Method for preparing conductive substance modified material layer, conductive glass electrode, conductive glass and dynamic window

Abstract

The present invention relates to the field of conductive materials and electrochromic technology, and in particular to a method for preparing a conductive material modified material layer, a conductive glass electrode, a conductive glass and a dynamic window. The preparation method comprises the following steps: performing plasma treatment, silanization reaction and polymerization reaction on indium tin oxide conductive glass, and finally adsorbing palladium ions as a catalyst through a polymer layer, thereby forming a more uniform catalyst layer on the surface, thereby effectively reducing the voltage difference between the center and the edge of the Pd-ITO conductive layer, thereby achieving a good metal deposition effect, and being able to well realize the transparent and opaque state conversion, and uniform and rapid deposition of metals at the center and the edge. In addition, the problems of raw material agglomeration and instability can be avoided, and the method has the advantages of low raw material cost, short preparation time, high preparation efficiency, simple and fast process, and is conducive to commercialization. The method can be well applied as an electric glass electrode and applied to the preparation of conductive glass and dynamic windows.

Description

Technical Field

[0001] The present invention relates to the technical field of conductive materials and electrochromic technology, and in particular to a method for preparing a conductive substance modified material layer, a conductive glass electrode, conductive glass and a dynamic window. Background Art

[0002] Dynamic windows are a type of window technology that automatically adjusts light transmittance based on environmental changes. These windows can switch between transparent and opaque states within a minute. They consist of two panes of glass sandwiching a conductive material whose light transmittance is controlled by an electric current. Dynamic windows have broad application prospects, particularly in improving building energy efficiency. They can automatically adjust light transmittance based on ambient light, reducing energy consumption while providing a more comfortable indoor environment. In the future, dynamic windows are expected to be used in more buildings, particularly in locations requiring precise control of light and temperature.

[0003] At present, metal electrodeposition dynamic windows require that the surface of the transparent conductive glass electrode has stability, conductive uniformity, more binding sites and free energy gain, etc. In order to achieve rapid dual-state switching in large-scale applications, the center and edge of the transparent conductive glass electrode must have good conductivity. At present, most of the modifications of transparent conductive glass in dynamic windows are based on electrochromic windows, which include the use of physical coating, chemical or electrochemical polymerization to coat conductive polymers on the ITO substrate of the conductive glass to prepare an electrochromic layer. However, this coated polymer film has problems such as low mechanical strength, easy breakage, hydrolysis instability, strong dependence on reaction conditions (such as pH, temperature, etc.), and there are also disadvantages such as weak adsorption between the polymer film and the ITO substrate and easy detachment from the ITO substrate. The above-mentioned shortcomings reduce the stability of the polymer film in the liquid electrolyte and limit its application.

[0004] In addition, for the modification of transparent conductive glass for metal electrodeposition dynamic windows, only Strand et al. have reported so far, in which a layer of 3-mercaptopropionic acid was modified on the ITO of the conductive glass, and then 3nm Pt nanoparticles were adsorbed. However, the existing method for modifying conductive glass ITO has the following disadvantages: (1) It is expensive: the Pt nanoparticle product used is Sigma's 3nm platinum nanoparticle solution, which costs about 4,500 yuan per 25ml; (2) The Pt nanoparticle solution is unstable: the platinum metal particles in the platinum nanoparticle solution used are in a suspension state. When dispersed by solvent, they will agglomerate and settle after being left for a long time, making the solution unusable, which is not conducive to commercialization; (3) The pre-treatment time of this modification method is long: This technology requires ITO to be soaked in 3-mercaptopropionic acid for 24 hours and then soaked in platinum nanoparticle solution for 24 hours; (4) Since the platinum nanoparticles modified on ITO are large in size and poor in uniformity, the voltage difference between the center and edge of the ITO modification layer is large, which is not conducive to the uniform and rapid deposition of the metal layer when applied to dynamic windows, thereby affecting the adjustment conversion of the dynamic windows. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the first purpose of the present invention is to provide a method for preparing a conductive substance modified material layer, which can effectively reduce the voltage difference between the center and the edge of the conductive layer, and has the advantages of low material cost and avoidance of particle agglomeration problems, short preparation time, and simple and quick process.

[0006] In order to overcome the shortcomings of the prior art, the second purpose of the present invention is to provide a conductive glass electrode, which can effectively reduce the voltage difference between the center and the edge of the conductive layer, enable the metal layer to be deposited uniformly and quickly, and has low preparation cost and high preparation efficiency.

[0007] The third object of the present invention is to provide a conductive glass that can effectively reduce the voltage difference between the center and edge of the conductive layer, enable the metal layer to be deposited uniformly and quickly, and has a low preparation cost. It can be well used in the preparation of dynamic windows and has high preparation efficiency, which is conducive to commercialization.

[0008] The fourth object of the present invention is to provide a dynamic window that is more uniform and rapid in switching between transparent and opaque states, and has low production cost and high production efficiency.

