Reversible metal electrodeposition flexible multi-band intelligent regulation and control device and preparation method thereof

Abstract

The invention provides a reversible metal electrodeposition flexible multiband intelligent regulation and control device and a preparation method thereof, and belongs to the field of electrochromism intelligent regulation and control. Dynamic regulation and control are achieved through deposition and dissolution of metal, due to the fact that a large number of free electrons exist in a metal material, extremely strong shielding and reflection effects are generated on infrared radiation, only a 20-30 nm metal layer can block visible light and near-infrared light, and the good optical contrast ratio is achieved; the flexible multiband transparent electrode is prepared by adopting a crack template method, so that the square resistance of the electrode is small, the transmittance in a wide wavelength range is high, and the device has multiband regulation and control capability. Results show that the flexible multi-band intelligent regulation and control device can realize the regulation and control of the reflectivity greater than 0.2 in visible light, the regulation and control of the reflectivity greater than 0.6 in near infrared, the regulation and control amplitude of the emissivity greater than 0.8 in an infrared band, the response time of deposition and dissolution is less than 5 seconds, and the flexible multi-band intelligent regulation and control device does not obviously decline after 1000 cycles.

Description

Technical Field

[0001] The present invention relates to the field of electrochromic intelligent regulation, and in particular to a reversible metal electrodeposition flexible multi-band intelligent regulation device and a preparation method thereof. Background Art

[0002] Multi-band regulation technology is an advanced technology involving the fields of material science, optics and thermal management. It can effectively regulate electromagnetic waves in multiple bands such as visible light and infrared light.

[0003] As a highly efficient multi-band spectral control technology, reversible metal electrodeposition technology controls the deposition and dissolution of metals under an electric field based on the high extinction coefficient of metals, and uses the unique optical properties of metal films of different thicknesses and shapes to achieve dynamic control. However, the scarcity of multi-band transparent electrodes is the main factor causing the poor performance of current multi-band control devices and limited application areas. Multi-band transparent electrodes need to have high transparency to light over a wide wavelength range while maintaining good conductivity to transmit current. Traditional conductive electrodes have problems such as low multi-band transmittance, insufficient flexibility, slow ion transmission of control devices, and short cycle life, which seriously restricts the promotion and application of multi-band control devices.

[0004] Therefore, how to overcome the problems of low band transmittance and poor flexibility of traditional conductive electrodes, complex structure and small control range of multi-band control devices, and improve the response speed and cycle life of multi-band control devices has become a technical problem that needs to be urgently solved in this field. Summary of the invention

[0005] The purpose of the present invention is to provide a reversible metal electrodeposition flexible multi-band intelligent control device and a preparation method thereof. The flexible multi-band intelligent control device provided by the present invention can achieve dynamic control compatible with visible light, near-infrared and mid-infrared bands, with a wide control band, a large control amplitude, a fast response time and a long cycle life.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a reversible metal electrodeposition flexible multi-band intelligent control device, which comprises, from top to bottom, a PE flexible substrate, a flexible multi-band transparent electrode, a deposited catalyst layer, an electrolyte, a counter electrode and a flexible substrate;

[0008] The material of the flexible multi-band transparent electrode includes any one of gold, silver, copper, zinc, aluminum, platinum, iron, manganese and magnesium, and the preparation method of the flexible multi-band transparent electrode is a crack template method.

[0009] Preferably, the light transmittance of the PE flexible substrate within the wavelength range of 0.4 to 25 μm is greater than 0.5.

[0010] Preferably, the square resistance of the flexible multi-band transparent electrode is 1-5000Ω / square; and the transmittance of the flexible multi-band transparent electrode within the wavelength range of 0.4-25μm is greater than 0.5.

[0011] Preferably, the material of the deposited catalytic layer includes any one of gold, platinum and silver.

[0012] Preferably, the electrolyte comprises an electrochromic material containing metal ions and a solvent.

[0013] Preferably, the metal ion is a metal ion that can achieve reversible electrodeposition and dissolution, and the metal ion is Cu 2+ 、Zn 2+ 、Ag + and Bi 3+ Any one of .

[0014] Preferably, the counter electrode is a metal single substance thin film.

[0015] Preferably, the flexible substrate is any one of a PET flexible film, a PE flexible film, a PP flexible film, a PDMS flexible film, a PI flexible film and a PEN flexible film.

[0016] Preferably, the thickness of the PE flexible substrate is 1 to 500 μm; the thickness of the flexible multi-band transparent electrode is 50 to 5000 nm; the thickness of the deposited catalytic layer is 2 to 50 nm; the thickness of the electrolyte is 0.1 to 10 mm; the thickness of the counter electrode is 1 to 500 μm; and the thickness of the flexible substrate is 1 to 1000 μm.

