CN113253534B - Electrochromic device and manufacturing method thereof - Google Patents
Electrochromic device and manufacturing method thereof Download PDFInfo
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- G—PHYSICS
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- 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
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- 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
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- 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
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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
- 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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- 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
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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
- G02F1/1533—Constructional details structural features not otherwise provided for
Abstract
The invention discloses an electrochromic device, which comprises a cathode, an anode and an electrolyte; a metal layer is arranged on the substrate of the cathode; the substrates of the cathode and the anode comprise fluorine-doped tin oxide conductive glass and graphene which grows on the tin oxide conductive glass and is modified by an atomic layer deposition technology, and the graphene is modified to obtain higher electrical performance. The thickness of the molybdenum oxide layer ranges between 50 nanometers and 100 nanometers. The electrolyte is one of a liquid or gel state electrolyte as well. The concentration of the aluminum ion electrolyte was 1 mol/L. The thickness of the metallic aluminum is between 20 nanometers and 80 nanometers.
Description
Technical Field
The invention belongs to the technical field of thin films, and particularly relates to an electrochromic device and a manufacturing method thereof.
Background
The electrochromic device is structurally characterized by comprising an electrochromic layer, an electrolyte and an ion storage layer, wherein the electrochromic layer is generally metal oxides such as tungsten oxide, molybdenum oxide and vanadium oxide, the ion storage layer is generally metal oxides such as vanadium oxide and titanium oxide, the oxides have certain energy storage effect, the structure is similar to that of a super capacitor, and the super capacitor stores energy through the metal oxides. In addition, the reaction mechanisms of the graphene film and the graphene are similar, the dual-function effects of energy storage and electrochromic can be realized by combining the two, and at present, as one of common materials for preparing a super capacitor, the graphene film has good electrical properties, and the graphene film has very high optical transmittance due to the fact that the graphene film is very thin. However, the currently produced graphene has many defect sites, and defects and wrinkles are inevitably generated during the graphene transfer process. The defect sites and the folds of the graphene film are further modified by an atomic layer deposition technology, the defects and the folds of the graphene film can be selectively modified by the atomic layer deposition by utilizing the characteristic of higher chemical activity of the defect sites of the graphene, and redundant treatment is not carried out at the complete place of the graphene. Finally, metal nano particles can grow on the defects and the folds of the graphene, the defects and the folds of the graphene are connected by the metal particles, the conductivity of the graphene is increased, and therefore the electrical property of the graphene is improved.
In a common electrochromic device, color change is usually realized by charging and discharging, and energy is wasted in the charging and discharging processes.
Disclosure of Invention
The present invention provides an electrochromic device for solving the above problems, comprising a cathode, an anode, and an electrolyte;
the anode and the cathode form a double-layer structure, and both the anode and the cathode include: the graphene-based photovoltaic module comprises a substrate, graphene arranged on the substrate, and molybdenum oxide arranged on the graphene;
an aluminum layer is arranged between the cathode and the anode;
the electrolyte is an aluminum ion electrolyte.
Preferably, the graphene is modified by metal through an atomic layer deposition method, a precursor used in the atomic layer deposition method is trimethyl methyl cyclopentadienyl platinum, and a product of the reaction is oxygen.
Preferably, the metal modified by the graphene is one of gold, silver and copper.
Preferably, the substrate is fluorine-doped tin oxide conductive glass or indium tin oxide conductive glass.
Preferably, the graphene is modified by an atomic layer deposition technology, and in the atomic layer deposition process, the used precursor solution is trimethyl methylcyclopentadienyl platinum, and the reactant is oxygen.
Preferably, the molybdenum oxide layer comprises molybdenum oxide, viologen, polyaniline, and viologen modified by chemical doping and derivatives thereof;
the thickness of the molybdenum oxide ranges between 50 nanometers and 1000 nanometers.
Preferably, the electrolyte is one of liquid or gel electrolyte, and the radius of the aluminum ion is less than 0.0053 nm;
the aluminum ion solution is an aluminum chloride solution or an aluminum sulfate solution, and the concentration of the aluminum ion electrolyte is 1mol/L to 5 mol/L.
