CN114163139A - Preparation method of composite nickel oxide film with two layers of different structures - Google Patents
Preparation method of composite nickel oxide film with two layers of different structures Download PDFInfo
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- CN114163139A CN114163139A CN202111586577.1A CN202111586577A CN114163139A CN 114163139 A CN114163139 A CN 114163139A CN 202111586577 A CN202111586577 A CN 202111586577A CN 114163139 A CN114163139 A CN 114163139A
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 56
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 30
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 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 8
- 238000004544 sputter deposition Methods 0.000 claims description 6
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 46
- 239000010410 layer Substances 0.000 description 33
- 239000012621 metal-organic framework Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004040 coloring Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- 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
- C03C17/245—Oxides by deposition from the vapour phase
-
- 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
- C03C2217/217—FeOx, CoOx, NiOx
-
- 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
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The invention discloses a preparation method of a composite nickel oxide film with two layers of different structures, which comprises the following steps: cleaning and drying the FTO glass sheet; performing magnetron sputtering on the cleaned FTO glass sheet by adopting a direct-current magnetron sputtering method to obtain a layer of magnetron sputtered nickel oxide film on the conductive surface of the FTO glass sheet; adding nickel salt and terephthalic acid into a beaker, adding N, N-dimethylformamide, adding deionized water after stirring, continuously stirring to obtain a precursor solution, transferring the precursor into a reaction kettle, vertically placing an FTO glass sheet subjected to magnetron sputtering into the reaction kettle, washing the surface of a film layer after hydrothermal reaction, removing residual impurities, and drying to obtain an @ NiO Ni-MOF composite film; and placing the sample in a tube furnace, heating the furnace, and cooling after heat preservation to obtain the composite nickel oxide film. The composite nickel oxide film prepared by the invention has excellent light modulation characteristic and energy storage characteristic.
Description
Technical Field
The invention relates to the field of electrochromism, in particular to a preparation method of a composite nickel oxide film with two layers of different structures.
Background
With the growing world population and the increasing demand for energy, innovative technologies are adopted to improve energy conservation or efficiency, and great interest is shown in many researchers and the public. At this time, electrochromic devices (CEs) having changed optical characteristics (absorbance, reversibly changing transmittance and reflectance by applying voltage) are considered to be capable of adapting to weather changes with low energy consumption in buildings by selectively adjusting the passage of light and temperature, and maintaining proper temperature, which is called "smart window", and electrochromic materials have now been applied to life design such as car skylights and mobile phone back cases using electrochromic technology to link the technology more directly with people's lives, so that people have more definite sensory enjoyment. Among the electrochromic materials, for example WO3、MnO2、NiO、TiO2Nickel oxide (NiO) has the advantages of wide dynamic range, low working voltage, good stability and the like, and is a promising EC anode material. NiO also has wide advantages, and is coast-friendly with low material content, abundant natural resources and environment friendliness. The EC performance of NiO is closely related to the morphology and size of NiO, so that the reasonable design of the nickel oxide morphology by changing an experimental method has long been considered as a research hotspot for scientific and technical development. Porous structures have gained much attention due to their attractive properties such as large void volume, low density, high surface to volume ratio, giving them a variety of potential applications in solar cells, drug delivery, energy storage/conversion and catalysis. Therefore, the preparation of porous nickel oxide films has attracted the attention of many researchers.
Metal Organic Frameworks (MOFs) are crystalline materials built up by coordination bonds between organic linkers and metal ions/clusters. The MOFs can be easily converted into micro/nano-structure materials such as porous metal oxides, porous metal sulfides, porous carbon and hybrids thereof as an effective self-template. Due to their regular porosity and adjustable pore composition, MOF materials are commonly used in supercapacitors as materials for enhancing energy storage performance and therefore are also commonly used in other fields for the construction of porous structures.
The existing single-layer nickel oxide film has the problem of low contrast, the nickel oxide prepared by a hydrothermal method has the problems of few active sites, large ion diffusion resistance and the like, and the magnetron sputtering nickel oxide film has the defect of difficult ion de-intercalation due to over compact structure.
