CN104710113B - Preparation method and application of nano silver electrochromic film - Google Patents
Preparation method and application of nano silver electrochromic film Download PDFInfo
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- CN104710113B CN104710113B CN201510148511.2A CN201510148511A CN104710113B CN 104710113 B CN104710113 B CN 104710113B CN 201510148511 A CN201510148511 A CN 201510148511A CN 104710113 B CN104710113 B CN 104710113B
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Abstract
The invention relates to a preparation method and application of an electrochromic film, particularly a preparation method and application of a nano silver electrochromic film. The invention widens the research field of the traditional electrochromic material spectrum, and implements display of the electrochromic film within the range of visible spectrum. The preparation method of the nano silver electrochromic film comprises the following steps: 1. adding citric acid into a silver nitrate solution, adding sodium borohydride until the solution becomes yellow, and collecting a nano silver crystal seed; and 2. adding polyethyleneglycol into the nano silver crystal seed water solution, and coating on the surface of conductive glass ITO (indium tin oxide). The electrochromic process of the nano silver film is implemented in a way that: oxydol, citric acid and polyvinylpyrrolidone are added into the silver nitrate solution, a constant voltage is applied to implement the coloring process, and the film discolors when a reverse voltage is applied. The method breaks through the discoloring process of the traditional electrochromic material by changing the material phase, and implements regulation and control on the electrochromic material discoloring spectrum by utilizing the surface plasma resonance of the noble-metal nano silver material.
Description
Technical field
The present invention relates to a kind of preparation method and applications of Nano Silver electrochomeric films.
Background technology
The quantum size effect of noble metal nanometer material and skin effect make it have the optical property of uniqueness, work as material
When being smaller in size than optical wavelength, its spectral absorption peak be in obvious spectrum transport property.When incident light frequency and metal inside
When plasma oscillation frequency is identical, that is, there is surface plasma body resonant vibration.Under resonance condition, precious metal material is to the light irradiating
Produce strong absorption and scattering, simultaneously with the fluctuation that electronics occurs and surface electronic polarization.The local of metal nanoparticle
In surface plasmon absorption spectrum, the position of resonance absorbing peak can be regulated and controled by adjusting the pattern of nano particle.
Therefore, using the surface plasma body resonant vibration property of noble metal nano particles, be can achieve to it by adjusting the pattern of material
The regulation and control of spectral quality.
Electrochromism refers to that the optical properties of material occur the stable, phenomenon of reversible change under DC Electric Field, outward
The change of color and transparency is shown as on sight, its essence is a kind of process of electrochemical reaction, that is, with the change applying electric field
Change, the thing phase of material changes, and leads to optical property to change.Conventional electrochromic material substantially may be used according to chemical attribute
It is divided into inorganic electrochromic material and organic electrochromic material, they are all using electric charge transfer (oxidation/reduction reaction)
Change the optical absorption band of material, thus realizing electrochromism, such as mineral-type electrochromic material is (as wo3、moo3、v2o5、
nb2o5、tio2、bio3), the change of its light absorbs is that the Dual Implantations/extraction of ion and electronics causes；Organic electrochromic material (three
Aniline, polythiophene, purple sieve essence etc.), its light absorbs is essentially from redox reaction.
Content of the invention
The invention aims to widening the research field of conventional electrochromic material spectrum, realize limit of visible spectrum
The display of interior electrochomeric films.Provide one kind and realize electrochromism using metal nano silver surface plasma resonance property
The preparation method and applications of film.
The preparation method of Nano Silver electrochomeric films of the present invention follow these steps to realize:
First, add citric acid in silver nitrate solution, obtain mixed solution, be subsequently adding sodium borohydride, until mixing is molten
Liquid obtains Nano Silver crystal seed by colourless yellowing, washing after separating；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution, adds polyethylene glycol
(peg200) carry out ultrasonic disperse, then scattered seed-solution is coated on electro-conductive glass ito surface, obtains being coated with nanometer
The substrate of silver-colored electrochomeric films.
It is as follows that application Nano Silver electrochomeric films carry out electrochromic method:
First, add hydrogen peroxide, citric acid and polyvinylpyrrolidone in silver nitrate solution, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in as working electrode in reaction solution, with platinized platinum
As to electrode, under conditions of constant voltage is -2.5～-1.0v, deposit 10ms～90s, ito electro-conductive glass is in coloured state；
3rd, when applying backward voltage for -0.5～1.0v, ito electro-conductive glass is in colour fading state.
