CN117406521A - Flexible electrochromic device capable of curling and preparation method thereof - Google Patents
Flexible electrochromic device capable of curling and preparation method thereof Download PDFInfo
- Publication number
- CN117406521A CN117406521A CN202210795535.7A CN202210795535A CN117406521A CN 117406521 A CN117406521 A CN 117406521A CN 202210795535 A CN202210795535 A CN 202210795535A CN 117406521 A CN117406521 A CN 117406521A
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- flexible
- sputtering
- electrochromic device
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Classifications
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- 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
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- 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
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Abstract
The invention relates to a flexible electrochromic device capable of curling and a preparation method thereof. The crimpable flexible electrochromic device includes: the first flexible composite electrode layer, the electrochromic layer, the organic ion storage layer and the second flexible composite electrode layer are sequentially laminated; the first flexible composite electrode layer or the second flexible substrate layer sequentially comprises a flexible substrate, a buffer layer, a metal layer and a transparent conductive layer.
Description
Technical Field
The invention relates to a flexible electrochromic device capable of curling and a preparation method thereof, belonging to the technical field of chemical material synthesis and functional materials.
Background
The energy is an important foundation for maintaining national economic sustainable development and guaranteeing the living standard of people's substances. Today, the problems of energy shortage, environmental pollution and the like are increasingly severe, and scientists are striving to find a method for saving energy and reducing consumption while developing new energy. The building is one of the main sites where human beings perform production and living activities, and in the total energy consumption of human beings, the building energy consumption accounts for a large proportion, while in the building energy consumption, the energy consumption of the lighting and air conditioning system for improving the comfort of the building accounts for more than 75 percent. Both parts of energy consumption are related to door and window glass, so developing building glass with energy-saving effect is an important way for realizing energy saving of building. The current way of controlling energy loss of architectural glass is static, for example Low-E glass with high reflectivity in the infrared band, which can prevent infrared from penetrating through the window; the hollow glass utilizes the low coefficient of thermal conductivity of air to reduce the conduction and heat dissipation between the indoor and outdoor. Scientists in the last century of 80 s put forward the concept of an intelligent window based on electrochromic materials, namely a building window structural material capable of actively regulating and controlling visible and near infrared transmission light intensity, dynamically regulating the intensity of the incident indoor light according to the difference between indoor and outdoor environments, reducing the use of an air conditioner and a lighting system, and combining with Low-E and hollow glass to achieve better energy-saving effect. The performance of electrochromic materials determines the intensity of the light adjusting capability of the intelligent window, and electrochromic materials are widely paid attention to. Electrochromic refers to the phenomenon that the optical properties of a material, such as transmittance, and reflectivity change reversibly under low voltage driving, and the appearance of the material shows reversible changes between blue and transparent states. Electrochromic is a hot spot studied nowadays and has a wide application range. The electrochromic device and the technology are mainly applied to the fields of energy-saving building glass, other movable body windows, anti-dazzle rearview mirrors of automobiles, display screens, electronic paper, camouflage and the like. Low-E is a Low emissivity glass, and the working principle is that most of infrared rays are reflected, so that heat entering a room is reduced. Hollow glass is a glass that reduces heat exchange between the inside and outside of a room. The aim is to reduce the indoor refrigeration energy consumption. Both windows and their combinations are only advantageous for cooling and cannot be controlled. That is, in winter cold, heat is still difficult to enter the room.
Conventional electrochromic devices are composed of five layers of thin films, including two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conducting layer. Wherein, the ion storage layer assists the electrochromic layer to apply low voltage on the first and second conductive layers to realize electrochromic reaction. Ion conductive layers are provided with lithium ions and a diffusion film layer, which is responsible for ensuring ion conductivity under the action of an electric field, and the structure and the preparation process of the ion conductive layers are one of the most important technologies for ensuring electrochromic performance of devices. The all-solid-state electrochromic device has stable structure and good capability of resisting water and oxygen and ultraviolet irradiation, so that the defects of easy liquid leakage, instability, poor cycle stability and the like of the liquid and quasi-solid-state device can be avoided, and the all-solid-state electrochromic device is widely applied.
With the continuous progress of technology, people gradually have wearable demands for intelligent electronic products. Wearable products require that the material have some mechanical strength that can be stretched, twisted, folded, crumpled without performance degradation. These products can accommodate complex non-planar surfaces with areas of application not found in rigid devices. Among them, the electrochromic material has a high application value because it can realize color change under a small voltage control. In order to meet the wearable requirement, the rigid electrochromic device assembled by using glass as a substrate cannot meet the requirement, and the flexible electrochromic device has gradually become a research hot spot. However, the development and application of flexible electrochromic devices are greatly restricted by the immaturity of the material preparation methods and flexible device assembly techniques available for flexible devices.
Transparent conductive oxides such as ITO have wide application as electrodes in electrochromic devices due to their high conductivity, high transmittance, firm film layers, high stability, and low electron transfer barriers. Because of the poor binding force between the common transparent conductive materials such as ITO and the flexible substrate, the traditional film can be strained, broken and even separated from the substrate after being bent under stress. Therefore, the synthesis process is simple, the transparent electrode with good flexibility is developed, and the assembly technology of the flexible electrochromic device is developed, so that the method has very important significance for the practical application of electrochromic materials.
