CN1067661C - Preparation of electro-allochromatic nickel oxide film - Google Patents

Abstract

The present invention relates to a method for preparing electrochromic films of nickel oxide, which belongs to the field of preparing the electrochromic films on transparent conductive glass. The present invention is characterized in that a sol-gel method is adopted; organic alkoxide of nickel is used for preparing a sol; after the processes of low temperature drying and high temperature treatment, the electrochromic films with brown in a coloring state and colorless in a decoloring state can be made on the transparent conductive glass by alternating a spraying method and a dipping coating method. The process for preparing the electrochromic films of nickel oxide by using the method of the present invention has the advantages of simple technologies, no requirement for expensive devices, low cost, high compactness of the films, uniform ingredients, short response time and wide color change range.

Description

A kind of method for preparing electro-allochromatic nickel oxide film

The invention belongs to preparation electrochomeric films field on transparent conducting glass, prepared electrochromic film can be used for large screen display, and no power consumption stores, Energy Saving Windows.

Nickel oxide film is a kind of anode electrochromic material of yellow type, the method of its preparation has multiple: as the empty sputter of magnetic, electron beam evaporation, anodic oxidation and electrochemical deposition etc., though these methods are used, in the material preparation process, all exist various different problems.As adopt electron-beam vapor deposition method to prepare electro-allochromatic nickel oxide film, need expensive plant and instrument, complicated preparation technology, system pleurodiaphragmatic in terspace material cost height, the system membrane area is limit by equipment, and the variable color time of response of film is longer, film coloured state transmittance is higher, transmittance is general 40%, and film variable color narrow dynamic range, i.e. the difference maximum of colour killing attitude and coloured state transmittance only are 25% (" nickel oxide film electrochromic property and mechanism research " " functional materials " 1998 29 volumes supplementary issue.)

The invention provides a kind of method for preparing electro-allochromatic nickel oxide film, this method technology is easy, need not expensive complex apparatus, less energy consumption, and cost is low, and prepared film component is even, and compactness is good, and the variable color time of response is short, the variable color wide dynamic range.

Based on the foregoing invention purpose, the inventive method adopts sol-gel method, the colloidal sol that makes with organic alkoxide of nickel, on transparent conducting glass, by spraying with after dip-coating replaces film forming, again through cryodrying and high temperature sintering, promptly make electro-allochromatic nickel oxide film, concrete processing step is as follows:

(1) main formulations prepared from solutions

Main solution materials prescription (weight %) is:

NiSO ₄, NiCl ₂Or a kind of 10%-30% in the nickel acetate

Cerous sulfate or Neodymium sulfate 0.1%-0.7%

Distilled water 35%-60%

Dehydrated alcohol 1%-15%

Methyl ethyl diketone 0.01%-0.1%

Trisodium Citrate 5%-20%

By said ratio, get a kind of in single nickel salt, nickelous chloride or the nickel acetate of a container, Trisodium Citrate,

Cerous sulfate or Neodymium sulfate are dissolved in the distilled water successively, add dehydrated alcohol, methyl ethyl diketone then respectively and mix and stir evenly, as main solution;

(2) adhesive transfer preparation

Adhesive transfer proportioning raw materials (weight %) is:

NH ₄0H 5％-30％

Distilled water 10%-40%

Dehydrated alcohol 50%-60%

By said ratio, other gets a container with NH ₄OH, dehydrated alcohol and distilled water mixing stir evenly as adhesive transfer;

(3) lotion preparation

By volume per-cent is got the 1%-10% adhesive transfer, slowly adds adhesive transfer under the situation that constantly stirs main solution, becomes translucent sol solutions until transparent main solution, and is stand-by as lotion;

(4) spraying fluid preparation

Get a container again, by volume per-cent is got the 11%-33% lotion to make spraying fluid with distilled water diluting stand-by;

(5) substrate is selected and is cleaned

Select electric conductivity＜60 ohm/cm ²The ITO transparent conducting glass as variable color film substrate, clean with dehydrated alcohol, clean with distilled water flushing then, oven dry again;

(6) spraying system film

Filming technology:

Nozzle diameter 0.1-0.8mm

Spray is apart from 20cm-50cm

Pressure 1bar-6bar

Injecting time 1min-15min

45 °-120 ° of jet angles

10-120 ℃ of spraying substrate temperature

To clean oven dry ito glass substrate and be placed on the thermostatically heating platform 10-120 ℃ of heating, with the spray gun that meets the said nozzle diameter, and with above-mentioned spray apart from, spraying pressure to the substrate continuous injection, obtain the spray gel film, directly put into the sintering kiln roasting then immediately, maturing temperature and soaking time are respectively 300-600 ℃, 5-30min, take out the back air cooling to room temperature, can obtain the first layer nickel oxide film;

(7) dip-coating system film

The above-mentioned substrate that has been loaded with the spraying nickel oxide film directly is immersed in the main solution for preparing, pull out with the constant rate of speed of≤10mm/s then, cover one deck liquid film on the former nickel oxide film, enter the loft drier cryodrying again, drying temperature and soaking time are respectively 30-100 ℃, 5-30min, directly put into the sintering oven sintering after drying, and sintering temperature and soaking time are respectively 300 ℃-600 ℃, 5-30min, back air cooling to the room temperature of coming out of the stove can obtain second layer nickel oxide film;

(8) above-mentioned spraying of process and dipping process are 2-6 time repeatedly, can obtain electro-allochromatic nickel oxide film on transparent conducting glass.

