CN114933420A - Gradient temperature-based hydrothermal preparation method of multilayer nano-sheet NiO electrochromic film - Google Patents
Gradient temperature-based hydrothermal preparation method of multilayer nano-sheet NiO electrochromic film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
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- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 15
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
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- 239000004202 carbamide Substances 0.000 claims description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
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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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
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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
- G02F1/1503—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 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
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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
- C03C2217/228—Other specific 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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Abstract
The invention discloses a hydrothermal preparation method of a multilayer nano-sheet NiO electrochromic film based on gradient temperature, which comprises the following steps: placing ITO conductive glass in a lining of a high-temperature reaction kettle, adding NiO precursor solution into the lining, and sealing; sequentially placing the sealed high-temperature reaction kettle in gradient temperature environments from low to high, and keeping the high-temperature reaction kettle in each temperature environment for a certain time to perform multiple hydrothermal reactions; and after the hydrothermal reaction is finished, carrying out heat treatment on the ITO conductive glass to obtain the layered nano flaky NiO electrochromic film. According to the invention, the multi-gap nanosheet film is formed by adjusting the hydrothermal reaction temperature gradient, the compact film has relatively strong bonding force with the substrate, the multi-gap film has large specific surface area and many reaction active sites, so that the film has excellent electrochromic performance and good circulation stability when subjected to electrochromic circulation in alkaline electrolyte.
Description
Technical Field
The invention belongs to the technical field of film preparation, and particularly relates to a gradient temperature-based hydrothermal preparation method of a multilayer nano-sheet NiO electrochromic film.
Background
With the dramatic increase of energy consumption brought by the development of science and technology, the production of green energy-saving materials becomes an important technology. The electric energy consumed by the display technologies such as the indoor heat preservation and refrigeration of the building, the outdoor large-scale advertising board and the like is huge. In addition, people have increasingly high pursuits for quality of life, for example, in order to pursue privacy, partition glasses of conference rooms and offices are required to have a color changing function; in order to seek indoor light comfort, the window glass is required to be capable of automatically adjusting the light transmittance according to the intensity of sunlight; the demand of society for adaptive color-changing materials is gradually increasing. Under the background, the development of an intelligent energy-saving display technology becomes more important, and the electrochromic material has better advantages as an intelligent display technology.
The electrochromic material can generate corresponding color change under the stimulation of lower external direct current voltage, and after power failure, the material can keep the color under the voltage for a long time, and has the advantage of bistable color maintenance.
At present, common electrochromic film preparation technologies mainly include a magnetron sputtering method, an evaporation coating method, a spray pyrolysis method, a hydrothermal method and the like. The hydrothermal method has unique advantages in the aspect of preparing the film with the micro-nano structure, and is convenient for preparing the film with the micro-nano structure such as a nano sheet, a nano column, a nano hole and the like under the working condition of low cost.
However, the film prepared by the conventional hydrothermal method is usually not strong in cohesive force, so that the film is easy to fall off from a substrate in the color-changing cycle process, the cycle stability of the film is influenced, and the engineering application of the technology for preparing the electrochromic film by the hydrothermal method is seriously hindered.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a gradient temperature-based hydrothermal preparation method of a multilayer nano-sheet NiO electrochromic film. The technical problem to be solved by the invention is realized by the following technical scheme:
in a first aspect, the invention provides a gradient temperature-based hydrothermal preparation method of a multilayer nano-sheet NiO electrochromic film, which comprises the following steps:
step 1: placing ITO conductive glass in a lining of a high-temperature reaction kettle, adding NiO precursor solution into the lining, and sealing;
step 2: sequentially placing the sealed high-temperature reaction kettle in gradient temperature environments from low to high, and keeping the high-temperature reaction kettle in each temperature environment for a certain time to perform multiple hydrothermal reactions;
and step 3: and after the hydrothermal reaction is finished, carrying out heat treatment on the ITO conductive glass to obtain the layered nano flaky NiO electrochromic film.