Disclosure of Invention
Aiming at the problems of the existing flexible device material preparation method and the flexible device assembly technology which are not mature, the invention aims to provide a flexible electrochromic device capable of curling and a preparation method thereof.
In one aspect, the invention provides a flexible electrochromic device capable of curling, comprising a first flexible composite electrode layer, an electrochromic layer, an organic ion storage layer and a second flexible composite electrode layer which are sequentially stacked; the first flexible composite electrode layer or the second flexible substrate layer sequentially comprises a flexible substrate, a buffer layer, a metal layer and a transparent conductive layer. The upper electrode and the lower electrode are the same electrodes and are symmetrically arranged.
Preferably, the flexible substrate is made of at least one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene, polyethylene and polyvinyl chloride; the thickness of the flexible substrate is 20-500 mu m;
the buffer layer is made of TiO x (1≤x＜2)、ZnO、SiO 2 、Si 3 N 4 、In 2 O 3 And Sn (Sn) 2 O 3 At least one of (a) and (b); the thickness of the buffer layer is 3-15 nm;
the metal layer is made of noble metal, preferably at least one selected from Au, ag, pd and Pt; the thickness of the metal layer is 2-10 nm;
the transparent conductive layer is made of transparent conductive oxide, preferably at least one selected from ITO, FTO, AZO; the thickness of the transparent conductive layer is 10-50 nm.
In the art, transparent conductive oxides such as ITO have wide application as electrodes in electrochromic devices due to their high conductivity, high transmittance, firm film and high stability. However, in element In ITO is expensive and toxic, and the film has harder texture and poorer toughness, and film grains are easy to form cracks In the bending process to influence the conductivity of the electrode. Moreover, due to the poor binding force between the transparent conductive materials such as common ITO and the flexible substrate, the traditional film can be strained, broken and even separated from the substrate after being bent under stress. Therefore, ITO has great limitations in the application of flexible electrochromic device devices.
Based on this, the inventors first thought that by depositing a metal layer (preferably a noble metal) between the flexible substrate and the ITO, the bonding properties and the conductive properties thereof are improved. According to the research of the inventor, the metal particles (noble metal particles) are directly injected into the flexible substrate, so that the discontinuity among the metal particles can be caused, the film resistance is high, meanwhile, the isolated metal particles can cause strong local surface plasmon resonance, and the absorption of partial visible light and near infrared light is generated, so that the transmittance of the film is reduced. Still further, the present inventors creatively selected an inorganic insulating material (TiO 2 、SiO 2 、Si 3 N 4 Etc.) as a surface deposition preparation buffer layer of a flexible substrate (e.g., a transparent flexible substrate). However, further experiments by the inventors have found that SiO 2 、Si 3 N 4 When inorganic insulating materials are deposited, a radio frequency power supply is often adopted, and high-power radio frequency magnetic control deposition of the radio frequency power supply can cause partial melting of the surface of the flexible substrate, so that the surface flatness of the film is reduced, the comprehensive transmittance of the film is reduced, and the subsequent metal layer is influenced to form a continuous film. The inventor directly selects TiO 2 Magnetron sputtering is performed as a target material, due to TiO 2 Has strong bond energy and can be directly preparedTiO of (C) 2 The oxygen vacancy content in the TiO is very low, and noble metal is difficult to nucleate and grow at the vacancy, so the TiO prepared by the process 2 Which is detrimental to the performance of the final device. The present patent preferably employs a process of depositing metal and then converting it into oxide by oxygen plasma treatment. The process has the following advantages: firstly, because the sputtering rate of metal is higher, uniform and compact ultrathin metal oxide can be prepared; secondly, the oxidation degree can be controlled, the density of oxygen vacancies on the surface can be regulated and controlled in real time, and the optimization of the device structure is facilitated; third, the preparation speed is faster and the efficiency is higher than that of directly preparing oxide. The oxygen-deficient titania surface has a large number of oxygen vacancies that can act as sites for subsequent noble metal deposition and growth, thereby increasing the density of noble metal nucleation sites. Obviously, the more nucleation sites. The more uniform the noble metal film growth, the more dense it is. More preferably, the invention creatively adopts low-power deposition of a material (metal simple substance Ti) with higher sputtering rate, and then adopts O surface plasma for treatment. Secondly, the deposition rate of the metal simple substance is higher, the obtained film is more uniform and compact, and uniform and compact oxide can be formed through mild O plasma treatment. Because the deposition rate is higher, a usable metal film layer can be obtained by using lower sputtering power, and the low-power deposition does not influence the deposition evenness. Its proper work function and conduction band position facilitate electron migration. The noble metal layer has high conductivity, so that the transparent conductive layer can have proper conductivity only by a small thickness. Transparent conductive oxide is chosen as the transparent conductive layer on top of the noble metal layer because of its better chemical inertness and suitable electron transfer barrier.