Preferably, the thickness of the aluminum layer is between 20 nanometers and 80 nanometers;
the metal layer of the anode is a linear aluminum layer or a latticed aluminum layer prepared by a mask.
The manufacturing method of the electrochromic device is used for manufacturing the electrochromic device and comprises the following steps:
s1: putting the substrate in deionized water for ultrasonic treatment for 10 min;
s2: placing the substrate in an oven for drying;
s3: cutting copper-based graphene into a shape as large as a substrate, spin-coating polymethyl methacrylate at 2000 rpm, and adding FeCl with a density of 0.1 g/ml in an amount of 200 ml 3 Etching the solution for 2 hours, transferring the copper foil into a new culture dish after the copper foil is completely corroded, repeatedly washing the copper foil with deionized water for 2-3 times, then putting the graphene film into an acetone solution, washing off polymethyl methacrylate, fishing out graphene sheets with fluorine-doped tin oxide conductive glass, and drying the graphene sheets in a 120-DEG oven;
s4: transferring graphene to fluorine-doped tin oxide conductive glass, controlling the temperature of a pipeline at 60-80 ℃ under the pressure of 0.8-1 torr by an atomic layer deposition technology, waiting for 10 seconds after a precursor trimethyl methylcyclopentadiene platinum pulse to enable the precursor to be adsorbed on the graphene, introducing nitrogen to remove redundant precursor, introducing oxygen, reacting the precursor trimethyl methylcyclopentadiene platinum with the oxygen after waiting for 10 seconds to generate platinum metal to be adsorbed at the defect part of the graphene, introducing nitrogen to remove redundant oxygen molecules and byproducts, and repeating the single atomic layer deposition cycle for 60-100 times;
s5: respectively evaporating metal aluminum and molybdenum oxide on the surface of the substrate;
s6: adding 1.33g of aluminum chloride into 10ml of water, and heating and stirring for 10min to 30min at the temperature of 60 ℃ to 90 ℃;
the evaporation method in step S5 includes: in a vacuum evaporation furnace, the temperature is controlled at 3X 10 -4 And (3) evaporating at a pressure of Pa and a current of 520A to 530A at an evaporation rate of 0.6A/s to 2A/s.
Another electrochromic device manufacturing method of the present invention is for manufacturing the above electrochromic device, and includes the steps of:
a: 2 to 4g of molybdenum oxide is put into 20ml of hydrogen peroxide;
b: heating and stirring the hydrogen peroxide in the step S1 at the temperature of 80-90 ℃;
c: when the hydrogen peroxide is cooled to room temperature, filtering impurities;
d: spin-coating the filtered solution at 3000 r/min for 30s to form a substrate;
e: at 3X 10 -4 The Pa condition is that evaporation is carried out in a vacuum evaporation furnace through the current of 110A to 120A, and the evaporation rate is controlled to be 1 angstrom/s to 2 angstrom/s;
f: adding 1.33g of aluminum chloride into 10ml of water, and heating and stirring for 10min to 30min at the temperature of 60 ℃ to 90 ℃;
g: the copper-based graphene is coated with polymethyl methacrylate by spin coating at 2000 r/min, and then put into 200 ml of FeCl with the concentration of 0.1 g/ml 3 Etching in the solution for 2 hours, transferring the copper foil into a new culture dish after the copper foil is completely corroded, repeatedly washing the copper foil with deionized water for 2-3 times, putting the graphene film into an acetone solution, washing off polymethyl methacrylate, and using fluorine-doped SnO 2 The graphene sheets are fished out of the conductive glass and dried in a 120-degree oven;
h: under the pressure of 0.8 to 1 torr, the temperature of a pipeline is controlled at 60 to 80 ℃ through an atomic layer deposition technology, after a precursor trimethyl methylcyclopentadiene platinum is pulsed, the precursor is enabled to be adsorbed on graphene after 10 seconds, nitrogen is introduced to remove redundant precursor, oxygen is introduced again, after 10 seconds, the precursor trimethyl methylcyclopentadiene platinum and the oxygen react to generate platinum metal which is adsorbed at the defect position of the graphene, the nitrogen is introduced to remove redundant oxygen molecules and byproducts, and the deposition cycle of the single atomic layer is repeated for 60 to 100 times.
