CN110109311B - All-solid-state electrochromic device and preparation method thereof - Google Patents
All-solid-state electrochromic device and preparation method thereof Download PDFInfo
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- CN110109311B CN110109311B CN201910315706.XA CN201910315706A CN110109311B CN 110109311 B CN110109311 B CN 110109311B CN 201910315706 A CN201910315706 A CN 201910315706A CN 110109311 B CN110109311 B CN 110109311B
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
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- 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
Abstract
An all-solid-state electrochromic device and a preparation method thereof comprise a substrate A and a substrate B, wherein a transparent conducting layer A and an anode electrochromic layer are sequentially arranged on the inner side of the substrate A; a transparent conducting layer B and a cathode electrochromic layer are sequentially arranged on the inner side of the substrate B; and a solid electrolyte layer is arranged between the anode electrochromic layer and the cathode electrochromic layer. The preparation method comprises the following steps: (1) processing a substrate A and a substrate B; (2) preparing an anode electrochromic layer; (3) preparing a cathode electrochromic layer; (4) preparing a solid electrolyte layer; (5) and (3) preparing an all-solid-state electrochromic device. The invention has the beneficial effects that: the method is simple and convenient, has high ionic conductivity and good ageing resistance, adopts the complementary electrochromic film, realizes the quick complementary discoloration of the electrochromic device under low voltage on the premise of ensuring the requirement of discoloration, improves the safety of glass use, has low driving voltage, and has huge application prospect.
Description
Technical Field
The invention belongs to the field of electrochromic devices, and particularly relates to an all-solid-state electrochromic device and a preparation method thereof.
Background
An electrochromic device is composed of electrochromic material and other functional material through sequential combination, and can realize stable reversible regulation of optical properties (transmittance, absorptivity, reflectivity, etc.) of a coloring film layer through bidirectional extraction/injection of charges (ions or electrons) in the device under the action of external high-low or positive-negative electric fields so as to realize that the device shows specific spectral modulation performance in a specific spectral range, and the appearance mainly shows high practicability device with color and transparency change. The electrochromic device has wide application prospect in the fields of intelligent energy-saving windows, displays, spacecraft temperature control modulation, automobile no-glare rearview mirrors, weapon equipment stealth and the like.
At present, the most mature process for preparing the electrochromic device at home and abroad is a magnetron sputtering method, the electrochromic device prepared by the process has good color-changing performance and good cycling stability, but sputtering equipment is complex, the size of coated glass is limited by a vacuum cavity of a machine, a vacuum environment is required, production conditions are harsh, the requirement on a production line is high, and therefore, the preparation cost is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an all-solid-state electrochromic device and a preparation method thereof, wherein each film material precursor is prepared by adopting a pure chemical method, and each film material is deposited on a substrate by using methods such as printing or electrodeposition, the preparation method only needs to be carried out under normal pressure, the preparation is simple, the preparation process requirement is lower, the preparation cost is low, and the large-area preparation of the device can be realized, so that the all-solid-state electrochromic device is suitable for industrial large-scale production.
The all-solid-state electrochromic device is characterized by being formed by combining a substrate A, a transparent conducting layer A, an anode electrochromic layer, a solid electrolyte layer, a cathode electrochromic layer, a transparent conducting layer B and a substrate B which are sequentially arranged.
The substrate A and the substrate B are glass substrates, PET films or PI films.
The transparent conducting layer A and the transparent conducting layer B are aluminum-doped zinc oxide films, tin-doped indium oxide films, fluorine-doped tin oxide films, silver nanowires, gold nanowires or network electrodes; the network electrode is a composite material of one or both of carbon nanotubes or metal oxides; the surface resistance of the transparent conducting layer A and the transparent conducting layer B is 5-50 omega/cm2。
The cathode electrochromic layer is a tungsten oxide film doped with metal atoms, and the molecular formula of the cathode electrochromic layer is MxWOyWherein M is one or more of molybdenum (Mo), lithium (Li), nickel (Ni), vanadium (V), niobium (Nb), tantalum (Ta), titanium (Ti), silicon (Si), zirconium (Zr), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cesium (Cs), copper (Cu), europium (Eu), gallium (Ga), indium (In), potassium (K), lanthanum (La), magnesium (Mg), sodium (Na), lead (Pb), selenium (Se), tin (Sn) and uranium (U), x and y respectively represent the mole number of M and O atoms, and 0<x<0.5，2.2<y<3。
The anode electrochromic layer is a nickel oxide film doped with metal atoms, and the molecular formula of the anode electrochromic layer is AzNiOrWherein A is zinc (Zn), lithium (Li), copper (Cu), titanium (Ti), silicon (Si), silver (Ag), aluminumThe alloy is characterized by comprising one or more of (Al), arsenic (As), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cesium (Cs), europium (Eu), gallium (Ga), indium (In), potassium (K), lanthanum (La), magnesium (Mg), sodium (Na), lead (Pb), selenium (Se), tin (Sn) and uranium (U), wherein z and r respectively represent the mole number of A and O atoms, and 0<z<0.5，1<r<2。
The components of the solid electrolyte layer contain a polymer plasticizer, an organic solvent, an electrolyte solvent and a lithium salt; wherein the mass ratio of the polymer plasticizer to the organic solvent is 1: 7-9, and the mass ratio of the electrolyte solvent to the lithium salt is 1: 3.77-7.56.
The high molecular plasticizer is one or more of polyvinyl alcohol, polyvinyl butyral or an alkene-vinyl acetate copolymer; the organic solvent is one or more of N, N-dimethylformamide, absolute ethyl alcohol, dimethylacetamide or methyl methacrylate; one or more of ethylene carbonate, propylene carbonate, butylene carbonate, Y-butyrolactone, dipropylene carbonate, N-methylpyrrolidone, N-methylacetamide, N-methylformamide, dimethylformamide, diethylformamide, acetonitrile or succinonitrile; the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate (V) or lithium sulfonate.
