CN110627372A - Method for preparing lithium titanate electrochromic film - Google Patents
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- CN110627372A CN110627372A CN201910937919.6A CN201910937919A CN110627372A CN 110627372 A CN110627372 A CN 110627372A CN 201910937919 A CN201910937919 A CN 201910937919A CN 110627372 A CN110627372 A CN 110627372A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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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
- G02F1/1524—Transition metal compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
- C03C2217/241—Doped oxides with halides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Abstract
The invention relates to a method for preparing a lithium titanate electrochromic film, which comprises the following steps: taking a lithium salt solution and an organic titanium salt solution, and mixing the solutes of the lithium salt solution and the organic titanium salt solution according to the mass ratio of the lithium salt solution to the organic titanium salt solution: uniformly mixing organic titanium salt (1-1.5) and 1 to obtain solution A; according to the quantity ratio of solute substances, oxalic acid: adding oxalic acid solution into the solution A, and uniformly mixing to form a lithium titanate sol precursor; taking a substrate containing a transparent conductive layer, coating a lithium titanate sol precursor on the surface of the transparent conductive layer of the substrate, and drying to prepare a lithium titanate sol precursor film; calcining the lithium titanate sol precursor film at the calcining temperature of 350-700 □ for 1-6 h, and cooling to obtain the lithium titanate electrochromic film. The method is simple to operate, and compared with the traditional color-changing layer material, the prepared electrochromic film has the advantages that the cycle performance, the service life and other performances of the color-changing layer material are greatly improved by applying the lithium titanate material.
Description
The technical field is as follows:
the invention belongs to the technical field of electrochromic devices, and particularly relates to a method for preparing a lithium titanate electrochromic film.
Background art:
electrochromism is a phenomenon that the optical properties (reflectivity, transmittance, absorptivity and the like) of a material generate stable and reversible color change under the action of an external electric field, and the electrochromism is represented as reversible change of color and transparency in appearance. The electrochromic intelligent glass has the adjustability of light absorption and transmission under the action of an electric field, can selectively absorb or reflect external heat radiation and internal heat diffusion, can greatly reduce the power consumption of heat supply or cold supply when applied to high-rise buildings, and can also solve the problem of continuously intensified light pollution in modern cities. Besides buildings, the electrochromic technology has wide application prospects in the fields of intelligent electronics and devices, automobiles, low-energy-consumption display, aerospace and the like.
Lithium titanate (Li)4Ti5O12) The crystal has a spinel structure, and the lattice constant and the volume change of the crystal are small and less than 1 percent when the crystal is inserted into or extracted from lithium ions, so that the crystal is a material with zero strain. Theoretically, under the circulating action of an external electric field, the characteristic of zero strain property can avoid the damage of the structure caused by the continuous insertion and extraction of lithium ions, thereby greatly improving the circulating performance and prolonging the service life of the material.
At present, most of research on lithium titanate is focused on the aspect of lithium ion battery cathode materials, and a few of application research on electrochromic materials is mainly focused on preparing an electrochromic material ion storage layer by using a magnetron sputtering method. The lithium titanate material is innovatively adopted as the electrochromic layer material, and the electrochromic layer material is Li4Ti5O12Under the action of an external electric field, Li4Ti5O12From Delithiated (DL) state (Li)4Ti5O12) Conversion to lithiated (L) state (Li)7Ti5O12) The appearance is then manifested by a thin film transition from a transparent colourless (delithiated) to a (lithiated) dark blue color, whose optical transmission in the visible wavelength range is greatly reduced, and, unlike conventional electrochromic layer materials, Li in the lithiated state7Ti5O12The transmittance in the near-middle far-infrared wavelength range is low, and the diffusion of thermal radiation is adjustable to a certain extent. Second Li4Ti5O12Material lithiation before and after visibleThe high emissivity adjustability is shown in the middle and far infrared wavelength range in the light range, so that the thermal camouflage paint can be applied to the field of thermal camouflage. Thus Li4Ti5O12The broadband electrochromic property of (LTO) has good application prospect in the fields of infrared camouflage and temperature regulation.
