CN106938892B - A kind of preparation method for the laminated film that visible near-infrared pair can be regulated and controled - Google Patents
A kind of preparation method for the laminated film that visible near-infrared pair can be regulated and controled Download PDFInfo
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- CN106938892B CN106938892B CN201710124479.3A CN201710124479A CN106938892B CN 106938892 B CN106938892 B CN 106938892B CN 201710124479 A CN201710124479 A CN 201710124479A CN 106938892 B CN106938892 B CN 106938892B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Abstract
It is a kind of to belong to field of material technology to the preparation method of the Novel compound film of visible near-infrared double regulations.The method comprises the following steps: preparing tungsten oxide nanometer material solution, polyoxometallic acid salting liquid and polyelectrolyte solution；It is spare to conductive transparent material substrate pretreatment；Substrate is alternately immersed into tungsten oxide nanometer material solution and polyelectrolyte solution；Substrate is alternately immersed to polyoxometallic acid salting liquid and polyelectrolyte solution again to get to using conductive transparent material as the multi-layer compound film material of substrate.The invention has the advantages that the laminated film obtained, which can be realized, distinguishes reversible regulation to visible light and near-infrared region, and have many advantages, such as that preparation process is simple, at low cost, switch efficiency is high, stability is good, good reversibility, and can require to adjust the type and the number of plies of tungsten oxide nanometer material and more metallized metal oxygen hydrochlorates according to different performance.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of system for the laminated film that can regulate and control to visible near-infrared pair
Preparation Method.
Background technique
Now, 40% and the carbon dioxide that the energy for maintaining building to use accounts for about annual total energy consumption are always arranged
High-volume 30%, for example, maintaining the energy used in room temperature and brightness of building etc..Disappear to further decrease the energy
It consumes and reduces environmental pollution, new energy-saving material need to be developed to help people and regulate and control the temperature of building according to the needs of environment
And light and shade environment, it is energy saving to achieve the purpose that.For sunlight as most important lamp, it reaches the light of earth surface
Can be divided into 53% or so near infrared light (regulating and controlling temperature variation), 42% or so visible light (regulation brightness variation) and
5% or so ultraviolet light, so new energy-saving material can be achieved the purpose that energy saving by the transmitance of regulation sunlight.
Electrochromic material can generate color and transmission under the action of extra electric field as a kind of advanced composite material (ACM)
The variation of rate, it can be used for regulating and controlling the transmitance of sunlight, realizes building brightness or the adjusting of temperature, builds so as to reduce
Build the energy consumption of object.
Although existing part electrochromic material reduces the energy loss of building by regulating and controlling solar radiation now, such as
The conductive film and nanocrystal of doped metal oxide nanocrystal and the complex thin film of glass, but still there is
Some problems, such as most materials are only capable of regulation visible light or near infrared light, regulation while cannot achieve the area Liang Zhongguang；Building is multiple
The process for closing thin-film material is complex；Material cost is too high；The problems such as regulating and controlling inefficient.
Summary of the invention
The purpose of the present invention is to solve problems of the prior art, provide a kind of regulation high-efficient, stability
It well and can be to the preparation method of the laminated film of visible near-infrared double regulations.At room temperature, pass through LBL self-assembly method
Tungsten oxide nanometer material and polyoxometallate are assembled on the electro-conductive glass pre-processed through electrostatic adsorption, pass through conjunction
Suitable packaging method prepares electrochromism composite film material.In addition, regulation tungsten oxide nanometer material and more metals can be passed through
The type and the number of plies of oxygen hydrochlorate obtain the electrochromic device of different performance.
Polyoxometallate (Polyoxometalates, abridge POMs, abbreviation polyacid) is as a kind of excellent electroluminescent change
Color material can form mixed valence by electroreduction, so as to cause the color change of polyacid, show in visible light region strong
It absorbs, and tungsten oxide nanometer material can produce strong infrared absorption under extraneous electric field action, when the two complicated utilization is suitable
When method is prepared into electrochromism composite film material, can get on-off ratio, regulation it is high-efficient, it can be achieved that near infrared light with it is visible
The new energy-saving material regulated and controled while light.
