CN110967888B - Method for regulating and controlling color of electrochromic nickel oxide film - Google Patents

Method for regulating and controlling color of electrochromic nickel oxide film Download PDF

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CN110967888B
CN110967888B CN201911134578.5A CN201911134578A CN110967888B CN 110967888 B CN110967888 B CN 110967888B CN 201911134578 A CN201911134578 A CN 201911134578A CN 110967888 B CN110967888 B CN 110967888B
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electrode
working electrode
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polystyrene microsphere
nickel oxide
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CN110967888A (en
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曲慧颖
潘帅池
童张法
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Guangxi University
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • 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
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor

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Abstract

The invention relates to a method for regulating and controlling the color of an electrochromic nickel oxide film, which comprises the following steps: providing a polystyrene microsphere template; will contain Ni (NO)3)2And NaNO3The aqueous solution of (2) is used as electrolyte, a three-electrode system is adopted, a polystyrene microsphere template is used as a working electrode, and Ni (OH) is filled in the polystyrene microsphere template under constant current2(ii) a Taking out the working electrode, and immersing in organic solvent to obtain Ni (OH) with inverse opal structure2A film; curing and annealing to obtain a NiO film with an inverse opal structure; and a three-electrode system is adopted, the NiO film is taken as a working electrode, and a voltage of-1.0V is applied to the working electrode, so that the color of the nickel oxide film is regulated and controlled. The film obtained by the invention has an inverse opal structure, can show the change of various colors, has stable performance and high response speed, and has wide application prospect in the fields of intelligent windows, displays, electronic paper and the like.

Description

Method for regulating and controlling color of electrochromic nickel oxide film
Technical Field
The invention relates to the technical field of electrochromism, in particular to a method for regulating and controlling the color of an electrochromism nickel oxide film.
Background
Color plays an important role in today's information age, and color-based technologies, one of which is electrochromic technology, can be used to display, communicate and exchange data information. Under the control of low voltage, the optical properties (transmittance, reflectivity and absorptivity) of the electrochromic material can be reversibly changed, so that the modulation effect on light is realized, and the visible light wave band shows reversible change of the color of the material. However, electrochromic materials, especially inorganic metal oxides, have the disadvantage of limited color control, and generally can only be converted between a colored state and a faded state of the material, so that the application of the electrochromic materials in the display field is greatly limited.
Disclosure of Invention
The invention provides a method for regulating the color of an electrochromic nickel oxide film, aiming at the problem that the conventional electrochromic film, particularly an inorganic metal oxide film, has limited color regulation and control and can only be generally converted between a colored state and a faded state of the material.
The invention provides the following technical scheme:
a method for regulating and controlling the color of an electrochromic nickel oxide film, comprising the steps of:
(1) vertically putting the conductive substrate into the polystyrene microsphere emulsion for constant-temperature culture to obtain a polystyrene microsphere template;
(2) will contain 0.4-1.8mol/L of Ni (NO)3)2And 0.04-0.12mol/L of NaNO3The water solution of (A) is used as electrolyte, a three-electrode system is adopted, a polystyrene microsphere template is used as a working electrode, and the concentration of the water solution is 0.4-2.4 mA-cm-2Under constant current, a cathode electrodeposition method is adopted to fill Ni (OH) into the polystyrene microsphere template2The deposition time is 100-1000 seconds;
(3) after the deposition is finished, taking out the working electrode, and immersing the working electrode into an organic solvent to obtain Ni (OH) with an inverse opal structure2A film;
(4) mixing Ni (OH) with inverse opal structure2Solidifying and annealing the film to obtain a NiO film with an inverse opal structure;
(5) and a three-electrode system is adopted, the NiO film is taken as a working electrode, and a voltage of-1.0V is applied to the working electrode, so that the color of the nickel oxide film is regulated and controlled.
Preferably, in step (5), in LiClO4And in the PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the nickel oxide film.
Preferably, in step (5), the reference electrode of the three-electrode system is a silver/silver chloride electrode and the counter electrode is a platinum electrode.
