CN112505975A - WO (WO)x-NiOxFlexible electrochromic device and preparation method thereof - Google Patents
WO (WO)x-NiOxFlexible electrochromic device and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000005684 electric field Effects 0.000 claims abstract description 14
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000001276 controlling effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 23
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007888 film coating Substances 0.000 claims description 7
- 238000009501 film coating Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 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 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002096 quantum dot Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 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 description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- QLJVFHXULZBBSH-UHFFFAOYSA-N [Ni]=O.[W]=O Chemical compound [Ni]=O.[W]=O QLJVFHXULZBBSH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/085—Oxides of iron group metals
Abstract
The invention relates to the technical field of electrochromism and discloses a WOX‑NiOXBased flexible electrochromic devices, by WOXColor change and NiOXA mixed electrolyte is arranged between the color-changing bodies, WOXAn ITO conductive film and NiO are arranged between the upper surface of the color-changing body and the first PET substrateXAn ITO conductive film is arranged between the lower surface of the color-changing body and the second PET substrate; regulating the color development of the electrolyte layer to yellow electrochromic body by controlling the content of the carbon nanodots and regulating WOX‑NiOXThe color development of the electrochromic system is blue electrochromic, and then the flexible device completes the color superposition: the blue electrode is superimposed with a yellow electrolyte layer to make the device display a green system electrochromic body. The flexible electrochromic material can realize wearability and portability, can realize yellow-green system conversion performance under an external electric field, and meets the requirement of controllable conversion of the yellow-green systemAnd (5) feeding. Therefore, the method has a wider application prospect in practical application.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to a WOX-NiOXA flexible electrochromic device and a preparation method thereof.
Background
The electrochromic technology is a technology in which the internal structure of a material changes under the action of an external electric field, so that the absorption characteristic of the material changes, and the color of the material changes along with the change of the external electric field. The electrochromic device can be designed into flexible and rigid types according to the using conditions and the performance of the used materials, and the flexible electrochromic device can be prepared into electrochromic yarns, cloth braided fabrics, flexible display devices and the like so as to realize the wearability and portability of the electrochromic device, so that the flexible electrochromic device has a larger application prospect in practical application. Although the research on flexible electrochromic devices by extensive researchers is still hot, research breakthroughs are still needed for flexible electrochromic materials capable of meeting the controllable conversion of yellow-green color systems.
Disclosure of Invention
The object of the present invention is to provide a WOX-NiOXThe flexible electrochromic device and the preparation method thereof can realize the yellow-green system conversion performance under an external electric field.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
WO (WO)X-NiOXFlexible electrochromic devices based thereon, including WOXColor change material, NiOXColor-changing body, mixed electrolyte, PET substrate and ITO conductive film, WOXColor change and NiOXA mixed electrolyte is arranged between the color-changing bodies, WOXAn ITO conductive film and NiO are arranged between the upper surface of the color-changing body and the first PET substrateXAn ITO conductive film is arranged between the lower surface of the color-changing body and the second PET substrate; constitute TO/WOXMixed electrolyte/NiO containing carbon nano-dotsXan/ITO structure; by controllingThe content of the carbon nano-dots is adjusted to adjust the color development of the electrolyte layer into yellow electrochromic body, and simultaneously, the O is adjusted by an external electric fieldX-NiOXThe color development of the electrochromic system is blue electrochromic, and then the flexible device completes the color superposition: the blue electrode is superimposed with a yellow electrolyte layer to make the device display a green system electrochromic body.
