CN106405969A - Method for adjusting near-infrared light based on silver nano-wire (Ag NW) substrate electrochromic material - Google Patents

Method for adjusting near-infrared light based on silver nano-wire (Ag NW) substrate electrochromic material Download PDF

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Publication number
CN106405969A
CN106405969A CN201610827225.3A CN201610827225A CN106405969A CN 106405969 A CN106405969 A CN 106405969A CN 201610827225 A CN201610827225 A CN 201610827225A CN 106405969 A CN106405969 A CN 106405969A
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China
Prior art keywords
nano silver
silver wire
substrate
infrared light
wire
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严辉
周开岭
汪浩
张永哲
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Beijing University of Technology
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Beijing University of Technology
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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153Constructional details
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153Constructional details
    • G02F1/155Electrodes

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

The invention discloses a method for adjusting near-infrared light based on a silver nano-wire (Ag NW) substrate electrochromic material, and belongs to the field of preparation and application of functional materials. The method comprises the following steps: preparing a silver nano-wire transparent conductive layer which is uniformly dispersed on a transparent substrate through a silver nano-wire with the length of at least 50 microns and the radius of 80 to 120 nm by a spin-coating method and a vacuum hot pressing method to obtain a transparent conductive electrode; depositing an electrochromic thin film on the surface of the silver nano-wire transparent conductive layer to obtain a silver nano-wire substrate electrochromic thin film; forming a three-electrode system by the obtained silver nano-wire substrate electrochromic thin film, a platinum electrode and an Ag/KCl reference electrode, forming an electrochromic electrochemical reaction system with an electrolyte, and performing colouring/decolouring transformation by controlling an applied voltage so as to perform optical regulation and control at different wavelengths of a near infrared band.