The method of present invention breakthrough conventional electrochromic material use change thing phase obtains the regulation and control to spectrum and light transmittance,
But the surface plasma body resonant vibration property of the nano silver material using different-shape, realize the regulation and control to spectrum property.Leading
Electric ito glass surface forms nano silver film, by applying different voltages, changes the pattern of nano-Ag particles in film, real
Existing electrochromism.The research frontier of conventional electrochromic material has been opened up in this invention, from inorganic, metal oxide to your gold
Belong to material, be the broader space of the exploitation developing of electrochromic material.The present invention is in building energy conservation smart window, automobile, display
The aspects such as device have broad application prospects.
Specific embodiment
Specific embodiment one: the preparation method of present embodiment Nano Silver electrochomeric films follow these steps to realize:
First, add citric acid in silver nitrate solution, obtain mixed solution, be subsequently adding sodium borohydride, until mixing is molten
Liquid obtains Nano Silver crystal seed by colourless yellowing, washing after separating；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution, adds polyethylene glycol
(peg200) carry out ultrasonic disperse, then scattered seed-solution is coated on electro-conductive glass ito surface, obtains being coated with nanometer
The substrate of silver-colored electrochomeric films.
The preparation method of present embodiment Nano Silver electrochomeric films has widened the research model of conventional electrochromic material
Enclose, realize electrochromism using precious metal surface plasma resonance property.Reduce silver nitrate solution in the solution first, obtain
Nano Silver crystal seed, is subsequently coated on conductive ito surface, using electrochemical method, reduces silver ion in seed surface, passes through
Electrodeposition process controls the amount of reduction silver ion, and the pattern of regulation and control nano silver material, due to receiving of different-shape (laminated structure)
Meter Yin has different surface plasma body resonant vibration properties, can assume different colors in visible light wave range, therefore in pattern control
During achieve electrochromic process, and when applying backward voltage, and nano-Ag particles are oxidized to silver ion, are dissolved in
In electrolyte, film color is gradually taken off it is achieved that colour fading process.The electrochomeric films being obtained using the method, spectrum is adjusted
Adjusting range width, environmental protection.
Specific embodiment two: present embodiment is molten from the silver nitrate described in step one unlike specific embodiment one
The concentration of liquid is 0.1 × 10-4Mol/l～100 × 10-4mol/l.Other steps and parameter are identical with specific embodiment one.
Specific embodiment three: present embodiment is molten from the silver nitrate described in step one unlike specific embodiment two
The concentration of liquid is 0.2 × 10-4Mol/l～5 × 10-4mol/l.Other steps and parameter are identical with specific embodiment two.
Specific embodiment four: described in step one unlike one of present embodiment and specific embodiment one to three
The concentration of the citric acid in mixed solution is 1 × 10-4Mol/l～10 × 10-4mol/l.Other steps and parameter be embodied as
One of mode one to three is identical.
Specific embodiment five: described in step 2 unlike one of present embodiment and specific embodiment one to four
The concentration of the Nano Silver crystal seed in the Nano Silver crystal seed aqueous solution is 0.005～0.1mg/ml.Other steps and parameter and specifically reality
Apply one of mode one to four identical.
Specific embodiment six: the preparation method of present embodiment application Nano Silver electrochomeric films carries out electrochromism
Method as follows:
First, add hydrogen peroxide, citric acid and polyvinylpyrrolidone in silver nitrate solution, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in as working electrode in reaction solution, with platinized platinum
As to electrode, under conditions of constant voltage is -2.5～-1.0v, deposit 10ms～90s, ito electro-conductive glass is in coloured state；
3rd, when applying backward voltage for -0.5～1.0v, ito electro-conductive glass is in colour fading state.
Present embodiment step 2 deposition processes under constant voltage, with the prolongation of sedimentation time, the silver ion in solution
Gradually it is reduced in seed surface, with the carrying out of deposition process, nano-Ag particles pattern is continually changing, the nanometer of different-shape
Silver has different surface plasmon resonance effects, can assume different colors, i.e. coloring process.When applying backward voltage,
It is deposited on the Argent grain gradually oxidized dissolving on ito surface, that is, realize colour fading process.
Specific embodiment seven: present embodiment and the reaction solution described in step one unlike specific embodiment six
The concentration of middle silver nitrate is 0.1 × 10-4Mol/l～3 × 10-4mol/l.Other steps and parameter and specific embodiment six phase
With.
Specific embodiment eight: present embodiment is from step 2 unlike specific embodiment six or seven in constant voltage
For depositing 10s～30s under conditions of -1.5～-1.0v.Other steps and parameter are identical with specific embodiment six or seven.