WO (WO)X-NiOXThe preparation method of the flexible electrochromic device comprises the following steps: including WOXColor change material, NiOXSelecting and preparing a color-changing body, a mixed electrolyte, a PET substrate and an ITO conductive film;
1) selecting the PET substrate material: the surface of the PET substrate is corroded for 1-90s by concentrated sulfuric acid at 10-90 ℃, then is sequentially put into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water for washing, and then is washed by N2Drying;
the ITO film is coated on the surface of the PET as the WOX-NiOXThe conductive substrate of the flexible electrochromic device has a smooth surface in the normal positive direction during coating, and the coating atmosphere is Ar: O2319:11, the pressure is 0.9pa, the power is direct current 280W, and the time is controlled to be 20-80 min;
2) the blue electrochromic system is selected from WOX-NiOXBased on electrochromic systems, in which WOXThe atmosphere of the electrode coating is Ar: O2The pressure is 2pa, the power is direct current 200W, the time is controlled to be 10-30min, and the film thickness is about 200 nm; NiOXThe atmosphere of the electrode coating is Ar: O216: 84, the pressure is 3pa, the power is direct current 250W, the time is controlled to be 20min, and the film thickness is 350 nm; the blue electrochromic system is used for realizing the conversion of blue to brown, and the conversion of blue to light yellowish-brown is realized by adjusting the thickness of the nickel oxide layer;
3) selecting a mixed solution of PC-lithium perchlorate or PC-lithium perchlorate/lithium carbonate dissolved with a proper amount of carbon nanodots as a mixed electrolyte in the middle electrolyte layer of the mixed electrolyte; the preparation steps are as follows:
firstly, preparing carbon nanodots, dissolving 3g of citric acid and 3g of urea in 5mol of distilled water, heating the solution to dark brown by microwave of 550W for 25min, and drying the solution in a vacuum drying oven at 80 ℃ for 2 h; then preparing a mixed electrolyte of the carbon nano-dots, propylene carbonate and lithium perchlorate/lithium carbonate, wherein the proportion of the propylene carbonate to the lithium perchlorate is 100 ml: 20.6g, uniformly mixing and putting into a beaker, and mixing the carbon nanodot solution with a proper amount of PC-lithium perchlorate or PC-lithium perchlorate/lithium carbonate; finally, preparing the sol electrolyte, wherein the volume ratio of the curing adhesive 6000 to the mixed electrolyte is 1: and 3, storing at normal temperature for later use.
The PC-lithium perchlorate or the mixed electrolyte layer of PC-lithium perchlorate/lithium carbonate dissolved with the carbon nanodots is bright yellow green, yellow, brown yellow and green by changing the molar addition amount of the carbon nanodots; the mixed electrolyte solution uses a mixed dilithium salt electrolyte of carbon nanodots, PC-lithium perchlorate and lithium carbonate; lithium chlorate: molar ratio of lithium carbonate 2: 0.5.
4）WOX-NiOXthe flexible electrochromic device of base through the development of plus electric field adjustment electrochromic system for blue, makes the electrolyte layer development yellow through the content of control carbon nanodot simultaneously, and then this flexible device can accomplish the stack of colour: the blue electrode is superposed with the yellow electrolyte layer to make the device display green, thereby realizing reversible conversion between yellow and green systems; under the control of an external electric field, the yellow and green colors in the initial state and after 1000 cycles can meet the requirements of yellow YE2345 and green MG1058 color systems.
5) Preparing an electrode: selecting PET as a substrate, corroding the surface of the PET for 1-30s by concentrated sulfuric acid (30-70 ℃) to form a diffuse reflection film with increased softness, and then sequentially putting the PET into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water for washing and drying for film coating; after being taken out, the ITO is pasted on one edge by an adhesive tape and is put into magnetron sputtering for coating; and after the film coating is finished, taking out the substrate, and putting the substrate into a sealing bag for storage for later use.
6) Assembling the flexible electrochromic device: the nickel oxide and tungsten oxide electrodes prepared by the process are attached along the positive direction of the normal line, a syringe is taken, the mixed electrolyte containing the carbon nanodots is extracted, and the mixed electrolyte is respectively injected into the two electrodes along the small opening of the interlayer; the device is inclined at a certain angle, the small opening is slightly upward, and then the device is cured by being irradiated by an ultraviolet lamp for 20min and then stored by a sealing bag for later testing.
7) Testing, adjusting the content of the carbon nanodots, and modulating the initial color development of the device, wherein the modulated color is a yellow color system and is used for the color development of the device without an external electric field; after testing, the color systems of the initial state and the cycle are consistent with those of yellow YE2345 and green MG 1058; in the power-off and intermittent power supply test, the device is continuously supplied with power at a small voltage for 18 days, and the color heat of the device is kept for 1 day in the power-off test; when the test is carried out intermittently, the device is activated by charging every 24 hours in the initial period, and then the green color can be maintained for 9 days by using the device for a longer time.
Due to the adoption of the technical scheme, the invention has the following advantages:
WO (WO)X-NiOXBased flexible electrochromic devices, by WOXColor change and NiOXA mixed electrolyte is arranged between the color-changing bodies, WOXAn ITO conductive film and NiO are arranged between the upper surface of the color-changing body and the first PET substrateXAn ITO conductive film is arranged between the lower surface of the color-changing body and the second PET substrate; form ITO/WOXMixed electrolyte/NiO containing carbon nano-dotsXan/ITO structure; regulating the color development of the electrolyte layer to yellow electrochromic body by controlling the content of the carbon nanodots, and regulating WO by an external electric fieldX-NiOXThe color development of the electrochromic system is blue electrochromic, and then the flexible device completes the color superposition: the blue electrode is superimposed with a yellow electrolyte layer to make the device display a green system electrochromic body. The flexible electrochromic device can be prepared into an electrochromic display device and the like to further realize the wearability and the portability of the flexible electrochromic device, so that the flexible electrochromic device has a larger application prospect in practical application. So that the yellow-green system conversion performance can be realized under the applied electric field. The flexible electrochromic material which can controllably change yellow-green color system is satisfied.
