CN101891403B - Method for preparing organic/inorganic compound electrochromic membrane - Google Patents
Method for preparing organic/inorganic compound electrochromic membrane Download PDFInfo
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- CN101891403B CN101891403B CN2010102322514A CN201010232251A CN101891403B CN 101891403 B CN101891403 B CN 101891403B CN 2010102322514 A CN2010102322514 A CN 2010102322514A CN 201010232251 A CN201010232251 A CN 201010232251A CN 101891403 B CN101891403 B CN 101891403B
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Abstract
The invention discloses a method for preparing an organic/inorganic compound electrochromic membrane. A compound membrane organic layer adopts aniline/ o-phenylenediamine, and an inorganic material is WO3. The preparation method comprises the following steps of: preparing a precursor by using tungsten powder, citric acid and polyethylene glycol; performing gelation, drying and calcining on the gelation to obtain nanometer WO3 powder; dissolving aniline and o-phenylenediamine into acidic aqueous solution, immersing processed ITO glass into the mixture uniformly, adding an oxidizing agent, and pulling the ITO glass out after a certain time period; and depositing the WO3 powder on an organic membrane through spraying, and performing aftertreatment to obtain the organic/inorganic compound membrane.
Description
Technical field
The invention belongs to electrochomeric films material technology field, relate to a kind of preparation method of organic/inorganic compound electrochromic membrane.
Background technology
Electrochromism is meant under impressed voltage or effect of electric field, the color of material or transparency stable reversible change.Electrochomeric films has that WV is low, energy consumption is little, environmental protection, vision are big, memory function is arranged, working range is wide, be easy to advantage such as large-area manufacturing, has a wide range of applications in fields such as display device, dimming glass, information storage.
Electrochomeric films can be divided into the inorganic electrochromic film (like WO
3, NiO
2, MoO
3, V
2O
5Deng) and organic electrochromic film two big classes.It is that two injection/extractions because of ion and electronics cause that its superior performance is stablized that the photoabsorption of inorganic electrochromic material changes, but color is more single, the time of response is longer.The photoabsorption of organic electrochromic material changes from redox reaction; Short (can reach femtosecond), rich color of its, contrast gradient be high time of response, be easy to carry out molecular designing, and can keep color changeable effect after the outage, has memory effect; But its less stable, the life-span is short.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of organic/inorganic compound electrochromic membrane; With the organic electrochromic film is the basis; Advantage in conjunction with the inorganic electrochromic film; The preparation inorganic-organic composite electrochromic film is to improve the stability and the life-span of organic electrochromic material.
The present invention realizes through following technical scheme:
A kind of preparation method of organic/inorganic compound electrochromic membrane may further comprise the steps:
1) Hydrocerol A being dissolved in volumetric concentration is wiring solution-forming A in 25～28% the ammoniacal liquor, and the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A;
It is wiring solution-forming B in 30% the superoxol that tungsten powder is dissolved in volumetric concentration, the amount of hydrogen peroxide so that the tungsten powder complete reaction be as the criterion;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 1.5～2.5 ratio; With solution A and solution B thorough mixing; Add absolute ethyl alcohol and polyoxyethylene glycol then, absolute ethyl alcohol and ammoniacal liquor volume ratio are 1: 1～1.5, and polyoxyethylene glycol is 1/3～1/2 of a Hydrocerol A quality; Stirring and dissolving, the PH that uses ammoniacal liquor to regulate colloidal sol again 5～7 is made into precursor;
3) precursor is evaporated until obtaining wet gel 80～90 ℃ of water-baths, then wet gel is carried out the drying foaming under 130～140 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 400～500 ℃, take out behind calcining 3～5h, obtain nanometer WO
3Powder;
4) the ito glass substrate immersion is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 is 0.2～0.25mol/L; 30～80 ℃ the reaction 2～24h, after the pulling film forming with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), WO after the pulling film forming
3The powder sprayed deposit, the repeatable operation several times obtain inorganic-organic composite electrochromic film.
