CN114149797B - Dual-regulation multi-color composite material, preparation method thereof and electrochromic device - Google Patents
Dual-regulation multi-color composite material, preparation method thereof and electrochromic device Download PDFInfo
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- CN114149797B CN114149797B CN202111481192.9A CN202111481192A CN114149797B CN 114149797 B CN114149797 B CN 114149797B CN 202111481192 A CN202111481192 A CN 202111481192A CN 114149797 B CN114149797 B CN 114149797B
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- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 34
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 5
- 238000007654 immersion Methods 0.000 claims abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 81
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 238000004040 coloring Methods 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 32
- 229910013684 LiClO 4 Inorganic materials 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 239000003086 colorant Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001429 visible spectrum Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 244000172533 Viola sororia Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
Abstract
The invention provides a double-regulated multi-color composite material, a preparation method thereof and an electrochromic device, wherein the method comprises the following steps: sequentially treating the PEI solution treated substrate material with PEI solution and K at specific pH 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, PEI solution and AR alizarin red solution, repeatedly soaking in the above solutions, and sealing with PEI solution to obtain composite material, denoted PEI/[ (PEI) x /(P 2 W 18 ) y /(PEI) p /(AR) q ] n PEI; x, y, p and q are the times of each immersion in the corresponding solution; n is the number of repeated cyclic soaks. The composite material combines dye color change under different pH values and polyacid color change under different voltages, and realizes pH and voltage double modulation. The composite film is used as a working electrode, tungsten oxide is used as a counter electrode, and LiClO 4 PC and polymethyl methacrylate are used as electrolytes to construct electrochromic devices.
Description
Technical Field
The invention belongs to the technical field of electrochromic films, and particularly relates to a double-adjustment multi-color composite material, a preparation method thereof and an electrochromic device.
Background
Electrochromic materials are one of new materials meeting sustainable and renewable requirements, can adapt to energy requirements and environmental challenges, and further obtain social benefits. The optical characteristics of the material such as absorption, transmission, reflectivity and the like are changed stably and reversibly under an external electric field, so that the material is widely applied to the aspects of electrochromic electronic skin, molecular imaging, intelligent vehicle windows, anti-glare rearview mirrors, military camouflage equipment and the like.
The polyoxometallate (polyacid for short) is a typical inorganic electrochromic material, is similar to a polymer macromolecule, can accurately control the structure, has good ultraviolet stability and thermal stability, generates reversible mixed valence states, well combines the advantages of the polymer and the inorganic electrochromic material, and is widely applied to the electrochromic field. However, single-component polyacid-based electrochromic materials still have the problem of single color change, and classical polyacids can only realize colorless to blue change. The current color-adjustable polyacid-based electrochromic material utilizes metal-substituted polyacid to change the color of the polyacid from colorless to pale yellow and the like; or compounding polyacids with other colored materials, such as metallic iron, copper complexes, dyes, etc., with the addition of colors to achieve multi-color changes. Therefore, the polyacid-based electrochromic material capable of being changed in multiple colors is of great significance to practical application.
Disclosure of Invention
In view of the above, the present invention aims to provide a dual-tuned multi-color composite material, and a preparation method and application thereof. And the composite material is used as a working electrode, and the tungsten oxide film is used as a counter electrode to construct an electrochromic device.
The invention provides a preparation method of a double-regulated multi-color composite material, which comprises the following steps:
sequentially treating the PEI solution treated substrate material in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, PEI solution and alizarin red solution, and repeatedly soaking in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 In the O solution, the PEI solution and the alizarin red solution, a PEI solution sealing layer is adopted to obtain a double-regulated multi-color composite material which is marked as a general formula PEI/[ (PEI) x /(P 2 W 18 ) y /(PEI) p /(AR) q ] n /PEI；
Wherein x, y, p and q are the times of each immersion in the corresponding solution;
n is the number of repeated cycles of soaking in the solution;
the pH value of the PEI solution is 1.5-5; the K is 6 [P 2 W 18 O 62 ]·14H 2 The pH value of the O solution is 1.5-4; the pH value of the alizarin red solution is 1.5-5.