Drawings
FIG. 1 is a schematic structural diagram of a flexible electrochromic device.
Detailed Description
Specific preferred embodiments of the flexible electrochromic device are described below:
example 1
As shown in FIG. 1, a WOX-NiOXFlexible electrochromic devices based thereon, including WOXColor change material, NiOXColor-changing body, mixed electrolyte, PET substrate and ITO conductive film, WOXColor change and NiOXA mixed electrolyte is arranged between the color-changing bodies, WOXAn ITO conductive film and NiO are arranged between the upper surface of the color-changing body and the first PET substrateXAn ITO conductive film is arranged between the lower surface of the color-changing body and the second PET substrate; constitute TO/WOXMixed electrolyte/NiO containing carbon nano-dotsXan/ITO structure; regulating the color development of the electrolyte layer to yellow electrochromic body by controlling the content of the carbon nanodots, and regulating O by an external electric fieldX-NiOXThe color development of the electrochromic system is blue electrochromic, and then the flexible device completes the color superposition: the blue electrode is superimposed with a yellow electrolyte layer to make the device display a green system electrochromic body.
WO (WO)X-NiOXThe preparation method of the flexible electrochromic device comprises the following steps: including WOXColor change material, NiOXSelecting and preparing a color-changing body, a mixed electrolyte Hhdjz, a PET substrate and an ITO conductive film; composition WOX-NiOXThe device structure of the flexible electrochromic device is as follows: ITO/WOXMixed electrolyte/NiO with dissolved carbon nano-dotsX/ITO。
WOX-NiOXThe substrate material of the flexible electrochromic device is selected from PET with one smooth surface and one frosted surface, and the smooth surface is in the normal positive direction during film coating. The surface of the PET substrate is corroded for 1-90s by concentrated sulfuric acid (10-90 ℃), and then is sequentially put into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water for washing and drying. Coating ITO film on PET surface as the WOX-NiOXThe conductive substrate of the flexible electrochromic device has a smooth surface in the normal positive direction during coating, and the coating atmosphere is Ar: O2＝319:11, the pressure is 0.9pa, the power is direct current 280W, and the time is controlled to be 20-80 min. WOX-NiOXThe electrochromic system used for the flexible electrochromic device of the flexible electrochromic device is a tungsten oxide-nickel oxide system. WO of ZhongXThe atmosphere of the electrode coating is Ar: O2The pressure is 2pa, the power is direct current 200W, the time is controlled to be 10-30min, and the film thickness is about 200 nm; NiOXThe atmosphere of the electrode coating is Ar: O2The pressure is 3pa, the power is 250W, the time is controlled at 20min, and the film thickness is about 350 nm. The electrochromic system can realize blue-brown conversion, and the blue-yellowish-brown conversion can be realized by adjusting the thickness of the nickel oxide layer.
WOX-NiOXThe middle electrolyte layer of the flexible electrochromic device selects a mixed solution of PC (propylene carbonate) -lithium perchlorate or PC-lithium perchlorate/lithium carbonate dissolved with carbon nanodots as a mixed electrolyte.
The PC-lithium perchlorate or the mixed electrolyte layer of PC-lithium perchlorate/lithium carbonate dissolved with the carbon nanodots can show bright yellow green, yellow, brown yellow and green by changing the molar addition of the carbon nanodots.
WOX-NiOXThe flexible electrochromic device of base can adjust the development of electrochromic system to blue through plus electric field, makes the electrolyte layer development yellow through the content of control carbon nanodot simultaneously, and then this flexible device can accomplish the stack of colour: the blue electrode is superposed with the yellow electrolyte layer to make the device display green, thereby realizing reversible conversion between yellow and green systems.
Under the control of an external electric field, the yellow and green of the flexible electrochromic device which finishes color superposition can meet the requirements of a yellow (YE 2345) green (MG 1058) color system in an initial state and after 1000 cycles.
