CN111286710A - V for electrochromic-based glass2O5Preparation method of multi-layer ion storage layer - Google Patents

V for electrochromic-based glass2O5Preparation method of multi-layer ion storage layer Download PDF

Info

Publication number
CN111286710A
CN111286710A CN202010237988.9A CN202010237988A CN111286710A CN 111286710 A CN111286710 A CN 111286710A CN 202010237988 A CN202010237988 A CN 202010237988A CN 111286710 A CN111286710 A CN 111286710A
Authority
CN
China
Prior art keywords
ion storage
glass
sol
electrochromic
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010237988.9A
Other languages
Chinese (zh)
Other versions
CN111286710B (en
Inventor
樊小伟
梁小平
刘鉴宁
淮旭国
耿平
李亚娟
张雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Syp Engineering Glass Group Co ltd
Original Assignee
Tianjin Syp Engineering Glass Group Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Syp Engineering Glass Group Co ltd filed Critical Tianjin Syp Engineering Glass Group Co ltd
Priority to CN202010237988.9A priority Critical patent/CN111286710B/en
Publication of CN111286710A publication Critical patent/CN111286710A/en
Application granted granted Critical
Publication of CN111286710B publication Critical patent/CN111286710B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1524—Transition metal compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The application provides a V for electrochromic-based glass2O5The preparation method of the multilayer ion storage layer comprises the following steps: magnetron sputtering coating: ITO glass cleaned by magnetron sputtering methodSputtering film on the glass substrate and annealing to obtain V2O5A film; sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step2O5Coating the surface of the film; heat treatment to obtain V for electrochromic glass2O5And a plurality of ion storage layers. The test result shows that V provided by the application2O5The 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 transmittance2O5Film and Sol gel V2O5Porous Membrane comparison, V2O5The multilayer film has the highest cyclic stability.

