阅读说明：本技术 一种基于高浓水系电解质的电致变色器件及其制备方法 (A kind of electrochromic device and preparation method thereof based on highly concentrated water system electrolyte ) 是由 孟鸿 刘雨萌 孙越 于 2019-07-10 设计创作，主要内容包括：本发明公开一种基于高浓水系电解质的电致变色器件及其制备方法,器件包括：第一电极基底,位于第一电极基底上的有机电致变色层,位于所述有机电致变色层上方的第二电极基底,所述有机电致变色层与所述第二电极基底之间形成有空腔,所述空腔中填充有高浓水系电解质,所述高浓水系电解质是浓度为13~21mol/L的含氟锂盐的水溶液；所述第二电极基底与所述有机电致变色层未覆盖的第一电极基底表面通过密封胶连接。本发明将高浓水系电解质替换传统低浓度水系电解质构建电致变色器件,克服了传统低浓度水系电解质对有机电致变色层的损坏及有机溶剂基电解质易挥发、毒性大等缺点,在保证可见光区高对比度的条件下实现近红外区较高的对比度。(The present invention discloses a kind of electrochromic device and preparation method thereof based on highly concentrated water system electrolyte, device includes: first electrode substrate, organic electrochromic layers in first electrode substrate, second electrode substrate above the organic electrochromic layers, cavity is formed between the organic electrochromic layers and the second electrode substrate, highly concentrated water system electrolyte is filled in the cavity, the highly concentrated water system electrolyte is the aqueous solution for the fluorine-containing lithium salts that concentration is 13 ~ 21mol/L；The second electrode substrate and the unlapped first electrode substrate surface of the organic electrochromic layers pass through sealing glue connection.Highly concentrated water system electrolyte is replaced traditional low concentration water system electrolyte and constructs electrochromic device by the present invention, the disadvantages of traditional low concentration water system electrolyte is volatile to the damage and organic solvent base electrolyte of organic electrochromic layers, toxicity is big is overcome, the higher contrast near infrared region is realized under conditions of guaranteeing visible region high contrast.)

1. a kind of electrochromic device based on highly concentrated water system electrolyte characterized by comprising first electrode substrate is located at Organic electrochromic layers in first electrode substrate, the second electrode substrate above the organic electrochromic layers are described It is formed with cavity between organic electrochromic layers and the second electrode substrate, is electrolysed in the cavity filled with highly concentrated water system Matter, the highly concentrated water system electrolyte are the aqueous solutions for the fluorine-containing lithium salts that concentration is 13 ~ 21mol/L；

The second electrode substrate and the unlapped first electrode substrate surface of the organic electrochromic layers pass through sealing glue connection It connects.

2. the electrochromic device according to claim 1 based on highly concentrated water system electrolyte, which is characterized in that described fluorine-containing Lithium salts is selected from double trifluoromethanesulfonimide lithiums, trifluoromethyl sulfonic acid lithium, LiBF4, lithium hexafluoro phosphate, double difluoro sulphonyl One of imine lithium is a variety of.

3. the electrochromic device according to claim 1 based on highly concentrated water system electrolyte, which is characterized in that described organic Electrochromism layer material is TQ1 or P3HT.

4. the electrochromic device according to claim 1 based on highly concentrated water system electrolyte, which is characterized in that described first The one kind of electrode basement, second electrode substrate independently selected from ito glass, PET/ITO, PDMS/Ag nano wire.

5. a kind of preparation method of the electrochromic device based on highly concentrated water system electrolyte as described in claim 1 ~ 4 is any, Characterized in that it comprises the following steps:

A, organic electrochromic layers are prepared in first electrode substrate；

B, sealant, and reserved inlet are coated in the unlapped first electrode substrate surface of organic electrochromic layers surrounding；

C, second electrode substrate is covered in above organic electrochromic layers and sealing glue laminating, second electrode substrate and Organic Electricity Cavity is formed between mutagens chromatograph；

D, by highly concentrated water system electrolyte from being added to from inlet in the cavity, then inlet is sealed with sealant.