[0017] The present invention provides a method for preparing the reversible metal electrodeposition flexible multi-band intelligent control device described in the above technical solution, comprising the following steps:

[0018] (1) preparing a flexible multi-band transparent electrode on a PE flexible substrate to obtain a PE flexible substrate@flexible multi-band transparent electrode;

[0019] (2) sputtering and depositing a catalytic layer on one side of the flexible multi-band transparent electrode of the PE flexible substrate@flexible multi-band transparent electrode obtained in step (1) to obtain a PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer;

[0020] (3) preparing a counter electrode on a flexible substrate to obtain a flexible substrate@counter electrode;

[0021] (4) using a packaging material, assembling and sealing the PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer obtained in step (2) and the flexible substrate@counter electrode obtained in step (3) to form a hollow stacked structure, and then adding an electrolyte into the cavity of the stacked structure to obtain a composite;

[0022] (5) sealing the composite obtained in step (4) and then pressing it to obtain a reversible metal electrodeposition flexible multi-band intelligent control device;

[0023] The preparation of step (2) and step (3) is not in any particular order.

[0024] The present invention provides a reversible metal electrodeposition flexible multi-band intelligent control device, which includes a PE flexible substrate, a flexible multi-band transparent electrode, a deposition catalyst layer, an electrolyte, a counter electrode and a flexible substrate from top to bottom; the material of the flexible multi-band transparent electrode includes any one of gold, silver, copper, zinc, aluminum, platinum, iron, manganese and magnesium, and the preparation method of the flexible multi-band transparent electrode is a crack template method. The structure of the flexible multi-band intelligent control device provided by the present invention is simple, and dynamic control is achieved by relying on the deposition and dissolution of metal. Due to the high extinction coefficient of the metal, the metal layer has extremely high reflectivity in the entire infrared band, and is an ideal infrared reflective material that can suppress infrared radiation. At the same time, due to the presence of a large number of free electrons in the metal material, it has a strong shielding and reflection effect on infrared radiation. Only a 20-30nm metal layer can block visible light and near infrared, and has good optical contrast; the use of the crack template method to prepare a flexible multi-band transparent electrode can make the obtained electrode square resistance small, and the transmittance is high in a wide wavelength range, so that the device has multi-band control capabilities. The results of the embodiments show that the reversible metal electrodeposition flexible multi-band intelligent control device provided by the present invention can achieve a reflectivity control greater than 0.2 in visible light, a reflectivity control greater than 0.6 in near-infrared, and an emissivity control amplitude greater than 0.8 in the infrared band. The response time of deposition and dissolution is less than 5 seconds, and there is no obvious decay after 1000 cycles. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic structural diagram of a reversible metal electrodeposition flexible multi-band intelligent control device prepared in Example 1 of the present invention;

[0026] Figure 2 This is a surface morphology image of the flexible multi-band transparent electrode prepared in Example 1 of the present invention;

[0027] Figure 3 This is a multi-band transmittance diagram of the flexible multi-band transparent electrode prepared in Example 1 of the present invention;

[0028] Figure 4A multi-band control spectrum diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention;

[0029] Figure 5 This is a response time diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention;

[0030] Figure 6 This is a cycle diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention;

[0031] Figure 7 This is a patterned design diagram of a flexible multi-band intelligent control device prepared in Example 2 of the present invention;

[0032] Figure 8 This is a wearable design diagram of a flexible multi-band intelligent control device prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0033] The present invention provides a reversible metal electrodeposition flexible multi-band intelligent control device, which comprises, from top to bottom, a PE flexible substrate, a flexible multi-band transparent electrode, a deposited catalyst layer, an electrolyte, a counter electrode and a flexible substrate.

[0034] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art.

[0035] In the present invention, the transmittance of the PE flexible substrate in the wavelength range of 0.4 to 25 μm is preferably greater than 0.5, more preferably greater than 0.8; the thickness of the PE flexible substrate is preferably 0.1 to 100 μm, more preferably 20 to 60 μm, and further preferably 40 to 50 μm. The present invention uses the above-mentioned PE flexible substrate to prepare a reversible metal electrodeposition flexible multi-band intelligent control device. The larger transmittance of the PE flexible substrate ensures that the device has a sufficient control range.

[0036] In the present invention, the material of the flexible multi-band transparent electrode preferably includes any one of gold, silver, copper, zinc, aluminum, platinum, iron, manganese and magnesium, and more preferably gold, silver or platinum. In the present invention, the preparation method of the flexible multi-band transparent electrode is preferably a crack template method. The present invention adopts the crack template method to prepare the flexible multi-band transparent electrode, so that the obtained flexible multi-band transparent electrode has high band transmittance and low square resistivity.

[0037] In the present invention, the square resistance of the flexible multi-band transparent electrode is preferably 1-5000Ω / square, more preferably 1-500Ω / square, and further preferably 1-100Ω / square; the thickness of the flexible multi-band transparent electrode is preferably 50-5000nm, more preferably 100-4000nm, and further preferably 100-2000nm; the light transmittance of the flexible multi-band transparent electrode in the wavelength range of 0.4-25μm is preferably >0.5, and more preferably >0.7. The present invention can further improve the conductivity of the flexible multi-band transparent electrode by controlling the material of the flexible multi-band transparent electrode.

[0038] In the present invention, the material of the deposited catalytic layer preferably includes any one of gold, platinum and silver, and is more preferably platinum; the thickness of the deposited catalytic layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and further preferably 1 to 20 nm.

[0039] In the present invention, the electrolyte preferably comprises an electrochromic material containing metal ions and a solvent.