To achieve the above object, the technical solution taken is as follows by the present invention:
A kind of preparation method for the laminated film that can regulate and control to visible near-infrared pair, specific step is as follows for the method:
Step 1: tungsten oxide nanometer material solution, the polyoxometallic acid with negative electrical charge for having negative electrical charge are prepared respectively
Salting liquid and polyelectrolyte solution with positive charge；
Step 2: using conductive transparent material as substrate, conductive transparent material being sized and is cut into fritter, successively in
Each ultrasound 15min, each ultrasound finish in acetone, isopropanol and water, and ultrapure water is washed away except residual organic solvent, prepare VH2O2:
VNH4OH:VH2O=1:1:5 solution, conductive transparent material is vertically placed in the solution, 80 DEG C of water-bath 1h, and taking-up is cooled to room
Temperature is cleaned with ultrapure water, N2Drying, conduction are placed in culture dish up, and toluene 20mL steams again after is added, takes in glove box
300 μ LAPTES out is added in the culture dish, and sealing is protected from light for 24 hours, takes out conductive transparent material, and toluene is abandoned in waste liquid
Bucket, conductive transparent material acetone are cleaned by ultrasonic 3 times, each 1min, and ultrapure water is cleaned, and are placed in ultrapure water and save backup for 4 DEG C；
Step 3: conductive substrates are alternately immersed to the polyelectrolyte solution of positive charge and the tungsten oxide nanometer material of negative electrical charge
It in solution, is dried with nitrogen, obtains polyelectrolyte and tungsten oxide nanometer material multilayer film；
Step 4: the plural layers are alternately immersed to the polyelectrolyte solution of positive charge and the polyoxometallic acid of negative electrical charge
It in salting liquid, is dried with nitrogen, prepares polyelectrolyte and polyoxometallate plural layers, finally obtain and be with conductive transparent material
The multi-layer compound film material of substrate carries out electrochromism test to it.
The beneficial effect of the present invention compared with the existing technology is:
(1) of the invention to be particularly advantageous in that its preparation step is extremely simple, it easily accomplishes scale production, and obtain device
Structure is uniform controllable.
(2) present invention laminated film obtained, which can be realized, distinguishes reversible regulation to visible light and near-infrared region, and has
Have the advantages that at low cost, switch efficiency is high, stability is good, good reversibility, and adjusting tungsten oxide can be required to receive according to different performance
The type and the number of plies of rice material and polyoxometallate.
Detailed description of the invention
Fig. 1 is W18O49The transmission electron microscope picture of nano wire；
Fig. 2 is electrochromism composite film material (PEI/W under different voltages18O49)20(PEI/P8W48)20Under different voltages
Transmitance variation diagram；
Fig. 3 is composite film material (PEI/W18O49)20(PEI/P8W48)20500 cyclical stabilities at 1060nm are surveyed
Attempt；
Fig. 4 is composite film material (PEI/W18O49)20(PEI/P8W48)20500 cyclical stabilities at 500nm are surveyed
Attempt；
Fig. 5 is that the transmitance of composite film material device near infrared light under different voltages changes test chart；
Fig. 6 is electrochromism composite film material (PAH/W under different voltages18O49)20(PAH/P8W48)20Under different voltages
Transmitance variation diagram；
Fig. 7 is electrochromism composite film material (PEI/W under different voltages18O49)20(PEI/P5W30)5Under different voltages
Transmitance variation diagram.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Specific embodiment: what present embodiment was recorded is a kind of system of laminated film that can regulate and control to visible near-infrared pair
Preparation Method, specific step is as follows for the method:
Step 1: tungsten oxide nanometer material solution, the polyoxometallic acid with negative electrical charge for having negative electrical charge are prepared respectively
Salting liquid and polyelectrolyte solution with positive charge；
Step 2: using conductive transparent material as substrate, conductive transparent material being sized and is cut into fritter, successively in
Each ultrasound 15min, each ultrasound finish in acetone, isopropanol and water, and ultrapure water is washed away except residual organic solvent, prepare VH2O2:
VNH4OH:VH2O=1:1:5 solution, conductive transparent material is vertically placed in the solution, 80 DEG C of water-bath 1h, and taking-up is cooled to room
Temperature is cleaned with ultrapure water, N2Drying, conduction are placed in culture dish up, and toluene 20mL steams again after is added, takes in glove box
300 μ LAPTES out is added in the culture dish, and sealing is protected from light for 24 hours, takes out conductive transparent material, and toluene is abandoned in waste liquid
Bucket, conductive transparent material acetone are cleaned by ultrasonic 3 times, each 1min, and ultrapure water is cleaned, and are placed in ultrapure water and save backup for 4 DEG C；
Step 3: conductive substrates are alternately immersed to the polyelectrolyte solution of positive charge and the tungsten oxide nanometer material of negative electrical charge
It in solution, is dried with nitrogen, obtains polyelectrolyte and tungsten oxide nanometer material multilayer film；
Step 4: the plural layers are alternately immersed to the polyelectrolyte solution of positive charge and the polyoxometallic acid of negative electrical charge
It in salting liquid, is dried with nitrogen, prepares polyelectrolyte and polyoxometallate plural layers, finally obtain and be with conductive transparent material
The multi-layer compound film material of substrate carries out electrochromism test to it；
Step 5: ultraviolet, visible and near infrared spectrometer (U-4100) and CHI860D electrochemical operation using Hitachi, Japan
Stand (Beijing China Tech Pu Tian Co., Ltd), analyze under different voltages, electrochromism composite film material it is visible-close red
The variation of the absorbent properties of outside line；High stable light source and the U.S. using CrownTech company, the U.S. (mono- 150W of CTTH)
THORLABS PM-100D digital light power and energy meter (PM100D), solar simulating radiation test device to visible and infrared
The changed power that area's wavelength penetrates；Using the color change of the real-time registering device of Canon (660D) camera.