Disclosure of Invention
The invention aims to provide a preparation method of a composite nickel oxide film with two layers of different structures, and the prepared composite nickel oxide film has excellent light modulation characteristics and energy storage characteristics.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a composite nickel oxide film with two layers of different structures comprises the following steps:
(1) exposing the conductive surface of the FTO glass sheet in acetone, ultrasonically cleaning for 20min, taking out, then sequentially placing in absolute ethyl alcohol and deionized water, ultrasonically cleaning for 20min respectively, taking out and drying;
(2) fixing a pure nickel target at a position corresponding to a target material by adopting a direct current magnetron sputtering method, placing a cleaned FTO glass sheet at a position corresponding to a sample, pumping an inner cavity to high vacuum, placing the dried FTO glass sheet in a cavity pumped to high vacuum, introducing argon-oxygen mixed gas, adjusting power and gas pressure, performing magnetron sputtering, and obtaining a layer of magnetron sputtering nickel oxide film on a conductive surface of the FTO glass sheet;
(3) adding a certain amount of nickel salt and terephthalic acid into a beaker according to a certain proportion, adding a certain amount of N, N-dimethylformamide, stirring, adding deionized water, continuously stirring to obtain a precursor solution, transferring the prepared precursor into a reaction kettle, vertically placing an FTO glass sheet after magnetron sputtering into the reaction kettle, performing hydrothermal reaction for a certain time, washing the surface of a film layer, removing residual impurities, and drying to obtain a composite film consisting of a layer of magnetron sputtering NiO and a layer of hydrothermal Ni-MOF, namely a hydrothermal NiO @ Ni-MOF composite film;
(4) and (4) placing the sample obtained in the step (3) in a tube furnace, heating the furnace to a certain temperature, and cooling after heat preservation to obtain the two layers of composite nickel oxide films with different structures.
Preferably, in the step (2), the high vacuum environment is 1 × 10-4～2x10-4Pa, the flow ratio of argon to oxygen in the argon-oxygen mixed gas is 90: 10-98: 2, the gas pressure is adjusted to be 1-3 Pa, the power is 35-40W, and after direct-current sputtering is carried out for 10min, the sample is sputtered for 5-20 min.
Preferably, in the step (3), the nickel salt is one of nickel acetate, nickel chloride or nickel nitrate hexahydrate.
Preferably, in the step (3), the nickel salt is nickel nitrate hexahydrate, and the molar ratio of the terephthalic acid to the nickel nitrate hexahydrate is 3-10: the molar ratio of the 1, N, N-dimethylformamide to the terephthalic acid is 180-90: the volume ratio of the 1, N, N-dimethylformamide to the deionized water is 10-20: 1.
Preferably, in the step (3), the stirring time is 20-40 min, and the stirring speed is 300-450 r/min.
Preferably, in the step (3), the hydrothermal reaction temperature is 120-130 ℃ and the time is 3-4 h.
Preferably, in the step (3), the washing manner is that 3-5 ml of organic solvent is absorbed by a rubber head dropper to wash slowly along the edge of the FTO glass sheet and not wash the surface of the reactant directly.
Preferably, the organic solvent is methanol or N, N-dimethylformamide.
Preferably, in the step (3), the drying temperature is 60 ℃ and the time is 2-3 h.
Preferably, in the step (4), the temperature rising speed is 2-5 ℃/min, the reaction temperature is 400-450 ℃, and the heat preservation time is 25-35 min.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, parameters such as power, pressure intensity, argon-oxygen flow ratio and the like of direct current magnetron sputtering are adjusted, a layer of compact and uniformly distributed NiO nano and micro particles is sputtered on FTO conductive glass to form a first nickel oxide film, a MOF template is selected on the basis of the previous step by using a hydrothermal method, a two-dimensional grid flaky Ni-MOF material is prepared by reacting for a period of time, and then the nano porous morphology on a two-dimensional grid flaky structure is obtained by adjusting annealing temperature, annealing time and annealing atmosphere, so that two layers of nickel oxide double-layer composite films with different structures are prepared. Secondly, the invention can adjust the size and the number of the pores of the nickel oxide porous structure of the hydrothermal layer by adjusting the amount of terephthalic acid.
2) The porous two-dimensional grid flaky nickel oxide grown on the basis of the magnetron sputtering preparation can grow more uniformly, and the size of the porous two-dimensional grid flaky nickel oxide is also more uniform.
3) The composition of the nickel oxide with different structures of the same substance avoids the disadvantages of lattice mismatching, poor compatibility and the like of a heterogeneous film, improves the charge storage capacity of any single-layer nickel oxide film and improves the optical modulation range.
4) The optical modulation range of the double-layer nickel oxide composite film prepared by the method in a KOH electrolyte solution with the wavelength of 550nm and the concentration of 1mol/L can reach 83%, the charge transfer impedance is 14.27 omega, the diffusion impedance is 3.62 omega, and the double-layer nickel oxide composite film has better circulation stability.
5) The invention solves the problems of low contrast of a single-layer nickel oxide sheet structure prepared by a single-layer hydrothermal method and a single-layer nickel oxide film prepared by a magnetic control method, and simultaneously solves the problems of few active sites, large ionic diffusion resistance and the like of the nickel oxide prepared by the hydrothermal method by using the MOF template, and realizes the controllability of a nickel oxide porous structure. The defect that the ion is difficult to de-embed due to the over compact structure of the magnetron sputtering nickel oxide film is overcome.
