CN113105127A - Preparation method of electrochromic nickel oxide film - Google Patents
Preparation method of electrochromic nickel oxide film Download PDFInfo
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- CN113105127A CN113105127A CN202110397423.1A CN202110397423A CN113105127A CN 113105127 A CN113105127 A CN 113105127A CN 202110397423 A CN202110397423 A CN 202110397423A CN 113105127 A CN113105127 A CN 113105127A
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 172
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000004528 spin coating Methods 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 47
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 19
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 13
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 116
- 238000002834 transmittance Methods 0.000 description 19
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- 102000004310 Ion Channels Human genes 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
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- 238000007709 nanocrystallization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006087 Brown hydroboration reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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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
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- 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
- C03C17/27—Oxides by oxidation of a coating previously applied
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The invention discloses a preparation method of an electrochromic nickel oxide film, belonging to the technical field of electrochromic devices and application. The method comprises the following steps: preparing a titanium-doped nickel oxide film precursor solution by using nickel acetate tetrahydrate, tetrabutyl titanate, monoethanolamine, PVP powder and ethylene glycol monomethyl ether as raw materials through a sol-gel method; and spin-coating the titanium-doped nickel oxide film precursor solution on the surface of a substrate, and then carrying out annealing treatment to obtain the titanium-doped nickel oxide electrochromic film. The method is simple and easy to implement, has obvious effect and universality, and has wide application prospect in the field of nickel oxide-based ion electrochromism.
Description
Technical Field
The invention relates to a preparation method of an electrochromic nickel oxide film, belonging to the technical field of electrochromic devices and application.
Background
The electrochromic material is an intelligent material which can generate stable and reversible color change under external electrical stimulation and has optical modulation capability. Since the electrochromic material can adjust the optical property under the action of small voltage, the electrochromic material is widely applied to the fields of intelligent windows, anti-dazzle mirrors, displays and the like. Nickel oxide NiO is an anode electrochromic material with a long research history, and can realize reversible change between a transparent reduction state and a dark brown oxidation state in both aqueous electrolytes and organic electrolytes. Therefore, NiO can be used as an auxiliary complementary counter electrode of a cathode color-changing material in an electrochromic device, and also can be used as a working electrode for core color changing to be matched with a counter electrode (such as Ce02 and the like) with smaller color changing contrast. And the NiO is circulated in the electrolyte for a long time, the performance of the NiO is attenuated, and the cycle stability of the NiO is poor. Therefore, how to improve the performance, especially the cycle stability, of the NiO film in the electrolyte has become a research focus in recent years.
The traditional method for improving the performance of the NiO film mainly comprises ion doping and nanocrystallization, so that reversible adsorption and desorption of the NiO film in NiO are improved. In the ion doping modification, the doping of lithium Li ions can provide an ion channel for the insertion/extraction process of Li in the NiO film in the color changing process, so that the irreversible aggregation of the Li ions in the film in the circulating process is reduced, and the electrochromic performance and the stability of the NiO film in an organic solvent electrolyte are further improved; and the titanium Ti-doped NiO shows excellent electrochemical cycling stability of nearly 7000 times in the circulation of an aqueous electrolyte, which is mainly attributed to the improvement effect of Ti doping on the adhesion of the film and the substrate. Other methods, such as nanocrystallization, can also improve performance, primarily through the design of NiO morphology and structure. However, this method is generally complicated in preparation process and high in cost.
