CN112850749A - Preparation method of electrochromic Prussian bletilla striata and analogue thin film thereof - Google Patents
Preparation method of electrochromic Prussian bletilla striata and analogue thin film thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010409 thin film Substances 0.000 title claims abstract description 8
- 241001313857 Bletilla striata Species 0.000 title claims description 3
- 239000010408 film Substances 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- -1 alkali metal salt Chemical class 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical group [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 10
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229910018965 MCl2 Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 230000004044 response Effects 0.000 description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000005562 fading Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to the technical field of preparation of Prussian white and analogue materials thereof, in particular to a preparation method of an electrochromic Prussian white and analogue thin film thereof, wherein the Prussian white and analogue thereof are A2M[Fe(CN)6]Wherein A is Li+、Na+、K+M is Fe2+、Co2+、Ni2+、Mn2+、Zn2+、Cu2+When M is Fe2+When, A2Fe[Fe(CN)6]The film is directly grown on the surface of the conductive substrate by a hydrothermal method; when M is non-Fe2+When, A2M[Fe(CN)6]The thin film is coated on the surface of the conductive substrate by a spin coating method. The Prussian white film and the Prussian-like white film prepared by the preparation method have good stability, strong bonding force with a transparent conductive substrate and good cycle stability. The film prepared by the preparation method has rich color change.
Description
Technical Field
The invention relates to the technical field of preparation of Prussian white and analogue materials thereof, in particular to a preparation method of an electrochromic Prussian white and analogue thin film thereof.
Background
Prussian albino compound with the molecular formula of A2Fe[Fe(CN)6]·nH2O (n is stoichiometric ratio). A praclase lushi albino compound with a molecular formula of A2M[Fe(CN)6]·nH2O wherein A is Li+、Na+、K+Alkali metal ions, M is transition metal ions such as Co, Ni, Mn, Zn, Cu, etc. The structure of the color filter is a three-dimensional network structure, and the oxidation state and the reduction state of the color filter can present different colors. Because the electrochemical reversibility is good, the stability is high, the preparation cost is low, and the preparation method can quickly generate an interactive reaction with alkali metal ions in a solution. Therefore, the prussian whitening compound is widely used in the field of secondary batteries.
Because the prussian white and the analogues thereof show different colors in an oxidation state and a reduction state, the prussian white and the analogues thereof are expressed by Na2Fe[Fe(CN)6]For example, the resulting film was colorless and transparent. When a Na+When the film is removed, the film becomes Prussian blue, and the film is blue; when there are two Na+When removed, it becomes Berlin green or PY (the difference between them is Fe3+The content of (a) in (b), wherein the color of the berlin green film is green and the color of the PY film is yellow, such materials can also be used in the field of electrochromism. Nowadays, in order to pursue beauty, a building uses glass as a wall body in a large area, most of indoor and outdoor energy exchange is carried out on a window, and then the requirement of a light source entering the building through the window regulation is very important, so that the electrochromic intelligent window walks into the visual field of people. The electrochromic material can be applied to intelligent windows, low-energy consumption display directions such as advertising boards, military directions such as infrared stealth airplanes and the like. The preparation method of prussian white and the like has been extensively studied but is mostly used in the direction of secondary batteries.
Disclosure of Invention
The invention aims to provide a preparation method of an electrochromic Prussian white film and an electrochromic Prussian white analogue film, which is simple and convenient in preparation process, easy to adjust, and good in circulation stability and high in response speed.
The scheme adopted by the invention for realizing the purpose is as follows: a method for preparing electrochromic Prussian white and its analogue film is disclosed, the Prussian white and its analogue are A2M[Fe(CN)6]Wherein A is Li+、Na+、K+M is Fe2+、Co2+、Ni2+、Mn2+、Zn2+、Cu2+When M is Fe2+When, A2Fe[Fe(CN)6]The film is directly grown on the surface of the conductive substrate by a hydrothermal method; when M is non-Fe2+When, A2M[Fe(CN)6]The thin film is coated on the surface of the conductive substrate by a spin coating method.
Preferably, preparation A by hydrothermal method2Fe[Fe(CN)6]The specific steps of the film are as follows:
a1, mixing ferrocyanide, ascorbic acid, a reducing agent, an alkali metal salt and water to obtain a precursor solution;
a2, placing a conductive substrate into the precursor solution obtained in the step (1), placing the conductive substrate with the conductive surface facing downwards, carrying out hydrothermal reaction at 80-130 ℃, cooling to room temperature after the reaction is finished, taking out the conductive substrate, washing and drying to obtain the conductive substrate A2Fe[Fe(CN)6]Prussian white film.
Preferably, in the step a1, ferrocyanide is sodium ferrocyanide or potassium ferrocyanide; the reducing agent is any one of glucose, oxalic acid and citric acid; the alkali metal salt is sodium salt or potassium salt.
Preferably, in the step A1, the concentration of the alkali metal salt in the precursor solution is more than 0.1mol/L, the concentration of the ferrocyanide is 2mmol/L-100mmol/L, and the mass ratio of the ascorbic acid to the ferrocyanide is 0.5: 1-5: 1; the molar ratio of the reducing agent to the ferrocyanide is 2: 1-10: 1.
Preferably, in the step A2, the hydrothermal reaction time is 0.1-72 h.
Preferably, in the step a2, the obtained prussian white surface structure is a cubic structure.
Preferably, spin coating method is used to prepare A2M[Fe(CN)6]The specific steps of the film are as follows:
b1, dissolving alkali metal salt and ferrocyanide in water to obtain solution A; mixing MCl2Alkali metal salt and complexing agent are dissolved in water to be used as solution B, wherein M is Fe2+、Co2+、Ni2+、Mn2+、Zn2+、Cu2+Any one of the above;
b2, dropwise adding the solution B into the solution A, stirring while adding under the condition of room temperature, reacting for a period of time, and then centrifuging, washing and drying to obtain prussian-like white solid powder;
b3, dispersing Prussian-like white solid powder into water at room temperature, filtering to remove particles with particle size larger than 1 μm to obtain pre-coating solution, uniformly coating the pre-coating solution on a transparent conductive substrate, and annealing at 90-120 deg.C to obtain A2M[Fe(CN)6]Prussian-like white films.
Preferably, in the step B1, ferrocyanide is sodium ferrocyanide or potassium ferrocyanide; the alkali metal salt is sodium salt or potassium salt, and the complexing agent is any one of sodium citrate, EDTA and sodium oxalate; the concentration of the alkali metal salt in the solution A and the solution B is more than 0.1mol/L, the concentration of the ferrocyanide in the solution A is 10mmol/L-100mmol/L, and the molar ratio of the complexing agent to the M atom in the solution B is 1: 1-2: 1.
Preferably, in the step B2, ferrocyanide and MCl2The mass ratio of (a) to (b) is 1:1 to 2: 1.
Preferably, in the step B3, the concentration of the Prussian-like white powder in the pre-coating liquid is 10-100 mg/mL.
The reaction mechanism for preparing the Prussian white film is as follows: under hydrothermal conditions, partially [ Fe (CN) ]6]4-Dissociation of Fe2+The reducing agent can inhibit Fe2+Is oxidized into Fe3+. Then Fe2+With the remainder [ Fe (CN)6]4-And Na+Combined to form a Prussian white film, anA prussian white film was grown on the conductive substrate.
The invention has the following advantages and beneficial effects:
1. the invention provides a method for preparing a Prussian white film and a Prussian-like white film.
2. The Prussian white film and the Prussian-like white film prepared by the preparation method have good stability, strong bonding force with a transparent conductive substrate and good cycle stability.
3. The film prepared by the preparation method has rich color change.
4. The preparation method disclosed by the invention is simple, low in reaction condition, low in cost, non-toxic, harmless and environment-friendly, and the obtained Prussian white film and the Prussian-like white film which are good in circulation stability and high in response speed can be applied to the field of electrochromism.
Drawings
Fig. 1 is an XRD pattern of prussian white film prepared by example 1 of the present invention;
FIG. 2 is a cyclic voltammogram (a) and a response time plot (b) of a Prussian white film prepared in example 2 of the present invention;
FIG. 3 shows a response time curve (a) and a transmitted light spectrum (b) of a Prussian white film prepared in example 3 of the present invention;
FIG. 4 shows a response time curve (a) and a transmitted light spectrum (b) of a Prussian white film prepared in example 4 of the present invention;
fig. 5 is an SEM image of the Ni-based prussian white film prepared by example 5 of the present invention;
fig. 6 is a response time curve of the Co-based prussian white film prepared by example 6 of the present invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
A preparation method of a Prussian white film for electrochromism comprises the following steps:
(1) 0.17g of sodium ferrocyanide, 0.85g of ascorbic acid, 0.14g of citric acid and 10.5g of sodium chloride were dissolved in 60mL of deionized water.
(2) Transferring the solution obtained in the step (1) to a polytetrafluoroethylene reaction kettle core of 100mL, putting a piece of ITO glass of 1cm multiplied by 2cm into the reaction kettle with the conductive surface facing downwards, putting the reaction kettle into an oven at 100 ℃ for reaction for 9 hours, and naturally cooling to room temperature.
(3) And (3) taking out the ITO glass after the reaction in the step (2), washing with deionized water, and drying in a vacuum drying oven to obtain the Prussian white film, wherein an XRD spectrogram of the Prussian white film is shown in figure 1.
Example 2
(1) 0.17g of sodium ferrocyanide, 0.17g of ascorbic acid, 0.63g of glucose and 10.50g of sodium chloride were dissolved in 60mL of deionized water.
(2) Transferring the solution obtained in the step (1) to a 100mL polytetrafluoroethylene reaction kettle core, putting a piece of ITO glass of 1cm multiplied by 2cm into the reaction kettle with the conductive surface facing downwards, putting the reaction kettle into an oven at 110 ℃ for reacting for 6h, and naturally cooling to room temperature.
(3) And (3) taking out the ITO glass after the reaction in the step (2), washing with deionized water, and drying in a vacuum drying oven to obtain the Prussian white film.
The Prussian white film prepared in the example is tested in a three-electrode system, and the electrolyte is 1M NaClO4and/PC. FIG. 2(a) is a cyclic voltammetry curve of the Prussian white film prepared in this example, and it can be seen from the graph that after the cycle number reaches 600 cycles, the film still has good reversibility, so the stability of the film is good; fig. 2(b) is a response time curve of the prussian white film of this example, from which it can be seen that the coloring response time of the film is 1.4s, the fading response time is 1.5s, and after 100 cycles, both the coloring response time and the fading response time are 1.8 s.
Example 3
(1) 0.17g of sodium ferrocyanide, 0.51g of ascorbic acid, 0.03g of oxalic acid and 5.23g of sodium chloride were dissolved in 60mL of deionized water.
(2) Transferring the solution obtained in the step (1) to a 100mL polytetrafluoroethylene reaction kettle core, putting a piece of ITO glass with the conductivity facing downwards, placing the ITO glass into an oil bath kettle with the temperature of 80 ℃ for reaction for 6 hours, and naturally cooling to room temperature.
(3) And (3) taking out the ITO glass after the reaction in the step (2), washing with deionized water, and drying in a vacuum drying oven to obtain the Prussian white film.
The Prussian white film prepared in the example is tested in a three-electrode system, and the electrolyte is 1MNaClO4and/PC. Fig. 3(a) is a response time curve of the prussian white film prepared in this example. Respectively applying a voltage of-0.3V and a voltage of 0.4V for 30s to the film, wherein the initial coloring response time is 2.9s, the fading response time is 5.1s, the coloring response time is 2.9s after the film is cycled for 100 circles, the fading response time is slightly shortened to 4.7s, and the response time is unchanged after the film is cycled for 200 circles; fig. 3(b) is a transmission spectrum of the prussian white film prepared in this example, voltages of-0.3V, 0.4V and 1.3V are applied to the prussian white film for 30s respectively, and then an ultraviolet-visible spectrophotometer is used to test the transmittance of the film in the visible wavelength range in different states, as can be seen from the graph, the light modulation amplitude is 58.8% when the film is converted between prussian white and prussian blue; the amplitude of the light modulation when the film was switched between prussian white and PY was 48%.
Example 4
(1) 0.17g of sodium ferrocyanide, 0.17g of ascorbic acid, 0.72g of glucose and 3.5g of sodium chloride were dissolved in 60mL of deionized water.
(2) Transferring the solution obtained in the step (1) to a polytetrafluoroethylene reaction kettle core of 100mL, putting a piece of ITO glass of 1cm multiplied by 2cm into the reaction kettle with the conductive surface facing downwards, putting the reaction kettle into an oven at 130 ℃ for reacting for 6h, and naturally cooling to room temperature.
(3) And (3) taking out the ITO glass after the reaction in the step (2), washing with deionized water, and drying in a vacuum drying oven to obtain the Prussian white film.
The Prussian white film prepared in the example is placed on a three-electrodeThe test is carried out in an aqueous electrolyte under the system, and the electrolyte is 1MNa2SO4An aqueous solution. Fig. 4(a) is a response time curve of the prussian white film prepared in this example. Respectively applying a voltage of-0.1V and a voltage of 0.2V for 30s to the film, wherein the initial coloring response time is 1.3s, the fading response time is 0.9s, and after 100 cycles, the coloring response time is 1.3s and the fading response time is 1.1 s; fig. 4(b) is a transmission spectrum of the prussian white film prepared in this example, voltages of-0.1V and 0.2V are applied to the prussian white film for 30s respectively, and then an ultraviolet-visible spectrophotometer is used to test the transmittance of the film in the visible wavelength range in different states, and it can be seen from the graph that the light modulation amplitude of the film is 35.6%.
Example 5
(1) Dissolving 4.84g of sodium ferrocyanide and 11.69g of sodium chloride in 100mL of water to obtain a solution A; 1.29g of nickel chloride, 11.69g of sodium chloride and 5.88g of sodium citrate were dissolved in 100mL of water to obtain solution B.
(2) Dropwise adding the solution B in the step (1) into the solution A, stirring at room temperature while dropwise adding, and continuing stirring for 4 hours after dropwise adding.
(3) And (3) centrifuging, washing and vacuum drying the liquid after the reaction in the step (2) to obtain the nickel-based Prussian white powder.
(4) And (3) weighing 0.25g of nickel-based Prussian white powder obtained in the step (3), dispersing in 10mL of water, carrying out ultrasonic treatment for 2 hours, continuing stirring for 1 day, and filtering to remove particles with the particle size of more than 1 mu m.
(5) And (4) carrying out spin coating on the filtrate obtained in the step (4), wherein the parameters of a spin coater are 1000rpm and 90s, and carrying out annealing treatment at 100 ℃ for three times.
Fig. 5 is an SEM picture of the resulting nickel-based prussian white film.
Example 6
(1) Dissolving 4.84g of sodium ferrocyanide and 11.69g of sodium chloride in 100mL of water to obtain a solution A; 0.12g of cobalt chloride, 11.69g of sodium chloride and 2.62g of sodium citrate were dissolved in 100mL of water to obtain solution B.
(2) Dropwise adding the solution B in the step (1) into the solution A, stirring while dropwise adding at room temperature, and continuing stirring for 5 hours after dropwise adding is finished.
(3) And (3) centrifuging, washing and vacuum drying the liquid after the reaction in the step (2) to obtain the nickel-based Prussian white powder.
(4) And (3) weighing 500mg of nickel-based Prussian white powder obtained in the step (3), dispersing the nickel-based Prussian white powder in 10mL of water, carrying out ultrasonic treatment for 2 hours, then continuing stirring for 1 week, and then filtering large particles by using filter paper with the pore diameter of 0.2 mu m.
(5) And (4) carrying out spin coating on the filtrate obtained in the step (4), wherein the parameters of a spin coater are 2000rpm and 60s, and carrying out annealing treatment at 100 ℃ for three times.
FIG. 6 is a response time curve of the cobalt-based Prussian white film of this example, from which it can be seen that the coloration response time and the fading response time of the film are 3.3s and 3.8s, respectively.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A preparation method of a Prussian bletilla striata and analogue thin film thereof for electrochromism is characterized in that: the Prussian white and the analogues thereof are A2M[Fe(CN)6]Wherein A is Li+、Na+、K+M is Fe2+、Co2+、Ni2+、Mn2 +、Zn2+、Cu2+When M is Fe2+When, A2Fe[Fe(CN)6]The film is directly grown on the surface of the conductive substrate by a hydrothermal method; when M is non-Fe2+When, A2M[Fe(CN)6]The thin film is coated on the surface of the conductive substrate by a spin coating method.
2. The method for preparing prussian and its analogues film for electrochromism according to claim 1, wherein said prussian and its analogues film are prepared by said methodIn hydrothermal preparation of A2Fe[Fe(CN)6]The specific steps of the film are as follows:
a1, mixing ferrocyanide, ascorbic acid, a reducing agent, an alkali metal salt and water to obtain a precursor solution;
a2, placing a conductive substrate into the precursor solution obtained in the step (1), placing the conductive substrate with the conductive surface facing downwards, carrying out hydrothermal reaction at 80-130 ℃, cooling to room temperature after the reaction is finished, taking out the conductive substrate, washing and drying to obtain the conductive substrate A2Fe[Fe(CN)6]Prussian white film.
3. The method for preparing the prussian and analogue films for electrochromism according to claim 2, which is characterized in that: in the step A1, ferrocyanide is sodium ferrocyanide or potassium ferrocyanide; the reducing agent is any one of glucose, oxalic acid and citric acid; the alkali metal salt is sodium salt or potassium salt.
4. The method for preparing the prussian and analogue films for electrochromism according to claim 2, which is characterized in that: in the step A1, the concentration of alkali metal salt in the precursor solution is more than 0.1mol/L, the concentration of ferrocyanide is 2mmol/L-100mmol/L, and the mass ratio of ascorbic acid to ferrocyanide is 0.5: 1-5: 1; the molar ratio of the reducing agent to the ferrocyanide is 2: 1-10: 1.
5. The method for preparing the prussian and analogue films for electrochromism according to claim 2, which is characterized in that: in the step A2, the hydrothermal reaction time is 0.1-72 h.
6. The method for preparing the prussian and analogue films for electrochromism according to claim 2, which is characterized in that: in the step A2, the obtained Prussian white surface structure is a cubic structure.
7. The method for electrochromic Prussian white and its analogue film according to claim 1The preparation method is characterized in that the spin coating method is used for preparing A2M[Fe(CN)6]The specific steps of the film are as follows:
b1, dissolving alkali metal salt and ferrocyanide in water to obtain solution A; mixing MCl2Alkali metal salt and complexing agent are dissolved in water to be used as solution B, wherein M is Fe2+、Co2+、Ni2+、Mn2+、Zn2+、Cu2+Any one of the above;
b2, dropwise adding the solution B into the solution A, stirring while adding under the condition of room temperature, reacting for a period of time, and then centrifuging, washing and drying to obtain prussian-like white solid powder;
b3, dispersing Prussian-like white solid powder into water at room temperature, filtering to remove particles with particle size larger than 1 μm to obtain pre-coating solution, uniformly coating the pre-coating solution on a transparent conductive substrate, and annealing at 90-120 deg.C to obtain A2M[Fe(CN)6]Prussian-like white films.
8. The method for preparing the prussian and analogue films for electrochromism according to claim 7, wherein the method comprises the following steps: in the step B1, ferrocyanide is sodium ferrocyanide or potassium ferrocyanide; the alkali metal salt is sodium salt or potassium salt, and the complexing agent is any one of sodium citrate, EDTA and sodium oxalate; the concentration of the alkali metal salt in the solution A and the solution B is more than 0.1mol/L, the concentration of the ferrocyanide in the solution A is 10mmol/L-100mmol/L, and the molar ratio of the complexing agent to the M atom in the solution B is 1: 1-2: 1.
9. The method for preparing the prussian and analogue films for electrochromism according to claim 7, wherein the method comprises the following steps: in the step B2, ferrocyanide and MCl2The mass ratio of (a) to (b) is 1:1 to 2: 1.
10. The method for preparing the prussian and analogue films for electrochromism according to claim 7, wherein the method comprises the following steps: in the step B3, the concentration of the Prussian-like white powder in the precoating liquid is 10-100 mg/mL.
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