CN111286710B - V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer - Google Patents
V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer Download PDFInfo
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Abstract
The application provides a V for electrochromic-based glass 2 O 5 The preparation method of the multilayer ion storage layer comprises the following steps: magnetron sputtering coating: sputtering and coating a film on the cleaned ITO glass substrate by a magnetron sputtering method, and annealing to obtain V 2 O 5 A film; sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step 2 O 5 Coating the surface of the film; heat treatment to obtain V for electrochromic glass 2 O 5 And a plurality of ion storage layers. The test result shows that V provided by the application 2 O 5 The multi-layer ion storage layer is matched with a single magnetron sputtering V under the condition of ensuring higher ion storage capacity and visible light transmittance 2 O 5 Film and Sol gel V 2 O 5 Porous Membrane comparison, V 2 O 5 The multilayer film has the highest cyclic stability.
Description
Technical Field
The application relates to an ion storage layer for electrochromic glass, in particular to a V based on electrochromic glass 2 O 5 A method for preparing a multi-layer ion storage layer.
Background
Currently, the widely accepted structure of electrochromic glass is a sandwich-type five-layer structure. Namely, the structure of glass/transparent conducting layer (TC) and electrochromic layer (EC) and ion conductor layer (IC) and ion storage layer (IS) and transparent conducting layer (TC) and glass.
The ion storage layer (IS layer for short) IS also called counter electrode layer (CE layer), and its function IS mainly to store and provide ions required for electrochromism, so as to balance the whole electrochromism process. It does not play much role in the color change response of the device, since its main role is to store the compensating ions. Therefore, the requirements for the ion storage material mainly include larger ion storage capacity, good reversibility when compensating ion injection/removal film material, good stability of multiple circulation, and high transparency of the film material when the whole glass device is in a fading state. The ion storage layer is one of key materials of the intelligent window, and the cycle durability and the optical contrast of the intelligent window are directly influenced by the performance of the ion storage layer. Currently, WO is commonly used 3 The counter electrode material of the electrochromic layer is Prussian Blue (PB) and IrO 2 、NiO x 、V 2 O 5 。
V 2 O 5 With WO 3 The electrochromic reaction formula of the composition is as follows:
anode:
cathode:
at present, in a transmission type electrochromic device, few single-electrode ion storage layer materials can simultaneously meet the requirements of high ion charge storage capacity, good cycle reversibility and high light transmittance. Therefore, modification research on the single-electrode ion storage layer is a way to find an ideal ion storage material.
Disclosure of Invention
In view of the above-mentioned drawbacks or deficiencies of the prior art, it would be desirable to provide a V for electrochromic-based glass 2 O 5 A method for preparing a multi-layer ion storage layer.
The application provides a V for electrochromic-based glass 2 O 5 The preparation method of the multilayer ion storage layer comprises the following steps:
magnetron sputtering coating: sputtering and coating a film on the cleaned ITO glass substrate by a magnetron sputtering method, and annealing to obtain V 2 O 5 A film;
sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step 2 O 5 Coating the surface of the film; heat treatment to obtain V for electrochromic glass 2 O 5 And a plurality of ion storage layers.
Preferably, in the magnetron sputtering step, the vacuum degree in the sputtering chamber reaches 3.4 x 10 -4 Pa。
Preferably, in the magnetron sputtering step, the magnetron sputtering time is 4 hours.
Preferably, in the magnetron sputtering step, the annealing temperature is 400 ℃ and the annealing time is 4 hours.
Preferably, V 2 O 5 The sol is prepared by a melt quenching method.
Preferably, in the sol-gel coating step, the coating method adopts a dip-coating method V 2 O 5 The speed of the film entering the sol is 4cm/min, the dipping time is 3min, and the pulling speed is 4 cm/min.
Preferably, in the sol-gel coating stepV adopted 2 O 5 The porous material template agent PEG is added into the sol.
Preferably, the amount of PEG added is 4-8g/200mL of sol.
Preferably, the number of coating layers in the sol-gel coating step is 2.
Preferably, in the sol-gel coating step, the heat treatment temperature is 300 ℃ and the time is 3 hours.
