CN107561812A - Outdoor billboard based on electrochromic device and preparation method thereof - Google Patents
Outdoor billboard based on electrochromic device and preparation method thereof Download PDFInfo
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- CN107561812A CN107561812A CN201710987523.3A CN201710987523A CN107561812A CN 107561812 A CN107561812 A CN 107561812A CN 201710987523 A CN201710987523 A CN 201710987523A CN 107561812 A CN107561812 A CN 107561812A
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Abstract
The invention discloses a kind of outdoor billboard based on electrochromic device and preparation method thereof, its structure and manufacture craft to electrochromic device is all improved, the characteristics of making it have self energizing, the obtained novel electrochromic device discoloration response time is short, photovoltaic energy conversion ultrahigh in efficiency, life, freexing tolerance can be good, and the method for the present invention is simple to operation, is easy to industrialization production.
Description
Technical field
The invention belongs to manufacturing field, is more particularly to based on the outdoor billboard of electrochromic device and its making side
Method.
Background technology
Billboard, it is a kind of display systems for showing the information such as product, service, refers to the media of all transmission informations.Family
Outer billboard, because the outdoor locations residing for it have particularity, it is desirable to which it can adjust information according to the power of sunshine
The brightness of display, however, existing outdoor billboard is made by materials such as metal, plank, glass, it is difficult to realize this work(
Energy.
The content of the invention
Present invention the problem of existing for background technology, there is provided a kind of outdoor billboard based on electrochromic device and its
Preparation method, its structure and manufacture craft to self energizing electrochromic device are all improved, so as to which photoelectric energy be made
Conversion efficiency is high, the billboard of life, and by electrochromic device, it can realize the power according to sunshine
To adjust the brightness of display information.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the outdoor billboard based on electrochromic device, electrochromic device use mechanical method
Billboard body outer surface is fixed on, is specifically included：Assemble billboard main body, electrochromic device and regulation and control module：
First, the making step for regulating and controlling module is as follows：
(1) rearrangeable switch is made, for connecting；
(2) control circuit is made, applies the electric current of electrochromic device for that can be continuously adjusted according to extraneous light intensity, when
Ambient light tunes up electric current when becoming strong, and electric current is turned down when ambient light dies down；
2nd, the electrochromic device making step of billboard is as follows：
(1)WO3It is prepared by nano film material electrochromic electrode：
A. to safety 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 higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 200-220nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 400-420 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 400-420 DEG C, is incubated 4-4.5 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nanometer stick array is thin
Film, that is, obtain electrochromic electrode；
Wherein nanorod length is 0.5-0.6 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. to safety glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 500-
525nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
1-2nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) are used with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be then slowly dropped into 0.02-
The 10g/L of 0.03 times of volume aqueous trehalose solution, and stir and to form uniform admixture, it is spun to clean FTO bases
On bottom, substrate is promoted solvent to wave by spin coating 3 times between each spin coating to obtain continuous nanoparticulate thin films with infrared lamps
Hair, finally substrate is annealed half an hour for 385 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area, institute
The thickness for stating Seed Layer is 22-28nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode entered；
(3) prepared by electrolyte：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
A kind of preparation method of the outdoor billboard based on electrochromic device, electrochromic device use mechanical method
Billboard body outer surface is fixed on, is specifically included：Assemble billboard main body, electrochromic device and regulation and control module：
First, the making step for regulating and controlling module is as follows：
(1) rearrangeable switch is made, for connecting；
(2) control circuit is made, applies the electric current of electrochromic device for that can be continuously adjusted according to extraneous light intensity, when
Ambient light tunes up electric current when becoming strong, and electric current is turned down when ambient light dies down；
2nd, the electrochromic device making step of billboard is as follows：
(1)WO3It is prepared by nano film material electrochromic electrode：
A. it is about to safety glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness
360nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 200nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 420 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 400 DEG C, is incubated 4.5 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film, i.e.,
Obtain electrochromic electrode；
Wherein nanorod length is 0.5 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness
525nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
1nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate and monoethanolamine are used using ethylene glycol monomethyl ether as solvent, be configured to 50mM equimolars than it is molten
Glue, then in the aqueous trehalose solution for the 10g/L for being slowly dropped into 0.03 times of volume, and stir and to form uniform admixture,
It is spun in clean FTO substrates, spin coating 3 times is to obtain continuous nanoparticulate thin films, by substrate with red between each spin coating
Outer lamp heating promotes solvent volatilization, and finally by substrate, 385 DEG C of annealing half an hour, formation large area are equally distributed in an atmosphere
ZnO nanoparticle Seed Layer, the thickness of the Seed Layer is 22nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode entered；
(3) prepared by electrolyte：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
The billboard being prepared using above-mentioned preparation method.
