阅读说明：本技术 一种电致变色用低电压紫外固化电解质薄膜及其制备与应用 (Low-voltage ultraviolet curing electrolyte film for electrochromism and preparation and application thereof ) 是由 王宏志 王广 白智元 李耀刚 张青红 侯成义 于 2019-10-08 设计创作，主要内容包括：本发明涉及一种电致变色用低电压紫外固化电解质薄膜及其制备与应用,由包括下列组分的体系反应得到：二茂铁Fc、紫外线固化胶、LiClO<Sub>4</Sub>溶液。本发明制备工艺简单、成本低廉。制得的电解质薄膜透明性好、离子电导率高、工作电压低,能有效提高器件的电致变色性能,克服大面积电致变色器件难以封装、驱动电压高的问题,在电致变色智能窗领域具有非常广阔的应用前景。(The invention relates to a low-voltage ultraviolet curing electrolyte film for electrochromism and preparation and application thereof, which is obtained by the reaction of a system comprising the following components: ferrocene Fc, ultraviolet curing adhesive and LiClO 4 And (3) solution. The invention has simple preparation process and low cost. The prepared electrolyte film has good transparency, high ionic conductivity and low working voltage, can effectively improve the electrochromic performance of devices, overcomes the problems of difficult packaging and high driving voltage of large-area electrochromic devices, and has very wide application prospect in the field of electrochromic intelligent windows.)

1. The ultraviolet curing electrolyte film is characterized by being obtained by reacting a system comprising the following components in parts by weight: 1 portion of ferrocene Fc, 300 portions of ultraviolet curing adhesive, 200 portions of LiClO and 1600 portions of ultraviolet curing adhesive₄And (3) solution.

2. A preparation method of an ultraviolet light curing electrolyte film comprises the following steps:

adding ultraviolet curing glue and ferrocene Fc into LiClO₄And heating and stirring the solution to obtain mixed slurry, coating the mixed slurry on the surface of a hard substrate after vacuum defoaming, and irradiating the hard substrate by ultraviolet light to obtain the ultraviolet curing electrolyte film.

3. The method according to claim 2, wherein said LiClO is₄The solution is specifically as follows: taking dried LiClO of lithium perchlorate₄Dissolving in 1-methyl-pyrrolidone NMP, adding activated molecular sieve after full dissolution, and removing water to obtain LiClO₄And (3) solution.

4. The preparation method according to claim 3, wherein the drying is vacuum drying, the drying temperature is 50-80 ℃, and the drying time is 2-5 h.

5. The method according to claim 2, wherein said LiClO is₄The concentration of the solution is 0.1-1.5 mol/L; the Fc, the ultraviolet curing adhesive and the LiClO₄The mass ratio of the solution is 1:300: 200-1: 400: 1600.

6. The preparation method according to claim 2, wherein the heating and stirring process conditions are as follows: the heating temperature is 40-60 ℃, the stirring speed is 600-1000 r/min, and the stirring time is 30-60 min; the process conditions of vacuum defoaming are as follows: the vacuum pressure is-1 kPa, and the vacuum time is 30-60 min.

7. The preparation method according to claim 2, wherein the coating thickness on the surface of the hard substrate is 1-5 mm; the ultraviolet irradiation is as follows: the power of the LED is 20W, and the irradiation time is 30-300 s.

8. An ultraviolet-curable electrolyte film prepared by the method of claim 2.

9. An electrochromic smart window comprising the uv-curable electrolyte film according to claim 1.

10. Use of the uv curable electrolyte film of claim 1.

Technical Field

The invention belongs to the field of electrochromic materials and preparation and application thereof, and particularly relates to a low-voltage ultraviolet curing electrolyte film for electrochromic as well as preparation and application thereof.

Background

At present, energy consumption is increasingly serious, wherein building energy consumption accounts for about one fourth of the total social energy consumption, so how to solve the energy consumption on buildings is one of the important problems facing human beings at present. The electrochromic intelligent window can adjust the light transmission value according to voltage, further reduce a large amount of energy consumption brought by building refrigeration and heating, and has huge market application requirements in the aspect of realizing building energy conservation.

The electrochromic intelligent window generally comprises a glass substrate, a conducting layer, an electrochromic layer, an electrolyte layer and an ion storage layer, wherein the electrolyte layer provides a transmission channel for ions between electrodes and is an important component of the electrochromic intelligent window. When a large-area electrochromic intelligent window is constructed, the solid electrolyte is the best choice, the problems of difficult packaging, easy leakage and the like do not exist, but the problems of long processing period, complex process and the like exist when the solid electrolyte is cured by heating at present. And the processing mode of ultraviolet curing is adopted, so that the preparation of the electrolyte is simpler and more convenient. For example, patent 201710289036.X prepares an all-solid-state ultraviolet curing electrolyte, and the assembled device has good performance, but the ion conductivity of the electrolyte after curing is low (2.15-2.31 mS/cm). CN109634016A discloses a low-voltage quasi-solid electrolyte film for electrochromic, but the film is relatively troublesome to form, and needs to be put into a vacuum oven, heated, and cooled to room temperature to obtain the low-voltage quasi-solid electrolyte for electrochromic, the vacuum heating time is relatively long, and the process is relatively complicated due to the cooling step.

