CN106371259A - All solid-state electrochromic intelligent glass and self-driving energy system thereof - Google Patents
All solid-state electrochromic intelligent glass and self-driving energy system thereof Download PDFInfo
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- CN106371259A CN106371259A CN201610968750.7A CN201610968750A CN106371259A CN 106371259 A CN106371259 A CN 106371259A CN 201610968750 A CN201610968750 A CN 201610968750A CN 106371259 A CN106371259 A CN 106371259A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/15—Devices 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
- G02F1/1506—Devices 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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—Devices 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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/15—Devices 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
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of novel energy integration and discloses all solid-state electrochromic intelligent glass which has an electrochemical energy storage function and enables users to visually determine a voltage state (or an energy storage state) with naked eyes, a preparation method thereof and a self-driving energy system based on the all solid-state electrochromic intelligent glass. The all solid-state electrochromic intelligent glass structurally comprises a transparent conductive substrate, an anode material, an electrolyte, a cathode material and a transparent conductive substrate. The anode material and the cathode material are disposed on the transparent conductive substrates respectively to form an electrochromic and super-capacitor film; the electrolyte is a gel electrolyte and is filled between the anode material and the cathode material; the periphery of the gel electrolyte is packaged with epoxy resin, and finally an electrochromic device is prepared. The anode material is nickel oxide or polyaniline. The cathode material is tungsten oxide, molybdenum oxide or vanadium oxide. The self-driving energy system obtained based on the all solid-state electrochromic intelligent glass can be applied to the fields such as building curtain walls, intelligent windows for means of transport and intelligent glasses and the like.
Description
Technical field
The invention belongs to novel energy integrated technology field, particularly to one kind have concurrently electrochemical energy storage, visually can be directly perceived
Judge full-solid electrochromic intelligent glass of voltage status (or energy storage state) and preparation method thereof；And it is based on this electroluminescent change
The self-driven energy resource system of color intelligent glass.
Background technology
Ultracapacitor, is electrochemical capacitor again, be a kind of performance between battery and traditional capacitor new,
Efficiently, practical energy storing device, has power density height, long service life, advantages of environment protection.According to energy storage mechnism
Difference, ultracapacitor is generally divided into double layer capacitor and pseudocapacitors, and the former is generally porous carbon materials by electrode material,
The latter's electrode material is generally transition metal oxide and conducting polymer.When ultracapacitor adopts unsymmetric structure, that is, just
When negative pole adopts the electrode material of different potentials window, the voltage window of device can greatly be expanded, thus storage is more
Many energy simultaneously adapt to more working condition.
Electrochromism refer to when change applied voltage when, device can reversibly change its optical property (include absorbance,
Reflectance, absorbance etc.) phenomenon, be frequently accompanied by the embedded of ion during this and deviate from.Electrochromic material, including
Transition metal oxide, conducting polymer etc., have been applied to the fields such as camouflage, aircraft windows.Based on tungsten oxide (wo3)
Electrochromic intelligent glass have been obtained for widespread commercial use, such as can effectively be adjusted using the building of intelligent glass
With the incidence controlling sunlight, save the energy consumption freezing, heat, illuminating to a certain extent, reduce ambient light contamination, be a kind of ring
Border friendly device.However, most of electrochromic intelligent window only occurs color change at present, do not make full use of electrochromism
During electric charge storage with release produce energy.
Ultracapacitor and electrochromic electrode material, reaction mechanism and device architecture are all very much like, simultaneously with
The continuous progress of technology, the intellectual material possessing several functions also enjoys expectation, therefore with regard to electrochromism function energy storage device
Research more and more many.Realize the integrated of energy-storage property and electrochromic property, for the application expanding smart window further and
Industrialization has great economic benefit.It is quick that quasiconductor Suo Shen state of Chinese Academy of Sciences shake et al. application discloses a kind of integral dye
Change the preparation method (Chinese Patent Application No. is 201410022410.6) of the self-driven electrochromic device of solaode, with
wo3·2h2O thin film is electrochromism working electrode, and explores its self-driven electrochromic device.Harbin Institute of Technology Zhao nine
Fluffy et al. application discloses one kind and is based on nio thin film, wo3- pani laminated film, the super electricity of intelligence of solid mixing polyelectrolyte
Container (Chinese Patent Application No. is 201410190529.4).However, electrochromic layer tungsten oxide in two above invention
Electrode is all to be obtained using solvent method deposition, therefore unavoidably can introduce water of crystallization, and water of crystallization to have a strong impact on variable color steady
The qualitative energy-storage property with open circuit memory characteristic and ultracapacitor.How to improve electrochromic layer tungsten oxide degree of crystallinity,
Improve grain size and aisle space, improve ion and embed and eliminating efficiency, have great challenge for realizing quick response variable color.