In an embodiment of the present invention, the NiO precursor solution in step 1 is prepared from nickel nitrate hexahydrate and hexamethylenetetramine, and the specific preparation method is as follows:
dissolving 0.125-0.15mol/l of hexamethylenetetramine and 0.05-0.1mol/l of urea in 70ml of deionized water, and magnetically stirring for 30min to fully dissolve the hexamethylenetetramine and the urea to form a solution A;
and (3) taking nickel nitrate hexahydrate as a nickel source, adding 0.125mol of nickel nitrate hexahydrate into the solution A, magnetically stirring for 30min, and fully dissolving to form a NiO precursor solution.
In one embodiment of the present invention, step 1, before placing the ITO conductive glass in the inner liner of the high temperature reaction kettle, further comprises:
mixing a 5% NaOH solution and a hydrogen peroxide solution according to a ratio of 30:1, mixing to form a mixed solution C;
soaking the ITO conductive glass in the solution C for a certain time;
and cleaning the soaked ITO conductive glass to remove the residual solution C.
In one embodiment of the present invention, step 2 comprises:
21) placing the sealed high-temperature reaction kettle in an oil bath kettle, and keeping the high-temperature reaction kettle for T1 time under a first temperature environment to perform hydrothermal reaction, so as to form a first nanosheet layer on the ITO conductive glass;
22) increasing the first temperature to a second temperature and continuing to hold for a time period T2 to effect a hydrothermal reaction to form a second nanosheet layer on the first nanosheet layer;
23) naturally cooling to room temperature to form the NiO film with a plurality of nano-sheet layers.
In one embodiment of the invention, the first temperature is 110 ℃ and the second temperature is 15-25 ℃ higher than the first temperature; t1 ═ 1h, and T2 > T1.
In one embodiment of the invention, the first temperature is 90 ℃ and the second temperature is 15-25 ℃ higher than the first temperature; t1 ═ 1h, and T2 > T1.
In an embodiment of the present invention, after step 22) and before step 23), further comprising:
the second temperature is raised to a third temperature and held for a time period of T3 to effect a hydrothermal reaction to form a third nanosheet layer on the second nanosheet layer.
In one embodiment of the invention, the third temperature is 15-25 ℃ higher than the second temperature, and T3 is more than or equal to T1.
In a second aspect, the present invention also provides a NiO electrochromic film, which is a multilayer structure and is prepared by using the preparation method provided in the above example.
The invention has the beneficial effects that:
according to the preparation method provided by the invention, the growth morphology of the NiO film is controlled by adjusting the temperature gradient of the hydrothermal reaction, namely the NiO film is slowly grown in a low-temperature environment, then the reaction temperature is properly increased, the growth of the film is accelerated, a layered multi-gap nanosheet film is formed, and the binding power between the film and the substrate is enhanced; and the specific surface area of the multi-gap film is large, and the number of reactive sites is large, so that the film has excellent electrochromic performance and good cycling stability when being subjected to electrochromic cycling in an alkaline electrolyte.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic diagram of a hydrothermal preparation method of a multilayer nanosheet NiO electrochromic film based on gradient temperature, provided by an embodiment of the present invention;
FIG. 2 is a cross-sectional SEM test photograph of a layered NiO electrochromic film prepared according to a third example of the invention;
FIG. 3 is a cross-sectional EDS map of a layered NiO electrochromic film prepared according to example three of the present invention;
fig. 4 is a graph of the cycle stability of a layered NiO electrochromic film prepared in example three of the present inventions.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
Referring to fig. 1, fig. 1 is a schematic diagram of a hydrothermal preparation method of a multilayer nanosheet NiO electrochromic film based on gradient temperature, which includes:
step 1: and (3) placing the ITO conductive glass in the lining of the high-temperature reaction kettle, adding NiO precursor solution into the lining, and sealing.
In this embodiment, before the operation of step 1, some preparation operations are also required, which mainly include preparing a required NiO precursor solution and pretreating the ITO conductive glass, and the specific processes are as follows:
11) preparation of NiO precursor solution
In this embodiment, a NiO precursor solution is mainly prepared from nickel nitrate hexahydrate and hexamethylenetetramine, and the specific preparation process is as follows:
a) dissolving 0.125-0.15mol/l of hexamethylenetetramine and 0.05-0.1mol/l of urea in 70ml of deionized water, and magnetically stirring for 30min to fully dissolve the hexamethylenetetramine and the urea to form a solution A;
b) and (3) taking nickel nitrate hexahydrate as a nickel source, adding 0.125mol of nickel nitrate hexahydrate into the solution A, magnetically stirring for 30min, and fully dissolving to obtain a solution B, wherein the solution B is a NiO precursor solution.