From inorganic WO3The benefit of nano-stick array thin film：
1) there is unstable chemcial property, bond defective tightness, anti-ultraviolet radiation energy with substrate in organic electrochromic material
The shortcomings of power is not strong；
2) inorganic electrochromic material (tungstic acid, vanadic anhydride, nickel oxide etc.) research is more early, and technology has compared
Maturation, see had been reported that for commercial applications.
Catalyst is made using Au, at low temperature the enterprising water-filling thermal growth ZnO nano of the Seed Layer with ZnO nanoparticle
Line.This kind of method growth ZnO nano process conditions are simple, efficiency high, can large area deposition and catalyst can be to nanometer
The parameter such as the length of line and diameter is regulated and controled.
From the benefit of ZnO nano-wire：
ZnO is broad stopband N-type semiconductor material, is widely used in dye-sensitized solar cells；
ZnO carrier mobilities are higher, are expected to further improve the current characteristics of battery；
ZnO can be prepared into a variety of nanostructureds, such as nano wire, nanotube, nanoparticulate thin films by simple process
Deng；
ZnO nano-wire has higher specific surface area, can adsorb more dyestuffs.
And the present invention produces the more excellent WO of performance further by optimized production process3Nano thin-film and ZnO receive
Rice noodles, and coordinate the optimization of other structures, prepare overall photovoltaic energy conversion ultrahigh in efficiency, the Novel electric mutagens of life
Color device.
The present invention is advantageous in that：The method of the present invention is simple to operation, is easy to industrialization production, obtained in addition
Novel electrochromic device photoelectric energy conversion efficiency is high, and life.
Brief description of the drawings
Accompanying drawing herein is merged in specification and forms the part of this specification, shows the implementation for meeting the present invention
Example, and for explaining principle of the invention together with specification.
Fig. 1 is the structural representation of the billboard of the application.
Embodiment
It is below in conjunction with the accompanying drawings and specific real to enable the above-mentioned purpose of the application, feature and advantage more obvious understandable
Mode is applied to be described in further detail the application.
Electrochromism (Electrochronism/EC) refers in the presence of electric current or electric field, the optical properties of material
The phenomenon of stable reversible change occurs for (transmissivity, reflectivity or absorptivity), then will appear as color and thoroughly in appearance
The reversible change of lightness, can then adjust sunshine transmission number.Material with electrochromic property is referred to as electroluminescent change
Color material.Since Deb.S.K. in 1969 has found the electrochromism phenomenon of WO3 films first, people have found that many tools
There is the material of electrochromic property.Electrochromic material can be substantially divided into inorganic electrochromic material and organic by material type
Electrochromic material.The stable performance of inorganic electrochromic material, the change of its light absorbs are due to the Dual Implantations of ion and electronics
Go out with black soy sauce caused.The light absorbs change of organic electrochromic material comes from redox reaction, and its is rich in color, easily carries out
MOLECULE DESIGN, so as to be favored.
Electrochromic device is broadly divided into three parts：Working electrode, to electrode, electrolyte.Working electrode generally covers
The electro-conductive glass for being stamped electrochomeric films is formed, and is then that (majority plays storage for the film that is worked by cooperating electrode to electrode
Deposit the effect of ion) the electro-conductive glass composition of covering, there is the electrolyte for supporting working electrode work in electrolyte.Whole device class
It is similar to sandwich structure, working electrode and asks during electrolyte is clipped in electrode, surrounding sealant sealing.Between two electrodes
During plus different driving voltage, the transmitance of device can change, and be changed usually between transparent state and coloured state.I.e.：Add
During upper a certain particular job voltage, device can be in pellucidity；When plus another particular job voltage, device can be changed into
Color state.By changing two interelectrode voltages, the change of device transmitance is realized.