Preferably, in step (4), the curing is carried out at 40-80 ℃; and/or
The annealing is carried out at the temperature of 250-350 ℃ and in the argon atmosphere; preferably, the annealing time is 1 to 3 hours.
Preferably, in step (3), the organic solvent is selected from toluene and/or tetrahydrofuran;
preferably, the working electrode is immersed in the organic solvent for 4 to 24 hours.
Preferably, in step (2), the reference electrode of the three-electrode system is a silver/silver chloride electrode and the counter electrode is a platinum electrode.
Preferably, the particle size of the polystyrene microsphere is 200-600 nm; and
the volume fraction of the polystyrene microsphere emulsion is 0.1-0.25%.
Preferably, the temperature condition of the constant temperature culture is 60-80 ℃, and the culture time is 48-120 hours.
Preferably, the conductive substrate is selected from any one of ITO conductive glass, FTO conductive glass, and ITO-plated polyimide substrate.
Preferably, the conductive substrate is ultrasonically cleaned with acetone, methanol and ultrapure water for 5 to 20 minutes in this order before use.
Advantageous effects
The technical scheme of the invention has the following advantages:
the invention introduces the inverse opal structure into the electrochromic nickel oxide film, so that the nickel oxide film has structural color. Because the nickel oxide film can be mutually converted between transparent and brown in the electrochromic process, the nickel oxide film with the inverse opal structure can present various colors after the structural color is compounded with the nickel oxide film, thereby realizing the regulation and control of the color of the nickel oxide film.
The electrochromic NiO film obtained by the invention has an inverse opal structure, can show various color changes, has stable performance and high response speed, and has wide application prospects in the fields of intelligent windows, displays, electronic paper and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a NiO film obtained in example 1;
FIG. 2 shows the reflectance spectra of NiO films obtained in examples 4 and 5, with the abscissa representing the Wavelength (Wavelength) and the ordinate representing the reflectance (reflextance); wherein a is example 4 and b is example 5;
FIG. 3 is a color change photograph of NiO films obtained in examples 4 and 5; wherein a is example 4 and b is example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a method for regulating and controlling the color of an electrochromic nickel oxide film. The method introduces an inverse opal structure into an electrochromic nickel oxide film, so that the nickel oxide film has structural color. Because the nickel oxide film can be mutually converted between transparent and brown in the electrochromic process, the nickel oxide film with the inverse opal structure can present various colors after the structural color is compounded with the nickel oxide film, thereby realizing the regulation and control of the color of the nickel oxide film.
Specifically, the method provided by the invention comprises the following steps:
(1) vertically putting the conductive substrate into the polystyrene microsphere emulsion for constant-temperature culture to obtain a polystyrene microsphere template;
(2) will contain 0.4-1.8mol/L of Ni (NO)3)2And 0.04-0.12mol/L of NaNO3The water solution of (A) is used as electrolyte, a three-electrode system is adopted, a polystyrene microsphere template is used as a working electrode, and the concentration of the water solution is 0.4-2.4 mA-cm-2Under constant current, a cathode electrodeposition method is adopted to fill Ni (OH) into the polystyrene microsphere template2The deposition time is 100-1000 seconds;
(3) after the deposition is finished, taking out the working electrode, and immersing the working electrode into an organic solvent to obtain Ni (OH) with an inverse opal structure2A film;
(4) mixing Ni (OH) with inverse opal structure2Solidifying and annealing the film to obtain a NiO film with an inverse opal structure;
(5) and a three-electrode system is adopted, the NiO film is taken as a working electrode, and a voltage of-1.0V is applied to the working electrode, so that the color of the nickel oxide film is regulated and controlled.
