CN113376917A - Electrochromic device and preparation method of working electrode thereof - Google Patents
Electrochromic device and preparation method of working electrode thereof Download PDFInfo
- Publication number
- CN113376917A CN113376917A CN202110625997.XA CN202110625997A CN113376917A CN 113376917 A CN113376917 A CN 113376917A CN 202110625997 A CN202110625997 A CN 202110625997A CN 113376917 A CN113376917 A CN 113376917A
- Authority
- CN
- China
- Prior art keywords
- working electrode
- heat treatment
- electrochromic device
- oxygen
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- G02F1/1514—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
Abstract
The invention relates to an electrochromic device and a preparation method of a working electrode thereof, wherein the device comprises a counter electrode, a working electrode and an electrolyte; the counter electrode is formed by Li-doped NiyW 1-y oxide, and has strong light absorption in the wavelength range of 380-500 nm in a coloring state; the working electrode is formed by doping Li and Ti with WOx, and has strong light absorption in the wavelength range of 500-780 nm in a coloring state. The optical absorption of the counter electrode and the working electrode is matched, so that the prepared electrochromic device has stronger optical absorption in the whole wavelength range of 380 nm-780 nm of visible light.
Description
Technical Field
The invention relates to an electrochromic technology, in particular to an electrochromic device and a preparation method of a working electrode of the electrochromic device.
Background
The electrochromic technology is researched and developed for decades, and the electrochromic device gradually realizes small-scale application, for example, the electrochromic device can be applied to a building window, and the energy consumption of indoor temperature control equipment is greatly reduced and the energy utilization rate is improved by changing the color of the window and regulating solar radiation. The transparent part of the vehicle (automobile and airplane) also has wide application, such as a roof window, a porthole and a windshield, and the light intensity is adjusted by adjusting the transmittance, so that a comfortable environment is provided for people.
In some application fields, there is a requirement for the depth of the colored state of the color-changing glass, so that black electrochromic devices are also one of the hot spots of research. The device for understanding black from the spectrum angle means that light in the whole visible light region is completely absorbed, and according to the knowledge, no electrochromic material which is colorless, transparent and reversibly changed into black is found at present, although some polymer materials are in a black state in a colored state, the fading transmittance of the polymer materials is low, and the regulation rate of the device for light transmission is reduced; in addition, when the device is prepared by adopting the matched polymer color-changing material, the problems of poor stability and low fading state transmittance exist, in addition, the black device can also be prepared by matching WO3 and NiO inorganic color-changing materials, but the charge amount of the NiO and WO3 color-changing film is not matched, and the light absorption intensity of the NiO color-changing film in the wavelength range of 380 nm-500 nm needs to be further improved.
Disclosure of Invention
The purpose of the invention is: the invention ensures that the prepared electrochromic device has stronger light absorption in the whole visible light range (380 nm-780 nm) by matching the optical absorption of the electrochromic counter electrode and the working electrode.
The technical scheme of the invention is as follows:
an electrochromic device is provided, including an electrolyte, a working electrode, and a counter electrode;
the color-changing material of the working electrode is Li and Ti co-doped WOx oxide, wherein x is more than 2.7 and less than 3;
the color-changing material of the counter electrode is Li-doped NiyW 1-y oxide, wherein y is more than 0.3 and less than 0.9.
The working electrode and the counter electrode form optical matching, so that the transmittance of the electrochromic device in a wavelength range of 380nm to 780nm in a coloring state is lower than 15%.
In addition, the preparation method of the working electrode of the electrochromic device comprises the following steps:
step 1) depositing an ITO conductive layer on a glass substrate, placing the glass substrate deposited with the ITO conductive layer in a protective atmosphere, and carrying out annealing heat treatment on the glass substrate;
step 2) depositing Ti-doped WOx on the surface of the annealed ITO conductive layer to form a Ti-doped WOx layer, wherein x is more than 2.7 and less than 3, and the mass percent of Ti and W is less than or equal to 20%;
step 3) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is more than 20 percent;
step 4) depositing Li on the surface of the annealed Ti-doped WOx layer to form a Li and Ti co-doped WOx oxide layer;
step 5) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is more than 20 percent.
Further, the thickness of the ITO conductive layer in the step 1) is 200 nm-500 nm.
Further, the thickness of the Li and Ti co-doped WOx oxide layer in the step 5) is 300 nm-500 nm.