And the invention that number of patent application is 201410190529.4 needs higher driving voltage (- 5v～+5v), limits this intelligence
The promotion and application of window.Chinese Academy of Sciences's Suzhou nanotechnology discloses one kind with nano bionic institute Zhao Zhigang et al. application and can show
Show the w of the intelligent ultracapacitor of capacitor electricity and energy storage state18o49(Chinese Patent Application No. is electrode
201410058316.6), this invention prepares tungsten oxide film using solvent method, equally introduces water of crystallization.Additionally, current restrict admittedly
Two main indexs of state electrochromic device application are: response time and cycle life (stability), how to carry further
This two performances high are difficult problems urgently to be resolved hurrily.Ji'nan University Mai Wenjie et al. application discloses one kind can electrochromism, electrification
Learn the preparation method (Chinese Patent Application No. is 201410306571.8) of the intelligent glass of energy storage and drive electronics, but device
The output services voltage window of part is still less, how to obtain broader operating voltage window, improves the energy-storage property of capacitor still
It is huge challenge.To sum up, by contrasting above-mentioned smart window patent of invention and embodiment, above-mentioned report does not all provide necessary device
Can the key messages such as cycle life, implement to shirk the heavy work and choose the light for patent is actual, and in fact, the skill of above-mentioned prior art at present
Art scheme is all difficult to meet corresponding technique effect requirement.
Content of the invention
In order to overcome shortcoming present in prior art with not enough, the voltage power supply window of such as electrochromic device is less than normal,
Energy density is low, the primary and foremost purpose of the present invention be to provide a kind of wide operating voltage, high-energy-density, high circulation stability complete
Solid-state electrochromic intelligent glass, achievable electrochemical energy storage, visually can the work(such as intuitive judgment voltage status (or energy storage state)
Can feature.The intelligent glass of the present invention is an independent Asymmetric Supercapacitor and electrochromism integrated device, by filling
Divide the chemical property in different voltage windows using different materials, substantially increase the energy density of device, highest works
Up to+1.4v, area capacitance reaches 28.3mf cm to voltage-2, energy density up to 7.7 × 10-3mwh·cm-2.
Another object of the present invention is to a kind of above-mentioned wide operating voltage of offer, high-energy-density, high circulation stability
The preparation method of full-solid electrochromic intelligent glass.The present invention adopts Vacuum sublimation, the tungsten oxide film preparing
There is high crystalline quality, it is to avoid solwution method is prepared tungsten oxide film and introduced water of crystallization, more conducively ion embedded or deviate from,
Can achieve and quickly become normal complexion energy storage, and reversible color can reach more than 5000 times between light green color and navy blue, average light is adjusted
Energy-conservation power is up to 43%.
Next, it is still another object of the present invention to provide a kind of self-powered energy source based on above-mentioned electrochromic intelligent glass
System.Electrochromic intelligent glass of the present invention is connected with commercial solar cell plate and obtains self-driven energy resource system, can drive
Move some miniaturized electronics, be applied to temporary power place, such as illumination, display, be charging of mobile devices etc..
The present invention is realized by following proposal:
A kind of electrochemical energy storage, simultaneously naked eyes can intuitive judgment voltage status (or energy storage state) full-solid electrochromic
Intelligent glass, its structure is electrically conducting transparent substrate-positive electrode-electrolyte-negative material-electrically conducting transparent substrate；Wherein, described
Positive electrode is deposited on electrically conducting transparent substrate and forms positive pole electrochromism and super capacitor material film, described negative material deposition
Form negative pole electrochromism and super capacitor thin film in electrically conducting transparent substrate；Described electrolyte is gel electrolyte, is just filled in
Between pole material and negative material；Described gel electrolyte surrounding adopts epoxy encapsulation, finally prepares electroluminescent change
Color device.
