CN105119158A - Transformer cabinet with electrochromic device outer box and production method - Google Patents
Transformer cabinet with electrochromic device outer box and production method Download PDFInfo
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- CN105119158A CN105119158A CN201510628924.0A CN201510628924A CN105119158A CN 105119158 A CN105119158 A CN 105119158A CN 201510628924 A CN201510628924 A CN 201510628924A CN 105119158 A CN105119158 A CN 105119158A
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- film
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02B—BOARDS, SUBSTATIONS OR SWITCHING ARRANGEMENTS FOR THE SUPPLY OR DISTRIBUTION OF ELECTRIC POWER
- H02B1/00—Frameworks, boards, panels, desks, casings; Details of substations or switching arrangements
- H02B1/26—Casings; Parts thereof or accessories therefor
- H02B1/30—Cabinet-type casings; Parts thereof or accessories therefor
- H02B1/306—Accessories, e.g. windows
-
- 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
-
- 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
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
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- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a transformer cabinet with an electrochromic device outer box and a production method. A structure and a production process of the transformer cabinet with the electrochromic device outer box are improved, the characteristic of self-function is realized, so that a novel electrochromic device that the electrochromic response time is short, the electrochromic range is wider and the service life is prolonged is produced, the production method is simple and easy to operate, and is easy for industrialized production.
Description
Technical field
The invention belongs to mechanical field, more specifically relate to and a kind of there is transformation cabinet of electrochromic device outer container and preparation method thereof.
Background technology
Transformation cabinet is a kind of final stage device of distribution system, is the general designation of motor control center, can provide protection, monitoring and controlling to load.
But existing transformation cabinet shell mostly is opaque material and makes, be unfavorable for real time inspection, monitoring inner case.
Summary of the invention
The present invention is directed to background technology Problems existing, there is provided a kind of and there is transformation cabinet of electrochromic device outer container and preparation method thereof, it all improves the structure of electrochromic device and manufacture craft, realize the feature of self energizing, photovoltaic energy conversion ultrahigh in efficiency, life, additionally by electrochromic device, the object changing cabinet light transmittance can be realized.
Object of the present invention is achieved through the following technical solutions:
Have a manufacture method for the transformation cabinet of electrochromic device outer container, electrochromism outer container uses the method for machinery to be close to transformation cabinet and fixes, and specifically comprises: assembling transformation cabinet main body, electrochromic device outer container and electric-regulating device:
One, the making step of electric-regulating device is as follows:
(1) rearrangeable switch is made, for connecting electrochromic device and electric-regulating device;
(2) make control circuit, for can regulate the electric current applying electrochromic device continuously according to extraneous light intensity, tune up electric current when ambient light grow, turn electric current down when ambient light dies down;
Two, the electrochromic device making step of transformation cabinet is as follows:
(1) WO
3prepared by nano film material electrochromic electrode:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 320-360nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 200-220nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 400-420 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, passes into Ar and protects gas, be heated to 400-420 DEG C, and insulation 4-4.5 hour, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film, namely obtains electrochromic electrode;
Wherein nanorod length is 0.5-0.6 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 500-525nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 1-2nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) is adopted with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, then at the aqueous trehalose solution of the 10g/L of slow instillation 0.02-0.03 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 22-28nm,
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode be improved with absolute ethyl alcohol;
(3) electrolyte preparation:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
Have a manufacture method for the transformation cabinet of electrochromic device outer container, electrochromism outer container uses the method for machinery to be close to transformation cabinet and fixes, and specifically comprises: assembling transformation cabinet main body, electrochromic device outer container and electric-regulating device:
One, the making step of electric-regulating device is as follows:
(1) rearrangeable switch is made, for connecting electrochromic device and electric-regulating device;
(2) make control circuit, for can regulate the electric current applying electrochromic device continuously according to extraneous light intensity, tune up electric current when ambient light grow, turn electric current down when ambient light dies down;
Two, the electrochromic device making step of transformation cabinet is as follows:
(1) WO
3prepared by nano film material electrochromic electrode:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 360nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 200nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 420 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 400 DEG C, be incubated 4.5 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film, namely obtains electrochromic electrode;
Wherein nanorod length is 0.5 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 525nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 1nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate and monoethanolamine is adopted to take EGME as solvent, be configured to the colloidal sol of 50mM equimolar ratio, then at the aqueous trehalose solution of the 10g/L of slow instillation 0.03 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 22nm;
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode be improved with absolute ethyl alcohol;
(3) electrolyte preparation:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
Adopt the transformation cabinet that above-mentioned manufacture method prepares.