Specific embodiment 2: one kind described in specific embodiment one can be to the laminated film of visible near-infrared double regulations
Preparation method, the preparation method of the polyelectrolyte solution, tungsten oxide nanometer material solution and polyoxometallic acid salting liquid are as follows:
Dissolve polyelectrolyte, tungsten oxide nanometer material and polyoxometallate respectively with deionized water, above-mentioned three kinds of solution concentrations are
0.1~10mg/mL.
Specific embodiment 3: the described one kind of specific embodiment one or two can be to the THIN COMPOSITE of visible near-infrared double regulations
The preparation method of film, the polyelectrolyte are polyethyleneimine, polyallyl ammonium hydrochloride or diallyl dimethyl ammonium
One of hydrochloride.
Specific embodiment 4: specific embodiment one or two it is described it is a kind of to visible and near-infrared region through controllable
The preparation method of laminated film, the tungsten oxide nanometer material are W18O49Nano wire, W18O49Nanosphere or W18O49Nanoneedle
One of.
Specific embodiment 5: the described one kind of specific embodiment one or two can be to the THIN COMPOSITE of visible near-infrared double regulations
The preparation method of film, the polyoxometallate are [PW12O40]3-、[P2W18O62]6-、[NaP5W30O110]14-Or
[H7P8W48O184]33-One of.
Specific embodiment 6: one kind described in specific embodiment one can be to the laminated film of visible near-infrared double regulations
Preparation method, in step 2, the substrate is using glass as the tin indium oxide of substrate or using flexible material as the indium oxide of substrate
Tin.
Specific embodiment 7: one kind described in specific embodiment one can be to the laminated film of visible near-infrared double regulations
Preparation method, in step 3, the tungsten oxide of polyelectrolyte solution and negative electrical charge that the conductive substrates alternately immerse positive charge is received
The rice material solution time is 5~20min；In step 4, the plural layers alternately immerse the polyelectrolyte solution of positive charge with
The polyoxometallate solution min of negative electrical charge is 5~20min.
Specific embodiment 8: one kind described in specific embodiment one can be to the laminated film of visible near-infrared double regulations
Preparation method, in step 3, the number of plies for obtaining the polyelectrolyte and tungsten oxide nanometer material multilayer film is 5~50 double
Layer.
Specific embodiment 9: one kind described in specific embodiment one can be to the laminated film of visible near-infrared double regulations
Preparation method, in step 4, the number of plies for obtaining the polyelectrolyte and polyoxometallate plural layers is 5~50 bilayers.
Embodiment 1:
(1) [the PW for the use of deionized water configuration concentration being 0.1~10mg/mL12O40]3-(PW12) solution, concentration be 0.1~
The W of 10mg/mL18O49Nanowire solution, concentration are polyethyleneimine (PEI) solution of 0.1~10mg/mL；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PEI solution, nitrogen cleaning drying is immersed in PW after repeating 20 layers of assembling125~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PEI solution, and nitrogen cleaning drying, after repeating 20 layers of assembling, holding outermost layer is
PW12, finally preparing structure is (PEI/W18O49)20(PEI/PW12)20Electrochromism composite film material；
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode)；
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 2:
(1) [the P for the use of deionized water configuration concentration being 0.1~10mg/mL2W18O62]6-(P2W18) solution, concentration 0.1
The W of~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyethyleneimine of 0.1~10mg/mL
(PEI) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PEI solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling2W185~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PEI solution, and nitrogen cleaning drying, after repeating 20 layers of assembling, holding outermost layer is
P2W18, finally preparing structure is (PEI/W18O49)20(PEI/P2W18)20Electrochromism composite film material；
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode)；
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 3:
(1) [the NaP for the use of deionized water configuration concentration being 0.1~10mg/mL5W30O110]14-(P5W30) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyethyleneimine of 0.1~10mg/mL
(PEI) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PEI solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling5W305~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PEI solution, and nitrogen cleaning drying, after repeating 20 layers of assembling, holding outermost layer is
P5W30, finally preparing structure is (PEI/W18O49)20(PEI/P5W30)20Electrochromism composite film material；
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode)；
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 4:
(1) [the H for the use of deionized water configuration concentration being 0.1~10mg/mL7P8W48O184]33-(P8W48) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyethyleneimine of 0.1~10mg/mL
(PEI) solution；
(2) pretreated ito glass is submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then immerse
5~20min into PEI solution, nitrogen cleaning drying are immersed in P after repeating 20 layers of assembling8W485~20min of solution, nitrogen are clear
Drying is washed, then is immersed in 5~20min in PEI solution, nitrogen cleaning drying, after repeating 20 layers of assembling, holding outermost layer is
P8W48, finally preparing structure is (PEI/W18O49)20(PEI/P8W48)20Electrochromism composite film material；
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode) test result such as Fig. 2, cyclical stability test such as Fig. 3 and 4；
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light, test result such as Fig. 5.