Embodiment one: the preparation method of the present embodiment Nano Silver electrochomeric films follow these steps to realize:
First, to 25ml concentration be 0.5 × 10-4Concentration is added to be 2.0 × 10 in the silver nitrate solution of mol/l-4Mol/l's
Citric acid, obtains mixed solution, is subsequently adding sodium borohydride, until mixed solution is by colourless yellowing, washing obtains after separating
To Nano Silver crystal seed；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution that concentration is 0.02mg/ml, plus
Enter polyethylene glycol (0.001g) and carry out ultrasonic disperse, then drip scattered seed-solution in electro-conductive glass ito surface, nitrogen
Dry up film forming to obtain being coated with the substrate of Nano Silver electrochomeric films.
Application Example one: the preparation method of the present embodiment application Nano Silver electrochomeric films carries out electrochromism and presses
Row step is implemented:
First, to 0.5 × 10-4Add in the silver nitrate solution of mol/l 10 μ l hydrogen peroxide (30%), 20 μ l citric acids (2.0 ×
10-4Mol/l) and 0.001g polyvinylpyrrolidone, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in as working electrode in reaction solution, with platinized platinum
As to electrode, under conditions of constant voltage is -1.2v, deposit 10s, ito electro-conductive glass is in blue-green；
3rd, when applying backward voltage for 0.1v, particle gradually dissolves, and ito electro-conductive glass is in colour fading state.
Embodiment two: the preparation method of the present embodiment Nano Silver electrochomeric films follow these steps to realize:
First, to 25ml concentration be 0.5 × 10-4Concentration is added to be 2.0 × 10 in the silver nitrate solution of mol/l-4Mol/l's
Citric acid, obtains mixed solution, is subsequently adding sodium borohydride, until mixed solution is by colourless yellowing, washing obtains after separating
To Nano Silver crystal seed；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution that concentration is 0.03mg/ml, plus
Enter polyethylene glycol (0.012g) and carry out ultrasonic disperse, then drip scattered seed-solution in electro-conductive glass ito surface, nitrogen
Dry up film forming to obtain being coated with the substrate of Nano Silver electrochomeric films.
Application Example two: the preparation method of the present embodiment application Nano Silver electrochomeric films carries out electrochromism and presses
Row step is implemented:
First, to 0.5 × 10-410 μ l hydrogen peroxide, 25 μ l citric acids (2.0 × 10 are added in the silver nitrate solution of mol/l- 4Mol/l) and 0.001g polyvinylpyrrolidone, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in as working electrode in reaction solution, with platinized platinum
As to electrode, under conditions of constant voltage is -1.2v, deposit 23s, ito electro-conductive glass is in blue-green；
3rd, apply backward voltage be 0.12v when, be deposited on ito surface silver gradually oxidized be dissolved in solution, shape
Become ag+, ito electro-conductive glass is in colour fading state.
Embodiment three: the preparation method of the present embodiment Nano Silver electrochomeric films follow these steps to realize:
First, to 25ml concentration be 0.5 × 10-4Concentration is added to be 2.0 × 10 in the silver nitrate solution of mol/l-4Mol/l's
Citric acid, obtains mixed solution, is subsequently adding sodium borohydride, until mixed solution is by colourless yellowing, washing obtains after separating
To Nano Silver crystal seed；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution that concentration is 0.02mg/ml, plus
Enter polyethylene glycol (0.015g) and carry out ultrasonic disperse, then drip scattered seed-solution in electro-conductive glass ito surface, nitrogen
Dry up film forming to obtain being coated with the substrate of Nano Silver electrochomeric films.
Application Example three: the preparation method of the present embodiment application Nano Silver electrochomeric films carries out electrochromism and presses
Row step is implemented:
First, to 0.5 × 10-410 μ l hydrogen peroxide, 28 μ l citric acids (2.0 × 10 are added in the silver nitrate solution of mol/l- 4Mol/l) and 0.001g polyvinylpyrrolidone, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in as working electrode in reaction solution, with platinized platinum
As to electrode, under conditions of constant voltage is -1.2v, deposit 25s, ito electro-conductive glass is in blue-green；
3rd, apply backward voltage be 0.12v when, be deposited on ito surface silver gradually oxidized be dissolved in solution, shape
Become ag+, ito electro-conductive glass is in colour fading state.
Claims (8)
1. the preparation method of Nano Silver electrochomeric films is it is characterised in that be to follow these steps to realize:
First, in silver nitrate solution add citric acid, obtain mixed solution, be subsequently adding sodium borohydride, until mixed solution by
Colourless yellowing, washing obtains Nano Silver crystal seed after separating；
2nd, the Nano Silver crystal seed that step one obtains is configured to the Nano Silver crystal seed aqueous solution, adds polyethylene glycol to carry out ultrasonic point
Dissipate, then scattered seed-solution is coated on electro-conductive glass ito surface, obtains being coated with the base of Nano Silver electrochomeric films
Bottom.
