CN1528855A - Nickel oxide nano electrochromism film and preparing method thereof - Google Patents
Nickel oxide nano electrochromism film and preparing method thereof Download PDFInfo
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- CN1528855A CN1528855A CNA031350976A CN03135097A CN1528855A CN 1528855 A CN1528855 A CN 1528855A CN A031350976 A CNA031350976 A CN A031350976A CN 03135097 A CN03135097 A CN 03135097A CN 1528855 A CN1528855 A CN 1528855A
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Abstract
The invention is nickel oxide nano electrochromism film and the manufacturing method, the method uses liquid-gelatum method to produce nickel colloidal sols, them the ITO glass piece is immersed into the liquid, and uses the film device to pull into film, the film can be get through drying, baking, quenching and cooling. The manufacturing method of colloidal sols uses inorganic nickel salt to dissolve in the compound organic solvent which uses waterless alcohol mainly, and they are back flowed every 78-82deg.C, then, adds in water and the organic acid to get the nickel colloidal sols. The invention is simple, the film is even, thick, the even particle radius is between 30-50mm, the light throughput varies in 7.9%-85%. The property of the product is stable.
Description
One, technical field
The present invention relates to a kind ofly attached to optically variable films on the device and preparation method thereof, exactly is a kind of electro-allochromatic nickel oxide film and preparation method thereof.
Two, background technology
The method of the electrochomeric films of preparation nickel is a lot, comprises anodic oxidation, electrochemical deposition, electron beam evaporation, sputter, high temperature direct oxidation etc.But this several method needs main equipment, complicated process of preparation, and the system membrane area is subjected to device-restrictive, is unsuitable for large-area preparation.
At present, preparing nickel oxide nano electrochomeric films great majority with sol-gel method all is the way that adopts the hydrolysis of alkoxide of nickel.But the prescription of traditional preparation process nickel oxide colloidal sol all is a more complicated, makes that the preparation technology of electro-allochromatic nickel oxide film is also very complicated, and the step of reaction needed control is many.Such as the disclosed a kind of method for preparing electro-allochromatic nickel oxide film of CN1067661C, at first nickel salt, cerous sulfate or Neodymium sulfate stirring and dissolving in the mixed solution of distilled water, dehydrated alcohol and methyl ethyl diketone is prepared main solution; Prepare adhesive transfer with ammoniacal liquor, distilled water and dehydrated alcohol again; Under agitation a certain amount of adhesive transfer is added to then and obtains translucent sol solutions in the main solution, this sol solutions is standby as coating liquid.Film forming method is complicated more, with spraying with dip-coating hockets and 2～6 times repeatedly, the i.e. film of spraying system earlier, 300～600 ℃ of sintering 5～30 minutes on the ITO transparent conducting glass, dip-coating system film, 30～100 ℃ of dryings 5～30 minutes 300～600 ℃ of sintering 5～30 minutes more again after the cooling, the film of spraying system again, so alternate repetition after the cooling.
" solid ionic " discloses the method that a kind of solution-gel method prepares the NiOx film, with NiCl
2In the mixed solvent of propyl carbinol and ethylene glycol, stir and make preceding body liquid half an hour, adding a certain amount of acetate, polyoxyethylene (PEO) and diethanolamine (DEA) then refluxed 3 hours down for 70 ℃, adding entry again continues to reflux 1 hour, cooling obtains colloidal sol, obtains electrochomeric films (" Solid State Ionics " 1998,113～115 volumes, p457～463) with soaking the pulling film forming method that stagnates.
Three, summary of the invention
The present invention also uses solution-gel method processing electro-allochromatic nickel oxide film, is intended to simplify prescription and film-forming process, to realize industrialization.
Prescription of the present invention is made up of and weight percent following:
Nickel salt 2～4%
Water 2～4%
The organic solvent surplus.
Described nickel salt can be nickelous chloride (NiCl
2) or nickelous nitrate (Ni (NO
3)
2) or single nickel salt (NiSO
4) in a kind of.
Described organic solvent is the mixed solvent based on dehydrated alcohol, be the unitary fatty alcohol of dehydrated alcohol with 3～7 carbon atoms, mix mixed mutually by 2: 0.5～1.5 as in propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, the enanthol one or more.