The nickel oxide film prepared by the existing method has low optical modulation rate and poor cycle stability, and the testing method is more complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for enhancing and detecting the performance of an electrochromic nickel oxide film. The method has simple process and low cost, and effectively improves the optical modulation rate and the cycle stability of the nickel oxide film.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of an electrochromic nickel oxide film comprises the following steps:
(1) preparing a titanium-doped nickel oxide film precursor solution by using nickel acetate tetrahydrate, tetrabutyl titanate, monoethanolamine, PVP powder and ethylene glycol monomethyl ether as raw materials through a sol-gel method;
(2) spin-coating the titanium-doped nickel oxide film precursor solution obtained in the step (1) on the surface of a substrate to obtain a titanium-doped nickel oxide film;
(3) annealing the titanium-doped nickel oxide film obtained in the step (2) to obtain a titanium-doped nickel oxide electrochromic film;
the metal ion concentration of the titanium-doped nickel oxide film precursor solution is 0.5mol/L, and the molar ratio of nickel to titanium is 2-8: 1.
The method of the invention utilizes the doping of titanium ions to provide more ion channels for the insertion and extraction of the titanium ions in the nickel oxide electrochromic film in the color changing process, reduces the irreversible aggregation of the titanium ions in the nickel oxide electrochromic film in the circulating process, and the doping of the titanium ions can improve the adhesion of the nickel oxide electrochromic film and the substrate, which are beneficial to improving the optical modulation rate and the circulating stability of the nickel oxide electrochromic film.
By doping titanium ions, the light modulation range of nickel oxide electrochromism can be greatly improved, and the effect of enhancing the cycle stability of the nickel oxide electrochromism can be achieved; by adjusting the molar ratio of nickel to titanium, better electrochromic properties are achieved. The mol ratio of nickel and titanium affects the stability of the nickel oxide precursor solution, and when the mol ratio of nickel and titanium is less than 2, the nickel oxide precursor solution can generate a large amount of precipitates after being placed for two days, and the stability is poor.
In a preferred embodiment of the method for preparing the electrochromic nickel oxide film, the molar ratio of nickel to titanium in the titanium-doped nickel oxide film precursor solution is 4-8: 1.
Under the molar ratio, the prepared nickel oxide electrochromic film has better optical modulation rate and cycling stability.
As a preferred embodiment of the method for preparing an electrochromic nickel oxide film according to the present invention, the method for preparing the titanium-doped nickel oxide film precursor solution comprises the steps of:
(1) adding nickel acetate tetrahydrate into ethylene glycol monomethyl ether, stirring and dissolving, and adding tetrabutyl titanate to obtain a mixed solution;
(2) adding monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) adding PVP powder into the clear blue solution, stirring uniformly, and placing in a water bath at 60 ℃ for stirring uniformly to obtain light green transparent sol;
(4) and (4) standing the light green transparent sol obtained in the step (3), and then filtering to obtain a filtrate, namely a precursor solution of titanium-doped nickel oxide.
As a preferred embodiment of the preparation method of the electrochromic nickel oxide film, the filtering membrane for filtering is a polytetrafluoroethylene membrane with the pore diameter of 0.2 mu m.
The filtering can filter out large-particle aggregates in the nickel oxide precursor liquid, control the size of nickel oxide in the nickel oxide precursor liquid and be beneficial to controlling the thickness of a nickel oxide film in the spin coating process.
As a preferred embodiment of the preparation method of the electrochromic nickel oxide film of the present invention, the spin coating comprises the following steps: drying the titanium-doped nickel oxide film precursor solution at 100 ℃ for 5min, then spin-coating the titanium-doped nickel oxide film precursor solution on the surface of a substrate, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps to enable the number of spin-coating layers to be 1-9, preferably 3.
The performance of the nickel oxide electrochromic film is affected by the number of spin-coating layers, and the film is not uniform due to the excessive number of spin-coating layers, so that bubbles and lumps are easily generated.
As a preferred embodiment of the preparation method of the electrochromic nickel oxide film of the present invention, the spin coating process parameters include: the glue dripping speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, and the spin coating time is 30 s.
The uniformity of the nickel oxide film can be influenced by spin-coating process parameters, and the nickel oxide film with good uniformity has better electrochromic property.
As a preferred embodiment of the preparation method of the electrochromic nickel oxide film, the substrate is any one of ITO, FTO and AZO conductive glass.