In summary, the flexible composite electrode of the flexible substrate/buffer layer/metal layer/transparent conductive layer (transparent conductive oxide layer) is designed, so that the flexibility and hardness of the electrode are synergistically improved, and the resistance remains unchanged after multiple curling/spreading. Electrochromic devices were prepared based on the flexible composite electrodes, exhibiting excellent bending and crimping properties. Preferably, the present inventors can further significantly improve the flexibility of the transparent conductive layer by reducing its overall thickness.
The patent adopts the process of depositing metal firstly and then converting the metal into oxide through oxygen plasma treatment. The process has the following advantages: firstly, because the sputtering rate of metal is higher, uniform and compact ultrathin metal oxide can be prepared; secondly, the oxidation degree can be controlled, the density of oxygen vacancies on the surface can be regulated and controlled in real time, and the optimization of the device structure is facilitated; third, the preparation speed is faster and the efficiency is higher than that of directly preparing oxide.
The oxygen-deficient titania surface has a large number of oxygen vacancies that can act as sites for subsequent noble metal deposition and growth, thereby increasing the density of noble metal nucleation sites. Obviously, the more nucleation sites. The more uniform the noble metal film growth, the more dense it is. The purpose of the uniform and dense noble metal layer is to improve the overall conductivity of the electrode.
Finally, a transparent oxide electrode is deposited on the surface of the noble metal layer, and the transparent oxide electrode has a proper energy band position so as to facilitate the migration of electrons in the device. The multilayer film composite electrode designed in the patent is provided with a buffer layer for preparing an ultrathin high-density noble metal layer; the purpose of the noble metal process is to reduce the thickness of the whole electrode, thereby improving the flexibility of the electrode; the transparent semiconductor electrode is used for adjusting the energy band of the electrode, facilitating the migration of electrons and improving the performance of the device.
Preferably, the sheet resistance of the first flexible composite electrode layer is 10 to 40 ohm/cm 2 The visible light transmittance is more than or equal to 75 percent; the first flexible composite electrode layer has a resistance change rate of less than 3% after being curled 100 times.
Preferably, the sheet resistance of the second flexible substrate layer is 10 to 40 ohm/cm 2 The visible light transmittance is more than or equal to 75 percent; the second flexible substrate layer has a resistivity less than 3% after being crimped 100 times. The top electrode and the bottom electrode are the same type of electrode.
Preferably, the electrochromic layer is made of WO 3 、MoO 3 And TiO 2 At least one of (a) and (b); the thickness of the electrochromic layer is 100-500 nm.
Preferably, the organic ion storage layer is gel-based solid state electrolysis containing lithium ion saltQuality is improved; the lithium ion salt is selected from lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, liPON, liTFSI and LiPF 6 At least one of them.
Preferably, the method for preparing the organic ion storage layer includes:
(1) According to the following steps of 1: (1-3): (0.05-0.2): (0.5-2): weighing the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium ion salt according to the mass ratio of (1-3), stirring until the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium ion salt are completely dissolved in the dark, adding the initiator, and further stirring fully to obtain a mixed solution;
(2) And (3) carrying out spin coating or lifting on the obtained mixed solution, and carrying out photo-curing under an ultraviolet lamp to obtain the organic ion storage layer.
Preferably, the photocurable resin is at least one selected from the group consisting of tetter TTA21, L-6206, L-6380H, L-6605;
the stabilizer is a transition metal organic compound, preferably ferrocene and derivatives thereof, more preferably ferrocene, vinylferrocene;
the organic precursor comprises an acid ester compound, preferably at least one of ethoxylation trimethylolpropane triacrylate ETPTA, TMPTA and trimethylolpropane triacrylate.
The initiator is at least one selected from azodiisobutyronitrile, azodiisoheptonitrile, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, tert-butyl peroxydibenzoate and tert-butyl peroxyvalerate, and the addition amount is 0.1-0.5% of the total mass;
the number of times of spin coating is at least 1, the rotating speed is 1000-3000 rpm, and the time of each spin coating is 10-30 s; the number of times of lifting is at least 1, and the lifting speed is 0.1-5 cm/s;
the photo-curing is performed by irradiating an ultraviolet lamp with the power of 100-300W for 5 seconds to 60 seconds.
Preferably, the response speed change of the curled flexible electrochromic device after being curled 100 times is less than 5%, and the adjusting capability is less than 3%.
On the other hand, the invention provides a preparation method of a flexible electrochromic device capable of curling, which adopts a physical method to prepare a flexible composite electrode layer, and comprises the following specific steps:
(1) Firstly, depositing a metal Ti film on the surface of a flexible substrate by adopting a magnetron sputtering method, and then performing O plasma treatment to obtain a buffer layer;
(2) And depositing a noble metal layer and a transparent conductive layer on the surface of the buffer layer by adopting a magnetron sputtering method to obtain the flexible composite electrode layer.
Preferably, in the step (1), the parameters of the magnetron sputtering method include: sputtering atmosphere Ar, sputtering power 20-40W, air pressure 0.2-1 Pa, sputtering temperature room temperature (20-40 ℃) and deposition time 0.5-5 min.
Preferably, in step (1), the parameters of the O plasma treatment include: high purity O in atmosphere 2 (purity is more than or equal to 99.99%), air pressure is 5-20 Pa, power is 50-180W, and time is 2-20 min.