Can also add 0.5～0.8% organic acid in above-mentioned prescription is formed, described organic acid is meant that the binary of 4～7 carbon atoms or ternary aliphatic acid are as one or more organic acids in citric acid, oxysuccinic acid, the pentanedioic acid etc.
The preparation method of film comprises the preparation of colloidal sol and soaks to stagnate and propose film and drying, roasting, annealing, cool off each unit process.
The preparation of colloidal sol adds nickel salt the also stirring and dissolving that heats up in the organic solvent earlier, refluxes half an hour under 78～82 ℃ of conditions, adds entry again or add organic acid simultaneously to continue to reflux 1～2 hour, promptly gets nickel sol.
Soaking stagnates carry film earlier the ito glass sheet is cleaned, dry, soak and stagnate in colloidal sol, then with film extracting apparatus with the speed that 10mm/ divides lift repeatedly, dry 2～3 times, 300～450 ℃ of roastings 0.5～2 hour in retort furnace at last, the after annealing of coming out of the stove, cooling promptly get nickel oxide nano electrochomeric films sheet glass.
This film performance characterizes as follows:
1, microscopic appearance
Shown in Fig. 1 SEM photo, the nickel oxide film of present method preparation is very even, and compactness extent is also very good.The mean diameter of crystalline particles has reached Nano grade between 30～50nm.So nickel oxide film transmittance in visible-range when coloured state is very little, can satisfy practical requirement.
2, transmitted spectrum
In the scope of 400～800nm, measure the variation of its transmittance with spectrophotometer.As shown in Figure 2, the transmittance minimum of film in 400～490 scopes, about 10%, along with the increase of lambda1-wavelength, the transmittance of film increases gradually.When wavelength during greater than 600nm, the transmittance of film just significantly increases, and at the 800nm place, transmittance has reached 70%, and film is very little to absorption of incident light.
3, electrochemical properties
Nickel oxide film is carried out electrochemical analysis.As shown in Figure 3, anodic current begins to rise near 0.59V, and expression anode coloring reaction begins, and peak value appears near 0.66V, and electric current began reverse increase near coloured state was formed on 0.59V, and expression negative electrode color fading reaction begins, and the cathodic current peak appears near 0.5V, the attitude of fading forms.The redox potential of film is still not significant when cycle index reaches 2000 times changes, and illustrates that film has satisfactory stability.
The present invention has adopted simple formulation and simple prepared nickel oxide nano electrochomeric films, its transmittance can change in 7.9～85% scope, time of response is 30～90s, grain-size is between 30～50nm, and homogeneity is very good, and compactness is also very good, hole is between 5～10nm, stability is good, can recycle several thousand times, has wide practical prospect.Such as indicating meter, smart window, automobile free from glare rear vision mirror etc.Preparation method of the present invention is simple, is suitable for industrialization.And can process the big area electrochomeric films.
Four, description of drawings
Fig. 1 is the SEM photo of film
Fig. 2 is the transmittance change curve of coloured state film
Fig. 3 is the cyclic voltammetric performance diagram.
Five, embodiment
(1), the preparation of nickel sol
1, gets the mixing of 48ml dehydrated alcohol and 12ml butanols and obtain organic solvent, stir adding 1.2g NiCl down
2And reflux half an hour when being warming up to 76 ℃, add 1.2g distilled water, continue to reflux 1 hour, promptly get nickel sol.
2, get the mixing of 40ml dehydrated alcohol and 20ml amylalcohol and obtain organic solvent, stir adding 1.8g Ni (NO down
3)
2Reflux half an hour when being warming up to 80 ℃, add 0.36g citric acid and 1.8g distilled water, continue to reflux 1.5 hours, promptly get nickel sol.
3, get the mixing of 35ml dehydrated alcohol and 25ml hexanol and obtain organic solvent, stir adding 2.4g NiSO down
4Reflux half an hour when being warming up to 82 ℃, add 0.48g pentanedioic acid and 2.4g distilled water, continue to reflux 2 hours, promptly get nickel sol.
(2), the nickel oxide electricity causes the preparation of film
Get one of ITO slide, also dry with ethanol/water solution in ultrasonic washes clean down.The exsiccant sheet glass soaked stagnate in nickel sol, with film extracting apparatus with the speed of 10mm/s lift, dry (sloughing solvent and water), lift repeatedly, dry 2～3 times, at last in retort furnace 300～450 ℃ of roasting temperatures 0.5～2 hour, the after annealing of coming out of the stove, cooling obtain the nickel oxide nano electricity and cause the film slide.