As a preferred embodiment of the preparation method of the electrochromic nickel oxide film, the annealing treatment comprises the following steps: and (3) placing the titanium-doped nickel oxide film in a muffle furnace, heating to 200-500 ℃ at the heating rate of 2 ℃/min in the air environment, preserving the heat for 1h, cooling to room temperature, and taking out to obtain the titanium-doped nickel oxide electrochromic film. Preferably, the annealing temperature is 300-350 ℃; preferably, the annealing temperature is 300 ℃.
The heat treatment temperature will affect the crystallinity of nickel oxide, with the crystallinity of nickel oxide being better at 300-350 ℃ and the optimum crystallinity of nickel oxide at 300 ℃. Meanwhile, the heat treatment time can affect the performance of the nickel oxide electrochromic film. Under the condition of insufficient heat treatment time, the non-volatile organic matter is wrapped on the surface area interface of the nickel oxide crystal grains to hinder the reaction; and the crystallization is over perfect due to the over long heat treatment time, and the reaction interface is correspondingly reduced, so that the occurrence of the color change reaction is hindered.
On the other hand, the invention also provides a preferable embodiment of the detection method for the performance of the electrochromic nickel oxide film, and a three-electrode test system comprises a counter electrode, a reference electrode, a working electrode and 1M potassium hydroxide
As a preferred embodiment of the method for detecting the performance of the electrochromic nickel oxide film according to the present invention, the counter electrode is a platinum electrode; the reference electrode is a silver/silver chloride electrode; the working electrode is a titanium-doped nickel oxide thin film electrode.
Compared with the prior art, the invention has the beneficial effects that: by doping titanium ions, the light modulation range of the nickel oxide electrochromic film can be greatly improved, and the effect of enhancing the cycle stability of the nickel oxide electrochromic film can be achieved; the better electrochromic performance is achieved by adjusting the molar ratio of nickel to titanium; the method is simple and easy to implement, has obvious effect and universality, and has wide application prospect in the field of nickel oxide-based ion electrochromism.
Drawings
FIG. 1 is a schematic diagram of a three-electrode test system, wherein 1 is a counter electrode, 2 is a reference electrode, 3 is a working electrode, and an electrolyte is 1M potassium hydroxide, wherein the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, and the working electrode is a titanium-doped nickel oxide thin film electrode;
FIG. 2 is a schematic diagram of an electrochemical process of a nickel oxide electrode;
FIG. 3 is the optical modulation ratios at 550nm for the comparative example 1 nickel oxide NiO electrochromic film and example 1 titanium doped nickel oxide Ti-NiO electrochromic film, respectively;
FIG. 4 is a graph showing the transmittance of the nickel oxide NiO electrochromic film of comparative example 1 and the titanium-doped nickel oxide Ti-NiO electrochromic film of example 1 at an excitation voltage as a function of time, respectively;
FIG. 5 is an XRD pattern of the nickel oxide thin films obtained in comparative examples 2 to 5.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed description and accompanying drawings.
Example 1
The embodiment provides a preparation method of an electrochromic nickel oxide film, which comprises the following steps:
(1) adding 2.49 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, adding 0.85 part by weight of tetrabutyl titanate, and uniformly stirring to obtain a mixed solution, wherein the molar ratio of nickel to titanium is respectively 4: 1, the total concentration of metal ions is 0.5 mol/L.
(2) Dropwise adding 0.632 weight part of monoethanolamine dropwise into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micrometer polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of titanium-doped nickel oxide;
(5) drying the titanium-doped nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the titanium-doped nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain the titanium-doped nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the titanium-doped nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at the temperature of 300 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after the heat preservation is finished, so as to obtain the titanium-doped nickel oxide electrochromic film.
