CN1560185A - Metal oxide pore material with excellent electrochromism performance and its preparation process - Google Patents
Metal oxide pore material with excellent electrochromism performance and its preparation process Download PDFInfo
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- CN1560185A CN1560185A CNA200410016855XA CN200410016855A CN1560185A CN 1560185 A CN1560185 A CN 1560185A CN A200410016855X A CNA200410016855X A CN A200410016855XA CN 200410016855 A CN200410016855 A CN 200410016855A CN 1560185 A CN1560185 A CN 1560185A
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- metal oxide
- mesoporous material
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- tensio
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Abstract
The invention is an excellently electrochromic metal oxide mesoporous material and its preparing method, firstly uniformly mixing surfactant with volatile organic solvent, then adding in corresponding metal alcoholate and metal halide, stirring uniformly, and rotationally smearing the mixed solution on the surface of a conductive glass, placing the glass in the air, volatilizing the organic solvent, then baking and eliminating the surfactant, and obtaining the mesoporous material. It is a film in shape and has order or orderless porthole structure, uniform aperture, specific surface 60-500 sq m/g and hole bulk 0.1-0.5 cu cm/g. The advantages are developing the structural types of electrochromic materials and electrochromic properties of the materials.
Description
Technical field
The invention belongs to inorganic advanced material technical field, be specifically related to a kind of metal oxide mesoporous material and preparation method thereof with good electrochromic property.
Technical background
Along with going deep into of mesoporous nano area research, the mesoporous nano material more and more receives investigator's concern because its performance at aspects such as electricity, magnetic, light, catalysis is far superior to monox mesoporous material.For example, nano mesoporous titania is in the news as splendid photocatalyst, and nano tin dioxide, Indium sesquioxide then are good electro-conductive material and semiconductor materials.So we have carried out the research that metal oxide mesoporous material is used in the electrochromism field.
The metal oxide electrochomeric films preparation methods of report has multiple at present: as magnetron sputtering, and electron beam evaporation and electrochemical deposition etc.Though these methods are used, in the material preparation process, but exist many problems, as the plant and instrument of costliness, complicated preparation technology, higher system film cost, limited system membrane area etc.More important usefulness be that the metal oxide film that aforesaid method obtains does not possess meso-hole structure, thereby the specific surface area of material is little, has influenced the electrochromic property of material to a certain extent.In the electrochromism research field, the metal oxide mesoporous material with orderly pore passage structure does not appear in the newspapers as yet.
With the surfactant molecule is structure directing agent, utilizes the synthetic electrochomeric films with mesoporous nano structure of sol-gel method, and method is easy, need not expensive complex apparatus, and cost is low, and the thin film composition of preparation is even.The metal oxide mesoporous material that adopts this method to synthesize has aperture, the higher specific surface area of homogeneous, shows good electrochromism ability.
Summary of the invention
The present invention proposes a kind of metal oxide mesoporous material and preparation method thereof with good electrochromic property, this material has big and adjustable aperture and different compositions, have multiple pore passage structure, high specific surface area can satisfy the needs of industrial application and research.
The preparation method of the metal oxide mesoporous material with good electrochromic property that the present invention proposes is as follows: at first with tensio-active agent and a certain amount of volatile organic solvent uniform mixing, add corresponding metal alkoxide and metal halide then, stir.Mixing solutions is spun on the surface of conductive glass, in air, places again, make the organic solvent volatilization.Through roasting tensio-active agent is removed then, promptly obtained the corresponding metal oxide mesoporous material.The profile of material is a film.
The aforesaid method that the present invention proposes carries out in organic solvent.Make tensio-active agent uniform distribution in organic solvent earlier, add corresponding metal alkoxide and metal halide again, make it to form colloidal sol with specific composition.Along with the volatilization of solvent, surfactant concentration increases, and reaches micelle-forming concentration, forms micella this moment, and inorganic sources i.e. hydrolysis, crosslinked around the micella of ordered arrangement, and tensio-active agent is guiding, three-dimensional network orderly, that be cross-linked with each other thereby form.Make removal of surfactant through roasting at last, can obtain oxide mesoporous material.Its concrete preparation process is as follows:
1, forms tensio-active agent homodisperse solution in organic solvent: nonionic surface active agent is dissolved in the appropriate amount of organic, stirred 0.5-3 hour, make it to mix.The mass ratio of general employing tensio-active agent and organic solvent is 1: 5-1: 100.
2, form the colloidal sol that contains tensio-active agent and metal oxide precursors: metal alkoxide and/or metal halide are joined in the prepared clear solution of step (1), and continue to stir 1-2 hour, controlled temperature is 5-50 ℃.The mass ratio of metal alkoxide and/or metal halide and organic solvent is 1: 4-1: 20.