Preferably, described positive electrode has variable color and capacitive property for nickel oxide (nio), polyaniline (pani) etc.
Metal-oxide or polymer.
Preferably, described negative material is tungsten oxide (wo3), molybdenum oxide (moo3), vanadium oxide (v2o5) etc. there is variable color
And the metal-oxide of capacitive property or conducting polymer.
Preferably, described electrically conducting transparent substrate is generally the glass of fluorine doped tin oxide (fto) or tin indium oxide (ito)
Substrate, alternatively CNT, Graphene, nano silver wire or pedote:pss.
The method of described deposition can be thermal evaporation, electrochemical deposition, chemical vapor deposition, physical vapour deposition (PVD), spin coating
Multiple method for manufacturing thin film such as method and hydro-thermal method.Wherein, when negative material is tungsten oxide (wo3), molybdenum oxide (moo3) when, institute
The method stating deposition is preferably thermal evaporation, more preferably Vacuum sublimation, to form corresponding metal-oxide film material
Material.
The deposition process of described positive electrode is preferably electrochemical deposition.
The film thickness that described deposition obtains can be 50～500nm.
Preferably, described gel electrolyte can be pva/h2so4Colloid or pva/koh colloid.
The thickness of described dielectric substrate can be 1～100 μm.
The preparation method of the full-solid electrochromic intelligent glass of the present invention, by distinguishing positive electrode and negative material
It is deposited on electrically conducting transparent substrate, obtain surface and deposit the saturating of positive pole and negative pole electrochromism and super capacitor material film respectively
Bright conductive substrates as positive pole and negative pole, according to electrically conducting transparent substrate-positive electrode-electrolyte-negative material-electrically conducting transparent base
The structure at bottom, positive pole and negative pole are oppositely arranged, and described gel electrolyte is filled between positive pole and negative pole, and device surrounding is adopted
With epoxy resin, gel electrolyte is encapsulated, finally give device.
With using pani as positive electrode, wo3For negative material, pva/h2so4Colloid is that the device of gel electrolyte is
Example, device maximum output voltage of the present invention is 1.4v, and area capacitance reaches 28.3mf cm-2, energy density up to 7.7 × 10- 3mwh·cm-2, average power density reaches 0.13mw cm-2.As an electrochromic device, voltage is provided to be 0v when extraneous
When, pani electrode is light green color, wo3Electrode is water white transparency, and whole device assumes light green color；Voltage is provided to be 1.4v when extraneous
When, pani electrode is navy blue, wo3Electrode is also navy blue, and whole device assumes navy blue.This intelligent glass can be within the several seconds
Complete colour fading state (0v) and the transformation of coloured state (1.4v), and after disconnecting external circuit, device color is able to maintain that constant.Fill
Electric process, voltage is gradually increased to 1.4v by 0v, and this intelligent glass assumes light green color, green, light blue, navy blue color successively
Change procedure.Conversely, discharge process then fades to light blue, green, light green color from navy blue.This abundant color change,
So that naked eyes can be with the voltage status of this intelligent glass of intuitive judgment.
Electrochromism pani and wo3Electrochemical reaction in charge and discharge process for the electrode is as follows:
When additional back bias voltage, hydrion and electronics will be embedded into wo3Among lattice, change on microcosmic for the lattice is led
Cause spaced to narrow, absorbed a part of visible ray, in the change macroscopically then showing as color and transmitance.Vacuum Heat
Evaporation can achieve that the large area of tungsten oxide film is uniformly prepared, and tungsten oxide layer is the nano-crystalline granule of amorphous/polycrystalline doping,
Being evenly distributed of grain, interparticle contact is good, and this uniqueness crystalline state nanometer structure advantageously reduces migration barrier, increases diffusion system
Number can transmit for ion and provide express passway, improve the transformation efficiency of color, obtain more excellent open circuit memory characteristic.This
The tungsten oxide photochromic layer of outer thermal evaporation preparation has the chemistry more excellent than solvent method preparation and structural stability, shows
Higher cyclical stability.Thermal evaporation is to obtain higher discoloration rate and the tungsten oxide photochromic layer in high circulation life-span is preferably square
Method.