Embodiment 5:
(1) [the H for the use of deionized water configuration concentration being 0.1~10mg/mL7P8W48O184]33-(P8W48) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyallyl ammonium of 0.1~10mg/mL
Hydrochloride (PAH) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PAH solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling8W485~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PAH solution, and nitrogen cleaning drying, after repeating 20 layers of assembling, holding outermost layer is
P8W48, finally preparing structure is (PAH/W18O49)20(PAH/P8W48)20Electrochromism composite film material.
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode).
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 6:
(1) [the H for the use of deionized water configuration concentration being 0.1~10mg/mL7P8W48O184]33-(P8W48) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyallyl ammonium of 0.1~10mg/mL
Hydrochloride (PAH) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PAH solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling8W485~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PAH solution, and nitrogen cleaning drying, after repeating 30 layers of assembling, holding outermost layer is
P8W48, finally preparing structure is (PAH/W18O49)20(PAH/P8W48)30Electrochromism composite film material.
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode).
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 7:
(1) [the H for the use of deionized water configuration concentration being 0.1~10mg/mL7P8W48O184]33-(P8W48) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polydiene propyl of 0.1~10mg/mL
Dimethyl ammonium hydrochloride (PDDA) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PDDA solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling8W485~20min of solution, nitrogen
Gas cleaning drying, then it is immersed in 5~20min in PDDA solution, nitrogen cleaning drying after repeating 20 layers of assembling, keeps outermost layer
For P8W48, finally preparing structure is (PDDA/W18O49)20(PDDA/P8W48)20Electrochromism composite film material.
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode).
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Embodiment 8:
(1) [the NaP for the use of deionized water configuration concentration being 0.1~10mg/mL5W30O110]14-(P5W30) solution, concentration is
The W of 0.1~10mg/mL18O49Nanowire solution (transmission electron microscope picture such as Fig. 1), concentration are the polyethyleneimine of 0.1~10mg/mL
(PEI) solution；
(2) pretreated conductive substrates are submerged initially in W18O495~20min in solution, nitrogen cleaning drying, then soak
Enter 5~20min into PEI solution, nitrogen cleaning drying is immersed in P after repeating 20 layers of assembling5W305~20min of solution, nitrogen
Cleaning dries up, then is immersed in 5~20min in PEI solution, and nitrogen cleaning drying, after repeating 5 layers of assembling, holding outermost layer is
P5W30, finally preparing structure is (PEI/W18O49)20(PEI/P5W30)5Electrochromism composite film material；
(3) with three-electrode system test composite film material electrochromic property and its under different voltages to visible
(saturation Ag/AgCl electrode is reference electrode to the variation of the transmitance of light area and near-infrared region, and platinum electrode is to electrode, conduction
Substrate is working electrode), such as Fig. 6 and Fig. 7；
It (4) is to assemble the conductive substrates of composite construction to electrode as to electrode, the light source analogy sun with blank conductive substrates
Light, using optical filter it will be seen that light and near infrared light are distinguished respectively, test composite film material is distinguished under different voltages effect
To the transmitance situation of change of visible light and near infrared light.