The application has the advantages and positive effects that: preparation of V by magnetron sputtering 2 O 5 Film, on the basis of which nano V is prepared by adopting sol-gel method 2 O 5 Porous ion storage layer to produce V 2 O 5 And a plurality of ion storage layers. Analyzing the electrochemical performance of the sample by a cyclic voltammetry test, and analyzing the visible light transmission performance of the sample by a double-beam ultraviolet-visible spectrophotometer test; the results show that V is prepared in the present application 2 O 5 The multi-level ion storage layer can simultaneously meet high ion charge storage capacity and high light transmittance, and has good cycle reversibility.
In addition to the technical problems addressed by the present application, the technical features constituting the technical solutions, and the advantages brought by the technical features of the technical solutions described above, other technical problems solved by the present application, other technical features included in the technical solutions, and advantages brought by the technical features will be described in further detail below.
Drawings
FIG. 1 shows the electrochromic glass-based V provided in example 1 2 O 5 A process flow diagram of a preparation method of a multi-layer ion storage layer;
FIG. 2(a) is V 2 O 5 Film, V 2 O 5 Porous film, V 2 O 5 Cyclic voltammetry of a multilayer film;
FIG. 2(b) is V 2 O 5 Film, V 2 O 5 Porous film, V 2 O 5 Multilayer film Li + Injection/expulsion capacity curve;
FIG. 3 is V 2 O 5 Film, V 2 O 5 Porous film, V 2 O 5 A multilayer thin film EIS curve;
FIG. 4(a) is V 2 O 5 Surface SEM of porous membrane;
FIG. 4(b) is V 2 O 5 SEM is the surface of the multilayer film;
FIG. 5 is V 2 O 5 Film, V 2 O 5 Porous film, V 2 O 5 Multilayer film transmission spectrogram.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
The embodiment provides a V for electrochromic-based glass 2 O 5 The preparation method of the multilayer ion storage layer is shown in a process flow diagram of fig. 1, and specifically comprises the following steps:
s1, magnetron sputtering coating: sputtering and coating a film on the cleaned ITO glass substrate by a magnetron sputtering method, and annealing to obtain V 2 O 5 A film;
s2, sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step 2 O 5 Coating the surface of the film; heat treatment to obtain V 2 O 5 Multilayer films, i.e. said electrochromic glass-based V 2 O 5 And a plurality of ion storage layers.
In this embodiment, the step of magnetron sputtering coating adopts an MSP-300C magnetron sputtering coating system, and the equipment mainly comprises the following four parts: (1) the cascade vacuum system consists of a mechanical pump and a molecular pump, and the vacuum degree in the sputtering chamber reaches 3.4 x 10 through the air pumping process -4 Pa to perform sputtering deposition coating (2) and a power supply consisting of a sputtering power supply and a direct current power supplyThe system can select different targets during sputtering; (3) the main control system for the whole sputtering deposition process is controlled through an AE power supply; (4) and a cooling circulation system for providing cooling water for the vacuum sputtering chamber and the molecular pump. The dielectric target is V 2 O 5 The target has the size phi of 101.6mm multiplied by 3mm and the purity of 99.99 percent. In the sputtering process, argon (Ar) is introduced to serve as nuclear energy particles to bombard the target material, the sputtering power and the sputtering pressure are adjusted, and V is carried out 2 O 5 And (3) preparing a film. The argon gas required during sputtering is a high purity gas (99.99% purity).
Referring to fig. 1, the magnetron sputtering coating process includes: preparation of V 2 O 5 Target material-vacuumizing-process parameter setting-pre-sputtering coating-annealing. Wherein, the steps of substrate cleaning-ITO glass installation and target material installation are also carried out before vacuum pumping.
Wherein prior to the experiment it should be noted that: (1) the ITO glass substrate is cleaned firstly, and the substrate is cleaned by ultrasonic wave with clean water, secondary water, acetone and ethanol solution in sequence, so as to ensure that the film can be well attached to the ITO glass substrate and is flat. (2) The vacuum chamber must be cleaned before the experiment, so as to avoid polluting the plated film sample. (3) Before sputtering, the target must be pumped to a certain vacuum degree to prevent particles bombarded from the target material from reacting with other gases in the air during sputtering, so that the components of the film are impure and V is further influenced 2 O 5 Electrochromic properties of the film. (4) Various experimental parameters in the experimental process must be strictly controlled to ensure the purity of the film.