6. the preparation method of the electrochromic device according to claim 5 based on highly concentrated water system electrolyte, feature exist In in step A, the method for preparing organic electrochromic layers is selected from one of spraying, electrochemical deposition and spin coating.

7. the preparation method of the electrochromic device according to claim 6 based on highly concentrated water system electrolyte, feature exist In the spraying specifically includes: organic electrochromic layers material is dissolved in after organic solvent and is sprayed on first electrode substrate surface, It is dry；The organic solvent is chloroform or chlorobenzene.

8. the preparation method of the electrochromic device according to claim 5 based on highly concentrated water system electrolyte, feature exist In in step D, the highly concentrated water system electrolyte preparation method is formed comprising steps of deionized water is mixed with fluorine-containing lithium salts Highly concentrated water system electrolyte.

9. the preparation method of the electrochromic device according to claim 8 based on highly concentrated water system electrolyte, feature exist In the mixed temperature is 25 ~ 60 DEG C.

10. the preparation method of the electrochromic device according to claim 8 based on highly concentrated water system electrolyte, feature exist In the mixed time is 2 ~ 6h.

Technical field

The present invention relates to electrochemical technology field more particularly to a kind of electrochromic devices based on highly concentrated water system electrolyte And preparation method thereof.

Background technique

Electrochromism refers to causes the invertibity optical properties of material (as transmitted by extra electric field driving redox reaction Rate, absorbance etc.) variation, macro manifestations are that the color of material changes with extra electric field and reversible coloring and bleached state occurs Between transformation or two kinds of colored states between transformation.Material with electrochromic property is known as electrochromism material Material, according to the difference of material structure, is divided into inorganic electrochromic material and organic electrochromic material, studies more nothing at present Machine electrochromic material has tungstic acid, Prussian blue etc.；Organic electrochromic material has purpurine organic micromolecule and poly- pyrrole It coughs up, the conducting high polymers object such as polythiophene, polyaniline.Inorganic electrochromic material narrow, optical contrast with color change interval Difference, the disadvantages of response speed is slow；Organic electrochromic material is strong with structure and color change interval controllability, discoloration is abundant, Yi Jia Work at device, fast response time advantage, but organic electrochromic material stability it is poor and only have in visible light region it is high right Its commercial applications is limited to than degree.

It is known as electrochromic device with the device that electrochromic material is made into, electrochromic device is generally by two layers of conductive base Bottom and positioned between the two electrochromic layer, electrolyte, ion storage constitute, wherein electrolyte is generally transparent, rise To the effect for stopping electron-transport.Electrochromic device mostly uses liquid electrolyte, gel electrolyte or class solid electrolytic at present Matter；As liquid electrolyte, although water system electrolyte is more more environmentally-friendly than organic system electrolyte in device commercial applications, peace Entirely, but organic electrochromic material is in traditional low concentration water system electrolyte (LiClO of such as 0.05 ~ 0.1M₄, LiCl, or CH₃COOLi etc.) in electrochemical stability it is poor, easy leakage causes device lifetime short, thus find a kind of conductivity it is high, Chemical stability is good, extremely urgent to the electrolyte that device is harmless.Further, since organic electrochromic material and water system electrolysis The limitation of matter effect, so that existing electrochromic device more can be only applied to visible light region, table in the near infrared region Reveal greatly insufficient.Although existing part organic electrochromic material can show to transmit under regulating and controlling voltage near infrared region The variation of rate, but due to the limitation of electrolyte, cause the transmission difference of electrochromic device smaller.

Therefore, the existing technology needs to be improved and developed.

Summary of the invention

In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of electricity based on highly concentrated water system electrolyte Mutagens color device and preparation method thereof, it is intended to solve existing organic electrochromic device service life is short and change in the near infrared region The problem of color performance difference.

Technical scheme is as follows:

A kind of electrochromic device based on highly concentrated water system electrolyte, wherein include: first electrode substrate, be located at first electrode Organic electrochromic layers in substrate, the second electrode substrate above the organic electrochromic layers, the organic electroluminescence It is formed with cavity between photochromic layer and the second electrode substrate, is filled with highly concentrated water system electrolyte, the height in the cavity Concentrated water system electrolyte is the aqueous solution for the fluorine-containing lithium salts that concentration is 13 ~ 21mol/L；

The second electrode substrate and the unlapped first electrode substrate surface of the organic electrochromic layers pass through sealing glue connection It connects.