The nickel oxide film with inverse opal structure belongs to photonic crystal. Photonic crystals are composed of periodic arrangements of at least two materials. If the refractive indices of the materials are very different, the photonic crystal will exhibit a photonic band gap where light of a wavelength cannot propagate in the photonic crystal but is totally reflected back. If the photon forbidden band is in the visible range, the photonic crystal will show structural color due to bragg diffraction. The invention introduces an inverse opal structure into the electrochromic nickel oxide film, changes the position of a photon forbidden band by changing the periodicity of the structure, thereby changing the structural color of the nickel oxide film, and simultaneously, the color of the composite material per se changes in the electrochromic process, thereby realizing the regulation and control of the color of the nickel oxide film. The method has wide regulation range, can realize the change of various colors of the nickel oxide film, can be widely applied to other electrochromic materials, and has universality.
In order to ensure the feasibility of the method, the inventors have conducted detailed studies on how to introduce an inverse opal structure into a nickel oxide film:
the invention adopts a cathodic electrodeposition method to fill Ni (OH) in a polystyrene microsphere template2The electrolyte used contains 0.4 to 1.8mol/L (for example, it may be 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L) of Ni (NO: 1 mol/L)3)2And NaNO of 0.04 to 0.12mol/L (for example, it may be 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L)3. The inventors have found that during cathodic electrodeposition, the deposition potential increases with decreasing electrolyte concentration. When the concentration of the electrolyte is too small, the deposition potential is too high to reach Ni (OH)2Separating out the needed polarization potential; when the concentration of the electrolyte is too high, the deposition potential is too low, Ni (OH)2Too fast a precipitation rate can lead to the destruction of the ordered structure of the template. Based on this, the present invention uses Ni (NO) containing 0.4-1.8mol/L3)2And 0.04-0.12mol/L of NaNO3The aqueous solution of (a) is used as an electrolyte to ensure the smooth deposition, so that Ni (a) with orderly structure arrangement is filled in the PS templateOH)2。
The invention carries out deposition under constant current and further limits the current density to be 0.4-2.4 mA-cm-2For example, it may be 0.4mA · cm-2、0.5mA·cm-2、0.6mA·cm-2、0.7mA·cm-2、0.8mA·cm-2、0.9mA·cm-2、1.0mA·cm-2、1.1mA·cm-2、1.2mA·cm-2、1.3mA·cm-2、1.4mA·cm-2、1.5mA·cm-2、1.6mA·cm-2、1.7mA·cm-2、1.8mA·cm-2、1.9mA·cm-2、2.0mA·cm-2、2.1mA·cm-2、2.2mA·cm-2、2.3mA·cm-2、2.4mA·cm-2. The inventor finds in research that when the current density is too small, the cathode polarization is too small, and the film is not easy to deposit; when the current density is too high, the cathode polarization is too high, and the ordered structure of the template can be damaged.
In addition, the invention further limits the deposition time to 100-1000 seconds, for example, 100 seconds, 200 seconds, 300 seconds, 400 seconds, 500 seconds, 600 seconds, 700 seconds, 800 seconds, 900 seconds, 1000 seconds. If the deposition time is too short, the film formation is too thin, and the color change of the film is not obvious in the subsequent regulation and control process. However, the deposition time is not too long, otherwise, the film is too thick, and the surface of the template is completely covered, so that the ordered structure is lost, and the color change of the film in the subsequent regulation and control process is influenced.
As a result, the inventors have conducted intensive studies on the process conditions in the deposition stage and have searched for more ideal electrolyte conditions, current density conditions during deposition, and deposition time conditions.
In some preferred embodiments, in step (5), in LiClO4And in the PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the nickel oxide film. In addition, LiClO used in the present invention4Reference is made to the prior art for PC electrolytes, the invention not being described in detail here.
Optionally, in step (5), the reference electrode of the three-electrode system is a silver/silver chloride electrode and the counter electrode is a platinum electrode.
In some preferred embodiments, in step (4), Ni (OH) having an inverse opal structure is reacted2The film is cured at 40-80 deg.C (for example, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C) for 20-40min (for example, 20min, 30min, 40 min).
In some preferred embodiments, in step (4), Ni (OH) having an inverse opal structure is added2After the film is cured, annealing is performed in an argon atmosphere at 250 ℃ to 350 ℃ (for example, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃). More preferably, the annealing time is 1 to 3 hours, for example, 1 hour, 2 hours, 3 hours.