Select inorganic WO
3the benefit of nano-stick array thin film:
1) there is unstable chemcial property, bond the shortcomings such as defective tightness, anti-ultraviolet radiation be indifferent with substrate in organic electrochromic material;
2) inorganic electrochromic material (tungstic acid, vanadic oxide, nickel oxide etc.) research comparatively early, and technology comparative maturity, has been shown in there is report for commercial applications.
Adopt Au to make catalyst, length has in the Seed Layer of ZnO nanoparticle and carries out Hydrothermal Growth ZnO nano-wire at low temperatures.This kind of method growth ZnO nano process conditions are simple, efficiency is high, can large area deposition and catalyst can regulate and control parameters such as the length of nano wire and diameters.
Select the benefit of ZnO nano-wire:
ZnO is broad stopband N type semiconductor material, is widely used in dye-sensitized solar cells;
ZnO carrier mobility is higher, is expected to the current characteristics improving battery further;
ZnO can be prepared into multiple nanostructure by simple process, such as nano wire, nanotube, nanoparticulate thin films etc.;
ZnO nano-wire has higher specific area, can adsorb more dyestuff.
And the present invention is further by optimized production process, produce the WO that performance is more excellent
3nano thin-film and ZnO nano-wire, and the optimization coordinating other structures, prepare overall photovoltaic energy conversion ultrahigh in efficiency, the novel electrochromic device of life.
Usefulness of the present invention is: method of the present invention is simple to operation, and be easy to industrialization and produce, novel electrochromic device photoelectric energy conversion efficiency obtained is in addition high, and life.
Accompanying drawing explanation
Accompanying drawing to be herein merged in specification and to form the part of this specification, shows embodiment according to the invention, and is used from specification one and explains principle of the present invention.
Fig. 1 is the structural representation of the transformation cabinet of the application.
Embodiment
For enabling above-mentioned purpose, the feature and advantage of the application more become apparent, below in conjunction with the drawings and specific embodiments, the application is described in further detail.
Electrochromism (Electrochronism/EC) refers under the effect of electric current or electric field, there is the phenomenon of stable reversible change in the optical properties (transmissivity, reflectivity or absorptivity) of material, just show as the reversible change of color and transparency so in appearance, then can regulate sunlight through number.The material with electrochromic property is called electrochromic material.Since the electrochromism phenomenon of Deb.S.K. Late Cambrian WO3 film in 1969, people have just found the material much with electrochromic property.Electrochromic material roughly can be divided into inorganic electrochromic material and organic electrochromic material by material type.The stable performance of inorganic electrochromic material, its light absorption change is because the Dual Implantations of ion and electronics and black soy sauce go out to cause.The light absorption change of organic electrochromic material is from redox reaction, and its rich color, easily carries out MOLECULE DESIGN, thus favored.
Electrochromic device is mainly divided into three parts: work electrode, to electrode, and electrolyte.Its structure is as shown below.Work electrode is generally the electro-conductive glass being coated with electrochomeric films and forms, the electro-conductive glass that electrode is then covered by the film (majority plays the effect of storage of ions) of cooperating electrode work is formed, in electrolyte, has the electrolyte of support performance electrode work.Whole device is similar to sandwich structure, work electrode and asking in being clipped in by electrolyte electrode, surrounding sealant sealing.When adding different driving voltage between two electrodes, the transmitance of device can change, and is generally change between clear state and coloured state.That is:, when adding a certain particular job voltage, device can be in pellucidity; When adding another particular job voltage, device can become colored state.By changing two interelectrode voltages, realize the change of device transmitance.