Claims (9)
1. one kind can be to the preparation method of the laminated film of visible near-infrared double regulations, it is characterised in that: the method specifically walks
It is rapid as follows:
Step 1: it is molten that tungsten oxide nanometer material solution, the polyoxometallate with negative electrical charge with negative electrical charge are prepared respectively
Liquid and polyelectrolyte solution with positive charge；
Step 2: using conductive transparent material as substrate, conductive transparent material is sized and is cut into fritter, successively in third
Each ultrasound 15min, each ultrasound finish in ketone, isopropanol and water, and ultrapure water is washed away except residual organic solvent, prepareConductive transparent material is vertically placed in the solution by solution, 80 DEG C of water-bath 1h, is taken out cold
But it to room temperature, is cleaned with ultrapure water, N2Drying, conduction are placed in culture dish up, toluene 20mL steams again after are added, in gloves
300 μ LAPTES are taken out in case, are added in the culture dish, and sealing is protected from light for 24 hours, takes out conductive transparent material, and toluene is abandoned
In waste liquid barrel, conductive transparent material acetone is cleaned by ultrasonic 3 times, each 1min, and ultrapure water is cleaned, and is placed in 4 DEG C of preservations in ultrapure water
It is spare；
Step 3: conductive substrates are alternately immersed to the polyelectrolyte solution of positive charge and the tungsten oxide nanometer material solution of negative electrical charge
In, it is dried with nitrogen, obtains polyelectrolyte and tungsten oxide nanometer material multilayer film；
Step 4: the polyoxometallate of polyelectrolyte solution and negative electrical charge that the plural layers are alternately immersed to positive charge is molten
It in liquid, is dried with nitrogen, prepares polyelectrolyte and polyoxometallate plural layers, finally obtain using conductive transparent material as substrate
Multi-layer compound film material, electrochromism test is carried out to it.
2. a kind of according to claim 1 can exist to the preparation method of the laminated film of visible near-infrared double regulations, feature
In the preparation method of the polyelectrolyte solution, tungsten oxide nanometer material solution and polyoxometallic acid salting liquid are as follows: spend from
Sub- water dissolves polyelectrolyte, tungsten oxide nanometer material and polyoxometallate respectively, and above-mentioned three kinds of solution concentrations are 0.1~
10mg/mL。
3. one kind according to claim 1 or claim 2 can be to the preparation method of the laminated film of visible near-infrared double regulations, feature
Be: the polyelectrolyte is in polyethyleneimine, polyallyl ammonium hydrochloride or diallyl dimethyl ammonium salt hydrochlorate
One kind.
4. one kind according to claim 1 or claim 2 can be to the preparation method of the laminated film of visible near-infrared double regulations, feature
Be: the tungsten oxide nanometer material is W18O49Nano wire, W18O49Nanosphere or W18O49One of nanoneedle.
5. one kind according to claim 1 or claim 2 can be to the preparation method of the laminated film of visible near-infrared double regulations, feature
Be: the polyoxometallate is [PW12O40]3-、[P2W18O62]6-、[NaP5W30O110]14-Or [H7P8W48O184]33-In
It is a kind of.
6. a kind of according to claim 1 can exist to the preparation method of the laminated film of visible near-infrared double regulations, feature
In: in step 2, the substrate is using glass as the tin indium oxide of substrate or using flexible material as the tin indium oxide of substrate.
7. a kind of according to claim 1 can exist to the preparation method of the laminated film of visible near-infrared double regulations, feature
In: in step 3, the conductive substrates alternately immerse the polyelectrolyte solution of positive charge and the tungsten oxide nanometer material of negative electrical charge
Solution min is 5~20min；In step 4, the plural layers alternately immerse the polyelectrolyte solution and negative electrical charge of positive charge
Polyoxometallate solution min be 5~20min.
8. a kind of according to claim 1 can exist to the preparation method of the laminated film of visible near-infrared double regulations, feature
In: in step 3, the number of plies for obtaining the polyelectrolyte and tungsten oxide nanometer material multilayer film is 5~50 bilayers.
9. a kind of according to claim 1 can exist to the preparation method of the laminated film of visible near-infrared double regulations, feature
In: in step 4, the number of plies for obtaining the polyelectrolyte and polyoxometallate plural layers is 5~50 bilayers.
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| CN106398208A (en) * | 2016-08-31 | 2017-02-15 | 西安电子科技大学 | Photosensitive composite thin film material and preparation method and application thereof |
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| CN103575781A (en) * | 2012-07-18 | 2014-02-12 | 国家纳米科学中心 | Electrochemical sensor and its preparation method |
| CN106398208A (en) * | 2016-08-31 | 2017-02-15 | 西安电子科技大学 | Photosensitive composite thin film material and preparation method and application thereof |
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| High performance visible and near-infrared region electrochromicsmart windows based on the different structures of polyoxometalates;Shi-Ming Wang etc.;《Electrochimina Acta》;20131006;第113卷;第240-247页 |
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