[0009] In order to achieve the first object of the above invention, the technical solution adopted by the present invention is as follows:

[0010] The present invention provides a method for preparing a conductive substance modified material layer, comprising the following steps:

[0011] S1. Plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment;

[0012] S2, silanization reaction: immersing the indium tin oxide conductive glass treated in step S1 in an acidic solution containing vinyl silane to perform a surface silanization reaction, and then washing with water and drying;

[0013] S3, polymerization reaction: immersing the indium tin oxide conductive glass that has completed the silanization reaction in step S2 in an aqueous solution containing methacryloyloxyethyltrimethylammonium chloride as an initiator to perform a heating polymerization reaction, and then washing with water and drying;

[0014] S4. Preparation of Pd-ITO conductive layer: Immerse the indium tin oxide conductive glass that has completed the polymerization reaction in step S3 in an aqueous solution of ammonium tetrachloropalladate to perform ion exchange adsorption reaction, and then wash and dry it to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive substance modified material layer.

[0015] The present invention provides a method for preparing a conductive material modified material layer, and the reaction mechanism is as follows: in step S1, plasma treatment is performed on indium tin oxide conductive glass, and then hydroxyl groups (-OH) are introduced on the indium tin oxide layer to make it hydrophilic. The hydroxyl groups participate in the silanization reaction in step S2, and the surface of the indium tin oxide layer is silanized with vinyl silane in an acidic solution, and vinyl groups are introduced through the hydroxyl groups in S1; then, methacryloyloxyethyltrimethylammonium chloride is used to perform an in-situ free radical polymerization reaction with the vinyl groups introduced by silanization, thereby forming a polymer layer on the surface of the indium tin oxide conductive glass; then, an aqueous solution of ammonium tetrachloropalladate is used to perform an ion exchange reaction with the polymer layer on the surface of the indium tin oxide conductive glass, and the Cl groups anchored on the polymer layer of the conductive glass are reacted with the ammonium tetrachloropalladate solution. - Will react with [Pd(Cl)4] 2- Ion exchange was performed to convert [Pd(Cl)4] 2- It is adsorbed on the surface of indium tin oxide conductive glass to produce Pd-ITO conductive glass.

[0016] The present invention discloses a method for preparing a conductive material modified material layer, wherein a polymer layer is formed on the surface of the indium tin oxide conductive glass by plasma treatment, followed by a silanization reaction, and then an in-situ free radical polymerization reaction. The polymer layer finally adsorbs palladium ions as a catalyst. Compared with the prior art in which metal particles are modified on the surface of the indium tin oxide conductive glass, the present application modifies the surface of the indium tin oxide conductive glass with palladium ions. Compared with metal particles, a more uniform catalyst layer can be formed on the surface of the indium tin oxide conductive glass, thereby effectively reducing the voltage difference between the center and the edge of the prepared Pd-ITO conductive layer. On the other hand, since an aqueous solution of ammonium tetrachloropalladate is used when introducing the metal catalyst during the preparation process of the present application, compared with the metal particle suspension used in the prior art, the problems of metal particle agglomeration and suspension instability can be avoided, and the present application also has the advantages of low raw material cost, short preparation time, and simple and quick process.

[0017] Furthermore, in step S1, the plasma cleaning machine performs the plasma treatment for 50 to 70 seconds. This plasma treatment time effectively introduces hydroxyl groups on the surface of the ITO conductive glass. The plasma cleaning machine uses its active particles to chemically react with the surface of the ITO layer of the ITO conductive glass, breaking existing chemical bonds and introducing hydrophilic functional groups such as hydroxyl groups. The introduction of these functional groups significantly increases the hydrophilicity of the ITO conductive glass surface and improves its wettability.

[0018] Furthermore, in step S2, the vinyl silane is vinyl trimethoxy silane or vinyl triethoxy silane, the solvent of the solution is ethanol, and the volume percentage of the vinyl silane in the ethanol is 0.1% to 5%. Vinyl trimethoxy silane or vinyl triethoxy silane is readily soluble in ethanol and has the advantage of low material cost. Furthermore, vinyl trimethoxy silane or vinyl triethoxy silane hydrolyzes the methoxy or ethoxy groups to form bonds with hydroxyl groups on the surface of the indium tin oxide conductive glass, thereby introducing vinyl groups on the surface of the indium tin oxide conductive glass.

[0019] The surface silanization reaction time is 30 min to 70 min. The surface silanization reaction time is short, but sufficient to fully react and well introduce vinyl groups.

[0020] Furthermore, in step S2, the pH of the vinyl silane solution is adjusted to 3-4.5 using glacial acetic acid. Adjusting the vinyl silane solution to an acidic solution using glacial acetic acid can promote the hydrolysis of the vinyl silane during the silanization reaction, thereby bonding the vinyl silane to the surface of the indium tin oxide conductive glass.

[0021] Furthermore, in step S3, the initiator is potassium persulfate, and the concentration of potassium persulfate in the aqueous solution is 0.1 g / L to 3 g / L; wherein, the initiator potassium persulfate can well promote free radical polymerization reaction and has the advantage of low material cost.

[0022] The mass concentration of the methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 5wt% to 25wt%. The aqueous solution of the methacryloyloxyethyltrimethylammonium chloride has good solution stability and cooperates with the aqueous solution of ammonium tetrachloropalladate to effectively avoid the particle agglomeration problem in the prior art.

[0023] Furthermore, in step S3, the heating temperature of the polymerization reaction is 50° C. to 90° C., and the polymerization reaction time is 20 min to 70 min. The polymerization reaction conditions are mild and the reaction time is short.