A preparation method of an all-solid-state electrochromic device is characterized by comprising the following steps:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: respectively and sequentially cleaning a substrate A with a transparent conducting layer A and a substrate B with a transparent conducting layer B with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and the substrate B subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
(1) According to AzNiOrCalculating the contents of nickel salt and metal salt, and weighingReady for use;
(2) mixing nickel salt and metal salt to form a mixture I, and dissolving the mixture I in a solvent to obtain a clarified solution II, wherein the mass ratio of the mixture I to the solvent is 1: 50-200;
dissolving oxalic acid in a solvent to obtain an oxalic acid solution III, wherein the mass ratio of the oxalic acid to the solvent is 1: 40-80;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 1.5-50 ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 0.5-48 h, taking out the light blue turbid liquid IV, performing centrifugal separation for 5-10 min, removing a supernatant, and washing with a solvent to prepare a precursor solution V; wherein the solvent is absolute ethyl alcohol;
(3) placing the precursor solution V in drying equipment for heat treatment at the temperature of 150-500 ℃ for 0.5-1.5 h to obtain nanocrystalline powder with the particle size of 5-100 nm;
(4) uniformly dispersing the nanocrystalline powder in a dispersion liquid to obtain a nanocrystalline dispersion liquid C, wherein the concentration of the nanocrystalline dispersion liquid C is 3-100 mg/ml; coating the nanocrystalline dispersion liquid C on the transparent conducting layer A of the processed substrate A through a coating process; wherein the dispersion liquid is one or more of water, ethanol or acetone;
(5) placing the substrate A coated with the nanocrystalline dispersion liquid C in heat treatment equipment for calcination, wherein the temperature in the heat treatment equipment is 150-500 ℃, the oxygen content in the heat treatment equipment accounts for 20-100%, and the anode electrochromic layer is obtained after calcination for 0.5-1.5 h;
and step 3: preparation of cathode electrochromic layer
(1) According to MxWOyCalculating the contents of the required tungsten salt and metal salt, and weighing for later use;
(2) mixing tungsten salt and metal salt to form a mixture VI, and dissolving the mixture VI in a solvent to obtain a clear solution VII, wherein the mass ratio of the mixture VI to the solvent is 1: 50-200;
dissolving oxalic acid in a solvent to obtain an oxalic acid solution VIII, wherein the oxalic acid and the solvent are 1: 30-90 in mass ratio;
dripping oxalic acid solution VIII into the clear solution VII at the flow rate of 1-80 ml/h to form light blue turbid liquid IX;
aging the light blue turbid liquid IX, standing for 12-48 h, taking out the light blue turbid liquid IX, performing centrifugal separation for 5-10 min, removing a supernatant, and washing with a solvent to prepare a precursor solution X; wherein the solvent is deionized water;
(3) placing the precursor solution X in drying equipment for heat treatment, wherein the heat treatment temperature is 150-500 ℃, and the heat treatment time is 0.5-1.5 h, so as to obtain nanocrystalline powder, and the grain diameter of the nanocrystalline powder is 5-100 nm;
(4) uniformly dispersing the nanocrystalline powder in a dispersion liquid to obtain a nanocrystalline dispersion liquid D, wherein the concentration of the nanocrystalline dispersion liquid D is 3-100 mg/ml; coating the nanocrystalline dispersion liquid D on the transparent conducting layer B of the processed substrate B through a coating process; wherein the dispersion liquid is one or more of water, ethanol or acetone;
(5) placing the substrate B coated with the nanocrystalline dispersion liquid D in heat treatment equipment for calcination, wherein the temperature in the heat treatment equipment is 150-500 ℃, the oxygen content in the heat treatment equipment accounts for 20-100%, and calcining for 15-120 min to obtain a cathode electrochromic layer;
and 4, step 4: preparation of solid electrolyte layer
(1) Mixing a polymer plasticizer and an organic solvent in proportion, and then placing the mixture in stirring equipment for stirring to fully mix the mixture to obtain a system A;
(2) mixing an electrolyte solvent and lithium salt in proportion, and then placing the mixture into stirring equipment for stirring to fully mix the mixture to obtain a system B;
(3) mixing the system A and the system B, and then placing the mixture into stirring equipment to be stirred, so that the mixture is fully mixed to obtain electrolyte solution; the system A and the system B are 1: 0.11-0.42 in volume ratio;
(4) coating the electrolyte solution on the anode electrochromic layer and/or the cathode electrochromic layer through a coating process, and placing the anode electrochromic layer and/or the cathode electrochromic layer in drying equipment to dry for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the substrate A and the substrate B obtained through the treatment in the steps (1) to (4), enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, and placing the buckled substrate A and the substrate B in hot pressing equipment for hot pressing for 5-30 min at the temperature of 110-180 ℃ to obtain the all-solid-state electrochromic device.
Adding an auxiliary agent and/or nanoparticles into the electrolyte solution in the step 4(3), wherein the auxiliary agent is one or more of an antioxidant, a UV (ultraviolet) absorbent or an anti-aging agent, and the mass ratio of the auxiliary agent to the electrolyte solution is 0.1-0.5% to 1; the nano particles are SiO2、TiO2、Al2O3、ZnO、ZrO2Or Ta2O5The particle size of the nano particles is less than 150 nm;
adding one or more of a thickening agent, a film forming agent or a leveling agent into the dispersion liquid in the step 2(4) and/or the step 3 (4); the thickening agent is hydroxyethyl cellulose; the film forming agent is a hydrophobically modified polyacrylic ammonium salt polymer (SN-5027); the leveling agent is diacetone alcohol.
The thickness of the anode electrochromic layer is 300-1000 nm;
the thickness of the cathode electrochromic layer is 300-1000 nm;
the thickness of the solid electrolyte layer is 0.5-30 μm;
the coating process comprises a blade coating method, a casting method, a double-screw extrusion casting method, spin coating, micro-convex plate coating, wire rod coating, dipping and drawing, slit extrusion coating, spray coating, screen printing, ink-jet printing or an electrodeposition method.
