CN109988551A - A kind of electrochromic material and its preparation method and application - Google Patents
A kind of electrochromic material and its preparation method and application Download PDFInfo
- Publication number
- CN109988551A CN109988551A CN201810004358.XA CN201810004358A CN109988551A CN 109988551 A CN109988551 A CN 109988551A CN 201810004358 A CN201810004358 A CN 201810004358A CN 109988551 A CN109988551 A CN 109988551A
- Authority
- CN
- China
- Prior art keywords
- zno
- array
- electrochromic material
- zno nano
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a kind of electrochromic material and its preparation method and application, the electrochromic material is poly- (3, the 4- dioxoethyl) thiophene composite of ZnO nano array-；Poly- (3,4- dioxoethyl) thiophene composite of ZnO nano array-includes ZnO nano array layer and poly- (3,4- dioxoethyl) the thiophene material layer for being formed in ZnO nano array layer surface.The electrochromic material is by the way that the ZnO nano array perpendicular to substrate is formed on the substrate, and on ZnO nano array surface, uniformly compound poly- (3,4- dioxoethyl) thiophene is made.Electrochromic material of the invention has orderly nano array structure, high specific surface area, provides good electrical contact and electronics access, improve electronic transmission performance of the polymer in electrochromic applications.
Description
Technical field
The present invention relates to nanocomposite technical fields.More particularly, to a kind of electrochromic material and its preparation
Methods and applications.
Background technique
Electrochromism refer to the optical properties (reflectivity, transmitance etc.) of material stablize under DC Electric Field,
The phenomenon that reversible color change, the reversible change of color and transparency is shown as in appearance.Electrochromic material is due to it
Information is shown, information stores, the related fieldss such as smart window have potential use, some electrochromic materials are to infrared and microwave
The emissivity of section has certain ability of regulation and control and receives more and more attention.
Organic material is fast with color change, color change is abundant, driving voltage is low, low power consumption and other advantages, and poly- (3,4- bis-
Oxygen ethyl) thiophene (i.e. PEDOT) is a kind of more common conducting polymer, coloration efficiency with higher, low band gaps, compared with
Fast response speed and be widely used in electrochromism field.The evaluation index of electrochromic property has response time, circulation
Service life, coloration efficiency and contrast, wherein contrast is the change degree of quantitative analysis electrochromism color.However, PEDOT
Because its lower contrast is in practical applications by very big restriction.
Elena Poverenov et al. discovery solvent plays a major role to the structure and electrochromic property of PEDOT film,
It is used as solvent using propene carbonate (i.e. PC) during electropolymerization prepares PEDOT, and the contrast of the PEDOT of preparation is up to
71%.Wherein, when main cause is using PC solvent, in polymerization initial stage, a large amount of short oligomer enters solution, on the electrode shape
At relatively long polymer chain, long polymer chain is conducive to the conversion of electrochromic property under voltage, and PC possess compared with
Big dielectric constant (65), higher dielectric are often conducive to polymer polymerizing and generate smoother film.
Er-Chieh Cho et al. replaces the contrast of PEDOT (i.e. PEDOT-F) to be increased to from 45.9% using perfluor
51.7%.Wherein, there is PEDOT-F biggish substituent group big interchain to be caused to separate, and can promote to ion motion, cause more preferable
Ion transmission.
Zhang Hangchuan et al. design construction three-dimensional ordered macroporous PEDOT film, contrast increase to 55% from 40%.It is three-dimensional
Orderly introducing is conducive to the fully doped of more PEDOT molecular structures so that the contact area of ion and film increases.
Zhang Sihang et al. using novel nano cellulose and PEDOT compound method by the contrast of PEDOT from
4.1% is increased to 24.4%.Porous space between nano-cellulose and polymer is conducive to dielectric diffusion, nano combined
Structure provides bigger surface area for redox reaction.
Although these above-mentioned research and utilizations nanostructure high-specific surface area and porous space, these structures are still nothing
Sequence, can not easy access preferably be provided for electron-transport using the order of nanostructure.In addition, having not yet to see will have
Sequence nano-tube array structure is compound with conducting polymer and is used for the document and patent report in electrochromism field.
Therefore, the present invention provides a kind of electrochromic material and its preparation method and application, by ZnO nanotube/array and
Poly- (3,4- dioxoethyl) thiophene is compound, is effectively utilized the order of nanostructure, improves the electronic transmission performance of material.
Summary of the invention
It is an object of the present invention to provide a kind of electrochromic materials.
It is another object of the present invention to provide a kind of preparation methods of electrochromic material.
Third object of the present invention is to provide a kind of application of electrochromic material.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of electrochromic material, the electrochromic material are that poly- (3, the 4- dioxoethyl) thiophene of ZnO nano array-is multiple
Condensation material；Poly- (3,4- dioxoethyl) thiophene composite of ZnO nano array-includes ZnO nano array layer and is formed in
Poly- (3,4- dioxoethyl) the thiophene material layer of ZnO nano array layer surface.