The lithium titanate as a novel cathode electrochromic material has less related research, how to prepare large-area Li with good performance by simple equipment and relatively loose environmental conditions is simple and convenient4Ti5O12The thin film is a problem to be solved urgently in the aspect of application of the thin film in electrochromic materials. Therefore, the invention provides a simple and cheap process and can prepare a large-area lithium titanate electrochromic film with good performance, which is very important.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a method for preparing a lithium titanate electrochromic film, which can realize the preparation of the lithium titanate electrochromic film with good performance; the method is simple and easy to realize, has low cost, and has the possibility of application and popularization in the electrochromic glass industry, the infrared camouflage field, intelligent electronics and devices and other aspects.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a lithium titanate electrochromic film comprises the following steps:
step 1, preparing a lithium titanate sol precursor:
(1) taking a lithium salt solution and an organic titanium salt solution, and mixing the solutes of the lithium salt solution and the organic titanium salt solution according to the mass ratio of the lithium salt solution to the organic titanium salt solution: uniformly mixing organic titanium salt (1-1.5) and 1 to obtain solution A;
(2) according to the quantity ratio of solute substances, oxalic acid: adding oxalic acid solution into the solution A, and uniformly mixing to form a lithium titanate sol precursor;
step 2, preparing a lithium titanate sol precursor film:
taking a substrate containing a transparent conductive layer, coating a lithium titanate sol precursor on the surface of the transparent conductive layer of the substrate, and drying to prepare a lithium titanate sol precursor film;
step 3, preparing the lithium titanate electrochromic film:
and calcining the lithium titanate sol precursor film at the calcining temperature of 350-700 ℃, keeping the temperature for 1-6 h, and naturally cooling to obtain the lithium titanate electrochromic film.
In the step 1 (1):
the preparation process of the lithium salt solution comprises the following steps: dissolving lithium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the lithium salt is 0.1-1.5 mol/L; the preparation process of the organic titanium salt solution comprises the following steps: dissolving organic titanium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the organic titanium salt is 0.1-2 mol/L;
mixing the two solutions, and then fully and magnetically stirring to form a clear mixed solution; wherein, the solvent adopted in the preparation process of the lithium salt solution and the organic titanium salt solution is absolute ethyl alcohol.
In the step 1 (1): the lithium salt is lithium acetate.
In the step 1 (1): the organic titanium salt is one of tetrabutyl titanate, titanium isopropoxide and isopropyl titanate.
In the step 1 (2):
the preparation process of the oxalic acid solution is as follows: dissolving oxalic acid in a solvent, and magnetically stirring to obtain a clear oxalic acid solution, wherein the concentration of the oxalic acid solution is 1-4 mol/L;
dripping the prepared oxalic acid solution into the clear mixed solution A in the step (1) at a slow speed, and fully and uniformly mixing to form a clear and transparent lithium titanate sol precursor;
in the step 2, the substrate is conductive glass, and the conductive glass is ITO conductive glass, FTO conductive glass or AZO conductive glass.
In the step 2, after the substrate is pretreated, coating is carried out, wherein the substrate pretreatment step is as follows:
ultrasonic cleaning treatment: sequentially cleaning the substrate with a detergent, deionized water, acetone and ethanol in an ultrasonic device, taking out, and drying with a drying device;
surface active treatment: performing surface active treatment on the substrate subjected to ultrasonic cleaning treatment for later use;
in the step 2, the coating process is a blade coating method, a spraying method, a wire rod coating method, a dip-coating method, a spin coating method or a slit extrusion coating method.
In the step 3, the lithium titanate electrochromic film prepared under the voltage of-3V to-1.5V obtains the transmittance of the lithiated film in the infrared wavelength range of 7-31%.
In the step 3, the prepared lithium titanate electrochromic film has the adjustability of emissivity of 0.50-0.68 in the visible light wavelength range and the adjustability of emissivity of 0.30-0.55 and 0.08-0.27 in the middle and far infrared wavelength range under the voltage of-3V to-1.5V.
In the step 3, the highest light modulation range of the lithium titanate electrochromic film in the visible light wavelength range is 40.51-50.63% under the voltage of-3V to-1.5V.
In the step 3, after the prepared lithium titanate electrochromic film is subjected to a cyclic test of an external electric field with a voltage of-3V to-1.5V for 5000-6000 times, the adjustment amplitude of the material in the visible light and infrared wavelength ranges is 83-90% of that of the initial test.
In the step 3, the lithiation process of the prepared lithium titanate electrochromic film is carried out in a liquid electrolyte, and platinum is used as a counter electrode.
In the step 3, after the lithium titanate electrochromic film is lithiated, certain electric energy can be stored, and electric quantity visualization is achieved.
In the step 3, the prepared lithium titanate electrochromic film can realize electrochromic under the action of an external voltage, and simultaneously can store certain electric energy, so that a super capacitor film is formed, an electric appliance and the like are connected to supply energy to the film and realize fading to a certain degree, and the state of the contained electric quantity can be judged through the depth degree of the coloring appearance, so that certain visualization is realized. The prepared lithium titanate electrochromic film has low infrared region transmittance after lithiation, has the characteristic of emissivity adjustability, and has a certain infrared camouflage effect.