3, the volatilization of organic solvent: will be spun on by the resulting colloidal sol of step (2) and make film on the conductive glass, and make the organic solvent volatilization.The temperature hold-in range of this moment is 20-80 ℃.
4, the removal of tensio-active agent: will be by the mixture of resulting metal oxide of step (3) and tensio-active agent at 200-500 ℃ of following roasting 2-8 hour, obtain having the metal oxide mesoporous material of the aperture of orderly or unordered pore passage structure, homogeneous, bigger specific surface and pore volume and good electrochromic property.
Among the present invention, the tensio-active agent that is adopted in the preparation process is a nonionic surface active agent.As EO
20PO
70EO
20(Pluronic P123), EO
106PO
70EO
106(Pluronic F127), EO
132PO
50EO
132(Pluronic F108) and EO
26PO
39EO
26(Pluronic P85) etc.
Employed volatile organic solvent is dehydrated alcohol, acetone, propyl alcohol and and tetrahydrofuran (THF) etc. a kind of among the present invention.
Among the present invention, according to the composition difference of want synthetic, the metal alkoxide that can select for use and metal halide are Ti (OR)
4, W (OR)
4O, W (OR)
6, CeCl
36H
2O, TiCl
4And WCl
6Deng a kind of.
Among the present invention, high-temperature roasting method is adopted in the removal of tensio-active agent, and maturing temperature is 200-500 ℃, and roasting time is 2-8 hour.
Among the present invention, the mesoporous material for preparing can be to form single metal oxide such as titanium oxide, Tungsten oxide 99.999 etc., also can be mixed metal oxide such as metatitanic acid cerium, the metatitanic acid tungsten of forming etc. more.
Among the present invention, the mesoporous material for preparing is the metal oxide mesoporous material of aperture homogeneous.Its space structure is respectively hexagonal structure, cubic structure and worm hole shape structure.
Among the present invention, the pore diameter range of the mesoporous material for preparing is 2-25nm; Specific surface area is 60-500m
2/ g.
Among the present invention, the moiety of the mesoporous material for preparing is even.
Among the present invention, the mesoporous material for preparing has bigger electrochromism scope in the range of wavelengths of 380-800nm, and the variation of its transmittance reaches as high as 20-70%.
Among the present invention, the mesoporous material for preparing has the fast characteristics of variable color response, and the time of response is no more than 300s.
Among the present invention, the mesoporous material for preparing has the low characteristics of variable color driving voltage, and painted needed driving voltage is more than or equal to 0.5V, and the needed driving voltage that fades is smaller or equal to-0.5V.
Among the present invention, the mesoporous material for preparing presents good electrochromism reversibility, and after 50-100 time the continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and changing value has only the 5-15% of initial observed value respectively.
Among the present invention, the mesoporous material for preparing presents good electrochromism memory effect, and the transmittance maximum changing value of 24h is respectively less than 15% of initial observed value under painted fully or bleached state.
Embodiment
Embodiment 1, and the titanium oxide of bidimensional hexagonal meso-hole structure is synthetic: 1g P123 is dissolved in the 10-30g ethanol, stirs 0.5-1h.Add 0.003mol titanium tetrachloride (TiCl
4) and 0.007mol tetra-n-butyl titanate (Ti (OC
4H
9)
4), continue to stir 1-2h.Resulting reaction mother liquor is spun on the conductive glass, in the 40-50 ℃ of film forming of volatilizing down.After 2 days, material is placed retort furnace,, promptly get material requested at 350 ℃ of following roasting 3h.Through the electrochemical method test, this material is in the 400-800nm range of wavelengths, and the variation of transmittance can reach 35%.Carry out paintedly with driving voltage for-1.5V, painted through 180s is that 1V fades with the driving voltage fully, fades fully through 40s.The coloration efficiency value of this material is 15cm
2C
-1After 80 times continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and the transmittance changing value is respectively 15% of initial observed value.The transmittance maximum changing value of 24h is respectively less than 10% of initial observed value under painted fully or bleached state.
Embodiment 2, and the metatitanic acid tungsten of bidimensional hexagonal meso-hole structure is synthetic: 1g F127 is dissolved in the 10-30g ethanol, stirs 0.5-1h.Add 0.002mol tungsten hexachloride (WCl
6) and 0.004mol isopropyl titanate (Ti (OC
3H
7)
4), continue to stir 1-2h.Resulting reaction mother liquor is spun on the conductive glass, in the 40-50 ℃ of film forming of volatilizing down.After 3 days, material is placed retort furnace,, promptly get material requested at 400 ℃ of following roasting 3h.Through the electrochemical method test, this material is in the 380-800nm range of wavelengths, and the variation of transmittance can reach 20%.Carry out paintedly with driving voltage for-1.5V, painted through 180s is that 0.5V fades with the driving voltage fully, fades fully through 50s.The coloration efficiency value of this material is 12cm
2C
-1After 50 times continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and the transmittance changing value is respectively 10% of initial observed value.The transmittance maximum changing value of 24h is respectively less than 10% of initial observed value under painted fully or bleached state.
Embodiment 3, and the metatitanic acid tungsten of three-dimensional cubic meso-hole structure is synthetic: 1g F108 is dissolved in the 10-30g ethanol, stirs 0.5-1h.Add 0.002mol tungsten hexachloride (WCl
6) and 0.006mol isopropyl titanate (Ti (OC
3H
7)
4), continue to stir 1-2h.Resulting reaction mother liquor is spun on the conductive glass, in the 40-50 ℃ of film forming of volatilizing down.After 3 days, material is placed retort furnace,, promptly get material requested at 350 ℃ of following roasting 5h.Through the electrochemical method test, this material is in the 380-800nm range of wavelengths, and the variation of transmittance can reach 50%.Carry out paintedly with driving voltage for-1.5V, painted through 180s is that 0.5V fades with the driving voltage fully, fades fully through 30s.The coloration efficiency value of this material is 22cm
2C
-1After 50 times continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and the transmittance changing value is respectively 10% of initial observed value.The transmittance maximum changing value of 24h is respectively less than 7% of initial observed value under painted fully or bleached state.
Embodiment 4, and the metatitanic acid tungsten of worm hole shape meso-hole structure is synthetic: 1g P123 is dissolved in the 10-30g ethanol, stirs 0.5-1h.Add 0.002mol tungsten hexachloride (WCl
6) and 0.007mol tetra-n-butyl titanate (Ti (OC
4H
9)
4), continue to stir 1-2h.Resulting reaction mother liquor is spun on the conductive glass, in the 40-50 ℃ of film forming of volatilizing down.After 3 days, material is placed retort furnace,, promptly get material requested at 400 ℃ of following roasting 5h.Through the electrochemical method test, the electrochromism scope of this material is 40%, and coloration efficiency is 17cm
2C
-1Through the electrochemical method test, this material is in the 400-800nm range of wavelengths, and the variation of transmittance can reach 40%.Carry out paintedly with driving voltage for-1.5V, painted through 180s is that 1V fades with the driving voltage fully, fades fully through 30s.The coloration efficiency value of this material is 15cm
2C
-1After 50 times continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and the transmittance changing value is respectively 10% of initial observed value.The transmittance maximum changing value of 24h is respectively less than 10% of initial observed value under painted fully or bleached state.
Embodiment 5, and the metatitanic acid cerium of worm hole shape meso-hole structure is synthetic: 1g P123 is dissolved in the 10-30g ethanol, stirs 0.5-1h.Add 0.003mol Cerium II Chloride (CeCl
36H
2O) and 0.008mol tetra-n-butyl titanate (Ti (OC
4H
9)
4), continue to stir 1-2h.Resulting reaction mother liquor is spun on the conductive glass, in the 40-50 ℃ of film forming of volatilizing down.After 2 days, material is placed retort furnace,, promptly get material requested at 350 ℃ of following roasting 3h.Through the electrochemical method test, this material is in the 400-800nm range of wavelengths, and the variation of transmittance all can reach 20%.Carry out paintedly with driving voltage for-2.5V, painted through 180s is that 0.5V fades with the driving voltage fully, fades fully through 50s.The coloration efficiency value of this material is 12cm
2C
-1After 80 times continuous scan round, the transmittance under its fully painted and bleached state tends towards stability, and the transmittance changing value is respectively 15% of initial observed value.The transmittance maximum changing value of 24h is respectively less than 15% of initial observed value under painted fully or bleached state.
Claims (10)
1, a kind of metal oxide mesoporous material with good electrochromic property is characterized in that this material has orderly or unordered pore passage structure, the aperture of homogeneous, and pore diameter range is 2-25nm, and specific surface is 60-500m
2/ g, pore volume are 0.1-0.5cm
3/ g, space structure are hexagonal structure, cubic structure or worm hole shape structure.
2, metal oxide mesoporous material according to claim 1 is characterized in that it is shaped as film, and the film size is 0.25-400cm
2, thickness is 0.1-500 μ m.
3, a kind of preparation method of metal oxide mesoporous material as claimed in claim 1 is characterized in that at first tensio-active agent and volatile organic solvent uniform mixing are added corresponding metal alkoxide and metal halide then, stirs; Mixing solutions is spun on the surface of conductive glass again, in air, places, make the organic solvent volatilization, through roasting tensio-active agent is removed then, promptly had the metal oxide mesoporous material of good electrochromic property accordingly.