[0024] Furthermore, in step S4, the mass volume concentration of the ammonium tetrachloropalladate in the aqueous solution is 0.1 g / L to 2 g / L. The amount of ammonium tetrachloropalladate used is small, the material cost is low, and because palladium ions are adsorbed, the problem of particle agglomeration in the prior art can be avoided.

[0025] The ion exchange adsorption reaction time is 30 minutes to 100 minutes. The ion exchange adsorption reaction time is short and has the advantage of high preparation efficiency.

[0026] In order to achieve the second purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0027] The present invention provides a conductive glass electrode. The above-mentioned method for preparing a conductive substance modified material layer is applied to prepare a conductive glass electrode, and the Pd-ITO conductive layer is used as an electrode.

[0028] The conductive glass electrode of the present invention has a Pd-ITO conductive layer, which is prepared by adsorbing palladium ions through a polymer layer and ammonium tetrachloropalladate. Therefore, the voltage difference between the center and the edge of the conductive layer can be effectively reduced, and the metal layer can be deposited uniformly and quickly. The preparation cost is low and the preparation efficiency is high.

[0029] In order to achieve the third purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0030] The present invention provides a conductive glass, and the above-mentioned method for preparing a conductive substance modified material layer is applied to prepare the conductive glass.

[0031] The conductive glass of the present invention is prepared by plasma-treating indium tin oxide conductive glass, performing a silanization reaction, and then performing an in-situ free radical polymerization reaction to form a polymer layer on the surface of the indium tin oxide conductive glass. The polymer layer ultimately adsorbs palladium ions as a catalyst to prepare conductive glass with a Pd-ITO conductive layer. Therefore, the conductive glass can effectively reduce the voltage difference between the center and the edge of the conductive layer, can enable uniform and rapid deposition of the metal layer, has low preparation cost, can be well applied to the preparation of dynamic windows, and has high preparation efficiency, which is conducive to commercialization.

[0032] In order to achieve the fourth object of the above invention, the technical solution adopted by the present invention is as follows:

[0033] The present invention provides a dynamic window, comprising conductive glass modified by the above-mentioned method for preparing a conductive substance modified material layer.

[0034] The dynamic window of the present invention can achieve more uniform and rapid transition between transparent and opaque states, as the conductive glass produced can effectively reduce the voltage difference between the center and edge of the conductive layer, allowing the metal layer to be deposited evenly and quickly. The dynamic window also has low preparation cost and high preparation efficiency.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The present invention provides a method for preparing a conductive material modified layer, wherein a polymer layer is formed on the surface of the indium tin oxide conductive glass by plasma treatment, followed by a silanization reaction, and then an in-situ free radical polymerization reaction. The polymer layer finally adsorbs palladium ions as a catalyst. Compared with the prior art that modifies the surface of the indium tin oxide conductive glass with metal particles, the present invention modifies the surface of the indium tin oxide conductive glass with palladium ions. Compared with metal particles, a more uniform catalyst layer can be formed on the surface of the indium tin oxide conductive glass, thereby effectively reducing the voltage difference between the center and the edge of the prepared Pd-ITO conductive layer. On the other hand, since an aqueous solution of ammonium tetrachloropalladate is used when introducing the metal catalyst during the preparation process of the present invention, compared with the metal particle suspension used in the prior art, the problem of metal particle agglomeration and suspension instability can be avoided. In addition, the present invention has the advantages of low raw material cost, short preparation time, and simple and quick process.

[0037] (2) The present invention provides a method for preparing a conductive material modified material layer. Compared with the platinum nanoparticle solution used in the prior art, the ammonium tetrachloropalladate solution used in the present invention is cheaper at about 180 yuan per 250 mg. The concentration used each time is 1 g / L and the amount used is 20 ml. Therefore, under the same conditions, the price per use is about 15 yuan, which can greatly reduce the cost of applying and preparing dynamic windows.

[0038] (3) The present invention's method for preparing a conductive material-modified layer requires only four steps, and the entire process can be prepared in less than 3 hours. Compared to the prior art, which takes more than 48 hours, the present invention has the advantage of shortened preparation time, significantly improving preparation efficiency and facilitating commercial applications. Furthermore, the entire preparation process is simple and convenient, enabling rapid mass production without the need for complex operational procedures.

[0039] (4) The conductive glass electrode of the present invention is a Pd-ITO conductive layer, which is made by adsorbing palladium ions through a polymer layer and ammonium tetrachloropalladate. It can effectively reduce the voltage difference between the center and edge of the conductive layer, enable the metal layer to be deposited uniformly and quickly, and has low preparation cost and high preparation efficiency.

[0040] (5) The conductive glass of the present invention is a conductive glass that is subjected to plasma treatment and then subjected to a silanization reaction, followed by an in-situ free radical polymerization reaction, so that a polymer layer is formed on the surface of the indium tin oxide conductive glass. The polymer layer finally adsorbs palladium ions as a catalyst to obtain a conductive glass with a Pd-ITO conductive layer. Therefore, the conductive glass can effectively reduce the voltage difference between the center and the edge of the conductive layer, and can enable the metal layer to be uniformly and quickly deposited. The preparation cost is low, and the conductive glass can be well applied to the preparation of dynamic windows. The preparation efficiency is high, which is conducive to commercialization.

[0041] (6) The dynamic window of the present invention can achieve a more uniform and rapid transition between transparent and opaque states because the conductive glass produced can effectively reduce the voltage difference between the center and edge of the conductive layer, allowing the metal layer to be deposited evenly and quickly. The dynamic window has low production cost and high production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0043] Figure 1 Schematic diagram of the preparation process of Example 1 of the present invention.

[0044] Figure 2 Graphs showing copper deposition and adhesion testing of Example 1, Comparative Example 1, and an indium tin oxide conductive glass sample that has not undergone any treatment.

[0045] Figure 3 Schematic diagram of the structure of the device assembled with conductive glass having a Pd-ITO conductive layer prepared in Example 1.

[0046] Figure 4 It is the transmittance of unmodified ITO conductive glass after copper deposition at the center and edge for 180s.

[0047] Figure 5 It is the transmittance of the Pd-ITO conductive glass of Example 1 after copper deposition at the center and edge for 180 seconds. DETAILED DESCRIPTION

[0048] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0049] The terms used in the embodiments of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. In the present invention, the singular forms "a," "an," "the," and "the" used in the embodiments and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0050] In the present invention, the code name ITO refers to indium tin oxide.

[0051] In an embodiment of the present invention, a method for preparing a conductive substance modified material layer includes the following steps:

[0052] S1. Plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment;

[0053] S2, silanization reaction: immersing the indium tin oxide conductive glass treated in step S1 in an acidic solution containing vinyl silane to perform a surface silanization reaction, and then washing with water and drying;

[0054] S3, polymerization reaction: immersing the indium tin oxide conductive glass that has completed the silanization reaction in step S2 in an aqueous solution containing methacryloyloxyethyltrimethylammonium chloride as an initiator to perform a heating polymerization reaction, and then washing with water and drying;

[0055] S4. Preparation of Pd-ITO conductive layer: Immerse the indium tin oxide conductive glass that has completed the polymerization reaction in step S3 in an aqueous solution of ammonium tetrachloropalladate to perform ion exchange adsorption reaction, and then wash and dry it to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive substance modified material layer.

[0056] In the embodiment, a method for preparing a conductive material modified material layer has the following reaction mechanism: in step S1, plasma treatment is performed on indium tin oxide conductive glass, thereby introducing hydroxyl groups (-OH) on the indium tin oxide layer to make it hydrophilic. The hydroxyl groups participate in the silanization reaction in step S2, and the surface of the indium tin oxide layer is silanized with vinyl silane in an acidic solution, and vinyl groups are introduced through the hydroxyl groups in S1; then, methacryloyloxyethyltrimethylammonium chloride and the vinyl groups introduced by silanization are subjected to in-situ free radical polymerization, thereby forming a polymer layer on the surface of the indium tin oxide conductive glass; then, an aqueous solution of ammonium tetrachloropalladate is subjected to an ion exchange reaction with the polymer layer on the surface of the indium tin oxide conductive glass, and the Cl groups anchored in the polymer layer of the conductive glass are anchored. - Will react with [Pd(Cl)4] 2- Ion exchange was performed to convert [Pd(Cl)4] 2- It is adsorbed on the surface of indium tin oxide conductive glass to produce Pd-ITO conductive glass.

[0057] In the embodiment, a method for preparing a conductive material modified material layer is provided, wherein a polymer layer is formed on the surface of the indium tin oxide conductive glass after plasma treatment and then subjected to a silanization reaction, followed by an in-situ free radical polymerization reaction, and the palladium ions used as a catalyst are finally adsorbed by the polymer layer. Compared with the prior art in which metal particles are modified on the surface of the indium tin oxide conductive glass, the present application modifies the surface of the indium tin oxide conductive glass with palladium ions. Compared with metal particles, a more uniform catalyst layer can be formed on the surface of the indium tin oxide conductive glass, thereby effectively reducing the voltage difference between the center and the edge of the prepared Pd-ITO conductive layer. On the other hand, since an aqueous solution of ammonium tetrachloropalladate is used when introducing the metal catalyst during the preparation process of the present application, compared with the metal particle suspension used in the prior art, the problems of metal particle agglomeration and suspension instability can be avoided, and the present application also has the advantages of low raw material cost, short preparation time, and simple and quick process.

[0058] In some embodiments, in step S1, the plasma cleaning machine performs the plasma treatment for 50 to 70 seconds. This plasma treatment time effectively introduces hydroxyl groups onto the surface of the indium tin oxide conductive glass. The plasma cleaning machine uses its active particles to chemically react with the surface of the indium tin oxide layer of the indium tin oxide conductive glass, breaking existing chemical bonds and introducing hydrophilic functional groups such as hydroxyl groups. The introduction of these functional groups significantly increases the hydrophilicity of the indium tin oxide conductive glass surface and improves its wettability.

[0059] In some embodiments, in step S2, the vinyl silane is vinyltrimethoxysilane or vinyltriethoxysilane, the solvent of the solution is ethanol, and the volume percentage of the vinyl silane in the ethanol is 0.1% to 5%. Vinyltrimethoxysilane or vinyltriethoxysilane is readily soluble in ethanol and has the advantage of low material cost. Furthermore, vinyltrimethoxysilane or vinyltriethoxysilane hydrolyzes the methoxy or ethoxy groups to form bonds with hydroxyl groups on the surface of the indium tin oxide conductive glass, thereby introducing vinyl groups on the surface of the indium tin oxide conductive glass.