The invention has the beneficial effects that:
(1) the method for preparing the lithium titanate electrochromic film is simple to operate, simple in equipment, loose in preparation requirement environmental conditions, low in preparation process energy consumption, capable of greatly reducing the production cost, beneficial to industrial large-area production, and expected to be popularized in the industrial process of the electrochromic film.
(2) The lithium titanate used by the method is different from a traditional electrochromic device color-changing layer material, and the lithium titanate material is a zero-strain material. The crystal has small lattice constant and volume change when lithium ions are inserted or removed, and compared with the traditional color changing layer material, the lithium titanate material is applied to improve the cycle performance and the service life of the color changing layer material.
(3) The lithium titanate used by the method is different from a traditional electrochromic device color-changing layer material, and the lithium titanate material has low transmittance in an infrared region after being lithiated, so that the lithium titanate material has certain adjustability for the diffusion of heat radiation. The lithium titanate material shows the adjustability of emissivity in visible light wavelength and middle and far infrared wavelength ranges before and after lithiation, so that the lithium titanate material can be applied to the field of thermal camouflage.
(4) The film prepared by the method is lithiated, shows color change in appearance and stores certain electric energy, forms a super capacitor film at the moment, is connected with an electric appliance and the like to supply energy to the super capacitor film and realize fading to a certain degree, and can judge the state of the contained electric quantity through the depth of coloring in appearance, so that the super capacitor film has certain visualization.
Description of the drawings:
FIG. 1 is an XRD pattern of a lithium titanate film prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of the surface of the lithium titanate electrochromic film prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of a cross section of an electrochromic film of lithium titanate prepared in example 1 of the present invention;
FIG. 4 is a digital photograph of the assembled device of example 1 after coloring;
FIG. 5 is a digital photograph of the assembled device of example 1 after color fading;
FIG. 6 is a graph of UV-visible light transmittance before and after lithiation of the lithium titanate electrochromic film prepared in example 1 of the present invention;
FIG. 7 is a current-potential diagram of an electrochromic film of lithium titanate prepared in example 1 of the present invention;
fig. 8 is a cyclic voltammogram of the lithium titanate electrochromic film prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
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.
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.
In the following examples, the starting materials used are all commercially available.
A method for preparing a lithium titanate electrochromic film comprises the following steps:
step 1, preparing a lithium titanate sol precursor:
(1) taking a lithium salt solution and an organic titanium salt solution, and mixing the solutes of the lithium salt solution and the organic titanium salt solution according to the mass ratio of the lithium salt solution to the organic titanium salt solution: uniformly mixing organic titanium salt (1-1.5) and 1 to obtain solution A;
(2) according to the quantity ratio of solute substances, oxalic acid: adding oxalic acid solution into the solution A, and uniformly mixing to form a lithium titanate sol precursor;
step 2, preparing a lithium titanate sol precursor film:
taking a substrate containing a transparent conductive layer, coating a lithium titanate sol precursor on the surface of the transparent conductive layer of the substrate, and drying to prepare a lithium titanate sol precursor film;
step 3, preparing the lithium titanate electrochromic film:
and calcining the lithium titanate sol precursor film at the calcining temperature of 350-700 ℃, keeping the temperature for 1-6 h, and naturally cooling to obtain the lithium titanate electrochromic film.
In the step 1 (1):
the preparation process of the lithium salt solution comprises the following steps: dissolving lithium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the lithium salt is 0.1-1.5 mol/L; the preparation process of the organic titanium salt solution comprises the following steps: dissolving organic titanium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the organic titanium salt is 0.1-2 mol/L;
mixing the two solutions, and then fully and magnetically stirring to form a clear mixed solution; wherein, the solvent adopted in the preparation process of the lithium salt solution and the organic titanium salt solution is absolute ethyl alcohol.
In the step 1 (1): the lithium salt is lithium acetate.
In the step 1 (1): the organic titanium salt is one of tetrabutyl titanate, titanium isopropoxide and isopropyl titanate.
In the step 1 (2):
the preparation process of the oxalic acid solution is as follows: dissolving oxalic acid in a solvent, and magnetically stirring to obtain a clear oxalic acid solution, wherein the concentration of the oxalic acid solution is 1-4 mol/L;
dripping the prepared oxalic acid solution into the clear mixed solution A in the step (1) at a slow speed, and fully and uniformly mixing to form a clear and transparent lithium titanate sol precursor;
in the step 2, the substrate is conductive glass, and the conductive glass is ITO conductive glass, FTO conductive glass and AZO conductive glass.
In the step 2, after the substrate is pretreated, coating is carried out, wherein the substrate pretreatment step is as follows:
ultrasonic cleaning treatment: sequentially cleaning the substrate with a detergent, deionized water, acetone and ethanol in an ultrasonic device, taking out, and drying with a drying device;
surface active treatment: performing surface active treatment on the substrate subjected to ultrasonic cleaning treatment for later use;
in the step 2, the coating process is a blade coating method, a spraying method, a wire rod coating method, a dip-coating method, a spin coating method or a slit extrusion coating method.
