CN104402240A - Film material with electrochromic properties and preparation method thereof - Google Patents
Film material with electrochromic properties and preparation method thereof Download PDFInfo
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- CN104402240A CN104402240A CN201410577527.0A CN201410577527A CN104402240A CN 104402240 A CN104402240 A CN 104402240A CN 201410577527 A CN201410577527 A CN 201410577527A CN 104402240 A CN104402240 A CN 104402240A
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Abstract
Belonging to the technical field of electrochromism, the invention discloses a nickel aluminum hydrotalcite film based electrochromic material and a preparation method thereof. According to a technical scheme involved in the invention, nickel aluminum hydrotalcite grows in situ on ITO conductive glass to obtain a hydrotalcite nanosheet film with a porous array structure. The film adopts the ITO conductive glass as the conductive layer, and the nickel aluminum hydrotalcite is the electrochromic film of an electrochromic layer. By applying the film, an electrochromic device from colorless to brown can be prepared. The nickel aluminum hydrotalcite based electrochromic film prepared by the invention is a novel photochromic material with inorganic hydrotalcite as the active material. The film has good optical contrast, fast response time, fast coloring and bleaching time, high coloring efficiency, high cyclic stability and other high photoelectrochemical properties.
Description
Affiliated field
The invention belongs to electrochromism technical field, in particular, provide a kind of electrochromic material based on nickel aluminum hydrotalcite film and preparation method thereof.
Background technology
Electrochromic material is, under the effect of external electric field or electric current, reversible photoabsorption or scattering of light to occur, thus produces reversible colour-change, has very important using value in smart window, automobile rearview mirror and indicating meter.1969, first S.K.Deb found WO
3the electrochromic property (S.K.Deb, Appl.Optics1969,3,192) of film, it is found that many transition metal oxides also had electrochromic characteristic afterwards.Inorganic electrochromic material based on its high coloration efficiency, high optical contrast and the advantage such as cheap and easy to get thereof, and obtain and study widely.Meanwhile, the time of response of inorganic electrochromic material is longer, time of response is because the redox characteristic of material itself determines, mainly be included in the Charger transfer at ionogen and electrode materials interface and ion diffuse two processes of electrode materials inside, the speed of response being only improved these two processes just likely makes its time of response promote to some extent.This kind of inorganic materials design is become rational nanostructure, is a kind of effective way improving the time of response to improve its specific surface area thus to increase reactive behavior site.
Containing the hydrotalcite stratified material of transition metal Ni, there is higher specific surface area and electrochemical activity, and environmentally friendly, easily synthesize, be the very promising electrochromic material of one.
Summary of the invention
The object of the present invention is to provide a kind of inorganic thin film material with electrochromic property and preparation method thereof, this thin-film material is a kind of electrochromic material with certain electric sensitivity energy.
Technical scheme of the present invention is: growth in situ nickel aluminum hydrotalcite on ITO conductive glass, obtains the hydrotalcite nano piece film of porous array structure, and this film is with ITO conductive glass for conductive layer, and nickel aluminum hydrotalcite is the electrochomeric films of photochromic layer.Apply this film can prepare by colourless to brown electrochromic device.
The preparation method with the thin-film material of electrochromic property of the present invention is:
A: after ITO conductive glass is carried out ultrasonic cleaning 10-15 minute respectively with acetone, deionized water, ethanol successively, dry for standby;
B: by solvable divalent nickel salt, solvable trivalent aluminium salt, urea, NH
4f is dissolved in deionized water and is mixed with mixing salt solution, and wherein the mol ratio of nickel and aluminium is (1-3): 1, and the total concn of nickel and aluminium is 2-4mmol/L, and the concentration of urea is 50-80mmol/L, NH
4the concentration of F is 1-3mmol/L, ultrasonic and stir make it mix after pour in autoclave, ITO conductive glass after processing of step A is tilted to put into reactor, react at 90-130 DEG C after 6-9 hour and take out, with deionized water rinsing, dry, namely obtain the thin-film material with electrochromic property.
Described solvable divalent nickel salt is nickelous nitrate or nickelous chloride; Described solvable trivalent aluminium salt is aluminum nitrate or aluminum chloride.
The described electrochromic property testing method with the thin-film material of electrochromic property: getting area is 1-3cm
2the thin-film material with electrochromic property of above-mentioned preparation is as electrode, and the LiOH solution of preparation 0.3-0.5M is as electrolyte solution, and under three-electrode system, test its electrochromic property, Pt electrode is supporting electrode, and mercurous chloride electrode is reference electrode.
The thin-film material with electrochromic property of above-mentioned preparation is applied to and prepares electrochromic device: get the thin-film material with electrochromic property of the above-mentioned preparation of a slice as positive pole, get a slice ito glass of the same area as negative pole, LiOH ionogen is injected between positive and negative electrode, after the surrounding of positive and negative electrode being encapsulated with thermoplastic, the electrochromic device based on nickel aluminum hydrotalcite can be obtained.