Preparing an electrode: PET is selected as a substrate of the substrate, concentrated sulfuric acid (30-70 ℃) corrodes the surface of the PET for 1-30s to form a diffuse reflection film, the softness of the diffuse reflection film is increased, and then the diffuse reflection film is sequentially placed into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water to be washed and dried for film coating. After being taken out, the ITO is pasted on one edge by an adhesive tape and is put into magnetron sputtering for coating. And after the film coating is finished, taking out the substrate, and putting the substrate into a sealing bag for storage for later use.
Preparing an electrolyte: firstly, preparing carbon nanodots, dissolving 3g of citric acid and 3g of urea in 5mol of distilled water, heating the solution to dark brown by microwave (550W for 25 min), and drying the solution in a vacuum drying oven at 80 ℃ for 2 h. Then preparing a mixed electrolyte of the carbon nano-dots, propylene carbonate and lithium perchlorate/lithium carbonate, wherein the proportion of the propylene carbonate to the lithium perchlorate is 100 ml: 20.6g, uniformly mixing and putting into a beaker, and mixing the carbon nano-dot solution with a proper amount of PC-lithium perchlorate or PC-lithium perchlorate/lithium carbonate. Finally, preparing the sol electrolyte, wherein the volume ratio of the curing adhesive 6000 to the mixed electrolyte used in the invention is 1: and 3, storing at normal temperature for later use.
Assembling the device: and (3) attaching the nickel oxide electrode and the tungsten oxide electrode prepared by the process along the positive direction of a normal line (smooth surface), taking an injector, extracting the mixed electrolyte containing the carbon nanodots, and injecting the mixed electrolyte into the two electrodes along the small opening of the interlayer respectively. The device is inclined at a certain angle, the small opening is slightly upward, and then the device is cured by being irradiated by an ultraviolet lamp for 20min and then stored by a sealing bag for later testing.
The initial color development of the device can be modulated by adjusting the content of the carbon nanodots, and the color modulated in the embodiment is a yellow color system and is used for the color development of the device without an external electric field. The devices prepared in this example were tested to be in the same color system as yellow (YE 2345) green (MG 1058) in the initial state and after 1000 cycles. The device is subjected to power-off and intermittent power supply tests, and the result shows that the device can be maintained to operate for 18 days under the condition of low-voltage continuous power supply, and the color heat of the device can be kept for 1 day during the power-off test; when the test is carried out intermittently, the device is activated by charging every 24 hours in the initial period, and then the device can be used for a longer time (the green color can be maintained for 9 days).
Example 2
In order to solve the problems of life cycle and high window voltage of the device, the preparation of the electrolyte is optimized in the embodiment, and other structures are used as above.The mixed electrolyte solution used was a mixed dilithium salt electrolyte of carbon nanodots, PC-lithium perchlorate, and lithium carbonate. Lithium chlorate: molar ratio of lithium carbonate 2: 0.5, and the other steps are the same as above. The test result shows that: very few (1) reached 1500 cycles, and nearly half (4, 11 in total) reached over 900 cycles. Another device is taken to carry out in-situ electrochemical-optical test on the device, and the calculation result is calculated to obtain the device with the coloring efficiency of 82 cm2/C。
Claims (2)
1. WO (WO)X-NiOXA flexible electrochromic device based on, characterized in that: including WOXColor change material, NiOXColor-changing body, mixed electrolyte, PET substrate and ITO conductive film, WOXColor change and NiOXA mixed electrolyte is arranged between the color-changing bodies, WOXAn ITO conductive film and NiO are arranged between the upper surface of the color-changing body and the first PET substrateXAn ITO conductive film is arranged between the lower surface of the color-changing body and the second PET substrate; constitute TO/WOXMixed electrolyte/NiO containing carbon nano-dotsXan/ITO structure; regulating the color development of the electrolyte layer to yellow electrochromic body by controlling the content of the carbon nanodots, and regulating O by an external electric fieldX-NiOXThe color development of the electrochromic system is blue electrochromic, and then the flexible device completes the color superposition: the blue electrode is superimposed with a yellow electrolyte layer to make the device display a green system electrochromic body.