[0060] The surface silanization reaction time is 30 min to 70 min. The surface silanization reaction time is short, but sufficient to fully react and well introduce vinyl groups.

[0061] In some embodiments, in step S2, the pH of the vinyl silane solution is adjusted to 3 to 4.5 using glacial acetic acid. Adjusting the vinyl silane solution to an acidic state using glacial acetic acid can promote the hydrolysis of the vinyl silane during the silanization reaction, thereby bonding the vinyl silane to the surface of the indium tin oxide conductive glass.

[0062] In some embodiments, in step S3, the initiator is potassium persulfate, and the concentration of potassium persulfate in the aqueous solution is 0.1 g / L to 3 g / L; wherein, the initiator potassium persulfate can well promote free radical polymerization reaction and has the advantage of low material cost.

[0063] The mass concentration of the methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 5wt% to 25wt%. The aqueous solution of the methacryloyloxyethyltrimethylammonium chloride has good solution stability and cooperates with the aqueous solution of ammonium tetrachloropalladate to effectively avoid the particle agglomeration problem in the prior art.

[0064] In some embodiments, in step S3, the heating temperature of the polymerization reaction is 50° C. to 90° C., and the polymerization reaction time is 20 min to 70 min. The polymerization reaction conditions are mild and the reaction time is short.

[0065] In some embodiments, in step S4, the mass volume concentration of the ammonium tetrachloropalladate in the aqueous solution is 0.1 g / L to 2 g / L; the amount of ammonium tetrachloropalladate used is small, the material cost is low, and because palladium ions are adsorbed, the problem of particle agglomeration in the prior art can be avoided.

[0066] The ion exchange adsorption reaction time is 30 minutes to 100 minutes. The ion exchange adsorption reaction time is short and has the advantage of high preparation efficiency.

[0067] In an embodiment of the present invention, a conductive glass electrode is provided. The above-mentioned method for preparing a conductive substance modified material layer is applied to prepare a conductive glass electrode, and the Pd-ITO conductive layer serves as an electrode.

[0068] A conductive glass electrode in the embodiment, since the electrode is a Pd-ITO conductive layer, is made by adsorbing palladium ions through a polymer layer and ammonium tetrachloropalladate, can effectively reduce the voltage difference between the center and edge of the conductive layer, can enable the metal layer to be uniformly and quickly deposited, and has low preparation cost and high preparation efficiency.

[0069] In an embodiment of the present invention, a conductive glass is provided, and the above-mentioned method for preparing a conductive substance modified material layer is applied to prepare the conductive glass.

[0070] A conductive glass in the embodiment is obtained by plasma-treating indium tin oxide conductive glass, performing a silanization reaction, and then performing an in-situ free radical polymerization reaction to form a polymer layer on the surface of the indium tin oxide conductive glass. The polymer layer ultimately adsorbs palladium ions as a catalyst to produce conductive glass with a Pd-ITO conductive layer. Therefore, the conductive glass can effectively reduce the voltage difference between the center and edge of the conductive layer, enable uniform and rapid deposition of the metal layer, and has a low preparation cost. It can be well applied to the preparation of dynamic windows, has high preparation efficiency, and is conducive to commercialization.

[0071] In an embodiment of the present invention, a dynamic window includes conductive glass modified by the above-mentioned method for preparing a conductive substance modified material layer.

[0072] A dynamic window in the embodiment, since the conductive glass produced can effectively reduce the voltage difference between the center and edge of the conductive layer, can make the metal layer deposited evenly and quickly, so the dynamic window is more uniform and rapid when realizing the transition between transparent and opaque states, and has low preparation cost and high preparation efficiency.

[0073] The following describes the details in conjunction with specific embodiments.

[0074] Example 1

[0075] A method for preparing a conductive substance modified material layer comprises the following steps:

[0076] S1, plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment for 60 seconds;

[0077] S2, Silanization reaction: Immerse the indium tin oxide conductive glass treated in step S1 in an ethanol solution containing vinyl trimethoxysilane, add glacial acetic acid to adjust the pH to 3, and then perform a surface silanization reaction for 30 minutes. The indium tin oxide conductive glass after the silanization reaction is then washed with water and dried. In this embodiment, the volume percentage of vinyl trimethoxysilane in ethanol is 5%;

[0078] S3. Polymerization reaction: The indium tin oxide conductive glass that has completed the silanization reaction in step S2 is immersed in an aqueous solution of methacryloyloxyethyltrimethylammonium chloride containing potassium persulfate as an initiator and heated to 50° C. for polymerization reaction for 70 minutes, followed by washing with water and drying with nitrogen gas. In this embodiment, the concentration of potassium persulfate in the aqueous solution is 3 g / L; the mass concentration of methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 25 wt %.

[0079] S4. Preparation of a Pd-ITO conductive layer: The indium tin oxide conductive glass, after the polymerization reaction in step S3, is immersed in an aqueous solution of ammonium tetrachloropalladate for 100 minutes of ion exchange adsorption reaction. The layer is then washed with water and dried with nitrogen to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive material modified layer. In this embodiment, the mass volume concentration of ammonium tetrachloropalladate in the aqueous solution is 0.6 g / L.