Why electrochromic material can show different colors under different driving voltages, is because redox state residing for it is different under different voltage, and then shows different band gaps, cause the change of color.
Embodiment 1:
Assembling transformation cabinet main body 10, electrochromic device outer container 20 and electric-regulating device 30.
Make electrochromic device 20 to comprise:
(1) WO
3prepared by nano thin-film 5 materials Electrochromic electrode:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 320nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 220nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 400 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 420 DEG C, be incubated 4 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film 5, namely obtains electrochromic electrode;
Wherein nanorod length is 0.6 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 500nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then 10 minutes are cleaned, at N after taking-up with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate
2dry up in atmosphere;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 2nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) is adopted with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, and then the aqueous trehalose solution of the 10g/L of slow instillation 0.02 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 28nm,
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed with absolute ethyl alcohol, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode 3 be improved;
(3) prepared by electrolyte 4:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte 4 of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
At room temperature, use 1000W simulated solar radiant xenon lamp (Oriel91192, USA), Keithly2400sourcemeter, irradiation intensity is 100W/cm
2, battery is 0.25cm by illuminating area
2measuring photovoltaic energy conversion efficiency under condition is 10.28%, and circulating, to measure photovoltaic energy conversion efficiency afterwards 5000 times be 9.56%.-20 DEG C deposit 3 months after, recover normal temperature, measure photovoltaic energy conversion efficiency and have no significant change.
Embodiment 2:
Assembling transformation cabinet main body 10, electrochromic device outer container 20 and electric-regulating device 30.
Make electrochromic device 20 to comprise:
(1) WO
3prepared by nano thin-film 5 materials Electrochromic electrode:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 360nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 200nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 420 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 400 DEG C, be incubated 4.5 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film 5, namely obtains electrochromic electrode;
Wherein nanorod length is 0.5 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 525nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then 10 minutes are cleaned, at N after taking-up with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate
2dry up in atmosphere;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 1nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) is adopted with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, and then the aqueous trehalose solution of the 10g/L of slow instillation 0.03 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 22nm,
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed with absolute ethyl alcohol, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode 3 be improved;
(3) prepared by electrolyte 4:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte 4 of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
At room temperature, use 1000W simulated solar radiant xenon lamp (Oriel91192, USA), Keithly2400sourcemeter, irradiation intensity is 100W/cm
2, battery is 0.25cm by illuminating area
2measuring photovoltaic energy conversion efficiency under condition is 10.50%, and circulating, to measure photovoltaic energy conversion efficiency afterwards 5000 times be 10.20%.-20 DEG C deposit 3 months after, recover normal temperature, measure photovoltaic energy conversion efficiency and have no significant change.
Embodiment 3:
Assembling transformation cabinet main body 10, electrochromic device outer container 20 and electric-regulating device 30.
Make electrochromic device 20 to comprise:
(1) WO
3prepared by nano thin-film 5 materials Electrochromic electrode:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 340nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 210nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 415 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 410 DEG C, be incubated 4.3 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film 5, namely obtains electrochromic electrode;
Wherein nanorod length is 0.6 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 515nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 2nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) is adopted with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, and then the aqueous trehalose solution of the 10g/L of slow instillation 0.02 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 27nm,
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed with absolute ethyl alcohol, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode 3 be improved;
(3) prepared by electrolyte 4:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte 4 of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
At room temperature, use 1000W simulated solar radiant xenon lamp (Oriel91192, USA), Keithly2400sourcemeter, irradiation intensity is 100W/cm
2, battery is 0.25cm by illuminating area
2measuring photovoltaic energy conversion efficiency under condition is 9.50%, and circulating, to measure photovoltaic energy conversion efficiency afterwards 5000 times be 9.34%.-20 DEG C deposit 3 months after, recover normal temperature, measure photovoltaic energy conversion efficiency and have no significant change.
