阅读说明：本技术 一种热响应电解质材料及其制备方法和应用 (Thermal response electrolyte material and preparation method and application thereof ) 是由 王向伟 于志伟 杨高峰 钱海宁 荣先辉 于 2020-05-25 设计创作，主要内容包括：本发明提供了一种热响应电解质材料及其制备方法和应用,(1)制备热响应颜填料：将颜料放入溶剂中,然后加入偶联剂进行超声,使颜料表面进行改性或包袱,离心烘干后分散到溶剂中并在超声状态下加入热响应材料,最后进行离心并烘干,即可得到热响应颜料；(2)制备热响应电解质材料：将有机高分子、增塑剂、溶剂以及锂盐等进行混合,然后将步骤(1)中得到的热响应颜料加入上述混合物种制得热响应电解质材料；通过热响应电解质进行电致变色器件的颜色调控。本发明在不同温度条件下热响应相变材料状态发生变化,使电解质表现出不同的颜色变化,进而使电致变色器件表现出不同的颜色。(The invention provides a thermal response electrolyte material and a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) preparing a thermal response pigment filler: putting a pigment into a solvent, adding a coupling agent for ultrasonic treatment to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasonic state, and finally centrifuging and drying to obtain the thermal response pigment; (2) preparing a thermal response electrolyte material: mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermal response pigment obtained in the step (1) into the mixture to prepare a thermal response electrolyte material; the color of the electrochromic device is regulated and controlled by the thermal response electrolyte. The state of the thermal response phase-change material is changed under different temperature conditions, so that the electrolyte shows different color changes, and further the electrochromic device shows different colors.)

1. The thermal response electrolyte material is characterized by being prepared by the following steps:

(1) preparing the thermal response pigment and filler: putting the pigment into a solvent, adding a coupling agent for ultrasound to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasound state, and finally centrifuging and drying to obtain the thermal response pigment.

(2) Preparing a thermal response electrolyte material: mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermal response pigment obtained in the step (1) into the mixture to prepare the thermal response electrolyte material.

2. The thermally responsive electrolyte material according to claim 1, wherein the pigment is an inorganic pigment such as one or more of chromate, sulfate, azo, phthalocyanine, anthraquinone, indigoid, quinacridone, dioxazine and arylmethane pigments; the coupling agent is one or more of organic chromium complex, silanes, titanates, aluminic acid compounds and the like; the thermal response material is one or more of polyacrylic acid-b-poly N-isopropylacrylamide, polymethacrylic acid-b-poly N-isopropylacrylamide, polymethacrylol-b-poly N-isopropylacrylamide triarylmethane phthalide, fluorane and triphenylmethane; the organic polymer is one or more of polyethylene glycol, polymethyl methacrylate, polymethyl acrylate, polybutyl methacrylate and polyacrylonitrile; the organic polymer, the plasticizer, the solvent, the lithium salt and the thermal response pigment are in a ratio of (0-100): (0-100): (0-100): (50-300): (0-100): (5-30).

3. A preparation method of a thermal response electrolyte material is characterized by comprising the following steps:

(1) preparing the thermal response pigment and filler: putting the pigment into a solvent, adding a coupling agent for ultrasound to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasound state, and finally centrifuging and drying to obtain the thermal response pigment.

(2) Preparing a thermal response electrolyte material: mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermal response pigment obtained in the step (1) into the mixture to prepare the thermal response electrolyte material.

4. The method for producing a thermally responsive electrolyte material as claimed in claim 3, wherein the pigment is an inorganic pigment such as one or more of chromate, sulfate, azo pigment, phthalocyanine pigment, anthraquinone, indigoid, quinacridone, dioxazine and arylmethane pigments.

5. The method for preparing a thermally responsive electrolyte material as claimed in claim 3, wherein the coupling agent is one or more of organic chromium complexes, silanes, titanates, and aluminate compounds.

6. The method for preparing the thermal response electrolyte material according to claim 3, wherein the thermal response material is one or more of polyacrylic acid-b-poly N-isopropylacrylamide, polymethacrylic acid-b-poly N-isopropylacrylamide, polymethacrylol-b-poly N-isopropylacrylamide triarylmethane phthalides, fluorans and triphenylmethane.

7. The method for preparing a thermal response electrolyte material according to claim 3, wherein the organic polymer is one or more of polyethylene glycol, polymethyl methacrylate, polymethyl acrylate, polybutyl methacrylate, and polyacrylonitrile.

8. The method for producing a thermally responsive electrolyte material according to claim 3, wherein the organic polymer, the plasticizer, the solvent, and the lithium salt and the thermally responsive pigment are in a ratio of (0 to 100): (0-100): (0-100): (50-300): (0-100): (5-30).

9. A color regulating method of response color-changing electrolyte material in a color-changing device is characterized by comprising the following steps:

firstly, spraying an electrochromic material polythiophene onto a first conductive layer ITO glass;

secondly, blade-coating the prepared thermal response electrolyte material on the surface of the color-changing thiophene layer;

thirdly, spraying polypyrrole on the ion storage layer to the surface of the second conductive layer ITO glass; and finally, adhering the ITO glass coated with the electrolyte and the color-changing layer and the ITO glass coated with the polypyrrole to prepare the electrochromic device.