The electrochromic device based on highly concentrated water system electrolyte, wherein the fluorine-containing lithium salts is selected from double fluoroforms One of alkane sulfimide lithium, trifluoromethyl sulfonic acid lithium, LiBF4, lithium hexafluoro phosphate, double difluoro sulfimide lithiums or It is a variety of.

The electrochromic device based on highly concentrated water system electrolyte, wherein the organic electrochromic layers material is TQ1 or P3HT.

The electrochromic device based on highly concentrated water system electrolyte, wherein the first electrode substrate, second electrode The one kind of substrate independently selected from ito glass, PET/ITO, PDMS/Ag nano wire.

The preparation method of a kind of as above any electrochromic device based on highly concentrated water system electrolyte, wherein packet Include step:

A, organic electrochromic layers are prepared in first electrode substrate；

B, sealant, and reserved inlet are coated in the unlapped first electrode substrate surface of organic electrochromic layers surrounding；

C, second electrode substrate is covered in above organic electrochromic layers and sealing glue laminating, second electrode substrate and Organic Electricity Cavity is formed between mutagens chromatograph；

D, by highly concentrated water system electrolyte from being added to from inlet in the cavity, then inlet is sealed with sealant.

The preparation method of the electrochromic device based on highly concentrated water system electrolyte, wherein in step A, the system The method of standby organic electrochromic layers is selected from one of spraying, electrochemical deposition and spin coating.

The preparation method of the electrochromic device based on highly concentrated water system electrolyte, wherein the specific packet of spraying It includes: organic electrochromic layers material being dissolved in after organic solvent and is sprayed on first electrode substrate surface, it is dry；The organic solvent For chloroform or chlorobenzene.

The preparation method of the electrochromic device based on highly concentrated water system electrolyte, wherein in step D, the height Concentrated water system electrolyte preparation method forms highly concentrated water system electrolyte comprising steps of deionized water is mixed with fluorine-containing lithium salts.

The preparation method of the electrochromic device based on highly concentrated water system electrolyte, wherein the mixed temperature It is 25 ~ 60 DEG C.

The preparation method of the electrochromic device based on highly concentrated water system electrolyte, wherein the mixed time For 2 ~ 6h.

The utility model has the advantages that the present invention is low by highly concentrated water system electrolyte (aqueous solution of the fluorine-containing lithium salts of 13 ~ 21mol/L) replacement tradition Concentration water system electrolyte is used for the electrochromic device based on highly concentrated water system electrolyte of organic electrochromic device building, overcomes Water system electrolyte leads to that organic electro-luminescence device lifetime is short, work to the damages of organic electrochromic layers under traditional low concentration The disadvantages of window narrows and organic solvent base electrolyte are volatile, toxicity is big, it is real under conditions of guaranteeing visible region high contrast The existing special higher contrast near infrared region；The electrochromic device based on highly concentrated water system electrolyte has service life length, rings Advantage fast, that Memorability is good is answered, highly concentrated water system electrolyte is answered in fields such as electrochromic display, smart window and camouflages With with directive significance.

Detailed description of the invention

Fig. 1 is the cross section structure schematic diagram of the electrochromic device based on highly concentrated water system electrolyte in the embodiment of the present invention.

Fig. 2 is the electrochromic device based on highly concentrated water system electrolyte made from the embodiment of the present invention 1 in different scanning speed The CV curve measured under rate.

Fig. 3 is the electrochromic device based on highly concentrated water system electrolyte made from the embodiment of the present invention 1 under different voltages The ultraviolet-visible absorption spectroscopy measured.

Fig. 4 is the different wave length of the obtained electrochromic device based on highly concentrated water system electrolyte in the embodiment of the present invention 1 The transmissivity variation diagram at place.

Fig. 5 is the electrochromic device based on highly concentrated water system electrolyte made from the embodiment of the present invention 4 in same sweep speed Under the CV curve that measures.