Has the advantages that: the invention provides an electrochromic device, which takes fluorine-doped tin oxide conductive glass as a substrate, graphene is arranged on the fluorine-doped tin oxide conductive glass, the graphene shows stronger electrical performance after being modified by metal particles, the color change effect is doubled compared with the original color change effect due to the design of a double-layer device, a molybdenum trioxide layer growing on the surface of the substrate is taken as a cathode, an aluminum chloride solution is taken as an electrolyte, aluminum is taken as an anode, and higher color rendering contrast and faster response time can be provided by the principle that trivalent aluminum can carry more electrons in redox reaction. The electro-variable device can shield light, protect privacy, adjust room temperature and be used as a standby power supply.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of the present invention;
in FIG. 2, a is a schematic view of a line of an aluminum layer, and b is a schematic view of a grid of the aluminum layer;
in fig. 3, a is a schematic diagram showing that transparency of the device is reduced when the device is charged, and b is a schematic diagram showing that transparency of the device is higher when the device is discharged.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second, third, etc. are used herein to describe various elements or components, but these elements or components are not limited by these terms. These terms are only used to distinguish one element or component from another element or component. Terms such as "first," "second," and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. For convenience of description, spatially relative terms such as "inner", "outer", "upper", "lower", "left", "right", "upper", "left", "right", and the like are used herein to describe the orientation of the components or parts in the present embodiment, but these spatially relative terms do not limit the orientation of the technical features in practical use.
As shown in fig. 1, the electrochromic device of the present invention can store energy during charging and discharging, reduce energy consumption, and relieve electricity consumption pressure.
The method specifically comprises the following steps: a cathode, an anode, an electrolyte; the anode and the cathode form a double-layer structure; the anode and the cathode each include: the graphene-based photovoltaic module comprises a substrate, graphene arranged on the substrate and molybdenum oxide arranged on the graphene; an aluminum layer is arranged between the cathode and the anode; the electrolyte is an aluminum ion electrolyte. The graphene is modified by metal through an atomic layer deposition method, a precursor used in the atomic layer deposition method is trimethyl methyl cyclopentadiene platinum, and a reaction product is oxygen. The metal modified by the graphene is one of gold, silver and copper. The substrate is fluorine-doped tin oxide conductive glass or indium tin oxide conductive glass. The graphene is modified by an atomic layer deposition technology, and in the atomic layer deposition process, the used precursor solution is trimethyl methyl cyclopentadiene platinum, and the reactant is oxygen. The molybdenum oxide layer comprises molybdenum oxide, viologen, polyaniline, and viologen modified by chemical doping and derivatives thereof; the thickness of the molybdenum oxide ranges between 50 nanometers and 1000 nanometers. The electrolyte is one of liquid or gel electrolyte, and the radius of aluminum ions is less than 0.0053 nm; the aluminum ion solution is aluminum chloride solution or aluminum sulfate solution, and the concentration of the aluminum ion electrolyte is 1mol/L to 5 mol/L. The thickness of the aluminum layer is between 20 nanometers and 80 nanometers; the metal layer of the anode is a linear aluminum layer or a latticed aluminum layer prepared by a mask. Wherein the plastic is a main component resin.
In one embodiment, the electrochromic device has a specific structure: comprises a substrate layer, a functional layer and an electrolyte; wherein both the cathode and the anode are provided with a substrate layer. The structure of the substrate layer is graphene modified by atomic layer deposition on fluorine-doped tin oxide conductive glass. The functional layer on the cathode is a molybdenum oxide layer, and the functional layer on the anode is a metal layer. The electrolyte solution is aluminum ions, wherein the electrolyte solution can be one of an aluminum chloride solution and an aluminum sulfate solution, and the radius of the aluminum ions is less than 0.0053 nanometer, so that the functional layer can be embedded or separated from the electrolyte, and higher transmittance contrast can be realized.
As the graphene serving as a common flexible energy storage device has high energy storage capacity and stable chemical performance, and is not easy to react with electrolyte, the graphene is generally provided with 3-5 layers.