Further, the heat treatment temperature in the step 1) is 300-500 ℃, and the heat treatment time is 10-60 minutes.
Further, the heat treatment temperature in the step 3) is 200-400 ℃, and the heat treatment time is 10-60 minutes.
Further, in the step 5), the heat treatment temperature is 300-500 ℃, and the heat treatment time is 30-120 minutes.
Further, the protective atmosphere is argon atmosphere.
The invention has the advantages that: the invention relates to a counter electrode based on Li-doped NixW 1-x oxide, and a counter electrode based on Li and Ti co-doped WO3Working electrode ofThe working electrode and the counter electrode form an optical matching assembly device, and the device has strong light absorption in the wavelength range of 380-780 nm of visible light in a coloring state. Wherein, under the same condition, the counter electrode based on Li-doped NixW 1-x oxide has strong light absorption in the wavelength range of 380-500 nm; based on Li and Ti co-doping WO3The working electrode has strong light absorption in the wavelength range of 500 nm-780 nm.
Drawings
FIG. 1 is a graph of the transmittance of a counter electrode, a working electrode and a device in the colored state;
Detailed Description
The present invention is described in further detail below.
Embodiment 1, there is provided an electrochromic device including an electrolyte, a working electrode, and a counter electrode;
the working electrode color-changing material is Li and Ti co-doped WOx oxide, wherein x is more than 2.7 and less than 3;
the counter electrode color-changing material is Li-doped NiyW 1-y oxide, wherein y is more than 0.3 and less than 0.9.
The working electrode and the counter electrode form optical matching, so that the transmittance of the electrochromic device in a wavelength range of 380nm to 780nm in a coloring state is lower than 15%.
A preparation method of a working electrode of an electrochromic device comprises the following steps:
step 1) depositing an ITO conductive layer on a glass substrate, wherein the thickness of the ITO conductive layer is 300nm, and placing the glass substrate deposited with the ITO conductive layer in an argon atmosphere for annealing heat treatment, wherein the heat treatment temperature is 400 ℃, and the heat treatment time is 15 minutes;
step 2) depositing Ti-doped WOx on the surface of the annealed ITO conductive layer to form a Ti-doped WOx layer, wherein x is more than 2.7 and less than 3, the mass percent of Ti and W is about 10%, and the thickness is 300 nm;
step 3) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is 80 percent, the heat treatment temperature is 300 ℃, and the heat treatment time is 30 minutes;
step 4) depositing Li on the surface of the annealed Ti-doped WOx layer to form a Li and Ti co-doped WOx oxide layer;
step 5) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein the volume percentage of oxygen in the oxygen-containing atmosphere is 60%, the heat treatment temperature is 400 ℃, and the heat treatment time is 60 minutes.
The counter electrode color-changing material is a Li-doped NiyW 1-y oxide layer, wherein y is more than 0.3 and less than 0.9, and the thickness is 400 nm.
The steps for preparing the device are as follows:
and step 1) dispensing and packaging the working electrode and the counter electrode by using ultraviolet hardening resin (UV glue), dispensing glue around the working electrode or the counter electrode, oppositely covering the counter electrode or the working electrode and leaving a liquid filling opening, wherein the distance between the two electrodes is 0.2mm, and curing the ultraviolet hardening resin around by using an ultraviolet lamp.
Step 2) filling the electrolyte prepolymer into the prepared device, filling the device, sealing the small hole with UV glue, and irradiating the device for 20s by using an ultraviolet lamp to cure the device;
and 3) solidifying the electrolyte prepolymer in the device by adopting a heating mode to form a polyelectrolyte layer, wherein the heating temperature is 70 ℃, the heating polymerization time is 10 hours, and the thickness of the electrolyte layer is 0.2mm, so that the electrochromic device is formed.
Embodiment 2, there is provided an electrochromic device including an electrolyte, a working electrode, and a counter electrode;
the working electrode is made of Li and Ti co-doped WOx oxide, wherein x is more than 2.7 and less than 3;
the counter electrode is made of Li-doped NiyW 1-y oxide, wherein y is more than 0.3 and less than 0.9.
The working electrode and the counter electrode form optical matching, so that the transmittance of the electrochromic device in a wavelength range of 380nm to 780nm in a coloring state is lower than 15%.