The electrochomeric films based on nickel aluminum hydrotalcite that the present invention prepares is with the novel electrochromic material of the inorganic hydrotalcite class that is active material.This film has the contour photoelectrochemical behaviour of good optical contrast, fast response time, faster painted and bleaching time and higher coloration efficiency, high cyclical stability.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram with the thin-film material of electrochromic property of the embodiment of the present invention 1 steps A synthesis, a is the X-ray diffractogram of ITO conductive glass, b is the X-ray diffractogram of the thin-film material with electrochromic property, and wherein X-coordinate is 2 θ, unit: degree; Ordinate zou is intensity.
Fig. 2 is the scanning electron microscope (SEM) photograph with the thin-film material of electrochromic property that the embodiment of the present invention 1 is synthesized.
Fig. 3 is the cyclic voltammetry curve of the thin-film material with electrochromic property in three electrode test systems of synthesis in the embodiment of the present invention 1.Wherein X-coordinate is current potential, unit: volt; Ordinate zou is electric current, unit: ampere.Scanning speed is 20 millivolts/second.Ionogen is 0.3MLiOH, Pt electrode is to electrode, and mercurous chloride electrode is reference electrode.
Fig. 4 is the digital photograph of the thin-film material with electrochromic property in three electrode test systems respectively when voltage is 0V and 0.58V that the embodiment of the present invention 1 is synthesized.
Fig. 5 is the transmittance curve in the ultraviolet-visible light district of the thin-film material with electrochromic property under different voltage (300-800 nanometer) that the embodiment of the present invention 1 is synthesized, the transmittance curve that a is voltage when being 0V, the transmittance curve that b is voltage when being 0.58V.Wherein X-coordinate is wavelength, unit: nanometer; Ordinate zou is transmitance, unit: 1.
Embodiment
Embodiment 1
A: ITO conductive glass is distinguished ultrasonic cleaning 15 minutes successively in acetone, deionized water, ethanol, is put in 60 DEG C of baking ovens, dry for standby;
B: by the Ni (NO of 0.436g
3)
26H
2al (the NO of O, 0.189g
3)
39H
2o, 0.3g urea, 0.074gNH
4f is dissolved in 100mL deionized water and is mixed with mixing salt solution, ultrasonic and stir make it mix after pour in autoclave, ITO conductive glass after step A process is tilted to put into this reactor, react at 110 DEG C after 8 hours and take out, with deionized water rinsing, dry, namely obtain the thin-film material with electrochromic property.
Electrochromic property is tested: getting area is 1*2cm
2the thin-film material with electrochromic property that obtains of step B as electrode, the LiOH solution of preparation 0.3M is as electrolyte solution.Under three-electrode system, test its electrochromic property, Pt electrode is supporting electrode, and mercurous chloride electrode is reference electrode.
The thin-film material with electrochromic property of above-mentioned preparation is applied to and prepares electrochromic device: getting a slice area is 1*2cm
2what step B obtained has the thin-film material of electrochromic property as positive pole, get a slice ito glass of the same area as negative pole, LiOH ionogen is injected between positive and negative electrode, after the surrounding of positive and negative electrode being encapsulated with thermoplastic, the electrochromic device based on nickel aluminum hydrotalcite can be obtained.
As shown in Figure 1, in XRD figure, the diffraction peak of (012), (110), (113) of hydrotalcite has appeared at 35 °, 60.2 °, 61.5 ° respectively, (003) (006) peak does not occur, illustrate that the growth of hydrotalcite has certain orientation, be perpendicular to ab planar growth.Fig. 2 also can find out the oriented growth of hydrotalcite sheets, sees the porous array structure of hydrotalcite simultaneously.The redox peak of obvious nickel can be found out by the cyclic voltammetry curve of Fig. 3, illustrate that electrochromic mechanism is just the reversible redox reaction of nickel hydroxide and hydroxy nickel oxide.The colour-change of what Fig. 4 was clear and definite have when the giving different voltage thin-film material electrode of electrochromic property, by brown to 0.58V of light green during 0V.Fig. 5, from the colour-change characterizing electrode slice of science transmittance curve, can find out that the change difference going out transmitance in 580 nanometers has 53%, calculate its optical contrast T simultaneously
0/ T
xbe 22%, showed the optical contrast that this material is higher.
Embodiment 2
A: ITO conductive glass is distinguished ultrasonic cleaning 15 minutes successively in acetone, deionized water, ethanolic soln, is put in 60 DEG C of baking ovens, dry for standby;
B: by the Ni (NO of 0.387g
3)
26H
2al (the NO of O, 0.253g
3)
39H
2o, 0.3g urea, 0.074gNH
4f is dissolved in 100mL deionized water and is mixed with mixing salt solution, ultrasonic and stir make it mix after pour in autoclave, ITO conductive glass after step A process is tilted to put into this reactor, react at 110 DEG C after 8 hours and take out, with deionized water rinsing, dry, namely obtain the thin-film material with electrochromic property.