[0080] Example 2

[0081] A method for preparing a conductive substance modified material layer comprises the following steps:

[0082] S1, plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment for 50 seconds;

[0083] S2, Silanization reaction: Immerse the indium tin oxide conductive glass treated in step S1 in an ethanol solution containing vinyl triethoxysilane, add glacial acetic acid to adjust the pH to 3.5, and then perform a surface silanization reaction for 45 minutes. The indium tin oxide conductive glass after the silanization reaction is then washed with water and dried. In this embodiment, the volume percentage of vinyl triethoxysilane in ethanol is 4%;

[0084] S3. Polymerization reaction: The indium tin oxide conductive glass that has completed the silanization reaction in step S2 is immersed in an aqueous solution of methacryloyloxyethyltrimethylammonium chloride containing potassium persulfate as an initiator and heated to 60° C. for polymerization reaction for 60 minutes, followed by washing with water and drying with nitrogen gas. In this embodiment, the concentration of potassium persulfate in the aqueous solution is 2.5 g / L; the mass concentration of methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 15 wt %.

[0085] S4. Preparation of a Pd-ITO conductive layer: The indium tin oxide conductive glass, after the polymerization reaction in step S3, is immersed in an aqueous solution of ammonium tetrachloropalladate for 80 minutes of ion exchange adsorption reaction. The layer is then washed with water and dried with nitrogen to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive material modified layer. In this embodiment, the mass volume concentration of ammonium tetrachloropalladate in the aqueous solution is 0.8 g / L.

[0086] Example 3

[0087] A method for preparing a conductive substance modified material layer comprises the following steps:

[0088] S1, plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment for 70 seconds;

[0089] S2, Silanization reaction: Immerse the indium tin oxide conductive glass treated in step S1 in an ethanol solution containing vinyl trimethoxysilane, add glacial acetic acid to adjust the pH to 3.8, and then perform a surface silanization reaction for 40 minutes. The indium tin oxide conductive glass after the silanization reaction is then washed with water and dried. In this embodiment, the volume percentage of vinyl trimethoxysilane in ethanol is 3%;

[0090] S3. Polymerization reaction: The indium tin oxide conductive glass that has completed the silanization reaction in step S2 is immersed in an aqueous solution of methacryloyloxyethyltrimethylammonium chloride containing potassium persulfate as an initiator and heated to 70° C. for polymerization reaction for 30 minutes, followed by washing with water and drying with nitrogen gas. In this embodiment, the concentration of potassium persulfate in the aqueous solution is 2 g / L; the mass concentration of methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 20 wt %.

[0091] S4. Preparation of a Pd-ITO conductive layer: The indium tin oxide conductive glass, after the polymerization reaction in step S3, is immersed in an aqueous solution of ammonium tetrachloropalladate for 30 minutes of ion exchange adsorption reaction. The glass is then washed with water and dried with nitrogen to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive material modified layer. In this embodiment, the mass volume concentration of ammonium tetrachloropalladate in the aqueous solution is 2 g / L.

[0092] Example 4

[0093] A method for preparing a conductive substance modified material layer comprises the following steps:

[0094] S1, plasma treatment: placing the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment for 55 seconds;

[0095] S2, Silanization reaction: Immerse the indium tin oxide conductive glass treated in step S1 in an ethanol solution containing vinyl trimethoxysilane, add glacial acetic acid to adjust the pH to 4, and then perform a surface silanization reaction for 70 minutes. The indium tin oxide conductive glass after the silanization reaction is then washed with water and dried. In this embodiment, the volume percentage of vinyl trimethoxysilane in ethanol is 2.5%;

[0096] S3. Polymerization reaction: The indium tin oxide conductive glass that has completed the silanization reaction in step S2 is immersed in an aqueous solution of methacryloyloxyethyltrimethylammonium chloride containing potassium persulfate as an initiator and heated to 90° C. for polymerization reaction for 20 minutes, followed by washing with water and drying with nitrogen gas. In this embodiment, the concentration of potassium persulfate in the aqueous solution is 1.5 g / L; the mass concentration of methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 5 wt %.

[0097] S4. Preparation of a Pd-ITO conductive layer: The indium tin oxide conductive glass, after the polymerization reaction in step S3, is immersed in an aqueous solution of ammonium tetrachloropalladate for 90 minutes of ion exchange adsorption reaction. The layer is then washed with water and dried with nitrogen to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive material modified layer. In this embodiment, the mass volume concentration of ammonium tetrachloropalladate in the aqueous solution is 0.5 g / L.

[0098] Example 5

[0099] A method for preparing a conductive substance modified material layer comprises the following steps:

[0100] S1, plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment for 65 seconds;

[0101] S2, Silanization reaction: Immerse the indium tin oxide conductive glass treated in step S1 in an ethanol solution containing vinyl trimethoxysilane, add glacial acetic acid to adjust the pH to 4.5, and then perform a surface silanization reaction for 60 minutes. The indium tin oxide conductive glass after the silanization reaction is then washed with water and dried. In this embodiment, the volume percentage of vinyl trimethoxysilane in ethanol is 0.1%;

[0102] S3. Polymerization reaction: The indium tin oxide conductive glass that has completed the silanization reaction in step S2 is immersed in an aqueous solution of methacryloyloxyethyltrimethylammonium chloride containing potassium persulfate as an initiator and heated to 80° C. for polymerization reaction for 30 minutes, followed by washing with water and drying with nitrogen gas. In this embodiment, the concentration of potassium persulfate in the aqueous solution is 0.1 g / L; the mass concentration of methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 10 wt %.