In the said hydrochloric acid soln that contains aniline and O-Phenylene Diamine, aniline concentration is 0.1～0.2mol/L, and concentration of hydrochloric acid is 0.5～1mol/L, and aniline and O-Phenylene Diamine mol ratio are 1: 0.8～0.5.
Described ito glass substrate with its sulfuric acid, Virahol, deionized water ultrasonic cleaning of using deionized water, volumetric concentration 98% successively, dries up with nitrogen before immersion contains the hydrochloric acid soln of aniline and O-Phenylene Diamine again.
Compared with prior art, the present invention has following beneficial technical effects:
The preparation method of organic/inorganic compound electrochromic membrane provided by the invention is the basis with the organic electrochromic film, on ito glass substrate, forms aniline/O-Phenylene Diamine organic layer sprayed deposit nanometer WO afterwards
3Powder immerses formation aniline/O-Phenylene Diamine organic layer, WO repeatedly after drying
3The powder spray operation obtains the compound film of multilayer organic-inorganic on ito glass substrate; Organic electrochromic film has combined the stable advantage of superior performance of inorganic electrochromic film like this.Compare the organic/inorganic compound electrochromic membrane of the present invention's preparation, stability and life-span that compound inorganic materials part can improve the organic electrochromic material with existing organic electrochromic film.
Embodiment
Below in conjunction with specific embodiment the preparation method of organic/inorganic compound electrochromic membrane is done detailed explanation, said is to explanation of the present invention rather than qualification.
Embodiment 1
The preparation method of organic/inorganic compound electrochromic membrane may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 200ml ammoniacal liquor, wiring solution-forming A;
It is wiring solution-forming B in 30% the 200ml superoxol that tungsten powder 122.56g (0.67mol) is dissolved in volume concentrations;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 1.5 ratio, with solution A and solution B thorough mixing, add the absolute ethyl alcohol of 200ml and the polyoxyethylene glycol of 96.07g then, stirring and dissolving is made into precursor;
3) precursor is evaporated until obtaining wet gel 80 ℃ of water-baths, then wet gel is carried out the drying foaming under 130 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 400 ℃, take out behind the calcining 5h, obtain nanometer WO
3Powder;
4) ito glass substrate is used successively sulfuric acid, Virahol, the deionized water ultrasonic cleaning of deionized water, volumetric concentration 98%, dried up with nitrogen again; Then ito glass substrate is immersed that (concentration of aniline is 0.1mol/L in the hydrochloric acid soln contain aniline and O-Phenylene Diamine; The concentration of hydrochloric acid is 0.5mol/L; The concentration of O-Phenylene Diamine is 0.08mol/L), add Ammonium Persulfate 98.5 again as oxygenant, make its concentration reach 0.2mol/L; 30 ℃ the reaction 24h, after the pulling film forming directly with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), sprayed deposit nanometer WO after the pulling film forming
3Powder, repeatable operation 3 times obtains inorganic-organic composite electrochromic film.
The organic electrochromic film that preparation is accomplished is a mazarine when adding negative electricity, and then variable color is a light green when adding positive electricity.
Embodiment 2
The preparation method of organic/inorganic compound electrochromic membrane may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 200ml ammoniacal liquor, wiring solution-forming A;
It is wiring solution-forming B in 30% the 200ml superoxol that tungsten powder 73.54g (0.4mol) is dissolved in volumetric concentration, the amount of hydrogen peroxide so that the tungsten powder complete reaction be as the criterion;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 2.5 ratio, with solution A and solution B thorough mixing, add the polyoxyethylene glycol of 130ml absolute ethyl alcohol and 64.04g then, stirring and dissolving is made into precursor;
3) precursor is evaporated until obtaining wet gel 90 ℃ of water-baths, then wet gel is carried out the drying foaming under 140 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 500 ℃, take out behind the calcining 3h, obtain nanometer WO
3Powder;
4) ito glass substrate is used successively sulfuric acid, Virahol, the deionized water ultrasonic cleaning of deionized water, volumetric concentration 98%, dried up with nitrogen again; Then ito glass substrate is immersed that (concentration of aniline is 0.2mol/L in the hydrochloric acid soln contain aniline and O-Phenylene Diamine; The concentration of hydrochloric acid is 1mol/L; The concentration of O-Phenylene Diamine is 0.1mol/L), add Ammonium Persulfate 98.5 again as oxygenant, make its concentration reach 0.25mol/L; 80 ℃ the reaction 2h, after the pulling film forming directly with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), sprayed deposit nanometer WO after the pulling film forming
3Powder, repeatable operation 2 times obtains inorganic-organic composite electrochromic film.