4, the preparation method of metal oxide mesoporous material according to claim 3, concrete steps are as follows:
(1) form tensio-active agent homodisperse solution in organic solvent: nonionic surface active agent is dissolved in the organic solvent, stirred 0.5-3 hour, make it to mix, the mass ratio of tensio-active agent and organic solvent is 1: 5-1: 100;
(2) form the colloidal sol that contains tensio-active agent and metal oxide precursors: metal alkoxide and/or metal halide are joined in the prepared clear solution of step (1), continue to stir 1-2 hour, controlled temperature is 5-50 ℃, and the mass ratio of metal alkoxide and/or metal halide and organic solvent is 1: 4-1: 20;
(3) volatilization of organic solvent: will be spun on by the resulting colloidal sol of step (2) and make film on the conductive glass, and make the organic solvent volatilization, this moment, the temperature hold-in range was 20-80 ℃;
(4) removal of tensio-active agent: will promptly obtain having the metal oxide mesoporous material of good electrochromic property by the mixture of resulting metal oxide of step (3) and tensio-active agent at 200-500 ℃ of following roasting 2-8 hour.
5, the preparation method of metal oxide mesoporous material according to claim 4 is characterized in that used nonionic surface active agent is EO
20PO
70EO
20, EO
106PO
70EO
106, EO
132PO
50EO
132And EO
26PO
39EO
26A kind of.
6, the preparation method of metal oxide mesoporous material according to claim 4 is characterized in that employed organic solvent is a kind of of dehydrated alcohol, acetone, propyl alcohol and tetrahydrofuran (THF).
7, the preparation method of metal oxide mesoporous material according to claim 4 is characterized in that the composition difference according to want synthetic, and selected metal alkoxide and metal halide are Ti (OR)
4, W (OR)
4O, W (OR)
6, CeCl
36H
2O, TiCl
4And WCl
6A kind of.
8, metal oxide mesoporous material according to claim 3 is characterized in that this mesoporous material is to form single metal oxide, or the mixed metal oxide of forming more.
9, metal oxide mesoporous material according to claim 3 is characterized in that this mesoporous material in the range of wavelengths of 380-800nm, has big electrochromism scope, and the variation of its transmittance is up to 20-70%.
10, metal oxide mesoporous material according to claim 3 is characterized in that this mesoporous material variable color time of response scope is 10-300s; Painted needed driving voltage is more than or equal to 0.5V, and the needed driving voltage that fades is smaller or equal to-0.5V.
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Cited By (6)
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|---|---|---|---|---|
| CN101219908B (en) * | 2007-09-21 | 2012-12-05 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| CN108117275A (en) * | 2017-12-04 | 2018-06-05 | 上海艾谡新材料有限公司 | A kind of porous MoO3The preparation method of electrochomeric films |
| CN108424006A (en) * | 2018-04-17 | 2018-08-21 | 上海艾谡新材料有限公司 | A kind of preparation method of nanometer of organic composite molybdenum oxide electrochomeric films |
| CN108663868A (en) * | 2018-07-05 | 2018-10-16 | 东华大学 | A kind of preparation method of tungsten oxide electrochromic electrode |
| WO2019014776A1 (en) * | 2017-07-20 | 2019-01-24 | Curtis Berlinguette | Photodeposition of metal oxides for electrochromic devices |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
Family Cites Families (3)
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|---|---|---|---|---|
| CN1057982C (en) * | 1998-01-14 | 2000-11-01 | 中国科学院固体物理研究所 | Large mass TiO2 mesohole solid and preparing method |
| CN1113817C (en) * | 2001-08-14 | 2003-07-09 | 复旦大学 | Preparation method of titanium oxide nano pore molecular sieve film |
| CN1202006C (en) * | 2003-01-30 | 2005-05-18 | 复旦大学 | Kinds of materials with multiple constituents of big bores oxide media and its preparing method |
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- 2004-03-10 CN CNB200410016855XA patent/CN1305997C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219908B (en) * | 2007-09-21 | 2012-12-05 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| WO2019014776A1 (en) * | 2017-07-20 | 2019-01-24 | Curtis Berlinguette | Photodeposition of metal oxides for electrochromic devices |
| CN111630134A (en) * | 2017-07-20 | 2020-09-04 | 克利克材料公司 | Photo-deposition of metal oxides for electrochromic devices |
| CN108117275A (en) * | 2017-12-04 | 2018-06-05 | 上海艾谡新材料有限公司 | A kind of porous MoO3The preparation method of electrochomeric films |
| CN108424006A (en) * | 2018-04-17 | 2018-08-21 | 上海艾谡新材料有限公司 | A kind of preparation method of nanometer of organic composite molybdenum oxide electrochomeric films |
| CN108663868A (en) * | 2018-07-05 | 2018-10-16 | 东华大学 | A kind of preparation method of tungsten oxide electrochromic electrode |
| CN108663868B (en) * | 2018-07-05 | 2021-01-05 | 东华大学 | Preparation method of tungsten oxide electrochromic electrode |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN114994997B (en) * | 2021-03-01 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
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