[0040] In the present invention, the metal ion is preferably a metal ion that can achieve reversible electrodeposition and dissolution, more preferably Cu 2+ 、Zn 2+ 、Ag + and Bi 3+ Any one of, more preferably Cu 2+ or Ag + The electrochromic material is preferably a salt of a metal ion, more preferably any one of cupric chloride, cupric perchlorate, zinc chloride, zinc acetate, zinc perchlorate, silver chloride, silver perchlorate and bismuth chloride, further preferably any one of cupric chloride, cupric perchlorate, silver chloride and silver perchlorate.

[0041] In the present invention, the solvent includes any one or both of water and DMSO. In the present invention, when the solvent includes both of water and DMSO, the water and DMSO are preferably mixed in any proportion. The present invention can make the prepared electrolyte have excellent conductive properties by controlling the composition of the solvent.

[0042] In the present invention, the electrolyte preferably further comprises a lithium salt, an acidic pH regulator and a binder. In the present invention, the lithium salt is preferably LiClO4; the acidic pH regulator is preferably HCl; and the binder is preferably PVA powder. In the present invention, the lithium salt is a component of the electrolyte, providing a freely movable Li +LiClO4 is an electrolyte lithium salt with relatively high solubility, exhibiting relatively high ionic conductivity, relatively good oxidation stability and a wide electrochemical stability window, which is beneficial to improving the response time and stability of the device; the addition of acidic pH regulator puts the entire electrolyte in an acidic environment, and the device has better deposition reversibility and device stability in an acidic environment; the addition of binder increases the viscosity of the electrolyte and appropriately reduces the deposition rate. Metal ions with faster deposition rates tend to agglomerate and deposit, which is not conducive to the uniform deposition required for spectral regulation. Therefore, the appropriate addition of binder is beneficial to the uniform deposition of metal and improves the regulation range.

[0043] In the present invention, the preparation method of the electrolyte preferably comprises the following steps:

[0044] I. adding an electrochromic material containing metal ions, a lithium salt and an acidic pH regulator into a solvent, and mixing them to obtain a mixed solution;

[0045] II. Add a binder to the mixed solution obtained in step I, and then heat and dissolve it to obtain an electrolyte.

[0046] In the present invention, preferably, an electrochromic material containing metal ions, a lithium salt and an acidic pH regulator are added to a solvent, and the mixture is mixed to obtain a mixed solution.

[0047] In the present invention, the mixing is preferably carried out under stirring conditions. The present invention has no particular limitation on the stirring rate and time, as long as the components can be mixed uniformly.

[0048] In the present invention, the concentration of the electrochromic material containing metal ions in the mixed solution is preferably 0.01-0.1 mol / L, more preferably 0.03-0.07 mol / L, and further preferably 0.05 mol / L; the concentration of the lithium salt in the mixed solution is preferably 0.4-0.5 mol / L, more preferably 0.45 mol / L; the concentration of the acidic pH regulator in the mixed solution is preferably 20-30 mmol / L, more preferably 24 mmol / L. The present invention can further improve the performance of the electrolyte solution by controlling the concentration of each component.

[0049] After obtaining the mixed solution, the present invention preferably adds a binder to the mixed solution, and then heats and dissolves the mixed solution to obtain an electrolyte.

[0050] In the present invention, the mass of the binder is preferably 5-8% of the mass of the mixed solution, and more preferably 6%. The viscosity of the electrolyte can be controlled by controlling the amount of the binder added.

[0051] In the present invention, the heat preservation temperature of the heating and dissolving is preferably 70-90°C, more preferably 80°C; the heating and dissolving time is preferably 3-5h, more preferably 4h; the heating and dissolving method is preferably water bath heating or oil bath heating. The present invention can help the binder to completely dissolve into the electrolyte under heating conditions to obtain a uniform electrolyte solution.

[0052] In the present invention, the heating and dissolving is preferably carried out under stirring conditions; the stirring rate is preferably 400-500 rpm, more preferably 450 rpm. The present invention can further improve the dispersibility of the binder by stirring.

[0053] In the present invention, the product dissolved by heating is preferably cooled naturally to obtain the electrolyte.

[0054] In the present invention, the thickness of the electrolyte is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and further preferably 1 to 4 μm.

[0055] In the present invention, the counter electrode is preferably a metal thin film, more preferably any one of Cu film, Zn film, Ag film and Bi film, and further preferably Cu film or Ag film. In the present invention, the type of metal used in the counter electrode is preferably the same as the type of metal ions in the electrolyte; when the metal ions in the electrolyte are Cu 2+ When the counter electrode is preferably a Cu film; when the metal ion in the electrolyte is Ag + The counter electrode is preferably an Ag film. The present invention controls the material of the counter electrode to be the same as the metal ions in the electrolyte. When the metal ions in the electrolyte are reduced to metal elements at the deposited catalyst layer, an oxidation reaction occurs on the counter electrode. The metal elements of the counter electrode are oxidized to metal ions and enter the electrolyte to supplement the reduced metal ions, so that the entire device is in a charge balance state, thereby improving the overall stability and cycle life of the device.