Why electrochromic material can show different colors under different driving voltages, be due in different electricity
It is different to depress its residing redox state, and then shows different band gaps, causes the change of color.
Embodiment 1：
Assemble billboard part 10, electrochromic device 20 and regulation and control module 30.
Making electrochromic device 20 includes：
(1)WO3It is prepared by the materials Electrochromic electrode of nano thin-film 5：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
320nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 220nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 400 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 420 DEG C, is incubated 4 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film 5, is produced
To electrochromic electrode；
Wherein nanorod length is 0.6 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
500nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine again after minute, in N after taking-up2Dried up in atmosphere；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
2nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) are used with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be then slowly dropped into 0.02 times again
The 10g/L of volume aqueous trehalose solution, and stir and to form uniform admixture, it is spun in clean FTO substrates, revolves
3 times are applied to obtain continuous nanoparticulate thin films, promotes solvent to volatilize with infrared lamps substrate between each spin coating, finally
Substrate is annealed half an hour for 385 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area, the seed
The thickness of layer is 28nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode 3 entered；
(3) prepared by electrolyte 4：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte 4 as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
At room temperature, using 1000W simulated solar radiants xenon lamp (Oriel 91192, USA),
Keithly2400source meter, irradiation intensity 100W/cm2, battery is 0.25cm by illuminating area2Under the conditions of measure light
Electric energy conversion efficiency is 10.28%, and it is 9.56% that photovoltaic energy conversion efficiency is measured after circulating 5000 times.- 20 DEG C are deposited 3
After month, recover normal temperature, measurement photovoltaic energy conversion efficiency has no significant change.
Embodiment 2：
Assemble billboard part 10, electrochromic device 20 and regulation and control module 30.
Making electrochromic device 20 includes：
(1)WO3It is prepared by the materials Electrochromic electrode of nano thin-film 5：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
360nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 200nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 420 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 400 DEG C, is incubated 4.5 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film 5, i.e.,
Obtain electrochromic electrode；
Wherein nanorod length is 0.5 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness
525nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine again after minute, in N after taking-up2Dried up in atmosphere；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
1nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) are used with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be then slowly dropped into 0.03 times again
The 10g/L of volume aqueous trehalose solution, and stir and to form uniform admixture, it is spun in clean FTO substrates, revolves
3 times are applied to obtain continuous nanoparticulate thin films, promotes solvent to volatilize with infrared lamps substrate between each spin coating, finally
Substrate is annealed half an hour for 385 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area, the seed
The thickness of layer is 22nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode 3 entered；
(3) prepared by electrolyte 4：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte 4 as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
At room temperature, using 1000W simulated solar radiants xenon lamp (Oriel 91192, USA),
Keithly2400source meter, irradiation intensity 100W/cm2, battery is 0.25cm by illuminating area2Under the conditions of measure light
Electric energy conversion efficiency is 10.50%, and it is 10.20% that photovoltaic energy conversion efficiency is measured after circulating 5000 times.- 20 DEG C of storages 3
After individual month, recover normal temperature, measurement photovoltaic energy conversion efficiency has no significant change.
Embodiment 3：
Assemble billboard part 10, electrochromic device 20 and regulation and control module 30.
Making electrochromic device 20 includes：
(1)WO3It is prepared by the materials Electrochromic electrode of nano thin-film 5：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness
340nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 210nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 415 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 410 DEG C, is incubated 4.3 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film 5, i.e.,
Obtain electrochromic electrode；
Wherein nanorod length is 0.6 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness
515nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
2nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) are used with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be then slowly dropped into 0.02 times again
The 10g/L of volume aqueous trehalose solution, and stir and to form uniform admixture, it is spun in clean FTO substrates, revolves
3 times are applied to obtain continuous nanoparticulate thin films, promotes solvent to volatilize with infrared lamps substrate between each spin coating, finally
Substrate is annealed half an hour for 385 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area, the seed
The thickness of layer is 27nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode 3 entered；
(3) prepared by electrolyte 4：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte 4 as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
At room temperature, using 1000W simulated solar radiants xenon lamp (Oriel 91192, USA),
Keithly2400source meter, irradiation intensity 100W/cm2, battery is 0.25cm by illuminating area2Under the conditions of measure light
Electric energy conversion efficiency is 9.50%, and it is 9.34% that photovoltaic energy conversion efficiency is measured after circulating 5000 times.- 20 DEG C are deposited 3
After month, recover normal temperature, measurement photovoltaic energy conversion efficiency has no significant change.
The comparative example of embodiment 4：
Assemble billboard part 10, electrochromic device 20 and regulation and control module 30.
Making electrochromic device 20 includes：
(1)WO3It is prepared by the materials Electrochromic electrode of nano thin-film 5：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
500nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 500nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 500 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 500 DEG C, is incubated 4.1 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film 5, i.e.,
Obtain electrochromic electrode；
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
520nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
1nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H20) and monoethanolamine (Monoethanolamine) are used with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be spun to clean FTO substrates
On, substrate is promoted solvent to wave by spin coating 3 times between each spin coating to obtain continuous nanoparticulate thin films with infrared lamps
Hair, finally substrate is annealed half an hour for 500 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode 3 entered；
(3) prepared by electrolyte 4：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte 4 as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
At room temperature, using 1000W simulated solar radiants xenon lamp (Oriel 91192, USA),
Keithly2400source meter, irradiation intensity 100W/cm2, battery is 0.25cm by illuminating area2Under the conditions of measure light
Electric energy conversion efficiency is 5.98%, and it is 3.98% that photovoltaic energy conversion efficiency is measured after circulating 5000 times.- 20 DEG C are deposited 3
After month, recover normal temperature, measurement photovoltaic energy conversion efficiency reduces 9.7%.
The comparative example of embodiment 5：
Assemble billboard part 10, electrochromic device 20 and regulation and control module 30.
Making electrochromic device 20 includes：
(1)WO3It is prepared by the materials Electrochromic electrode of nano thin-film 5：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
600nm；
B. the high temperature anneal is carried out to it, obtains the higher FTO electro-conductive glass of intensity, then according to ultra-pure water, acetone,
FTO electro-conductive glass is cleaned by ultrasonic 15min by the order of ethanol successively, is dried for standby；Then, using magnetron sputtering method in FTO glass
W films are plated on glass, its thickness is 400nm；W films are used as WO3The growth source of nano wire；
C. 0.3mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced,
Gained precipitation is dissolved in hydrogen peroxide after centrifuge washing and obtains vitreosol, vitreosol is applied to the ITO conductions for being coated with W films
Glass surface, calcining 40min obtains WO at 500 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protections
Gas, is heated to 600 DEG C, is incubated 5 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film 5, is produced
To electrochromic electrode；
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. it is about to safety glass 1 surface magnetic control sputtering fluorine-doped tin oxide (FTO) film 2 of specific dimensions, thickness
600nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, is about as catalyst, golden film thickness in one layer of golden film of FTO surfaces spraying plating
5nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate (Zn (CH3C00) 2-2H is used20) and monoethanolamine (Monoethanolamine) is with second two
Alcohol methyl ether (2-methoxyethanol) is solvent, be configured to 50mM equimolars than colloidal sol, be spun to clean FTO substrates
On, substrate is promoted solvent to wave by spin coating 3 times between each spin coating to obtain continuous nanoparticulate thin films with infrared lamps
Hair, finally substrate is annealed half an hour for 500 DEG C in an atmosphere, forms the equally distributed ZnO nanoparticle Seed Layer of large area；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution
In, 95 DEG C of baking oven is put into after sealing, 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration
For 0.5mM, ZnO nano-wire is immersed in D102, is kept in dark place 5 hours, after taking-up, D102 sensitizations are rinsed with absolute ethyl alcohol
ZnO nano-wire afterwards, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are changed
The photoactive electrode 3 entered；
(3) prepared by electrolyte 4：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte 4 as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and the blank that both ends reserve 5mm or so width is led
Electrode of the electric glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead apply
Compacting is smeared, makes to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, is obtained after glue all solidification
Self energizing electrochromic device.