On the basis of adopting the chemical method to prepare, the invention adopts the complementary color change of the positive and negative electrochromic layers, can effectively improve the optical modulation amplitude of the device, realizes the rapid complementary color change design of the electrochromic thin film device under low voltage by adopting the solid electrolyte, and compared with the current mainstream liquid electrolyte or the thick liquid electrolyte, the electrolyte has high electrochemical stability, is easy to package by using the device and has better use stability, and the structure of the electrochromic device designed by the invention is as follows: the electrochromic material is formed between two electrodes facing each other and then is bonded through a solid electrolyte layer capable of ionic conduction, and compared with other glasses, the designed structure similar to the laminated glass has the performances of shock resistance, theft prevention, bullet prevention and explosion prevention, and the use safety of the glass is greatly improved.
The invention has the beneficial effects that: the solid device obtained by the cyclic voltammetry test team is characterized to verify that the all-solid-state device has electrochromic performance, namely the discoloring change of the device can be realized in a certain voltage range, and the ionic conductivity of the solid electrolyte is tested by the cyclic voltammetry to verify that the electrochromic performance is good and the response speed is high, so that the all-solid-state device is a solid device with excellent electrochromic performance. Compared with the prior art, the invention adopts a chemical preparation process, has simpler preparation process and low preparation cost compared with methods such as magnetron sputtering and the like, is easy to realize large-area preparation of devices, and is suitable for industrialized large-scale production; the all-solid-state electrochromic device has high stability and good electrochromic performance, can effectively prolong the service life of the device, and broadens the application field of the electrochromic device; the design structure similar to the laminated glass is adopted, so that the safety of the device in use is higher.
Drawings
FIG. 1 is a schematic structural diagram of an all-solid electrochromic device prepared according to the present invention;
FIG. 2 is a graphical representation of cyclic voltammogram of an assembled device of example 1 of the present invention;
FIG. 3a is a schematic representation of an assembled all-solid-state electrochromic device in example 1 of the present invention in the energized state (3V);
FIG. 3b is a schematic representation of an assembled all-solid-state electrochromic device in inventive example 1 in the unpowered state (0V);
FIG. 4 is a graph showing UV-visible transmittance of an assembled device in example 1 of the present invention;
FIG. 5 is a graphical representation of cyclic voltammogram of an assembled device of example 2 of the present invention;
FIG. 6 is a graphical representation of cyclic voltammogram of an assembled device of example 3 of the present invention;
FIG. 7 is a graphical representation of cyclic voltammogram of an assembled device of example 4 of the present invention;
fig. 8 is a graphical representation of cyclic voltammograms of an assembled device of example 5 of the present invention.
Detailed Description
For better understanding of the present invention, the technical solutions and effects of the present invention will be described in detail by the following embodiments with reference to the accompanying drawings.
In the following examples, the electrodeposition method adjusts the concentration and deposition time of the colloidal ink according to the thickness and size of the film, and the printing method adjusts the spraying deposition rate, the dimension specification of the filament rod, the opening thickness of the scraper and the moving rate according to the thickness and size of the film.
The substrate and transparent conductive layer in the following examples are commercially available.
The following preferred examples further illustrate the present invention and it will be understood by those skilled in the art that the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.
Example 1
A preparation method of an all-solid-state electrochromic device comprises the following steps:
step 1: treatment of substrate A and FTO glass (2 cm. times.3 cm)
(1) Ultrasonic cleaning treatment: sequentially cleaning a substrate A with a transparent conducting layer A and FTO glass (2cm multiplied by 3cm) with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and FTO glass (2cm multiplied by 3cm) subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
7.145g of nickel nitrate is weighed and dissolved in 125ml of absolute ethyl alcohol to be evenly stirred; weighing 0.65g of lithium acetate, dissolving the lithium acetate in 125ml of absolute ethyl alcohol, uniformly stirring, mixing the two solutions together, and uniformly stirring to obtain a clear solution II;
weighing 3.278g of oxalic acid, dissolving in 130ml of absolute ethyl alcohol, and uniformly stirring to obtain an oxalic acid solution III;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 2ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 1h, taking out the light blue turbid liquid IV, carrying out centrifugal separation for 5min at the rotating speed of 6500rpm, pouring out the supernatant, and washing with absolute ethyl alcohol for more than two times to prepare a precursor solution V;
placing the precursor solution V in a constant-temperature oven at 85 ℃ for drying for more than 12h, then fully grinding, and then placing in a muffle furnace at 380 ℃ for calcining for 5h to obtain nanocrystalline powder, wherein the grain diameter of the nanocrystalline powder is 20 nm;
placing the nanocrystalline powder in an ultrasonic cell disruption instrument, performing ultrasonic treatment in deionized water with the concentration of 10mg/mL for 3s every time at intervals of 3s for 30min, and uniformly dispersing to obtain nanocrystalline dispersion liquid C, wherein the concentration of the nanocrystalline dispersion liquid C is 10 mg/mL; placing the transparent conductive layer A of the substrate A on a hot bench at 120 ℃ in an upward manner, dropping the nanocrystalline dispersion liquid C on the transparent conductive layer A, and coating the substrate by using a coater with a scraper opening of 60 mu m at a uniform speed;
after the solvent is volatilized, naturally cooling to obtain an anode electrochromic layer;
and step 3: preparation of cathode electrochromic layer
Weighing 6.596g of sodium tungstate hydrate, dissolving in 20ml of deionized water to prepare a 0.4mol/L solution, after the sodium tungstate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium tungstate into a tungstic acid precipitate, centrifugally separating the tungstic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing with the deionized water for more than two times to prepare a tungsten oxide precursor;
adding 30% hydrogen peroxide solution drop by drop to the tungsten oxide precursorDissolving the sol in the body to finally form transparent sol; spraying transparent sol on FTO glass (2cm multiplied by 3cm) on a hot bench by using a dispenser, wherein the spraying speed of a sprayer is 0.25ml/min, the cycle time is 10 times, the thermal state temperature is set to be 40 ℃, and a uniform layer of WO is obtained3And (3) placing the film in a tube furnace at 250 ℃ for heat treatment for 15min, wherein the oxygen content in the tube furnace is controlled at 80%, and thus the cathode electrochromic layer is prepared.