And during pani electrochromism, the doping of redox reaction and Bronsted acid exists simultaneously.Applied voltage
Bigger, the degree of oxidation of pani is higher, and phenyl ring gradually becomes quinoid structure, and polyaniline film is reversible among following several states
Ground conversion: reduction-state polyaniline, emeraldine salt and oxidation state polyaniline, its color is gradually deepened.
Therefore, the reaction equation of whole device is:
Wherein x is less, and the degree of oxidation of pani is higher；0<y<1.
Further, multiple electrochromic intelligent glass of the present invention are integrated (in series or in parallel) and external circuit
After connection, control output voltage range, you can uses as independent current source, for illuminating, display, to charging of mobile devices
Deng.
The present invention also provides a kind of self-driven energy resource system based on above-mentioned full-solid electrochromic intelligent glass.By inciting somebody to action
Electrochromic intelligent glass of the present invention is connected with commercial solar cell plate and obtains self-driven energy resource system.This self-powered energy source system
System includes two changeable loops, and a series loop for electrochromic intelligent glass and commercial solar cell, by too
Sun can cell panel be charged to intelligent glass；One is that electrochromic intelligent glass forms loop with dispatch from foreign news agency pipeline equipment, thus
Drive dispatch from foreign news agency pipeline equipment.Two loops can be switched over using single-pole double-throw switch (SPDT).For other batteries as driving power supply, mesh
Front urgently to be resolved hurrily the problems such as still have such as stability, and the present invention, using ripe silica-based solar cell technology, is more beneficial for
Realize self-driven energy resource system popularization and application.
Above-mentioned self-driven energy resource system can drive some miniaturized electronics, can be applicable to temporary power place, such as shines
Bright, display, for charging of mobile devices etc..
Further specifically, self-driven energy resource system work process is as follows: when sunlight is sufficient, above-mentioned self-powered energy source
System is that the intelligent glass with energy-storage function charges automatically by solar panel, and it is dark blue so that intelligent glass is gradually presented
Color, thus absorbing most of sunlight, reduces the incident indoor intensity of sunlight；And it is stored in the electric energy in intelligent glass, must
Can pass through switching circuit when wanting, external output current, for driving external electronic device, such as illumination, display, or to moving
Equipment charge etc..The potential using value of the present invention and meaning are the selective absorbing of solar energy to external world, simultaneously profit
Realize the storage to electric charge and release, the transmitance to visible ray for the Self Adaptive Control intelligent glass with ultracapacitor.
The self-driven energy resource system of the present invention can be widely applied to building curtain wall, the intelligent window of the vehicles, Brilliant Eyes
The fields such as mirror.
Brief description
Fig. 1 is the intelligent glass structural representation of the present invention.
Fig. 2 is the electrochemical properties curve under the voltage window of 1.4v for the intelligent glass of the present invention: a is different scanning speed
Cyclic voltammogram under degree；B is the constant current charge-discharge curve under different electric current densities.
Fig. 3 is the intelligent glass of the present invention under 0v (uncharged, light green color) state with 1.4v (fully charged, navy blue)
In the state of transmitted spectrum and photo, it is saturating in 5000 later colour fading states of circulation and coloured state that dotted line is this intelligent glass
Penetrate spectrum.
Fig. 4 is that the intelligent glass of the present invention is corresponding to device table when biasing 0v, 0.3v, 0.6v, 0.9v, 1.2v, 1.4v
See color camera.
Fig. 5 is the circuit diagram under different working condition for the self-driven energy resource system of the present invention, and wherein, a is solar-electricity
Pond plate charges for intelligent glass；B powers for external circuit for intelligent glass.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, but embodiments of the present invention do not limit
In this.
Used in the following example, reagent all can obtain from commercial channel.
Embodiment one:
One kind can electrochromism, electrochemical energy storage, simultaneously naked eyes can intuitive judgment voltage status (or energy storage state) intelligence
Energy glass structure (as shown in Figure 1), electrically conducting transparent substrate-positive electrode-electrolyte-negative material-electrically conducting transparent substrate is successively
Superposition, negative material is wo3, positive electrode is nio.