Fourthly, the voltage regulating device changes color, and meanwhile, the temperature regulating thermal response color changing electrolyte is controlled to realize regulation and control of different colors.

10. The method of claim 9 wherein said control voltage is in the range of-5V to 5V; the temperature regulation and control range is 15-80 ℃; the color-changing layer and the ion storage layer can be one or more of polyaniline and derivatives thereof, polythiophene and derivatives thereof, transition metal oxide and polypyrrole respectively; the color variation range is one or more of red system, yellow system, green system and blue system.

Technical Field

The invention relates to an electrolyte material, a preparation method and application thereof, in particular to a thermal response electrolyte material, a preparation method and application thereof, and belongs to the field of electronic materials.

Background

Electrochromism is a phenomenon in which optical properties (reflectivity, transmittance, absorption, and the like) of a material undergo a stable and reversible color change under the action of an applied electric field, and is manifested as a reversible change in color, transparency, and the like in appearance. Materials having electrochromic properties are referred to as electrochromic materials, and devices made with electrochromic materials are referred to as electrochromic devices.

The electrochromic intelligent glass has adjustability of light absorption and transmission under the action of an electric field, can selectively absorb or reflect external heat radiation and internal heat diffusion, reduces a large amount of energy which is consumed for keeping an office building and a civil house cool in summer and warm in winter, plays a role in improving the natural illumination degree and preventing peeping, solves the problem of urban light pollution which is continuously worsened in modern times, and is a development direction of energy-saving building materials; the electrochromic material has bistable performance, and the electrochromic display device made of the electrochromic material does not need a backlight lamp, does not consume power as long as the display content is not changed after a static image is displayed, has obvious energy-saving effect, and has the advantages of no visual blind angle, high contrast and the like; the automatic anti-dazzling rearview mirror prepared from the electrochromic material can adjust the intensity of reflected light according to the intensity of external light through an electronic induction system, so that the anti-dazzling effect is achieved, and driving is safer; the electrochromic device is an absorption type device and has the infrared variable emissivity characteristic, and can be used as an intelligent optical camouflage or temperature regulation material in the military and aerospace fields.

In the electrochromic device, the electrolyte provides a channel for ion transmission in the electrochromic process, and the performance and the state of the electrolyte have great influence on the color-changing performance and the color state of the device. The invention provides a preparation method of an electrolyte with thermal response characteristics, and the electrolyte can be used for regulating and controlling the color of an electrochromic device.

Disclosure of Invention

The invention aims to provide a thermal response electrolyte material capable of realizing switching regulation of multiple colors, and a preparation method and application thereof.

The purpose of the invention is realized as follows:

a thermal response electrolyte material is prepared by the following steps:

(1) preparing the thermal response pigment and filler: putting the pigment into a solvent, adding a coupling agent for ultrasound to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasound state, and finally centrifuging and drying to obtain the thermal response pigment.

(2) Preparing a thermal response electrolyte material: mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermal response pigment obtained in the step (1) into the mixture to prepare the thermal response electrolyte material.

The pigment is an inorganic pigment, such as one or more of chromate, sulfate, azo pigment, phthalocyanine pigment, anthraquinone, indigoid, quinacridone, dioxazine and arylmethane series pigment; the coupling agent is one or more of organic chromium complex, silanes, titanates, aluminic acid compounds and the like; the thermal response material is one or more of polyacrylic acid-b-poly N-isopropylacrylamide, polymethacrylic acid-b-poly N-isopropylacrylamide, polymethacrylol-b-poly N-isopropylacrylamide triarylmethane phthalide, fluorane and triphenylmethane; the organic polymer is one or more of polyethylene glycol, polymethyl methacrylate, polymethyl acrylate, polybutyl methacrylate and polyacrylonitrile; the organic polymer, the plasticizer, the solvent, the lithium salt and the thermal response pigment are in a ratio of (0-100): (0-100): (0-100): (50-300): (0-100): (5-30);

a preparation method of a thermal response electrolyte material comprises the following steps:

(1) preparing the thermal response pigment and filler: putting the pigment into a solvent, adding a coupling agent for ultrasound to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasound state, and finally centrifuging and drying to obtain the thermal response pigment.

(2) Preparing a thermal response electrolyte material: mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermal response pigment obtained in the step (1) into the mixture to prepare the thermal response electrolyte material.