In some preferred embodiments, in step (3), the organic solvent is selected from toluene and/or tetrahydrofuran; preferably, the working electrode is immersed in the organic solvent for 4 to 24 hours, for example, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours. The PS template can be sufficiently removed by soaking in this kind of organic solvent for 4-24 hours.
In some preferred embodiments, in step (2), the reference electrode of the three-electrode system is a silver/silver chloride electrode and the counter electrode is a platinum electrode.
The inventors have also studied the process conditions of the PS template, exploring a template preparation process for use in the present invention:
the position of the photon forbidden band can be calculated according to the Bragg Snell's law,
Figure BDA0002279238260000061
Figure BDA0002279238260000062
wherein d is the lattice spacing, neffIs the effective refractive index, theta isThe angle between the incident light and the normal line, and D is the distance between the centers of adjacent holes.
From the above formula, the position of the photon forbidden band λ is related to the pore size and the wall thickness of the inverse opal structure, and the pore size and the wall thickness of the inverse opal structure depend on the particle size of the polystyrene microsphere in the polystyrene microsphere template. Therefore, the nickel oxide films with different structural colors can be prepared by selecting the particle size of the polystyrene microspheres. The invention preferably adopts polystyrene microspheres with the particle size of 200-600nm, and the pore diameter of the nickel oxide film obtained after annealing is 140-500 nm. In addition, in some preferred embodiments, the volume fraction of the polystyrene microsphere emulsion used in the present invention is 0.1 to 0.25%, for example, 0.1%, 0.15%, 0.2%, 0.25%. In addition, in some preferred embodiments, the temperature conditions for the isothermal cultivation are 60 to 80 ℃, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃ and the cultivation time is 48 to 120 hours.
In some preferred embodiments, the conductive substrate is selected from any one of ITO conductive glass, FTO conductive glass, ITO-plated polyimide substrate. Preferably, the conductive substrate is ultrasonically cleaned with acetone, methanol and ultrapure water for 5 to 20 minutes in this order before use.
More fully, the method provided by the invention comprises the following steps:
(1) vertically putting the conductive substrate into the polystyrene microsphere emulsion for constant-temperature culture to obtain a polystyrene microsphere template;
(2) will contain 0.4-1.8mol/L of Ni (NO)3)2And 0.04-0.12mol/L of NaNO3The water solution of (A) is used as electrolyte, a three-electrode system is adopted, a polystyrene microsphere template is used as a working electrode, and the concentration of the water solution is 0.4-2.4 mA-cm-2Under constant current, a cathode electrodeposition method is adopted to fill Ni (OH) into the polystyrene microsphere template2The deposition time is 100-1000 seconds;
(3) after the deposition is finished, taking out the working electrode, and immersing the working electrode into an organic solvent to obtain the inverse opal noduleStructural Ni (OH)2A film;
(4) mixing Ni (OH) with inverse opal structure2Solidifying and annealing the film to obtain a NiO film with an inverse opal structure;
(5) and a three-electrode system is adopted, the NiO film is taken as a working electrode, and a voltage of-1.0V is applied to the working electrode, so that the color of the nickel oxide film is regulated and controlled.
In step (5), in LiClO4In a PC electrolyte, applying a voltage of-1.0V to a working electrode to realize the regulation and control of the color of the nickel oxide film; the reference electrode of the three-electrode system is a silver/silver chloride electrode, and the counter electrode is a platinum electrode.
In the step (4), the curing is performed at 40 to 80 ℃; the annealing is carried out at the temperature of 250-350 ℃ and in the argon atmosphere; the annealing time is 1-3 hours.
In step (3), the organic solvent is selected from toluene and/or tetrahydrofuran; and immersing the working electrode in an organic solvent for 4-24 hours.
In the step (2), the reference electrode of the three-electrode system is a silver/silver chloride electrode, and the counter electrode is a platinum electrode.