On the other hand, the embodiment also provides a detection method of the electrochromic nickel oxide film, which comprises the following steps of connecting a digital source meter and an ultraviolet visible light spectrophotometer to the electrochromic performance of the titanium-doped nickel oxide film by adopting a three-electrode test system. The working principle is shown in fig. 1, fig. 1 is a three-electrode test system, in the figure, 1 is a counter electrode, 2 is a reference electrode, 3 is a working electrode, and an electrolyte is 1M potassium hydroxide, wherein the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, and the working electrode is a titanium-doped nickel oxide thin film electrode. The counter electrode, the reference electrode and the working electrode of the Keithley2450 digital source meter three-electrode measurement system are respectively connected with a platinum electrode, a silver/silver chloride electrode and a sample conducting end which are immersed in an electrolyte, and then a voltage is applied between the working electrode and the reference electrode by using the digital source meter.
Example 2
The embodiment provides a method for detecting the performance of an electrochromic nickel oxide film, which comprises the following steps:
(1) adding 2.074 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, adding 1.418 parts by weight of tetrabutyl titanate, and uniformly stirring to obtain a mixed solution, wherein the molar ratio of nickel to titanium is respectively 2: 1, the total concentration of metal ions is 0.5mol/L
(2) Dropwise adding 0.632 weight part of monoethanolamine dropwise into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micrometer polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of titanium-doped nickel oxide;
(5) drying the titanium-doped nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the titanium-doped nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain the titanium-doped nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the titanium-doped nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 200 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the titanium-doped nickel oxide electrochromic film.
On the other hand, the embodiment also provides a detection method of the electrochromic nickel oxide film, which comprises the following steps of connecting a digital source meter and an ultraviolet visible light spectrophotometer to the electrochromic performance of the titanium-doped nickel oxide film by adopting a three-electrode test system. The working principle is shown in fig. 1, fig. 1 is a three-electrode test system, in the figure, 1 is a counter electrode, 2 is a reference electrode, 3 is a working electrode, and an electrolyte is 1M potassium hydroxide, wherein the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, and the working electrode is a titanium-doped nickel oxide thin film electrode. The counter electrode, the reference electrode and the working electrode of the Keithley2450 digital source meter three-electrode measurement system are respectively connected with a platinum electrode, a silver/silver chloride electrode and a sample conducting end which are immersed in an electrolyte, and then a voltage is applied between the working electrode and the reference electrode by using the digital source meter.
Example 3
The embodiment provides a method for detecting the performance of an electrochromic nickel oxide film, which comprises the following steps:
(1) 2.765 parts by weight of nickel acetate tetrahydrate is added into 24.125 parts by weight of ethylene glycol monomethyl ether, after stirring and dissolving, 0.473 part by weight of tetrabutyl titanate is added, and after stirring uniformly, a mixed solution is obtained, wherein the molar ratio of nickel to titanium is respectively 8:1, the total concentration of metal ions is 0.5 mol/L;
(2) dropwise adding 0.632 weight part of monoethanolamine dropwise into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micrometer polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of titanium-doped nickel oxide;
(5) drying the titanium-doped nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the titanium-doped nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain the titanium-doped nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the titanium-doped nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 500 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the titanium-doped nickel oxide electrochromic film.
On the other hand, the embodiment also provides a detection method of the electrochromic nickel oxide film, which comprises the following steps of connecting a digital source meter and an ultraviolet visible light spectrophotometer to the electrochromic performance of the titanium-doped nickel oxide film by adopting a three-electrode test system. The working principle is shown in fig. 1, fig. 1 is a three-electrode test system, in the figure, 1 is a counter electrode, 2 is a reference electrode, 3 is a working electrode, and an electrolyte is 1M potassium hydroxide, wherein the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, and the working electrode is a titanium-doped nickel oxide thin film electrode. The counter electrode, the reference electrode and the working electrode of the Keithley2450 digital source meter three-electrode measurement system are respectively connected with a platinum electrode, a silver/silver chloride electrode and a sample conducting end which are immersed in an electrolyte, and then a voltage is applied between the working electrode and the reference electrode by using the digital source meter.