In addition, the NiO precursor solution can be obtained in other ways, which is not specifically required in this embodiment.
12) Pretreating ITO conductive glass
Firstly, the ITO conductive glass is ultrasonically cleaned in acetone solution, absolute ethyl alcohol solution and deionized water for 20min respectively so as to fully wash grease on the surface of the ITO conductive glass.
Further, in order to increase the hydrophilicity of the ITO conductive glass, the ITO conductive glass is soaked in a mixed solution of NaOH and hydrogen peroxide before being placed in the inner liner of the high-temperature reaction kettle.
Specifically, a 5% NaOH solution and a hydrogen peroxide solution are mixed according to a ratio of 30:1 to form a mixed solution C;
and soaking the ITO conductive glass in the solution C for a certain time. The preferred soaking time in this example is 2 hours.
And finally, cleaning the soaked ITO conductive glass to remove the residual solution C.
Specifically, the ITO conductive glass soaked in the solution C is ultrasonically cleaned for 30min by using deionized water, so that residual solution C can be removed, and then the ITO conductive glass is soaked in absolute ethyl alcohol for later use.
After all the preparation works are finished, the pretreated ITO conductive glass is placed in the lining of the high-temperature reaction kettle, 2 pieces of the ITO conductive glass are placed in each time, the ITO conductive glass is obliquely placed from the middle of the bottom to the inner wall, and the prepared NiO precursor solution is added into the lining and sealed.
Step 2: and (3) sequentially placing the sealed high-temperature reaction kettle in gradient temperature environments from low to high, and keeping the high-temperature reaction kettle in each temperature environment for a certain time to perform multiple hydrothermal reactions.
In the embodiment, the hydrothermal reaction is mainly realized by adopting an oil bath heating mode. It is understood that other heating methods, such as oven heating, may be used to achieve the hydrothermal reaction, and this embodiment is not particularly limited.
The specific implementation of step 2 will be described in detail below, taking the oil bath heating as an example.
21) And placing the sealed high-temperature reaction kettle in an oil bath kettle, and keeping the high-temperature reaction kettle for T1 time under a first temperature environment to perform hydrothermal reaction so as to form a first nanosheet layer on the ITO conductive glass.
22) Increasing the first temperature to a second temperature and continuing to hold for a time period T2 to effect a hydrothermal reaction to form a second nanosheet layer on the first nanosheet layer;
23) naturally cooling to room temperature to form the NiO film with a plurality of nano-sheet layers.
In this example, the first temperature was within a lower temperature range that decomposed or partially decomposed the NiO precursor solution so that the NiO film could be slowly grown. The second temperature is within a higher temperature range that allows complete decomposition of the NiO precursor solution, allowing faster growth of the NiO film.
Alternatively, as an implementation, the first temperature may be 110 ℃, the second temperature is 15-25 ℃ higher than the first temperature, T1 ═ 1h, and T2 > T1.
Preferably, the second temperature is 130 ℃, T2 ═ 3h, and the specific implementation process of step 2 can be described as follows:
firstly, a sealed high-temperature reaction kettle is placed in an oil bath pot, the temperature gradient is set to be 110 ℃, and heat preservation is carried out for 1 hour, so that a first nanosheet layer is formed on the ITO conductive glass.
The temperature was then raised to 130 ℃ and incubated for 3h to form a second nanosheet layer on the first nanosheet layer.
And finally, taking out the high-temperature reaction kettle from the oil bath pot, naturally cooling to room temperature, taking out the ITO conductive glass, washing surface impurities with deionized water, and drying in an oven at 80 ℃ for 30min to form the NiO film with two nanosheet layers.
In another embodiment of the present invention, the first temperature may also be 90 ℃ and the second temperature is 15 to 25 ℃ higher than the first temperature; t1 ═ 1h, and T2 > T1.
Preferably, the second temperature is 110 ℃, T2 is 2h, and the specific implementation process of step 2 can be described as follows:
firstly, a sealed high-temperature reaction kettle is placed in an oil bath pot, the temperature gradient is set to be 90 ℃, and heat preservation is carried out for 1 hour, so that a first nanosheet layer is formed on the ITO conductive glass.