Claims (3)
1, a kind of nickel oxide nano electrochomeric films, form and weight percent by following:
Nickel salt 2～4%
Water 2～4%
The organic solvent surplus,
Described nickel salt can be a kind of nickel salt in nickelous chloride or nickelous nitrate or the single nickel salt,
Described organic solvent is a dehydrated alcohol with one or more organic solvents that obtain with 2: 0.5～1.5 mixed in the unitary fatty alcohol of 3～7 carbon atoms.
2, film according to claim 1 is characterized in that: also contain the binary of 4～7 carbon atoms of 0.5～0.8% or one or more organic acids in the ternary aliphatic acid during described prescription is formed.
3, a kind of preparation method of nickel oxide nano electrochomeric films, comprise colloidal sol preparation, film forming, drying, roasting, annealing, cool off each unit process, it is characterized in that:
(1) preparation of colloidal sol, nickel salt with 2～4% adds in the organic solvent, and the intensification stirring and dissolving refluxes half an hour under 78～82 ℃ of conditions, add 2～4% distilled water again or add 0.5～0.8% organic acid simultaneously and continue to reflux 1～2 hour, promptly obtain nickel sol;
(2) described film forming will be cleaned, exsiccant ito glass sheet soaks and stagnate in colloidal sol, with film extracting apparatus with the speed that 10mm/ divides lift repeatedly, dry 2～3 times, at last with the roasting 0.5～2 hour under 300～450 ℃ of conditions of exsiccant sheet glass.
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| CN 03135097 CN1233785C (en) | 2003-09-28 | 2003-09-28 | Nickel oxide nano electrochromism film and preparing method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515564A (en) * | 2011-12-08 | 2012-06-27 | 浙江理工大学 | Nickel oxide electrochromic film and preparation method thereof |
| CN104492675A (en) * | 2014-11-17 | 2015-04-08 | 中山大学 | Low-temperature electrochromic NiO film preparation method |
| CN105731822A (en) * | 2014-12-12 | 2016-07-06 | 中国海洋大学 | Solvothermal preparation method of nickel oxide electrochromic film |
| CN110965317A (en) * | 2019-12-23 | 2020-04-07 | 武汉纺织大学 | Anti-electromagnetic radiation silk fabric and preparation method thereof |
| CN113548809A (en) * | 2021-08-12 | 2021-10-26 | 合肥工业大学 | NiOxElectrochromic porous material and preparation method thereof |
| CN116243528A (en) * | 2022-12-15 | 2023-06-09 | 安徽立光电子材料股份有限公司 | Production method of solid electrochromic device with uniform color and solid electrochromic device |
-
2003
- 2003-09-28 CN CN 03135097 patent/CN1233785C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515564A (en) * | 2011-12-08 | 2012-06-27 | 浙江理工大学 | Nickel oxide electrochromic film and preparation method thereof |
| CN104492675A (en) * | 2014-11-17 | 2015-04-08 | 中山大学 | Low-temperature electrochromic NiO film preparation method |
| CN105731822A (en) * | 2014-12-12 | 2016-07-06 | 中国海洋大学 | Solvothermal preparation method of nickel oxide electrochromic film |
| CN105731822B (en) * | 2014-12-12 | 2019-12-27 | 中国海洋大学 | Solvothermal preparation method of nickel oxide electrochromic film |
| CN110965317A (en) * | 2019-12-23 | 2020-04-07 | 武汉纺织大学 | Anti-electromagnetic radiation silk fabric and preparation method thereof |
| CN110965317B (en) * | 2019-12-23 | 2022-06-14 | 深圳市娜尔思时装有限公司 | Anti-electromagnetic radiation silk fabric and preparation method thereof |
| CN113548809A (en) * | 2021-08-12 | 2021-10-26 | 合肥工业大学 | NiOxElectrochromic porous material and preparation method thereof |
| CN116243528A (en) * | 2022-12-15 | 2023-06-09 | 安徽立光电子材料股份有限公司 | Production method of solid electrochromic device with uniform color and solid electrochromic device |
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| Publication number | Publication date |
|---|---|
| CN1233785C (en) | 2005-12-28 |
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