In the invention, x is 10-20 min;
y is 10-20 min; p is 10-20 min; q is 5-15 min;
n has a value of 20 to 35.
In a specific embodiment, x is 10min, y is 10min, p is 10min, and q is 7min.
In the invention, the concentration of the PEI solution is 5-10 mmol/L;
the K is 6 [P 2 W 18 O 62 ]·14H 2 The concentration of the O solution is 5-10 mmol/L;
the concentration of the alizarin red solution is 5-10 mmol/L.
In the specific embodiment of the invention, the concentration of the PEI solution is 5mmol/L, and the pH value is 2; the K is 6 [P 2 W 18 O 62 ]·14H 2 The concentration of the O solution is 5mmol/L;
the concentration of the alizarin red solution is 7.6mmol/L, and the pH value is 2.
In the invention, the time for sealing the layer by adopting the PEI solution is 18-30 min. In a specific embodiment, the time for the PEI solution seal is 20 minutes.
In the present invention, the base material is FTO glass.
In the invention, after each soaking, the soaked material is washed by distilled water and dried.
In the invention, the PEI solution treated base material is prepared according to the following method:
soaking the clean substrate material into a polyethyleneimine solution with the concentration of 5-10 mmol/L, adjusting the pH to 1.5-5 by hydrochloric acid, and soaking for 55-65 min to obtain the substrate material treated by the PEI solution.
In the invention, the concentration of the polyethyleneimine solution adopted for treating the substrate material is 5mmol/L, and the pH value is 2; the soaking time is 60min.
The invention provides a double-regulated multi-color composite material, which is prepared by the preparation method according to the technical scheme. The dual tuned multi-color composite is preferably applied in electrochromic devices in the form of electrochromic films.
The invention provides an electrochromic device, which comprises the double-adjustment multi-color composite material.
In the invention, the electrochromic device takes a mixture of lithium perchlorate particles, polymethyl methacrylate particles and propylene carbonate as a solid electrolyte;
a tungsten oxide film is used as a counter electrode;
the double-regulated multi-color composite material is used as a working electrode.
In the present invention, the preparation process of the solid electrolyte comprises: 1.5g of lithium perchlorate (LiClO) 4 ) Adding 10mL of Propylene Carbonate (PC), heating and stirring, adding 3g of polymethyl methacrylate, controlling the temperature to be about 50 ℃, and continuously stirring to be sticky, thus obtaining the required solid electrolyte.
When the device is assembled, the solid electrolyte is uniformly smeared on the counter electrode, the working electrode is assembled on the counter electrode, bubbles are removed, and the device is dried at 60 ℃. In electrochromic devices, the working electrode thickness is preferably 260nm.
The electrochromic device provided by the invention can realize double adjustment of voltage and pH, so that more color changes are obtained.
The invention provides a preparation method of a double-regulated multi-color composite material, which comprises the following steps: sequentially treating the PEI solution treated substrate material in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, PEI solution and alizarin red solution, repeatedly soaking in the above solutions, and sealing with PEI solution to obtain double-regulated multi-color composite material, denoted by general formula PEI/[ (PEI) x /(P 2 W 18 ) y /(PEI) p /(AR) q ] n PEI; wherein x, y, p and q are the times of each immersion in the corresponding solution; n is the number of repeated cycles of soaking in the above solution. The composite material prepared by the method not only has good electrochromic performance and stability, but also can be applied through pH and voltage double adjustmentThe voltage is applied to change the color of the polyacid, the dye has different colors under different pH values, and the dye and the polyacid are overlapped to have multi-color change, namely, the color change of a plurality of colors from yellow, green to bluish green, orange pink, light green to bluish violet, dark pink to gray pink to purple is realized. The optical contrast of the electrochromic material can be more than 39% under the step voltage of +1.0V and-1.0V; the cycle stability of the electrochromic material is more than 1000 times and still remains stable; storage stability of electrochromic materials: the composite material is placed for 120 days, and compared with the visible absorption spectrum of the newly prepared composite material, the spectrum is not obviously changed; electrochromic devices are also capable of achieving dual-modulation color change of voltage and pH.