In the step 3, the lithium titanate electrochromic film prepared under the voltage of-3V to-1.5V obtains the transmittance of the lithiated film in the infrared wavelength range of 7-31%.
In the step 3, the prepared lithium titanate electrochromic film has the emissivity adjustability of 0.50-0.68 in the visible light wavelength range, the emissivity adjustability of 0.30-0.55 and the emissivity adjustability of 0.08-0.27 in the middle and far infrared wavelength range under the voltage of-3V to-1.5V, namely the emissivity adjustability of 0.30-0.55 in the middle and far infrared wavelength range and the emissivity adjustability of 0.08-0.27 in the far infrared wavelength range.
In the step 3, the highest light modulation range of the lithium titanate electrochromic film in the visible light wavelength range is 40.51-50.63% under the voltage of-3V to-1.5V.
In the step 3, after the prepared lithium titanate electrochromic film is subjected to a cyclic test of an external electric field with a voltage of-3V to-1.5V for 5000-6000 times, the adjustment amplitude of the material in the visible light and infrared wavelength range (namely the whole wavelength range from visible light to infrared) is 83-90% of that of the initial test.
In the step 3, the lithiation process of the prepared lithium titanate electrochromic film is carried out in a liquid electrolyte, and platinum is used as a counter electrode.
In the step 3, after the lithium titanate electrochromic film is lithiated, certain electric energy can be stored, and electric quantity visualization is achieved.
In the step 3, the prepared lithium titanate electrochromic film can realize electrochromic under the action of an external voltage, and simultaneously can store certain electric energy, so that a super capacitor film is formed, an electric appliance and the like are connected to supply energy to the film and realize fading to a certain degree, and the state of the contained electric quantity can be judged through the depth degree of the coloring appearance, so that certain visualization is realized. The prepared lithium titanate electrochromic film has low infrared region transmittance after lithiation, and has a certain infrared camouflage effect.
Example 1:
(1) dissolving 1.224g of lithium acetate in 10mL of absolute ethanol, and stirring to obtain a clear solution with the concentration of 1.2 mol/L; 2.341g of oxalic acid is dissolved in 12.568mL of absolute ethyl alcohol, and a clear solution with the concentration of 2.069mol/L is obtained after stirring; 3.432ml of tetrabutyl titanate is dissolved in 10ml of absolute ethyl alcohol, and the concentration is 1 mol/L; and uniformly mixing the prepared lithium acetate solution and tetrabutyl titanate solution according to the solute substance mass ratio of 1.2:1, and stirring to obtain a clear solution.
(2) The ratio of oxalic acid to (lithium acetate + tetrabutyl titanate) in terms of the amount of solute substances is 1.181: 1, dripping the uniformly stirred oxalic acid ethanol solution into a lithium acetate and tetrabutyl titanate mixed solution by a separating funnel at a slow flow rate; after the dropwise addition is finished, a transparent and clear sol precursor is formed and placed for standby application under the condition of magnetic stirring.
(3) The following steps are the processing of ITO or FTO conductive glass:
ultrasonic cleaning treatment: cleaning ITO or FTO conductive glass with deionized water, detergent mixed solution, deionized water and absolute ethyl alcohol in an ultrasonic device for 5min, taking out, and drying in a constant-temperature oven at 70 deg.C;
surface active treatment: placing the ITO or FTO conductive glass subjected to ultrasonic cleaning treatment in an oxygen plasma cleaning instrument, performing surface active treatment, controlling the working power to be 200W and the time to be 6min, controlling the oxygen pressure of a chamber to be 300Pa, and placing for later use after treatment;
(4) and (3) dropping the prepared lithium titanate sol precursor on a cleaned FTO conductive glass substrate, coating the substrate at a uniform speed by using a blade coating method through a coater with a scraper opening of 90 mu m, and naturally cooling after the solvent volatilizes to obtain a layer of lithium titanate sol precursor film.
(5) And (3) putting the prepared sol precursor film into a muffle furnace for calcination, wherein the calcination temperature is 550 ℃, the heat preservation time is 6 hours, and naturally cooling to obtain the lithium titanate electrochromic film with the thickness of 400 nm. The XRD pattern of the lithium titanate film on the FTO conductive glass substrate obtained after the lithium titanate sol precursor is prepared into the film and then sintered is shown as figure 1 (SnO in the pattern)2From linersBottom FTO conductive glass), the SEM photographs of the surface of the film are shown in fig. 2, and the SEM photographs of the cross section of the film are shown in fig. 3.