Preferably, in the step (2), the parameters of the magnetron sputtering method of the noble metal layer include: at least one of Au, ag, pd and Pt is used as a target, the sputtering atmosphere Ar, the air pressure is 1-2Pa, the sputtering temperature is room temperature (20-40 ℃), the sputtering power is 10-40W, and the working time is 2 s-1 min.
Preferably, in the step (2), the parameters of the magnetron sputtering method of the transparent conductive layer include: ITO, FTO or AZO is used as a target, sputtering gas is argon, the total pressure is 0.2-0.6 Pa, the distance between the target and a substrate is 10-20 cm (preferably 15 cm), the initial substrate temperature is room temperature (20-40 ℃), the deposition power is 50-150W, and the deposition time is 5-10 minutes.
The beneficial effects are that:
1. according to the invention, the buffer layer/the metal layer/the transparent conductive layer are sequentially deposited on the surface of the flexible substrate to serve as the composite electrode, so that the thickness of the film is sufficiently reduced on the premise of ensuring the transmittance and the resistance of the electrode, and the electrode has excellent flexibility and hardness;
2. in the invention, the composite electrode is prepared by adopting a physical method, the process is simple, and the production cost is low. The structure and the composition can be simply regulated and controlled, so that the structure and the composition are suitable for different devices, and have excellent universality.
Drawings
FIG. 1 is a schematic structural view of a rollable flexible electrochromic device according to the present invention;
FIG. 2 is an anoxic state TiO prepared in example 1 x XPS map of film.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, a flexible composite electrode composed of a flexible substrate/buffer layer/metal layer/transparent conductive layer is designed, the flexibility and hardness of the electrode are synergistically improved, the resistance remains unchanged after multiple curling/spreading, and a curled electrochromic device is prepared based on the flexible composite electrode. Specifically, the structure of the rollable flexible electrochromic device (e.g., fig. 1) includes: the flexible composite electrode, the electrochromic layer, the organic ion storage layer and the top electrode are sequentially stacked. The upper and lower electrodes are identical.
In the invention, the electrochromic layer is prepared on the surface of the transparent electrode by adopting film forming modes such as magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spray coating or lifting and the like. And preparing a buffer layer, a metal layer, a transparent conductive layer and the like by adopting a magnetron sputtering method. The direct current magnetron sputtering system equipment used for magnetron sputtering deposition can comprise a deposition chamber, a sample injection chamber, a plurality of target heads, a substrate plate, a direct current and a series of mechanical pumps and vacuum pumps, wherein the target heads form a certain angle with the substrate plate and are separated by a certain distance, and a direct current power supply is connected to the target heads. And ultrasonically cleaning the substrate, respectively ultrasonically cleaning the substrate for 20min by using acetone, absolute ethyl alcohol and deionized water, and drying by using compressed air. Covering a certain part of conductive substrate with high temperature adhesive tape as electrode, fixing on substrate tray, placing into sample chamber, opening mechanical pump to below 5Pa, opening baffle valve, and feeding into vacuum degree (background vacuum degree) of 10 -4 Pa and below.
The specific sputtering deposition process is as follows: high-purity argon and oxygen are respectively introduced into the sputtering chamber, the purity of the adopted argon and oxygen is 99.99 percent or more, the total pressure and the oxygen partial pressure in the cavity are controlled to be respectively in the range of 0.5-2.0 Pa and 0-50 percent, and the oxygen partial pressure is preferably 0-25 percent. The vertical distance between the target and the substrate is controlled to be 10-20 cm, and the initial substrate temperature is room temperature. And (3) switching on a direct current power supply, controlling the power of the direct current power supply to be 30-200W, pre-sputtering for 5-30 min, sputtering for 10-60 min, and controlling the temperature of the substrate to be room temperature. And after the sputtering is finished, the substrate is taken out after the temperature of the substrate is reduced to the room temperature.
A flexible material such as PEN (polyethylene naphthalate), PET (polyethylene terephthalate) or PI (polyimide) is used as a substrate, and a composite electrode material is deposited on the surface of the substrate to prepare the flexible composite electrode.
And (3) preparation of a buffer layer. Firstly, a metal Ti film is deposited on the surface of a flexible substrate by magnetron sputtering. Wherein the controlled sputtering atmosphere may be Ar. The sputtering power may be 20 to 40W. The air pressure can be 0.2 Pa to 1Pa. The sputtering temperature may be room temperature. The working time can be 0.5-5 min. The thickness of the obtained metal Ti film can be 3-15 nm. And (3) treating the metal Ti film by adopting O plasma to obtain a compact TiOx layer (x is more than or equal to 1 and less than 2). Wherein the atmosphere used for O plasma treatment can be high-purity O 2 The air pressure can be 5-20 Pa, the power can be 50-180W, and the time can be 2-20 min.
A metal layer (preferably a noble metal) is deposited using magnetron sputtering. Wherein the noble metal is at least one of Au, ag, pd or Pt as a target material. The sputtering atmosphere is controlled to be Ar, and the air pressure can be 1-2Pa. The sputtering temperature may be room temperature. The sputtering power may be 10 to 40W. The working time can be 2 s-1 min. The thickness of the metal layer obtained may be 2 to 10nm.
