivity 10
-7～10
-4The dielectric substrate 3 of S/cm.
4, will prepare the electrode layer 2, dielectric substrate 3, environment encapsulated layer 6, auxiliary electrode 7 of electrochromism active layer 5 and substrate layer 1 and be combined with each other, obtain becoming emissivity, reflectivity-variable electrochromism intelligence thermal control coating by lamination.
Below in conjunction with specific embodiment the present invention is described.
Embodiment 1
Configuration concentration is the aniline of 0.2M and the sulfuric acid mixed solution 100ml of diphenylamine (mol ratio is 4: 96), the polymethyl-benzene sulfonic acid potassium salt that adds 100ml 0.2M, (4cm * 4cm) is substrate, and Pt is to electrode, saturated Ag/AgCl with indium tin oxide (ITO) conducting film of 0.2mm
-Be contrast electrode, constant voltage 0.5v deposits 30min, prepares the electric activation photochromic layer 5 of 5um.10g polyacrylonitrile, 10g lithium perchlorate are dissolved in the mixed solution of dimethyl carbonate and acetone, and the mixed solution of preparation 0.1M is sprayed at electrochromism active layer 5 surfaces and obtains dielectric substrate 3.Multilayer film and polyester base, golden auxiliary electrode are carried out compound, prepare six layers of full-solid electrochromic coating [structure 1] of polyester/ITO/ polyaniline/lithium perchlorate (polyacrylonitrile)/gold electrode/polyester.Apply the 1.8v positive voltage, coating is become transparent by original bottle green, and emissivity becomes 0.46 by 0.7, and the solar spectrum reflectivity becomes 0.25 by 0.45.
With 10g polyacrylonitrile, 20g lithium perchlorate, 5g[emim] BF
4Be dissolved in the mixed solution of dimethyl carbonate and tetrahydrofuran, be mixed with the mixed solution of 0.1M, be sprayed on the gold-plated substrate of glass of default auxiliary gold electrode (7), obtain dielectric substrate 3; Soluble conductive macromolecular solution polyaniline is dissolved in metacresol, the methyl pyrrolidone equal solvent, is mixed with 0.1M solution, add the 0.01M camphorsulfonic acid, be sprayed on the dielectric substrate surface after grinding is uniformly dispersed, prepare 1um electrochromism active layer; Adopt the lamination composite methods to prepare the Electro-Discolor Coating of tygon/polyaniline/lithium perchlorate (polyacrylonitrile)/gold electrode/glass.Apply the 3v positive voltage, coating is become light green by original bottle green, and emissivity becomes 0.14 by 0.48, and the solar spectrum reflectivity becomes 0.5 by 0.1.
Compound concentration is 0.1M 3, and the sulfuric acid mixed solution 50ml of 4-enedioxy thiophene adds the lithium perchlorate of 100ml0.2M, and (4cm * 4cm) is substrate, and Pt is to electrode, saturated Ag/AgGl with indium tin oxide (ITO) conducting film of 0.2mm
-Be contrast electrode, constant voltage 0.8v deposits 60min, prepares the electrochromism active layer 5 of 2um.10g polyacrylonitrile, 10g lithium perchlorate are dissolved in the mixed solution of dimethyl carbonate and acetone, and the mixed solution of preparation 0.1M is sprayed at electrochromism active layer 5 surfaces and obtains dielectric substrate 3.Multilayer film and polyester base, golden auxiliary electrode are carried out compound, prepare six layers of full-solid electrochromic coating of polyester/ITO/ polythiophene/lithium perchlorate (polyacrylonitrile)/gold electrode/polyester.Apply the 1.2v positive voltage, coating is become light blue by original mazarine, and emissivity becomes 0.45 by 0.68, and the solar spectrum reflectivity becomes 0.1 by 0.35.
Embodiment 4
10g Kynoar, 10g trifluoromethyl sulfonic acid lithium are dissolved in the mixed solution of dimethyl carbonate and diethyl carbonate, are mixed with the mixed solution of 0.1M, be sprayed in the gold-plated polyimide substrate of default auxiliary gold electrode (7), obtain dielectric substrate 3; With soluble conductive macromolecular solution polythiophene dissolving N, in the dinethylformamide solvent, be mixed with 0.01M solution, add 0.01M polymethyl-benzene potassium sulfonate, after being uniformly dispersed, grinding is sprayed on the dielectric substrate surface, prepare 2um electrochromism active layer; Adopt the lamination composite methods to prepare the Electro-Discolor Coating of tygon/polythiophene/trifluoromethyl sulfonic acid lithium (Kynoar)/gold electrode/polyimide.Apply the 1.5v positive voltage, coating is become light blue by original mazarine, and emissivity becomes 0.21 by 0.39, and the solar spectrum reflectivity becomes 0.4 by 0.23.