The lithium titanate electrochromic film prepared obtains Li in lithiation state under the voltage of-3V to-1.5V (tested in liquid electrolyte, Pt is counter electrode)7Ti5O12The transmittance in the near-middle far-infrared wavelength range is 10-25%, and the method has certain adjustability on the diffusion of heat radiation. The prepared lithium titanate electrochromic film has the adjustability of emissivity of 0.58-0.65 in the visible light wavelength range and the adjustability of emissivity of 0.35-0.51 and 0.10-0.25 in the middle and far infrared wavelength range under the voltage of-3V to-1.5V.
In order to further understand the electrochromic performance of the lithium titanate thin film prepared in example 1, the thin film on the FTO conductive glass substrate and another FTO conductive glass substrate prepared in the above manner are coated with an electrolyte, and then vacuum drying, hot pressing and other steps are performed to assemble a device, and when a positive pressure (4.5V) is applied to the device, the device becomes dark blue, as shown in fig. 4; when a negative pressure (-4.5V) was applied to the dark blue device, the device faded, as shown in FIG. 5. The device is in coloration (Li in lithiated state7Ti5O12The material stores certain electric energy), small bulbs are clamped at two ends of the combined device and are lightened, and the double functions of electrochromism and energy storage can be realized.
Ultraviolet-visible light transmittance graphs before and after lithiation of the prepared lithium titanate electrochromic film are shown in fig. 6, and the highest light modulation range in the visible light range is 50.63%, which shows that the lithium titanate electrochromic film has good spectrum modulation amplitude.
The current-potential diagram of the prepared lithium titanate electrochromic film is shown in fig. 7, and the cyclic voltammetry curve is shown in fig. 8.
After 6000 times of the prepared lithium titanate electrochromic film under the action of an external electric field circulation test with a voltage of-3V to-1.5V, the transmittance of the material in the visible light wavelength and infrared wavelength ranges is adjusted to 83-87% of that of the material in the primary test.
Example 2
(1) Dissolving 1.53g of lithium acetate in 10mL of absolute ethyl alcohol, and stirring to obtain a clear solution with the concentration of 1.5 mol/L; 2.476g of oxalic acid is dissolved in 17.568mL of absolute ethyl alcohol, and a clear solution with the concentration of 1.565mol/L is obtained after stirring; 3.432ml of tetrabutyl titanate is dissolved in 5ml of absolute ethyl alcohol, and the concentration is 2 mol/L; and uniformly mixing the prepared lithium acetate solution and tetrabutyl titanate solution according to the solute substance mass ratio of 1.5:1, and stirring to obtain a clear solution.
(2) The quantity ratio of oxalic acid to (lithium acetate + tetrabutyl titanate) according to solute substances is 1.1: 1, dripping the uniformly stirred oxalic acid ethanol solution into a lithium acetate and tetrabutyl titanate mixed solution by a separating funnel at a slow flow rate; after the dropwise addition is finished, a transparent and clear sol precursor is formed and placed for standby application under the condition of magnetic stirring.
(3) The following steps are the processing of ITO or FTO conductive glass:
ultrasonic cleaning treatment: cleaning ITO or FTO conductive glass with deionized water, detergent mixed solution, deionized water and absolute ethyl alcohol in an ultrasonic device for 5min, taking out, and drying in a constant-temperature oven at 70 deg.C;
surface active treatment: placing the ITO or FTO conductive glass subjected to ultrasonic cleaning treatment in an oxygen plasma cleaning instrument, performing surface active treatment, controlling the working power to be 200W and the time to be 6min, controlling the oxygen pressure of a chamber to be 300Pa, and placing for later use after treatment;
(4) and (2) using a spraying method, filling the prepared lithium titanate sol precursor into an injector, installing the injector on an injection pump, starting an ultrasonic atomization device, installing a spray head on a dispenser, setting a spray head spraying process program, adjusting the distance between the spray head and the cleaned FTO conductive glass substrate to be 10cm, adjusting the injection speed of the injection pump to be 175ul/min, simultaneously operating the injection pump and the dispenser to uniformly spray the lithium titanate sol precursor on the substrate, repeating the spraying for 4 times with the steps after the solvent volatilizes, and naturally cooling to obtain a layer of lithium titanate sol precursor film.
(5) And (3) putting the prepared sol precursor film into a muffle furnace for calcination, wherein the calcination temperature is 600 ℃, the heat preservation time is 4 hours, and naturally cooling to obtain the lithium titanate electrochromic film with the thickness of 900 nm. The highest light modulation range of the electrochromic film in the visible range was tested to be 45.22%. The transmittance of the obtained lithiated film in the near-middle far-infrared wavelength range is 8-21%, and the film has certain adjustability on the diffusion of heat radiation. The prepared lithium titanate electrochromic film has the adjustability of emissivity of 0.58-0.64 in the visible light wavelength range, and has the adjustability of emissivity of 0.36-0.52 and 0.12-0.24 in the middle and far infrared wavelength range. After the prepared lithium titanate electrochromic film is subjected to 5000 times of external electric field cycle test, the transmittance of the material in the visible light wavelength range, near-middle far-infrared wavelength range is adjusted to 86-90% of that of the initial test.