6) The composite nickel oxide film prepared by the invention has excellent light modulation characteristic and energy storage characteristic, so that the composite nickel oxide film has a very high application prospect in future intelligent equipment application.
Drawings
FIG. 1 is a scanning electron microscope photograph of a single layer film prepared by magnetron sputtering according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope photomicrograph of a single layer film prepared from the MOF template of example 1 of the invention;
FIG. 3 is a SEM photograph of two composite nickel oxide films of different structures according to example 1 of the present invention;
FIG. 4 is an electrochromic spectrum of a composite nickel oxide thin film based on two layers with different structures prepared in example 1 of the present invention;
FIG. 5 is an XRD diffraction pattern of an FTO conductive glass of the present invention and a composite nickel oxide thin film based on two layers with different structures prepared in example 1;
FIG. 6 is a graph (550nm) showing the electrochromic kinetics of silver-coated copper powders prepared in examples 1 and 2 of the present invention;
FIG. 7 is a SEM photograph of two layers of composite nickel oxide films with different structures prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a composite nickel oxide film with two layers of different structures comprises the following steps:
(1) cleaning the FTO glass: and putting the FTO glass sheet with the conductive surface facing outwards into acetone, carrying out ultrasonic cleaning for 20min, taking out, then sequentially putting into absolute ethyl alcohol and deionized water, carrying out ultrasonic cleaning for 20min, taking out, and drying.
(2) Preparing a first nickel oxide film by magnetron sputtering: fixing a pure nickel target at a position corresponding to the target material, placing the cleaned FTO glass sheet at a position corresponding to the sample, and pumping the environment in the cavity of the magnetron sputtering equipment to 2x10-4pa in a high vacuum environment, and the vacuum environment,introducing argon and oxygen according to the flow ratio of 98:2, adjusting the pressure to be Pa and the power to be 40W, sputtering the sample for 15min after DC sputtering for 10min, and obtaining a layer of magnetron sputtering nickel oxide film on the conductive surface of the FTO glass sheet.
(3) Preparing a precursor solution: terephthalic acid and nickel nitrate hexahydrate are mixed according to a molar ratio of 3: 1 is weighed and placed in a 50ml beaker, 20ml of N, N-dimethylformamide is added, the rotating speed is 400r/min, the stirring is carried out for 30min, 1ml of deionized water is added, and the stirring is continued for 2min, so as to obtain a precursor solution.
(4) Preparing a NiO @ Ni-MOF composite membrane: transferring the precursor prepared in the step (3) to a 50ml reaction kettle, and vertically placing the FTO glass sheet prepared in the step (2) into the reaction kettle. And then reacting for 3h at 120 ℃, naturally cooling to room temperature, taking out the glass sheet, washing the surface of the film layer by using N, N-dimethylformamide solution, washing the surface of the film layer by using methanol, removing residual impurities, and drying for 2h at 60 ℃ to obtain a composite film consisting of a layer of magnetron sputtering NiO and a layer of hydrothermal Ni-MOF, namely the hydrothermal NiO @ Ni-MOF composite film.
(5) Preparation of NiO @ NiO: and (3) placing the prepared sample in the step (4) in a tubular furnace, heating the furnace to 400 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 30min, and then naturally cooling to obtain NiO composite membranes with different structures, namely the sample NiO @ NiO, prepared by magnetron sputtering and an MOF template method.
Example 2
A preparation method of a composite nickel oxide film with two layers of different structures comprises the following steps:
(1) cleaning the FTO glass: and putting the FTO glass sheet with the conductive surface facing outwards into acetone, carrying out ultrasonic cleaning for 20min, taking out, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol and deionized water for 20min, taking out, and drying.
(2) Preparing a first nickel oxide film by magnetron sputtering: fixing a pure nickel target at a position corresponding to the target material, and placing the cleaned conductive glass at a position corresponding to the sample. Pumping the environment in the cavity to 2x10-4Introducing argon and oxygen according to the flow ratio of 98:2 in a Pa high vacuum environment, adjusting the pressure to 3Pa and the power to 40W, sputtering the sample for 20min after DC sputtering for 10min, and performing FTAnd a layer of magnetron sputtering nickel oxide film is obtained on the conductive surface of the O glass sheet.
(3) Preparing a precursor solution: terephthalic acid and nickel nitrate hexahydrate are mixed according to a molar ratio of 3: 1 is weighed and placed in a 50ml beaker, 20ml of N, N-dimethylformamide is added, the rotating speed is 450r/min, the stirring is carried out for 30min, 1ml of deionized water is added, and the stirring is continued for 3min, thus obtaining the precursor solution.