In the magnetron sputtering coating step of the embodiment, the sputtering time is 4 hours, the annealing time is 4 hours, and the annealing temperature is 400 ℃. The argon flow is 30sccm, the working pressure is 2Pa, the sputtering power is 200w, and the temperature of the ITO glass substrate is 300 ℃.
In this embodiment, the sol-gel coating step specifically includes:
s21, sol preparation: preparation of V by melt quenching 2 O 5 And (3) sol. The method comprises the following specific steps: 3.6g of analytically pure V are weighed out 2 O 5 Placing the powder in a crucible, placing in a high temperature furnace, and heating to 850 deg.C at a speed of 4 deg.C/minAnd keeping the temperature for 12min to fully melt the mixture, then taking out the mixture and quickly pouring the mixture into a beaker filled with 200mL of distilled water, adding 6g of pore-forming agent polyethylene glycol (PEG), and placing the mixture in a 70 ℃ water bath kettle to heat and stir for 30min to fully melt the mixture. Then taking out and continuing stirring for 6h at room temperature, finally filtering and aging the mixture, and standing for 1 week for later use.
S22、V 2 O 5 Preparing a multilayer film: v obtained by magnetron sputtering coating step 2 O 5 The thin film is used as a substrate, and a film is formed on the substrate by a sol-gel method. The method comprises the following specific steps: v prepared by magnetron sputtering method 2 O 5 Fixing the film substrate on a dip coater, and immersing the substrate in PEG-V at a speed of 4cm/min 2 O 5 And soaking the composite sol for 3min to reach surface adsorption equilibrium, and then pulling the glass substrate at the same speed. The film was dried at room temperature and then placed in an oven at 200 ℃ for 12 h. The film substrate was again mounted on a draw coater and the substrate was dipped into PEG-V at 4cm/min 2 O 5 Soaking in the composite sol for 3min to reach surface adsorption balance, and then pulling the glass substrate at the same speed; drying the film at room temperature, and then placing the film in an oven at 200 ℃ for heat preservation for 12 hours; then the film is thermally treated for 3 hours at 300 ℃ to obtain V with uniform surface and no cracks 2 O 5 Multilayer films, i.e. said electrochromic glass-based V 2 O 5 And a plurality of ion storage layers.
Comparative example 1
This comparative example provides a V 2 O 5 The main steps of the porous membrane preparation method are the same as those of S2 and the sol-gel coating step in example 1, and the details of the same parts are omitted. This comparative example is different from step S2 in example 1 in that an ITO glass substrate which had not been subjected to the magnetron sputtering step was used as the substrate.
Test analysis
V obtained in step S1 of example 1 of the present application 2 O 5 Film, V obtained in step S2 2 O 5 Multilayer film, and V obtained in comparative example 1 2 O 5 Electrochemical performance measurement of porous membraneAnd (6) testing. Cyclic Voltammetry (CV) tests were performed using an electrochemical workstation to study the electrochemical performance of the ion storage layer. The study is mainly to analyze the electrochemical reversible performance of the ion storage layer and Li thereof by testing and characterizing the cyclic voltammetry characteristics of the ion storage layer + /e - The injection/extraction charge capacity of (a) and its cycling stability. In the experiment, a standard three-electrode method is adopted for measuring the cyclic voltammetry curve, a composite ion storage layer plated on ITO conductive glass is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. With 1MLiClO 4 The PC solution of (3) is used as an electrolyte. The scanning voltage range is-1.0V-1.0V, the scanning speed is 50mV/s, and the scanning times are 50 times.