And 4, step 4: preparation of solid electrolyte layer
Adding 2g of high-molecular plasticizer polyvinyl alcohol and 18.98ml of organic solvent N, N-dimethylformamide into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at 75 ℃ for stirring for 5 hours, and simultaneously carrying out condensation reflux by using a spherical condensing tube to fully mix the mixture to obtain a system A;
adding 9ml of electrolyte solvent propylene carbonate and 1.4364g of lithium salt lithium perchlorate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at the temperature of 75 ℃, and stirring for 5 hours to fully mix the mixture to obtain a system B;
mixing the system A and the system B according to the volume ratio of 1:0.4, placing the mixture in a constant-temperature magnetic stirrer at 70 ℃ for stirring for 3 hours to fully mix the mixture to obtain an organic electrolyte solution, adding 6.85mg of an anti-aging agent Tinuvin571 into the organic electrolyte solution, and fully mixing the mixture uniformly for later use;
uniformly coating the organic electrolyte solution added with the age resister on the cathode electrochromic layer by a coating method by using a 120-micron standard coater, wherein the temperature of a hot platform is room temperature during coating, and placing the cathode electrochromic layer in drying equipment for drying for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the solid electrolyte layer and the anode electrochromic layer together, enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, placing the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer in a vacuum drying oven for drying for 2 hours as shown in figure 1, and then carrying out vacuum hot pressing for 5min by using a hot press at the hot pressing temperature of 110 ℃ to obtain the all-solid-state electrochromic device.
The electrochromic device was tested for its colorfast effect using cyclic voltammetry, fig. 2 is a cyclic voltammetry curve of the solid electrolyte layer, a change from blue to transparent of the device was observed, fig. 3a is the color of the device in the energized state (3V), fig. 3b is the color of the device in the non-energized state (0V), and fig. 4 is a graph of the uv-visible transmittance of the electrochromic device.
Example 2
A preparation method of an all-solid-state electrochromic device comprises the following steps:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: sequentially cleaning a substrate A with a transparent conducting layer A and FTO glass (2cm multiplied by 3cm) with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and FTO glass (2cm multiplied by 3cm) subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
7.145g of nickel nitrate is weighed and dissolved in 125ml of absolute ethyl alcohol to be evenly stirred; weighing 0.65g of lithium acetate, dissolving the lithium acetate in 125ml of absolute ethyl alcohol, uniformly stirring, mixing the two solutions together, and uniformly stirring to obtain a clear solution II;
weighing 3.278g of oxalic acid, dissolving in 130ml of absolute ethyl alcohol, and uniformly stirring to obtain an oxalic acid solution III;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 2ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 1h, taking out the light blue turbid liquid IV, carrying out centrifugal separation for 5min at the rotating speed of 6500rpm, pouring out the supernatant, and washing with absolute ethyl alcohol for more than two times to prepare a precursor solution V;
placing the precursor solution V in a constant-temperature oven at 85 ℃ for drying for more than 12h, then fully grinding, and then placing in a muffle furnace at 400 ℃ for calcining for 0.5h to obtain nanocrystalline powder, wherein the grain diameter of the nanocrystalline powder is 20 nm;
placing the nanocrystalline powder in an ultrasonic cell disruption instrument, performing ultrasonic treatment in deionized water with the concentration of 15mg/mL for 3s every time at intervals of 3s for 30min, and uniformly dispersing to obtain nanocrystalline dispersion liquid C, wherein the concentration of the nanocrystalline dispersion liquid C is 15 mg/mL; placing the transparent conductive layer A of the substrate A on a hot bench at 120 ℃ in an upward manner, dropping the nanocrystalline dispersion liquid C on the transparent conductive layer A, and coating the substrate by using a coater with a scraper opening of 60 mu m at a uniform speed;
after the solvent is volatilized, naturally cooling to obtain an anode electrochromic layer;
and step 3: preparation of cathode electrochromic layer
Weighing 6.596g of sodium tungstate hydrate, dissolving in 20ml of deionized water to prepare a 0.4mol/L solution, after the sodium tungstate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium tungstate into a tungstic acid precipitate, centrifugally separating the tungstic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing with the deionized water for more than two times to prepare a tungsten oxide precursor;
dropwise adding 30% hydrogen peroxide solution into the tungsten oxide precursor, and dissolving to finally form transparent sol; spraying transparent sol on FTO glass (2cm multiplied by 3cm) on a hot bench by using a dispenser, wherein the spraying speed of a sprayer is 0.5ml/min, the cycle time is 10 times, the thermal state temperature is set to be 40 ℃, and a uniform layer of WO is obtained3And (3) placing the film in a 350 ℃ tube furnace for heat treatment for 1h, wherein the oxygen content in the tube furnace is controlled at 40%, and thus the cathode electrochromic layer is prepared.
And 4, step 4: preparation of solid electrolyte layer
Adding 2g of high molecular plasticizer polyvinyl butyral and 22.05ml of absolute ethyl alcohol into a round-bottom flask for mixing, and placing the mixture in a magnetic stirrer for stirring for 5 hours to fully mix the mixture to obtain a system A;
adding 9ml of electrolyte solvent propylene carbonate and 1.4364g of lithium salt lithium perchlorate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at the temperature of 75 ℃, and stirring for 5 hours to fully mix the mixture to obtain a system B;
mixing the system A and the system B according to the volume ratio of 1:0.2, placing the mixture in a constant-temperature magnetic stirrer at the temperature of 60 ℃ for stirring for 3 hours, fully mixing the mixture to obtain an organic electrolyte solution, adding 6.85mg of an anti-aging agent Tinuvin571 into the organic electrolyte solution, and fully and uniformly mixing the mixture for later use;
uniformly coating the organic electrolyte solution added with the age resister on the cathode electrochromic layer by a coating method by using a 120-micron standard coater, wherein the temperature of a hot platform is room temperature during coating, and placing the cathode electrochromic layer in drying equipment for drying for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And buckling the solid electrolyte layer and the anode electrochromic layer together, enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, placing the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer in a vacuum drying oven for drying for 2 hours, and then carrying out vacuum hot pressing for 5min by using a hot press at the hot pressing temperature of 120 ℃ to obtain the all-solid-state electrochromic device.
