CN114959662A - Porous crystalline tungsten oxide film and method for preparing porous crystalline tungsten oxide film by adopting electrode electrospray - Google Patents
Porous crystalline tungsten oxide film and method for preparing porous crystalline tungsten oxide film by adopting electrode electrospray Download PDFInfo
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 40
- 239000010937 tungsten Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000005507 spraying Methods 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 43
- 238000000137 annealing Methods 0.000 claims description 18
- 150000001735 carboxylic acids Chemical class 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- WKUHYPLZMSDBPZ-UHFFFAOYSA-N hydrogen peroxide tungsten Chemical compound [W].OO WKUHYPLZMSDBPZ-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000007787 electrohydrodynamic spraying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 3
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000033228 biological regulation Effects 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 citrate ions Chemical class 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1233—Organic substrates
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
A porous crystalline tungsten oxide film and a method for preparing the porous crystalline tungsten oxide film by adopting electrode electrospray belong to the technical field of electrode preparation, and particularly relate to a porous tungsten oxide film and a preparation method thereof. The invention aims to solve the problems of poor regulation capability and poor solar spectrum waveband regulation capability of the existing crystalline tungsten oxide film. The porous crystalline tungsten oxide film is prepared by preparing tungsten precursor powder from tungsten powder, hydrogen peroxide solution and carboxylic acid, taking ethanol as a dispersing agent and adopting electrode electrospray. The preparation method comprises the following steps: firstly, preparing tungsten precursor powder; secondly, electrode electric spraying is carried out to obtain the porous crystalline tungsten oxide film. The advantages are that: the preparation of the porous crystalline tungsten oxide film is realized, the performance of the tungsten oxide electrochromic film is improved, and the preparation method has obvious advantages in transmittance modulation capability, cycling stability and coloring time. The method is mainly used for preparing the porous crystalline tungsten oxide film.
Description
Technical Field
The invention belongs to the technical field of electrode preparation, and particularly relates to a porous tungsten oxide and tungsten oxide film and a preparation method thereof.
Background
The electrochromic material has large-scale application potential due to the advantage of actively regulating the color, tungsten oxide (WO3) is a typical electrochromic material, and under the action of an external electric field, the material undergoes redox reaction, so that the absorption spectrum of the material is reversibly changed, and the electrochromic material is widely applied at present. The preparation method mainly comprises magnetron sputtering, vacuum evaporation, electrochemical deposition, hydrothermal/solvothermal method, sol-gel method, electrospray coating method and the like.
However, the tungsten oxide electrochromic material has the following problems to be solved: 1. the amorphous tungsten oxide film has poor cycle life, generally fails after 2000 cycles, and is far from having commercial value. 2. The crystalline tungsten oxide film has poor regulation capability, and the defect content in the crystalline oxide is low, so that the injection in the color change process is difficult, and the modulation capability of the crystalline tungsten oxide film in the solar spectrum waveband is poor. 3. The industrial production is difficult, the performance of the film prepared by the preparation methods such as magnetron sputtering, vacuum evaporation and the like is good, but the cost of instruments is high, the large-area preparation cannot be carried out by a hydrothermal/solvothermal method, a sol-gel method and electrochemical deposition, and the performance guarantee of the film is difficult to modify by an electronic spraying coating method although the cost is low.
In summary, the tungsten oxide electrochromic film has a serious limitation on its industrialization potential due to the mismatch between lifetime and performance and cost, and therefore, a preparation method is needed to prepare a tungsten oxide film with long lifetime and high performance at low cost.
Disclosure of Invention
The invention aims to solve the problems of poor regulation capability and poor solar spectrum waveband regulation capability of the existing crystalline tungsten oxide film, and provides a porous crystalline tungsten oxide film and a method for preparing the porous crystalline tungsten oxide film by adopting electrode electrospray.
A porous crystalline tungsten oxide film is prepared by preparing tungsten precursor powder from tungsten powder, 30 mass percent hydrogen peroxide solution and carboxylic acid, and then preparing the porous crystalline tungsten oxide film by using ethanol as a dispersing agent and adopting electrode electrospray, wherein the porosity of the porous crystalline tungsten oxide film is 8-12%, and the diameter of a hole in the porous crystalline tungsten oxide film is 50-100 nm.