[0056] In the present invention, the thickness of the counter electrode is preferably 1 to 20 μm, more preferably 5 to 10 μm. By controlling the thickness of the counter electrode, the present invention can maintain charge balance and enable the device to operate normally.

[0057] In the present invention, the flexible substrate is preferably any one of a PET flexible film, a PE flexible film, a PP flexible film, a PDMS flexible film, a PI flexible film and a PEN flexible film; the thickness of the flexible substrate is preferably 10 to 1000 μm, more preferably 10 to 500 μm. The present invention uses a flexible film as the substrate material of the reversible metal electrodeposition flexible multi-band intelligent control device, which can ensure that it remains intact under complex shapes, thereby increasing its service life.

[0058] In the present invention, the size of the reversible metal electrodeposition flexible multi-band intelligent control device is preferably 2cm×2cm to 4cm×4cm, and more preferably 3cm×3cm.

[0059] The flexible multi-band intelligent control device provided by the present invention has a simple structure and realizes dynamic control by metal deposition and dissolution. Due to the high extinction coefficient of the metal, the metal layer has extremely high reflectivity in the entire infrared band, and is an ideal infrared reflective material that can suppress infrared radiation. At the same time, due to the presence of a large number of free electrons in the metal material, a strong shielding and reflection effect is produced on infrared radiation. A metal layer of only 20 to 30 nm can block visible light and near infrared and has good optical contrast. The flexible multi-band transparent electrode is prepared by a crack template method, so that the obtained electrode has a small square resistance and a high transmittance in a wide wavelength range, so that the device has multi-band control capability. The flexible multi-band intelligent control device prepared by using the electrode can realize reflectivity control greater than 0.2 in visible light, reflectivity control greater than 0.6 in near infrared, and emissivity control amplitude greater than 0.8 in the infrared band. The response time of deposition and dissolution is less than 5 seconds, and there is no obvious decay after 1000 cycles.

[0060] The core idea of ​​the present invention is to utilize the unique optical properties of metal films of different thicknesses and shapes to achieve dynamic regulation, so that the flexible multi-band intelligent regulation device can achieve dynamic regulation compatible with visible light, near-infrared and mid-infrared bands, with a wide regulation band, large regulation amplitude, fast response time and long cycle life.

[0061] The reversible metal electrodeposition flexible multi-band intelligent control device provided by the present invention can achieve dynamic control compatible with visible light, near-infrared and mid-infrared bands, with a wide control band, a large control amplitude, and a fast response time. At the same time, the flexible design is compatible with wearables and various surfaces.

[0062] The multi-band intelligent control device provided by the present invention solves the problems of low band transmittance of traditional conductive electrodes and slow ion transmission and short cycle life of multi-band control devices, and provides a feasible solution and strategy for the design and development of high-performance reversible metal electrodeposition flexible multi-band intelligent control devices.

[0063] The present invention provides a method for preparing the reversible metal electrodeposition flexible multi-band intelligent control device described in the above technical solution, comprising the following steps:

[0064] (1) preparing a flexible multi-band transparent electrode on a PE flexible substrate to obtain a PE flexible substrate@flexible multi-band transparent electrode;

[0065] (2) sputtering and depositing a catalytic layer on one side of the flexible multi-band transparent electrode of the PE flexible substrate@flexible multi-band transparent electrode obtained in step (1) to obtain a PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer;

[0066] (3) preparing a counter electrode on a flexible substrate to obtain a flexible substrate@counter electrode;

[0067] (4) using a packaging material, assembling and sealing the PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer obtained in step (2) and the flexible substrate@counter electrode obtained in step (3) to form a hollow stacked structure, and then adding an electrolyte into the cavity of the stacked structure to obtain a composite;

[0068] (5) sealing the composite obtained in step (4) and then pressing it to obtain a reversible metal electrodeposition flexible multi-band intelligent control device;

[0069] The preparation of step (2) and step (3) is not in any particular order.

[0070] The present invention prepares a flexible multi-band transparent electrode on a PE flexible substrate to obtain a PE flexible substrate@flexible multi-band transparent electrode.

[0071] In the present invention, the preparation method of the flexible multi-band transparent electrode is preferably a crack template method; the preparation method of the crack template method preferably includes the following steps:

[0072] 1) Physically sticking the PE flexible substrate and the thermal peeling tape to obtain the thermal peeling tape@PE flexible substrate;

[0073] 2) mixing an aqueous acrylic resin and anhydrous ethanol to form a suspension, and then spin-coating the suspension on one side of the PE flexible substrate of the thermal peelable tape@PE flexible substrate obtained in step 1) to form a uniform thin film, and finally drying to obtain a crack template;

[0074] 3) sputtering metal on the crack template obtained in step 2) by ion sputtering, then soaking it with propylene glycol methyl ether acetate, and finally washing it to obtain a thermal peeling tape @ PE flexible substrate @ flexible multi-band transparent electrode;

[0075] 4) placing the thermal peelable tape@PE flexible substrate@flexible multi-band transparent electrode obtained in step 3) on a heating table for separation to obtain PE flexible substrate@flexible multi-band transparent electrode.

[0076] In the present invention, the PE flexible substrate and the heat-peelable tape are preferably physically bonded to obtain the heat-peelable tape@PE flexible substrate.

