CN101633566B - Method for preparing organic composite WO3 electrochomeric films - Google Patents
Method for preparing organic composite WO3 electrochomeric films Download PDFInfo
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- CN101633566B CN101633566B CN2009100236812A CN200910023681A CN101633566B CN 101633566 B CN101633566 B CN 101633566B CN 2009100236812 A CN2009100236812 A CN 2009100236812A CN 200910023681 A CN200910023681 A CN 200910023681A CN 101633566 B CN101633566 B CN 101633566B
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- ito glass
- deionized water
- aniline
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- electrochomeric films
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Abstract
The present invention provides a method for preparing organic composite WO3 electrochomeric films. The method comprises the following steps: firstly, adding ammonium para-tungstate and polyethylene glycol to deionized water to obtain precursor sol; soaking ITO (indium tin oxide) glass substrates to the precursor sol, taking the ITO glass substrates out, drying and calcining to obtain mesoporous WO3 filmson the ITO glass substrates; adding aniline and o-phenylenediamine to a hydrochloric acid solution, and stirring until the aniline and o-phenylenediamine dissolve, so as to obtain a mixed solution; putting the ITO glass into the mixed solution, then adding ammonium persulfate to the mixed solution, and pulling the ITO glass out after the polymerization reaction is completely conducted; and subjecting the ITO glass to deionized water washing and alcohol washing and holding at a room temperature to obtain the organic composite WO3 electrochomeric films. The organic composite WO3 electrochomericfilms prepared by the invention are characterized by using porous WO3 films as substrates and poly(aniline/o-phenylenediamine) as an organic layer, for the WO3 film is the inorganic electrochomeric material with the best performance in the prior art and has the advantages of stable performance and long service life, while the poly(aniline/o-phenylenediamine) film has the advantages of short response time and good cyclic reversibility.
Description
Technical field
The present invention relates to a kind of preparation method of electrochomeric films, particularly a kind of organic compound WO
3The preparation method of electrochomeric films.
Background technology
According to the difference that causes the variable color condition, off-color material can be divided into electrochromic material, thermochromic material, photochromic material, gas-discoloration material etc.So-called electrochromism is meant under impressed voltage or effect of electric field, the color of material or transparency stable reversible change.Electrochomeric films has that operating voltage is low, energy consumption is little, the restriction of no vision, have that memory function, working range are wide, energy-conserving and environment-protective, 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 organic electrochromic film and inorganic electrochromic film two big classes.The photoabsorption of organic electrochromic material changes from redox reaction, short (can reach femtosecond), rich color, contrast gradient height of its, be easy to carry out molecular designing time of response, and can keep color changeable effect after the outage, have memory effect, but its less stable, the life-span is short.It is that two injections/extractions because of ion and electronics cause that its superior performance is stablized, wherein WO that the photoabsorption of inorganic electrochromic material changes
3Electrochomeric films is owing to its superior performance is used widely, but it still exists shortcomings such as color is more single, the time of response is long.Organic compound WO
3Electrochomeric films has utilized the advantage of organic electrochromic material, learns from other's strong points to offset one's weaknesses, and helps WO
3The performance of electrochromic material improves and uses.
Summary of the invention
The objective of the invention is color, response speed and contrast gradient, and propose a kind of organic compound WO in order to improve inorganic electrochromic material
3Electrochromic material and preparation method thereof.
For achieving the above object, the concrete steps that the present invention adopts are:
1) at first, ammonium metawolframate and polyoxyethylene glycol are pressed 1: 0.5～2 mol ratio adding deionized water, stir down in 60～80 ℃ and be configured to precursor sol, wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 4～5;
2) secondly, after leaving standstill 5～10min in the ito glass substrate immersion precursor sol, change dry 30～60min in 120～130 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 1.5～3 hours 400～500 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 1～0.5 mol ratio, and to make aniline concentration be 0.1～0.2mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.5～1mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.2～0.25mol/L, at 30～80 ℃, reacted 2～24 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
The relative molecular mass of polyoxyethylene glycol of the present invention is 400～6000; Immerse the preceding ito glass substrate of precursor sol and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up.
The organic compound WO of the present invention's preparation
3Electrochomeric films is with porous WO
3Film is substrate, and organic layer adopts poly-(aniline/O-Phenylene Diamine), WO
3Film is the best inorganic electrochromic material of present performance, and its stable performance, life-span are long, have advantages such as monomer is cheap, environmental stability is better, the time of response is short, cyclic reversibility is good and gather (aniline/O-Phenylene Diamine) film.
