CN102432193B - Preparation method of organic electrochromic composite membrane - Google Patents
Preparation method of organic electrochromic composite membrane Download PDFInfo
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- CN102432193B CN102432193B CN 201110243076 CN201110243076A CN102432193B CN 102432193 B CN102432193 B CN 102432193B CN 201110243076 CN201110243076 CN 201110243076 CN 201110243076 A CN201110243076 A CN 201110243076A CN 102432193 B CN102432193 B CN 102432193B
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- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000013078 crystal Substances 0.000 claims abstract description 71
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 46
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 46
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 210
- 239000000243 solution Substances 0.000 claims description 113
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 88
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 88
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 84
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 70
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 56
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 56
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 56
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 56
- 239000000725 suspension Substances 0.000 claims description 42
- 239000011022 opal Substances 0.000 claims description 29
- 239000012798 spherical particle Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 28
- 229910021529 ammonia Inorganic materials 0.000 claims description 28
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 28
- 238000007654 immersion Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- -1 polyoxyethylene Polymers 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000011240 wet gel Substances 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 206010013786 Dry skin Diseases 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 14
- 238000007605 air drying Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 14
- 238000005187 foaming Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 11
- 229920005591 polysilicon Polymers 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract 1
- 239000011246 composite particle Substances 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses an organic electrochromic composite membrane and its preparation method. The prepared organic thin membrane is an aniline/o-phenylenediamine thin membrane. WO3 is selected as an inorganic dopant. The method comprises: preparing a double-size colloidal crystal with inorganic composite particles and SiO2, removing an SiO2 colloid from the double-size colloidal crystal structure, then immersing the colloidal crystal in an organic matter precursor solution, then conducting polymerization, pulling, and drying, thus obtaining an organic electrochromic composite membrane material.
Description
Technical field
The present invention relates to a kind of preparation method of electrochomeric films, particularly a kind of preparation method of organic electrochromic composite 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 operating voltage 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.At present the development obstacle of electrochromic material mainly is that the reversibility of electrochromic material is poor, the time of response is long, in long-time with various envrionment conditionss under material the use unstable commercialization of electrochromism technology in display industry.So in the research of inorganic electrochromic and organic electrochromic material, should require and produced inorganic organic electrochromic matrix material.Compound electrochromic membrane is in conjunction with the advantage of inorganic electrochromic film and organic electrochromic film, learn from other's strong points to offset one's weaknesses, not only longer as stable performance as the inorganic electrochromic material, life-span, and combine organic electrochromic film rich color, short advantage of time of response.The preparation method of organic/inorganic compound electrochromic membrane determines the combination between the organic-inorganic material, this performance to electrochomeric films is extremely important, in addition, what distribute between the organic and inorganic materials evenly also has influence on its performance, and at present prepared composite electrochromic material is skewness often between the two.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of organic electrochromic composite membrane, based on organic electrochromic film, composite inorganic electrochromic particles, the stability and the life-span of improving the organic electrochromic material.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, preparation SiO
2Nanometer or sub-micron ball;
Second step, it is in 25～28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 1.5～2.5 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1～2, polyoxyethylene glycol is 1/3～1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5～7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80～90 ℃ of water-bath evaporations under 130～140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400～500 ℃, take out behind calcining 3～5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5～8: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=3～6: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2～3h, two suspension are mixed the back continue ultrasonic 2～3h, obtain mixing suspension, its particulate massfraction is 1%～2%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40～50 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface;
In the 5th step, it is etching 12～24h in 1%～2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50～60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2～0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1～0.8, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2～0.25mol/L, 30～80 ℃ of reaction 2～24h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Wherein,
The described the first step prepares SiO
2Nanometer or sub-micron ball are realized according to following steps:
At first, the dehydrated alcohol that tetraethoxy is dissolved in a part is configured to solution A;
Secondly, be that the dehydrated alcohol that 25%～28% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1～2 with the mass concentration of 0.8～5 times of tetraethoxy volume;
Then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.2～0.6mol/L in the mixed solution, and behind the reaction 20h, precipitation separation in 50～60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball.
Organic solvent in described the 3rd step is ethanol, methyl alcohol, acetone, acetonitrile or Virahol.
Substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond in described the 4th step.
Organic electrochromic composite membrane provided by the invention and preparation method thereof is with prepared WO
3Nano powder and SiO
2Submicron particles is prepared into two size colloidal crystals, afterwards with SiO
2Remove through etching, again it is immersed in organic electrochromic material presoma, through polymerization, lift, promptly obtain the organic electrochromic composite membrane after the drying; Organic electrochromic film combines the stable advantage of superior performance of inorganic electrochromic film like this, and because inorganic complex is closely to arrange in the organic membrane of preparation, formed space is an opal colloidal crystal structure in the inorganic particle, its size and distribution are evenly and clocklike, make inorganic particle tight and even with combining of organic granular.