Drawings
FIG. 1 is a graph of absorbance versus number of layers for the composite;
FIG. 2 is a scanning electron microscope image of the composite material;
FIG. 3 is a visible spectrum of the composite on days 1 and 120;
FIG. 4 is a schematic device diagram of the composite material;
fig. 5 is a visible spectrum of the composite material before and after applying a voltage at ph=6.50, 7.00, 7.50, 8.00;
FIG. 6 is [ PEI/P ] 2 W 15 V 3 /PEI/CR] 20 Visible spectrum before and after applying voltage at different pH;
fig. 7 is a visible spectrum of the composite material (preparation condition ph=6.00) before and after applying a voltage.
Detailed Description
For further explanation of the present invention, a dual-tuned multi-color composite material, a method for preparing the same, and applications thereof, provided herein below, are described in detail with reference to the examples, but should not be construed as limiting the scope of the present invention.
Example 1
1.1 preparation of raw materials
Preparation of Polyethylenimine (PEI) solution:
0.0198g of PEI was dissolved in 90mL of water, 5.256g of sodium chloride was added to the solution to dissolve, and the pH was adjusted to 2 with hydrochloric acid to prepare a 5mmol/L PEI solution.
K 6 [P 2 W 18 O 62 ]·14H 2 O (abbreviated as P) 2 W 18 ) Preparing a solution:
0.497g of raw material P is taken 2 W 18 Dissolved in 25mL of distilled water to prepare a 5mmol/L solution.
Preparation of Alizarin Red (AR) solution:
0.1370g of alizarin red is taken and dissolved in 50mL of distilled water, and the pH value is adjusted to 2 by hydrochloric acid, so that 7.6mmol/L alizarin red solution is prepared.
1.2 preparation of composite materials
Clean FTO glass was immersed in a PEI solution (ph=2 adjusted with hydrochloric acid) at a concentration of 5mmol/L for 60min. Taking out, washing with distilled water, drying, sequentially soaking in 5mmol/L PEI solution, 5mmol/L K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, 5mmol/L PEI solution and 7.6mmol/L alizarin red solution, washing with distilled water, blow drying, repeatedly soaking in four solutions for 10min, and collecting P 2 W 18 Soaking in solution for 10min and alizarin red solution for 7min, and preparing the composite material with the layer number of 30 at room temperature.
1.3 preparation of composite devices
The composite material is treated in different pH solutions [0.1mol/L HCl solution (pH 2.00), 0.2mol/L HAc-NaAc solution (pH 4.00), 0.2mol/L HAc-NaAc solution (pH 6.00)]After soaking and WO 3 The nano-block films are assembled separately, wherein LiClO 4 PC and polymethyl methacrylate as solid electrolytes. Then, the test was performed after drying at 60 ℃.
Example 2
2.1 growth monitoring of composite materials
Monitoring ultraviolet-visible absorption spectrum of composite material with quartz as substrate, and gradually increasing absorbance of two characteristic peaks of the composite material with increasing layer number (figure 1), which proves PEI and P 2 W 18 And alizarin red growth are uniformly stable.
2.2 micro-morphology and Structure of composite materials
The microscopic morphology of the composite material is detected by a scanning electron microscope, and as can be seen from fig. 2, a large number of uniform fine particles are distributed on the surface of the composite material, which may be P 2 W 18 Aggregation of anions, PEI and alizarin red.
2.3 storage stability of composite materials
To demonstrate the good stability of the composite, the change in transmittance of the composite after 120 days of standing was tested (see fig. 3). The transmittance change curve at day 120 was almost the same as the initial state, indicating that the film did not cause structural change or loss after long-term placement.