10g polyacrylonitrile, 20g lithium perchlorate are dissolved in the mixed solution of dimethyl carbonate and tetrahydrofuran, are mixed with the mixed solution of 0.1M, be sprayed on the gold-plated substrate of glass of default auxiliary gold electrode (7), obtain dielectric substrate 3; Soluble conductive macromolecular solution polyaniline is dissolved in metacresol, the methyl pyrrolidone equal solvent, is mixed with 0.1M solution, add the 0.05M camphorsulfonic acid, be sprayed on the dielectric substrate surface after grinding is uniformly dispersed, prepare 1um electrochromism active layer; Adopt the lamination composite methods to prepare the Electro-Discolor Coating of tygon/polyaniline/lithium perchlorate (polyacrylonitrile)/gold electrode/glass.Apply the 3v positive voltage, coating is become light green by original bottle green, and emissivity becomes 0.17 by 0.33, and the solar spectrum reflectivity becomes 0.34 by 0.15.
Following table obtains 3 kinds of change emissivity of embodiment 2, reflectivity-variable electrochromism intelligence thermal control coating changes back (100～100 ℃, 100 times) at high low temperature emissivity situation of change for adopting the present invention.
The unspecified part of the present invention belongs to general knowledge as well known to those skilled in the art.
Claims (11)
1. become emissivity, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: adopt multi-layer compound structure, multi-layer compound structure is followed successively by environment encapsulated layer (6), electrochromism active layer (5), dielectric substrate (3), electrode layer (2) and substrate layer (1) from top to bottom, a pair of auxiliary electrode (7) is being installed between electrode layer (2) and the dielectric substrate (3) and between electrochromism active layer (5) and the environment encapsulated layer (6)
Wherein, substrate layer (1) and environment encapsulated layer (6) are glass, quartz, polyimide, polyester, tygon, polypropylene, polycarbonate, polyurethane or organic siliconresin, electrode layer (2) and auxiliary electrode (7) are gold, aluminium, silver, calcium or indium tin oxide ITO, the conductive materials of dielectric substrate (3) is lithium perchlorate, ionic liquid, trifluoromethyl sulfonic acid lithium or sodium chloride, and electrochromism active layer (5) is that in polyaniline, polythiophene or the polypyrrole one or both are compound.
2. change emissivity according to claim 1, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: described multi-layer compound structure is followed successively by environment encapsulated layer (6), electrode layer (2), electrochromism active layer (5), dielectric substrate (3) and substrate layer (1) from top to bottom, between dielectric substrate (3) and the substrate layer (1) and between electrode layer (2) and the electrochromism active layer (5) a pair of auxiliary electrode (7) is being installed, wherein electrode layer (2) is indium tin oxide ITO.
3. change emissivity according to claim 1 and 2, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: the thickness of described electrochromism active layer (3) is not more than 200um.
4. change emissivity according to claim 1 and 2, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: the conductivity of described dielectric substrate (3) is 10
-7～10
-4S/cm.
5. change emissivity according to claim 1 and 2, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: the width of described auxiliary electrode (7) is not more than 0.1cm.
6. change emissivity according to claim 1 and 2, reflectivity-variable electrochromism intelligence thermal control coating, it is characterized in that: described ionic liquid comprises [emim] BF
4, [emim] PF
6, [emim] CF
3COO or [emim] CF
3SO
3
7. method for preparing the described change emissivity of claim 1, reflectivity-variable electrochromism intelligence thermal control coating is characterized in that realizing by following steps:
The first step goes up formation electrode layer (2) with gold, aluminium, silver, calcium or indium tin oxide ITO by sputtering at substrate layer (1);
Second step, preparation dielectric substrate (3),
A2.1, the ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts;
A2.2, in the solution that steps A 2.1 obtains, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution;
A2.3, mixed solution is heated to is not less than 60 ℃, stir;
A2.4, the mixed solution that steps A 2.3 is obtained adopt The tape casting to obtain conductivity 10
-7～10
-4The S/cm thin layer of electrolyte is placed on thin layer of electrolyte that electrode layer (2) that the first step obtains obtains dielectric substrate (3) by hot pressing or mixed solution that steps A 2.3 is obtained forms conductivity 10 by the electrode layer (2) that is sprayed on the first step and obtains
-7～10
-4The dielectric substrate of S/cm (3);
The 3rd step, utilize steps A 3.1～A3.2 or step B3.1～B3.2 to prepare electrochromism active layer (5),
A3.1 is 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine with mol ratio, and one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M;
A3.2, to obtain in the mixed liquor adding volumetric molar concentration in steps A 3.1 be the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, the dielectric substrate (3) that obtains in second step is gone up electro-deposition and is obtained the electrochromism active layer (5) that thickness is 0.4～100um;
B3.1, in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M;
B3.2, to add volumetric molar concentration in the polymer solution that step B3.1 obtains be the adulterant of 0.01～10M, adopt spraying method after grinding is uniformly dispersed, it is the electrochromism active layer (5) of 0.1um～200um that the dielectric substrate (3) that obtains in second step is gone up preparation thickness;
The 4th step, with second preparation that obtain of step the dielectric substrate (3) of electrochromism active layer (5), electrode layer (2) and environment encapsulated layer (6), auxiliary electrode (7) and substrate layer (1) be combined with each other by lamination, obtain becoming emissivity, the intelligent thermal control coating of reflectivity-variable electrochromism.