In the step (1), the particle size of the polystyrene microsphere is 200-600 nm; the volume fraction of the polystyrene microsphere emulsion is 0.1-0.25%; the temperature condition of the constant temperature culture is 60-80 ℃, and the culture time is 48-120 hours; the conductive substrate is selected from any one of ITO conductive glass, FTO conductive glass and an ITO-plated polyimide substrate; and ultrasonically cleaning the conductive substrate for 5-20 minutes by using acetone, methanol and ultrapure water in sequence before use.
The following are examples of the present invention.
Example 1
And S1, ultrasonically cleaning the transparent conductive substrate for 10min by using acetone, methanol and ultrapure water in sequence. And (2) preparing a PS microsphere emulsion with the volume fraction of 0.15% by taking water as a solvent, wherein the particle size of the PS microsphere is 420nm, vertically putting the cleaned transparent conductive substrate into the PS microsphere emulsion, and culturing at the constant temperature of 70 ℃ for 96h to obtain the PS template.
S2, Ni (N) of 1.0mol/LO3)2And 0.08mol/L of NaNO3The aqueous solution of (A) was used as an electrolyte, a three-electrode system was used, a PS template prepared from S1 was used as a working electrode, Ag/AgCl was used as a reference electrode, a Pt electrode was used as a counter electrode, and the concentration of the electrolyte solution was controlled at 1.8mA · cm-2Under constant current, filling Ni (OH) into PS template by cathode electrodeposition2The deposition time was 500 s.
S3, after the deposition is finished, taking out the working electrode, immersing the working electrode in organic solvent toluene for 8h to remove the PS template, and obtaining Ni (OH) with an inverse opal structure2And (3) a membrane.
S4, Ni (OH) with inverse opal structure2The film is solidified at 60 ℃ and then is annealed for 2h in argon atmosphere at 300 ℃ to obtain the photonic crystal NiO film with an inverse opal structure, and an SEM picture is shown in figure 1.
S5, using NiO film prepared by S4 as working electrode, Ag/AgCl as reference electrode, Pt as counter electrode, in LiClO4And in a PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the NiO film.
Example 2
And S1, ultrasonically cleaning the transparent conductive substrate for 10min by using acetone, methanol and ultrapure water in sequence. Preparing a PS microsphere emulsion with the volume fraction of 0.1% by taking water as a solvent, wherein the particle size of the PS microsphere is 200nm, vertically putting the cleaned transparent conductive substrate into the PS microsphere emulsion, and culturing at the constant temperature of 60 ℃ for 48h to obtain the PS template.
S2, Ni (NO) content of 0.4mol/L3)2And 0.04mol/L of NaNO3The aqueous solution of (A) was used as an electrolyte, a three-electrode system was used, a PS template prepared from S1 was used as a working electrode, Ag/AgCl was used as a reference electrode, a Pt electrode was used as a counter electrode, and the concentration of the electrolyte solution was controlled at 0.4mA · cm-2Under constant current, filling Ni (OH) into PS template by cathode electrodeposition2The deposition time was 1000 s.
S3, after deposition is finished, taking out the working electrode, immersing the working electrode in tetrahydrofuran organic solvent for 5h to remove the PS template, and obtaining Ni (OH) with inverse opal structure2And (3) a membrane.
S4, Ni (OH) with inverse opal structure2Curing the film at 40 deg.C, and thenAnd annealing for 1h in an argon atmosphere at 250 ℃ to obtain the photonic crystal NiO film with the inverse opal structure.
S5, using NiO film prepared by S4 as working electrode, Ag/AgCl as reference electrode, Pt as counter electrode, in LiClO4And in a PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the NiO film.
Example 3
And S1, ultrasonically cleaning the transparent conductive substrate for 10min by using acetone, methanol and ultrapure water in sequence. Preparing a PS microsphere emulsion with the volume fraction of 0.25% by taking water as a solvent, wherein the particle size of the PS microsphere is 600nm, vertically putting the cleaned transparent conductive substrate into the PS microsphere emulsion, and culturing at the constant temperature of 80 ℃ for 120h to obtain the PS template.