The temperature was then raised to 110 ℃ and incubated for 2h to form a second nanosheet layer on the first nanosheet layer.
And finally, taking out the high-temperature reaction kettle from the oil bath pot, naturally cooling to room temperature, taking out the ITO conductive glass, washing surface impurities with deionized water, and drying in an oven at 80 ℃ for 30min to form the NiO film with two nanosheet layers.
In addition, in another embodiment of the present invention, after step 22) and before step 23), the method further comprises:
the second temperature is raised to a third temperature and held for a time period T3 to effect a hydrothermal reaction to form a third nanosheet layer on the second nanosheet layer. Wherein the third temperature is 15-25 ℃ higher than the second temperature, and T3 is more than or equal to T1.
Preferably, the third temperature is 130 ℃, T3 ═ 1h, T3 ═ 2h, or T3 ═ 3h, and then the specific implementation process of step 2 can be described as follows:
firstly, a sealed high-temperature reaction kettle is placed in an oil bath pot, the temperature gradient is set to be 90 ℃, and heat preservation is carried out for 1 hour, so that a first nanosheet layer is formed on the ITO conductive glass.
Then raising the temperature to 110 ℃, and preserving the temperature for 2h, thereby forming a second nanosheet layer on the first nanosheet layer;
continuing to raise the temperature to 130 ℃, and preserving the temperature for 1h, so as to form a third nanosheet layer on the second nanosheet layer;
and finally, taking out the high-temperature reaction kettle from the oil bath pot, naturally cooling to room temperature, taking out the ITO conductive glass, washing surface impurities with deionized water, and drying in an oven at 80 ℃ for 30min to form the NiO film with three nanosheet layers.
It should be noted that, in this embodiment, the first temperature, the second temperature, the third temperature, and the times T1, T2, and T3 are not strictly limited, and may be adaptively adjusted according to actual needs in a specific implementation process.
And 3, step 3: and after the hydrothermal reaction is finished, carrying out heat treatment on the ITO conductive glass to obtain the layered nano flaky NiO electrochromic film.
Specifically, in this embodiment, the film obtained in step 2 is subjected to heat treatment in an argon atmosphere for a certain time, for example, the heat treatment at 350 ℃ may be adopted for 3 hours, so as to obtain the layered nano flaky NiO electrochromic film.
According to the preparation method provided by the embodiment, the growth morphology of the NiO film is controlled by adjusting the temperature gradient of the hydrothermal reaction, namely the NiO film is slowly grown in a low-temperature environment, then the reaction temperature is properly increased, the film growth is accelerated, the layered multi-gap nanosheet film is formed, and the binding power between the film and the substrate is enhanced; and the porous film has large specific surface area and many reactive sites, thereby ensuring that the film has excellent electrochromic performance and better cycling stability when the film is subjected to electrochromic cycling in alkaline electrolyte.
Example two
The preparation method of the present invention will be described in detail below by taking the preparation of an electrochromic film having two nano-layered NiO flakes as an example.
Step one, providing an alkaline environment by using hexamethylenetetramine, and taking urea as a precipitator. Dissolving 0.125mol/l of hexamethylenetetramine and 0.05mol/l of urea in 70ml of deionized water, and magnetically stirring for 30min to fully dissolve the hexamethylenetetramine and the urea to form a solution A;
step two, adding 0.125mol of nickel nitrate hexahydrate serving as a nickel source into the solution A obtained in the step one by taking the nickel nitrate hexahydrate as the nickel source, magnetically stirring for 30min, and fully dissolving to form a precursor solution B;
step three, preparing a 5% NaOH solution and a hydrogen peroxide solution according to the proportion of 30:1 to form a solution C;
ultrasonically cleaning the ITO conductive glass in an acetone solution, an absolute ethyl alcohol solution and deionized water for 20min respectively to fully wash grease on the surface of the ITO conductive glass;
step five, soaking the ITO conductive glass treated in the step four in the solution C obtained in the step three for 2 hours to enhance the hydrophilicity, then taking out the ITO conductive glass, ultrasonically cleaning the ITO conductive glass in deionized water for 30 minutes to wash away the residual solution C, and then soaking the ITO conductive glass in absolute ethyl alcohol for later use;
and sixthly, obliquely placing the ITO conductive glass obtained in the fifth step in a polytetrafluoroethylene lining of a high-temperature reaction kettle, wherein 2 sheets are placed at a time, and the ITO conductive glass is inclined from the middle of the bottom to the inner wall. And D, adding the precursor solution B obtained in the step two into the lining, and placing the lining into a high-temperature reaction kettle for sealing.
