CN113376917A - Electrochromic device and preparation method of working electrode thereof - Google Patents

Electrochromic device and preparation method of working electrode thereof Download PDF

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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
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China
Prior art keywords
working electrode
heat treatment
electrochromic device
oxygen
doped
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CN202110625997.XA
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Chinese (zh)
Inventor
韦友秀
颜悦
付子怡
望咏林
霍钟祺
刘伟明
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AECC Beijing Institute of Aeronautical Materials
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AECC Beijing Institute of Aeronautical Materials
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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
    • G02F1/153—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

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

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

Electrochromic device and preparation method of working electrode thereof
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.
CN202110625997.XA 2021-06-04 2021-06-04 Electrochromic device and preparation method of working electrode thereof Pending CN113376917A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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》 *

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