Example 3
(1) Dissolving 1.224g of lithium acetate in 20mL of absolute ethanol, and stirring to obtain a clear solution with the concentration of 0.65 mol/L; 2.377g of oxalic acid is dissolved in 7.5mL of absolute ethyl alcohol, and a clear solution with the concentration of 3.52mol/L is obtained after stirring; dissolving 3ml of titanium isopropoxide in 5ml of absolute ethyl alcohol, wherein the concentration is 2 mol/L; and uniformly mixing the prepared lithium acetate solution and the prepared titanium isopropoxide solution according to the solute substance quantity ratio of 1.2:1, and stirring to obtain a clear solution.
(2) The ratio of oxalic acid to (lithium acetate + titanium isopropoxide) in terms of the amount of solute substances is 1.2:1, dripping the uniformly stirred oxalic acid ethanol solution into a lithium acetate and titanium isopropoxide mixed solution by using a separating funnel at a slow flow rate; after the dropwise addition is finished, a transparent and clear sol precursor is formed and placed for standby application under the condition of magnetic stirring.
(3) The following steps are the processing of ITO or FTO conductive glass:
ultrasonic cleaning treatment: cleaning ITO or FTO conductive glass with deionized water, detergent mixed solution, deionized water and absolute ethyl alcohol in an ultrasonic device for 5min, taking out, and drying in a constant-temperature oven at 70 deg.C;
surface active treatment: placing the ITO or FTO conductive glass subjected to ultrasonic cleaning treatment in an oxygen plasma cleaning instrument, performing surface active treatment, controlling the working power to be 200W and the time to be 6min, controlling the oxygen pressure of a chamber to be 300Pa, and placing for later use after treatment;
(4) and (3) dropping the prepared lithium titanate sol precursor on a cleaned FTO conductive glass substrate, coating the substrate at a uniform speed by using a blade coating method through a coater with a scraper opening of 60 mu m, and naturally cooling after the solvent volatilizes to obtain a layer of lithium titanate sol precursor film.
(5) And (3) putting the prepared sol precursor film into a muffle furnace for calcination, wherein the calcination temperature is 450 ℃, the heat preservation time is 2 hours, and naturally cooling to obtain the lithium titanate electrochromic film with the film thickness of 300 nm. The highest light modulation range of the electrochromic film in the visible range was tested to be 40.51%. The transmittance of the obtained lithiated film in the near-middle far-infrared wavelength range is 17-31%, and the film has certain adjustability on the diffusion of heat radiation. The prepared lithium titanate electrochromic film has the adjustability of emissivity of 0.50-0.56 in the visible light wavelength range and has the emissivity of 0.31-0.45 and 0.08-0.26 in the middle and far infrared wavelength range. After the prepared lithium titanate electrochromic film is subjected to a cyclic test action of an external electric field with a voltage of-3V to-1.5V for 5000 times, the transmittance of the material in the visible light wavelength and infrared wavelength ranges is adjusted to 85-90% of that of the material in the primary test.
Example 4
(1) Dissolving 1.224g of lithium acetate in 10mL of absolute ethanol, and stirring to obtain a clear solution with the concentration of 1.2 mol/L; 2.971g of oxalic acid is dissolved in 12.568mL of absolute ethyl alcohol, and a clear solution with the concentration of 2.626mol/L is obtained after stirring; 2.96ml of isopropyl titanate is dissolved in 10ml of absolute ethyl alcohol, and the concentration is 1 mol/L; and uniformly mixing the prepared lithium acetate solution and the prepared isopropyl titanate solution according to the solute substance quantity ratio of 1.2:1, and stirring to obtain a clear solution.
(2) The ratio of oxalic acid to (lithium acetate + isopropyl titanate) in the amount of solute substance is 1.5:1, dripping the uniformly stirred oxalic acid ethanol solution into a lithium acetate and tetrabutyl titanate mixed solution by a separating funnel at a slow flow rate; after the dropwise addition is finished, a transparent and clear sol precursor is formed and placed for standby application under the condition of magnetic stirring.