Adopt the inventive method can obtain in the 300nm-860nm scope, the coloured state transmittance is 25%-50%, the electro-allochromatic nickel oxide film of colour killing attitude transmittance＞90%.

Compared with prior art, the invention has the advantages that: film material is pure, and chemical composition is even, the film densification, and no crack performance, maturing temperature is low, and is easy to operation, and the variable color time of response is short, film variable color wide dynamic range.

Embodiment

Adopt the inventive method on the ITO conductive glass, to prepare three batches of electro-allochromatic nickel oxide films, wherein the chemical ingredients of main solution and proportioning (weight %) see Table 1, the chemical ingredients and the proportioning of adhesive transfer see Table 2, the proportioning of lotion sees Table 3, the proportioning of spraying fluid sees Table 4, spray art and dipping process see Table 5, in order to contrast, adopt electron beam evaporation method to prepare a collection of electro-allochromatic nickel oxide film, preparation technology sees Table 6, and the performance that adopts the performance of the obtained three batches of electro-allochromatic nickel oxide films of the present invention and adopt electron-beam vapor deposition method to make a collection of electro-allochromatic nickel oxide film sees Table 7.Can find out that from table 7 adopt the prepared film compactness of the inventive method good, the time of response is short, the variable color wide dynamic range.The chemical ingredients of the main solution of table 1 and proportioning (weight %)

The chemical ingredients of table 2 adhesive transfer and proportioning (weight %)

The proportioning of table 3 lotion (volume %)

The proportioning of table 4 spraying fluid (volume %)

Table 5 spraying and dipping process

Adopt 6 electric beam evaporation technologies

Metallic nickel purity	Base vacuum degree before the plating	Charge into O 2Atmospheric pressure	Substrate temperature	Sedimentation rate	Thickness
4N	3×10 -3Pa	2×10 -2Pa	＜100℃	0.1nm/s	200nm

The performance comparison that table 7 adopts the inventive method and adopts electron-beam vapor deposition method institute made membrane

Claims (1)

1, a kind of method for preparing electro-allochromatic nickel oxide film, it is characterized in that: the colloidal sol that makes with organic alkoxide of nickel, on transparent conducting glass, by spraying with after dip-coating replaces film forming, through cryodrying and pyroprocessing, promptly make electro-allochromatic nickel oxide film, concrete processing step is as follows:

(1) main formulations prepared from solutions

Main solution materials prescription (weight %) is:

NiSO ₄, NiCl ₂Or a kind of 10%-30% in the nickel acetate

Cerous sulfate or Neodymium sulfate 0.1%-0.7%

Distilled water 35%-60%

Dehydrated alcohol 1%-15%

Methyl ethyl diketone 0.01%-0.1%

Trisodium Citrate 5%-20%

By said ratio, get a kind of in single nickel salt, nickelous chloride or the nickel acetate of a container, lemon acid sodium, cerous sulfate or Neodymium sulfate are dissolved in the distilled water successively, add dehydrated alcohol, methyl ethyl diketone then respectively and mix and stir evenly, as main solution;

(2) adhesive transfer preparation

Adhesive transfer proportioning raw materials (weight %) is:

NH ₄OH 5％-30％

Distilled water 10%-40%

Dehydrated alcohol 50%-60%

By said ratio, other gets a container with NH ₄OH, dehydrated alcohol and distilled water mixing stir evenly as adhesive transfer;

(3) lotion preparation

By volume per-cent is got the 1%-10% adhesive transfer, slowly adds adhesive transfer under the situation that constantly stirs main solution, becomes translucent sol solutions until transparent main solution, and is stand-by as lotion;

(4) spraying fluid preparation

Get a container again, by volume per-cent is got the 11%-33% lotion to make spraying fluid with distilled water diluting stand-by;

(5) substrate is selected and is cleaned

Select electric conductivity＜60 ohm/cm ²The ITO transparent conducting glass as variable color film substrate, clean with dehydrated alcohol, clean with distilled water flushing then, oven dry again;

(6) spraying system film

Filming technology:

Nozzle diameter 0.1-0.8mm

Spray is apart from 20cm-50cm

Pressure 1bar-6bar

Injecting time 1min-15min

45 °-120 ° of jet angles

10-120 ℃ of spraying substrate temperature

To clean oven dry ito glass substrate and be placed on the thermostatically heating platform 10-120 ℃ of heating, with the spray gun that meets the said nozzle diameter, and with above-mentioned spray apart from, spraying pressure to the substrate continuous injection, obtain the spray gel film, directly put into the sintering kiln roasting then immediately, maturing temperature and soaking time are respectively 300-600 ℃, 5-30min, take out the back air cooling to room temperature, can obtain the first layer nickel oxide film;

(7) dip-coating system film

The above-mentioned substrate that has been loaded with the spraying nickel oxide film directly is immersed in the main solution for preparing, pull out with the constant rate of speed of≤10mm/s then, cover one deck liquid film on the former nickel oxide film, enter the loft drier cryodrying again, drying temperature and soaking time are respectively 30-100 ℃, 5-30min, directly put into the sintering oven sintering after drying, and sintering temperature and soaking time are respectively 300 ℃-600 ℃, 5-30min, back air cooling to the room temperature of coming out of the stove can obtain second layer nickel oxide film;

(8) above-mentioned spraying of process and dipping process are 2-6 time repeatedly, can obtain electro-allochromatic nickel oxide film on transparent conducting glass.