And preparing the transparent conductive layer by adopting a magnetron sputtering process. The transparent conductive material such as ITO, FTO, AZO is used as a target, the sputtering gas is argon, the total pressure can be 0.2-0.6 Pa, the distance between the target and the substrate can be 10-20 cm (preferably 15 cm), the initial substrate temperature can be room temperature, and the deposition power can be 50-150W. The thickness of the transparent conductive layer obtained may be 10 to 50nm.
Preparation of electrochromic layer. The metal tungsten, molybdenum or titanium is used as a target, sputtering gas is argon and oxygen, the total pressure is 0.5 to 2.0Pa, and the oxygen partial pressure is 0 to 50 percentThe distance between the target and the substrate is 10-20 cm, the initial substrate temperature is room temperature, the power of the direct current power supply applied to the target is 30-150W or the power density is 0.6-3.0W/cm 2 And depositing by using a direct current power supply to obtain the electrochromic layer film with the thickness of 100-500 nm.
The organic ion storage layer takes UV curing resin as a base material, and proper amount of solvent, cation salt, stabilizer, reducing agent and initiator are added, and after full stirring and dissolution, stable photocuring electrolyte precursor liquid is obtained. Wherein, dispose the light and solidify the electrolyte precursor solution, include: 1) According to the following steps of 1: (1-3): (0.05-0.2): (0.5-2): (1-3) weighing the photo-curing resin, the solvent, the ferrocene, the ETPTA and the lithium ion salt according to the proportion, and stirring in a dark place until the photo-curing resin, the solvent, the ferrocene, the ETPTA and the lithium ion salt are completely dissolved to obtain a mixed solution 1; 3) And adding (0.1-0.5)% of an initiator into the mixed solution 1, and further fully stirring to obtain the photo-curing electrolyte precursor solution.
The photo-curing electrolyte precursor solution is dip-coated on the surface of the electrochromic layer by adopting a lifting process, the immersion time is controlled to be 0.5-5 minutes (preferably 1 minute), and the lifting speed is 0.1-5 cm/s (preferably 0.5 cm/s). Or dipping the photocuring electrolyte precursor liquid on the surface of the electrochromic layer by adopting a process. Wherein, the rotating speed of the spin coating can be 1000-revolutions per minute, and the time can be 10s-30 s-minutes. The prepared device was uniformly irradiated with a 100W ultraviolet lamp for 5 seconds. Repeating the pulling operation or the spin coating operation for 1-4 times, and controlling the thickness of the film layer of the uncured organic ion storage layer to be 5-20 mu m. Wherein the thickness of the organic ion storage layer is not greatly different before and after curing, and the thickness of the film layer of the organic ion storage layer is 5-20 mu m. After completion, the flexible transparent electrode is covered with the same as the bottom electrode.
After the device is completely cured, organic solvents are used to remove organics from the surface of the excess device. Finally, the preparation process of the flexible electrochromic device capable of curling is completed.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific time, temperature, pressure, power, etc. of the process parameters in the examples below are also only one example of suitable ranges, i.e., one skilled in the art can select from the description herein within the suitable ranges and are not intended to be limited to the specific values of the examples below.
Example 1
(1) First, a flexible composite electrode layer was prepared using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, wherein the sputtering atmosphere Ar has sputtering power of 30W, the air pressure of 0.4Pa, the sputtering temperature is room temperature, the working time is 1min, and the film thickness is 5nm. Adopting O plasma to treat metal Ti film, atmosphere high purity O 2 The air pressure is 10Pa, the power is 120W, the time is 10min, and the obtained compact TiO is obtained x The thickness was 5nm. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Au, the sputtering atmosphere Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 8s, and the film thickness is 5nm. The magnetron sputtering process is adopted, ITO transparent conductive material is used as a target, sputtering gas is argon, the total pressure is 0.3Pa, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, the deposition power is 100W, and the film thickness is 35nm;
(2) The method comprises the steps of using a metal tungsten target, wherein sputtering gas is argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 15%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the surface of the target, which is applied with 70W of DC power, is a 400nm electrochromic layer film deposited by using a DC power supply;
(3) And preparing a photo-curing electrolyte precursor liquid. According to the following steps of 1:2:0.1:1:2 weighing a photo-curing resin (material is Talter TTA 21), a solvent (material is PMA), ferrocene, ETPTA and 1mol/L of propylene carbonate solution of lithium perchlorate in proportion, and stirring in a dark place until the solution is completely dissolved; then adding 0.2% of initiator (the material is azodiisobutyronitrile), and further stirring fully to obtain a photocuring electrolyte precursor solution;
(4) The photo-curing electrolyte precursor solution is dip-coated on the surface of the electrochromic layer by adopting a lifting process, the immersion time is 1 minute, the lifting speed is 0.5cm/s, and the prepared device is uniformly irradiated for 5 seconds by a lamp under the condition of 100W ultraviolet. The above pulling operation was repeated 3 times, and the thickness of the film layer was 15. Mu.m. After completion, the flexible transparent electrode is covered. After the device is completely cured, organic solvents are used to remove organics from the surface of the excess device. Finally, the preparation process of the flexible electrochromic device capable of curling is completed. The value of x in the supplemental TiOx was about 1.5, according to either spectroscopy or XPS testing.