[0077] In the present invention, the viscosity of the thermal peeling tape is preferably low viscosity, medium viscosity or high viscosity, and more preferably high viscosity; the peeling temperature of the thermal peeling tape is preferably 80 to 100° C., and more preferably 90° C. The present invention has no particular limitation on the specific source of the thermal peeling tape, and commercially available thermal peeling tapes well known to those skilled in the art can be used.

[0078] The present invention has no special limitation on the specific operation of the physical bonding, and the operation is performed according to the technical common sense of those skilled in the art to ensure that there are no bubbles at the bonding site when the PE flexible substrate and the heat-peelable tape are physically bonded.

[0079] In the present invention, the shape and size of the thermal peeling tape are preferably the same as those of the PE flexible substrate; when the shape and size of the thermal peeling tape are different from those of the PE flexible substrate, the present invention preferably cuts the thermal peeling tape. The present invention supports the PE flexible substrate by pasting the thermal peeling tape, so that the PE flexible substrate is not easily deformed during the spin coating process, and a crack template with better performance is obtained.

[0080] After obtaining the thermal peelable tape @ PE flexible substrate, the present invention preferably mixes an aqueous acrylic resin and anhydrous ethanol to form a suspension, and then forms a uniform thin film on one side of the PE flexible substrate of the thermal peelable tape @ PE flexible substrate by spin coating, and finally dries to obtain a crack template.

[0081] In the present invention, the volume ratio of the aqueous acrylic resin to anhydrous ethanol is preferably (1-5):(1-5), more preferably (2-4):(2-4). The present invention can ensure that a crack template that meets the requirements is obtained after drying by controlling the dosage relationship of the aqueous acrylic resin and anhydrous ethanol.

[0082] In the present invention, the aqueous acrylic resin and anhydrous ethanol are preferably mixed by first stirring with magnetic force for 30 minutes and then standing at room temperature for 12 hours. The present invention can ensure that the aqueous acrylic resin and anhydrous ethanol are mixed uniformly by adopting the above mixing method.

[0083] In the present invention, the number of revolutions during the spin coating is preferably 500 to 5000 rpm, more preferably 1000 to 4000 rpm, and further preferably 2000 to 3000 rpm; the spin coating time is preferably 5 to 100 s, more preferably 10 to 80 s, and further preferably 20 to 50 s. The present invention can ensure that a film with a thickness that meets the requirements is obtained by controlling the spin coating parameters.

[0084] The present invention has no particular limitation on the drying temperature and time, as long as the anhydrous ethanol can be completely evaporated.

[0085] After obtaining the crack template, the present invention preferably uses ion sputtering to sputter metal on the crack template, then soaks it with propylene glycol methyl ether acetate, and finally washes it to obtain a thermal peeling tape@PE flexible substrate@flexible multi-band transparent electrode.

[0086] In the present invention, the sputtering current of the ion sputtering is preferably 20-40 mA, more preferably 30-40 mA, and further preferably 30-35 mA; the sputtering time of the ion sputtering is preferably 50-300 s, and further preferably 100-250 s; the vacuum degree of the ion sputtering is preferably 0.01-0.5 mbar, more preferably 0.02-0.4 mbar, and further preferably 0.05-0.2 mbar. The present invention can control the thickness of the flexible multi-band transparent electrode by controlling the parameters of the ion sputtering.

[0087] The present invention has no particular limitation on the specific amount of the propylene glycol methyl ether acetate, as long as it can be completely immersed. In the present invention, the immersion time is preferably 1 to 48 hours, more preferably 12 to 36 hours, and further preferably 24 hours. The present invention can make the crack template fall off by immersing the sputtered PE flexible substrate in propylene glycol methyl ether acetate.

[0088] The present invention has no particular limitation on the specific operation of the washing, and water washing or anhydrous ethanol washing can be used as long as the propylene glycol methyl ether acetate can be completely removed.

[0089] After obtaining the heat-stripping tape@PE flexible substrate@flexible multi-band transparent electrode, the present invention preferably places the heat-stripping tape@PE flexible substrate@flexible multi-band transparent electrode on a heating table for separation to obtain the PE flexible substrate@flexible multi-band transparent electrode.

[0090] In the present invention, the heating temperature of the heating stage is preferably 80-100°C, more preferably 90°C; the heating time of the heating stage is preferably 10-20 minutes, more preferably 15 minutes; the separation method is preferably manual peeling. The present invention can make the hot peeling tape lose its stickiness by controlling the temperature and time of the heating stage, thereby facilitating subsequent manual peeling.

[0091] The present invention adopts a crack template method to prepare a flexible multi-band transparent electrode, using anhydrous ethanol as a dispersant. During the drying process, stress is generated inside the formed uniform film, cracks are gradually generated under the action of the stress, and then metal is sputtered and finally demolded, so that the obtained flexible multi-band transparent electrode has higher wide-band transmittance and lower square resistivity.

[0092] After obtaining the PE flexible substrate @ flexible multi-band transparent electrode, the present invention sputter-deposit a catalytic layer on one side of the flexible multi-band transparent electrode of the PE flexible substrate @ flexible multi-band transparent electrode to obtain the PE flexible substrate @ flexible multi-band transparent electrode @ deposited catalytic layer.

