CN113253534A - Electrochromic device and manufacturing method thereof - Google Patents
Electrochromic device and manufacturing method thereof Download PDFInfo
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- CN113253534A CN113253534A CN202110521337.7A CN202110521337A CN113253534A CN 113253534 A CN113253534 A CN 113253534A CN 202110521337 A CN202110521337 A CN 202110521337A CN 113253534 A CN113253534 A CN 113253534A
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- 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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- 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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- 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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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 in that the electrochromic device comprises an electrochromic layer, an electrolyte and an ion storage layer, wherein the electrochromic layer is generally made of metal oxides such as tungsten oxide, molybdenum oxide and vanadium oxide, the ion storage layer is generally made of 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 two materials are similar, the two materials are combined together to realize the dual-function effects of energy storage and electrochromism, and at present, as one of common materials for preparing a super capacitor, the graphene film has good electrical properties, and the graphene 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, in the atomic layer deposition process, the used precursor solution is trimethyl methyl cyclopentadiene 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 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 a speed of 2000 rpm, and adding FeCl with a density of 0.1 g/ml to 200 ml3Etching in the solution for 2 hours, transferring to a new culture dish after the copper foil is completely corroded, repeatedly washing with deionized water for 2-3 times, putting the graphene film into an acetone solution, washing off polymethyl methacrylate, and using tin oxide doped with fluorineThe graphene sheets are fished out of the conductive glass and dried in a 120-degree 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 and plating 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 vapor deposition method in step S5 includes: in a vacuum evaporation furnace, the temperature is controlled at 3X 10-4And (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 a method for manufacturing the above electrochromic device, including the steps of:
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 10-4The Pa condition is that evaporation is carried out in a vacuum evaporation furnace by current from 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: copper-based graphene with 2000 revolutionsPermin, after spin-coating polymethyl methacrylate, 200 ml of 0.1 g/ml FeCl was added3Etching 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 SnO2The 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 shape of an aluminum layer, and b is a schematic view of a grid shape 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 the technical solutions of the present invention better understood, 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 components or features, but these components or features are not limited by these terms. These terms are only used to distinguish one element or part from another element or part. 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 relation 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. Graphene is modified by an atomic layer deposition technology, in the atomic layer deposition process, a used precursor solution is trimethyl methyl cyclopentadiene platinum, and a 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 on the fluorine-doped tin oxide conductive glass through atomic layer deposition. 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.
Since graphene is high in energy storage and stable in chemical property as a common flexible energy storage device and is not easy to react with an 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: tailoring copper-based graphene to be as large as the substrateThe shape was prepared by spin-coating polymethyl methacrylate at 2000 rpm, and then charging FeCl having a density of 0.1 g/ml to 200 ml3Etching 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 and plating 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 vapor deposition method in step S5 includes: in a vacuum evaporation furnace, the temperature is controlled at 3X 10-4And (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 10-4Pa is under the condition of trueIn the air evaporation furnace, evaporation is carried out through currents from 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/ml3Etching 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 SnO2The 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 solutions of the present invention and are not limited thereto, and any modification or equivalent replacement without departing from the spirit and scope of the present invention should be covered within the technical solutions of the present invention.
Claims (10)
1. An electrochromic device, which is characterized by 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.
2. The electrochromic device according to claim 1, wherein the graphene is modified with metal by an atomic layer deposition method, a precursor used in the atomic layer deposition method is trimethylmethylcyclopentadiene platinum, and a product of the reaction is oxygen.
3. The electrochromic device according to claim 2, wherein the metal modified by the graphene is one of gold, silver and copper.
4. 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.
5. The electrochromic device according to claim 1, wherein the graphene is modified by an atomic layer deposition technique, and during the atomic layer deposition process, a precursor solution used is trimethylmethylcyclopentadienyl platinum, and a reactant is oxygen.
6. The electrochromic device according to claim 1, wherein said molybdenum oxide layer comprises molybdenum oxide, viologen, polyaniline, chemically doped modified viologen, and derivatives thereof;
the thickness of the molybdenum oxide ranges between 50 nanometers and 1000 nanometers.
7. An electrochromic device according to claim 1, characterized in that the electrolyte is one of a liquid or gel electrolyte, the radius of the aluminium ions being 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.
8. An electrochromic device as claimed in claim 1, characterized in that the thickness of the aluminium layer is between 20 nm and 80 nm;
the metal layer of the anode is a linear aluminum layer or a latticed aluminum layer prepared by a mask.
9. A method for manufacturing an electrochromic device, characterized by comprising, for manufacturing an electrochromic device according to any one of claims 1 to 8, 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 a speed of 2000 rpm, and adding FeCl with a density of 0.1 g/ml to 200 ml3Etching 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 and plating 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 vapor deposition method in step S5 includes: in a vacuum evaporation furnaceIn 3 × 10-4And (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.
10. A method for manufacturing an electrochromic device, characterized by comprising, for manufacturing an electrochromic device according to any one of claims 1 to 8, the steps of:
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 10-4The Pa condition is that evaporation is carried out in a vacuum evaporation furnace by current from 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/ml3Etching 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 SnO2The 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110521337.7A CN113253534B (en) | 2021-05-13 | 2021-05-13 | Electrochromic device and manufacturing method thereof |
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