Step seven, placing the high-temperature reaction kettle in the step six into an oil bath pan, setting the temperature gradient to 90 ℃, preserving heat for 1h, then heating to 110 ℃, and preserving heat for 3 h; and then taking the high-temperature reaction kettle out of the oil bath kettle, naturally cooling the high-temperature reaction kettle to room temperature for 3 hours, taking out the ITO conductive glass, washing surface impurities with deionized water, and drying the ITO conductive glass in an oven at 80 ℃ for 30 min.
And step eight, carrying out heat treatment on the film obtained in the step seven at 350 ℃ for 3h in an argon atmosphere to obtain a two-layer nano flaky NiO electrochromic film.
EXAMPLE III
The preparation method of the invention is described in detail below by taking the preparation of the three-layer nano flaky NiO electrochromic film as an example.
Step A, providing an alkaline environment by using hexamethylenetetramine and taking urea as a precipitator. Dissolving 0.15mol/l of hexamethylenetetramine and 0.1mol/l of urea in 70ml of deionized water, and magnetically stirring for 30min to fully dissolve the hexamethylenetetramine and the urea to form a solution A;
step B, adding 0.125mol of nickel nitrate hexahydrate serving as a nickel source into the solution A obtained in the step one, magnetically stirring for 30min, and fully dissolving to form a precursor solution B;
step C, preparing a 5% NaOH solution and a hydrogen peroxide solution according to the proportion of 30:1 to form a solution C;
step D, ultrasonically cleaning the ITO conductive glass in an acetone solution, an absolute ethyl alcohol solution and deionized water for 20min respectively to fully wash grease on the surface of the ITO conductive glass;
step E, soaking the ITO conductive glass treated in the step D in the solution C obtained in the step C for 2 hours to enhance the hydrophilicity, then taking out the ITO conductive glass, ultrasonically cleaning the ITO conductive glass in deionized water for 30 minutes to wash away the residual solution C, and then soaking the ITO conductive glass in absolute ethyl alcohol for later use;
and F, obliquely placing the ITO conductive glass obtained in the step E in a polytetrafluoroethylene lining of a high-temperature reaction kettle, and placing 2 sheets of ITO conductive glass at each time, wherein the ITO conductive glass is inclined towards the inner wall from the middle of the bottom. And D, adding the precursor solution B obtained in the step B into the lining, and placing the lining into a high-temperature reaction kettle for sealing.
Step G, putting the high-temperature reaction kettle in the step six into an oil bath kettle, and setting the temperature gradient to be 90 ℃ and preserving heat for 1 h; then heating to 110 ℃, and preserving the heat for 2 hours; then continuously heating to 130 ℃, and preserving heat for 1 h; and then taking the high-temperature reaction kettle out of the oil bath kettle, naturally cooling the high-temperature reaction kettle to room temperature for 3 hours, taking out the ITO conductive glass, washing surface impurities with deionized water, and drying the ITO conductive glass in an oven at 80 ℃ for 30 min.
And H, carrying out heat treatment on the film obtained in the step G at 350 ℃ for 3H in an argon atmosphere to obtain the three-layer nano flaky NiO electrochromic film.
To further illustrate the beneficial effects of the present invention, the three-layer nano flaky NiO electrochromic film prepared in the third embodiment was subjected to performance tests.
Referring to fig. 2-4, fig. 2 is a cross-sectional SEM test photograph of a layered NiO electrochromic film prepared according to example three of the present invention, and the SEM photograph results in fig. 2 show that the film has a multilayer structure. According to different temperature gradients, the nano-particles are divided into 3 nano-particle layers. FIG. 3 is a cross-sectional EDS spectrum of a layered NiO electrochromic film prepared in example three of the instant invention; as can be seen from FIG. 3, the prepared Ni element and O element are distributed relatively uniformly to form a NiO film. Fig. 4 is a graph of the cycling stability of the layered NiO electrochromic film prepared in example three of the present invention. The cycling stability curve of the film of fig. 4 shows that the film was stable for up to 14000 electrochromic cycles without peeling off from the ITO substrate, and gradually shows a decrease in performance after 10000 cycles, and it can be seen that the NiO electrochromic film prepared by the method of the present invention has very good cycling stability.