Preparation method is as follows:
(1)wo3Prepared by electrode: tungsten boat is fixed on vacuum coating machine electrode, adds 1g wo3Nano-particle (granularity
For 50nm), uniformly it is layered on tungsten boat bottom.Fto glass high temperature adhesive plaster is fixed on sample stage, and glass front is down just to tungsten
Boat, at a distance of about 15cm.Vacuum chamber is extracted into (5 × 10 after setting pressure-4Pa), it is deposited with 10min, gained wo3Thickness degree is about
300nm；
(2) nio electrode preparation: configure 0.5mol l first-1na2so4、0.05mol·l-1Niso4 is electrolyte, with
Fto glass is substrate, adopts three-electrode method (being as reference electrode to electrode, ag/agcl with platinum), and electric current density is 1ma cm-2, electroplating time is 60s, you can prepared nio electrode；
(3) prepare pva/h2so4Gel electrolyte: 3g pva is added to 30ml 1mol l-1h2so4In solution, 85
Stir 1 hour in DEG C water-bath, finally assume homogeneous colloids state, obtain pva/h2so4Gel electrolyte；
(4) step (1) gained wo3Electrode and step (2) gained nio electrode, by step (3) gained pva/h2so4Gel
Two cube electrodes are stacked by electrolyte relatively, and gel electrolyte is encapsulated by device surrounding using epoxy resin, obtains based on wo3
With nio can electrochromic ultracapacitor intelligent glass.
Multiple devices are integrated (in series or in parallel), output voltage can be controlled.When be connected with external circuit with
Afterwards, you can use as independent current source, for illuminating, display, to charging of mobile devices etc..
Embodiment two:
One kind can electrochromism, electrochemical energy storage, simultaneously naked eyes can intuitive judgment voltage status (energy storage state) intelligence
Glass structure as shown in figure 1, electrically conducting transparent substrate-positive electrode-electrolyte-negative material-electrically conducting transparent substrate is sequentially overlapped,
Negative material is wo3, positive electrode is pani.
Preparation method is as follows:
(1)wo3Prepared by electrode: tungsten boat is fixed on vacuum coating machine electrode, adds 1g wo3Nano-particle, uniformly spreads
In tungsten boat bottom.Fto glass high temperature adhesive plaster is fixed on sample stage, glass front down just to tungsten boat, at a distance of about 15cm.Will
Vacuum chamber is extracted into (5 × 10 after setting pressure-4Pa), it is deposited with 10min, gained wo3Thickness degree is about 300nm；
(2) pani electrode preparation: configure 0.5mol l first-1h2so4、0.5mol·l-1na2so4、0.05mol·l-1
Aniline is electrolyte, with fto glass as substrate, adopts three-electrode method (being as reference electrode to electrode, ag/agcl with platinum), electricity
Current density is 0.1ma cm-2, electroplating time is 60min, you can prepared pani electrode；
(3) prepare pva/h2so4Gel electrolyte: 3g pva is added to 30ml 1mol l-1h2so4In solution, 85
Stir in DEG C water-bath 1 hour, be in finally homogeneous colloids state, obtain pva/h2so4Gel electrolyte；
(4) step (1) gained wo3Electrode and step (2) gained pani electrode, by step (3) gained pva/h2so4Solidifying
Two cube electrodes are stacked by glue electrolyte relatively, and gel electrolyte is encapsulated by device surrounding using epoxy resin, is based on
wo3With pani electrode can electrochromism ultracapacitor intelligent glass.Can electrochromism ultracapacitor exist described in this method
Can steady operation (see Fig. 2) under the window voltage of 1.4v.
That is developed electrochromism can have the intelligent glass of electrochemical energy storage concurrently and assumes excellent performance, and Fig. 3 is this intelligence
Glass, should under 0v (uncharged, light green color) state and the transmission spectrum in the state of 1.4v (fully charged, navy blue) and photo
Intelligent glass is in the transmission spectrum of 5000 later colour fading states of circulation and coloured state.It is light green color under uncharged state, be full of
After electricity, in navy blue, the color of intermediate state as shown in figure 4, color contrast clearly, therefore naked eyes can intuitive judgment voltage shape
State (or energy storage state).The maximum output voltage of this device is 1.4v, and area capacitance reaches 28.3mf cm-2, energy density is up to
7.7×10-3mwh·cm-2, average power density reaches 0.13mw cm-2.