Electrochromic property is tested: getting area is 1*3cm
2the thin-film material with electrochromic property that obtains of step B as electrode, the LiOH solution of preparation 0.5M is as electrolyte solution.Under three-electrode system, test its electrochromic property, Pt electrode is supporting electrode, and mercurous chloride electrode is reference electrode.
The thin-film material with electrochromic property of above-mentioned preparation is applied to and prepares electrochromic device: getting a slice area is 1*2cm
2what step B obtained has the thin-film material of electrochromic property as positive pole, get a slice ito glass of the same area as negative pole, LiOH ionogen is injected between positive and negative electrode, after the surrounding of positive and negative electrode being encapsulated with thermoplastic, the electrochromic device based on nickel aluminum hydrotalcite can be obtained.
Through characterizing: above-mentioned obtaining has porous array structure based on the hydrotalcite in the electrochromic electrode structure of nickel aluminum hydrotalcite, and the growth of hydrotalcite nano piece has certain orientation; After tested: electrochromic device presents light green and brown two kinds of different colours states respectively at-0.1V and 0.58V, and measure the optical contrast obtained is 24% simultaneously.
Claims (5)
1. have a preparation method for the thin-film material of electrochromic property, it is characterized in that, its concrete operation step is:
A: after ITO conductive glass is carried out ultrasonic cleaning 10-15 minute respectively with acetone, deionized water, ethanol successively, dry for standby;
B: by solvable divalent nickel salt, solvable trivalent aluminium salt, urea, NH
4f is dissolved in deionized water and is mixed with mixing salt solution, and wherein the mol ratio of nickel and aluminium is (1-3): 1, and the total concn of nickel and aluminium is 2-4mmol/L, and the concentration of urea is 50-80mmol/L, NH
4the concentration of F is 1-3mmol/L, ultrasonic and stir make it mix after pour in autoclave, ITO conductive glass after processing of step A is tilted to put into reactor, react at 90-130 DEG C after 6-9 hour and take out, with deionized water rinsing, dry, namely obtain the thin-film material with electrochromic property.
2. preparation method according to claim 1, is characterized in that, described solvable divalent nickel salt is nickelous nitrate or nickelous chloride; Described solvable trivalent aluminium salt is aluminum nitrate or aluminum chloride.
3. preparation method according to claim 1, is characterized in that, the electrochromic property testing method with the thin-film material of electrochromic property prepared is: getting area is 1-3cm
2the thin-film material with electrochromic property as electrode, preparation 0.3-0.5M LiOH solution as electrolyte solution, under three-electrode system, test its electrochromic property, Pt electrode is supporting electrode, and mercurous chloride electrode is reference electrode.
4. the application in electrochromic device prepared by the thin-film material with electrochromic property that prepared by method according to claim 1.
5. application according to claim 4, it is characterized in that, the described method preparing electrochromic device is: get a slice and have the thin-film material of electrochromic property as positive pole, get a slice ito glass of the same area as negative pole, LiOH ionogen is injected between positive and negative electrode, after the surrounding of positive and negative electrode being encapsulated with thermoplastic, the electrochromic device based on nickel aluminum hydrotalcite can be obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265741A (en) * | 2019-06-14 | 2019-09-20 | 浙江工业大学 | The electrochemical cell and test method of energy home position observation electrode material open simulation lithium battery of state change in charge and discharge process |
| CN112250881A (en) * | 2020-10-23 | 2021-01-22 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102109725A (en) * | 2011-01-24 | 2011-06-29 | 电子科技大学 | Electrochromic device and preparation method thereof |
| CN102610393A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Preparation method of ultracapacitor material with layered double hydroxide-poly(3, 4-ethylenedioxythiophene) core-shell structure |
| CN103811199A (en) * | 2013-11-29 | 2014-05-21 | 北京化工大学 | Preparation method of all-solid-state flexible supercapacitor based on nickel aluminum hydrotalcite |
-
2014
- 2014-10-24 CN CN201410577527.0A patent/CN104402240A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102109725A (en) * | 2011-01-24 | 2011-06-29 | 电子科技大学 | Electrochromic device and preparation method thereof |
| CN102610393A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Preparation method of ultracapacitor material with layered double hydroxide-poly(3, 4-ethylenedioxythiophene) core-shell structure |
| CN103811199A (en) * | 2013-11-29 | 2014-05-21 | 北京化工大学 | Preparation method of all-solid-state flexible supercapacitor based on nickel aluminum hydrotalcite |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265741A (en) * | 2019-06-14 | 2019-09-20 | 浙江工业大学 | The electrochemical cell and test method of energy home position observation electrode material open simulation lithium battery of state change in charge and discharge process |
| CN112250881A (en) * | 2020-10-23 | 2021-01-22 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
| CN112250881B (en) * | 2020-10-23 | 2022-06-14 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
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Application publication date: 20150311 |
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