Embodiment 4 comparative example:
Assembling transformation cabinet main body 10, electrochromic device outer container 20 and electric-regulating device 30.
Make electrochromic device 20 to comprise:
(1) WO
3prepared by nano thin-film 5 materials Electrochromic electrode:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 500nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 500nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 500 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 500 DEG C, be incubated 4.1 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film 5, namely obtains electrochromic electrode;
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 520nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 1nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) is adopted with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 500 DEG C annealing half an hour, formed Large-Area-Uniform distribution ZnO nanoparticle Seed Layer;
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed with absolute ethyl alcohol, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode 3 be improved;
(3) prepared by electrolyte 4:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte 4 of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
At room temperature, use 1000W simulated solar radiant xenon lamp (Oriel91192, USA), Keithly2400sourcemeter, irradiation intensity is 100W/cm
2, battery is 0.25cm by illuminating area
2measuring photovoltaic energy conversion efficiency under condition is 5.98%, and circulating, to measure photovoltaic energy conversion efficiency afterwards 5000 times be 3.98%.-20 DEG C deposit 3 months after, recover normal temperature, measure photovoltaic energy conversion efficiency and reduce 9.7%.
Embodiment 5 comparative example:
Assembling transformation cabinet main body 10, electrochromic device outer container 20 and electric-regulating device 30.
Make electrochromic device 20 to comprise:
(1) WO
3prepared by nano thin-film 5 materials Electrochromic electrode:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 600nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 400nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.3mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 500 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, and pass into Ar and protect gas, be heated to 600 DEG C, be incubated 5 hours, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film 5, namely obtains electrochromic electrode;
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness is about 600nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 5nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H is adopted
20) and monoethanolamine (Monoethanolamine) with EGME (2-methoxyethanol) for solvent, be configured to the colloidal sol of 50mM equimolar ratio, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 500 DEG C annealing half an hour, formed Large-Area-Uniform distribution ZnO nanoparticle Seed Layer;
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed with absolute ethyl alcohol, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode 3 be improved;
(3) prepared by electrolyte 4:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte 4 of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
At room temperature, use 1000W simulated solar radiant xenon lamp (Oriel91192, USA), Keithly2400sourcemeter, irradiation intensity is 100W/cm
2, battery is 0.25cm by illuminating area
2measuring photovoltaic energy conversion efficiency under condition is 6.12%, and circulating, to measure photovoltaic energy conversion efficiency afterwards 5000 times be 5.39%.-20 DEG C deposit 3 months after, recover normal temperature, measure photovoltaic energy conversion efficiency and reduce 10.1%.