The electrochromic device was tested for discoloration and fading effects using cyclic voltammetry, and fig. 5 is a cyclic voltammetry curve of the assembled device.
Example 3
A preparation method of an all-solid-state electrochromic device comprises the following steps:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: sequentially cleaning a substrate A with a transparent conducting layer A and FTO glass (2cm multiplied by 3cm) with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and FTO glass (2cm multiplied by 3cm) subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
7.145g of nickel nitrate is weighed and dissolved in 125ml of absolute ethyl alcohol to be evenly stirred; weighing 0.65g of lithium acetate, dissolving the lithium acetate in 125ml of absolute ethyl alcohol, uniformly stirring, mixing the two solutions together, and uniformly stirring to obtain a clear solution II;
weighing 3.278g of oxalic acid, dissolving in 130ml of absolute ethyl alcohol, and uniformly stirring to obtain an oxalic acid solution III;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 5ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 1h, taking out the light blue turbid liquid IV, carrying out centrifugal separation for 5min at the rotating speed of 6500rpm, pouring out the supernatant, and washing with absolute ethyl alcohol for more than two times to prepare a precursor solution V;
placing the precursor solution V in a constant-temperature oven at 85 ℃ for drying for more than 12h, then fully grinding, and then placing in a muffle furnace at 300 ℃ for calcining for 1.5h to obtain nanocrystalline powder, wherein the grain diameter of the nanocrystalline powder is 35 nm;
placing the nanocrystalline powder in an ultrasonic cell disruption instrument, performing ultrasonic treatment in deionized water with the concentration of 20mg/mL for 3s every time at intervals of 3s for 30min, and uniformly dispersing to obtain nanocrystalline dispersion liquid C with the concentration of 20 mg/mL; placing the transparent conductive layer A of the substrate A on a hot bench at 120 ℃ in an upward manner, dropping the nanocrystalline dispersion liquid C on the transparent conductive layer A, and coating the substrate by using a coater with a scraper opening of 90 μm at a uniform speed;
after the solvent is volatilized, naturally cooling to obtain an anode electrochromic layer;
and step 3: preparation of cathode electrochromic layer
Weighing 6.596g of sodium tungstate hydrate, dissolving in 20ml of deionized water to prepare a 0.4mol/L solution, after the sodium tungstate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium tungstate into a tungstic acid precipitate, centrifugally separating the tungstic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing with the deionized water for more than two times to prepare a tungsten oxide precursor;
dropwise adding 30% hydrogen peroxide solution into the tungsten oxide precursor, and dissolving to finally form transparent sol; spraying transparent sol on FTO glass (2cm multiplied by 3cm) on a hot bench by using a dispenser, wherein the spraying speed of a sprayer is 0.75ml/min, the cycle time is 5 times, the thermal state temperature is set to be 40 ℃, and a uniform layer of WO is obtained3The film is put in a tube furnace with the temperature of 400 ℃ for heat treatment for 1.5h, the oxygen content in the tube furnace is controlled at 60 percent, and the cathode electric field change is preparedAnd (5) a color layer.
And 4, step 4: preparation of solid electrolyte layer
Adding 2g of high molecular plasticizer polyvinyl butyral and 19.21ml of dimethylacetamide into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer for stirring for 5 hours, and fully mixing to obtain a system A;
adding 9ml of electrolyte solvent propylene carbonate and 1.4364g of lithium salt lithium perchlorate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at the temperature of 75 ℃, and stirring for 5 hours to fully mix the mixture to obtain a system B;
mixing the system A and the system B according to the volume ratio of 1:0.32, placing the mixture in a constant-temperature magnetic stirrer at 80 ℃ for stirring for 3 hours to fully mix the mixture to obtain an organic electrolyte solution, adding 6.85mg of an anti-aging agent Tinuvin571 into the organic electrolyte solution, and fully mixing the mixture uniformly for later use;
coating the organic electrolyte solution added with the anti-aging agent on the cathode electrochromic layer by using a slit extrusion tape casting method, wherein the temperature of a hot platform is room temperature during coating, and placing the cathode electrochromic layer in drying equipment for drying for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the solid electrolyte layer and the anode electrochromic layer together, enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, placing the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer in a vacuum drying oven for drying for 2 hours, and then carrying out vacuum hot pressing for 5min by using a hot press at the hot pressing temperature of 125 ℃ to obtain the all-solid-state electrochromic device.
The electrochromic device was tested for discoloration and fading effects using cyclic voltammetry, and fig. 6 is a cyclic voltammetry curve of the assembled device.
Example 4
A preparation method of an all-solid-state electrochromic device comprises the following steps:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: sequentially cleaning a substrate A with a transparent conducting layer A and FTO glass (2cm multiplied by 3cm) with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and FTO glass (2cm multiplied by 3cm) subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
4.643g of anhydrous nickel ethoxide is weighed and dissolved in 125ml of anhydrous ethanol to be uniformly stirred; weighing 0.65g of lithium acetate, dissolving the lithium acetate in 125ml of absolute ethyl alcohol, uniformly stirring, mixing the two solutions together, and uniformly stirring to obtain a clear solution II;
weighing 3.278g of oxalic acid, dissolving in 130ml of absolute ethyl alcohol, and uniformly stirring to obtain an oxalic acid solution III;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 2ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 1h, taking out the light blue turbid liquid IV, carrying out centrifugal separation for 5min at the rotating speed of 6500rpm, pouring out the supernatant, and washing with absolute ethyl alcohol for more than two times to prepare a precursor solution V;
placing the precursor solution V in a constant-temperature oven at 85 ℃ for drying for more than 12h, then fully grinding, and then placing in a muffle furnace at 400 ℃ for calcining for 1h to obtain nanocrystalline powder, wherein the grain diameter of the nanocrystalline powder is 20 nm;
placing the nanocrystalline powder in an ultrasonic cell disruption instrument, performing ultrasonic treatment in deionized water with the concentration of 75mg/mL for 3s every time at intervals of 3s for 30min, and uniformly dispersing to obtain nanocrystalline dispersion liquid C with the concentration of 75 mg/mL; placing the transparent conductive layer A of the substrate A on a hot bench at 120 ℃ in an upward manner, dropping the nanocrystalline dispersion liquid C on the transparent conductive layer A, and coating the substrate by using a coater with a scraper opening of 60 mu m at a uniform speed;
after the solvent is volatilized, naturally cooling to obtain an anode electrochromic layer;
and step 3: preparation of cathode electrochromic layer
Weighing 6.596g of sodium tungstate hydrate, dissolving in 20ml of deionized water to prepare a 0.4mol/L solution, after the sodium tungstate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium tungstate into a tungstic acid precipitate, centrifugally separating the tungstic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing with the deionized water for more than two times to prepare a tungsten oxide precursor;
dropwise adding 30% hydrogen peroxide solution into the tungsten oxide precursor, and dissolving to finally form transparent sol; spraying transparent sol on FTO glass (2cm multiplied by 3cm) on a hot bench by using a dispenser, wherein the spraying speed of a sprayer is 0.25ml/min, the cycle time is 10 times, the thermal state temperature is set to be 40 ℃, and a uniform layer of WO is obtained3And (3) placing the film in a tube furnace at 450 ℃ for heat treatment for 0.5h, wherein the oxygen content in the tube furnace is controlled at 50%, and thus the cathode electrochromic layer is prepared.