2.4 electrochromic Properties of the composite
2.4.1 color and maximum absorption wavelength variation of composite materials at different voltages
The color of the composite material can be adjusted by the pH value or by different application voltages. When an external voltage of-0.4 to-1.0V is applied, the wavelength change range of the composite material in 0.1mol/L HCl solution (pH 2.00) is 582-669nm, and the color change from yellow, green to blue-green is realized; the wavelength change range in a 0.2mol/L HAc-NaAc solution (pH 4.00) is 583-646nm, so that the orange pink, light green to blue-purple color change is realized; the wavelength change range in the 0.2mol/L HAc-NaAc solution (pH 6.00) is 604-657nm, and the color change from dark pink, gray pink to purple is realized. The polyacid-alizarin red composite material is shown to exhibit obvious multi-color tone change.
2.4.2 coloring, fade time and stability of composite materials
To further investigate the electrochromic properties of the composites, the composites were subjected to step tests (+1.0V and-1.0V) in different pH solutions (0.1 mol/L HCl solution (pH 2.00), 0.2mol/L HAc-NaAc solution (pH 4.00), 0.2mol/L HAc-NaAc solution (pH 6.00). As shown in Table 1, the optical contrast of the composites at three pH values was 39.71%, 37.94% and 35.96%, respectively, and the coloring/fading times were 6.29s/11.10s, 6.98s/0.94s and 5.72s/5.68s, respectively, after 1000 cycles of the composites, the loss of the optical contrast was 35.08%, 34.71% and 9.29% at three pH values, respectively, indicating that the same composites exhibited superior electrochromic properties under different conditions.
Table 1 electrochromic properties of composites under different test conditions
2.4.3 coloring efficiency of composite materials
The coloring efficiency is one of important parameters for evaluating electrochromic performance of a material, and refers to the ratio of the difference value of absorbance of a coloring state and a fading state to the change of the charge quantity of a unit electrode area, and the calculating method is CE=delta OD/delta Q. The test results are shown in Table 1, and the coloring efficiency of the composite materials in electrolytes with different pH values is 67.00cm respectively 2 /C、82.15cm 2 Cand 83.23cm 2 /C。
In summary, the composite material has good electrochromic performance and stability as an electrochromic material, and can realize the change of multiple colors through the double adjustment of pH and voltage, namely the multi-color tone change of yellow, green to bluish green, orange pink, light green to bluish purple, deep pink and gray pink to purple.
2.5.4 color Change of composite device
The composite material was soaked in three solutions (ph=2.00, ph=4.00, ph=6.00) respectively and used as a working electrode, and a tungsten oxide thin film was used as a counter electrode, and lithium perchlorate particles, polymethyl methacrylate particles, and propylene carbonate were mixed to prepare a solid electrolyte, to form an electrochromic device, as shown in fig. 4. Before and after the voltage is applied, the colors respectively realize the change from yellow to blue-green, orange pink to blue-purple and deep pink to purple, and the color change is more than that of a pure polyacid material.
Electrochromic Properties of 2.5.5 composite in electrolyte (pH > 6)
Fig. 5 is a graph of the visible absorption spectra of the composite material in solutions at different ph=6.50, 7.00, 7.50, 8.00. At 0V, the maximum absorption peak of the solution composite film of the composite film is about 490nm in three pH values, and the composite film is yellow and has no obvious change in color; when a voltage of-1.0V is applied, the maximum absorption peak of the composite film in three pH solutions is about 589nm, and the composite film has bluish purple color without obvious difference in color. Indicating that the composite film does not undergo more modulation of its color in an electrolyte with a pH greater than 6.
Comparative example 1
[PEI/P 2 W 15 V 3 /PEI/CR] 20 Composite material
1.1 preparation of raw materials
Preparation of Polyethylenimine (PEI) solution: 0.0198g of PEI was dissolved in 90mL of water, 5.256g of sodium chloride was added to the solution to dissolve, and the pH was adjusted to 4 with hydrochloric acid to prepare a 5mmol/L PEI solution.
K 8 [P 2 W 15 V 3 O 62 ]·9H 2 O (abbreviated as P) 2 W 15 V 3 ) Preparing a solution: 0.1110g of raw material P 2 W 15 V 3 Dissolving in 10mL distilled water, and constant volume to 25mL to obtain 1×10 -3 mol/L solution.