Multiple devices are integrated (in series or in parallel), the scope of output voltage can be controlled.When with external circuit
After connection, you can use as independent current source, for illuminating, display, to charging of mobile devices etc..
Embodiment three:
As shown in figure 5, this intelligent glass (serial or parallel connection) and commercial solar cell plate are together in series shape with wire
Become loop, intelligent glass drives other electronic equipment such as LED lamp to form loop, cuts in two loops using single-pole double-throw switch (SPDT)
Change, form a self-driven energy resource system.This system can be intelligence when daytime is sunny by solar panel automatically
Glass can charge, and make intelligent glass assume coloured state (navy blue), reduce incident interior sunlight strength；And it is stored in intelligent glass
Electric energy in glass, can drive external electronic device when necessary, such as illumination, display, or to charging of mobile devices etc..
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (10)
1. a kind of full-solid electrochromic intelligent glass is it is characterised in that its structure is electrically conducting transparent substrate-positive electrode-electrolysis
Matter-negative material-electrically conducting transparent substrate；Wherein, described positive electrode is deposited on electrically conducting transparent substrate and forms positive pole electrochromism
And super capacitor material film, described negative material is deposited on the formation negative pole electrochromism of electrically conducting transparent substrate and super capacitor is thin
Film；Described electrolyte is gel electrolyte, is filled between positive electrode and negative material；Described gel electrolyte surrounding is adopted
With epoxy encapsulation, finally prepare electrochromic device；
Described positive electrode is nickel oxide or polyaniline；
Described negative material is tungsten oxide, molybdenum oxide or vanadium oxide.
2. full-solid electrochromic intelligent glass according to claim 1 it is characterised in that: described electrically conducting transparent substrate
For the substrate of glass of fluorine doped tin oxide or tin indium oxide, CNT, Graphene, nano silver wire or pedote:pss；Described
Gel electrolyte be pva/h2so4Colloid or pva/koh colloid.
3. full-solid electrochromic intelligent glass according to claim 1 it is characterised in that: the method for described deposition be heat
Evaporation, electrochemical deposition, chemical vapor deposition, physical vapour deposition (PVD), spin-coating method or hydro-thermal method.
4. full-solid electrochromic intelligent glass according to claim 1 it is characterised in that: when negative material is tungsten oxide
Or during molybdenum oxide, the method for described deposition is thermal evaporation；
The deposition process of described positive electrode is electrochemical deposition.
5. full-solid electrochromic intelligent glass according to claim 1 it is characterised in that: the thin film that described deposition obtains
Thickness is 50～500nm；The thickness of described dielectric substrate is 1～100 μm.
6. the full-solid electrochromic intelligent glass described in a kind of any one of Claims 1 to 5 it is characterised in that: by will just
Pole material and negative material are respectively deposited at electrically conducting transparent substrate, obtain surface deposited respectively positive pole and negative pole electrochromism and
The electrically conducting transparent substrate of super capacitor material film as positive pole and negative pole, according to electrically conducting transparent substrate-positive electrode-electrolysis
The structure of matter-negative material-electrically conducting transparent substrate, positive pole and negative pole are oppositely arranged, and described gel electrolyte is just filled in
Between pole and negative pole, gel electrolyte is encapsulated by device surrounding using epoxy resin, finally gives device.
7. the self-driven energy resource system of the full-solid electrochromic intelligent glass described in a kind of any one based on Claims 1 to 5,
It is characterized in that being obtained by being connected described full-solid electrochromic intelligent glass with commercial solar cell plate.
8. it is characterised in that specifically including two switching circuits, one is self-driven energy resource system according to claim 7
Electrochromic intelligent glass and the series loop of commercial solar cell,；One is set with external circuit for electrochromic intelligent glass
Standby formation loop, two loops are switched over using single-pole double-throw switch (SPDT).
9. the self-driven energy resource system described in any one of claim 7～8 drives miniaturized electronics in temporary power place
Application.
10. the self-driven energy resource system described in any one of claim 7～8 is in building curtain wall, the intelligent window of the vehicles, intelligence
Application in energy eyewear art.
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