A preparation method of a working electrode of an electrochromic device comprises the following steps:
step 1) depositing an ITO conductive layer on a glass substrate, wherein the thickness of the ITO conductive layer is 300nm, and placing the glass substrate deposited with the ITO conductive layer in an argon atmosphere for annealing heat treatment, wherein the heat treatment temperature is 400 ℃, and the heat treatment time is 15 minutes;
step 2) depositing Ti-doped WOx on the surface of the annealed ITO conductive layer to form a Ti-doped WOx layer, wherein x is more than 2.7 and less than 3, the mass percent of Ti and W is about 5%, and the thickness is 300 nm;
step 3) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is 80 percent, the heat treatment temperature is 300 ℃, and the heat treatment time is 30 minutes;
step 4) depositing Li on the surface of the annealed Ti-doped WOx layer to form a Li and Ti co-doped WOx oxide layer;
step 5) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein the volume percentage of oxygen in the oxygen-containing atmosphere is 60%, the heat treatment temperature is 400 ℃, and the heat treatment time is 60 minutes.
The counter electrode color-changing material is a Li-doped NiyW 1-y oxide layer, wherein y is more than 0.3 and less than 0.9, and the thickness is 450 nm.
The steps for preparing the device are as follows:
and step 1) dispensing and packaging the working electrode and the counter electrode by using ultraviolet hardening resin (UV glue), dispensing glue around the working electrode or the counter electrode, oppositely covering the counter electrode or the working electrode and leaving a liquid filling opening, wherein the distance between the two electrodes is 0.2mm, and curing the ultraviolet hardening resin around by using an ultraviolet lamp.
Step 2) filling the electrolyte prepolymer into the prepared device, filling the device, sealing the small hole with UV glue, and irradiating the device for 20s by using an ultraviolet lamp to cure the device;
and 3) solidifying the electrolyte prepolymer in the device by adopting a heating mode to form a polyelectrolyte layer, wherein the heating temperature is 80 ℃, the heating polymerization time is 8h, and the thickness of the electrolyte layer is 0.2mm, so that the electrochromic device is formed.
Claims (8)
1. An electrochromic device, characterized in that: comprises an electrolyte, a working electrode and a counter electrode;
the color-changing material of the working electrode is Li and Ti co-doped WOx oxide, wherein x is more than 2.7 and less than 3;
the color-changing material of the counter electrode is Li-doped NiyW 1-y oxide, wherein y is more than 0.3 and less than 0.9.
The working electrode and the counter electrode form optical matching, so that the transmittance of the electrochromic device in a wavelength range of 380nm to 780nm in a coloring state is lower than 15%.
2. A preparation method of a working electrode of an electrochromic device is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1) depositing an ITO conductive layer on a glass substrate, placing the glass substrate deposited with the ITO conductive layer in a protective atmosphere, and carrying out annealing heat treatment on the glass substrate;
step 2) depositing Ti-doped WOx on the surface of the annealed ITO conductive layer to form a Ti-doped WOx layer, wherein x is more than 2.7 and less than 3, and the mass percent of Ti and W is less than or equal to 20%;
step 3) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is more than 20 percent;
step 4) depositing Li on the surface of the annealed Ti-doped WOx layer to form a Li and Ti co-doped WOx oxide layer;
step 5) placing the glass substrate in an oxygen-containing atmosphere for annealing heat treatment; wherein, the volume percentage of oxygen in the oxygen-containing atmosphere is more than 20 percent.
3. The method of claim 2, wherein the step of preparing the working electrode of the electrochromic device comprises: the thickness of the ITO conductive layer in the step 1) is 200 nm-500 nm.
4. The method of claim 2, wherein the step of preparing the working electrode of the electrochromic device comprises: the thickness of the Li and Ti co-doped WOx oxide layer in the step 5) is 300-500 nm.
5. A method of preparing a working electrode for an electrochromic device according to claim 3, characterized in that: the heat treatment temperature in the step 1) is 300-500 ℃, and the heat treatment time is 10-60 minutes.
6. The method of claim 2, wherein the step of preparing the working electrode of the electrochromic device comprises: the heat treatment temperature in the step 3) is 200-400 ℃, and the heat treatment time is 10-60 minutes.
7. The method of claim 4, wherein the step of preparing the working electrode of the electrochromic device comprises: in the step 5), the heat treatment temperature is 300-500 ℃, and the heat treatment time is 30-120 minutes.