Example 2
The procedure for the preparation of the crimpable flexible electrochromic device of this example 2 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PET (polyethylene terephthalate) as a flexible substrate.
Example 3
The procedure for the preparation of the crimpable flexible electrochromic device of this example 3 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PI (polyimide) as a substrate.
Example 4
The procedure for the preparation of the crimpable flexible electrochromic device of this example 4 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, wherein the sputtering atmosphere Ar has the sputtering power of 30W, the air pressure of 0.4Pa, the sputtering temperature of room temperature, the working time of 0.5min and the film thickness of 3nm. Adopting O plasma to treat metal Ti film, atmosphere high purity O 2 The air pressure is 10Pa, the power is 120W, the time is 10min, and the obtained compact TiO is obtained x The thickness was 3nm.
Example 5
The procedure for the preparation of the crimpable flexible electrochromic device of this example 5 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, wherein the sputtering atmosphere Ar has sputtering power of 30W, the air pressure of 0.4Pa, the sputtering temperature is room temperature, the working time is 5min, and the film thickness is 15nm. Adopting O plasma to treat metal Ti film, atmosphere high purity O 2 The air pressure is 10Pa, the workThe rate is 120W, the time is 10min, and the obtained compact TiO is x The thickness was 15nm.
Example 6
The procedure for the preparation of the crimpable flexible electrochromic device of this example 6 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Au, the sputtering atmosphere Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 2s, and the film thickness is 2nm.
Example 7
The procedure for the preparation of the crimpable flexible electrochromic device of this example 7 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Au, the sputtering atmosphere is Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 1min, and the film thickness is 10nm.
Example 8
The procedure for the preparation of the crimpable flexible electrochromic device of this example 8 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. The magnetron sputtering process is adopted, ITO transparent conductive material is used as a target, sputtering gas is argon, the total pressure is 0.3Pa, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, the deposition power is 100W, and the film thickness is 10nm.
Example 9
The procedure for the preparation of the crimpable flexible electrochromic device of this example 9 is described with reference to example 1, with the only difference: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. The magnetron sputtering process is adopted, ITO transparent conductive material is used as a target, sputtering gas is argon, the total pressure is 0.3Pa, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, the deposition power is 100W, and the film thickness is 50nm.
Example 10
The procedure for the preparation of the crimpable flexible electrochromic device of this example 10 was as described in reference to example 1, except that: in the step (4), a lifting process is adopted to dip-coat the photocuring electrolyte precursor liquid on the surface of the electrochromic layer, the immersion time is 1 minute, the lifting speed is 0.5cm/s, and the prepared device is uniformly irradiated for 5s by a lamp under the condition of 100W ultraviolet. The above pulling operation was repeated 1 time, and the film thickness was 5. Mu.m.
Example 11
The procedure for the preparation of the crimpable flexible electrochromic device of this example 11 was as described in reference to example 1, except that: in the step (4), a lifting process is adopted to dip-coat the photocuring electrolyte precursor liquid on the surface of the electrochromic layer, the immersion time is 1 minute, the lifting speed is 0.5cm/s, and the prepared device is uniformly irradiated for 5s by a lamp under the condition of 100W ultraviolet. The above pulling operation was repeated 4 times, and the thickness of the film layer was 20. Mu.m.
Example 12
The procedure for the preparation of the crimpable flexible electrochromic device of this example 12 is described with reference to example 1, the only difference being: in the step (4), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Ag, the sputtering atmosphere is Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 8s, and the film thickness is 5nm.
Example 13
The procedure for the preparation of the crimpable flexible electrochromic device of this example 13 is described with reference to example 1, with the only difference: in the step (4), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Pt, the sputtering atmosphere is Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 8s, and the film thickness is 5nm.
Example 14
The procedure for the preparation of the crimpable flexible electrochromic device of this example 14 was as described in reference to example 1, except that: in the step (4), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit a thin layer of noble metal, wherein the noble metal is Pd, the sputtering atmosphere is Ar, the air pressure is 1.8Pa, the sputtering temperature is room temperature, the sputtering power is 20W, the working time is 8s, and the film thickness is 5nm.
Example 15
The procedure for the preparation of the crimpable flexible electrochromic device of this example 15 was as described in example 1, except that: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, wherein the sputtering atmosphere Ar has sputtering power of 30W, the air pressure of 0.4Pa, the sputtering temperature is room temperature, the working time is min, and the film thickness is 10nm. Adopting O plasma to treat metal Ti film, atmosphere high purity O 2 The air pressure is 10Pa, the power is 120W, the time is 10min, and the obtained compact TiO is obtained x The thickness was 10nm.