[0093] In the present invention, the method of sputtering and depositing the catalyst layer is preferably ion sputtering; the sputtering current of the ion sputtering is preferably 20-40 mA, more preferably 30-40 mA; the sputtering time of the ion sputtering is preferably 1-50 s, more preferably 2-20 s; the vacuum degree of the ion sputtering is preferably 0.01-0.5 mbar, more preferably 0.02-0.4 mbar, and further preferably 0.05-0.2 mbar. The present invention prepares the deposited catalyst layer by ion sputtering, which can act as a nucleation site for the metal, making the deposited metal particles finer and more evenly distributed; the macroscopic performance is a stronger blocking ability for the spectrum and better device cyclicity.

[0094] The present invention has no special requirements on the size of the PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer, and those skilled in the art can select appropriate sizes according to actual needs.

[0095] The present invention prepares a counter electrode on a flexible substrate to obtain a flexible substrate@counter electrode;

[0096] In the present invention, the method for preparing the counter electrode on the flexible substrate is preferably to use double-sided tape to stick the counter electrode on the flexible substrate; the thickness of the double-sided tape is preferably 1 to 500 μm, more preferably 1 to 100 μm. The present invention has no special limitation on the specific source of the double-sided tape, and commercially available double-sided tape well known to those skilled in the art can be used to tightly stick the counter electrode and the flexible substrate.

[0097] The present invention has no special requirements on the size of the flexible substrate@counter electrode, and those skilled in the art can select a suitable size according to actual needs.

[0098] After obtaining the PE flexible substrate @ flexible multi-band transparent electrode @ deposited catalytic layer and the flexible substrate @ counter electrode, the present invention uses packaging materials to assemble and seal the PE flexible substrate @ flexible multi-band transparent electrode @ deposited catalytic layer and the flexible substrate @ counter electrode to form a hollow stacking structure, and then adds an electrolyte into the cavity of the stacking structure to obtain a composite.

[0099] In the present invention, the packaging material preferably includes any one of a load-bearing material, a mold protection material, an adhesive material and a ceramic packaging material, more preferably an adhesive material, and further preferably a 3M double-sided tape; the thickness of the packaging material is preferably 0.1 to 10 mm, more preferably 0.2 to 2 mm.

[0100] After obtaining the composite, the present invention seals the composite and then presses it to obtain a reversible metal electrodeposition flexible multi-band intelligent control device.

[0101] The present invention has no special limitation on the specific pressure of the pressing, which can be determined according to the common technical knowledge of those skilled in the art. The present invention can improve the bonding effect through pressing.

[0102] The preparation method provided by the present invention has simple process, short preparation cycle, expandable preparation area, low cost, and can also carry out pattern design and wearable design.

[0103] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0104] Example 1

[0105] A method for preparing a reversible metal electrodeposition flexible multi-band intelligent control device comprises the following steps:

[0106] (1) preparing a flexible multi-band transparent electrode on a PE flexible substrate to obtain a PE flexible substrate@flexible multi-band transparent electrode; the thickness of the PE flexible substrate is 40 μm; the thickness of the flexible multi-band transparent electrode is 120 nm;

[0107] (2) sputtering and depositing a catalyst layer on one side of the flexible multi-band transparent electrode of the PE flexible substrate @ flexible multi-band transparent electrode obtained in step (1) by an ion sputtering method to obtain a PE flexible substrate @ flexible multi-band transparent electrode @ deposited catalyst layer; the sputtering current of the ion sputtering is 40 mA, the sputtering time of the ion sputtering is 9 s, and the vacuum degree of the ion sputtering is 0.02 mbar; the material of the deposited catalyst layer is platinum, and the thickness of the deposited catalyst layer is 9 nm;

[0108] (3) using double-sided tape to adhere the counter electrode to a flexible substrate to prepare a counter electrode, thereby obtaining a flexible substrate@counter electrode; the thickness of the double-sided tape is 75 μm; the flexible substrate is a PE flexible film, and the thickness of the flexible substrate is 40 μm; the counter electrode is a Cu film, and the thickness of the counter electrode is 9 μm;

[0109] (4) using a packaging material, assembling and sealing the PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer obtained in step (2) and the flexible substrate@counter electrode obtained in step (3) to form a hollow stacked structure, and then adding an electrolyte into the cavity of the stacked structure to obtain a composite; the packaging material is 3M double-sided tape, and the thickness of the packaging material is 1 mm; the thickness of the electrolyte is 1 mm;

[0110] (5) The composite obtained in step (4) is sealed and pressed to obtain a reversible metal electrodeposition flexible multi-band intelligent control device; the size of the reversible metal electrodeposition flexible multi-band intelligent control device is 3 cm×3 cm.