A method for preparing a porous crystalline tungsten oxide film by adopting electrode electrospray comprises the following steps:
firstly, preparing tungsten precursor powder: firstly, dissolving tungsten powder in a hydrogen peroxide solution with the mass fraction of 30% to obtain a tungsten-hydrogen peroxide solution; the concentration of the tungsten element in the tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; adding carboxylic acid into the tungsten-hydrogen peroxide solution, and uniformly mixing to obtain a carboxylic acid-tungsten-hydrogen peroxide solution; the concentration of-COOH in the carboxylic acid-tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; thirdly, evaporating the carboxylic acid-tungsten-hydrogen peroxide solution to dryness at the temperature of 40-70 ℃ to obtain tungsten precursor powder;
secondly, electrode electrospraying: firstly, dispersing tungsten precursor powder in an ethanol solvent to obtain tungsten precursor-ethanol dispersion liquid; the volume ratio of the mass of the tungsten precursor powder to the volume of the ethanol is 20g (10-50) mL, the tungsten precursor-ethanol dispersion is sprayed on a clean substrate by adopting an electrode electric spraying mode to coat a film, then the substrate is dried for 1-2 h at the temperature of 60-80 ℃, and finally the substrate is annealed in an inert atmosphere to obtain the porous crystalline tungsten oxide film.
The invention has the advantages that:
the invention optimizes the electrospray precursor powder, adopts carboxylic acid as a ligand in the tungsten precursor powder, combines with an annealing process, and oxidizes the carboxylic acid ligand in the annealing process to inhibit the growth of grains and form pores in the annealing process, and the pore size of the porous crystalline tungsten oxide film can be controlled by using carboxylic acid with different sizes, so that the invention realizes the preparation of the porous crystalline tungsten oxide film, improves the performance of the tungsten oxide electrochromic film, and has remarkable advantages in transmittance modulation capability, cycling stability and coloring time compared with the crystalline film.
Secondly, the porous crystalline tungsten oxide film prepared by the method has obvious pseudocapacitance characteristics, which are reflected by the characteristics of a polycrystalline film, compared with the crystalline film, the modulation performance and the response time are obviously improved, and the change amplitude of the transmittance reaches more than 40%.
Drawings
FIG. 1 is an XRD pattern of a tungsten precursor powder obtained in step one of example 1;
FIG. 2 is an XRD pattern of the porous crystalline tungsten oxide film obtained in example 1;
FIG. 3 is a transmission spectrum of porous crystalline tungsten oxide film obtained in example 1 in a colored state and a discolored state before and after discoloration;
FIG. 4 is a CV diagram of the porous crystalline tungsten oxide film obtained in example 1;
FIG. 5 is an SEM photograph of the porous crystalline tungsten oxide film obtained in example 1;
FIG. 6 is an SEM photograph of the porous crystalline tungsten oxide film obtained in example 2;
FIG. 7 is an SEM image of a crystalline tungsten oxide film;
FIG. 8 is a schematic representation of the separation effect of carboxylic acid on PTA.
Detailed Description
The first embodiment is as follows: the embodiment is a porous crystalline tungsten oxide film, which is prepared by preparing tungsten powder, 30 mass percent hydrogen peroxide solution and carboxylic acid into tungsten precursor powder, then using ethanol as a dispersing agent and adopting electrode electrospray to prepare the porous crystalline tungsten oxide film, wherein the porosity of the porous crystalline tungsten oxide film is 8-12%, and the diameter of a hole in the porous crystalline tungsten oxide film is 50-100 nm.
The second embodiment is as follows: the embodiment is a method for preparing a porous crystalline tungsten oxide film by adopting electrode electrospray, which is specifically completed by the following steps:
firstly, preparing tungsten precursor powder: firstly, dissolving tungsten powder in a hydrogen peroxide solution with the mass fraction of 30% to obtain a tungsten-hydrogen peroxide solution; the concentration of the tungsten element in the tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; adding carboxylic acid into the tungsten-hydrogen peroxide solution, and uniformly mixing to obtain a carboxylic acid-tungsten-hydrogen peroxide solution; the concentration of-COOH in the carboxylic acid-tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; thirdly, evaporating the carboxylic acid-tungsten-hydrogen peroxide solution to dryness at the temperature of 40-70 ℃ to obtain tungsten precursor powder;
secondly, electrode electrospraying: firstly, dispersing tungsten precursor powder in an ethanol solvent to obtain tungsten precursor-ethanol dispersion liquid; the volume ratio of the mass of the tungsten precursor powder to the volume of the ethanol is 20g (10-50) mL, the tungsten precursor-ethanol dispersion is sprayed on a clean substrate by adopting an electrode electric spraying mode to coat a film, then the substrate is dried for 1-2 h at the temperature of 60-80 ℃, and finally the substrate is annealed in an inert atmosphere to obtain the porous crystalline tungsten oxide film.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: in the first step, the carboxylic acid is one or more of formic acid, acetic acid, oxalic acid and citric acid. The rest is the same as the second embodiment.
The fourth concrete implementation mode is as follows: the present embodiment differs from the second or third embodiment in that: the clean substrate in the second step is obtained by the following operations: and (3) pickling the substrate, then sequentially cleaning the substrate by using ethanol and deionized water, and drying to obtain a clean substrate. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the present embodiment is different from the fourth embodiment in that: the substrate is ITO glass, FTO glass, AZO glass or a PET-ITO transparent conductive film. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fourth or fifth embodiment is different from the first or second embodiment in that: and ultrasonically cleaning the substrate for 20min by adopting a 1mol/L sulfuric acid solution, ultrasonically cleaning the substrate for 20min by adopting ethanol, finally ultrasonically cleaning the substrate for 20min by using deionized water, and drying to obtain a clean substrate. The others are the same as the fourth or fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: and in the second step, the voltage of the electrode electric spraying mode is 17kV, and the distance between the spray head and the clean substrate is 15 cm. The rest is the same as the second to sixth embodiments.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: and the gas of the inert atmosphere in the second step is argon or nitrogen. The rest is the same as the second to sixth embodiments.
The specific implementation method nine: the second to eighth differences from the first embodiment are as follows: the annealing parameters in the second step: the annealing temperature is 400-600 ℃, and the annealing time is 10-120 min. The rest is the same as the second to eighth embodiments.
The specific implementation mode is ten: the present embodiment differs from the second to ninth embodiments in that: and in the second step, the temperature is raised to the annealing temperature at the heating rate of 5 ℃/min, and then the annealing is carried out in the inert atmosphere. The rest is the same as the second to ninth embodiments.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests are adopted to verify the effect of the invention:
example 1: a method for preparing a porous crystalline tungsten oxide film by adopting electrode electrospray comprises the following steps:
firstly, preparing tungsten precursor powder: dissolving 1.8g of tungsten powder in 20mL of hydrogen peroxide solution with the mass fraction of 30% to obtain a tungsten-hydrogen peroxide solution; adding 2.2g of oxalic acid into the tungsten-hydrogen peroxide solution, and uniformly mixing to obtain a carboxylic acid-tungsten-hydrogen peroxide solution; thirdly, evaporating the carboxylic acid-tungsten-hydrogen peroxide solution to dryness at the temperature of 60 ℃ to obtain tungsten precursor powder;
secondly, electrode electrospraying: firstly, dispersing 20g of tungsten precursor powder in 20mL of ethanol solvent to obtain tungsten precursor-ethanol dispersion liquid; spraying a tungsten precursor-ethanol dispersion liquid on a clean substrate by adopting an electrode electric spraying mode to coat a film, then drying at the temperature of 80 ℃ for 2h, and finally annealing at the temperature of 450 ℃ for 60min under a nitrogen atmosphere to obtain a porous crystalline tungsten oxide film; the porosity of the porous crystalline tungsten oxide film was 9.8%, and the average diameter of pores in the porous crystalline tungsten oxide film was about 51 nm.
Example 1 the clean substrate described in step two was obtained as follows: ultrasonically cleaning a substrate for 20min by adopting 1mol/L sulfuric acid solution, ultrasonically cleaning the substrate for 20min by using ethanol, ultrasonically cleaning the substrate for 20min by using deionized water, and drying to obtain a clean substrate; the substrate is ITO glass.
In the second step of example 1, the voltage of the electrode electro-spray method was 17kV, and the distance between the spray head and the clean substrate was 15 cm.
XRD characterization is performed on the tungsten precursor powder obtained in the first step of example 1 and the porous crystalline tungsten oxide film obtained in example 1, as shown in FIGS. 1 and 2, FIG. 1 is an XRD pattern of the tungsten precursor powder obtained in the first step of example 1, FIG. 2 is an XRD pattern of the porous crystalline tungsten oxide film obtained in example 1, and comparison between FIGS. 2 and 1 shows that the prepared precursor powder is WO 3 A complex product with oxalic acid.