Preparation of Congo Red (CR) solution: dissolving 0.0049g CR in 30mL water, and fixing volume to 50mL to obtain 1.4X10 -4 Congo red solution in mol/L.
1.2[PEI/P 2 W 15 V 3 /PEI/CR] 20 Preparation of composite membranes
Soaking clean FTO glass to a concentration of 5×10 -3 The pH was adjusted to 4 with hydrochloric acid in a mol/L PEI solution for 24 hours. Taking out, washing with distilled water, drying, and sequentially soaking in 5×10 -3 mol/LPEI solution, 1X 10 -3 mol/L P 2 W 15 V 3 Solution, 5X 10 -3 mol/L PEI solution and 1.4X10 -4 Soaking in Congo red solution, washing with distilled water, blow drying, repeatedly soaking in four solutions, soaking PEI for 10min, and collecting P 2 W 15 V 3 Soaking in Congo red solution for 10min, soaking in Congo red solution for 3min, and preparing 20 layers of [ PEI/P ] 2 W 15 V 3 /PEI/CR] 20 Is a composite material of (a).
1.3 color Change of composite materials
FIG. 6 is [ PEI/P ] 2 W 15 V 3 /PEI/CR] 20 Visible absorption spectra of the composite film in solutions with different pHs of 2.00, 4.00 and 6.00. At 0V, the maximum absorption peak of the composite film in three pH solutions is 495nm, and the composite film presents light red color without change of color; when a voltage of-1.0V is applied, the maximum absorption peak of the composite film in three pH solutions is 512nm, and the composite film presents bluish purple with no obvious difference in color. This shows that the composite film has the same modulation performance under different pH solutions and has no obvious difference in color.
Comparative example 2
PEI/[ PEI/P prepared in solution with pH=6 2 W 18 /PEI/AR] 30 PEI composite material
1.1 preparation of raw materials
Preparation of Polyethylenimine (PEI) solution: 0.0198g of PEI was dissolved in 90mL of water, 5.256g of sodium chloride was added to the solution to dissolve, and the pH was adjusted to 6 with hydrochloric acid to prepare a 5mmol/L PEI solution.
K 6 [P 2 W 18 O 62 ]·14H 2 O (abbreviated as P) 2 W 18 ) Preparing a solution: 0.497g of raw material P is taken 2 W 18 Dissolved in 25mL of distilled water to prepare a 5mmol/L solution.
Preparation of Alizarin Red (AR) solution: 0.1370g of alizarin red is taken and dissolved in 50mL of distilled water, and the pH value is adjusted to 6 by hydrochloric acid, so that 7.6mmol/L alizarin red solution is prepared.
1.2 composite PEI/[ PEI/P 2 W 18 /PEI/AR] 30 Preparation of PEI film (pH 6.00)
Clean FTO glass was immersed in a PEI solution (ph=6 with hydrochloric acid) at a concentration of 5mmol/L for 60min. Taking out, washing with distilled water, drying, soaking in 5mmol/LPEI solution, 5mmol/L K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, 5mmol/L PEI solution and 7.6mmol/L alizarin red solution, washing with distilled water, blow drying, and repeatedly soakingSoaking PEI in the solution for 10min, P 2 W 18 Soaking in solution for 10min and alizarin red solution for 7min, and preparing the composite material with the layer number of 30 at room temperature.
1.3 color Change of composite materials
PEI/[ PEI/P prepared at pH6.00 2 W 18 /PEI/AR] 30 PEI composites were tested in a 0.2mol/LHAc-NaAc solution (pH 6.00). As shown in fig. 7, at 0V, the maximum absorption wavelength of the composite material is about 487nm, exhibiting a purple color; when a voltage of-1.0V is applied, the maximum absorption wavelength of the composite material is about 583nm, and the composite material presents a deep purple blue color. It can be seen that the color of the composite material prepared in the solution at pH6 changed from violet to deep blue-violet only, with no apparent color modulation.