[0111] The method for preparing the flexible multi-band transparent electrode in step (1) is a crack template method; the preparation method of the crack template method comprises the following steps:

[0112] 1) Physically sticking a PE flexible substrate with a thickness of 40 μm and a high-viscosity thermal peeling tape, and removing internal bubbles with a scraper to obtain a thermal peeling tape @PE flexible substrate; the peeling temperature of the thermal peeling tape is 90° C.;

[0113] 2) Mixing aqueous acrylic resin and anhydrous ethanol in a volume ratio of 2:1, stirring with a magnetic force for 30 minutes, and then standing at room temperature for 12 hours to form a suspension, placing the thermal peelable tape @ PE flexible substrate obtained in step 1) in a coating machine, and then spin coating the suspension on the PE flexible substrate side of the thermal peelable tape @ PE flexible substrate to form a uniform film that completely covers the thermal peelable tape @ PE flexible substrate, and finally standing in a vacuum drying oven for 6 hours to obtain a crack template; the rotation speed during the spin coating is 2000 rpm, and the spin coating time is 15 seconds;

[0114] 3) placing the crack template obtained in step 2) inside an ion sputtering instrument, then repeatedly flushing the internal gas of the ion sputtering instrument with argon gas, sputtering silver by ion sputtering, then soaking it with propylene glycol methyl ether acetate for 12 hours, and finally washing it with anhydrous ethanol to obtain a thermal peeling tape @ PE flexible substrate @ flexible multi-band transparent electrode; the sputtering current of the ion sputtering is 30 mA, the sputtering time of the ion sputtering is 200 s, and the vacuum degree of the ion sputtering is 0.02 mbar; the material of the flexible multi-band transparent electrode is silver, and the thickness of the flexible multi-band transparent electrode is 120 nm;

[0115] 4) placing the thermal peelable tape@PE flexible substrate@flexible multi-band transparent electrode obtained in step 3) on a heating table at 90° C. for 15 minutes, and then manually peeling it off to obtain a PE flexible substrate@flexible multi-band transparent electrode.

[0116] The preparation method of the electrolyte in step (4) is the following steps:

[0117] I. Mix water and DMSO in a mass ratio of 3:7 and stir thoroughly to obtain a solvent;

[0118] II. Add CuCl2, LiClO4 and HCl to the solvent obtained in step I, and stir thoroughly to obtain a mixed solution; the concentration of CuCl2 in the mixed solution is 0.05 mol / L, the concentration of LiClO4 is 0.45 mol / L, and the concentration of HCl is 24 mmol / L;

[0119] III. Place the mixed solution obtained in step II in an oil bath, add PVA powder, stir at 450 rpm for 4 hours under 80° C. oil bath conditions, take out and cool naturally to obtain an electrolyte; the mass of the PVA powder is 6% of the mass of the mixed solution.

[0120] Figure 1 This is a schematic diagram of the structure of the flexible multi-band intelligent control device prepared in Example 1 of the present invention. Figure 1 It can be seen that the reversible metal electrodeposition flexible control device prepared by the present invention includes a PE flexible substrate, a flexible multi-band transparent electrode, a deposited catalyst layer, an electrolyte, a counter electrode and a flexible substrate from top to bottom.

[0121] Figure 2 This is a surface morphology of the flexible multi-band transparent electrode prepared in Example 1 of the present invention. Figure 2 It can be seen that although the flexible multi-band transparent electrodes prepared by the present invention are randomly distributed, they are interconnected to form a conductive network. Using a four-probe test system, the square resistance thereof is tested to be 40Ω / square.

[0122] Figure 3 This is a transmittance diagram of the flexible multi-band transparent electrode prepared in Example 1 of the present invention. Figure 3 It can be seen that the transmittance of the PE flexible substrate @ flexible multi-band transparent electrode is greater than 0.7 in the wavelength range of 0.4 to 25 μm, and there are three peaks in the infrared band, which are the absorption characteristic peaks of the PE flexible substrate.

[0123] Figure 4 This is a multi-band control spectrum diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention. Figure 4It can be seen that before deposition, the device is in a state of low reflection in the visible light, low reflection in the near-infrared and high emission in the mid-infrared; after deposition, the device is in a state of relatively low reflection in the visible light, high reflection in the near-infrared and low emission in the mid-infrared; the control amplitude of the device in the visible light band of 0.4-0.8μm is 0.24; the control amplitude of the device in the near-infrared band of 0.8-2μm is 0.67; the control amplitude of the device in the mid-infrared band of 3-5μm is 0.68; the control amplitude of the device in the mid-infrared band of 8-13μm is 0.82.

[0124] Figure 5 The response time diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention; Figure 5 It can be seen that when a voltage of -1 V is applied, the coloring time of the device is 2.7 seconds; when a voltage of 0.8 V is applied, the fading time of the device is 2.4 seconds.

[0125] Figure 6 A cycle diagram of the flexible multi-band intelligent control device prepared in Example 1 of the present invention; Figure 6 It can be seen that the device can still maintain nearly 100% spectral control capability after 1000 cycles.

[0126] Example 2

[0127] The preparation method of the present invention is the same as that of Example 1, with the only difference being that: before preparing the deposited catalytic layer, a pre-prepared pattern sheet is used to cover one side of the flexible multi-band transparent electrode of the PE flexible substrate @ flexible multi-band transparent electrode; the size of the above-mentioned pattern sheet is smaller than the size of the PE flexible substrate, and during ion sputtering, platinum in the covered area will be deposited on the above-mentioned pattern sheet, and platinum in the area not covered by the pattern sheet will be deposited on the flexible multi-band transparent electrode. After the ion sputtering is completed, the pattern sheet is removed, and the flexible multi-band transparent electrode at this time will display two different areas, namely, the area covered by the pattern does not contain platinum, and the area outside the pattern coverage contains platinum.