[0103] S4. Preparation of a Pd-ITO conductive layer: The indium tin oxide conductive glass, after the polymerization reaction in step S3, is immersed in an aqueous solution of ammonium tetrachloropalladate for 100 minutes of ion exchange adsorption reaction. The resulting layer is then washed with water and dried with nitrogen to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive material modified layer. In this embodiment, the mass volume concentration of ammonium tetrachloropalladate in the aqueous solution is 0.1 g / L.

[0104] Example 6

[0105] A conductive glass electrode, wherein the preparation method of any one of embodiments 1 to 5 of the conductive substance modified material layer is applied to prepare the conductive glass electrode, wherein the Pd-ITO conductive layer is used as the electrode.

[0106] Example 7

[0107] A conductive glass, wherein the preparation method of any one of embodiments 1 to 5 of the conductive substance modified material layer is applied to prepare the conductive glass.

[0108] Example 8

[0109] A dynamic window comprises conductive glass modified by the preparation method of a conductive substance modified material layer according to any one of embodiments 1 to 5.

[0110] Comparative Example 1

[0111] A method for preparing a conductive material modified material layer. The difference between this comparative example and Example 1 is that steps S1, S2, and S3 of Example 1 are omitted in this comparative example, and the indium tin oxide conductive glass is directly immersed in an aqueous solution of ammonium tetrachloropalladate. The remaining steps and condition parameters are the same as step S4 of Example 1.

[0112] Experimental testing

[0113] (1) Copper deposition experimental detection

[0114] Three samples of indium tin oxide conductive glass without any treatment, the conductive glass with a Pd-ITO conductive layer prepared in Example 1, and the conductive glass prepared in Comparative Example 1 were used for copper deposition testing. The experimental testing method is as follows:

[0115] First, prepare the plating solution: 0.1M copper sulfate, 0.2M potassium sodium tartrate, 0.1M formaldehyde, and adjust the pH value to 12 with sodium hydroxide.

[0116] Then, the three samples prepared above were immersed in the plating solution and reacted at 40℃ for 2 minutes. Then, the three samples were taken out and rinsed with deionized water and dried with nitrogen. Then, the surface of the conductive glass was observed to see if there was copper deposition. Figure 2 shown.

[0117] Figure 2 Among them, sample 1 is a sample of "indium tin oxide conductive glass without any treatment", sample 2 is a sample of "conductive glass prepared in comparative example 1", and sample 3 is a sample of "conductive glass with Pd-ITO conductive layer prepared in example 1".

[0118] from Figure 2 From the copper deposition experimental results, it can be seen that sample 1 of the "indium tin oxide conductive glass without any treatment" does not deposit copper, the "conductive glass prepared in comparative example 1" deposits a small amount of copper, and the "conductive glass with Pd-ITO conductive layer prepared in example 1" deposits an obvious copper layer, and the uniformity of the copper layer is very good.

[0119] Therefore, it can be seen that the indium tin oxide conductive glass in Comparative Example 1, which did not undergo plasma treatment, silanization reaction, and polymerization reaction, was directly immersed in an aqueous solution of ammonium tetrachloropalladate, resulting in only a small amount of Pd ions modified, and the Pd ions were uneven, leading to a small and uneven copper deposition. However, the indium tin oxide conductive glass of Example 1, which underwent plasma treatment, silanization reaction, and polymerization reaction before being immersed in an aqueous solution of ammonium tetrachloropalladate, was uniformly modified with a large amount of Pd ions, thereby enabling a uniform deposition of a large amount of copper layer.

[0120] (2) Adhesion test of copper deposit layer

[0121] The conductive glass with the Pd-ITO conductive layer prepared in Example 1 and the conductive glass prepared in Comparative Example 1 were used as two samples, and copper deposition experiments were performed on each of them. The adhesion of the deposited copper layers was then tested.

[0122] The adhesion test is as follows: cut a 3M tape of appropriate length and stick it on the copper surface of the two samples. Scrape it flat to make the tape fit tightly to the copper surface, then tear it off and observe. Figure 2 shown.

[0123] Depend on Figure 2 It can be seen that the copper deposited layer in the sample of Comparative Example 1 will be removed by the 3M tape, while the copper deposited layer in the sample of Example 1 will not be removed by the 3M tape, which shows that the Pd-ITO conductive layer prepared after plasma treatment, silanization reaction and polymerization reaction in Example 1 can make the copper deposited layer have better adhesion.

[0124] (III) Transmittance, center and edge metal deposition rate detection

[0125] The transmittance of unmodified indium tin oxide conductive glass (hereinafter referred to as "Sample 1") and the conductive glass with a Pd-ITO conductive layer prepared in Example 1 (hereinafter referred to as "Sample 2") was tested at the center and edge to measure the sedimentation rate at the center and edge. The specific test experiment is as follows:

[0126] Preparation of the plating solution: prepare an aqueous solution of 15 mM copper chloride, 5 mM bismuth chloride, 10 mM hydrochloric acid and 1 M lithium bromide, add 0.1 wt % polyvinyl alcohol, and heat and stir at 80° C. overnight.