FIG. 2(a) shows the three types of V 2 O 5 Cyclic voltammetry curve of the film, curve A in the figure is V prepared by magnetron sputtering method 2 O 5 Film, curve B is V prepared by sol-gel method 2 O 5 Porous membrane, C curve is V prepared by magnetron sputtering-sol-gel composite method 2 O 5 And (3) a multilayer film. From the graph, it can be seen that the peak currents of the curve A, B, C are 5.82mA, 6.78mA, 13.26mA, respectively, which indicates V 2 O 5 Multilayer thin film surface and Li + The electron transfer rate between solutions is fastest. The reason for this is due to V 2 O 5 A large amount of double electric layer structures are formed on the surface of the multilayer film, so that the V is improved 2 O 5 Specific surface area of the multilayer film. In addition, the high specific surface and pore volume can improve the efficiency of oxidation-reduction reaction, facilitate the easy and stable movement of electrolyte ions, and reduce the mass transfer resistance. FIG. 2(b) shows Li + Injection/expulsion capacity curve, after 50 cycles, the ion storage of curve A, B, C decreased by 11.04%, 8.46%, 7.01% in order, indicating that V prepared by the composite process 2 O 5 The multi-layer film has the highest circulating stability and can better meet the requirements of the ion storage layer.
FIG. 3 is EIS spectra of different electrode films, and impedance frequency is 0.01 Hz-10 5 Hz, wherein the curve A is V prepared by magnetron sputtering 2 O 5 Film, curve B is V prepared by sol-gel method 2 O 5 Porous membrane, C curve is V prepared by magnetron sputtering-sol-gel composite method 2 O 5 And (3) a multilayer film. The interface impedances of curve A, B, C are 386 Ω, 463 Ω, 329 Ω, respectively. Wherein V 2 O 5 Multilayer film and LiClO 4 The interfacial resistance of the solution is minimal because the double layer structure is more favorable for promoting Li between the electrolyte and the electrodes + Transfer, decrease ion transmission resistance [84] 。
Surface and cross-sectional topography analysis of the samples was performed using a field emission scanning electron microscope (FE-SEM) (S-4800). FIG. 4(a) is V 2 O 5 SEM of porous Membrane surface, V in FIG. 4(b) 2 O 5 And (5) SEM of the surface of the multilayer film. The comparison results in less hole collapse on the surface of the multilayer film, which is caused by the fact that the part V on the substrate is generated during the PEG volatilization process 2 O 5 The crystal grains are used as an inorganic framework, and the stability of the pore structure is ensured.
The optical performance was tested using a TU-1901 model dual beam uv-vis spectrophotometer. FIG. 5 shows 3 kinds of V 2 O 5 A transmission spectrum of the electrode film. Wherein the curve A, B, C has an average visible light transmission of 85.68%, 83.25%, 81.29%, wherein the curve C represents V 2 O 5 The average visible light transmittance of the multilayer film is reduced due to V 2 O 5 The film thickness is increased to block the transmission of partial visible light, but the average visible light transmission of the multilayer film is 81.29%, which meets the application requirements.
From the test and analysis results, the ITO conductive glass/magnetron sputtering V is prepared by a sol-gel/magnetron sputtering composite method 2 O 5 film/Sol gel V 2 O 5 V prepared by porous membrane 2 O 5 Multi-layer film, ensuring higher ion storage capacity and visible light transmittance, and single magnetron sputtering V 2 O 5 Film and Sol gel V 2 O 5 Porous Membrane phase, V 2 O 5 The multilayer film has the highest cyclic stability.
In example 1, the amount of PEG template added was 6 g;in other embodiments of the present application, the amount of PEG added can also be any amount between 4g and 8 g. The experimental result shows that the cyclic voltammetry curves of the sample obtained by adding PEG between 4g and 8g are all closed curves, which shows that the prepared V 2 O 5 The porous film still had Li after 50 cycles + Reversibility of injection/expulsion. In addition, the cyclic voltammogram shows an oxidation peak and a reduction peak, which indicates that the prepared porous membrane has Li + Both the intercalation and deintercalation undergo redox reactions in the process, which react with V 2 O 5 The characteristic of double coloring is consistent; wherein when the addition amount of PEG is 6g, the peak current of the sample is the highest, which is in favor of Li + The transmission of (1); when the addition amount of PEG is 8g, the peak current is reduced because the volatilization amount of PEG after heat treatment is too large, the holes on the surface of the film collapse to a certain extent, the specific surface area of the sample is reduced, and Li is prevented + The transfer of (2). The visible light transmittance of the samples obtained by adding 4g-8g of PEG is respectively more than 80 percent, which meets the use requirement.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (4)
1. V for electrochromic-based glass 2 O 5 The preparation method of the multilayer ion storage layer is characterized by comprising the following steps:
magnetron sputtering coating: sputtering and coating a film on the cleaned ITO glass substrate by a magnetron sputtering method, and annealing to obtain V 2 O 5 A film; the magnetron sputtering time is 4 h; the annealing temperature is 400 ℃, and the annealing time is 4 hours; sputtering chamberThe degree of hollowness reaches 3.4 x 10 -4 Pa；
Sol-gel coating: v prepared by sol-gel method in magnetron sputtering step 2 O 5 Coating the surface of the film; heat treatment to obtain the electrochromic glass-based V 2 O 5 A multi-layered ion storage layer; v adopted 2 O 5 Adding a porous material template agent PEG into the sol, wherein the adding amount of the PEG is 4-8g/200mL of the sol;
wherein, the coating layer number in the sol-gel coating step is 2.