Embodiment
Embodiment 1:1) at first, being 400～6000 polyoxyethylene glycol with ammonium metawolframate and relative molecular mass adds deionized water by 1: 2 mol ratio, stirs down in 60 ℃ and is configured to precursor sol, and wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 4;
2) secondly, get the ito glass substrate and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up, after leaving standstill 10min in the ito glass substrate immersion precursor sol, change dry 30min in 130 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 3 hours 400 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 1 mol ratio, and to make aniline concentration be 0.1mol/L, and concentration of hydrochloric acid is the mixing solutions of 1mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.2mol/L, at 50 ℃, reacted 18 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
Embodiment 2:1) at first, being 400～6000 polyoxyethylene glycol with ammonium metawolframate and relative molecular mass adds deionized water by 1: 1 mol ratio, stirs down in 80 ℃ and is configured to precursor sol, and wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 5;
2) secondly, get the ito glass substrate and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up, after leaving standstill 8min in the ito glass substrate immersion precursor sol, change dry 60min in 120 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 2 hours 480 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 0.8 mol ratio, and to make aniline concentration be 0.2mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.5mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.23mol/L, at 70 ℃, reacted 8 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
Embodiment 3:1) at first, being 400～6000 polyoxyethylene glycol with ammonium metawolframate and relative molecular mass adds deionized water by 1: 0.5 mol ratio, stirs down in 65 ℃ and is configured to precursor sol, and wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 4.5;
2) secondly, get the ito glass substrate and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up, after leaving standstill 5min in the ito glass substrate immersion precursor sol, change dry 45min in 125 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 2.5 hours 420 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 0.5 mol ratio, and to make aniline concentration be 0.2mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.7mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.25mol/L, at 30 ℃, reacted 24 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
Embodiment 4:1) at first, being 400～6000 polyoxyethylene glycol with ammonium metawolframate and relative molecular mass adds deionized water by 1: 1.5 mol ratio, stirs down in 75 ℃ and is configured to precursor sol, and wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 4;
2) secondly, get the ito glass substrate and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up, after leaving standstill 7min in the ito glass substrate immersion precursor sol, change dry 40min in 128 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 2.5 hours 450 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 0.7 mol ratio, and to make aniline concentration be 0.1mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.9mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.21mol/L, at 60 ℃, reacted 12 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
Embodiment 5:1) at first, being 400～6000 polyoxyethylene glycol with ammonium metawolframate and relative molecular mass adds deionized water by 1: 1.3 mol ratio, stirs down in 70 ℃ and is configured to precursor sol, and wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 5;
2) secondly, get the ito glass substrate and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up, after leaving standstill 6min in the ito glass substrate immersion precursor sol, change dry 50min in 123 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 1.5 hours 500 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 0.6 mol ratio, and to make aniline concentration be 0.2mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.6mol/L;
4) last, ito glass after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.24mol/L, at 80 ℃, reacted 2 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
Claims (3)
1. organic compound WO
3The preparation method of electrochomeric films is characterized in that:
1) at first, ammonium metawolframate and polyoxyethylene glycol are pressed 1: 0.5～2 mol ratio adding deionized water, stir down in 60～80 ℃ and be configured to precursor sol, wherein the mass ratio of deionized water and polyoxyethylene glycol is 1: 4～5;
2) secondly, after leaving standstill 5～10min in the ito glass substrate immersion precursor sol, change dry 30～60min in 120～130 ℃ of baking ovens over to, promptly on the ito glass substrate, made mesoporous WO in 1.5～3 hours 400～500 ℃ of calcinings again
3Film;
3) then, aniline and O-Phenylene Diamine are joined in the aqueous hydrochloric acid stirring and dissolving by 1: 1～0.5 mol ratio, and to make aniline concentration be 0.1～0.2mol/L, and concentration of hydrochloric acid is the mixing solutions of 0.5～1mol/L;
4) last, ito glass substrate after step (2) processing is put into mixing solutions, in mixing solutions, add Ammonium Persulfate 98.5 then, the concentration that makes Ammonium Persulfate 98.5 in the mixing solutions is 0.2～0.25mol/L, at 30～80 ℃, reacted 2～24 hours, treat that polyreaction fully after, lift out through deionization washing, alcohol and wash, room temperature leaves standstill and obtains organic compound WO
3Electrochomeric films.
2. organic compound WO according to claim 1
3The preparation method of electrochomeric films is characterized in that: the relative molecular mass of said polyoxyethylene glycol is 400～6000.
3. organic compound WO according to claim 1
3The preparation method of electrochomeric films is characterized in that: immerse the preceding ito glass substrate of precursor sol and use deionized water, 98% sulfuric acid, Virahol, deionized water ultrasonic cleaning successively, use N at last
2Dry up.
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| CN101891402B (en) * | 2010-07-21 | 2012-07-04 | 陕西科技大学 | Method for preparing organic/inorganic electrochromic film |
| CN101891403B (en) * | 2010-07-21 | 2012-07-04 | 陕西科技大学 | Method for preparing organic/inorganic compound electrochromic membrane |
| CN102071009A (en) * | 2011-01-21 | 2011-05-25 | 电子科技大学 | Preparation method of organic-inorganic composite electrochromic material |
| CN102352109B (en) * | 2011-07-05 | 2012-11-21 | 浙江大学 | Organic-inorganic composite electrochromic film and preparation method thereof |
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| CN102417608B (en) * | 2011-08-23 | 2013-06-05 | 陕西科技大学 | Preparation method of inorganic electrochromic composite membrane |
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