[0128] The reversible metal electrodeposition flexible multi-band intelligent control device of Example 2 is prepared by referring to the preparation method of Example 1. Figure 7 This is a pattern design diagram of the flexible multi-band intelligent control device prepared in Example 2 of the present invention. Figure 7 It can be seen that since nano-platinum is in a highly absorbing state in the infrared, even if the deposited catalytic layer is divided into two regions, the infrared image of the device shows that the aircraft image is not obvious in the initial state; after depositing the metal, an obvious aircraft pattern can be observed inside the device.

[0129] Example 3

[0130] The preparation method of the present invention is the same as that of Example 1, with the only difference being that the size of the reversible metal electrodeposition flexible multi-band intelligent control is 3 cm×7 cm.

[0131] The reversible metal electrodeposition flexible multi-band intelligent control device of Example 3 was prepared with reference to the preparation method of Example 1. Figure 8 This is a wearable design diagram of a flexible multi-band intelligent control device prepared in Example 3 of the present invention. Figure 8 It can be seen that the device has good flexible design and can fit the human wrist. At the same time, it can be deposited and dissolved in a flexible state. It can show color changes under an infrared camera and has potential application value in the fields of intelligent thermal control and infrared stealth.

[0132] Due to the presence of the flexible multi-band transparent electrode, the device has the ability of multi-band regulation. At the same time, the square resistance of the flexible multi-band transparent electrode is only 40Ω / square, which greatly improves the response time and cycle life of the device. In Chinese patent CN111025812A, since the device does not have a flexible multi-band transparent electrode, the device only has regulation performance in the infrared band, the response time is 15 seconds, and the number of cycles is less than 400, and the performance is far worse than the flexible multi-band intelligent regulation device of the present invention; in Chinese patent CN111176047B, due to the insufficient transmittance of the flexible electrode and the large square resistance, the device only has regulation performance in the infrared band, and the regulation range is limited, and the response time is long.

[0133] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A reversible metal electrodeposition flexible multi-band intelligent control device, which includes, from top to bottom, a PE flexible substrate, a flexible multi-band transparent electrode, a deposited catalyst layer, an electrolyte, a counter electrode and a flexible substrate; The material of the flexible multi-band transparent electrode includes any one of gold, silver, copper, zinc, aluminum, platinum, iron, manganese and magnesium, and the preparation method of the flexible multi-band transparent electrode is a crack template method.

2. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The light transmittance of the PE flexible substrate within the wavelength range of 0.4 to 25 μm is greater than 0.

5.

3. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The square resistance of the flexible multi-band transparent electrode is 1-5000Ω / square; the light transmittance of the flexible multi-band transparent electrode within the wavelength range of 0.4-25μm is greater than 0.

5.

4. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The material of the deposited catalytic layer includes any one of gold, platinum and silver.

5. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The electrolyte comprises an electrochromic material containing metal ions and a solvent.

6. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 5, characterized in that: The metal ion is a metal ion that can achieve reversible electrodeposition and dissolution, and the metal ion is Cu 2+ 、Zn 2+ 、Ag + and Bi 3+ Any one of .

7. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The counter electrode is a metal single substance thin film.

8. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The flexible substrate is any one of a PET flexible film, a PE flexible film, a PP flexible film, a PDMS flexible film, a PI flexible film and a PEN flexible film.

9. The reversible metal electrodeposition flexible multi-band intelligent control device according to claim 1, characterized in that: The thickness of the PE flexible substrate is 1 to 500 μm; the thickness of the flexible multi-band transparent electrode is 50 to 5000 nm; the thickness of the deposited catalyst layer is 2 to 50 nm; the thickness of the electrolyte is 0.1 to 10 mm; the thickness of the counter electrode is 1 to 500 μm; and the thickness of the flexible substrate is 1 to 1000 μm.

10. The method for preparing the reversible metal electrodeposition flexible multi-band intelligent control device according to any one of claims 1 to 9, comprising the following steps: (1) preparing a flexible multi-band transparent electrode on a PE flexible substrate to obtain a PE flexible substrate@flexible multi-band transparent electrode; (2) sputtering and depositing a catalytic layer on one side of the flexible multi-band transparent electrode of the PE flexible substrate@flexible multi-band transparent electrode obtained in step (1) to obtain a PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer; (3) preparing a counter electrode on a flexible substrate to obtain a flexible substrate@counter electrode; (4) using a packaging material, assembling and sealing the PE flexible substrate@flexible multi-band transparent electrode@deposited catalytic layer obtained in step (2) and the flexible substrate@counter electrode obtained in step (3) to form a hollow stacked structure, and then adding an electrolyte into the cavity of the stacked structure to obtain a composite; (5) sealing the composite obtained in step (4) and then pressing it to obtain a reversible metal electrodeposition flexible multi-band intelligent control device; The preparation of step (2) and step (3) is not in any particular order.

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