(3) The following steps are the processing of ITO or FTO conductive glass:
ultrasonic cleaning treatment: cleaning ITO or FTO conductive glass with deionized water, detergent mixed solution, deionized water and absolute ethyl alcohol in an ultrasonic device for 5min, taking out, and drying in a constant-temperature oven at 70 deg.C;
surface active treatment: placing the ITO or FTO conductive glass subjected to ultrasonic cleaning treatment in an oxygen plasma cleaning instrument, performing surface active treatment, controlling the working power to be 200W and the time to be 6min, controlling the oxygen pressure of a chamber to be 300Pa, and placing for later use after treatment;
(4) and (3) dripping the prepared lithium titanate sol precursor on a cleaned FTO conductive glass substrate, coating the substrate at a uniform speed by using a blade coating method through a coater with a scraper opening of 120 microns, volatilizing the solvent, and naturally cooling to obtain a layer of lithium titanate sol precursor film.
(5) And (3) putting the prepared sol precursor film into a muffle furnace for calcination, wherein the calcination temperature is 500 ℃, the heat preservation time is 4 hours, and naturally cooling to obtain the lithium titanate electrochromic film with the film thickness of 550 nm. The highest light modulation range of the electrochromic film in the visible range was tested to be 42.38%. The transmittance of the obtained lithiated film in the near-middle far-infrared wavelength range is 12-25%, and the film has certain adjustability on the diffusion of heat radiation. The prepared lithium titanate electrochromic film has the emissivity adjustability of 0.51-0.60 in the visible light wavelength range and the emissivity adjustability of 0.30-0.46 and 0.01-0.23 in the middle and far infrared wavelength range. After the prepared lithium titanate electrochromic film is subjected to 5000 times of external electric field cycle test, the transmittance of the material in the visible light wavelength range, near-middle far-infrared wavelength range is adjusted to 86-89% of that of the initial test.
Example 5
(1) Dissolving 1.02g of lithium acetate in 10mL of absolute ethanol, and stirring to obtain a clear solution with the concentration of 1 mol/L; 2.341g of oxalic acid is dissolved in 6.5mL of absolute ethyl alcohol, and a clear solution with the concentration of 4mol/L is obtained after stirring; 3.432ml of tetrabutyl titanate is dissolved in 8ml of absolute ethyl alcohol, and the concentration is 1.25 mol/L; and uniformly mixing the prepared lithium acetate solution and tetrabutyl titanate solution according to the solute substance mass ratio of 1:1, and stirring to obtain a clear solution.
(2) The quantity ratio of oxalic acid to (lithium acetate + tetrabutyl titanate) according to solute substances is 1.3: 1, dripping the uniformly stirred oxalic acid ethanol solution into a lithium acetate and titanium isopropoxide mixed solution by using a separating funnel at a slow flow rate; after the dropwise addition is finished, a transparent and clear sol precursor is formed and placed for standby application under the condition of magnetic stirring.
(3) The following steps are the processing of ITO or FTO conductive glass:
ultrasonic cleaning treatment: cleaning ITO or FTO conductive glass with deionized water, detergent mixed solution, deionized water and absolute ethyl alcohol in an ultrasonic device for 5min, taking out, and drying in a constant-temperature oven at 70 deg.C;
surface active treatment: placing the ITO or FTO conductive glass subjected to ultrasonic cleaning treatment in an oxygen plasma cleaning instrument, performing surface active treatment, controlling the working power to be 200W and the time to be 6min, controlling the oxygen pressure of a chamber to be 300Pa, and placing for later use after treatment;
(4) and (2) using a spraying method, filling the prepared lithium titanate sol precursor into an injector, installing the injector on an injection pump, opening an ultrasonic atomization device, installing a spray head on a dispenser, setting a spray head spraying process program, adjusting the distance between the spray head and the cleaned FTO conductive glass substrate to be 12cm, adjusting the injection speed of the injection pump to be 200ul/min, simultaneously operating the injection pump and the dispenser to uniformly spray the lithium titanate sol precursor on the substrate, repeating the spraying for 5 times with the steps after the solvent volatilizes, and naturally cooling to obtain a layer of lithium titanate sol precursor film.
(5) And (3) putting the prepared sol precursor film into a muffle furnace for calcination, wherein the calcination temperature is 650 ℃, the heat preservation time is 3 hours, and naturally cooling to obtain the lithium titanate electrochromic film with the film thickness of 1 um. The electrochromic film was tested to have a maximum light modulation range of 44.64% in the visible range. The transmittance of the obtained lithiated film in the near-middle far-infrared wavelength range is 7-15%, and the film has certain adjustability on the diffusion of heat radiation. The prepared lithium titanate electrochromic film has the adjustability of emissivity of 0.60-0.68 in the visible light wavelength range and the adjustability of emissivity of 0.40-0.55 and 0.13-0.27 in the middle and far infrared wavelength range. After the prepared lithium titanate electrochromic film is subjected to a cyclic test action of an external electric field with a voltage of-3V to-1.5V for 5000 times, the transmittance of the material in the visible light wavelength and infrared wavelength ranges is adjusted to 85-88% of that of the material in the primary test.