And 4, step 4: preparation of solid electrolyte layer
Adding 2g of high-molecular plasticizer alkene-vinyl acetate copolymer and 19.06ml of methyl methacrylate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer for stirring for 5 hours, and fully mixing to obtain a system A;
adding 9ml of electrolyte solvent propylene carbonate and 1.4364g of lithium salt lithium perchlorate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at the temperature of 75 ℃, and stirring for 5 hours to fully mix the mixture to obtain a system B;
mixing the system A and the system B according to the volume ratio of 1:0.23, placing the mixture in a constant-temperature magnetic stirrer at 70 ℃ for stirring for 3 hours to fully mix the mixture to obtain an organic electrolyte solution, adding 6.85mg of an anti-aging agent Tinuvin571 into the organic electrolyte solution, and fully mixing the mixture uniformly for later use;
uniformly coating the organic electrolyte solution added with the age resister on the cathode electrochromic layer by a coating method by using a 120-micron standard coater, wherein the temperature of a hot platform is room temperature during coating, and placing the cathode electrochromic layer in drying equipment for drying for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the solid electrolyte layer and the anode electrochromic layer together, enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, placing the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer in a vacuum drying oven for drying for 2 hours, and then carrying out vacuum hot pressing for 5min by using a hot press at the hot pressing temperature of 130 ℃ to obtain the all-solid-state electrochromic device.
The electrochromic device was tested for discoloration and fading effects using cyclic voltammetry, and fig. 7 is a cyclic voltammetry curve of the assembled device.
Example 5
A preparation method of an all-solid-state electrochromic device comprises the following steps:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: sequentially cleaning a substrate A with a transparent conducting layer A and FTO glass (2cm multiplied by 3cm) with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and FTO glass (2cm multiplied by 3cm) subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
6.9645g of anhydrous nickel acetate is weighed and dissolved in 125ml of anhydrous ethanol to be stirred evenly; weighing 0.975g of lithium acetate, dissolving the lithium acetate in 125ml of absolute ethyl alcohol, uniformly stirring, mixing the two solutions together, and uniformly stirring to obtain a clear solution II;
weighing 4.917g of oxalic acid, dissolving in 130ml of absolute ethyl alcohol, and uniformly stirring to obtain an oxalic acid solution III;
dripping oxalic acid solution III into the clear solution II at the flow rate of 30ml/min to form light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 1h, taking out the light blue turbid liquid IV, carrying out centrifugal separation for 5min at the rotating speed of 6500rpm, pouring out the supernatant, and washing with absolute ethyl alcohol for more than two times to prepare a precursor solution V;
placing the precursor solution V in a constant-temperature oven at 85 ℃ for drying for more than 12h, then fully grinding, and then placing in a muffle furnace at 400 ℃ for calcining for 0.5h to obtain nanocrystalline powder, wherein the grain diameter of the nanocrystalline powder is 20 nm;
placing the nanocrystalline powder in an ultrasonic cell disruption instrument, performing ultrasonic treatment in deionized water with the concentration of 75mg/mL for 3s every time at intervals of 3s for 30min, and uniformly dispersing to obtain nanocrystalline dispersion liquid C with the concentration of 75 mg/mL; placing the transparent conductive layer A of the substrate A on a hot bench at 120 ℃ in an upward manner, dropping the nanocrystalline dispersion liquid C on the transparent conductive layer A, and coating the substrate by using a coater with a scraper opening of 120 mu m at a uniform speed;
after the solvent is volatilized, naturally cooling to obtain an anode electrochromic layer;
and step 3: preparation of cathode electrochromic layer
Weighing 6.596g of sodium tungstate hydrate, dissolving in 20ml of deionized water to prepare a 0.4mol/L solution, after the sodium tungstate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium tungstate into a tungstic acid precipitate, centrifugally separating the tungstic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing with the deionized water for more than two times to prepare a tungsten oxide precursor;
weighing 0.968g of hydrated sodium molybdate, dissolving the hydrated sodium molybdate in 5ml of deionized water to prepare a 0.32mol/L solution, after the sodium molybdate is completely dissolved, dropwise adding 1.5mol/L hydrochloric acid solution while stirring, converting the sodium molybdate into molybdic acid precipitate, centrifugally separating the molybdic acid precipitate for 5min at the rotating speed of 6500rpm, pouring out supernatant, and washing the molybdic acid precipitate with the deionized water for more than two times to prepare a molybdenum oxide precursor;
uniformly mixing a tungsten oxide precursor and a molybdenum oxide precursor;
dropwise adding 30% hydrogen peroxide solution into the precursor, and dissolving to finally form transparent sol; spraying transparent sol on FTO glass (2cm multiplied by 3cm) on a hot bench by using a dispenser, wherein the spraying speed of a sprayer is 0.5ml/min, the cycle time is 10 times, the thermal state temperature is set to be 40 ℃, and a uniform layer of WO is obtained3And (3) placing the film in a tube furnace at 450 ℃ for heat treatment for 0.5h, wherein the oxygen content in the tube furnace is controlled at 80%, and thus the cathode electrochromic layer is prepared.