2. WO (WO)X-NiOXThe preparation method of the flexible electrochromic device is characterized by comprising the following steps: the method comprises the following steps: including WOXColor change material, NiOXSelecting and preparing a color-changing body, a mixed electrolyte, a PET substrate and an ITO conductive film;
1) selecting the PET substrate material: the surface of the PET substrate is corroded for 1-90s by concentrated sulfuric acid at 10-90 ℃, then is sequentially put into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water for washing, and then is washed by N2Drying;
the PET surface is coated with an ITO filmAs the WOX-NiOXThe conductive substrate of the flexible electrochromic device has a smooth surface in the normal positive direction during coating, and the coating atmosphere is Ar: O2319:11, the pressure is 0.9pa, the power is direct current 280W, and the time is controlled to be 20-80 min;
2) the blue electrochromic system is selected from WOX-NiOXBased on electrochromic systems, in which WOXThe atmosphere of the electrode coating is Ar: O2The pressure is 2pa, the power is direct current 200W, the time is controlled to be 10-30min, and the film thickness is about 200 nm; NiOXThe atmosphere of the electrode coating is Ar: O216: 84, the pressure is 3pa, the power is direct current 250W, the time is controlled to be 20min, and the film thickness is 350 nm; the blue electrochromic system is used for realizing the conversion of blue to brown, and the conversion of blue to light yellowish-brown is realized by adjusting the thickness of the nickel oxide layer;
3) selecting a mixed solution of PC-lithium perchlorate or PC-lithium perchlorate/lithium carbonate dissolved with a proper amount of carbon nanodots as a mixed electrolyte in the middle electrolyte layer of the mixed electrolyte; the preparation steps are as follows:
firstly, preparing carbon nanodots, dissolving 3g of citric acid and 3g of urea in 5mol of distilled water, heating the solution to dark brown by microwave of 550W for 25min, and drying the solution in a vacuum drying oven at 80 ℃ for 2 h; then preparing a mixed electrolyte of the carbon nano-dots, propylene carbonate and lithium perchlorate/lithium carbonate, wherein the proportion of the propylene carbonate to the lithium perchlorate is 100 ml: 20.6g, uniformly mixing and putting into a beaker, and mixing the carbon nanodot solution with a proper amount of PC-lithium perchlorate or PC-lithium perchlorate/lithium carbonate; finally, preparing the sol electrolyte, wherein the volume ratio of the curing adhesive 6000 to the mixed electrolyte is 1: 3, storing at normal temperature for subsequent use;
the PC-lithium perchlorate or the mixed electrolyte layer of PC-lithium perchlorate/lithium carbonate dissolved with the carbon nanodots is bright yellow green, yellow, brown yellow and green by changing the molar addition amount of the carbon nanodots; the mixed electrolyte solution uses a mixed dilithium salt electrolyte of carbon nanodots, PC-lithium perchlorate and lithium carbonate; lithium chlorate: molar ratio of lithium carbonate 2: 0.5;
4）WOX-NiOXof the groupThe flexible electrochromic device adjusts the color development of an electrochromic system to be blue through an external electric field, and simultaneously enables the color development of an electrolyte layer to be yellow through controlling the content of carbon nanodots, so that the flexible device can complete the color superposition: the blue electrode is superposed with the yellow electrolyte layer to make the device display green, thereby realizing reversible conversion between yellow and green systems; under the control of an external electric field, the yellow and green colors in an initial state and after 1000 cycles can meet the requirements of yellow YE2345 and green MG1058 color systems;
5) preparing an electrode: selecting PET as a substrate, corroding the surface of the PET for 1-30s by concentrated sulfuric acid (30-70 ℃) to form a diffuse reflection film with increased softness, and then sequentially putting the PET into absolute ethyl alcohol, saturated sodium hydroxide solution and deionized water for washing and drying for film coating; after being taken out, the ITO is pasted on one edge by an adhesive tape and is put into magnetron sputtering for coating; after the film coating is finished, taking out the substrate, and putting the substrate into a sealing bag for storage for later use;
6) assembling the flexible electrochromic device: the nickel oxide and tungsten oxide electrodes prepared by the process are attached along the positive direction of the normal line, a syringe is taken, the mixed electrolyte containing the carbon nanodots is extracted, and the mixed electrolyte is respectively injected into the two electrodes along the small opening of the interlayer; inclining the device at a certain angle, slightly opening upwards, curing by irradiating with an ultraviolet lamp for 20min, and storing with a sealing bag for subsequent test;
7) testing, adjusting the content of the carbon nanodots, and modulating the initial color development of the device, wherein the modulated color is a yellow color system and is used for the color development of the device without an external electric field; after testing, the color systems of the initial state and the cycle are consistent with those of yellow YE2345 and green MG 1058; in the power-off and intermittent power supply test, the device is continuously supplied with power at a small voltage for 18 days, and the color heat of the device is kept for 1 day in the power-off test; when the test is carried out intermittently, the device is activated by charging every 24 hours in the initial period, and then the green color can be maintained for 9 days by using the device for a longer time.
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