Description

One kind is based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light Method
Technical field
The present invention relates to the preparation of nano silver wire substrate electrochomeric films and its application that near infrared light is adjusted, belong to Functional material preparation and application.
Background technology
Develop rapidly with industrial, energy shortage and environmental pollution have become the key that human society is badly in need of solving and asked Topic.Mass energy is applied to the temperature adjustment of building by developed country, and wherein air conditioning energy consumption accounts for first place.Therefore, take various Measure reducing energy consumption is increasingly becoming the common recognition of people, for example, to adjust the smart window of solar spectrum with energy-conservation and comfort requirement, Have broad application prospects in future architecture thing, receive the extensive concern of people.Many materials are being heated, illumination, power up outward During the external influences such as field, its color can change, that is, produce coloring phenomenon.Off-color material is caused to refer in extraneous conditioning Under, can continuous reversible regulation solar electromagnetic radiation material, mutagens color can be divided into photochromic, thermochromism, electrochromism, Gas-discoloration and Photoelectrochromic etc., wherein electrochromic material are one of focuses of Recent study.
Electrochromism refers to that material color under electric field action produces and stablizes reversible change phenomenon.When material is in electrochemistry When the injection of effect lower generation electronics and ion is with extracting out, its valence state and chemical constituent will change, so that material is anti- Penetrate and transmission performance changes, the reversible change of color and transparency is shown as on appearance property.Its main feature is as follows:(1) In electrochromic material the injection of electric charge and extract out can conveniently realize by the change of external voltage or electric current, inject or Extract out electric charge number directly determine the coloring degree of material, adjust external voltage or electric current can control electrochromic material Coloring degree;(2) polarity passing through to change voltage can conveniently realize coloring or colour killing;(3) colored material is being cut Power-off stream and in the case of there is not redox reaction, can hold color state, that is, there is memory function.Electrochromism The excellent properties of thin film and the application prospect in terms of energy-conservation, by the common concern of people, meet sending out of following intellectual material Exhibition trend.
Traditional electrochomeric films great majority are with ito glass as conductive substrates.But, ITO there are some problems:1、 Ito glass poor toughness, preparation processing and application to electrochromic material have very strict restriction and requirement.2nd, in the face of having The selenium resource of limit and its increasing consumption demand, ito thin film cost price becomes more and more expensive.3rd, because ITO is in ripple There is plasma resonance, this makes optics in the range of near infrared band (780-2500nm) for the ito film at a length of 1300nm Transmitance seriously reduces.The well-known, near infrared light of earth surface has accounted for the 50% of whole earth surface solar energy. Therefore, suitable near-infrared intelligent glass is developed to seem very necessary using infrared light for mankind's service to greatest extent. Simultaneously, infrared adjustable electrochromic device not only has very big captivation in terms of heat energy regulation and control, in Spacecraft Launch detector, War camouflage material, there is very big application potential in the field such as optic communication.
Due to high transmitance, good electric conductivity and high mechanical flexibility, nano silver wire become replacement ITO and extensive The conductive electrode material of new generation of research.In recent years, flexible, the stretchable and folding electricity with nano silver wire as conductive electrode Mutagens color device has begun to be studied by increasing people.However, currently focusing primarily upon flexible device and visible region The research of regulation and control aspect, the research for near-infrared intelligent control does not almost have.The therefore present invention, by with reference to electrochromism and The unique advantage of both nano silver wires, develops the electrochromic device to both infrared light and visible ray intelligent control simultaneously. This all has very big expansion and enlightening significance to electrochromism and conductive electrode field.
Content of the invention
The present invention carries out near infrared light wave band by the nano silver wire conductive substrates electrochomeric films preparing Intelligent control acts on.
For realizing this purpose, length is longer, appropriate size radius nano silver wire firstly the need of preparation for the present invention.
The method based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light of the present invention, its feature It is, comprise the following steps:
(1) nano silver wire of at least 50 microns of length, radius 80-12nm is passed through spin coating and vacuum hot-pressing transparent Prepare one layer of homodisperse nano silver wire transparency conducting layer on substrate, and then obtain transparency conductive electrode;Saturating in nano silver wire Bright conductive layer surface deposits one layer of electrochomeric films, obtains nano silver wire substrate electrochomeric films;
(2) pass through obtained nano silver wire substrate electrochomeric films, platinum plate electrode, Ag/KCl reference electrode composition Three-electrode system, forms electrochromism electrochemical reaction system with electrolyte, by controlling applied voltage size, carry out colouring- Fade and convert, carry out the optics regulation and control near infrared band different wave length.