Preferably, the electrochromic material be by the way that the ZnO nano array perpendicular to substrate is formed on the substrate,
Uniformly compound poly- (3,4- dioxoethyl) thiophene is made on ZnO nano array surface；Wherein, ZnO nano array is formed as compound
PEDOT provides big specific surface area and ordered structure, ZnO nano array perpendicular to substrate, provide good electrical contact and
Electron channel.
Preferably, the ZnO nano array layer is ZnO nano-rod array layer or ZnO nanotube/array layer.
Preferably, the length of ZnO nanorod or ZnO nanotube/is 0.1~1.5 μm in the ZnO nano array layer；Into one
Step ground, in certain specific embodiments of the invention, for example, ZnO nanorod or ZnO nano in the ZnO nano array layer
The length of pipe be 0.1~1.3 μm, 0.1~1.22 μm, 0.1~1.2 μm, 0.1~1.0 μm, 1.0~1.5 μm, 1.0~1.3 μm,
1.0~1.22 μm, 1.0~1.2 μm, 1.2~1.5 μm, 1.2~1.3 μm, 1.2~1.22 μm, 1.22~1.5 μm, 1.22~
1.3 μm, 1.3~1.5 μm etc., more preferably 1.2~1.3 μm；Wherein, the more preferably obtained electrochromic material of length range
Performance is more excellent.
Preferably, ZnO nanorod or the mean outside diameter of ZnO nanotube/are 100~400nm in the ZnO nano array layer；
Further, in certain specific embodiments of the invention, for example, ZnO nanorod or ZnO in the ZnO nano array layer
The mean outside diameter of nanotube is 100~350nm, 100~348nm, 100~345nm, 100~340nm, 100~280nm, 280
~400nm, 280~350nm, 280~348nm, 280~345nm, 280~340nm, 340~400nm, 340~350nm, 340
~348nm, 340~345nm, 345~400nm, 345~350nm, 345~348nm, 348~400nm, 348~350nm, 350
~400nm etc., more preferably 340~360nm；Wherein, the more preferably obtained electrochromic material performance of mean outside diameter range
It is more excellent.
Preferably, the mean inside diameter of ZnO nanotube/is 240~328nm in the ZnO nanotube/array layer.Further,
In certain specific embodiments of the invention, for example, the mean inside diameter of ZnO nanotube/is in the ZnO nanotube/array layer
240~328nm, 240~312nm, 240~309nm, 240~302nm, 240~300nm, 240~280nm, 240~265nm,
265~328nm, 265~312nm, 265~309nm, 265~302nm, 265~300nm, 265~280nm, 280~328nm,
280~312nm, 280~309nm, 280~302nm, 280~300nm, 300~328nm, 300~312nm, 300~309nm,
300~302nm, 302~328nm, 302~312nm, 302~309nm, 309~328nm, 309~312nm, 312~328nm
Deng.
Preferably, poly- (3,4- dioxoethyl) the thiophene material layer with a thickness of 1.3~2.5 μm.Further, at this
Invention certain specific embodiments in, for example, poly- (3,4- dioxoethyl) the thiophene material layer with a thickness of 1.3~1.6 μ
M, 1.3~1.5 μm, 1.3~1.4 μm, 1.4~2.5 μm, 1.4~1.6 μm, 1.4~1.5 μm, 1.5~2.5 μm, 1.5~1.6 μ
M, 1.6~2.5 μm etc..
The present invention passes through preferably suitable nano-array length, inside/outside diameter size, poly- (3,4- dioxoethyl) thiophene material
The thickness etc. of layer, so that poly- (3,4- dioxoethyl) the thiophene composites of ZnO nano array-are in electrochromic applications,
It is capable of providing more convenient and fast electronics access, bigger specific surface area is provided, improve electronic transmission performance, be more advantageous to poly- (3,4-
Dioxoethyl) thiophene material electrochemical doping.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of above-mentioned electrochromic material, includes the following steps:
1) ZnO nano array perpendicular to substrate is formed on the substrate；
2) poly- (3,4- dioxoethyl) thiophene polymeric is grown in by ZnO nano battle array made from step 1) using electrochemical method
The electrochromic material is made in the surface of column.
Preferably, in step 1), the substrate is ito glass substrate.
Preferably, the specific steps being formed on the substrate described in step 1) perpendicular to the ZnO nano array of substrate include:
Using electrochemical method in substrate growth of vertical in the ZnO nano-rod array of substrate.The preparation side of the ZnO nano-rod array
Method is with reference to Guang-Wei She etc. in document (APPLIED PHYSICS LETTERS 92,053111Controlled
synthesis of oriented single-crystal ZnO nanotube arrays on transparent
Conductive substrates) described in method, specific steps include: take zinc acetate solution and Klorvess Liquid mixed
Liquid is closed as reaction solution, using three-electrode system, reaction solution is heated to 85 DEG C, first the voltage of application -1.3V.vs.SCE
10s is reacted, then applies voltage response 100s~4000s of -1.0V.vs.SCE, ZnO nano-rod array is made.
Preferably, the specific steps being formed on the substrate described in step 1) perpendicular to the ZnO nano array of substrate include:
Using electrochemical method in substrate growth of vertical in the ZnO nano-rod array of substrate；ZnO nano-rod array obtained is carried out
ZnO nanotube/array is made in etching.