(4) Preparing a NiO @ Ni-MOF composite membrane: transferring the precursor prepared in the step (3) to a 50ml reaction kettle, and vertically placing the glass sheet prepared in the step (2) into the reaction kettle. And then reacting for 3h at 120 ℃, naturally cooling to room temperature, taking out the glass sheet, washing the surface of the film layer by using N, N-dimethylformamide solution, washing the surface of the film layer by using methanol, removing residual impurities, and drying for 3h at 60 ℃ to obtain a composite film consisting of a layer of magnetron sputtering NiO and a layer of hydrothermal Ni-MOF, namely the hydrothermal NiO @ Ni-MOF composite film.
(5) Preparation of NiO @ NiO: and (3) placing the prepared sample in the step (4) in a tubular furnace, heating the furnace to 400 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 30min, and then naturally cooling to obtain NiO composite membranes with different structures, namely the sample NiO @ NiO, prepared by magnetron sputtering and an MOF template method.
The pictures of the scanning electron microscope of fig. 1, 2, 3 and 7 show that the porous sheet layer of the double-layer film prepared by the invention has more obvious porous structure and more uniform distribution of sheet-mounted structure on the basis of the magnetron sputtering layer. The spectrum in fig. 4 shows that the optical modulation amplitude of the composite film in the full band reaches 83%, and the transmittance in the faded state approaches 94%. The xrd graph of FIG. 5 shows a diffraction peak which is very clear in comparison with FTO conductive glass, and FIG. 6 shows the dynamics graph of the composite film, the composite film prepared in example 1 fades for 2S and has a coloring time of 3.4S, the composite film prepared in example 2 fades for 2.1S and has a coloring time of 3.2S.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (10)
1. A preparation method of a composite nickel oxide film with two layers of different structures is characterized by comprising the following steps:
(1) exposing the conductive surface of the FTO glass sheet in acetone, ultrasonically cleaning for 20min, taking out, then sequentially placing in absolute ethyl alcohol and deionized water, ultrasonically cleaning for 20min respectively, taking out and drying;
(2) fixing a pure nickel target at a position corresponding to a target material by adopting a direct current magnetron sputtering method, placing a cleaned FTO glass sheet at a position corresponding to a sample, pumping an inner cavity to high vacuum, introducing argon-oxygen mixed gas, adjusting power and gas pressure, performing magnetron sputtering, and obtaining a layer of magnetron sputtering nickel oxide film on a conductive surface of the FTO glass sheet;
(3) adding a certain amount of nickel salt and terephthalic acid into a beaker according to a certain proportion, adding a certain amount of N, N-dimethylformamide, stirring, adding deionized water, continuously stirring to obtain a precursor solution, transferring the prepared precursor into a reaction kettle, vertically placing an FTO glass sheet after magnetron sputtering into the reaction kettle, performing hydrothermal reaction for a certain time, washing the surface of a film layer, removing residual impurities, and drying to obtain a composite film consisting of a layer of magnetron sputtering NiO and a layer of hydrothermal Ni-MOF, namely a hydrothermal NiO @ Ni-MOF composite film;
(4) and (4) placing the sample obtained in the step (3) in a tube furnace, heating the furnace to a certain temperature, and cooling after heat preservation to obtain the two layers of composite nickel oxide films with different structures.
2. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (2), the high vacuum environment is 1x10-4～2x10-4Pa, the flow ratio of argon to oxygen in the argon-oxygen mixed gas is 90: 10-98: 2, the gas pressure is adjusted to be 1-3 Pa, the power is 35-40W, and after direct-current sputtering is carried out for 10min, the sample is sputtered for 5-20 min.
3. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the nickel salt is one of nickel acetate, nickel chloride or nickel nitrate hexahydrate.
4. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the nickel salt is nickel nitrate hexahydrate, and the molar ratio of the terephthalic acid to the nickel nitrate hexahydrate is 3-10: the molar ratio of the 1, N, N-dimethylformamide to the terephthalic acid is 180-90: the volume ratio of the 1, N, N-dimethylformamide to the deionized water is 10-20: 1.
5. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the stirring time is 20-40 min, and the stirring speed is 300-450 r/min.
6. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the hydrothermal reaction temperature is 120-130 ℃ and the time is 3-4 h.
7. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the washing mode is that 3-5 ml of organic solvent is absorbed by a rubber head dropper to be washed slowly along the edge of the FTO glass sheet and the surface of the reactant is not washed directly.
8. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 7, which is characterized in that: the organic solvent is methanol or N, N-dimethylformamide.
9. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (3), the drying temperature is 60 ℃ and the time is 2-3 h.
10. The method for preparing a composite nickel oxide film with two layers of different structures according to claim 1, which is characterized in that: in the step (4), the temperature rising speed is 2-5 ℃/min, the reaction temperature is 400-450 ℃, and the heat preservation time is 25-35 min.
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