Comparative example 1
The comparative example provides a method for detecting the performance of an electrochromic nickel oxide film, which comprises the following steps:
(1) adding 3.11 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, and continuously stirring uniformly to obtain a mixed solution, wherein the total concentration of metal ions is 0.5 mol/L;
(2) dropwise adding 0.78 parts by weight of monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micron polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of nickel oxide;
(5) drying the nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain a nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at the temperature of 300 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the nickel oxide electrochromic film.
On the other hand, the comparative example also provides a detection method of the electrochromic nickel oxide film, which comprises the following steps of adopting a three-electrode test system, connecting a digital source meter and an ultraviolet visible spectrophotometer and testing the electrochromic performance of the nickel oxide film. The working principle is shown in fig. 1, fig. 1 is a three-electrode test system, in the figure, 1 is a counter electrode, 2 is a reference electrode, 3 is a working electrode, and an electrolyte is 1M potassium hydroxide, wherein the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, and the working electrode is a nickel oxide film electrode. The counter electrode, the reference electrode and the working electrode of the Keithley2450 digital source meter three-electrode measurement system are respectively connected with a platinum electrode, a silver/silver chloride electrode and a sample conducting end which are immersed in an electrolyte, and then a voltage is applied between the working electrode and the reference electrode by using the digital source meter.
Comparative example 2
The comparative example provides a method for detecting the performance of an electrochromic nickel oxide film, which comprises the following steps:
(1) adding 1.24 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, and then continuously stirring uniformly to obtain a mixed solution, wherein the total concentration of metal ions is 0.2 mol/L;
(2) dropwise adding 0.31 part by weight of monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micron polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of nickel oxide;
(5) drying the nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain a nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 500 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the nickel oxide electrochromic film.
Comparative example 3
The comparative example provides a method for preparing an electrochromic nickel oxide film, comprising the following steps:
(1) adding 1.87 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring to dissolve, and continuously stirring uniformly to obtain a mixed solution, wherein the total concentration of metal ions is 0.3 mol/L.
(2) Dropwise adding 0.46 part by weight of monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micron polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of nickel oxide;
(5) drying the nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain a nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 500 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the nickel oxide electrochromic film.
Comparative example 4
The comparative example provides a method for preparing an electrochromic nickel oxide film, comprising the following steps:
(1) adding 2.49 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, and continuously stirring uniformly to obtain a mixed solution, wherein the total concentration of metal ions is 0.4 mol/L.
(2) Dropwise adding 0.61 part by weight of monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micron polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of nickel oxide;
(5) drying the nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain a nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 500 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the nickel oxide electrochromic film.
Comparative example 5
The comparative example provides a method for detecting the performance of an electrochromic nickel oxide film, which comprises the following steps:
(1) adding 3.11 parts by weight of nickel acetate tetrahydrate into 24.125 parts by weight of ethylene glycol monomethyl ether, stirring for dissolving, and continuously stirring uniformly to obtain a mixed solution, wherein the total concentration of metal ions is 0.5 mol/L;
(2) dropwise adding 0.78 parts by weight of monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) slowly adding 0.1 weight part of PVP powder into the clear blue solution, uniformly stirring, and placing in a water bath at 60 ℃ for stirring for 2 hours to obtain light green transparent sol;
(4) standing the light green transparent sol obtained in the step (3) for 24 hours, and then filtering by using a 0.2-micron polytetrafluoroethylene filter membrane to obtain a filtrate which is a precursor solution of nickel oxide;
(5) drying the nickel oxide film precursor solution obtained in the step (4) at 100 ℃ for 5min, spin-coating the nickel oxide film precursor solution on the surface of cleaned and dried ITO glass, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps for 3 times to obtain a nickel oxide film, wherein the spin-coating process parameters are as follows: the rotating speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, the spin coating time is 30 s;
(6) and (3) placing the nickel oxide film obtained in the step (5) in a muffle furnace, preserving heat for 1h at 500 ℃ in an air environment, wherein the heating rate of the muffle furnace is 2 ℃/min, and cooling to room temperature after heat preservation is finished to obtain the nickel oxide electrochromic film.