And (3) performing electrochemical cyclic voltammetry characteristic and spectral analysis: detecting the transmission spectra of the porous crystalline tungsten oxide film obtained in example 1 in the colored state and the bleached state, as shown in FIG. 3, wherein FIG. 3 is a transmission spectrum of the porous crystalline tungsten oxide film obtained in example 1 in the colored state and the bleached state before and after discoloration; the CV curve of the porous crystalline tungsten oxide thin film obtained in example 1 was measured in a 0.1mol/L aqueous solution of lithium sulfate, and as shown in FIG. 4, FIG. 4 is a CV curve of the porous crystalline tungsten oxide thin film obtained in example 1; as seen from fig. 3, a certain capacitance charge-discharge characteristic appears, which illustrates that the surface pores play a significant role in adsorption, and as seen from fig. 4, the modulation capability of the transmission spectrum in the near-infrared region is significantly improved, which is very beneficial to the whole injection process, so that not only can the near-infrared modulation capability be effectively enhanced, but also the response rate can be improved, and the combination of the advantages of amorphous state and crystalline state is realized to a certain extent; therefore, as shown in fig. 3, the film has a significant pseudocapacitance characteristic, and as shown in fig. 4, the modulation of the colored state and the faded state at the near infrared 950nm is about 50%, and the response time is about 20s, which is reflected in the characteristic of the polycrystalline film, which significantly improves the modulation performance and the response time compared with the crystalline film.
Example 2: a method for preparing a porous crystalline tungsten oxide film by adopting electrode electrospray comprises the following steps:
firstly, preparing tungsten precursor powder: firstly, dissolving 1.8g of tungsten powder in 20mL of hydrogen peroxide solution with the mass fraction of 30% to obtain a tungsten-hydrogen peroxide solution; adding 2.2g of citric acid into the tungsten-hydrogen peroxide solution, and uniformly mixing to obtain a carboxylic acid-tungsten-hydrogen peroxide solution; thirdly, evaporating the carboxylic acid-tungsten-hydrogen peroxide solution to dryness at the temperature of 60 ℃ to obtain tungsten precursor powder;
secondly, electrode electrospraying: firstly, dispersing 20g of tungsten precursor powder in 20mL of ethanol solvent to obtain a tungsten precursor-ethanol dispersion liquid; spraying a tungsten precursor-ethanol dispersion liquid on a clean substrate by adopting an electrode electric spraying mode to coat a film, then drying at the temperature of 80 ℃ for 2h, and finally annealing at the temperature of 450 ℃ for 60min under a nitrogen atmosphere to obtain a porous crystalline tungsten oxide film; the porosity of the porous crystalline tungsten oxide film was 10.6%, and the average diameter of pores in the porous crystalline tungsten oxide film was about 93 nm.
Example 2 the clean substrate in step two was obtained as follows: ultrasonically cleaning a substrate for 20min by adopting 1mol/L sulfuric acid solution, ultrasonically cleaning the substrate for 20min by using ethanol, ultrasonically cleaning the substrate for 20min by using deionized water, and drying to obtain a clean substrate; the substrate is ITO glass.
In the second step of example 2, the voltage of the electrode electric spraying mode is 17kV, and the distance between the spray head and the clean substrate is 15 cm.
SEM characterization of surface morphology of the porous crystalline tungsten oxide thin film obtained in example 1, the porous crystalline tungsten oxide thin film obtained in example 2, and the existing crystalline tungsten oxide thin film is performed, as shown in fig. 5, 6, and 7, fig. 5 is an SEM image of the porous crystalline tungsten oxide thin film obtained in example 1, fig. 6 is an SEM image of the porous crystalline tungsten oxide thin film obtained in example 2, and fig. 7 is an SEM image of the crystalline tungsten oxide thin film; as can be seen from fig. 5 and 6, the surface crystal grain size is only about several tens of nanometers, and many fine pores are present between the crystal grains. The larger volume occupied by the citrate ions effectively separates the ion complexes and increases the diffusion distance so that grain growth inhibition is most pronounced during annealing. As can be seen by comparing fig. 5 and 6 with fig. 7, the pure PTA (polyperoxytungstic acid) deposited film has the lowest porosity, agglomerated only by the bulk clusters, and is large in size, but due to the strong bonding between the closely packed clusters, there is no delamination and porosity between the clusters, which is not favorable for ion implantation, while the specific surface area is much smaller than that of the carboxylic acid film, in which the porosity is increased by delamination, which occurs largely due to the separation effect of the conjugate base. This effect of separation on PTA containing oxalic acid is less than that of PTA containing citric acid, and separation between individual particles is greatest, and therefore porosity is greatest.
Fig. 8 is a schematic diagram illustrating the separation effect of carboxylic acid on PTA, and it can be seen from fig. 8 that during the annealing process, the presence of the external carboxylic acid ligand coated on the PTA ions is oxidized during the annealing process, the growth of crystal grains is inhibited, and pores are formed, and further, the pore size of the film can be controlled by using carboxylic acids with different sizes.
Claims (10)
1. A porous crystalline tungsten oxide film is characterized in that tungsten powder, 30 mass percent hydrogen peroxide solution and carboxylic acid are prepared into tungsten precursor powder, ethanol is used as a dispersing agent, and an electrode is adopted for electrospraying to prepare the porous crystalline tungsten oxide film, wherein the porosity of the porous crystalline tungsten oxide film is 8-12%, and the diameter of a hole in the porous crystalline tungsten oxide film is 50-100 nm.
2. A method for preparing a porous crystalline tungsten oxide film according to claim 1 by electro-spraying, comprising the steps of:
firstly, preparing tungsten precursor powder: firstly, dissolving tungsten powder in a hydrogen peroxide solution with the mass fraction of 30% to obtain a tungsten-hydrogen peroxide solution; the concentration of the tungsten element in the tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; adding carboxylic acid into the tungsten-hydrogen peroxide solution, and uniformly mixing to obtain a carboxylic acid-tungsten-hydrogen peroxide solution; the concentration of-COOH in the carboxylic acid-tungsten-hydrogen peroxide solution is 0.05 mol/L-0.5 mol/L; thirdly, evaporating the carboxylic acid-tungsten-hydrogen peroxide solution to dryness at the temperature of 40-70 ℃ to obtain tungsten precursor powder;
secondly, electrode electrospraying: firstly, dispersing tungsten precursor powder in an ethanol solvent to obtain tungsten precursor-ethanol dispersion liquid; the volume ratio of the mass of the tungsten precursor powder to the volume of the ethanol is 20g (10-50) mL, the tungsten precursor-ethanol dispersion is sprayed on a clean substrate by adopting an electrode electric spraying mode to coat a film, then the substrate is dried for 1-2 h at the temperature of 60-80 ℃, and finally the substrate is annealed in an inert atmosphere to obtain the porous crystalline tungsten oxide film.
3. The method for preparing porous crystalline tungsten oxide film according to claim 2, wherein the carboxylic acid is one or more of formic acid, acetic acid, oxalic acid and citric acid in the step one.
4. The method of claim 3, wherein the clean substrate in step two is obtained by the following steps: and (3) pickling the substrate, then sequentially cleaning the substrate by using ethanol and deionized water, and drying to obtain a clean substrate.
5. The method for preparing porous crystalline tungsten oxide film by electrode electrospray according to claim 4, wherein the substrate is ITO glass, FTO glass, AZO glass or PET-ITO transparent conductive film.
6. The method for preparing porous crystalline tungsten oxide film by electrode electrospray according to claim 5, characterized in that the substrate is firstly cleaned by ultrasonic cleaning with 1mol/L sulfuric acid solution for 20min, then cleaned by ultrasonic cleaning with ethanol for 20min, finally cleaned by ultrasonic cleaning with deionized water for 20min, and dried to obtain a clean substrate.
7. The method according to claim 1, wherein the voltage of the electro-spray method in step two is 17kV, and the distance between the nozzle and the clean substrate is 15 cm.
8. The method according to claim 7, wherein the inert atmosphere in step two is argon or nitrogen.
9. The method according to claim 8, wherein the annealing parameters in step two are as follows: the annealing temperature is 400-600 ℃, and the annealing time is 10-120 min.
10. The method according to claim 9, wherein the second step is carried out by heating to an annealing temperature at a heating rate of 5 ℃/min, and then annealing under an inert atmosphere.
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