Fig. 6 is the electrochromic device based on highly concentrated water system electrolyte made from the embodiment of the present invention 4 in different voltages Under the ultraviolet-visible absorption spectroscopy that measures.

Fig. 7 is at the different wave length of the electrochromic device based on highly concentrated water system electrolyte made from the embodiment of the present invention 4 Transmissivity variation diagram: 7a be 530nm at transmissivity variation diagram；7b is the transmissivity variation diagram at 1500nm.

Fig. 8 is the transmissivity variation diagram at the 1500nm of electrochromic device made from comparative example 1 of the present invention.

Fig. 9 is the transmissivity variation diagram at the different wave length of electrochromic device made from comparative example 2 of the present invention.

Specific embodiment

The present invention provides a kind of electrochromic device and preparation method thereof based on highly concentrated water system electrolyte, to make the present invention Purpose, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that this place The specific embodiment of description is only used to explain the present invention, is not intended to limit the present invention.

The embodiment of the present invention provides a kind of electrochromic device based on highly concentrated water system electrolyte, wherein includes: the first electricity Pole substrate, the organic electrochromic layers in first electrode substrate, the second electricity above the organic electrochromic layers Pole substrate is formed with cavity, is filled with height in the cavity between the organic electrochromic layers and the second electrode substrate Concentrated water system electrolyte, the highly concentrated water system electrolyte are the aqueous solutions for the fluorine-containing lithium salts that concentration is 13 ~ 21mol/L；

The second electrode substrate and the unlapped first electrode substrate surface of the organic electrochromic layers pass through sealing glue connection It connects.

Specifically, the electrochromic device based on highly concentrated water system electrolyte of the present embodiment cross section structure as shown in Figure 1, 1 is first electrode substrate；2 be organic electrochromic layers；3 be cavity, and highly concentrated water system electrolyte is located in cavity 3；4 be the second electricity Pole substrate；5 regions namely sealant region not covered by organic electrochromic layers for first electrode substrate surface.

Highly concentrated water system electrolyte (aqueous solution of the fluorine-containing lithium salts of 13 ~ 21mol/L) is replaced traditional low concentration of water by the present embodiment It is electrolyte for electrochromic device of the organic electrochromic device building based on highly concentrated water system electrolyte, it is low overcomes tradition Under concentration water system electrolyte organic electro-luminescence device lifetime is short, operation window is narrow is caused to the damage of organic electrochromic layers and The disadvantages of organic solvent base electrolyte is volatile, toxicity is big, it is special to realize under conditions of guaranteeing visible region high contrast The higher contrast near infrared region；The electrochromic device based on highly concentrated water system electrolyte has service life length, responds fast, memory Property good advantage, the application to highly concentrated water system electrolyte in fields such as electrochromic display, smart window and camouflages, which has, to be referred to Lead meaning.Specifically, the ion in the highly concentrated water system electrolyte in the present embodiment (aqueous solution of the fluorine-containing lithium salts of 13 ~ 21mol/L) Diffusion velocity is fast, and ionic conductivity is high, so that the response of electrochromic device is fast.And the highly concentrated water system electrolyte in the present embodiment Fluorine ion in (aqueous solution of the fluorine-containing lithium salts of 13 ~ 21mol/L) is strong electron-withdrawing group group, and the existence form of water is no longer freely Water, but the crystallization water；No longer be 4 water in >=13M electrolyte, around lithium ion, but as concentration increases, electrolyte yin from Sub (anion) participates in lithium ion coordination, is formed Li (anion)_x(H₂O)_4-xStructure；Although stabilization of the organic material in light water Property is poor, and structure is easily destroyed, but the crystallization water has no influence to the stability of organic material, can be efficiently avoided in electrolyte Influence of the water to organic material, so that electrolyte is deposited within the scope of limiting concentration (13 ~ 21mol/L) with similar gels state , but concentration is more than 21mol/L, and having electrolytic salt under room temperature can be precipitated, so that the conductivity of electrolyte ion reduces, thus Influence the responsiveness of electrochromic device.Electrolyte is gel state, as concentration is bigger, is infinitely close to class solid-state；Thus exist There are a large amount of Li (anion) with electrochromism bed boundary for electrolyte_x(H₂O)_4-x, after removing applied voltage, ion deinsertion speed pole To be slow, then the present embodiment containing highly concentrated water system electrolyte can electrochromic device Memorability it is good.

It should be noted that first electrode substrate is anode base when organic electrochromic layers material is oxidation stain material Bottom, second electrode substrate are cathode substrate；When organic electrochromic layers material is reduction off-color material, first electrode substrate is Cathode substrate, second electrode substrate are anode substrate；The first electrode substrate, second electrode substrate are transparent electrode base Bottom.

In a kind of way of example, the fluorine-containing lithium salts may be selected from but not limited to double trifluoromethanesulfonimide lithiums, three One of methyl fluoride Sulfonic Lithium, LiBF4, lithium hexafluoro phosphate, double difluoro sulfimide lithiums are a variety of.Above-mentioned fluorine-containing lithium The highly concentrated water system electrolyte that salt is dissolved in water formation can enable electrolyte ion show the electricity of itself by the free movement of limitation water Chemical property；Highly concentrated water system electrolyte high in environmental protection itself.

In a kind of way of example, the organic electrochromic layers material can be but be not limited to TQ1 or P3HT.Specifically Ground, poly- [[2,3- bis- (3- octyloxyphenyl) -5,8- quinoxaline diyls] -2,5- thiophene diyl] (Poly [[2,3-bis (3- Octyloxyphenyl) -5,8-quinoxalinediyl] -2,5-thiophenediyl], TQ1) structural formula be, poly- 3- hexyl thiophene (Poly (3-hexyl-thiophene-2,5- Diyl), P3HT) structural formula be.In the electrochromic device containing highly concentrated water system electrolyte, electroluminescent change Chromatograph storage charge increases, and concentration increases, and more polyanionic is promoted to participate in reaction；And the absorption at near-infrared and electrochromism material The band gap of material is related, and when applying positive voltage to working electrode, electrochromism oxidation process is doping process, anti-with participating in The increase of anion number is answered, electrochromic polymeric compounds polymeric chain is gradually realized fully doped；Apply backward voltage, then goes to adulterate Ion populations increase accordingly.

In a kind of way of example, the first electrode substrate, second electrode substrate independently selected from ito glass, One kind of PET/ITO, PDMS/Ag nano wire.Specifically, ITO is tin indium oxide；PET is poly terephthalic acid class plastics, such as Polyethylene terephthalate (Polyethylene terephthalate)；PDMS is dimethyl silicone polymer (Polyethylene terephthalate).

The embodiment of the present invention also provides a kind of as above any electrochromic device based on highly concentrated water system electrolyte Preparation method, wherein comprising steps of

A, organic electrochromic layers are prepared in first electrode substrate；

B, sealant, and reserved inlet are coated in the unlapped first electrode substrate surface of organic electrochromic layers；

C, second electrode substrate is covered in above organic electrochromic layers and sealing glue laminating, second electrode substrate and Organic Electricity Cavity is formed between mutagens chromatograph；

D, by highly concentrated water system electrolyte from being added to from inlet in the cavity, then inlet is sealed with sealant.

The preparation process of the electrochromic device based on highly concentrated water system electrolyte of the present embodiment is simple, is conducive to realize industry Change production application；It can be achieved to adjust the light of electrochromic device in the near infrared region by the concentration for controlling highly concentrated water system electrolyte Learn contrast, optical memory, color conversion rate.

In one embodiment, in step A, the method for preparing organic electrochromic layers is selected from spraying, electrochemistry One of deposition and spin coating.Wherein, the spraying specifically includes: spraying after organic electrochromic layers material is dissolved in organic solvent It is coated in first electrode substrate surface, it is dry；The organic solvent is chloroform or chlorobenzene.

In a kind of embodiment, in step D, the highly concentrated water system electrolyte preparation method is comprising steps of deionized water It is mixed with fluorine-containing lithium salts, that is, forms highly concentrated water system electrolyte.Wherein, the mixed temperature is 25 ~ 60 DEG C；When described mixed Between be 2 ~ 6h.

Below by specific embodiment, the present invention is described in detail.