8. The method of claim 4, wherein the step of preparing the working electrode of the electrochromic device comprises: the protective atmosphere is argon atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110625997.XA CN113376917A (en) | 2021-06-04 | 2021-06-04 | Electrochromic device and preparation method of working electrode thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110625997.XA CN113376917A (en) | 2021-06-04 | 2021-06-04 | Electrochromic device and preparation method of working electrode thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113376917A true CN113376917A (en) | 2021-09-10 |
Family
ID=77575899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110625997.XA Pending CN113376917A (en) | 2021-06-04 | 2021-06-04 | Electrochromic device and preparation method of working electrode thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113376917A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060209383A1 (en) * | 2005-02-23 | 2006-09-21 | Sage Electrochromics, Inc. | Electrochromic devices and methods |
| US20100245973A1 (en) * | 2009-03-31 | 2010-09-30 | Soladigm, Inc. | Electrochromic devices |
| US20180004058A1 (en) * | 2014-12-31 | 2018-01-04 | Saint-Gobain Glass France | Fast heat treatment method for a complete all-solid-state electrochromic stack |
| CN107744804A (en) * | 2017-11-21 | 2018-03-02 | 陕西盛迈石油有限公司 | A kind of preparation method of titania additive anhydrous wolframic acid powder body catalyst |
-
2021
- 2021-06-04 CN CN202110625997.XA patent/CN113376917A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060209383A1 (en) * | 2005-02-23 | 2006-09-21 | Sage Electrochromics, Inc. | Electrochromic devices and methods |
| US20100245973A1 (en) * | 2009-03-31 | 2010-09-30 | Soladigm, Inc. | Electrochromic devices |
| US20180004058A1 (en) * | 2014-12-31 | 2018-01-04 | Saint-Gobain Glass France | Fast heat treatment method for a complete all-solid-state electrochromic stack |
| CN107744804A (en) * | 2017-11-21 | 2018-03-02 | 陕西盛迈石油有限公司 | A kind of preparation method of titania additive anhydrous wolframic acid powder body catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 代强等: "钛掺杂氧化钨薄膜结构与电致变色性能研究", 《真空》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Responsive smart windows from nanoparticle–polymer composites | |
| JP2023059908A (en) | Optical filter comprising variable transmittance layer | |
| US9720299B1 (en) | Electrochromic multi-layer devices with cross-linked ion conducting polymer | |
| US20120301642A1 (en) | Smart window | |
| JP6665210B2 (en) | Electrochromic device and smart window with electrochromic device | |
| KR101471551B1 (en) | Polymer dispersed liquid crystal light control bodies used nickel based electrodes and manufacturing method of the same | |
| CN104768892A (en) | Glazing having switchable optical properties | |
| WO2018196054A1 (en) | Ultraviolet all-solid-state electrolyte and preparation process and application thereof | |
| CN106405881A (en) | Optical module and method for manufacturing the same, optical devices | |
| CN109709704B (en) | Light modulation glass and preparation method thereof | |
| CN103692730A (en) | Thermochromic smart window and preparation method thereof | |
| CN109634021A (en) | A kind of quasi- solid-state tungstic acid electrochromic device and preparation method thereof | |
| CN113917729B (en) | Trans-form dimming glass based on electric response and preparation method thereof | |
| CN109143632A (en) | A kind of automobile smart glass and preparation method thereof | |
| CN113355030A (en) | Preparation method of intelligent dimming glass color-changing heat insulation adhesive film based on quantum dots | |
| CN106249500B (en) | It is a kind of based on amorphous state-nanocomposite structure flexible electro-chromic device and preparation method thereof | |
| JP2009042578A (en) | Light control multilayer film structure, and light modulation structure | |
| CN113376917A (en) | Electrochromic device and preparation method of working electrode thereof | |
| KR20100112464A (en) | The heat shielding film having heat shieling layer which used a variable chromatic metallic peroxide binder and manufacturing method thereof | |
| KR102230604B1 (en) | Method of manufacturing light-sensitive photochromic device and the device thereof | |
| CN109270761B (en) | Flexible hot melt adhesive type all-solid-state flexible electrochromic device | |
| CN215551557U (en) | Controllable laminated light-adjusting glass based on liquid crystal-based thermochromic film | |
| CN215813629U (en) | Light modulation film with light selectivity | |
| CN108483939A (en) | A kind of electrochomeric films and preparation method thereof of effective modulation sunlight transmittance | |
| KR20170120455A (en) | Electrochromic device containing polymer electrolyte in gel state and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |