CN110129850B - Stepwise deposition preparation method of ferric ferrocyanide film - Google Patents

Stepwise deposition preparation method of ferric ferrocyanide film Download PDF

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CN110129850B
CN110129850B CN201910355440.1A CN201910355440A CN110129850B CN 110129850 B CN110129850 B CN 110129850B CN 201910355440 A CN201910355440 A CN 201910355440A CN 110129850 B CN110129850 B CN 110129850B
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颜悦
付子怡
韦友秀
陈牧
马一博
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AECC Beijing Institute of Aeronautical Materials
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Abstract

The invention relates to a step-by-step deposition preparation method of a ferrous cyanide film, which comprises the following steps of: preparing a precursor solution; preparing before deposition; a deposition process; and (4) step-by-step deposition. The invention provides an electrochemical deposition method applied to an iron ferrocyanide film, which is used for obtaining a Prussian blue film with uniform thickness, smooth surface and thicker thickness in the deposition process; the operation is simple during deposition, expensive experimental equipment is omitted, and the film coating cost is reduced.

Description

Stepwise deposition preparation method of ferric ferrocyanide film
Technical Field
The invention belongs to the electrochromic film preparation technology, and relates to a step-by-step deposition preparation method of an iron ferrocyanide film.
Background
Electrochromic (EC) materials are characterized by a change in the optical properties of the material driven by an external voltage through an electrochemical redox reaction. The function of the electrochromic material enables the electrochromic material to be applied to many fields, such as intelligent windows, automobile anti-dazzle rearview mirrors, high contrast displays and the like, and research in the field of devices promotes the development of electrochromic technology.
Electrochromic (EC) materials fall into two broad categories: inorganic materials and organic materials. The organic electrochromic material is easy to carry out molecular design, rich in color, high in color change speed and wide in absorption wavelength range, but is unstable in chemical property, poor in water oxygen and ultraviolet resistance, complex to prepare and high in cost. The inorganic electrochromic material has the advantages of stable structure, low color change speed, little influence of water and oxygen in the air, almost no influence of sunlight ultraviolet rays, and good weather resistance, and is widely concerned by people.
Prussian Blue (PB) is an inorganic EC material, which is a mixed-valence complex of formula MI x[MII y(CN)6]. For PB, MI，MIIIs an ion of two valence states of Fe (Fe)2+，Fe3+) Under different redox voltages, PB can be converted among Prussian brown (PX), Prussian Green (PG), Prussian Blue (PB) and Prussian White (PW), the color is converted among brown, green, blue and colorless, PX is obtained under the condition that PB is completely oxidized and is in an irreversible state, reversible conversion between PB blue and colorless is mainly utilized in practical application, and the novel high-performance solid oxide polymer has the characteristics of high response speed and high cycle stabilityThe process of oxidation-reduction is as follows:
[FeIIIFeII(CN)6]-(PB)→FeIII[{FeIII(CN)6}2/3{FeII(CN)6}1/3]1/3-(PG)+2/3e-
[FeIIIFeII(CN)6]-(PB)→[FeIIIFeIII(CN)6]0(PX)+e-
[FeIIIFeII(CN)6]-(PB)→[FeIIFeII(CN)6]2-(PW)-e-
there are many methods for preparing PB films, for example spray pyrolysis method can prepare Prussian blue films with good reversibility, see "A simple chemical method for displacement of electrochemical Prussian blue films", Demiri S, Najdoski M, Velevska J. et al, Materials research Bulletin, 2011 46, P.2484. The Prussian blue nano-film with uniform surface can be prepared by a constant potential electrodeposition method, which is referred to as Visible photochemical sensing film by in situ generated CdSquantum dots purified branched-TiO2nanorowed with Prussian blue electrochemical display, Yanhu Wanga, Shengueng Gea et al, Biosensors and Bioelements, 89 2017, P.859. PB films with good adhesion to substrates can be prepared by hydrothermal method, see "electrochromism properties of hydrothermally grown plasma film and device", Qian J, Ma D, Xu Z et al, Solar Energy Materials&Solar Cells, stage 177 2018, P.9. The disadvantages of the above preparation method are: the PB film prepared by the spray pyrolysis method has low optical contrast; the PB film prepared by the constant voltage deposition method and the hydrothermal method has rough surface and uneven thickness.
Disclosure of Invention
The purpose of the invention is: the electrochemical deposition method applied to the electrochromic PB film is provided, and the technical problems of uneven thickness and unsmooth surface caused by the increase of the thickness of the electrochromic PB film in the deposition process are solved, and particularly, when the thickness of the electrochromic PB film is increased to more than 200nm, preferably more than 250nm, the extreme unevenness of the thickness and the roughness of the surface are solved.
The technical scheme of the invention is as follows: a method for preparing a ferrous cyanide film by step deposition, wherein the thickness of the potassium ferricyanide film is more than 200nm, particularly more than 250nm, and the steps of electrodeposition are as follows:
step 1, preparation of precursor solution: dissolving a certain amount of potassium ferricyanide powder and ferric trichloride powder in deionized water to form a precursor solution, wherein the concentration of the potassium ferricyanide is 0.005-0.5 mol/L, the concentration of the ferric trichloride is 0.005-0.5 mol/L, and adding hydrochloric acid, wherein the concentration of the added hydrochloric acid is 0.002-0.9 mol/L; the hydrochloric acid is added, so that the size of precipitated particles in the solution can be effectively reduced, and the ferric ferrocyanide particles are prevented from being rapidly polymerized and precipitated;
step 2, preparation before deposition: placing the precursor solution in an electrolytic bath, immersing a substrate plated with a transparent conducting layer, a counter electrode and a reference electrode into the precursor solution, wherein the substrate plated with the transparent conducting layer is a working electrode, the substrate plated with the transparent conducting layer is connected with the negative electrode of an electrolytic power supply, the counter electrode is connected with the positive electrode of the electrolytic power supply, the counter electrode is an electrode plated with an ITO transparent conducting layer, a platinum electrode, an aluminum foil electrode, a stainless steel electrode or a graphite electrode, a silver wire or a platinum wire is used as the reference electrode, and the reference electrode is arranged between the working electrode and the counter electrode;
step 3, step-by-step deposition process: and applying direct current voltage between the substrate plated with the transparent conductive layer and the counter electrode to carry out multiple times of electrodeposition, wherein the single deposition time is not more than 10s, the direct current voltage is not more than-1V, and the times are carried out until the target thickness is reached.
Further, in the step 3, the transparent conductive substrate is taken out after each time, washed by deionized water until the residual precursor solution on the surface is cleaned, and then naturally dried in the air.
Further, the direct current voltage is-0.01V to-1V.
Further, the transparent conductive layer in the substrate plated with the transparent conductive layer is an ITO material or an FTO material.
Further, the concentration of potassium ferricyanide in the precursor solution in the step 1 is 0.005-0.5 mol/L.
Further, the concentration of ferric trichloride in the precursor solution in the step 1 is 0.005-0.5 mol/L.
Furthermore, the concentration of the hydrochloric acid in the step 1 is 0.005-0.5 mol/L.
Further, the single deposition time is 1 s-5 s. Preferably 1 s.
Further, the ratio of the number of times of deposition to the deposition time is not less than 1.5 times/second.
The invention has the advantages that: providing an electrochemical deposition method applied to an electrochromic PB film, and obtaining the PB film with uniform thickness, smooth surface and thicker thickness in the deposition process; the operation is simple during deposition, expensive experimental equipment is omitted, and the film coating cost is reduced.
Detailed Description
The present invention is described in further detail below. A step-by-step deposition preparation method of a ferrocyanide film comprises the following steps of electrodeposition:
example 1
1. Preparing a precursor solution: dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, wherein the concentration of potassium ferricyanide is 0.005-0.5 mol/L, and the concentration of ferric trichloride is 0.005-0.5 mol/L, and then adding hydrochloric acid, wherein the concentration of hydrochloric acid is 0.005-0.5 mol/L;
2. preparation before deposition: placing the precursor solution in an electrolytic bath, immersing a substrate plated with a transparent conductive layer, a counter electrode and a reference electrode into the precursor solution, wherein the substrate plated with the transparent conductive layer is connected with the negative electrode of a power supply, the counter electrode is connected with the positive electrode of the power supply, the counter electrode is an ITO transparent conductive layer, a platinum electrode, an aluminum foil electrode, a stainless steel electrode or a graphite electrode, and a silver wire or a platinum wire is used as the reference electrode and is placed between the two electrodes;
3. the distributed deposition process comprises the following steps: applying a direct current voltage of-0.01V to-1V between the substrate plated with the transparent conducting layer and the counter electrode at normal temperature for electrodeposition, wherein the deposition time is 1s to 10 s; and (3) taking out the transparent conductive substrate after each deposition, washing with deionized water until the residual precursor solution on the surface is cleaned, naturally airing in the air, continuously putting the transparent conductive substrate into the precursor solution, and repeating for 3 times to increase the thickness of the film until the target thickness is reached.
Example 2
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.025mol/L potassium ferricyanide, 0.025mol/L ferric trichloride and 0.025mol/L hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, depositing for two times, taking out the transparent conductive substrate after the first deposition, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, then putting the transparent conductive substrate into the air for naturally airing, and then continuously putting the transparent conductive substrate into the precursor solution to obtain the PB film with the thickness of 250-350 nm.
Example 3
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.025mol/L potassium ferricyanide, 0.025mol/L ferric trichloride and 0.025mol/L hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 2 times to obtain the PB film with the thickness of 500-600 nm.
Example 4
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.025mol/L potassium ferricyanide, 0.025mol/L ferric trichloride and 0.025mol/L hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 3 times to obtain the PB film with the thickness of 600-700 nm.
Example 5
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.025mol/L potassium ferricyanide, 0.025mol/L ferric trichloride and 0.025mol/L hydrochloric acid. And taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into the precursor solution together, applying a constant deposition voltage of-0.01V for 5s, taking out the transparent conductive substrate after deposition once, washing the transparent conductive substrate in a water tank until the residual precursor solution on the surface is cleaned, and naturally airing the transparent conductive substrate in the air to obtain the PB film with the thickness of 400-500 nm.
Example 6
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.0125mol/L of potassium ferricyanide, 0.0125mol/L of ferric trichloride and 0.0125mol/L of hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 2 times to obtain the PB film with the thickness of 200 nm.
Example 7
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.0125mol/L of potassium ferricyanide, 0.0125mol/L of ferric trichloride and 0.0125mol/L of hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 3 times to obtain the PB film with the thickness of 200-270 nm.
Example 8
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.0125mol/L of potassium ferricyanide, 0.0125mol/L of ferric trichloride and 0.0125mol/L of hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 4 times to obtain the PB film with the thickness of 270-350 nm.
Example 9
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.0125mol/L of potassium ferricyanide, 0.0125mol/L of ferric trichloride and 0.0125mol/L of hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 5 times to obtain the PB film with the thickness of 500-650 nm.
Example 10
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing 0.0125mol/L of potassium ferricyanide, 0.0125mol/L of ferric trichloride and 0.0125mol/L of hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, taking a substrate plated with a transparent conductive layer as the working electrode, immersing the platinum sheet and the substrate into a precursor solution together, applying a constant deposition voltage of-0.01V for 1s, taking out the transparent conductive substrate after deposition once, putting the transparent conductive substrate into a water tank for washing until the residual precursor solution on the surface is cleaned, naturally airing the precursor solution in the air, continuously putting the precursor solution into the precursor solution, and repeatedly depositing for 6 times to obtain the PB film with the thickness of 580-650 nm.
Dissolving a certain amount of potassium ferricyanide and ferric trichloride powder in deionized water, and then dropwise adding a proper amount of hydrochloric acid to prepare a precursor solution containing potassium ferricyanide, ferric trichloride and hydrochloric acid. Taking a platinum sheet as a working electrode, a silver wire as a reference electrode, and a substrate plated with an ITO transparent conductive layer as the working electrode, and immersing the platinum sheet, the silver wire and the substrate into a precursor solution together, wherein the specific parameters are as follows
Figure BDA0002045272760000051
Figure BDA0002045272760000061

Claims (10)

1. A step-by-step deposition preparation method of a ferrous cyanide film is disclosed, wherein the thickness of the potassium ferricyanide film is more than 200nm, and the steps of electrodeposition are as follows:
step 1, preparation of precursor solution: dissolving potassium ferricyanide powder and ferric trichloride powder in deionized water to form a precursor solution, wherein the concentration of the potassium ferricyanide is 0.005-0.5 mol/L, the concentration of the ferric trichloride is 0.005-0.5 mol/L, and adding hydrochloric acid, wherein the concentration of the added hydrochloric acid is 0.002-0.9 mol/L;
step 2, preparation before deposition: placing the precursor solution in an electrolytic bath, immersing a substrate plated with a transparent conducting layer, a counter electrode and a reference electrode into the precursor solution, wherein the substrate plated with the transparent conducting layer is a working electrode, the substrate plated with the transparent conducting layer is connected with the negative electrode of an electrolytic power supply, the counter electrode is connected with the positive electrode of the electrolytic power supply, the counter electrode is an electrode plated with an ITO transparent conducting layer, a platinum electrode, an aluminum foil electrode, a stainless steel electrode or a graphite electrode, a silver wire or a platinum wire is used as the reference electrode, and the reference electrode is arranged between the working electrode and the counter electrode;
step 3, step-by-step deposition process: applying direct current voltage between the substrate plated with the transparent conducting layer and the counter electrode to carry out multiple times of electrodeposition, wherein the single deposition time does not exceed 10s, the direct current voltage does not exceed-1V, and the times are carried out until the target thickness is reached; and taking out the transparent conductive substrate after each single deposition, washing with deionized water until the residual precursor solution on the surface is cleaned, and then naturally airing in the air.
2. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the thickness of the potassium ferricyanide film is more than 250 nm.
3. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the single deposition time is 1 s-5 s.
4. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the direct current voltage is-0.01V to-1V.
5. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the transparent conducting layer in the substrate plated with the transparent conducting layer is made of ITO materials or FTO materials.
6. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the concentration of potassium ferricyanide in the precursor solution in the step 1 is 0.005-0.5 mol/L.
7. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the concentration of ferric trichloride in the precursor solution in the step 1 is 0.005-0.5 mol/L.
8. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the concentration of the hydrochloric acid in the step 1 is 0.005-0.5 mol/L.
9. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the ratio of the deposition times to the deposition time is not less than 1.5 times/second.
10. The method according to claim 1, wherein the step-by-step deposition of the ferric ferrocyanide film comprises: the single deposition time was 1 s.
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