Embodiment 3
The preparation method of organic/inorganic compound electrochromic membrane may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 200ml ammoniacal liquor, wiring solution-forming A;
It is wiring solution-forming B in 30% the 200ml superoxol that tungsten powder 91.925g (0.5mol) is dissolved in volumetric concentration, the amount of hydrogen peroxide so that the tungsten powder complete reaction be as the criterion;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 2 ratio, with solution A and solution B thorough mixing, add the absolute ethyl alcohol of 100ml and the polyoxyethylene glycol of 80g then, stirring and dissolving is made into precursor;
3) precursor is evaporated until obtaining wet gel 85 ℃ of water-baths, then wet gel is carried out the drying foaming under 135 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 4h, obtain nanometer WO
3Powder;
4) ito glass substrate is used successively sulfuric acid, Virahol, the deionized water ultrasonic cleaning of deionized water, volumetric concentration 98%, dried up with nitrogen again; Then ito glass substrate is immersed that (concentration of aniline is 0.15mol/L in the hydrochloric acid soln contain aniline and O-Phenylene Diamine; The concentration of hydrochloric acid is 0.8mol/L; The concentration of O-Phenylene Diamine is 0.09mol/L), add Ammonium Persulfate 98.5 again as oxygenant, make its concentration reach 0.22mol/L; 60 ℃ the reaction 10h, after the pulling film forming directly with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), sprayed deposit nanometer WO after the pulling film forming
3Powder, repeatable operation 5 times obtains inorganic-organic composite electrochromic film.
Embodiment 4
The preparation method of organic/inorganic compound electrochromic membrane may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 200ml ammoniacal liquor, wiring solution-forming A;
It is wiring solution-forming B in 30% the 200ml superoxol that tungsten powder 101.11g (0.55mol) is dissolved in volumetric concentration, the amount of hydrogen peroxide so that the tungsten powder complete reaction be as the criterion;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 1.8 ratio, with solution A and solution B thorough mixing, add the absolute ethyl alcohol of 100ml and the polyoxyethylene glycol of 85g then, stirring and dissolving is made into precursor;
3) precursor is evaporated until obtaining wet gel 86 ℃ of water-baths, then wet gel is carried out the drying foaming under 138 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 480 ℃, take out behind the calcining 4.5h, obtain nanometer WO
3Powder;
4) then ito glass substrate is immersed that (concentration of aniline is 0.12mol/L in the hydrochloric acid soln contain aniline and O-Phenylene Diamine; The concentration of hydrochloric acid is 0.6mol/L; The concentration of O-Phenylene Diamine is 0.072mol/L), add Ammonium Persulfate 98.5 again as oxygenant, make its concentration reach 0.24mol/L; 50 ℃ the reaction 20h, after the pulling film forming directly with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), sprayed deposit nanometer WO after the pulling film forming
3Powder, repeatable operation 5 times obtains inorganic-organic composite electrochromic film.