FIG. 2 is a schematic diagram of the electrochemical process of the nickel oxide thin film electrode. When the NiO film is electrified with positive voltage, OH in the electrolyte is attracted—The reaction equation reacts rightwards
The equation reacts to the left when a negative voltage is applied.
Fig. 3 is a transmittance test of a test system consisting of a three-electrode test system in which the titanium-doped nickel oxide thin film electrode described in comparative example 1 and example 1 is connected with a Keithley2450 digital source table and an ultraviolet-visible spectrophotometer in a visible light region and a near infrared region at an excitation voltage of ± 2.3V. The abscissa indicates the wavelength, the ordinate indicates the transmittance, and Δ T indicates the optical modulation range, i.e., the difference in transmittance between the colored and bleached states at the corresponding wavelength. It can be seen from the figure that when the wavelength of the bare nickel oxide NiO film is 550nm, the transmittance corresponding to the colored state is 48.5%, and the transmittance corresponding to the bleached state is 92.5%, the optical modulation range of the device at 550nm is 44%, and when the wavelength of the titanium-doped nickel oxide Ti-NiO film is 550nm, the transmittance corresponding to the colored state is 21.3%, and the transmittance corresponding to the bleached state is 94.1%, the optical modulation range of the device at 550nm is 72.8%, which is far greater than the optical modulation rate of the bare nickel oxide, and a better electrochromic effect is shown.
Fig. 4 is a graph showing the transmittance of the titanium-doped nickel oxide thin film electrode according to comparative example 1 and example 1 as a function of time at an excitation voltage of ± 2V, with the abscissa representing time and the ordinate representing the transmittance. The scanning was performed for 100 cycles at an excitation voltage of ± 2V, each cycle was 60s, and positive and negative voltages were applied for 30s, respectively. Wherein +2V corresponds to the coloration voltage and-2V corresponds to the bleaching voltage. It can be seen from the figure that in the process of continuously scanning 100 times, the faded state transmittance and the colored state transmittance of the bare nickel oxide NiO film continuously decrease in the first 15 cycles, then the colored state transmittance slightly increases, the faded state transmittance remains stable, the optical modulation rate decreases until the light modulation range becomes very small after about 75 cycles, and at this time, the faded state transmittance and the colored state transmittance decrease to about half of the original state. Compared with bare nickel oxide, the bleaching state transmittance of the titanium-doped nickel oxide Ti-NiO film is more stable, the change is more stable in the circulating process, the trend of reduction is basically avoided, the coloring state transmittance of the titanium-doped nickel oxide Ti-NiO film is basically kept stable, and the light modulation range is not greatly changed. The characterization of the change of optical transmittance in the continuous circulation process of the two films shows that the titanium ion doping effectively increases the circulation stability of the nickel oxide film.
FIG. 5 is an XRD pattern of the nickel oxide thin films obtained in comparative examples 2 to 5, and it can be seen from the XRD pattern that when the concentration of total metal ions in the solution is not 0.5mol/L, no diffraction peak is evident on the surface of the thin film, and the nickel oxide thin film cannot be obtained.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of an electrochromic nickel oxide film is characterized by comprising the following steps:
(1) preparing a titanium-doped nickel oxide film precursor solution by using nickel acetate tetrahydrate, tetrabutyl titanate, monoethanolamine, PVP powder and ethylene glycol monomethyl ether as raw materials through a sol-gel method;
(2) spin-coating the titanium-doped nickel oxide film precursor solution obtained in the step (1) on the surface of a substrate to obtain a titanium-doped nickel oxide film;
(3) annealing the titanium-doped nickel oxide film obtained in the step (2) to obtain a titanium-doped nickel oxide electrochromic film;
the total concentration of metal ions in the titanium-doped nickel oxide film precursor liquid is 0.5mol/L, and the molar ratio of nickel to titanium in the titanium-doped nickel oxide film precursor liquid is 2-8: 1.