Wherein, the metal layer of the anode is one of a linear aluminum layer or a latticed aluminum layer prepared by a mask. As shown in fig. 2 a, a line-shaped aluminum layer prepared for a mask is illustrated, and b in fig. 2 is a grid-shaped aluminum layer prepared for a mask is illustrated.
The manufacturing method of the electrochromic device comprises the following steps:
s1: putting the substrate in deionized water and carrying out ultrasonic treatment for 10 min;
s2: placing the substrate in an oven for drying;
s3: cutting copper-based graphene into a shape as large as a substrate, spin-coating polymethyl methacrylate at 2000 rpm, and adding FeCl with a density of 0.1 g/ml in an amount of 200 ml 3 Etching the solution for 2 hours, transferring the copper foil into a new culture dish after the copper foil is completely corroded, repeatedly washing the copper foil with deionized water for 2-3 times, putting the graphene film into an acetone solution, washing off polymethyl methacrylate, fishing out graphene sheets with fluorine-doped tin oxide conductive glass, and drying the graphene sheets in a 120-DEG oven;
s4: transferring graphene to fluorine-doped tin oxide conductive glass, controlling the temperature of a pipeline at 60-80 ℃ under the pressure of 0.8-1 torr by an atomic layer deposition technology, waiting for 10 seconds after a precursor trimethyl methylcyclopentadiene platinum pulse to enable the precursor to be adsorbed on the graphene, introducing nitrogen to remove redundant precursor, introducing oxygen, reacting the precursor trimethyl methylcyclopentadiene platinum with the oxygen after waiting for 10 seconds to generate platinum metal to be adsorbed at the defect part of the graphene, introducing nitrogen to remove redundant oxygen molecules and byproducts, and repeating the single atomic layer deposition cycle for 60-100 times;
s5: respectively evaporating metal aluminum and molybdenum oxide on the surface of the substrate;
s6: adding 1.33g of aluminum chloride into 10ml of water, and heating and stirring for 10-30 min at the temperature of 60-90 ℃;
the evaporation method in step S5 includes: in a vacuum evaporation furnace, the temperature is controlled at 3X 10 -4 And (3) evaporating at a pressure of Pa and a current of 520A to 530A at an evaporation rate of 0.6A/s to 2A/s.
Another method for manufacturing the electrochromic device comprises the following steps:
a: 2g to 4g of molybdenum oxide is put into 20ml of hydrogen peroxide;
b: heating and stirring the hydrogen peroxide in the step S1 at the temperature of 80-90 ℃;
c: when the hydrogen peroxide is cooled to room temperature, filtering impurities;
d: spin-coating the filtered solution at 3000 r/min for 30s to form a substrate;
e: at 3X 10 -4 The Pa condition is that evaporation is carried out in a vacuum evaporation furnace through the current of 110A to 120A, and the evaporation rate is controlled to be 1 angstrom/s to 2 angstrom/s;
f: adding 1.33g of aluminum chloride into 10ml of water, and heating and stirring for 10min to 30min at the temperature of 60 ℃ to 90 ℃;
g: the copper-based graphene is coated with polymethyl methacrylate by spin coating at 2000 r/min, and then is put into 200 ml of FeCl with the concentration of 0.1 g/ml 3 Etching in the solution for 2 hours, transferring the copper foil into a new culture dish after the copper foil is completely corroded, repeatedly washing the copper foil with deionized water for 2-3 times, putting the graphene film into an acetone solution, washing off polymethyl methacrylate, and using fluorine-doped SnO 2 The graphene sheets are fished out of the conductive glass and dried in a 120-degree oven;
h: under the pressure of 0.8 to 1 torr, the temperature of a pipeline is controlled at 60 to 80 ℃ through an atomic layer deposition technology, after a precursor trimethyl methylcyclopentadiene platinum is pulsed, the precursor is enabled to be adsorbed on graphene after 10 seconds, nitrogen is introduced to remove redundant precursor, oxygen is introduced again, after 10 seconds, the precursor trimethyl methylcyclopentadiene platinum and the oxygen react to generate platinum metal which is adsorbed at the defect position of the graphene, the nitrogen is introduced to remove redundant oxygen molecules and byproducts, and the deposition cycle of the single atomic layer is repeated for 60 to 100 times.