And 4, step 4: preparation of solid electrolyte layer
Adding 2g of high-molecular plasticizer alkene-vinyl acetate copolymer and 19.06ml of methyl methacrylate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer for stirring for 5 hours, and fully mixing to obtain a system A;
adding 9ml of electrolyte solvent propylene carbonate and 1.4364g of lithium salt lithium perchlorate into a round-bottom flask for mixing, placing the mixture into a magnetic stirrer at the temperature of 75 ℃, and stirring for 5 hours to fully mix the mixture to obtain a system B;
mixing the system A and the system B according to the volume ratio of 1:0.23, placing the mixture in a constant-temperature magnetic stirrer at 70 ℃ for stirring for 3 hours to fully mix the mixture to obtain an organic electrolyte solution, adding 6.85mg of an anti-aging agent Tinuvin571 into the organic electrolyte solution, and fully mixing the mixture uniformly for later use;
uniformly coating the organic electrolyte solution added with the age resister on the cathode electrochromic layer by a coating method by using a 120-micron standard coater, wherein the temperature of a hot platform is room temperature during coating, and placing the cathode electrochromic layer in drying equipment for drying for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the solid electrolyte layer and the anode electrochromic layer together, enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, placing the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer in a vacuum drying oven for drying for 2 hours, and then carrying out vacuum hot pressing for 5min by using a hot press at the hot pressing temperature of 130 ℃ to obtain the all-solid-state electrochromic device.
The electrochromic device was tested for discoloration and fading effects using cyclic voltammetry, and fig. 8 is a cyclic voltammetry curve of the assembled device.
Claims (7)
1. An all-solid-state electrochromic device is characterized by comprising a substrate A, a transparent conducting layer A, an anode electrochromic layer, a solid electrolyte layer, a cathode electrochromic layer, a transparent conducting layer B and a substrate B which are sequentially arranged;
the transparent conducting layer A and the transparent conducting layer B are aluminum-doped zinc oxide films, tin-doped indium oxide films, fluorine-doped tin oxide films, silver nanowires, gold nanowires or network electrodes; the network electrode is a composite material of one or both of carbon nanotubes or metal oxides; the transparent conductive layerThe surface resistance of the layer A and the transparent conductive layer B is 5-50 omega/cm2；
The cathode electrochromic layer is a tungsten oxide film doped with metal atoms, and the molecular formula of the cathode electrochromic layer is MxWOyWherein M is one or more of molybdenum, lithium, nickel, vanadium, niobium, tantalum, titanium, silicon, zirconium, gold, boron, barium, beryllium, bismuth, calcium, cesium, copper, europium, gallium, indium, potassium, lanthanum, magnesium, sodium, lead, selenium, tin and uranium, x and y respectively represent the mole number of M and O atoms, and 0<x<0.5，2.2<y<3；
The anode electrochromic layer is a nickel oxide film doped with metal atoms, and the molecular formula of the anode electrochromic layer is AzNiOrWherein A is one or more of zinc, lithium, copper, titanium, silicon, silver, aluminum, arsenic, gold, boron, barium, beryllium, bismuth, calcium, cesium, europium, gallium, indium, potassium, lanthanum, magnesium, sodium, lead, selenium, tin and uranium, z and r respectively represent the mole number of A and O atoms, and 0<z<0.5，1<r<2。
2. The all-solid-state electrochromic device according to claim 1, wherein the substrate a and the substrate B are glass substrates, PET films or PI films.
3. The all-solid electrochromic device according to claim 1, wherein the composition of said solid electrolyte layer comprises polymeric plasticizer, organic solvent, electrolyte solvent and lithium salt; wherein the mass ratio of the polymer plasticizer to the organic solvent is 1: 7-9, and the mass ratio of the electrolyte solvent to the lithium salt is 1: 3.77-7.56.
4. The all-solid-state electrochromic device according to claim 3, wherein the polymeric plasticizer is one or more of polyvinyl alcohol, polyvinyl butyral or an ene-vinyl acetate copolymer; the organic solvent is one or more of N, N-dimethylformamide, absolute ethyl alcohol, dimethylacetamide or methyl methacrylate; one or more of ethylene carbonate, propylene carbonate, butylene carbonate, Y-butyrolactone, dipropylene carbonate, N-methylpyrrolidone, N-methylacetamide, N-methylformamide, dimethylformamide, diethylformamide, acetonitrile or succinonitrile; the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate (V) or lithium sulfonate.