S2, Ni (NO) content of 1.8mol/L3)2And 0.12mol/L of NaNO3The aqueous solution of (A) was used as an electrolyte, a three-electrode system was used, a PS template prepared from S1 was used as a working electrode, Ag/AgCl was used as a reference electrode, a Pt electrode was used as a counter electrode, and the concentration of the electrolyte solution was controlled at 2.4mA · cm-2Under constant current, filling Ni (OH) into PS template by cathode electrodeposition2The deposition time was 100 s.
S3, after the deposition is finished, taking out the working electrode, immersing the working electrode in an organic solvent for 10h to remove the PS template, and obtaining Ni (OH) with an inverse opal structure2And (3) a membrane.
S4, Ni (OH) with inverse opal structure2The film is solidified at 80 ℃, and then is annealed for 3h in argon atmosphere at 350 ℃ to obtain the photonic crystal NiO film with the inverse opal structure.
S5, using NiO film prepared by S4 as working electrode, Ag/AgCl as reference electrode, Pt as counter electrode, in LiClO4And in a PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the NiO film.
Example 4 and example 5
Example 4 and example 5 are essentially the same as the process of example 1, except that:
example 4: preparing a PS microsphere emulsion with the volume fraction of 0.20%, wherein the particle size of the used PS microspheres is 333 nm; will contain 0.9 mol-Ni (NO) of L3)2And 0.075mol/L of NaNO3The aqueous solution of (A) was used as an electrolyte, a three-electrode system was used, a PS template prepared in S1 was used as a working electrode, Ag/AgCl was used as a reference electrode, a Pt electrode was used as a counter electrode, and the concentration of the electrolyte solution was controlled at 2mA · cm-2Under constant current, filling Ni (OH) into PS template by cathode electrodeposition2The deposition time is 200 s;
example 5: preparing PS microsphere emulsion with the volume fraction of 0.20%, wherein the particle size of the used PS microspheres is 435 nm; will contain 0.9mol/L of Ni (NO)3)2And 0.075mol/L of NaNO3The aqueous solution of (A) was used as an electrolyte, a three-electrode system was used, a PS template prepared in S1 was used as a working electrode, Ag/AgCl was used as a reference electrode, a Pt electrode was used as a counter electrode, and the concentration of the electrolyte solution was controlled at 2mA · cm-2Under constant current, filling Ni (OH) into PS template by cathode electrodeposition2The deposition time was 200 s.
Fig. 2 and 3 reflect the reflectance spectra and color change photographs of the NiO films prepared in examples 4 and 5.
Example 6 and example 7
Example 6 and example 7 are essentially the same as the process of example 1, except that: filling Ni (OH) in polystyrene microsphere template by adopting a cathodic electrodeposition method2When the current density was 0.1mA · cm, respectively-2And 3.0mA · cm-2。
Example 8 and example 9
Example 8 and example 9 are essentially the same as the process of example 1, except that: filling Ni (OH) in polystyrene microsphere template by adopting a cathodic electrodeposition method2The deposition times were 50 seconds and 1300 seconds, respectively.
Examples 10 and 11
Example 10 and example 11 are essentially the same as the process of example 1, except that:
example 10: filling Ni (OH) in polystyrene microsphere template by adopting a cathodic electrodeposition method2When the alloy contains 0.2mol/L of Ni (NO)3)2And 0.02mol/L of NaNO3The aqueous solution of (a) serves as an electrolyte.
Examples11: filling Ni (OH) in polystyrene microsphere template by adopting a cathodic electrodeposition method2When the alloy contains 2.0mol/L of Ni (NO)3)2And 0.15mol/L of NaNO3The aqueous solution of (a) serves as an electrolyte.
Example 12 and example 13
Example 12 and example 13 are essentially the same as the process of example 1, except that: when preparing the polystyrene microsphere template, the volume fractions of the polystyrene microsphere emulsions used were 0.05% and 0.30%, respectively.