Description

V for electrochromic-based glass2O5Preparation method of multi-layer ion storage layer
Technical Field
The application relates to an ion storage layer for electrochromic glass, in particular to a V based on electrochromic glass2O5A 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 performance of the ion storage layer directly influences the cycle of the intelligent windowRing durability and optical contrast. Currently, WO is commonly used3The counter electrode material of the electrochromic layer is Prussian Blue (PB) and IrO2、NiOx、V2O5。
V2O5With WO3The electrochromic reaction formula of the composition is as follows:
anode:
Figure BDA0002431644180000011
cathode:
Figure BDA0002431644180000012
at present, in a transmission type electrochromic device, few single-electrode ion storage layer materials can simultaneously meet 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 glass2O5A method for preparing a multi-layer ion storage layer.
The application provides a V for electrochromic-based glass2O5The 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 V2O5A film;
sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step2O5Coating the surface of the film; heat treatment to obtain V for electrochromic glass2O5And a plurality of ion storage layers.
Preferably, in the magnetron sputtering step, the vacuum degree in the sputtering chamber reaches 3.4 x 10-4Pa。
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, V2O5The sol is prepared by a melt quenching method.
Preferably, in the sol-gel coating step, the coating method adopts a dip-coating method V2O5The speed of the film entering the sol is 4cm/min, the dipping time is 3min, and the pulling speed is 4 cm/min.
Preferably, V is used in the sol-gel coating step2O5The 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 sputtering2O5Film, on the basis of which nano V is prepared by adopting sol-gel method2O5Porous ion storage layer to produce V2O5And 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 application2O5The 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 is a drawing ofExample 1 provides a V for electrochromic-based glass2O5A process flow diagram of a preparation method of a multi-layer ion storage layer;
FIG. 2(a) is V2O5Film, V2O5Porous film, V2O5Cyclic voltammetry of a multilayer film;
FIG. 2(b) is V2O5Film, V2O5Porous film, V2O5Multilayer film Li+Injection/expulsion capacity curve;
FIG. 3 is V2O5Film, V2O5Porous film, V2O5A multilayer thin film EIS curve;
FIG. 4(a) is V2O5SEM of the surface of the porous membrane;
FIG. 4(b) is V2O5SEM is the surface of the multilayer film;
FIG. 5 is V2O5Film, V2O5Porous film, V2O5Multilayer 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 glass2O5The 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 V2O5A film;
s2, sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step2O5Coating the surface of the film; heat treatment to obtain V2O5Multilayer films, i.e. said electrochromic glass-based V2O5And 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-4Pa, so as to carry out sputtering deposition coating (2), a power supply system consisting of a sputtering power supply and a direct current power supply 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 V2O5The 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 out2O5And (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 V2O5Target 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 influenced2O5Electrochromic 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 quenching2O5And (3) sol. The method comprises the following specific steps: 3.6g of analytically pure V are weighed out2O5Putting the powder into a crucible, putting the crucible into a high-temperature furnace, heating to 850 ℃ at the speed of 4 ℃/min, keeping the temperature for 12min to fully melt the powder, then taking out the powder, quickly pouring the powder into a beaker filled with 200mL of distilled water, adding 6g of pore-forming agent polyethylene glycol (PEG), and putting the beaker into a 70 ℃ water bath kettle to heat and stir for 30min to fully melt the powder. 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、V2O5Preparing a multilayer film: v obtained by magnetron sputtering coating step2O5The 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 method2O5Fixing the film substrate on a dip coater, and immersing the substrate in PEG-V at a speed of 4cm/min2O5And 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. Fixing the film substrate on a pulling film coating machine again, and immersing the substrate into PEG-V at the same speed of 4cm/min2O5Soaking 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 cracks2O5Multilayer films, i.e. said electrochromic glass-based V2O5And a plurality of ion storage layers.
Comparative example 1
This comparative example provides a V2O5The 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 application2O5Film, V obtained in step S22O5Multilayer film, and V obtained in comparative example 12O5The porous membrane was tested for electrochemical performance. 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 taken as a working electrode, a platinum sheet is taken as a counter electrode, and a saturated calomel electrode is taken as a reference electrode. With 1MLiClO4The 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 V2O5Cyclic voltammetry curve of the film, curve A in the figure is V prepared by magnetron sputtering method2O5Film, curve B is V prepared by sol-gel method2O5Porous membrane, C curve is V prepared by magnetron sputtering-sol-gel composite method2O5And (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 V2O5Multilayer thin film surface and Li+The electron transfer rate between solutions is fastest. The reason for this is due to V2O5A large amount of double electric layer structures are formed on the surface of the multilayer film, so that the V is improved2O5Specific surface area of the multilayer film. In addition, the high specific surface area and pore volume can improve the efficiency of the redox reaction, which is beneficial to promoting the easy and stable movement of electrolyte ionsAnd mass transfer resistance is reduced. 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 process2O5The 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-105Hz, wherein the curve A is V prepared by magnetron sputtering2O5Film, curve B is V prepared by sol-gel method2O5Porous membrane, C curve is V prepared by magnetron sputtering-sol-gel composite method2O5And (3) a multilayer film. The interface impedances of curve A, B, C are 386 Ω, 463 Ω, 329 Ω, respectively. Wherein V2O5Multilayer film and LiClO4The 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 V2O5SEM of porous Membrane surface, V in FIG. 4(b)2O5And (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 process2O5The 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 V2O5A transmission spectrum of the electrode film. Wherein the curve A, B, C has an average visible light transmittance of 85.68%, 83.25%, 81.29%, wherein the curve C represents V2O5The average visible light transmittance of the multilayer film is reduced due to V2O5The 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.
Analysis from the above testsAs a result, the ITO conductive glass/magnetron sputtering V prepared by the sol-gel/magnetron sputtering composite method2O5film/Sol gel V2O5V prepared by porous membrane2O5Multi-layer film, ensuring higher ion storage capacity and visible light transmittance, and single magnetron sputtering V2O5Film and Sol gel V2O5Porous Membrane comparison, V2O5The 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 V2O5The 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 V2O5The 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 (10)

1. V for electrochromic-based glass2O5The 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 V2O5A film;
sol-gel coating: v prepared by a sol-gel process in a magnetron sputtering step2O5Coating the surface of the film; heat treatment to obtain the electrochromic glass-based V2O5And a plurality of ion storage layers.
2. The electrochromic glass-based V according to claim 12O5The preparation method of the multilayer ion storage layer is characterized in that the number of coating layers in the sol-gel coating step is 2.
3. V for electrochromic-glass-based glass according to claim 1 or 22O5The preparation method of the multilayer ion storage layer is characterized in that V adopted in the sol-gel coating step2O5The porous material template agent PEG is added into the sol.
4. The electrochromic glass-based V according to claim 32O5The preparation method of the multilayer ion storage layer is characterized in that the adding amount of PEG is 4-8g/200mL of sol.
5. The electrochromic glass-based V according to claim 32O5The preparation method of the multi-layer ion storage layer is characterized in that V is2O5The sol is prepared by a melt quenching method.
6. V for electrochromic-glass-based glass according to claim 1 or 22O5The 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.
7. V for electrochromic-glass-based glass according to claim 1 or 22O5The 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 V2O5The speed of the film entering the sol is 4cm/min, the dipping time is 3min, and the pulling speed is 4 cm/min.
8. V for electrochromic-glass-based glass according to claim 1 or 22O5The preparation method of the multi-layer ion storage layer is characterized in that in the magnetron sputtering step, the magnetron sputtering time is 4 hours.
9. V for electrochromic-glass-based glass according to claim 1 or 22O5The preparation method of the multi-layer ion storage layer is characterized in that in the magnetron sputtering step, the annealing temperature is 400 ℃, and the annealing time is 4 hours.
10. V for electrochromic-glass-based glass according to claim 1 or 22O5The preparation method of the multilayer ion storage layer is characterized in that in the magnetron sputtering step, the vacuum degree in the sputtering chamber reaches 3.4 x 10-4Pa。
CN202010237988.9A 2020-03-30 2020-03-30 V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer Active CN111286710B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010237988.9A CN111286710B (en) 2020-03-30 2020-03-30 V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010237988.9A CN111286710B (en) 2020-03-30 2020-03-30 V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer

Publications (2)

Publication Number Publication Date
CN111286710A true CN111286710A (en) 2020-06-16
CN111286710B CN111286710B (en) 2022-08-05

Family

ID=71019860

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010237988.9A Active CN111286710B (en) 2020-03-30 2020-03-30 V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer

Country Status (1)

Country Link
CN (1) CN111286710B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114859611A (en) * 2022-05-13 2022-08-05 厦门大学 Colorful electrochromic film, device and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
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
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
CN102222575A (en) * 2011-03-30 2011-10-19 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
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
CN103777424A (en) * 2012-10-17 2014-05-07 珠海兴业绿色建筑科技有限公司 Photochromic device
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
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
CN101186448A (en) * 2007-12-06 2008-05-28 同济大学 Method for increasing gas-chromism thin film gas-chromism speed
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
CN102222575A (en) * 2011-03-30 2011-10-19 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
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)

* Cited by examiner, † Cited by third party
Title
A. CREMONESI,ET AL: "《Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications》", 《THIN SOLID FILMS》 *
CHIH-MING WANG,ET AL: "《Electrochromic properties of TiO2 thin films prepared by chemical solution deposition method》", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114859611A (en) * 2022-05-13 2022-08-05 厦门大学 Colorful electrochromic film, device and preparation method thereof
CN114859611B (en) * 2022-05-13 2024-01-09 厦门大学 Multi-color electrochromic film, device and preparation method thereof

Also Published As

Publication number Publication date
CN111286710B (en) 2022-08-05

Similar Documents

Publication Publication Date Title
Chen et al. A scalable electrodeposition route to the low-cost, versatile and controllable fabrication of perovskite solar cells
Sivakumar et al. Investigation of x-ray photoelectron spectroscopic (XPS), cyclic voltammetric analyses of WO3 films and their electrochromic response in FTO/WO3/electrolyte/FTO cells
Wang et al. Transparent flexible Pt counter electrodes for high performance dye-sensitized solar cells
CN106746724B (en) A kind of molybdenum oxide electrochromism nano thin-film and preparation method thereof
CN111364015A (en) WO for intelligent window3Preparation method of laminated composite electrochromic film
CN101418214A (en) Electrochromic material and preparation method thereof
CN103172274A (en) Preparation method of nickel oxide/polyaniline composite electrochromic film
Sarangika et al. Polyethylene oxide and ionic liquid-based solid polymer electrolyte for rechargeable magnesium batteries
CN108279541A (en) A kind of inorganic full-solid electric driven color-changing thin-film device and preparation method thereof that reliability is high
CN112456813A (en) Nickel oxide electrochromic film and preparation method and application thereof
CN111286710B (en) V for electrochromic-based glass 2 O 5 Preparation method of multi-layer ion storage layer
CN109267028B (en) Nickel-zinc oxide photoelectric film and preparation method thereof
CN109881198B (en) Preparation method of multi-color electrochromic film with tin dioxide/vanadium pentoxide core-shell structure
Liu et al. Preparation of WO3 gel electrochromic device by simple two-step method
Dewan et al. A multi-chromic supercapacitor of high coloration efficiency integrating a MOF-derived V 2 O 5 electrode
CN113264690B (en) Porous tungsten oxide electrochromic film and preparation method thereof
CN107315298B (en) Brown electrochromic charge storage electrode and preparation method thereof
CN112164593B (en) MoO3Per P6ICA composite electrode material, preparation method thereof and supercapacitor
Yoo et al. Application of Pt sputter-deposited counter electrodes based on micro-patterned ITO glass to quasi-solid state dye-sensitized solar cells
CN116632329A (en) Oxide solid electrolyte, composite solid electrolyte membrane and preparation method thereof
CN116189799A (en) Nickel tin oxide solid ion storage layer and preparation method and application thereof
Tang et al. Time-resolved electrochromic properties of MoO 3 thin films electrodeposited on a flexible substrate
KR20150091447A (en) Electrochemical method of graphene oxide deposition, graphene oxide deposited substrate made by the same, and electric device including the same
Feng et al. Reversible Zn 2+/Al 3+ intercalation in niobium-substituted polyoxometalates and demonstration of energy storage smart windows
CN107022746B (en) A kind of preparation method of full-inorganic solid-state electrochromic device electrolytic thin-membrane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant