CN112662316A

CN112662316A - Cation-conducting resin slurry and preparation method and application thereof

Info

Publication number: CN112662316A
Application number: CN201910984487.4A
Authority: CN
Inventors: 包山虎; 黄爱彬; 金平实; 谢玲玲; 朱莹
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2019-10-16
Filing date: 2019-10-16
Publication date: 2021-04-16

Abstract

The invention relates to cation-conducting resin slurry, a preparation method and application thereof, wherein the cation-conducting resin slurry comprises the following components: the organic precursor comprises an acid ester compound, preferably one of ethoxylated trimethylolpropane triacrylate ETPTA and trimethylolpropane triacrylate TMPTA, and the resin comprises a light-cured resin or/and a heat-cured resin; the mass ratio of the solvent, the resin, the stabilizer, the ultraviolet absorbent, the organic precursor and the ion source solution is (1-5): 0.5-5): 0.1-2): 0.01-0.2): 0.5-5): 1.

Description

Cation-conducting resin slurry and preparation method and application thereof

Technical Field

The invention relates to cation-conducting resin slurry and a preparation method and application thereof, belonging to the technical field of chemical material synthesis and functional materials.

Background

Under the large background of energy conservation and emission reduction, an electrochromic device mainly comprises five films and comprises two transparent conducting layers, an ion storage layer, an electrochromic layer and an ion conducting layer. The ion storage layer assists the electrochromic layer to apply low voltage to the first conducting layer and the second conducting layer to realize electrochromic reaction. The ion conducting layer is used for providing a lithium ion and diffusion film layer and ensuring ion conductivity under the action of an electric field, and the structure and the preparation process of the ion conducting layer are one of the most important technologies for ensuring the electrochromic performance of the device. Electrochromic devices can be classified into three types according to the state of the ion conducting layer, which are: the liquid electrochromic device, the gel state electrochromic device and the all-solid state electrochromic device, wherein the gel state electrochromic device is also a quasi-solid state electrochromic device. The problems of packaging, liquid leakage and the like relative to the liquid electrochromic device; compared with the problems of slow response time, poor ionic conductivity and the like of the all-solid-state electrochromic device, the quasi-solid-state electrochromic device has better stability, simple preparation process and longer response time than the all-solid-state electrochromic device. Therefore, the resin paste capable of conducting cations, which is provided by the invention, is applied to quasi-solid-state electrochromism, so that the performance of a device can be remarkably improved.

Lithium batteries have the advantages of high specific energy, long cycle life, no environmental pollution and the like, are gradually replacing lead-acid batteries, nickel-hydrogen batteries and nickel-cadmium batteries, and are widely applied to portable electronic equipment. In recent years, the application of lithium batteries in the fields of electric vehicles, hybrid vehicles, energy storage batteries and the like has attracted great attention. The lithium battery mainly comprises four parts, namely positive and negative electrode materials, electrolyte, a diaphragm and a battery shell, wherein the solid electrolyte cannot be completely attached to the positive and negative electrode materials when in contact, and the interface resistance is obviously improved due to gaps. The cation-conducting resin slurry has high wettability on the surface of the electrode, can fully fill gaps on the surfaces of various electrodes, and is cured in an external mode, so that a solid-solid interface with compact combination is obtained.

Disclosure of Invention

Aiming at the problems of complex preparation process or high interface resistance of an ion conducting layer in the prior art, the invention aims to provide resin slurry capable of conducting cations and a preparation method and application thereof.

In one aspect, the present invention provides a cation-conducting resin paste, the composition of which comprises: the organic precursor comprises an acid ester precursor, preferably one of ethoxylated trimethylolpropane triacrylate ETPTA and trimethylolpropane triacrylate TMPTA, and the resin comprises a light-cured resin or/and a heat-cured resin; the mass ratio of the solvent, the resin, the stabilizer, the ultraviolet absorbent, the organic precursor and the ion source solution is (1-5): 0.5-5): 0.1-2): 0.01-0.2): 0.5-5): 1.

In the invention, a certain amount of frame organic matter (such as acid ester precursor) with the mass ratio (0.5-5):1 of the organic precursor to the ion source solution) is added into the resin slurry, so that the porosity and the pore size of the film after the slurry is cured can be improved, the cation conduction is facilitated, and the conduction speed and the conduction efficiency of the cations are improved. The organic precursor is used as an oxidation-reduction pair in the electrochromic process, so that the electrochromic cycle stability can be remarkably improved.

Preferably, the solvent is at least one of isopropanol, propylene glycol methyl ether acetate, dimethyl nylon acid, dimethylformamide and dimethyl sulfoxide.

Preferably, the thermosetting resin is at least one of polyethylene oxide, PVB, uv-curable and polyacrylic resin, and the photo-curable resin is a uv-curable resin.

Preferably, the stabilizer is a transition metal organic compound, preferably ferrocene and its derivatives. For example, ferrocene and ferrocene derivatives can be directly assembled with each other to form a sub-nano pore channel, which is convenient for cation transmission and prevents the electrochromic device from being incapable of being completely removed in the circulating process. Compared with the sample without ferrocene, the stability of the ferrocene is obviously increased. Namely, the existence of ferrocene and the derivatives thereof forms a stable framework to construct an ion transmission channel, but the ferrocene and the derivatives thereof have red color, and the transmittance of the film is reduced by excessively adding the ferrocene and the derivatives thereof.

Preferably, the solute in the ion source solution is perchlorate, preferably at least one of lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, zinc perchlorate and aluminum perchlorate.

Further, preferably, the solvent of the ion source solution is selected from one of propylene carbonate and acetonitrile; the mass ratio of the perchlorate to the solvent is 1 (0.5-20).

Preferably, the ultraviolet absorbent is selected from one of BYK1130 and BYK 292.

In another aspect, the present invention also provides a method for preparing the cation conductive resin paste, including:

(1) preparing an ion source solution:

(2) and weighing and mixing a solvent, resin, a stabilizer, an ultraviolet absorbent, an organic precursor and an ion source solution according to a mass ratio to obtain the cation-conducting resin slurry. And the film forming process of the slurry can be simplified by selecting proper resin. The resin-based slurry can continuously coat the surface of the substrate, and can obviously reduce the construction cost.

In another aspect, the present invention provides a cation-conducting resin film, which is obtained by coating the cation-conducting resin slurry on the surface of a substrate and then curing the coated substrate. The organic precursor, the stabilizer and the ultraviolet absorber are used in the invention, so that the stability of the resin film after curing can be improved, the process is simpler, and the processes such as hot pressing and the like are not needed only by simple coating. Since the resulting resin film has larger pores, the conduction velocity of cations is higher.

Preferably, the curing treatment mode is light curing treatment or heat curing treatment; the photocuring treatment is to irradiate for 30 seconds to 30 minutes under an ultraviolet lamp of 10 to 300W; the temperature of the heat curing treatment is 50-100 ℃, and the time is 10 minutes-2 hours.

The invention has the following beneficial effects:

1) can accommodate more cations (i.e., can carry a higher concentration of cations), and can increase the conduction velocity of cations;

2) the obtained resin slurry has good wettability and stability, can fully wet the surface of a substrate (base material), and reduces the interface resistance. For example, resin pastes have better wetting and significantly reduced interfacial steric hindrance compared to directly preparing solid ion conducting layers in devices;

3) the obtained resin sizing agent is simple in preparation and convenient for mass production and transportation;

4) the ionic conductivity of the film after the resin slurry is cured is higher. The resin slurry is not only limited to an electrochromic ion conducting layer, but also can be applied to other energy related fields such as lithium batteries and the like;

5) by adding a proper amount of frame polymer, micro-channels can be formed in the film, so that large-size ions can be conducted conveniently, and the response speed and the color memory of the electrochromic intelligent window are improved.

The resin slurry capable of conducting cations has good wettability, and the corresponding interface resistance is obviously reduced after the resin slurry is cured in different devices. Meanwhile, the conductive coating can effectively conduct various cations and keep good circulation stability. Therefore, the invention can be widely applied to the fields of electrochromic, lithium batteries and the like which relate to cation conduction.

Drawings

FIG. 1 is a graph showing contact angles of various cation-based resin pastes on a substrate surface, wherein (a) is Li in example 1⁺And (b) is Na in example 3⁺And (c) is Al in example 4³⁺It can be seen from the figure that the prepared slurry can be practically applied to the preparation of devices only if the slurry can wet the substrate as much as possible and spread on the surface of the substrate. If the wetting of the slurry is not sufficient, air bubbles are present in the final device, which will ultimately affect the transmittance of the device. As can be seen, the three types of cations proposed in the patent have smaller contact angles and better wettability, and can be used for preparing devices;

FIG. 2 is a schematic diagram of a device structure (a) based on cation-conducting resin paste as an electrochromic ion storage layer and a structure of a resin film based on cation-conducting resin paste (b);

fig. 3 is a comparison of electrochromic properties of devices prepared by adding cation-conducting resin pastes of different proportions of organic precursors and cation solutions, wherein hexagons are those of example 1, diamonds are those of example 5, and circles are those of visible light transmittance after color change of example 6, triangles are those of initial transmittance of example 1, and since the electrochromic components hardly absorb visible light when external pressure is not applied, the initial transmittance of samples of different proportions is almost the same. It can be seen that when the ratio of the organic precursor to the cationic solution is 1:1, the electrochromic properties are the best. This is because the best electrochromic properties are achieved only if the redox balances during the electrochromic process.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the disclosure, a resin slurry capable of conducting cations and a preparation method thereof are provided, and the obtained resin slurry capable of conducting cations can be cured into a film through subsequent treatment.

In one embodiment of the present invention, the basic composition of the resin syrup capable of conducting cations includes: solvent, resin, stabilizer, ultraviolet absorbent, organic precursor, ion source solution and the like. Wherein, the mass ratio of the solvent, the resin, the stabilizer, the ultraviolet absorbent, the organic precursor and the ion source solution can be (1-5): 0.5-5): 0.1-2): 0.01-0.2): 0.5-5): 1. The ion conduction speed and efficiency in the finally cured film can be regulated and controlled by controlling the proportion of each component and the kind of cations, and the method can be applied to the field of electrochromic energy sources, so that the electrochromic response speed is improved. The purpose of ferrocene and ferrocene derivatives is to form a framework structure by two self ring structures, so that cations can be more rapidly transmitted under the driving of an external bias, and the structure has the following advantages: firstly, the presence of the framework channels makes the cation transport more direct, avoiding "detours"; secondly, the transport of cations is faster compared to the pores in the organic matter; finally, the problem that the cations are not timely removed in the cyclic color change process can be effectively avoided. Then, the ferrocene and the ferrocene derivatives have orange yellow color, and the device has the orange yellow color due to excessive addition amount, so the addition amount needs to be controlled. The organic precursor functions as a redox couple to balance the electrochemical reactions during the insertion and extraction of cations. Moreover, the organic precursor is used as an oxidation-reduction balance couple in the color changing process of the electrochromic device, so that the device has higher stability and longer service life. Therefore, if the addition amount of ferrocene is large, although the stability of the device can be further improved, the red color of the ferrocene can influence the transmittance of the device, so that the device has no practical significance, and the requirement of balancing the electricity pair cannot be met if the addition amount is too small.

The solvent used is capable of completely dissolving all the components and maintaining stability, while the fluidity of the slurry can be adjusted. The solvent may be at least one of isopropyl alcohol, propylene glycol methyl ether acetate, dimethyl nylon acid, dimethyl formamide, dimethyl sulfoxide, and the like.

The resin is the main component of the final film. The resin comprises light curing resin and heat curing resin according to different curing modes. The resin comprises: polyethylene oxides of different molecular weights (for example, molecular weights of 5 to 500 ten thousand, preferably 5 to 100 ten thousand), one of high-functional group uv curable resins.

The combination of the stabilizing agent and the long-chain polymer can improve the stability of the polymer and construct a channel suitable for cation conduction. The stabilizer comprises transition metal organic compounds such as ferrocene and derivatives thereof.

The ion source solution primarily functions to provide the appropriate amount and type of cations (which may be provided by an ionic salt). The ionic salt mainly comprises perchlorate of cations such as Li, Na, K, Mg, Zn, Al and the like. The solvent in the ion source solution includes propylene carbonate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and the like. The mass ratio of the ionic salt to the solvent is 1 (0.5-20).

The ultraviolet absorbent has the main function of absorbing ultraviolet rays in sunlight, avoids the damage of the ultraviolet rays to the resin slurry or the resin film in the long-term use process, and improves the overall stability of the resin slurry or the resin film. The UV absorbers mainly include BYK1130 and BYK 292 series.

The organic precursor is mainly used for obtaining the polymer capable of storing and attaching active cations by enabling precursor substances to pass through the reaction processes of chain initiation, chain growth induction and chain termination through a curing means. The organic precursor comprises various acid esters, such as ethoxylated trimethylolpropane triacrylate and the like.

The invention has the advantages that the preparation and construction process of the obtained cation-conducting resin slurry is simple, the popularization is convenient, and the cation-conducting resin slurry is suitable for various special-shaped or 3D structures. The following exemplarily illustrates a method for preparing the cation-conducting resin paste.

And preparing an ion source solution. For example, the cationic salt and the solvent are weighed according to the mass ratio of 1:2, mixed and fully stirred for 4-6h to form a clear and transparent solution, and the clear and transparent solution is stored in a dark place.

Mixing a solvent, a resin, a stabilizer, an ultraviolet absorbent, an organic precursor and an ion source solution according to the mass ratio of (1-5): (0.5-5): 0.1-2): 0.01-0.2): 0.5-5):1 to obtain cation-conducting resin slurry (or cation-conducting resin slurry). As an example, the solvent, the resin, the stabilizer, the ultraviolet absorber, the organic precursor, and the ion source solution are weighed according to a mass ratio of 2:1:1:0.1:1:1, and are sufficiently stirred for 30min before being stored in a dark place. The prepared solution is the resin slurry capable of conducting cations. In the scheme, the solvent is at least one of isopropanol, propylene glycol methyl ether acetate, dimethyl nylon acid, dimethylformamide, dimethyl sulfoxide and the like. In the scheme, the resin is one of polyethylene oxide with different molecular weights and ultraviolet curing resin with high functional groups. In the scheme, the stabilizer is a transition metal organic compound such as ferrocene and derivatives thereof. In the scheme, the organic precursor is various acid esters, such as ethoxylated trimethylolpropane triacrylate and the like. In the scheme, the ultraviolet absorbent mainly comprises BYK1130, BYK 292 series and the like. In the above scheme, the ion source is perchlorate of cations such as Li, Na, K, Mg, Zn, Al, etc., and the solvent in the solution includes propylene carbonate, acetonitrile, etc.

In one embodiment of the present invention, the cation conductive resin paste is coated on the surface of a substrate (e.g., FTO, ITO, etc.), and then cured to form a film through a subsequent process. The curing treatment may be a photo-curing treatment or a thermal curing treatment. The light curing treatment can be performed for 30 seconds to 30 minutes under the irradiation of an ultraviolet lamp with the power of 10 to 300W. The temperature of the heat curing treatment can be 50-100 ℃, and the time is 10 minutes-2 hours. The thickness of the obtained film can be adjusted according to the needs to form a sub-nanometer pore channel.

In the disclosure, the obtained cation-conducting resin paste or cation-conducting resin thin film is used as an ion conducting layer to directly prepare a corresponding electrochromic device structure (or fast response electrochromic smart window). The resin-based ions in the electrochromic structure are transferred to the layer, so that the electrochromic performance of the device can be improved, and the cycling stability of the device can be improved. When an external voltage is applied, the ion storage layer and the electrochromic layer can generate relative color change, and simultaneously, the direct contact of electrolyte and an electrode is blocked, so that the electrolyte layer is prevented from being damaged by the direct impact of large current. Moreover, the resin selected by the invention has simple structure and large aperture, and can accommodate cations with larger radius, thereby improving the memory of the device. Meanwhile, the resin curing mode selected in the invention is simple, and high-temperature and high-pressure equipment is not needed for defoaming, so that the production cost is directly reduced, and the industrial popularization is facilitated.

