阅读说明：本技术 一类电致变色材料及其制备方法与应用 (A kind of electrochromic material and the preparation method and application thereof ) 是由 姜猛进 喻媛媛 徐建军 高慧慧 李大哲 杨晨 齐世凯 刘鹏清 游彦 于 2019-09-04 设计创作，主要内容包括：本发明公开了一类芳香族聚噁二唑电致变色材料及其制备方法与应用,分别将对苯二甲酸、间苯二甲酸、4,4’-联苯二甲酸、5-羟基间苯二甲酸、5-氨基间苯二甲酸与硫酸肼和4,4’-联苯醚二甲酸聚合,利用碱金属碳酸盐溶液、碱金属碳酸氢盐溶液或碱金属氢氧化物溶液处理,所得材料具有n-掺杂材料极高的光学对比度、成本耗费低,颜色的可调控以及其自掺杂特性带来的简单的三层器件结构,其具有很好的应用前景。(The invention discloses a kind of aromatic series polyoxadiazoles electrochromic materials and the preparation method and application thereof, respectively by terephthalic acid (TPA), M-phthalic acid, 4, 4'- biphenyl dicarboxylic acid, 5- Hydroxy M Phthalic Acid, 5- amino isophthalic acid and hydrazine sulfate and 4, the polymerization of 4'- Biphenyl Ether dioctyl phthalate, utilize alkali metal carbonate solution, alkali metal bicarbonate solution or alkali hydroxide soln processing, the optical contrast that resulting materials have n- dopant material high, cost consumption is low, controllable and its simple three layer devices structure of auto-dope characteristic bring of color, it has a good application prospect.)

1. a kind of electrochromic device, which is characterized in that the device includes: the cathode layer and anode layer being oppositely arranged, and Electrochromic layer between the cathode layer and the anode layer；The electrochromic layer is aromatic series polyoxadiazoles material Material.

2. the aromatic series polyoxadiazoles material that one kind is used for electrochromic device, which is characterized in that including the structure as shown in following formula I Unit:

Wherein, any one in X=Li, Na or K.

3. the aromatic series polyoxadiazoles material according to claim 2 for electrochromic device, which is characterized in that also wrap Include any structure unit as shown in following formula II-VI:

4. a kind of preparation method of the aromatic series polyoxadiazoles material for electrochromic device, which is characterized in that it include with Lower step:

By the first monomer 4,4'- Biphenyl Ether dioctyl phthalate, second comonomer with and hydrazine sulfate be dissolved in oleum；

Heating carries out polymerization reaction；

End-capping reagent is added after polymerization reaction；

Continue heating and carries out cyclization；

After cyclization, resulting polymers are frozen into silk strip in deionized water, after being washed to neutrality, in alkali metal In carbonate solution, alkali metal bicarbonate solution or alkali hydroxide soln impregnate to get；

The second comonomer is aromatic binary carboxylic acid monomer.

5. the preparation method according to claim 4, which is characterized in that the aromatic binary carboxylic acid monomer is selected to benzene two It is any one in formic acid, M-phthalic acid, 5- Hydroxy M Phthalic Acid, 5- amino isophthalic acid or 4,4'- biphenyl dicarboxylic acid Kind.

6. the preparation method according to claim 4, which is characterized in that the alkali metal carbonate solution is that lithium carbonate is molten Any one in liquid, sodium carbonate liquor or solution of potassium carbonate.

7. the preparation method according to claim 4, which is characterized in that the alkali metal bicarbonate solution is sodium bicarbonate Solution or potassium bicarbonate solution.

8. the preparation method according to claim 4, which is characterized in that the alkali hydroxide soln is lithium hydroxide Any one in solution, sodium hydroxide solution or potassium hydroxide solution.

9. the preparation method according to claim 4, which is characterized in that the end-capping reagent is benzoic acid.

10. being existed according to application of the aromatic series polyoxadiazoles material in electrochromic device, feature described in claim 2-3 In the aromatic series polyoxadiazoles material is used as the electrochromic layer of electrochromic device.

Technical field

The present invention relates to electrochromic device fields, and in particular to a kind of aromatic series polyoxadiazoles electrochromic material and its Preparation method and application.

Background technique

Polymer electrochromic material has low driving voltage, and high contrast, visual angle is broad, and Color tunable etc. is unique excellent Point has a good application prospect it in fields such as the hot smart window of tunable optical tune, anti-glare automobile rearview mirror, displays.

Aromatic series polyoxadiazoles is made of very high conjugated chain, make its optical device using it is upper have well before Scape, but be insoluble in general reagent, to limit its development.Wherein have that some literature reports aromatic series polyoxadiazoles Grafted aliphatic branch is mainly used for electroluminescent material to increase its dissolubility.Fragrant adoption is reported in the document in one's early years Oxadiazoles can carry out n- doping under applied voltage, generate the change of color, but be not introduced into in-depth study.Currently, Common electrochromic device is five-layer structure, conductive glass layer/electrochromic material/electrolyte/ion storage layer/conduction glass Glass layer (as shown in Figure 1), structure is complex, increases the cost of element manufacturing.Meanwhile existing electrochromic material is deposited The problems such as contrast is lower, its development is limited.