The pigment is an inorganic pigment, such as one or more of chromate, sulfate, azo pigment, phthalocyanine pigment, anthraquinone, indigoid, quinacridone, dioxazine and arylmethane series pigment;

the coupling agent is one or more of organic chromium complex, silanes, titanates, aluminic acid compounds and the like;

the thermal response material is one or more of polyacrylic acid-b-poly N-isopropylacrylamide, polymethacrylic acid-b-poly N-isopropylacrylamide, polymethacrylol-b-poly N-isopropylacrylamide triarylmethane phthalide, fluorane and triphenylmethane;

the organic polymer is one or more of polyethylene glycol, polymethyl methacrylate, polymethyl acrylate, polybutyl methacrylate and polyacrylonitrile;

the organic polymer, the plasticizer, the solvent, the lithium salt and the thermal response pigment are in a ratio of (0-100): (0-100): (0-100): (50-300): (0-100): (5-30);

a color regulating method of response color-changing electrolyte material in a color-changing device comprises the following steps:

firstly, spraying an electrochromic material polythiophene onto a first conductive layer ITO glass;

secondly, blade-coating the prepared thermal response electrolyte material on the surface of the color-changing thiophene layer;

thirdly, spraying polypyrrole on the ion storage layer to the surface of the second conductive layer ITO glass; and finally, adhering the ITO glass coated with the electrolyte and the color-changing layer and the ITO glass coated with the polypyrrole to prepare the electrochromic device.

Fourthly, the voltage regulating device changes color, and meanwhile, the temperature regulating thermal response color changing electrolyte is controlled to realize regulation and control of different colors.

The regulating voltage range is-5V; the temperature regulation and control range is 15-80 ℃; the color-changing layer and the ion storage layer can be one or more of polyaniline and derivatives thereof, polythiophene and derivatives thereof, transition metal oxide and polypyrrole respectively; the color variation range is one or more of red system, yellow system, green system and blue system.

Compared with the prior art, the invention has the beneficial effects that:

the electrolyte material is simple to prepare, the color in the color-changing device can be simply regulated and controlled, the switching regulation and control of various colors can be realized, and the electrolyte material has very important civil and military values;

the state of the thermal response phase-change material is changed under different temperature conditions, so that the electrolyte shows different color changes, and further the electrochromic device shows different colors.

Detailed Description

The invention is described in more detail below by way of example, describing embodiments and specific procedures:

a preparation of response color-changing electrolyte material and a color regulation and control application technology thereof in electrochromism, which comprises the following steps:

(1) preparation of thermal response pigment and filler

Putting the pigment into a solvent, adding a coupling agent for ultrasound to modify or load-wrap the surface of the pigment, centrifugally drying, dispersing into the solvent, adding a thermal response material under an ultrasound state, and finally centrifuging and drying to obtain the thermal response pigment.

(2) Preparation of thermal response electrolyte material

Mixing an organic polymer, a plasticizer, a solvent, a lithium salt and the like, and then adding the thermally responsive pigment obtained in (1) to the mixture to prepare a thermally responsive electrolyte material.

(3) Preparation of multicolor electrochromic device

The multicolor electrochromic device comprises a first conducting layer, a color changing layer, a thermal response electrolyte, an ion storage layer and a second conducting layer, wherein when the voltage regulating and controlling device changes color, the thermal response color changing electrolyte is regulated and controlled by controlling temperature to realize regulation and control of different colors.

The pigment in the step (1) can be an inorganic pigment or an inorganic pigment, such as one or more of chromate, sulfate, azo pigment, phthalocyanine pigment, anthraquinone, indigoid, quinacridone, dioxazine, arylmethane pigment and the like;

the coupling agent in the step (1) can be one or more of organic chromium complex, silanes, titanates, aluminate compounds and the like;

the thermal response material in the step (1) can be one or more of high molecular polymer (polyacrylic acid-b-poly-N-isopropylacrylamide, polymethacrylic acid-b-poly-N-isopropylacrylamide, polymethacrylol-b-poly-N-isopropylacrylamide), thermochromic dye (triarylmethane phthalides, fluorans, triphenylmethane and the like) and the like;

the plasticizer in the step (1) comprises one or more of phthalate, aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon, alkyl sulfonate and the like;

the organic polymer in the step (2) comprises one or more of polyethylene glycol, polymethyl methacrylate, polymethyl acrylate, polybutyl methacrylate, polyacrylonitrile and the like;

the solvent in the step (2) comprises one or more of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and the like;

the lithium salt in the step (2) comprises one or more of lithium perchlorate (L iClO4), lithium hexafluorophosphate (L iPF6), lithium tetrafluoroborate (L iBF4) and the like;

the proportion of the organic polymer, the plasticizer, the solvent, the lithium salt and the thermal response pigment in the step (2) is (0-100): (0-100): (0-100): (50-300): (0-100): (5-30);

the ion conductivity range of the thermal response electrolyte material in the step (2) is 10 < -2 > to 10 < -5 > S/cm;

the first conducting layer and the second conducting layer in the step (3) can be one or more of indium tin oxide conducting materials, aluminum foils, copper foils, nano metal wire conducting materials and the like;

the voltage regulation and control range in the step (3) is-5V;

the color-changing layer and the ion storage layer in the step (3) can be one or more of polyaniline and derivatives thereof, polythiophene and derivatives thereof, transition metal oxides, polypyrrole and the like;

the temperature regulation and control range of the step (3) is 15-80 ℃;

the color variation range in the step (3) is one or more of red, yellow, green, blue and the like.