In one embodiment of the present invention, the electrochromic smart window has a structure including: the upper and lower transparent electrode layers (a first transparent electrode layer (TC layer) and a second transparent electrode layer (TC layer)), and the ion storage layer (IS layer), the ion conductive layer (IC layer), and the electrochromic layer (EC layer) sequentially disposed between the two transparent electrode layers are sequentially constructed, as shown in fig. 1. Wherein the ion conducting layer is a cation conducting resin film obtained by curing the obtained cation conducting slurry, and the thickness of the ion conducting layer can be 3-100 μm. Compared with the disclosed method, the resin-based ion conducting layer introduced by the invention has a simple process method. More importantly, the organic precursor contains three functional groups of olefin, ester and ether, so that the organic precursor contains a large amount of lone-pair electrons, the cation conduction speed is higher, the electrochromic response speed is correspondingly higher, and the electrochromic response time is less than 5 s. And the obtained resin-based ion conducting layer has more holes and larger pore diameter, so that the cation conducting speed is higher, the electrochromic response speed is correspondingly higher, and the electrochromic response time is less than 3 s.

In an optional embodiment, the sheet resistance of the transparent electrode layer (or called transparent electrode conductive layer) is generally 3-100 Ω/cm²The transmittance is more than 75 percent. For example, ITO transparent conductive glass, FTO transparent conductive glass, AZO transparent conductive glass, ATO transparent conductive glass, and the like. The thickness of the transparent electrode layer can be 100-400 nm.

In an alternative embodiment, the material composition of the electrochromic layer is WO_3-x(0＜x＜0.2)、Mo_3-y(0＜y＜0.2)、TiO₂And one or more of the pets (poly 3, 4-ethylenedioxythiophene) are compounded. The electrochromic layer can be prepared by physical coating deposition, and the thickness of the electrochromic layer can be 100-500 nm.

In an alternative embodiment, the material composition of the ion storage layer is NiO_z(1＜z＜1.5)、CoO_a(1 < a < 1.5) and V₂O₅One or more of the above components are compounded. The ion storage layer can be prepared by physical coating depositionThe thickness of the film is 50 to 200 nm.

In one embodiment of the invention, the contact state between interfaces of each layer is adjusted by adjusting the thickness and the preparation process of each functional layer in the device, so that the electrochromic intelligent window which can be widely popularized and has use value is obtained.

In the invention, firstly, an ion storage layer and an electrochromic layer are respectively deposited on a transparent conductive substrate (a first transparent conductive layer and a second transparent conductive layer) by adopting a physical coating method; and then coating resin slurry (cation-conducting resin slurry) containing corresponding cations between the two layers of films, and carrying out curing treatment to obtain the quick-response electrochromic intelligent window. The physical coating method comprises vacuum evaporation, electron beam evaporation, magnetron sputtering, plasma pulse deposition and the like. The coating method comprises blade coating, spraying, vacuum drip irrigation, screen printing and the like. The preparation process of the fast response electrochromic intelligent window is illustrated by taking a magnetron sputtering method as an example.

The direct current magnetron sputtering system equipment used for magnetron sputtering deposition in the invention can comprise a deposition chamber, a sample 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 and the substrate plate form a certain angle and are separated by a certain distance, and a direct current power supply is connected on the target heads.

And (4) cleaning the substrate. Ultrasonically cleaning the substrate, ultrasonically cleaning the substrate with acetone, absolute ethyl alcohol and deionized water for 20min respectively, and blow-drying with compressed air.

Covering a certain part of transparent conductive substrate with high-temperature adhesive tape as electrode, fixing on substrate tray, placing into sample introduction chamber, pumping to below 5Pa, opening baffle valve, and feeding into vacuum degree (background vacuum degree) of 10^- ⁴Pa or less.

A specific sputtering deposition process. Respectively introducing high-purity argon and oxygen into the sputtering chamber, wherein the purity of the argon and the purity of the oxygen are 99.99% or more, the total pressure and the oxygen partial pressure in the cavity are controlled to be within the ranges of 0.5-2.0Pa and 0-50%, and the oxygen partial pressure is preferably 0-25%. The vertical distance between the target and the substrate is controlled to be 10-20cm, and the initial substrate temperature is room temperature. And turning 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 10-60min, and keeping the temperature of the substrate at room temperature.