Example four
On the basis of the first embodiment, this embodiment provides a NiO-based electrochromic film, which is a multilayer structure and is prepared by using the preparation method of the first embodiment, and the detailed preparation process is not described in detail here.
The NiO electrochromic film has a multilayer nanosheet structure, so that the compact film has relatively strong bonding force with a substrate, the multi-gap film has a large specific surface area and a plurality of reactive sites, and the film has excellent electrochromic performance and good cycling stability when subjected to electrochromic cycling in alkaline electrolyte.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (9)
1. A hydrothermal preparation method of a multilayer nanosheet NiO electrochromic film based on gradient temperature is characterized by comprising the following steps:
step 1: placing ITO conductive glass in an inner liner of a high-temperature reaction kettle, adding NiO precursor solution into the inner liner, and sealing;
step 2: sequentially placing the sealed high-temperature reaction kettle in gradient temperature environments from low to high, and keeping the high-temperature reaction kettle in each temperature environment for a certain time to perform multiple hydrothermal reactions;
and step 3: and after the hydrothermal reaction is finished, carrying out heat treatment on the ITO conductive glass to obtain the layered nano flaky NiO electrochromic film.
2. The gradient temperature-based hydrothermal preparation method of the multilayer nanosheet NiO electrochromic film as claimed in claim 1, wherein the NiO precursor solution in step 1 is prepared from nickel nitrate hexahydrate and hexamethylenetetramine, and the specific preparation method is as follows:
dissolving 0.125-0.15mol/l of hexamethylenetetramine and 0.05-0.1mol/l of urea in 70ml of deionized water, and magnetically stirring for 30min to fully dissolve the hexamethylenetetramine and the urea to form a solution A;
and (3) taking nickel nitrate hexahydrate as a nickel source, adding 0.125mol of nickel nitrate hexahydrate into the solution A, magnetically stirring for 30min, and fully dissolving to form a NiO precursor solution.
3. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film as claimed in claim 1, wherein in step 1, before placing the ITO conductive glass in the inner liner of the high temperature reaction vessel, further comprising:
mixing a 5% NaOH solution and a hydrogen peroxide solution according to a ratio of 30:1, mixing to form a mixed solution C;
soaking the ITO conductive glass in the solution C for a certain time;
and cleaning the soaked ITO conductive glass to remove the residual solution C.
4. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film as claimed in claim 1, wherein step 2 comprises:
21) placing the sealed high-temperature reaction kettle in an oil bath kettle, and keeping the high-temperature reaction kettle for T1 time under a first temperature environment to perform hydrothermal reaction, so as to form a first nanosheet layer on the ITO conductive glass;
22) increasing the first temperature to a second temperature and continuing for a time period T2 to effect a hydrothermal reaction to form a second nanosheet layer on the first nanosheet layer;
23) naturally cooling to room temperature to form the NiO film with a plurality of nano-sheet layers.
5. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film of claim 4, wherein the first temperature is 110 ℃ and the second temperature is 15-25 ℃ higher than the first temperature; t1 ═ 1h, and T2 > T1.
6. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film of claim 4, wherein the first temperature is 90 ℃ and the second temperature is 15-25 ℃ higher than the first temperature; t1 ═ 1h, and T2 > T1.
7. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film of claim 6, after step 22) and before step 23), further comprising:
the second temperature is raised to a third temperature and held for a duration of T3 to effect a hydrothermal reaction to form a third nanosheet layer on the second nanosheet layer.
8. The gradient temperature-based hydrothermal preparation method of multilayer nanosheet NiO electrochromic film of claim 7, the third temperature being 15-25 ℃ higher than the second temperature and T3 being greater than or equal to T1.
9. A NiO electrochromic film, characterized in that the NiO electrochromic film is a multilayer structure, which is formed by the production method according to any one of claims 1 to 8.
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