Summary of the invention

The present invention provides a kind of aromatic series polyoxadiazoles electrochromic material and the preparation method and application thereof, solve existing There is the problem of optical contrast existing for technology is low, structure is complicated.

In order to solve the technical problem, the present invention provides the following technical scheme that

A kind of electrochromic device, the device include: the cathode layer and anode layer being oppositely arranged, and are located at the yin Electrochromic layer between pole layer and the anode layer；The electrochromic layer is aromatic series polyoxadiazoles material.

The cathode layer and anode layer double-layer structure in outside are preferably transparent electro-conductive glass matrix, intermediate electrochromism The aromatic series polyoxadiazoles material that layer synthesizes for the present invention.

One kind of the invention is used for the aromatic series polyoxadiazoles material of electrochromic device, and the material includes such as following formula I Shown structural unit:

Wherein, any one in X=Li, Na or K.

Preferably, the material further includes any structure unit as shown in II-formula of following formula VI:

The present invention also provides a kind of preparation method of aromatic series polyoxadiazoles material for electrochromic device, packets Include following steps:

By the first monomer 4,4'- Biphenyl Ether dioctyl phthalate, second comonomer with and hydrazine sulfate be dissolved in oleum；

Heating carries out polymerization reaction；

End-capping reagent is added after polymerization reaction；

Continue heating and carries out cyclization；

After cyclization, resulting polymers are frozen into silk strip in deionized water, after being washed to neutrality, in alkali In metal carbonate salting liquid, alkali metal bicarbonate solution or alkali hydroxide soln impregnate to get；

The second comonomer is aromatic binary carboxylic acid monomer.

Preferably, the aromatic binary carboxylic acid monomer is selected from terephthalic acid (TPA), M-phthalic acid, 5- hydroxyl isophthalic diformazan Appointing in acid, 5- amino isophthalic acid, 4,4'- biphenyl dicarboxylic acid, 1,4- naphthalenedicarboxylic acid or 4,6- dihydroxy M-phthalic acid It anticipates one kind.

Preferably, the alkali metal carbonate solution is appointing in Lithium carbonate solution, sodium carbonate liquor or solution of potassium carbonate It anticipates one kind；

Preferably, the alkali metal bicarbonate solution is sodium bicarbonate solution or potassium bicarbonate solution；

Preferably, the alkali hydroxide soln is that lithium hydroxide solution, sodium hydroxide solution or potassium hydroxide are molten Any one in liquid.

Preferably, the end-capping reagent is benzoic acid.

Preferably, the mole of the hydrazine sulfate and the ratio between the first monomer and the mole of second comonomer are 1.05:1.

Preferably, the mol ratio of second comonomer and the first monomer is 2:8-8:2.

Preferably, the mol ratio of second comonomer and the first monomer is 3:7.

The application of aromatic series polyoxadiazoles material of the invention in electrochromic device, the aromatic series polyoxadiazoles material Material is used as the electrochromic layer of electrochromic device.

Compared to the prior art the present invention, has the advantage that

Aromatic series polyoxadiazoles electrochromic material of the invention, oxadiazoles ring and phenyl ring generate conjugation, reduce The energy gap of polymer makes it at the lower voltage and just can be carried out n doping, combined on the sulfonate radical of polymer lithium (sodium or potassium) sun from Son can carry out auto-dope after applied voltage, so as to which three-decker is made in material, wherein outside double-layer structure is led for ITO Electric glass matrix, intermediate electrochromic layer are the polymer of synthesis.After applied voltage, a side of cathode is connected to electrochromism Layer injection electronics, the side for connecting anode store corresponding positive charge, the Li in positive electrochromic material⁺(Na⁺Or K⁺) occur The anionic polymer that transfer is obtained with cathode matches, and loses Li⁺(Na⁺Or K⁺) material and anode between form electric double layer, material Material generates n doping and changes colour.After removing applied voltage, electronics is extracted out from electrochromic layer, by external circuit and positive charge With Li⁺It returns on the polymer chain of anode, material occurs bleaching process and fades for pellucidity.

Three-decker simplifies the assembling steps of electrochromic material, which expends less, reduction with synthesis Production cost, and the polymer synthesized is dissolved in DMSO and being in a liquid state, and has very high adhesiveness, is not easy it from conductive glass It falls off on glass.

It is tested using the device electrochromic property that aromatic series polyoxadiazoles electrochromic material of the invention assembles Show that there is high optical contrast, electrochromism efficiency and color abundant after material of the invention carries out n- doping, leads to The color under material colored state can be regulated and controled by crossing change polymer pendant groups.

Detailed description of the invention

Attached drawing described herein is used to provide to further understand the embodiment of the present invention, constitutes one of the application Point, do not constitute the restriction to the embodiment of the present invention.In the accompanying drawings:

Fig. 1 is prior art electrochromic device schematic diagram.

Fig. 2 is electrochromic device schematic diagram of the present invention.

Fig. 3 is the embodiment of the present invention 1 to benzene POD device original state schematic diagram.

Fig. 4 is the embodiment of the present invention 1 to schematic diagram after the coloring of benzene POD device.

Fig. 5 is the embodiment of the present invention 1 to schematic diagram after the bleaching of benzene POD device.

Specific embodiment

To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment and attached drawing, to this Invention is described in further detail, and exemplary embodiment of the invention and its explanation for explaining only the invention, are not made For limitation of the invention.