And after the sputtering is finished, taking out the sample when the temperature of the substrate is reduced to the room temperature. A resin-based ion conducting layer is then applied between the electrochromic layer and the ion storage layer and cured using uv light or heat. The ion storage layer and the electrochromic layer are respectively deposited on the surface of the transparent electrode by a physical coating method, the ion conducting layer can be a membrane prepared in advance and is clamped between the two layers of membranes, or processed slurry is coated between the two layers of membranes and is solidified into a membrane in a post-processing mode. As an example, a resin slurry prepared by mixing an organic solvent, a stabilizer, a curing resin, an organic precursor and an ion source solution in a certain proportion is coated between an ion storage layer and an electrochromic layer by a method such as blade coating, spray coating, vacuum drop irrigation, screen printing and the like, and then the complete device is formed by ultraviolet curing or thermal curing. The thickness of the resin layer is controlled to be 3-100 μm by the surface tension of the hard template and the resin solution. The choice of curing method depends on the choice of resin type. Wherein the light curing treatment is to uniformly irradiate the device for 30 s-30 min under 100W ultraviolet. The thermal curing treatment is to place the device on an oven or a heater and keep the temperature at 50-100 ℃ for 10 min-2 h. After the device is solidified, organic matter on the surface of the redundant device is removed by using an organic solvent, and the quick-response electrochromic intelligent window can be obtained.

In an alternative embodiment, the ion storage layer and the electrochromic layer are prepared separately on the surface with an ITO transparent conductive glass substrate. As an example of the preparation of the ion storage layer, there are: by a magnetron sputtering method, metal such as nickel, cobalt or vanadium is used as a target material, sputtering gas is argon and oxygen, total pressure is 0.5-2.0Pa, oxygen partial pressure is 0-50%, the distance between the target material and a substrate is 10-20cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 50-300W or the power density is 0.7-6.0W/cm²Applied on the surface of a substrateDepositing 50-200nm ion storage layer film by DC power supply. As an example of the preparation of the electrochromic layer, there is included: by magnetron sputtering method, metal tungsten, molybdenum or titanium is used as target material, sputtering gas is argon and oxygen, total pressure is 0.5-2.0Pa, oxygen partial pressure is 0-50%, the distance between the target material and the substrate is 10-20cm, the initial substrate temperature is room temperature, the power of DC power supply applied on the target material is 30-150W or the power density is 0.6-3.0W/cm²The surface of the electrochromic layer film is deposited with 100 nm-400 nm by using a direct current power supply.

In the invention, the electrochromic intelligent window belongs to a quasi-solid electrochromic device, and an ion conducting layer of the electrochromic intelligent window is based on MClO₄The cation organic electrolyte such as solution (M: Li, Na, K, Mg, Zn, Al) comprises ion source, precursor, stabilizer, curing resin and organic solvent. The quasi-solid electrochromic device is obtained through ultraviolet curing (UV curing technology) or thermal curing, and the device has the advantages of good stability, simple preparation process and excellent performance of quick response. And compared with a liquid electrochromic device, the liquid electrochromic device has the advantages of no problems of packaging, liquid leakage and the like and good stability. Compared with an all-solid-state electrochromic device, the ion conducting layer has large aperture, is easy for cation transmission, and shortens response time. By optimizing the matching property between the resin and the cation, the prepared organic-inorganic composite electrochromic intelligent window has the advantages of ultra-fast response speed, excellent electrochromic performance and good cycle stability.

The electrochromic intelligent window has the following beneficial effects:

(1) the ion conducting layer has large aperture and many pore channels, and is easy for the transmission of cations, thereby improving the response speed of the device;

(2) the solid-liquid interface has good wettability and is contacted with a solid-solid interface, so that the steric hindrance between the interfaces is reduced, and the stability and the cycle performance of the device are improved;

(3) the preparation process is simple, the preparation of large-size devices is supported, and the industrial popularization is facilitated.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. The stirrer, vessel and reagents used in the present invention were not specially treated.