According to the preparation method for preparing the lithium titanate electrochromic film, the lithium titanate electrochromic film is prepared by a sol-gel method, and the preparation method is a simple and convenient method for preparing a large-area electrochromic layer, is simple in preparation process, low in requirements on equipment and preparation environment, low in preparation energy consumption and suitable for industrial large-scale production and preparation of the film. Different from the traditional electrochromic material, the lithium titanate zero-strain material has good repeated cycling performance due to the unique structural characteristics. And the lithium titanate film is lithiated, not only is the appearance changed from white to dark blue, but also the passing rate of the lithium titanate film in an infrared region is low, and the lithium titanate film has certain adjustability on thermal radiation, and the prepared lithium titanate film displays certain emissivity adjustability in a visible light range and a middle and far infrared wavelength range, so that Li4Ti5O12The broadband electrochromic property of (LTO) has good application prospect in the fields of infrared camouflage and temperature regulation. Certain electric energy can be stored while the lithium titanate film is lithiated, and at the moment, the super-capacitor film is formed, so that certain electric appliances can be driven, and higher energy-saving and emission-reducing benefits are achieved.
Claims (10)
1. A method for preparing a lithium titanate electrochromic film is characterized by comprising the following steps:
step 1, preparing a lithium titanate sol precursor:
(1) taking a lithium salt solution and an organic titanium salt solution, and mixing the solutes of the lithium salt solution and the organic titanium salt solution according to the mass ratio of the lithium salt solution to the organic titanium salt solution: uniformly mixing organic titanium salt (1-1.5) and 1 to obtain solution A;
(2) according to the quantity ratio of solute substances, oxalic acid: adding oxalic acid solution into the solution A, and uniformly mixing to form a lithium titanate sol precursor;
step 2, preparing a lithium titanate sol precursor film:
taking a substrate containing a transparent conductive layer, coating a lithium titanate sol precursor on the surface of the transparent conductive layer of the substrate, and drying to prepare a lithium titanate sol precursor film;
step 3, preparing the lithium titanate electrochromic film:
and calcining the lithium titanate sol precursor film at the calcining temperature of 350-700 ℃, keeping the temperature for 1-6 h, and cooling to obtain the lithium titanate electrochromic film.
2. The method for preparing lithium titanate electrochromic film according to claim 1, wherein in step 1(1), the lithium salt solution is prepared by: dissolving lithium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the lithium salt is 0.1-1.5 mol/L; the preparation process of the organic titanium salt solution comprises the following steps: dissolving organic titanium salt in a solvent, and magnetically stirring to obtain a clear solution, wherein the mass concentration of the organic titanium salt is 0.1-2 mol/L; mixing the two solutions, and then fully and magnetically stirring to form a clear mixed solution; wherein, the solvent adopted in the preparation process of the lithium salt solution and the organic titanium salt solution is absolute ethyl alcohol.
3. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 1 (1): the lithium salt is lithium acetate, and the organic titanium salt is one of tetrabutyl titanate, titanium isopropoxide and isopropyl titanate.
4. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 1 (2): the preparation process of the oxalic acid solution is as follows: dissolving oxalic acid in a solvent and stirring to obtain a clear oxalic acid solution, wherein the concentration of the oxalic acid solution is 1-4 mol/L.
5. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 2, the substrate is conductive glass, and the conductive glass is ITO conductive glass, FTO conductive glass or AZO conductive glass.
6. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 3, the transmittance of the lithium titanate electrochromic film in a lithiated state in an infrared wavelength range is 7-31% under a voltage of-3V to-1.5V.
7. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 3, the prepared lithium titanate electrochromic film has an emissivity adjustability of 0.50-0.68 in a visible light wavelength range and an emissivity adjustability of 0.30-0.55 and an emissivity of 0.08-0.27 in a middle and far infrared wavelength range under a voltage of-3V-1.5V.
8. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 3, the highest light modulation range of the prepared lithium titanate electrochromic film in a visible light wavelength range is 40.51-50.63% under a voltage of-3V-1.5V.
9. The method for preparing the lithium titanate electrochromic film according to claim 1, wherein in the step 3, after the prepared lithium titanate electrochromic film is subjected to an external electric field cycling test at a voltage of-3V to-1.5V for 5000-6000 times, the adjustment amplitude of the material in the visible light and infrared wavelength ranges is 83-90% of that of the initial test.
10. The method for preparing the lithium titanate electrochromic film as claimed in claim 1, wherein in the step 3, the prepared lithium titanate electrochromic film can store electric energy after being lithiated, and has electric quantity visualization.
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