Claims (3)
1. the preparation method of an organic/inorganic compound electrochromic membrane is characterized in that, may further comprise the steps:
1) Hydrocerol A is dissolved in wiring solution-forming A in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A;
Tungsten powder is dissolved in wiring solution-forming B in the superoxol, the amount of hydrogen peroxide so that the tungsten powder complete reaction be as the criterion;
2) according to the mol ratio of tungsten powder and Hydrocerol A be 1: 1.5～2.5 ratio; With solution A and solution B thorough mixing; Add absolute ethyl alcohol and polyoxyethylene glycol then, absolute ethyl alcohol and ammoniacal liquor volume ratio are 1: 1～1.5, and polyoxyethylene glycol is 1/3～1/2 of a Hydrocerol A quality; Stirring and dissolving, the pH that uses ammoniacal liquor to regulate colloidal sol again 5～7 is made into precursor;
3) precursor is evaporated until obtaining wet gel 80～90 ℃ of water-baths, then wet gel is carried out the drying foaming under 130～140 ℃ of conditions and obtain xerogel, again xerogel is carried out calcining at constant temperature at 400～500 ℃, take out behind calcining 3～5h, obtain nanometer WO
3Powder;
4) the ito glass substrate immersion is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.1～0.2mol/L, and concentration of hydrochloric acid is 0.5～1mol/L, and the mol ratio of aniline and O-Phenylene Diamine is 1: 0.8～0.5; Add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 is 0.2～0.25mol/L; 30～80 ℃ the reaction 2～24h, after the pulling film forming with nanometer WO
3The powder sprayed deposit on ito glass substrate, Air drying;
5) with dried glass substrate once more according to step 4), sprayed deposit nanometer WO after the pulling film forming
3Powder, the repeatable operation several times obtain inorganic-organic composite electrochromic film.
2. the preparation method of organic/inorganic compound electrochromic membrane as claimed in claim 1 is characterized in that, the volumetric concentration of described ammoniacal liquor is 25～28%, and the volumetric concentration of superoxol is 30%.
3. the preparation method of organic/inorganic compound electrochromic membrane as claimed in claim 1; It is characterized in that; Described ito glass substrate is before immersion contains the hydrochloric acid soln of aniline and O-Phenylene Diamine; With its sulfuric acid, Virahol, deionized water ultrasonic cleaning of using deionized water, volumetric concentration 98% successively, dry up with nitrogen again.
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| CN102417607B (en) * | 2011-08-23 | 2012-11-21 | 陕西科技大学 | Preparation method of organic-base electrochromic composite film |
| CN102417608B (en) * | 2011-08-23 | 2013-06-05 | 陕西科技大学 | Preparation method of inorganic electrochromic composite membrane |
| CN102417307B (en) * | 2011-08-23 | 2013-07-31 | 陕西科技大学 | Preparation method of inorganic and organic electrochromic film |
| CN102432192B (en) * | 2011-08-23 | 2013-12-18 | 陕西科技大学 | Method for preparing organic/inorganic electrochromic composite film |
| CN102540610A (en) * | 2011-12-08 | 2012-07-04 | 电子科技大学 | Flexible electrochromic film and device and methods for producing same |
| CN104216177A (en) * | 2014-08-01 | 2014-12-17 | 京东方科技集团股份有限公司 | Display panel, display device and preparation method of display panel |
| CN116243528A (en) * | 2022-12-15 | 2023-06-09 | 安徽立光电子材料股份有限公司 | Production method of solid electrochromic device with uniform color and solid electrochromic device |
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| JPS60235746A (en) * | 1984-05-09 | 1985-11-22 | Nippon Sheet Glass Co Ltd | Near infrared-shielding glass |
| JPH0912338A (en) * | 1995-06-28 | 1997-01-14 | Nissan Motor Co Ltd | Heat-insulating glass |
| US6596398B1 (en) * | 1998-08-21 | 2003-07-22 | Atofina Chemicals, Inc. | Solar control coated glass |
| CN101357330B (en) * | 2008-09-03 | 2011-05-25 | 同济大学 | Photochemical catalyst nano-material for ultraviolet light and visible photocatalysis active material |
| CN101576695A (en) * | 2009-04-28 | 2009-11-11 | 电子科技大学 | WO3 electrochromic thin film preparation method |
| CN101633566B (en) * | 2009-08-25 | 2011-08-10 | 陕西科技大学 | Method for preparing organic composite WO3 electrochomeric films |
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