Preferably length is prepared by chemical method in step (1) and be about 70 μm, radius is about the nano silver wire of 100nm. Secondly preparation has visible ray and infrared light district transmitance height (more than 70%), good conductivity (less than 50 Ω) and good stability Transparency conductive electrode is second mandatory requirements that achieve the goal.Therefore, the present invention has prepared first and has had high-adhesion, colourless Bright and PVA solution (as concentration 0.01g/ml) that chemical stability is good, prepare nano silver wire ethanol solution (as concentration 3mg/L). Employ spin coating coating process, continue one layer of PVA tack coat of spin coating in selected transparent substrates (preferably with 2500 revs/min Rotating speed continues 20min and continues one layer of PVA tack coat of spin coating in selected transparent substrates), after on PVA layer spin coating silver nanoparticle again (preferably 30s spin coating silver nanoparticle being continued with 3500 revs/min of rotating speed).The number of plies controlling spin coating nanowires solution can obtain phase Answer the nano silver wire conductive electrode of electric conductivity and light transmission.Then pass through mechanical hot pressing technique in vacuum environment to increase each layer Between combination, reduce nano silver wire contact resistance.So as to the silver obtaining good stability, dispersed and electric conductivity is high Nano wire transparency conductive electrode.
Certain thickness electrochromism is deposited in prepared nano silver wire electrode surface by physics or chemical method thin Film.According to the demand to infrared performance of control size for the electrochomeric films, the electrochromic layer of different-thickness can be prepared.Then Under the driving of electric field, variable color manipulation is carried out to electrochomeric films, by different conditions before and after thin film variable color, near infrared light is entered Row selectivity passes through.By controlling applied voltage size, thin film coloring, saturating near infrared light under colour fading different conditions can be obtained Cross the of different sizes of rate.Therefore, can be playing to closely red by nano silver wire base electrochomeric films are carried out with voltage manipulation The effect of outer smooth intelligent control
Brief description
Fig. 1 is the nano silver wire scanning electron microscope (SEM) photograph prepared by the present invention.
Fig. 2 nano silver wire square resistance and the graph of a relation of transmitance
The WO of the nano silver wire substrate of Fig. 3 preparation3Electrochomeric films scanning electron microscope (SEM) photograph
Fig. 4 nano silver wire substrate and the WO of ITO substrate3Electrochomeric films colour the transmitance under bleached state.
Specific embodiment
With reference to the accompanying drawings and detailed description, it is further elucidated with substantive distinguishing features and the remarkable advantage of the present invention, this Invention is limited only to by no means stated embodiment.
1). the larger nano silver wire of preparation draw ratio, needed for being prepared by spin coating and vacuum hot-pressing, electric conductivity is transparent Conductive electrode.
2). with electrochemical deposition method or magnetron sputtering method, electrochromic material is deposited on nano silver wire, obtain electroluminescent Optically variable films.
3). by electrochemical workstation, by obtained nano silver wire substrate electrochomeric films and platinum plate electrode, Ag/ KCl reference electrode forms three-electrode system, selects electrolyte to carry out colouring-fade conversion.
4). data record is carried out to the transmitance of the near infrared light wave band under different colorings, bleached state, obtains near-infrared Optics ability of regulation and control size at wave band different wave length.
4). test assessment is carried out to the variable color cyclical stability of the electrochomeric films of nano silver wire conductive electrode substrate.
Embodiment 1
Nano silver wire (Ag NW) substrate WO3Electrochromic material regulating near-infrared light
1) nano silver wire (radius is about 100nm) that draw ratio is 700 is prepared by hydro-thermal method, prepared afterwards and there is high gluing The PVA solution of knot property, water white transparency and the good 0.01g/ml of chemical stability.Simultaneously, the nano silver wire ethanol preparing 3mg/L is molten Liquid.Using spin coating coating process, one layer of PVA tack coat of 20min spin coating is continued in glass substrate with 2500 revs/min of rotating speed On, after on PVA layer again with 3500 revs/min of rotating speed continue 30s spin coating silver nanoparticle.Afterwards at 150 DEG C, -0.1MPa vacuum Transparency conductive electrode is prepared by electrode is applied with the pressure of 100N in environment.
2). system prepares WO by electrochemical deposition method in nano silver wire Conducting Glass3Electrochomeric films, so Afterwards with LiClO4Make to synthesize electrochromism electrochemical reaction body to electrode group for electrolyte, Ag/AgCl reference electrode, platinum plate electrode System.
2). with electrochemical workstation, thin film is carried out colouring/fade change operation..
3). by ultraviolet-visible-near infrared spectrometer, the transmitance under thin film difference coloring-bleached state is entered Row test analysis, draw infrared band ability of regulation and control size and with the ITO base WO under identical preparation condition3The infrared tune of thin film Control performance is contrasted.
4). the nano silver wire base WO under record multi cycle state3The stable circulation that the infrared light of electrochromic material is adjusted Property.
Nano silver wire square resistance and the graph of a relation of transmitance, are shown in Fig. 2;The WO of the nano silver wire substrate of preparation3Electroluminescent change Color film scanning electron microscope is shown in Fig. 3;Nano silver wire substrate and the WO of ITO substrate3Under electrochomeric films coloring bleached state Transmitance is shown in Fig. 4.
By relative analyses draw with nano silver wire base electrochomeric films near infrared light adjustable superiority and latent Using value.