[0127] Device assembly: Place a circle of copper conductive tape around the working electrode ITO of sample 1 and the working electrode Pd-ITO of sample 2, and extend a piece of conductive tape to facilitate power supply. Then place a layer of polyimide tape on the copper conductive tape. Use Kraft glue to attach the working electrode to the device frame to prevent leakage. On the other side, use ordinary glass and copper metal frames of the same size as the counter electrode and reference electrode, and use Kraft glue to attach the two to the device frame to prevent leakage. Figure 3 , which is a schematic structural diagram of a device assembled with conductive glass having a Pd-ITO conductive layer prepared in Example 1.

[0128] Transmittance test: This experiment used 50*50mm glass and a UV-3600plus SHIMADZU UV-Vis-NIR spectrophotometer from Japan for transmittance testing. A CHI440C quartz crystal microbalance from Shanghai Chenhua Instrument Co., Ltd. provided a constant voltage. The prepared device was injected with plating solution, sealed, and then tested for real-time transmittance using a UV-Vis-NIR spectrophotometer. The CHI440C was set to provide a constant voltage of -0.6V. The center and edge metal deposition rates of the device were tested within 180s.

[0129] like Figure 4 As shown in the figure, the transmittance of the unmodified ITO conductive glass after copper deposition for 180s at the center and edge shows that the metal deposition speed of the unmodified ITO conductive glass is slow, especially at the center where the transmittance of the conductive glass is still 50% after 180s of sedimentation, indicating that the metal deposition effect of the unmodified ITO conductive glass is poor, and it is difficult to achieve the transition between transparent and opaque states. In addition, the voltage difference between the center and the edge is relatively large, which leads to a large difference in sedimentation rate at the center and the edge. Therefore, the unmodified ITO conductive glass cannot deposit metal uniformly and quickly.

[0130] like Figure 5As shown in the graph, the transmittance of the conductive glass with a Pd-ITO conductive layer prepared in Example 1 after copper deposition for 180 seconds at the center and edges shows that the Pd-ITO conductive glass prepared in Example 1 has a fast metal deposition rate. The transmittance of the conductive glass is close to 0% after 180 seconds of deposition at both the center and the edges, indicating that the Pd-ITO conductive glass prepared in Example 1 has good metal deposition effect and can well achieve the transition between transparent and opaque states. In addition, the voltage difference between the center and the edge is greatly reduced, thereby making the deposition rate at the center and the edge consistent. Therefore, the Pd-ITO conductive glass prepared in Example 1 can well achieve uniform and rapid metal deposition.

[0131] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a conductive substance modified material layer, characterized in that: The following steps are involved: S1. Plasma treatment: Place the indium tin oxide conductive glass in a plasma cleaning machine for plasma treatment; S2, silanization reaction: immersing the indium tin oxide conductive glass treated in step S1 in an acidic solution containing vinyl silane to perform a surface silanization reaction, and then washing with water and drying; S3, polymerization reaction: immersing the indium tin oxide conductive glass that has completed the silanization reaction in step S2 in an aqueous solution containing methacryloyloxyethyltrimethylammonium chloride as an initiator to perform a heating polymerization reaction, and then washing with water and drying; S4. Preparation of Pd-ITO conductive layer: Immerse the indium tin oxide conductive glass that has completed the polymerization reaction in step S3 in an aqueous solution of ammonium tetrachloropalladate to perform ion exchange adsorption reaction, and then wash and dry it to obtain a Pd-ITO conductive layer, thereby completing the preparation of the conductive substance modified material layer.

2. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In step S1 , the plasma cleaning machine performs plasma treatment for 50 seconds to 70 seconds.

3. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In step S2, the vinyl silane is vinyl trimethoxy silane or vinyl triethoxy silane, the solvent of the solution is ethanol, and the volume percentage of the vinyl silane in the ethanol is 0.1% to 5%; The surface silanization reaction time is 30 minutes to 70 minutes.

4. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In the step S2, the pH of the vinyl silane solution is adjusted to 3-4.5 using glacial acetic acid.

5. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In step S3, the initiator is potassium persulfate, and the concentration of potassium persulfate in the aqueous solution is 0.1 g / L to 3 g / L; The mass concentration of the methacryloyloxyethyltrimethylammonium chloride in the aqueous solution is 5 wt % to 25 wt %.

6. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In the step S3, the heating temperature of the polymerization reaction is 50° C. to 90° C., and the polymerization reaction time is 20 min to 70 min.

7. The method for preparing a conductive substance modified material layer according to claim 1, wherein: In step S4, the mass volume concentration of the ammonium tetrachloropalladate in the aqueous solution is 0.1 g / L to 2 g / L; The ion exchange adsorption reaction time is 30 minutes to 100 minutes.

8. A conductive glass electrode, characterized in that: The method for preparing a conductive substance modified material layer according to any one of claims 1 to 7 is applied to prepare a conductive glass electrode, wherein the Pd-ITO conductive layer is used as an electrode.

9. A conductive glass, characterized in that: The method for preparing a conductive substance modified material layer according to any one of claims 1 to 7 is used to prepare conductive glass.

10. A dynamic window, characterized in that: Conductive glass prepared by the method for preparing a conductive substance modified material layer according to any one of claims 1 to 7.

Images