At room temperature, using 1000W simulated solar radiants xenon lamp (Oriel 91192, USA),
Keithly2400source meter, irradiation intensity 100W/cm2, battery is 0.25cm by illuminating area2Under the conditions of measure light
Electric energy conversion efficiency is 6.12%, and it is 5.39% that photovoltaic energy conversion efficiency is measured after circulating 5000 times.- 20 DEG C are deposited 3
After month, recover normal temperature, measurement photovoltaic energy conversion efficiency reduces 10.1%.
As can be seen here, novel electrochromic device photoelectric energy conversion efficiency produced by the present invention is high, and the life-span prolongs
Long, freexing tolerance can be also more preferable.Each parameter of comparative example is significantly lower than technical scheme, the overall work of this explanation present invention
Skill serves certain synergy, and each component and proportioning of integral formula are all most important, change any one key element all
The reduction of photovoltaic energy conversion efficiency, the lost of life can be caused.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (2)
1. a kind of preparation method of the outdoor billboard based on electrochromic device, electrochromic device is consolidated using the method for machinery
Billboard body outer surface is scheduled on, is specifically included：Assemble billboard main body, electrochromic device and regulation and control module：
First, the making step for regulating and controlling module is as follows：
(1) rearrangeable switch is made, for connecting；
(2) control circuit is made, applies the electric current of electrochromic device for that can be continuously adjusted according to extraneous light intensity, works as the external world
Light tunes up electric current when becoming strong, and electric current is turned down when ambient light dies down；
2nd, the electrochromic device making step of billboard is as follows：
(1)WO3It is prepared by nano film material electrochromic electrode：
A. to safety 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, the higher FTO electro-conductive glass of intensity is obtained, then according to ultra-pure water, acetone, ethanol
Order FTO electro-conductive glass is cleaned by ultrasonic 15min successively, be dried for standby；Then, using magnetron sputtering method on FTO glass
W films are plated, its thickness is 200-220nm；W films are used as WO3The growth source of nano wire；
C. 0.2mol/L wolframic acid sodium water solution is prepared, 3mol/L hydrochloric acid is then added dropwise untill no longer precipitation is produced, by institute
It must precipitate to be dissolved in hydrogen peroxide after centrifuge washing and obtain vitreosol, vitreosol is applied to the ITO electro-conductive glass for being coated with W films
Surface, calcining 40min obtains WO at 400-420 DEG C3Crystal seed layer；
D. WO is carried by obtained above3The FTO electro-conductive glass of crystal seed layer is put into box-type high-temperature furnace, is passed through Ar protection gas, heating
To 400-420 DEG C, be incubated 4-4.5 hours, after be naturally cooling to room temperature, that is, obtain cylindrical WO3Nano-stick array thin film, produce
To electrochromic electrode；
Wherein nanorod length is 0.5-0.6 μm, density of nanorods about 106/cm2。
(2) prepared by improved ZnO nano-wire film photoactive electrode：
A. to safety glass surface magnetic control sputtering fluorine-doped tin oxide (FTO) film of specific dimensions, thickness is about 500-
525nm, the high temperature anneal then is carried out to it, obtain the higher FTO electro-conductive glass of intensity, then clean 20 with EtOH Sonicate
Cleaned 10 minutes with UV ozone cleaning machine after minute, dried up after taking-up in N2 atmosphere again；
B. FTO glass is put into gold spraying instrument, as catalyst, golden film thickness is about 1- in one layer of golden film of FTO surfaces spraying plating
2nm, after method of the FTO glass according to a steps is cleaned again；
C. Zinc diacetate dihydrate and monoethanolamine are used using ethylene glycol monomethyl ether as solvent, be configured to 50mM equimolars than colloidal sol, so