Example 14 and example 15
Example 14 and example 15 are essentially the same as the process of example 1, except that: when preparing the polystyrene microsphere template, the particle sizes of the polystyrene microspheres in the polystyrene microsphere emulsion are 150nm and 650nm respectively.
The effects of the examples are shown in table 1.
TABLE 1
Figure BDA0002279238260000111
Figure BDA0002279238260000121
Figure BDA0002279238260000131
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (11)

1. A method for regulating and controlling the color of an electrochromic nickel oxide film is characterized by comprising the following steps:
(1) vertically putting the conductive substrate into the polystyrene microsphere emulsion for constant-temperature culture to obtain a polystyrene microsphere template; wherein the particle size of the polystyrene microsphere is 200-600 nm; the volume fraction of the polystyrene microsphere emulsion is 0.1-0.25%;
(2) will contain 0.4-1.8mol/L of Ni (NO)3)2And 0.04-0.12mol/L of NaNO3The water solution of (A) is used as electrolyte, a three-electrode system is adopted, a polystyrene microsphere template is used as a working electrode, and the concentration of the water solution is 0.4-2.4 mA-cm-2Under constant current, a cathode electrodeposition method is adopted to fill Ni (OH) into the polystyrene microsphere template2The deposition time is 100-1000 seconds;
(3) after the deposition is finished, taking out the working electrode, and immersing the working electrode into an organic solvent to obtain Ni (OH) with an inverse opal structure2A film;
(4) mixing Ni (OH) with inverse opal structure2Solidifying and annealing the film to obtain a NiO film with an inverse opal structure;
(5) and a three-electrode system is adopted, the NiO film is taken as a working electrode, and a voltage of-1.0V is applied to the working electrode, so that the color of the nickel oxide film is regulated and controlled.
2. The method of claim 1,
in step (5), in LiClO4And in the PC electrolyte, applying a voltage of-1.0V to the working electrode to realize the regulation and control of the color of the nickel oxide film.
3. The method of claim 1,
in the step (5), the reference electrode of the three-electrode system is a silver/silver chloride electrode, and the counter electrode is a platinum electrode.
4. The method of claim 1,
in the step (4), the curing is performed at 40 to 80 ℃; and/or
The annealing is performed at 250-350 deg.C under argon atmosphere.
5. The method of claim 1,
in the step (4), the annealing time is 1 to 3 hours.
6. The method of claim 1,
in step (3), the organic solvent is selected from toluene and/or tetrahydrofuran.
7. The method of claim 1,
in the step (3), the working electrode is immersed in an organic solvent for 4 to 24 hours.
8. The method of claim 1,
in the step (2), the reference electrode of the three-electrode system is a silver/silver chloride electrode, and the counter electrode is a platinum electrode.
9. The method of claim 1,
the temperature condition of the constant temperature culture is 60-80 ℃, and the culture time is 48-120 hours.
10. The method of claim 1,
the conductive substrate is selected from any one of ITO conductive glass, FTO conductive glass and ITO-plated polyimide substrate.
11. The method of claim 1,
and ultrasonically cleaning the conductive substrate for 5-20 minutes by using acetone, methanol and ultrapure water in sequence before use.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515564A (en) * 2011-12-08 2012-06-27 浙江理工大学 Nickel oxide electrochromic film and preparation method thereof
CN104962969A (en) * 2015-07-10 2015-10-07 哈尔滨工业大学 Preparation method for three-dimensional electrochromic nickel oxide thin film
WO2017173439A2 (en) * 2016-04-01 2017-10-05 President And Fellows Of Harvard College Formation of high quality titania, alumina and other metal oxide templated materials through coassembly

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515564A (en) * 2011-12-08 2012-06-27 浙江理工大学 Nickel oxide electrochromic film and preparation method thereof
CN104962969A (en) * 2015-07-10 2015-10-07 哈尔滨工业大学 Preparation method for three-dimensional electrochromic nickel oxide thin film
WO2017173439A2 (en) * 2016-04-01 2017-10-05 President And Fellows Of Harvard College Formation of high quality titania, alumina and other metal oxide templated materials through coassembly

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