As can be seen from the above examples, the present invention provides a method for preparing a dual-tuned multi-color composite material, comprising the following steps: sequentially treating the PEI solution treated substrate material in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, PEI solution and alizarin red solution, repeatedly soaking in the above solutions, and sealing with PEI solution to obtain double-regulated multi-color composite material, denoted by general formula PEI/[ (PEI) x /(P 2 W 18 ) y /(PEI) p /(AR) q ] n PEI; wherein x, y, p and q are the times of each immersion in the corresponding solution; n is the number of repeated cycles of soaking in the above solution. The composite material prepared by the method has good electrochromic performance and stability, the color of polyacid can be changed by applying voltage through double adjustment of pH and voltage, the dye has different colors under different pH, and the two colors are overlapped to change the colors, namely, the color tone of yellow, green to bluish green, orange pink, light green to bluish purple, deep pink and gray pink to purple is changed. The optical contrast of the electrochromic material can be more than 39% under the step voltage of +1.0V and-1.0V; the cycle stability of the electrochromic material is more than 1000 times and still remains stable; storage stability of electrochromic materials: placing the film material for 120 days, and preparing the film with new technologyCompared with the visible absorption spectrum of (2), the spectrum has no obvious change; electrochromic devices are also capable of achieving dual-modulation color change of voltage and pH.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A method of preparing a dual-tuned multi-color composite comprising the steps of:
sequentially treating the PEI solution treated substrate material in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 Soaking in O solution, PEI solution and alizarin red solution, and repeatedly soaking in PEI solution and K 6 [P 2 W 18 O 62 ]·14H 2 In the O solution, the PEI solution and the alizarin red solution, a PEI solution sealing layer is adopted to obtain a double-regulated multi-color composite material which is marked as a general formula PEI/[ (PEI) x /(P 2 W 18 ) y /(PEI) p /(AR) q ] n /PEI；
Wherein x, y, p and q are the times of each immersion in the corresponding solution;
n is the number of repeated cycles of soaking in the solution;
the pH value of the PEI solution is 1.5-5; the K is 6 [P 2 W 18 O 62 ]·14H 2 The pH value of the O solution is 1.5-4; the pH value of the alizarin red solution is 1.5-5;
the x is 10-20 min; y is 10-20 min; p is 10-20 min; q is 5-15 min;
n is 20-35;
the concentration of the PEI solution is 5-10 mmol/L;
the K is 6 [P 2 W 18 O 62 ]·14H 2 The concentration of the O solution is 5-10 mmol/L;
the concentration of the alizarin red solution is 5-10 mmol/L;
and adopting PEI solution for sealing for 18-30 min.
2. The method according to claim 1, wherein the concentration of the PEI solution is 5mmol/L and the pH value is 2;
the K is 6 [P 2 W 18 O 62 ]·14H 2 The concentration of the O solution is 5mmol/L;
the concentration of the alizarin red solution is 7.6mmol/L, and the pH value is 2.
3. The preparation method according to claim 1, wherein the PEI solution treated base material is prepared according to the following method:
and (3) soaking the clean substrate material into a polyethyleneimine solution with the concentration of 5-10 mmol/L, adjusting the pH to 1.5-5 by using hydrochloric acid, and soaking for 55-65 min to obtain the substrate material treated by the PEI solution.
4. A dual-tuned multi-color composite made by the method of any one of claims 1-3.
5. The dual-tuned multi-color composite of claim 4, wherein the pH of the electrolyte is 2-6 when the dual-tuned multi-color composite is electrochromic;
the range of the applied voltage is-0.9 to-1.5V when the double-adjusted multi-color composite material is subjected to electrochromic coloring.
6. An electrochromic device comprising the dual-tuned multi-color composite of any one of claims 4-5.
7. The electrochromic device according to claim 6, characterized in that the electrochromic device is provided with a solid electrolyte of a mixture of lithium perchlorate particles, polymethyl methacrylate particles and propylene carbonate;
a tungsten oxide film is used as a counter electrode;
the double-regulated multi-color composite material is used as a working electrode.
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