Claims (5)

1. a kind of method Ji Yu nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light is it is characterised in that wrap Include following steps:
(1) nano silver wire of at least 50 microns of length, radius 80-12nm is passed through spin coating and vacuum hot-pressing in transparent substrates One layer of homodisperse nano silver wire transparency conducting layer of upper preparation, and then obtain transparency conductive electrode;Lead nano silver wire is transparent Electric layer surface deposits one layer of electrochomeric films, obtains nano silver wire substrate electrochomeric films;
(2) pass through obtained nano silver wire substrate electrochomeric films, platinum plate electrode, Ag/KCl reference electrode composition three electricity Polar body system, forms electrochromism electrochemical reaction system with electrolyte, by controlling applied voltage size, carries out colouring-fading Conversion, carries out the optics regulation and control near infrared band different wave length.
2. it is based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light according to the one kind described in claim 1 Method it is characterised in that in step (1) by chemical method prepare length be 70 μm, radius be 100nm silver nanoparticle Line.
3. it is based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light according to the one kind described in claim 1 Method it is characterised in that preferred nano silver wire conductive layer is single layer structure, the conductive layer of nano silver wire diameter thickness.
4. it is based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light according to the one kind described in claim 1 Method it is characterised in that nano silver wire substrate has extraordinary permeability near infrared light.
5. it is based on nano silver wire (Ag NW) substrate electrochromic material regulating near-infrared light according to the one kind described in claim 1 Method it is characterised in that nano silver wire draw ratio is not less than 700.
CN201610827225.3A 2016-09-14 2016-09-14 Method for adjusting near-infrared light based on silver nano-wire (Ag NW) substrate electrochromic material Pending CN106405969A (en)

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Cited By (5)

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CN107203081A (en) * 2017-05-08 2017-09-26 东南大学 A kind of intelligent color-changing glass of phasmon wide spectrum regulation and control
CN108877992A (en) * 2018-07-10 2018-11-23 北京工业大学 A kind of preparation method based on overlength silver-platinum alloy hollow Nano line transparent conductive electrode
CN109256281A (en) * 2018-09-03 2019-01-22 上海奥威科技开发有限公司 Super-capacitor pole piece of changeable colour and preparation method thereof
CN111665674A (en) * 2020-06-17 2020-09-15 中国科学技术大学 Selective light absorption-electrochromic film, preparation method thereof and selective light absorption-electrochromic device
CN113549882A (en) * 2021-06-03 2021-10-26 电子科技大学 Preparation method of tungsten trioxide nanowire electrochromic film

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107203081A (en) * 2017-05-08 2017-09-26 东南大学 A kind of intelligent color-changing glass of phasmon wide spectrum regulation and control
CN107203081B (en) * 2017-05-08 2020-01-07 东南大学 Intelligent color-changing glass regulated and controlled by plasmon wide spectrum
CN108877992A (en) * 2018-07-10 2018-11-23 北京工业大学 A kind of preparation method based on overlength silver-platinum alloy hollow Nano line transparent conductive electrode
CN109256281A (en) * 2018-09-03 2019-01-22 上海奥威科技开发有限公司 Super-capacitor pole piece of changeable colour and preparation method thereof
CN109256281B (en) * 2018-09-03 2020-08-07 上海奥威科技开发有限公司 Color-changeable super capacitor pole piece and preparation method thereof
CN111665674A (en) * 2020-06-17 2020-09-15 中国科学技术大学 Selective light absorption-electrochromic film, preparation method thereof and selective light absorption-electrochromic device
CN113549882A (en) * 2021-06-03 2021-10-26 电子科技大学 Preparation method of tungsten trioxide nanowire electrochromic film
CN113549882B (en) * 2021-06-03 2022-06-14 电子科技大学 Preparation method of tungsten trioxide nanowire electrochromic film

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Application publication date: 20170215