Afterwards in the aqueous trehalose solution for the 10g/L for being slowly dropped into 0.02-0.03 times of volume, and stir and to form uniform admixture,
It is spun in clean FTO substrates, spin coating 3 times is to obtain continuous nanoparticulate thin films, by substrate with red between each spin coating
Outer lamp heating promotes solvent volatilization, and finally by substrate, 385 DEG C of annealing half an hour, formation large area are equally distributed in an atmosphere
ZnO nanoparticle Seed Layer, the thickness of the Seed Layer is 22-28nm；
D. 0.15M ZnSO is prepared4The aqueous solution, pH value is adjusted to 10 with concentrated ammonia solution, ito substrate is put into solution, sealed
95 DEG C of baking oven is put into afterwards, and 2 were as a child taken out, and were cleaned with deionized water, and zinc oxide nanowire is produced after drying；
E. pure organic doline dyes D102 is dissolved into volume ratio as 1:In 1 second eyeball and the solution of the tert-butyl alcohol, concentration is
0.5mM, ZnO nano-wire is immersed in D102, be kept in dark place 5 hours, after taking-up, after rinsing D102 sensitizations with absolute ethyl alcohol
ZnO nano-wire, the D102 molecules on ZnO nano-wire surface are adsorbed onto by physical adsorption way with abundant removal, are improved
Photoactive electrode；
(3) prepared by electrolyte：
It is made into 0.1M LiI and 0.001M I2PC solution, the supporting electrolyte as self energizing electrochromic device.
(4) device assembles：
Effective working face of electrochromic electrode and photoactive electrode is relative, and both ends reserve the blank conduction glass of 5mm or so width
Electrode of the glass as reserved access external circuit, the two-component aviation glue that surrounding is mixed with a diameter of 100 μm of bead smear pressure
It is real, make to leave 100 μm of space, and the filling electrolyte in this space between two electrodes, confessed after glue all solidification
Can electrochromic device.
2. the outdoor billboard that the preparation method described in claim 1 is prepared.
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|---|---|---|---|---|
| CN105093769A (en) * | 2015-09-28 | 2015-11-25 | 董超超 | Electrochromic device based intelligent electronic curtain and production method thereof |
| CN105119158A (en) * | 2015-09-28 | 2015-12-02 | 吴本刚 | Transformer cabinet with electrochromic device outer box and production method |
| CN105137691A (en) * | 2015-09-28 | 2015-12-09 | 周丽娜 | Electrochromic device based sunlight room and manufacturing method thereof |
| CN105204263A (en) * | 2015-09-28 | 2015-12-30 | 杨林 | High-sun-blocking automobile window based on electrochromism device and manufacturing method thereof |
| CN106057081A (en) * | 2016-02-18 | 2016-10-26 | 吴桂广 | Outdoor advertising board based on electrochromic device and manufacturing method of advertising board |
| CN106200189A (en) * | 2016-07-19 | 2016-12-07 | 吴桂广 | Outdoor billboard based on electrochromic device and preparation method thereof |
-
2017
- 2017-10-20 CN CN201710987523.3A patent/CN107561812A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105093769A (en) * | 2015-09-28 | 2015-11-25 | 董超超 | Electrochromic device based intelligent electronic curtain and production method thereof |
| CN105119158A (en) * | 2015-09-28 | 2015-12-02 | 吴本刚 | Transformer cabinet with electrochromic device outer box and production method |
| CN105137691A (en) * | 2015-09-28 | 2015-12-09 | 周丽娜 | Electrochromic device based sunlight room and manufacturing method thereof |
| CN105204263A (en) * | 2015-09-28 | 2015-12-30 | 杨林 | High-sun-blocking automobile window based on electrochromism device and manufacturing method thereof |
| CN106057081A (en) * | 2016-02-18 | 2016-10-26 | 吴桂广 | Outdoor advertising board based on electrochromic device and manufacturing method of advertising board |
| CN106200189A (en) * | 2016-07-19 | 2016-12-07 | 吴桂广 | Outdoor billboard based on electrochromic device and preparation method thereof |
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