At present, when the electrochromic intelligent window is applied, along with the increase of the area of a device to be constructed or when the selected color-changing material is an inorganic metal oxide (such as tungsten oxide), the problem of electrolyte decomposition caused by the rise of driving voltage exists, so that the cycle stability of the electrochromic device is poor, and the requirement of practical application is not met. Aiming at the problem, electron donor (such as ferrocene) is introduced into the electrolyte, so that the ionic conductivity of the electrolyte is improved, the internal charge transmission quantity of the device is increased, and further, the driving voltage of the device is reduced, and a solution is provided for the large-area application of the electrochromic intelligent window. Meanwhile, an ultraviolet curing mode is selected for film forming, so that the film forming time is short, and the practical application and production are facilitated.

Disclosure of Invention

The invention aims to solve the technical problem of providing a low-voltage ultraviolet curing electrolyte film for electrochromism and preparation and application thereof, solving the problems of difficult packaging of large-area electrochromism devices, over high driving voltage and the like, and having the advantage of more convenient preparation method compared with heating curing and other methods, thus laying a solid foundation for industrialization of large-area electrochromism intelligent windows. The invention relates to an ultraviolet curing electrolyte film which is obtained by the reaction of a system comprising the following components in parts by weight:

1 portion of ferrocene Fc, 300 portions of ultraviolet curing adhesive, 200 portions of LiClO and 1600 portions of ultraviolet curing adhesive₄And (3) solution.

The invention relates to a preparation method of an ultraviolet curing electrolyte film, which comprises the following steps:

adding ferrocene Fc and ultraviolet curing adhesive into LiClO₄Heating and stirring the solution to obtain light yellow mixed slurry, coating the slurry on the surface of a hard substrate after vacuum defoaming, and irradiating the hard substrate by ultraviolet light to obtain the ultraviolet light curing electrolyte film.

The preferred mode of the above preparation method is as follows:

further, LiClO in the preparation method₄The solution, the ultraviolet curing adhesive and the Fc are sequentially added into a container.

The LiClO₄The solution is specifically as follows: taking dried LiClO of lithium perchlorate₄Dissolving in 1-methyl-pyrrolidone NMP, adding activated molecular sieve after full dissolution, and removing water to obtain LiClO₄And (3) solution.

The drying is vacuum drying, the drying temperature is 50-80 ℃, and the drying time is 2-5 hours.

The LiClO₄The concentration of the solution is 0.1-1.5 mol/L.

The Fc, the ultraviolet curing adhesive and the LiClO₄The mass ratio of the solution is 1:300: 200-1: 400: 1600.

The heating and stirring process conditions are as follows: the heating temperature is 40-60 ℃, the stirring speed is 600-1000 r/min, and the stirring time is 30-60 min; the process conditions of vacuum defoaming are as follows: the vacuum pressure is-1 kPa, and the vacuum time is 30-60 min.

The thickness of the coating on the surface of the hard substrate is 1-5 mm; the ultraviolet irradiation is as follows: the power of the LED is 20W, and the irradiation time is 30-300 s.

The invention relates to an ultraviolet curing electrolyte film prepared by the method.

The present invention provides an electrochromic smart window comprising the uv-curable electrolyte film according to claim 1.

The invention provides an application of the ultraviolet curing electrolyte film.

Advantageous effects

(1) The invention adopts the processing mode of ultraviolet curing, so that the electrolyte preparation process is simpler, and the large-scale application of the electrochromic intelligent window is facilitated;

(2) the preparation process is simple, the cost is low, the prepared electrolyte film has good transparency, high ionic conductivity, certain mechanical strength (as shown in figure 2), low working voltage, and can effectively improve the electrochromic performance of the device, overcome the problems that large-area electrochromic devices are difficult to package and high in driving voltage, and have very wide application prospect in the field of electrochromic intelligent windows;

(3) according to the invention, the ferrocene and the ultraviolet curing adhesive are added, so that the ionic conductivity of the electrolyte film is improved, the driving voltage (-3.2V to-2V) of the tungsten oxide-based electrochromic device is reduced, and the cycling stability of the electrochromic device is improved.

Drawings

FIG. 1 is a graph showing the AC impedance of a low voltage UV-curable electrolyte film for electrochromic prepared in example 1; wherein the inset is an AC impedance plot in the high frequency region;

FIG. 2 is a stress-strain diagram of a low-voltage UV-curable electrolyte film for electrochromic prepared in example 1;

FIG. 3 is a schematic structural diagram of an electrochromic device prepared in examples 1, 2 and 3;

FIG. 4 is a digital photograph of an electrochromic device prepared in example 1; wherein a is a faded state and b is a colored state;

FIG. 5 is a rheological curve of a low voltage UV-curable electrolyte prepared in example 2;

FIG. 6 is a cyclic voltammogram of an electrochromic device assembled from a low voltage UV-cured electrolyte film prepared in example 2; wherein the insets are cyclic voltammetry curves of an electrochromic device assembled by liquid electrolyte without adding Fc and ultraviolet curing glue;

FIG. 7 is a transmittance spectrum in a colored state and a bleached state of an electrochromic device assembled from the low-voltage UV-curable electrolyte film prepared in example 2;

FIG. 8 is an in-situ current response curve for an electrochromic device assembled from the low voltage UV-cured electrolyte film prepared in example 3;

fig. 9 is an in-situ transmittance spectrum of an electrochromic device assembled from the low voltage uv-curable electrolyte film prepared in example 3.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.