Example 16 (direct build deposit TiO) 2 Poor performance
The procedure for the preparation of the crimpable flexible electrochromic device of this example 16 was as described in example 1, except that: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. TiO deposition on flexible substrate surface by magnetron sputtering 2 The layer, its parameter includes: . Adopting metallic titanium as a target, sputtering gas of argon and oxygen, total pressure of 1.5Pa, oxygen partial pressure of 15%, distance between the target and a substrate of 15cm, initial substrate temperature of room temperature, direct current power of 200W applied to the target, and depositing to obtain the electrochromic layer film with thickness of 5nm. Due to TiO 2 TiO directly prepared with strong bond energy 2 The oxygen vacancy content in the TiO is very low, and noble metal is difficult to nucleate and grow at the vacancy, so the TiO prepared by the process 2 Which is detrimental to the performance of the final device.
Comparative example 1
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 1 was as described with reference to example 1, except that: in the step (1), PEN (polyethylene naphthalate) is used as a substrate to prepare a flexible composite electrode layer, a metal simple substance Ti film is not deposited, and compact TiO is not prepared x I.e. compact TiO x Is 0nm thick.
Comparative example 2
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 2 was as described in reference to example 1, with the only differenceIn the following steps: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, wherein the sputtering atmosphere Ar has sputtering power of 30W, the air pressure of 0.4Pa, the sputtering temperature is room temperature, the working time is min, and the film thickness is 20nm. Adopting O plasma to treat metal Ti film, atmosphere high purity O 2 The air pressure is 10Pa, the power is 120W, the time is 10min, and the obtained compact TiO is obtained x The thickness was 20nm.
Comparative example 3
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 3 was as described with reference to example 1, except that: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. And (3) adopting magnetron sputtering to deposit thin-layer metal Ti on the surface of the flexible substrate, sputtering Ar in the sputtering atmosphere at the sputtering power of 30W and the air pressure of 0.4Pa, sputtering temperature of room temperature, working time of 5min and film thickness of 5nm, and adopting no subsequent O plasma treatment.
Comparative example 4
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 4 was as described with reference to example 1, except that: in the step (1), a flexible composite electrode layer was prepared using PEN (polyethylene naphthalate) as a substrate, and no Au layer was prepared, i.e., the thickness of the Au layer was 0nm.
Comparative example 5
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 5 was as described with reference to example 1, except that: in the step (1), a flexible composite electrode layer is prepared by using PEN (polyethylene naphthalate) as a substrate. SiO preparation on flexible substrate surface by radio frequency current 2 Layer (5 nm), the preparation parameters of which include: adopting silicon as a target, sputtering gas of argon and oxygen, total pressure of 1.5Pa, oxygen partial pressure of 10%, distance between the target and a substrate of 15cm, initial substrate temperature of room temperature, and RF power of 200W applied to the target, and depositing to obtain SiO with thickness of 5nm 2 A film.
Comparative example 6
The procedure for the preparation of the crimpable flexible electrochromic device of this comparative example 6 was as described in reference to example 1, except that: in the step (1), P isEN (polyethylene naphthalate) is used as a substrate to prepare a flexible composite electrode layer. Preparation of Si on the surface of a flexible substrate by radio frequency current 3 N 4 Layer (5 nm), the preparation parameters of which include: adopting metal tungsten as a target, sputtering gas of argon and nitrogen, total pressure of 2Pa, nitrogen partial pressure of 25%, distance between the target and a substrate of 15cm, initial substrate temperature of room temperature, and RF power of 200W applied to the target, and depositing to obtain Si with thickness of 5nm 3 N 4 A film.
Comparative example 5 and comparative example 6 Si 3 N 4 And SiO 2 The preparation process adopts radio frequency, the power deposition power of the power supply is higher, and excessive heat is accumulated on the substrate, so that the micro-area part of the substrate is melted, and the transmittance of the device is affected. Second, si 3 N 4 And SiO 2 The surface vacancies are less, and it is difficult to provide sufficient vacancies to deposit the noble metal layer, affecting the overall conductivity of the electrode.
Table 1 shows the composition and performance parameters of the flexible composite electrode prepared according to the invention:
the transmittance is visible light transmittance, and the testing method can be that an ultraviolet spectrophotometer is adopted, and then the average transmittance of a visible light wave band is obtained. The method for testing the sheet resistance can be a four-probe test method, and the sheet resistance of the device is directly obtained.
Table 2 shows the partial composition and performance parameters of the crimpable flexible electrochromic device:
wherein, regulatory capability: when high and low potentials are applied to the device, the transmittance at 670nm is different. The change in adjustability refers to the ratio of the initial adjustability of the device to the adjustability after 3000 bends. Response speed: the device was applied with a cyclic voltage, high potential of 1.5V, low potential of-3V, voltage time of 0.05s, hold time of 30s,1min1 cycle. The time required for the device to be adequately colored from the discolored state. The response speed change refers to the ratio of the initial response speed of the device to the response speed after 3000 bends.
Claims (10)
1. The flexible electrochromic device is characterized by comprising a first flexible composite electrode layer, an electrochromic layer, an organic ion storage layer and a second flexible composite electrode layer which are sequentially stacked; the first flexible composite electrode layer or the second flexible substrate layer sequentially comprises a flexible substrate, a buffer layer, a metal layer and a transparent conductive layer.