Compared with prior art, stability and life-span that the inorganic-organic composite electrochromic film of the present invention's preparation can improve the organic electrochromic material, and with respect to existing composite electrochromic film, inorganic and organic the combination is uniform, being evenly distributed of inorganic particle has periodically closely arrangement, helps the application of electrochromic film.
Embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment one
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1 again with the mass concentration of 0.8 times of tetraethoxy volume, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.4mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 2.5 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400 ℃, take out behind the calcining 5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=6: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in ethanol, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 2h, obtains mixing suspension, its particulate massfraction is 2%;
The 4th step, the vertical immersion of non-crystalline silicon substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at the non-crystalline silicon substrate surface;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 30 ℃ of reaction 24h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Embodiment two
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1 again with the mass concentration of 5 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.2mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 50 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 1.5 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 90 ℃ of water-bath evaporations under 140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 500 ℃, take out behind the calcining 3h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=3: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in methyl alcohol, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%;
The 4th step, the vertical immersion of monocrystal silicon substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, go out the two size colloidal crystals of one deck in the monocrystal silicon substrate surface growth;
In the 5th step, it is etching 12h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 0.8, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.25mol/L, 80 ℃ of reaction 2h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Embodiment three
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1 again with the mass concentration of 2 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.6mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 2 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 2, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 4h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=6: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in acetone, ultrasonic time is 3h, two suspension is mixed the back continue ultrasonic 2h, obtains mixing suspension, its particulate massfraction is 2%;
The 4th step, the straight immersion of diamond based dolly has been placed stably in the mixing suspension, 50 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at diamond based basal surface;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.22mol/L, 60 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Embodiment four
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1 again with the mass concentration of 0.8 times of tetraethoxy volume, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.6mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 50 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 1.5 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1, polyoxyethylene glycol is 1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 3h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=6: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=4: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in acetonitrile, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 2%;
The 4th step, the vertical immersion of non-crystalline silicon has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck in amorphous silicon surfaces;
In the 5th step, it is etching 14h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 50 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Embodiment five
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 2 again with the mass concentration of 3 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.4mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 56 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 1.5 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1, polyoxyethylene glycol is 1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 134 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 4h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=5: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in Virahol, ultrasonic time is 3h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%;
The 4th step, the vertical immersion of polysilicon has been placed stably in the mixing suspension, 45 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at polysilicon surface;
In the 5th step, it is etching 14h in 1% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 55 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 50 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
Embodiment six
The preparation method of organic electrochromic composite membrane may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a: b=1: 1 again with the mass concentration of 4 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.5mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 26% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, it according to the mol ratio of tungsten powder and citric acid 1: 2 ratio, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1: 1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 6 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 85 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400 ℃, take out behind the calcining 5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5: 1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999Respectively take by weighing at=5: 1, then respectively with two kinds of spherical particles ultra-sonic dispersion in ethanol, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%;
The 4th step, the vertical immersion of silicon single crystal has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at monocrystalline silicon surface;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1: 1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.25mol/L, 80 ℃ of reaction 4h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
More than among each embodiment, the organic solvent that the spherical particles ultra-sonic dispersion is used also can have multiple choices; Among each embodiment, substrate can be silicon single crystal, polysilicon, non-crystalline silicon or diamond etc., needs to stand the long-time etching of hydrofluoric acid.
Claims (10)
1. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, preparation SiO
2Nanometer or sub-micron ball;
Second step, it is in 25～28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:1.5～2.5, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1～2, polyoxyethylene glycol is 1/3～1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5～7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80～90 ℃ of water-bath evaporations under 130～140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400～500 ℃, take out behind calcining 3～5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5～8:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=3～6:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2～3h, two suspension is mixed the back continue ultrasonic 2～3h, obtains mixing suspension, its particulate massfraction is 1%～2%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40～50 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface;
In the 5th step, it is etching 12～24h in 1%～2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50～60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2～0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1～0.8, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2～0.25mol/L, 30～80 ℃ of reaction 2～24h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
2. the preparation method of a kind of organic electrochromic composite membrane according to claim 1 is characterized in that, the described the first step prepares SiO
2Nanometer or sub-micron ball are realized according to following steps:
At first, the dehydrated alcohol that tetraethoxy is dissolved in a part is configured to solution A;
Secondly, be that the dehydrated alcohol that 25%～28% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1～2 with the mass concentration of 0.8～5 times of tetraethoxy volume;
Then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.2～0.6mol/L in the mixed solution, and behind the reaction 20h, precipitation separation in 50～60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball.
3. the preparation method of organic electrochromic composite membrane according to claim 1 is characterized in that, the organic solvent in described the 3rd step is ethanol, methyl alcohol, acetone, acetonitrile or Virahol.
4. the preparation method of organic electrochromic composite membrane according to claim 1 is characterized in that, substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond in described the 4th step.
5. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1 again with the mass concentration of 0.8 times of tetraethoxy volume, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.4mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:2.5, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400 ℃, take out behind the calcining 5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=6:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 2h, obtains mixing suspension, its particulate massfraction is 2% wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 30 ℃ of reaction 24h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
6. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1 again with the mass concentration of 5 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.2mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 50 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:1.5, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 90 ℃ of water-bath evaporations under 140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 500 ℃, take out behind the calcining 3h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=3:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 12h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:0.8, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.25mol/L, 80 ℃ of reaction 2h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
7. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1 again with the mass concentration of 2 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.6mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 25% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:2, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:2, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 4h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=6:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 3h, two suspension is mixed the back continue ultrasonic 2h, obtains mixing suspension, its particulate massfraction is 2%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 50 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.22mol/L, 60 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
8. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1 again with the mass concentration of 0.8 times of tetraethoxy volume, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.6mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 50 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:1.5, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1, polyoxyethylene glycol is 1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 5 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 140 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 3h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=6:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=4:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 2%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 14h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 60 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.2mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 50 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
9. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 25% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:2 again with the mass concentration of 3 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.4mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 56 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 28% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:1.5, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1, polyoxyethylene glycol is 1/2 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 7 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 80 ℃ of water-bath evaporations under 134 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 450 ℃, take out behind the calcining 4h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=8:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=5:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 3h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 45 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 14h in 1% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 55 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.2mol/L, 50 ℃ of reaction 14h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
10. the preparation method of organic electrochromic composite membrane is characterized in that, may further comprise the steps:
The first step, the dehydrated alcohol that earlier tetraethoxy is dissolved in a part is configured to solution A, is that the dehydrated alcohol that 28% ammoniacal liquor is dissolved in b part is configured to solution B, a:b=1:1 again with the mass concentration of 4 times of tetraethoxy volumes, then, solution A is placed magnetic agitation equipment, under not stopping stirring solution B is added in the solution A, the concentration of tetraethoxy is 0.5mol/L in the mixed solution, behind the reaction 20h, precipitation separation in 60 ℃ of dryings, obtains SiO behind the centrifuge washing
2Nanometer or sub-micron ball;
Second step, it is in 26% ammoniacal liquor that tungsten powder and citric acid are dissolved in mass concentration respectively, ammoniacal liquor is can dissolve tungsten powder and citric acid is as the criterion, mol ratio according to tungsten powder and citric acid is the ratio of 1:2, the ammonia soln of tungsten powder is mixed with the ammonia soln of citric acid, add dehydrated alcohol and polyoxyethylene glycol then, the volume ratio of dehydrated alcohol and ammoniacal liquor total amount is 1:1, polyoxyethylene glycol is 1/3 of a citric acid quality, stirring and dissolving, the PH that regulates colloidal sol with ammoniacal liquor 6 is made into precursor again, precursor, carries out wet gel the drying foaming then and obtains xerogel until obtaining wet gel 85 ℃ of water-bath evaporations under 130 ℃ of conditions, again xerogel is carried out calcining at constant temperature at 400 ℃, take out behind the calcining 5h, obtain nanometer WO
3Powder;
The 3rd step was D with particle diameter ratio
SiO2: D
Tungsten oxide 99.999Two kinds of spherical particles of=5:1 are m by mass ratio
SiO2: m
Tungsten oxide 99.999=5:1 takes by weighing respectively, then respectively with two kinds of spherical particles ultra-sonic dispersion in organic solvent, ultrasonic time is 2h, two suspension is mixed the back continue ultrasonic 3h, obtains mixing suspension, its particulate massfraction is 1%, wherein: D
SiO2Expression SiO
2Diameter, D
Tungsten oxide 99.999The diameter of expression Tungsten oxide 99.999, m
SiO2Expression SiO
2Quality, m
Tungsten oxide 99.999The quality of expression Tungsten oxide 99.999, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol;
The 4th step, the vertical immersion of substrate has been placed stably in the mixing suspension, 40 ℃ of following vacuum-dryings, treat that solution evaporates fully after, grow the two size colloidal crystals of one deck at substrate surface, described substrate is silicon single crystal, polysilicon, non-crystalline silicon or diamond;
In the 5th step, it is etching 24h in 2% the hydrofluoric acid solution that two size colloidal crystals are immersed mass concentrations, removes unnecessary hydrofluoric acid solution with cleaning in the deionized water then, dries down at 50 ℃ and promptly gets counter opal type Tungsten oxide 99.999 colloidal crystal;
The 6th step, the immersion of gained counter opal type Tungsten oxide 99.999 colloidal crystal is contained in the hydrochloric acid soln of aniline and O-Phenylene Diamine, aniline concentration is 0.3mol/L in the hydrochloric acid soln, aniline and O-Phenylene Diamine mol ratio are 1:1, add Ammonium Persulfate 98.5 again, the concentration that makes Ammonium Persulfate 98.5 in the hydrochloric acid soln is 0.25mol/L, 80 ℃ of reaction 4h, pulling film forming promptly obtains the organic electrochromic composite membrane behind the Air drying.
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