2. The method of claim 1, wherein the molar ratio of nickel to titanium in the titanium-doped nickel oxide film precursor solution is 4-8: 1.
3. The method for preparing the electrochromic nickel oxide film according to claim 1, wherein the method for preparing the titanium-doped nickel oxide film precursor solution comprises the following steps:
(1) adding nickel acetate tetrahydrate into ethylene glycol monomethyl ether, stirring and dissolving, and adding tetrabutyl titanate to obtain a mixed solution;
(2) adding monoethanolamine into the mixed solution obtained in the step (1), and uniformly stirring to obtain a clear blue solution, wherein the molar ratio of monoethanolamine to metal ions is 1: 1;
(3) adding PVP powder into the clear blue solution, stirring uniformly, and placing in a water bath at 60 ℃ for stirring uniformly to obtain light green transparent sol;
(4) and (4) standing the light green transparent sol obtained in the step (3), and then filtering to obtain a filtrate, namely a precursor solution of titanium-doped nickel oxide.
4. The method of preparing an electrochromic nickel oxide film according to claim 3, wherein the filtration membrane for filtration is a polytetrafluoroethylene membrane having a pore size of 0.2 μm.
5. The method for preparing an electrochromic nickel oxide film according to claim 1, wherein the spin coating comprises the steps of: drying the titanium-doped nickel oxide film precursor liquid at 100 ℃ for 5min, then spin-coating the titanium-doped nickel oxide film precursor liquid on the surface of a substrate, drying the spin-coated substrate at 100 ℃ for 10min, and repeating the steps to enable the number of spin-coated layers to be 1-9.
6. The method for preparing an electrochromic nickel oxide film according to claim 5, wherein the spin coating process parameters include: the glue dripping speed is 1000r/min, and the glue dripping time is 12 s; the spin rate of spin coating is 3000r/min, and the spin coating time is 30 s.
7. The method for preparing an electrochromic nickel oxide film according to claim 1, wherein the substrate is any one of ITO, FTO, AZO conductive glass.
8. The method for preparing an electrochromic nickel oxide film according to claim 1, wherein the annealing step comprises: and (3) placing the titanium-doped nickel oxide film in a muffle furnace, heating to 300 ℃ at a heating rate of 2 ℃/min in an air environment, preserving heat for 1h, cooling to room temperature, and taking out to obtain the titanium-doped nickel oxide electrochromic film.
9. The method for detecting the performance of the electrochromic nickel oxide film as claimed in claim 1, characterized by comprising the following steps of connecting a digital source meter and an ultraviolet visible spectrophotometer to test the electrochromic performance of the titanium-doped nickel oxide film by adopting a three-electrode test system;
the three-electrode test system is composed of a counter electrode, a reference electrode, a working electrode and 1M potassium hydroxide serving as an electrolyte.
10. The method of claim 9, wherein the counter electrode is a platinum electrode; the reference electrode is a silver/silver chloride electrode; the working electrode is a titanium-doped nickel oxide film.
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| CN114477789A (en) * | 2022-02-11 | 2022-05-13 | 中国海洋大学 | Solvothermal preparation method of titanium-doped nickel oxide electrochromic film |
| CN114716155A (en) * | 2022-03-24 | 2022-07-08 | 厦门理工学院 | Preparation method of thin film electrode for electrochromic device, thin film electrode and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114477789A (en) * | 2022-02-11 | 2022-05-13 | 中国海洋大学 | Solvothermal preparation method of titanium-doped nickel oxide electrochromic film |
| CN114716155A (en) * | 2022-03-24 | 2022-07-08 | 厦门理工学院 | Preparation method of thin film electrode for electrochromic device, thin film electrode and application |
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