Example 1

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, a light-cured resin UC-35 (Zhejiang Nameji), a stabilizer ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:1:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

and coating the resin slurry capable of conducting cations on the surface of a base material, and uniformly irradiating for 15min by using a lamp under 100W ultraviolet to obtain the resin film. The thickness of the resulting resin film was 80 μm. By judging the performance of the electrochromic, example 1 is the most excellent.

Example 2

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. Then, propylene glycol methyl ether acetate, polyethylene oxide with the molecular weight of 50 ten thousand, ferrocene, BYK1130, ETPTA and lithium ion solution are weighed according to the mass ratio of 2:1:1:0.1:1:1, fully stirred for 30min and then stored in a dark place. The prepared solution is the resin slurry capable of conducting cations.

Example 3

Firstly, preparing an ion source solution, weighing sodium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. Then, the propylene glycol monomethyl ether acetate, the light-cured resin UC-35, the ferrocene, the BYK1130, the ETPTA and the sodium ion solution are weighed according to the mass ratio of 2:1:1:0.1:1:1, fully stirred for 30min and then stored in a dark place. The prepared solution is resin slurry capable of conducting cations;

and coating the resin slurry capable of conducting cations on the surface of a base material, and uniformly irradiating for 15min by using a lamp under 100W ultraviolet to obtain the resin film. The thickness of the resulting resin film was 80 μm.

Example 4

Firstly, preparing an ion source solution, weighing aluminum perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and an aluminum ion solution according to the mass ratio of 2:1:1:0.1:1:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

Example 5

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. Then, DMF, light-cured resin UC-35, ferrocene, BYK1130, ETPTA and lithium ion solution are weighed according to the mass ratio of 2:1:1:0.1:1:1, and are fully stirred for 30min and then are stored in a dark place. The prepared solution is resin slurry capable of conducting cations;

Example 6

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:2:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

Example 7

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:3:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

Example 8

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:5:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

Example 9

Ultrasonic cleaning the substrate with acetone, ethanol and deionized water for 20min, and fixing on a substrate tray with high temperature adhesive tapePutting the sample into a sample chamber, starting a mechanical pump to below 5Pa, opening a baffle valve, and sending into a vacuum degree (background vacuum degree) of 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct-current power supply applied to the target is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 1 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 10

Ultrasonic cleaning the substrate with acetone, ethanol, and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) of 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target material through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6 percent, the distance between the target material and a substrate is 15cm, and an initial base isThe bottom temperature is room temperature, the power of a direct current power supply applied to the target material is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 2 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And cured in an oven at 80 ℃ for 2 hours. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 11

Ultrasonic cleaning the substrate with acetone, ethanol, and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) of 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 10min, and an ion storage layer film with the thickness of about 20nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct-current power supply applied to the target is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 3 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 12

Ultrasonically cleaning the substrate with acetone, ethanol and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa with a mechanical pump,the flapper valve was opened and vacuum (background) was applied to 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct-current power supply applied to the target is 70W or the power density is 1.54W/cm²And the deposition time is 150min, and the electrochromic layer film with the thickness of about 200nm is obtained. The cation-conducting resin paste obtained in example 4 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 13

Ultrasonic cleaning the substrate with acetone, ethanol, and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) of 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target material through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6 percent, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, and direct current applied to the target materialThe power supply power is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 5 was selected to prepare a thin film having a thickness of about 100 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 14

Ultrasonic cleaning the substrate with acetone, ethanol, and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) of 10^-4Pa or less. Preparing an ion storage layer by taking metal cobalt as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using metal tungsten as a target through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct-current power supply applied to the target is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 6 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Example 15

Ultrasonic cleaning the substrate with acetone, ethanol, and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) to obtain the final productUp to 10^-4Pa or less. Preparing an ion storage layer by taking metal nickel as a target material, wherein sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 1.23W/cm²The sputtering time is 30min, and an ion storage layer film with the thickness of about 60nm is obtained on the surface of the substrate. Preparing an electrochromic layer by using molybdenum as a target through a magnetron sputtering method, wherein sputtering gases are argon and oxygen, the total pressure is 2.0Pa, the oxygen partial pressure is 6%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct-current power supply applied to the target is 70W or the power density is 1.54W/cm²And the deposition time is 30min, and the electrochromic layer film with the thickness of about 350nm is obtained. The cation-conducting resin paste obtained in example 7 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Comparative example 1

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:0:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

and coating the resin slurry capable of conducting cations on the surface of a base material, and uniformly irradiating for 15min by using a lamp under 100W ultraviolet to obtain the resin film. The thickness of the resulting resin film was 80 μm, and it was confirmed that the film was formed as well.