As can be seen here, the novel electrochromic device photoelectric energy conversion efficiency that the present invention obtains is high, and life, and freexing tolerance can be also better.Each parameter of comparative example is starkly lower than technical scheme of the present invention, this illustrates that integrated artistic of the present invention serves certain synergy, each component of integral formula and proportioning are all most important, change any one key element and photovoltaic energy conversion efficiency all can be caused to reduce, the lost of life.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (2)
1. have a manufacture method for the transformation cabinet of electrochromic device outer container, electrochromism outer container uses the method for machinery to be close to transformation cabinet and fixes, and specifically comprises: assembling transformation cabinet main body, electrochromic device outer container and electric-regulating device:
One, the making step of electric-regulating device is as follows:
(1) rearrangeable switch is made, for connecting electrochromic device and electric-regulating device;
(2) make control circuit, for can regulate the electric current applying electrochromic device continuously according to extraneous light intensity, tune up electric current when ambient light grow, turn electric current down when ambient light dies down;
Two, the electrochromic device making step of transformation cabinet is as follows:
(1) WO
3prepared by nano film material electrochromic electrode:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 320-360nm;
B. the high temperature anneal is carried out to it, obtains the FTO electro-conductive glass that intensity is higher, then according to the order of ultra-pure water, acetone, ethanol by FTO electro-conductive glass successively ultrasonic cleaning 15min, dry for standby; Then, utilize magnetron sputtering method to plate W film on FTO glass, its thickness is 200-220nm; W film is used as WO
3the growth source of nano wire;
C. the sodium tungstate aqueous solution of 0.2mol/L is prepared, then the hydrochloric acid of 3mol/L is dripped to no longer producing precipitation, gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductive glass surface being coated with W film, at 400-420 DEG C, calcines 40min obtain WO
3crystal seed layer;
D. by obtained above with WO
3box-type high-temperature furnace put into by the FTO electro-conductive glass of crystal seed layer, passes into Ar and protects gas, be heated to 400-420 DEG C, and insulation 4-4.5 hour, rear Temperature fall, to room temperature, namely obtains cylindrical WO
3nano-stick array thin film, namely obtains electrochromic electrode;
Wherein nanorod length is 0.5-0.6 μm, density of nanorods about 10
6/ cm
2.
(2) the ZnO nano-wire film photoactive electrode preparation improved:
A. to toughened glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 500-525nm, then the high temperature anneal is carried out to it, obtain the FTO electro-conductive glass that intensity is higher, then clean 10 minutes with UV ozone cleaning machine again after cleaning 20 minutes with EtOH Sonicate, dry up in N2 atmosphere after taking-up;
B. FTO glass is put into gold spraying instrument, at FTO surface spraying plating one deck gold film as catalyst, golden film thickness is about 1-2nm, again cleans the method for FTO glass according to a step afterwards;
C. Zinc diacetate dihydrate and monoethanolamine is adopted to take EGME as solvent, be configured to the colloidal sol of 50mM equimolar ratio, then at the aqueous trehalose solution of the 10g/L of slow instillation 0.02-0.03 times of volume, and the formation Homogeneous phase mixing state that stirs, be spun in clean FTO substrate, spin coating 3 times is to obtain continuous print nanoparticulate thin films, between each spin coating, substrate infrared lamps is promoted solvent evaporates, finally by substrate in an atmosphere 385 DEG C annealing half an hour, form the ZnO nanoparticle Seed Layer of Large-Area-Uniform distribution, the thickness of described Seed Layer is 22-28nm,
D. the ZnSO of 0.15M is prepared
4the aqueous solution, by concentrated ammonia solution adjust ph to 10, ito substrate is put into solution, put into the baking oven of 95 DEG C after sealing, 2 as a child took out, and by washed with de-ionized water, namely obtained zinc oxide nanowire after drying;
E. pure organic doline dyes D102 being dissolved into volume ratio is in the second eyeball of 1:1 and the solution of the tert-butyl alcohol, concentration is 0.5mM, ZnO nano-wire is immersed in D102, keep in Dark Place 5 hours, after taking-up, the ZnO nano-wire after D102 sensitization is rinsed, fully to remove the D102 molecule being adsorbed onto ZnO nano-wire surface by physical adsorption way, the photoactive electrode be improved with absolute ethyl alcohol;
(3) electrolyte preparation:
Be made into 0.1MLiI and 0.001MI
2pC solution, as the supporting electrolyte of self energizing electrochromic device.
(4) device assembling:
Electrochromic electrode is relative with effective working face of photoactive electrode, two ends reserve the electrode of blank electro-conductive glass as reserved access external circuit of about 5mm width, surrounding diameter is that compacting smeared by two component aviation glue of the bead mixing of 100 μm, make the space leaving 100 μm between two electrodes, and in this space filling electrolyte, after glue all solidifies, obtain self energizing electrochromic device.
2. the transformation cabinet for preparing of manufacture method according to claim 1.
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