2. The electrochromic glass-based V according to claim 1 2 O 5 The preparation method of the multi-layer ion storage layer is characterized in that V is 2 O 5 The sol is prepared by a melt quenching method.
3. The electrochromic glass-based V according to claim 1 2 O 5 The preparation method of the multi-layer ion storage layer is characterized in that in the sol-gel coating step, the heat treatment temperature is 300 ℃ and the time is 3 hours.
4. The electrochromic glass-based V according to claim 1 2 O 5 The preparation method of the multi-layer ion storage layer is characterized in that in the sol-gel coating step, the coating method adopts a dipping and pulling method V 2 O 5 The speed of the film entering the sol is 4cm/min, the dipping time is 3min, and the pulling speed is 4 cm/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080304130A1 (en) * | 2007-06-07 | 2008-12-11 | Paul Nguyen | Electrochromic device and method of making the same |
| CN101728092A (en) * | 2008-10-10 | 2010-06-09 | 比亚迪股份有限公司 | Semiconductor electrode, manufacturing method thereof and solar cell having semiconductor electrode |
| CN102636931A (en) * | 2011-02-15 | 2012-08-15 | 鸿富锦精密工业（深圳）有限公司 | Electro-chromic layer, coated element and preparation method of coated element |
| CN203838454U (en) * | 2014-04-10 | 2014-09-17 | 吉林大学 | WO3-Ta2O5-NiO solid state composite electrochromism glass device |
| CN108803183A (en) * | 2018-04-18 | 2018-11-13 | 南通繁华新材料科技有限公司 | A kind of bilayer full-inorganic electrochromic device and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186448A (en) * | 2007-12-06 | 2008-05-28 | 同济大学 | Method for increasing gas-chromism thin film gas-chromism speed |
| CN102222575B (en) * | 2011-03-30 | 2012-11-28 | 东南大学 | Preparation method for photoanode of dye-sensitized solar cell |
| CN102249552A (en) * | 2011-04-22 | 2011-11-23 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide intelligent temperature control film and preparation method thereof |
| CN103777424A (en) * | 2012-10-17 | 2014-05-07 | 珠海兴业绿色建筑科技有限公司 | Photochromic device |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080304130A1 (en) * | 2007-06-07 | 2008-12-11 | Paul Nguyen | Electrochromic device and method of making the same |
| CN101728092A (en) * | 2008-10-10 | 2010-06-09 | 比亚迪股份有限公司 | Semiconductor electrode, manufacturing method thereof and solar cell having semiconductor electrode |
| CN102636931A (en) * | 2011-02-15 | 2012-08-15 | 鸿富锦精密工业（深圳）有限公司 | Electro-chromic layer, coated element and preparation method of coated element |
| CN203838454U (en) * | 2014-04-10 | 2014-09-17 | 吉林大学 | WO3-Ta2O5-NiO solid state composite electrochromism glass device |
| CN108803183A (en) * | 2018-04-18 | 2018-11-13 | 南通繁华新材料科技有限公司 | A kind of bilayer full-inorganic electrochromic device and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Electrochromic properties of TiO2 thin films prepared by chemical solution deposition method》;Chih-Ming Wang,et al;《Journal of Physics and Chemistry of Solids》;20080331;第1500-1505页 * |
| 《Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications》;A. Cremonesi,et al;《Thin Solid Films》;20060605;第451-455页 * |
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