Comparative example 2

Referring to example 9, a fast response electrochromic smart window was prepared, except that: the cation-conducting resin paste obtained in comparative example 1 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Comparative example 3

Firstly, preparing an ion source solution, weighing lithium perchlorate and propylene carbonate according to the mass ratio of 1:2, mixing, fully stirring for 4-6h to form a clear and transparent solution, and storing in a dark place. And then weighing propylene glycol methyl ether acetate, the light-cured resin UC-35, ferrocene, BYK1130, ETPTA and a lithium ion solution according to the mass ratio of 2:1:1:0.1:6:1, fully stirring for 30min, and storing in a dark place. The prepared solution is resin slurry capable of conducting cations;

Comparative example 4

Referring to example 9, a fast response electrochromic smart window was prepared, except that: the cation-conducting resin paste obtained in comparative example 3 was selected to prepare a thin film having a thickness of about 20 μm by screen printing in the electrochromic layer and the ion-conducting layer. And irradiating with 100W ultraviolet rays for 5 min. And finally, simply cleaning the surface of the device by using ethanol to obtain a complete device.

Claims

1. A cation conducting resin paste, characterized in that the composition of the cation conducting resin paste comprises: the organic precursor comprises an acid ester compound, preferably one of ethoxylated trimethylolpropane triacrylate ETPTA and trimethylolpropane triacrylate TMPTA, and the resin comprises a light-cured resin or/and a heat-cured resin; the mass ratio of the solvent, the resin, the stabilizer, the ultraviolet absorbent, the organic precursor and the ion source solution is (1-5): 0.5-5): 0.1-2): 0.01-0.2): 0.5-5): 1.

2. The resin syrup according to claim 1, wherein the solvent is at least one of isopropyl alcohol, propylene glycol methyl ether acetate, dimethyl nylon acid, dimethyl formamide, and dimethyl sulfoxide.

3. The resin syrup according to claim 1 or 2, wherein the thermosetting resin is at least one of polyethylene oxide, polyvinyl butyral (PVB), polypropylene resin, and a photo-curing resin, and the photo-curing resin is a UV-curable resin.

4. Resin paste according to any of claims 1-3, characterised in that the stabiliser is a transition metal organic compound, preferably ferrocene and its derivatives.

5. The resin syrup according to any of claims 1 to 4, wherein the solute in the ion source solution is perchlorate, preferably at least one of lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, zinc perchlorate and aluminum perchlorate.

6. The resin syrup according to claim 5, wherein the solvent of the ion source solution is selected from one of propylene carbonate and acetonitrile; the mass ratio of the perchlorate to the solvent is 1 (0.5-20).

7. The resin syrup according to any of claims 1-6, wherein the UV absorber is selected from the group consisting of BYK1130 and BYK 292.

8. A method of preparing the cation conducting resin paste according to any one of claims 1 to 7, comprising:

(1) preparing an ion source solution:

(2) and weighing and mixing a solvent, resin, a stabilizer, an ultraviolet absorbent, an organic precursor and an ion source solution according to a mass ratio to obtain the cation-conducting resin slurry.

9. A cation-conducting resin film, which is obtained by applying the cation-conducting resin paste according to any one of claims 1 to 7 to the surface of a substrate and then curing the applied cation-conducting resin paste.

10. The cation conducting resin film according to claim 9, wherein the curing treatment is a photo-curing treatment or a thermal curing treatment; the photocuring treatment is to irradiate for 30 seconds to 30 minutes under an ultraviolet lamp of 10 to 300W; the temperature of the heat curing treatment is 50-100 ℃, and the time is 10 minutes-2 hours.