5. The method for preparing an all-solid-state electrochromic device according to claim 1, comprising the steps of:
step 1: treatment of substrate A and substrate B
(1) Ultrasonic cleaning treatment: respectively and sequentially cleaning a substrate A with a transparent conducting layer A and a substrate B with a transparent conducting layer B with a detergent, deionized water, acetone and ethanol in an ultrasonic device for 5-10 min, taking out, and drying with a drying device;
(2) surface active treatment: respectively carrying out surface active treatment on the substrate A and the substrate B subjected to ultrasonic cleaning treatment for later use;
step 2: preparation of anodic electrochromic layer
(1) According to AzNiOrCalculating the content of the required nickel salt and metal salt, and weighing for later use;
(2) mixing nickel salt and metal salt to form a mixture I, and dissolving the mixture I in a solvent to obtain a clarified solution II, wherein the mass ratio of the mixture I to the solvent is 1: 50-200;
dissolving oxalic acid in a solvent to obtain an oxalic acid solution III, wherein the mass ratio of the oxalic acid to the solvent is 1: 40-80;
dripping the oxalic acid solution III into the clear solution II at the flow rate of 1.5-50 ml/min to form a light blue turbid solution IV;
aging the light blue turbid liquid IV, standing for 0.5-48 h, taking out the light blue turbid liquid IV, performing centrifugal separation for 5-10 min, removing a supernatant, and washing with a solvent to prepare a precursor solution V; wherein the solvent is absolute ethyl alcohol;
(3) placing the precursor solution V in drying equipment for heat treatment at the temperature of 150-500 ℃ for 0.5-1.5 h to obtain nanocrystalline powder with the particle size of 5-100 nm;
(4) uniformly dispersing the nanocrystalline powder in a dispersion liquid to obtain a nanocrystalline dispersion liquid C, wherein the concentration of the nanocrystalline dispersion liquid C is 3-100 mg/ml; coating the nanocrystalline dispersion liquid C on the transparent conducting layer A of the processed substrate A through a coating process; wherein the dispersion liquid is one or more of water, ethanol or acetone;
(5) placing the substrate A coated with the nanocrystalline dispersion liquid C in heat treatment equipment for calcination, wherein the temperature in the heat treatment equipment is 150-500 ℃, the oxygen content in the heat treatment equipment accounts for 20-100%, and the anode electrochromic layer is obtained after calcination for 0.5-1.5 h;
and step 3: preparation of cathode electrochromic layer
(1) According to MxWOyCalculating the contents of the required tungsten salt and metal salt, and weighing for later use;
(2) mixing tungsten salt and metal salt to form a mixture VI, and dissolving the mixture VI in a solvent to obtain a clear solution VII, wherein the mass ratio of the mixture VI to the solvent is 1: 50-200;
dissolving oxalic acid in a solvent to obtain an oxalic acid solution VIII, wherein the oxalic acid and the solvent are 1: 30-90 in mass ratio;
dripping oxalic acid solution VIII into the clear solution VII at the flow rate of 1-80 ml/h to form light blue turbid liquid IX;
aging the light blue turbid liquid IX, standing for 12-48 h, taking out the light blue turbid liquid IX, performing centrifugal separation for 5-10 min, removing a supernatant, and washing with a solvent to prepare a precursor solution X; wherein the solvent is deionized water;
(3) placing the precursor solution X in drying equipment for heat treatment, wherein the heat treatment temperature is 150-500 ℃, and the heat treatment time is 0.5-1.5 h, so as to obtain nanocrystalline powder, and the grain diameter of the nanocrystalline powder is 5-100 nm;
(4) uniformly dispersing the nanocrystalline powder in a dispersion liquid to obtain a nanocrystalline dispersion liquid D, wherein the concentration of the nanocrystalline dispersion liquid D is 3-100 mg/ml; coating the nanocrystalline dispersion liquid D on the transparent conducting layer B of the processed substrate B through a coating process; wherein the dispersion liquid is one or more of water, ethanol or acetone;
(5) placing the substrate B coated with the nanocrystalline dispersion liquid D in heat treatment equipment for calcination, wherein the temperature in the heat treatment equipment is 150-500 ℃, the oxygen content in the heat treatment equipment accounts for 20-100%, and calcining for 15-120 min to obtain a cathode electrochromic layer;
and 4, step 4: preparation of solid electrolyte layer
(1) Mixing a polymer plasticizer and an organic solvent in proportion, and then placing the mixture in stirring equipment for stirring to fully mix the mixture to obtain a system A;
(2) mixing an electrolyte solvent and lithium salt in proportion, and then placing the mixture into stirring equipment for stirring to fully mix the mixture to obtain a system B;
(3) mixing the system A and the system B, and then placing the mixture into stirring equipment to be stirred, so that the mixture is fully mixed to obtain electrolyte solution; the system A and the system B are 1: 0.11-0.42 in volume ratio;
(4) coating the electrolyte solution on the anode electrochromic layer and/or the cathode electrochromic layer through a coating process, and placing the anode electrochromic layer and/or the cathode electrochromic layer in drying equipment to dry for more than 12 hours to obtain a solid electrolyte layer;
and 5: preparation of all-solid-state electrochromic device
And (3) buckling the substrate A and the substrate B obtained through the treatment in the steps (1) to (4), enabling the anode electrochromic layer, the solid electrolyte layer and the cathode electrochromic layer to be in contact in sequence, and placing the buckled substrate A and the substrate B in hot pressing equipment for hot pressing for 5-30 min at the temperature of 110-180 ℃ to obtain the all-solid-state electrochromic device.
6. The method for preparing an all-solid-state electrochromic device according to claim 5, wherein:
in the step 4(3), an auxiliary agent and/or nanoparticles are added into the electrolyte solution, wherein the auxiliary agent is one or more of an antioxidant, a UV (ultraviolet) absorbent or an anti-aging agent, and the mass ratio of the auxiliary agent to the electrolyte solution is 0.1%0.5 percent to 1; the nano particles are SiO2、TiO2、Al2O3、ZnO、ZrO2Or Ta2O5The particle size of the nano particles is less than 150 nm;
adding one or more of a thickening agent, a film forming agent or a leveling agent into the dispersion liquid in the step 2(4) and/or the step 3 (4); the thickening agent is hydroxyethyl cellulose; the film forming agent is a hydrophobically modified polyacrylic ammonium salt polymer (SN-5027); the leveling agent is diacetone alcohol.
7. The method for preparing an all-solid-state electrochromic device according to claim 5, wherein:
the thickness of the anode electrochromic layer is 300-1000 nm;
the thickness of the cathode electrochromic layer is 300-1000 nm;
the thickness of the solid electrolyte layer is 0.5-30 μm;
the coating process comprises a blade coating method, a casting method, a double-screw extrusion casting method, spin coating, micro-convex plate coating, wire rod coating, dipping and drawing, slit extrusion coating, spray coating, screen printing, ink-jet printing or an electrodeposition method.
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| CN115308960A (en) * | 2022-07-11 | 2022-11-08 | 贵州大学 | Colorful electrochromic trademark and preparation method thereof |
| CN114994999B (en) * | 2022-07-12 | 2023-08-25 | 延安大学 | Preparation method of core-shell zinc oxide @ tungsten trioxide @ molybdenum trioxide Eu QDs nanosheet microcrystalline electrode material |
| CN116300233A (en) * | 2022-12-15 | 2023-06-23 | 安徽立光电子材料股份有限公司 | Electrochromic element with high conversion rate and preparation method thereof |
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