2. The flexible electrochromic device according to claim 1, wherein the flexible substrate is at least one of polyethylene terephthalate, PET, polyethylene naphthalate, PEN, polypropylene, polyethylene, and polyvinyl chloride; the thickness of the flexible substrate is 20-500 mu m;
the buffer layer is made of TiO x （1≤x＜2）、ZnO、SiO 2 、Si 3 N 4、 In 2 O 3 And Sn (Sn) 2 O 3 At least one of (a) and (b); the thickness of the buffer layer is 3-15 nm;
the metal layer is made of noble metal, preferably at least one selected from Au, ag, pd and Pt; the thickness of the metal layer is 2-10 nm;
the transparent conductive layer is made of transparent conductive oxide, preferably at least one selected from ITO, FTO, AZO; the thickness of the transparent conductive layer is 10-50 and nm.
3. The flexible electrochromic device according to claim 1 or 2, wherein the sheet resistance of the first flexible composite electrode layer or the second flexible substrate layer is 10-40 Ω/cm 2 The visible light transmittance is more than or equal to 75 percent; the first flexible composite electrode layer or the second flexible substrate layer has a resistance change rate of less than 3% after being curled 100 times.
4. A flexible electrochromic device according to any one of claims 1-3, characterized in that the electrochromic layer is of a material WO 3 、MoO 3 And TiO 2 At least one of (a) and (b); the thickness of the electrochromic layer is 100-500 a nm a.
5. The flexible electrochromic device according to any one of claims 1-4, wherein the organic ion storage layer is a lithium ion salt-containing gel-based solid state electrolyte; the lithium ion salt is selected from lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, liPON, liTFSI and LiPF 6 At least one of them.
6. The flexible electrochromic device according to claim 5, wherein said organic ion storage layer is prepared by a process comprising:
(1) According to the following steps of 1: (1-3): (0.05-0.2): (0.5-2): weighing the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium ion salt according to the mass ratio of (1-3), stirring in the dark until the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium ion salt are completely dissolved, adding the initiator, and further stirring fully to obtain the photo-curing electrolyte precursor solution;
(2) And (3) carrying out spin coating or lifting on the obtained photocuring electrolyte precursor liquid, and carrying out photocuring under an ultraviolet lamp to obtain the organic ion storage layer.
7. The flexible electrochromic device according to claim 6, wherein said photocurable resin is selected from at least one of tetter TTA21, L-6206, L-6380H, L-6605;
the stabilizer is a transition metal organic compound, preferably ferrocene and derivatives thereof, more preferably ferrocene, vinylferrocene;
the organic precursor comprises an acid ester compound, preferably at least one of ethoxylation trimethylolpropane triacrylate ETPTA, TMPTA and trimethylolpropane triacrylate;
the initiator is at least one selected from azodiisobutyronitrile, azodiisoheptonitrile, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, tert-butyl peroxydibenzoate and tert-butyl peroxyvalerate, and the addition amount is 0.1-0.5% of the total mass;
the number of times of spin coating is at least 1, the rotating speed is 1000-3000 rpm, and the time of each spin coating is 10-30 s; the number of times of lifting is at least 1, and the lifting speed is 0.1-5 cm/s;
the photo-curing is performed by irradiating an ultraviolet lamp with the power of 100-300W for 5 seconds to 60 seconds.
8. The flexible electrochromic device according to any of claims 1-7, wherein said flexible electrochromic device has a response speed change of less than 5% after 100 crimps and a conditioning capacity of less than 3%.
9. A method of manufacturing a flexible electrochromic device according to any one of claims 1 to 8, wherein the first flexible composite electrode layer or the second flexible composite electrode is manufactured by a physical method, comprising the steps of:
(1) Firstly, depositing a metal Ti film on the surface of a flexible substrate by adopting a magnetron sputtering method, and then performing O plasma treatment to obtain a buffer layer;
(2) And depositing a noble metal layer and a transparent conductive layer on the surface of the buffer layer by adopting a magnetron sputtering method to obtain the first flexible composite electrode layer or the second flexible composite electrode.
10. The method according to claim 9, wherein in the step (1), the parameters of the magnetron sputtering method include: sputtering atmosphere Ar, sputtering power of 20-40W, air pressure of 0.2-1 Pa, sputtering temperature of room temperature (20-40 ℃) and deposition time of 0.5-5 min;
in step (1), the parameters of the O plasma treatment include: high purity O in atmosphere 2 (purity is more than or equal to 99.99%), air pressure is 5-20 Pa, power is 50-180W, and time is 2-20 min;
in the step (2), the parameters of the magnetron sputtering method of the noble metal layer include: taking at least one of Au, ag, pd and Pt as a target, sputtering Ar in a sputtering atmosphere under the air pressure of 1-2Pa, sputtering at room temperature (20-40 ℃), sputtering power of 10-40W and working time of 2 s-1 min;
in the step (2), the parameters of the magnetron sputtering method of the transparent conductive layer include: ITO, FTO or AZO is used as a target, sputtering gas is argon, the total pressure is 0.2-0.6 Pa, the distance between the target and a substrate is 10-20 cm (preferably 15 cm), the initial substrate temperature is room temperature (20-40 ℃), the deposition power is 50-150W, and the deposition time is 5-10 minutes.
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