8. method for preparing the described change emissivity of claim 2, reflectivity-variable electrochromism intelligence thermal control coating is characterized in that realizing by following steps:
The first step goes up formation electrode layer (2) with indium tin oxide ITO by sputtering at environment encapsulated layer (6);
Second step, utilize steps A C2.1～C2.2 or step D2.1～D2.2 to prepare electrochromism active layer (5),
C2.1 is 4: 96～96: 4 the aniline and the potpourri, 3 of diphenylamine with mol ratio, and one or both among 4-enedioxy thiophene or the 3-hydroxy ethoxy pyrroles are dissolved in and are configured to the mixed liquor that volumetric molar concentration is 0.2～0.8M in the sulfuric acid that volumetric molar concentration is 0.01～0.5M;
C2.2, to obtain in the mixed liquor adding volumetric molar concentration at step C2.1 be the adulterant of 0.2～0.8M, under constant voltage 0.1～1.2v, is to electrode, saturated Ag/AgCl with Pt
-Be contrast electrode, sedimentation time 30min～6h, the last electro-deposition of electrode layer (2) that obtains in the first step obtains the electrochromism active layer (5) that thickness is 0.4～100um;
D2.1, in polyaniline, polythiophene or the polypyrrole one or both are dissolved in metacresol, crassitude ketone solvent or N, in the dinethylformamide solvent, configuration obtains the polymer solution that volumetric molar concentration is 0.01～1M;
D2.2, to add volumetric molar concentration in the polymer solution that step D2.1 obtains be the adulterant of 0.01～10M, spraying method is adopted in the grinding back that is uniformly dispersed, and it is the electrochromism active layer (5) of 0.1um～200um that the electrode layer (2) that obtains in the first step is gone up preparation thickness;
The 3rd step, preparation dielectric substrate (3),
E3.1, the ionic medium component is dissolved in the mixed liquor of dimethyl carbonate DMC, diethyl carbonate DEC or dimethyl carbonate DMC, diethyl carbonate DEC with the conduction component prepares the solution that volumetric molar concentration is 0.001～10M, wherein the ionic medium component is one or more the potpourri among Kynoar PVDF, polyacrylonitrile (PAN) or poly-(biasfluoroethylene-hexafluoropropylene) PVDF-HFP, and the conduction component is LiClO
4, NaClO
4, LiCF
3SO
3, one or more potpourris in other lithium salts or other sodium salts;
E3.2, in the solution that step e 3.1 obtains, add tetrahydrofuran, acetone or butyl acetate solvent and obtain mixed solution;
E3.3, mixed solution is heated to is not less than 60 ℃, stir;
E3.4, the mixed solution that step e 3.3 is obtained adopt The tape casting to obtain conductivity 10
-7～10
-4The S/cm thin layer of electrolyte is placed on substrate layer (1) with thin layer of electrolyte and goes up by hot pressing and obtain dielectric substrate (3) or mixed solution that step e 3.3 is obtained forms conductivity 10 by being sprayed on electrochromism active layer (5) or the substrate layer (1) that second step obtained
-7～10
-4The dielectric substrate of S/cm (3);
The 4th step, with second preparation that obtain of step the electrode layer (2) of electrochromism active layer (5), dielectric substrate (3), environment encapsulated layer (6), auxiliary electrode (7) and substrate layer (1) be combined with each other by lamination, obtain becoming emissivity, the intelligent thermal control coating of reflectivity-variable electrochromism.
9. change emissivity according to claim 7, reflectivity-variable electrochromism intelligence thermal control coating preparation method, it is characterized in that: the conduction component also comprises ionic liquid in the described steps A 2.1.
10. change emissivity according to claim 8, reflectivity-variable electrochromism intelligence thermal control coating preparation method, it is characterized in that: the conduction component also comprises ionic liquid in the described step e 2.1.
11. change emissivity according to claim 7, reflectivity-variable electrochromism intelligence thermal control coating preparation method, it is characterized in that: adulterant is poly-potassium sulfonate, camphorsulfonic acid, polymethyl-benzene sulfonic acid potassium salt, lithium perchlorate, sulfuric acid or hydrochloric acid among described steps A 3.2 or the step B3.2.
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