2. the preparation method of Nano Silver electrochomeric films according to claim 1 is it is characterised in that described in step one
The concentration of silver nitrate solution is 0.1 × 10-4Mol/l～100 × 10-4mol/l.
3. the preparation method of Nano Silver electrochomeric films according to claim 2 is it is characterised in that described in step one
The concentration of silver nitrate solution is 0.2 × 10-4Mol/l～5 × 10-4mol/l.
4. the preparation method of Nano Silver electrochomeric films according to claim 1 is it is characterised in that described in step one
The concentration of the citric acid in mixed solution is 1 × 10-4Mol/l～10 × 10-4mol/l.
5. the preparation method of Nano Silver electrochomeric films according to claim 1 is it is characterised in that described in step 2
The concentration of the Nano Silver crystal seed in the Nano Silver crystal seed aqueous solution is 0.005～0.1mg/ml.
6. application Nano Silver electrochomeric films carry out electrochromic method it is characterised in that being to follow these steps to realize:
First, add hydrogen peroxide, citric acid and polyvinylpyrrolidone in silver nitrate solution, obtain reaction solution；
2nd, the substrate being coated with Nano Silver electrochomeric films is placed in reaction solution as working electrode, using platinized platinum as
To electrode, under conditions of constant voltage is -2.5～-1.0v, deposit 10s～90s, ito electro-conductive glass is in coloured state；
3rd, when applying backward voltage for -0.5～1.0v, ito electro-conductive glass is in colour fading state；
The preparation method being wherein coated with the substrate of Nano Silver electrochomeric films described in step 2 is as follows:
S1, in silver nitrate solution add citric acid, obtain mixed solution, be subsequently adding sodium borohydride, until mixed solution by
Colourless yellowing, washing obtains Nano Silver crystal seed after separating；
S2, the Nano Silver crystal seed obtaining s1 are configured to the Nano Silver crystal seed aqueous solution, add polyethylene glycol to carry out ultrasonic disperse, so
Afterwards scattered seed-solution is coated on electro-conductive glass ito surface, obtains being coated with the substrate of Nano Silver electrochomeric films.
7. according to claim 6 application Nano Silver electrochomeric films carry out electrochromic method it is characterised in that
In reaction solution described in step one, the concentration of silver nitrate is 0.1 × 10-4Mol/l～3 × 10-4mol/l.
8. according to claim 6 application Nano Silver electrochomeric films carry out electrochromic method it is characterised in that
Step 2 deposits 10s～30s under conditions of constant voltage is -1.5～-1.0v.
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| CN106479478B (en) * | 2015-08-24 | 2018-10-02 | 北京大学 | A kind of electrochromic material and device based on metal nanoparticle |
| CN106637356B (en) * | 2016-12-22 | 2018-08-21 | 东南大学 | A kind of preparation method of three-dimensional black nano metal wide spectrum extinction film |
| CN107151808B (en) * | 2017-06-05 | 2019-04-09 | 哈尔滨工业大学 | A kind of preparation method of polychrome low emissivity glass |
| CN110667019B (en) * | 2019-09-06 | 2021-07-16 | 山东大学 | Plasma resonance reversible regulation silver nanoparticle film and preparation method and application thereof |
| CN111999954A (en) * | 2020-09-07 | 2020-11-27 | 济南嘉源电子有限公司 | Optical device based on super-surface-electric dimming material and preparation method thereof |
| CN117361614B (en) * | 2023-10-11 | 2024-04-09 | 西南石油大学 | Preparation method of reversible color-changing titanium metal material under illumination and chemical stimulation conditions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407342A (en) * | 2011-10-31 | 2012-04-11 | 山东大学 | Preparation method of nano silver powder with accurately controllable particle size |
| CN103817346A (en) * | 2014-03-11 | 2014-05-28 | 上海交通大学 | Shape-controlled triangle flaky nano silver powder preparation method |
| CN104216192A (en) * | 2014-09-16 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of novel fast-response high-contrast electrochromic device |
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| US11292962B2 (en) * | 2011-09-29 | 2022-04-05 | The Research Foundation For The State University Of New York | Doped nanoparticles and methods of making and using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407342A (en) * | 2011-10-31 | 2012-04-11 | 山东大学 | Preparation method of nano silver powder with accurately controllable particle size |
| CN103817346A (en) * | 2014-03-11 | 2014-05-28 | 上海交通大学 | Shape-controlled triangle flaky nano silver powder preparation method |
| CN104216192A (en) * | 2014-09-16 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of novel fast-response high-contrast electrochromic device |
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