The above embodiments are not limited to the technical solutions of the embodiments themselves, and the embodiments may be combined with each other into a new embodiment. The above embodiments are only for illustrating the technical solution of the present invention and are not limited thereto, and any modifications or equivalent substitutions which do not depart from the spirit and scope of the present invention should be covered within the technical solution of the present invention.
Claims (5)
1. An electrochromic device is characterized by comprising a cathode, an anode, an electrolyte and an aluminum layer;
the anode and the cathode both have a double-layer structure, and both the anode and the cathode are composed of a substrate, a graphene film arranged on the substrate and a molybdenum oxide layer arranged on the graphene film;
the aluminum layer is positioned on the molybdenum oxide layer of the anode, and the shape of the aluminum layer is a linear aluminum layer or a latticed aluminum layer prepared by a mask;
the electrolyte is an aluminum ion electrolyte;
the electrolyte is one of liquid or gel electrolyte, and the radius of the aluminum ions is less than 0.053 nm; the aluminum ion solution is an aluminum chloride solution or an aluminum sulfate solution, and the concentration of the aluminum ion electrolyte is 1mol/L to 5 mol/L; the thickness of the aluminum layer is between 20 nanometers and 80 nanometers.
2. The electrochromic device according to claim 1, wherein the graphene thin film is modified with metal by an atomic layer deposition method, a precursor used in the atomic layer deposition method is trimethyl methyl cyclopentadienyl platinum, and a product of the reaction is oxygen.
3. An electrochromic device as claimed in claim 1, characterized in that the substrate is a fluorine-doped tin oxide conducting glass or an indium tin oxide conducting glass.
4. The electrochromic device according to claim 1, wherein said molybdenum oxide layer comprises molybdenum oxide, polyaniline, chemically doped modified viologen and derivatives thereof;
the thickness of the molybdenum oxide layer ranges between 50 nanometers and 1000 nanometers.
5. A method for manufacturing an electrochromic device, characterized in that it is used for manufacturing an electrochromic device according to any one of claims 1 to 4, comprising the steps of:
s1: putting the substrate in deionized water and carrying out ultrasonic treatment for 10 min;
s2: placing the substrate in an oven for drying;
s3: cutting copper-based graphene into a shape as large as a substrate, spin-coating polymethyl methacrylate at 2000 rpm, and adding FeCl with a density of 0.1 g/ml in an amount of 200 ml 3 Etching the solution for 2 hours, transferring the copper foil into a new culture dish after the copper foil is completely corroded, repeatedly washing the copper foil with deionized water for 2-3 times, putting the graphene film into an acetone solution, washing off polymethyl methacrylate, fishing up the graphene film with fluorine-doped tin oxide conductive glass, and drying the graphene film in a 120-DEG oven;
s4: transferring graphene to fluorine-doped tin oxide conductive glass, controlling the temperature of a pipeline at 60-80 ℃ under the pressure of 0.8-1 torr and by an atomic layer deposition technology, after a precursor trimethyl methylcyclopentadiene platinum is pulsed, waiting for 10 seconds to enable the precursor to be adsorbed on a graphene film, introducing nitrogen to remove redundant precursor, introducing oxygen, after waiting for 10 seconds, reacting the precursor trimethyl methylcyclopentadiene platinum with the oxygen to generate platinum metal, adsorbing the platinum metal at the defect position of the graphene film, introducing nitrogen to remove redundant oxygen molecules and byproducts, and repeating the atomic layer deposition for 60-100 times;
s5: respectively evaporating a molybdenum oxide layer on the graphene film of the substrate of the anode and the graphene film of the substrate of the cathode, and evaporating an aluminum layer on the molybdenum oxide layer of the anode;
s6: adding 1.33g of aluminum chloride into 10ml of water, and heating and stirring for 10min to 30min at the temperature of 60 ℃ to 90 ℃;
the vapor deposition method in step S5 includes: in a vacuum evaporation furnace, the temperature is controlled at 3X 10 -4 Pa pressure and 520A to 530A current, and the evaporation rate is 0.6 angstrom/s to 2 angstrom/s.
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