Preferably, the lithographic method with reference to above-mentioned Guang-Wei She etc. document, using chemical etching method, because
For fibre ore ZnO crystal, there are two polar surface (001)There is high surface can belong to metastable phase in the two faces, and put down
Row is then most stable of crystal face in the non-polar plane of c-axis, therefore the speed in (001) crystal face etching will be higher than non-polar plane far away
Etching speed, therefore can etch by the method for etching, on the basis of ZnO nano-rod array and form the nanotube battle array of ZnO
Column.
Preferably, the chemical etching method is harsh etching method or alkaline etching method；ZnO is both sexes oxidation in the present invention
Object can be with H+Ion or OH-Ion reacts, and product is soluble-salt, therefore optional harsh etching method or alkaline etching method, but
Due to harsh etching method poor repeatability, therefore preferably alkaline etching method.
Preferably, when being performed etching using the alkaline etching method, by the substrate obtained for growing and having ZnO nano-rod array
It is immersed in aqueous slkali after cleaning-drying and carries out alkaline etching.
Preferably, the cleaning is to be cleaned using deionized water and dehydrated alcohol.
Preferably, the aqueous slkali is the sodium hydroxide solution that temperature is 75~95 DEG C, pH is 11.2~13.4.Further
Ground, in certain specific embodiments of the invention, for example, the temperature of the sodium hydroxide solution is 75~85 DEG C, 85~95
DEG C etc.；The pH of the sodium hydroxide solution is 11.2~12.8,12.8~13.4 etc..
Preferably, the time of the alkaline etching is 5~30min.Further, in certain specific embodiments of the invention
In, for example, the time of the alkaline etching is 5~15min, 15~30min etc..
Preferably, electrochemical method described in step 2) uses three-electrode system, and wherein platinized platinum is used as to electrode, is saturated sweet
Mercury electrode has the ito glass of ZnO nano array as working electrode as reference electrode, growth.
Preferably, poly- (3,4- dioxoethyl) thiophene polymeric is grown in by step 1) system using electrochemical method in step 2)
Detailed process is as follows on the surface of the ZnO nano array obtained: it is put into electrolyte after combining three-electrode system, application 0.8V~
The voltage of 1.5V.vs.SCE reacts 40s~200s, obtains poly- (3, the 4- dioxoethyl) thiophene composite of ZnO nano array-.
Be in the present invention using the advantage of electrochemical method: polymerization and doping can carry out simultaneously, can be facilitated by changing polymerization current potential
Control film redox state, the thickness of film can also be controlled by electricity, generate the process or life of polymer on the electrode
At polymer be convenient to through electrochemistry or the technique study of pop etc..
Preferably, the electrolyte is the aqueous solution containing paratoluenesulfonic acid sodium salt He (3,4- dioxoethyl) thiophene；It is described
In electrolyte, the concentration of paratoluenesulfonic acid sodium salt and (3,4- dioxoethyl) thiophene i.e. (EDOT) is 0.1mol/L.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of application of above-mentioned electrochromic material in electrochromism field.Electrochromic material of the invention is for electroluminescent
Discoloration field improves the contrast of PEDOT.
In addition, unless otherwise specified, it is raw materials used in the present invention can be by commercially available commercially available, documented by the present invention
Any range includes that any numerical value between end value and end value and any number between end value or end value are constituted
Any subrange.
Beneficial effects of the present invention are as follows:
(1) present invention is compound with PEDOT by ZnO nano array, using the ordered structure of ZnO nano array, with perpendicular to
The ZnO nano array of substrate be carrier, compound upper conducting polymer PEDOT, on the basis of not destroying polymer inherent characteristic,
Improve its optical characteristics.
(2) present invention is carried out ZnO nano array with PEDOT by electrochemical method compound, under relatively lower temp
ZnO seed layer and ZnO nano-structure can be grown in substrate, furthermore growth of the electrochemical method in the surface ZnO growth PEDOT
Mild condition, preparation method is simple, and production cost is low, is easy to large-scale industrial production.
(3) on the one hand the high-specific surface area of orderly ZnO nano array is utilized in electrochromic material of the invention, is oxygen
Change reduction chromophore absorption and the porous matrix structure supported is provided；On the other hand between the ZnO and substrate using electrochemistry preparation
Good electrical contact and one-dimensional ZnO nano-structure direct electric pathway is provided, improve polymer in electrochromic applications
When electronic transmission performance, make ZnO nano array-PEDOT composite material electrochromism performance in contrast it is more individual
PEDOT material has very big promotion.
(4) array structure of the invention in terms of, hence it is evident that better than the effect of unordered nanostructure.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the stereoscan photograph of ZnO nano-rod array in the embodiment of the present invention 1.
Fig. 2 shows the stereoscan photographs of ZnO nanotube/array in the embodiment of the present invention 7.
Fig. 3 shows the stereoscan photograph of ZnO nanotube/array-PEDOT composite material in the embodiment of the present invention 7.
Fig. 4 shows transmitance-time graph of PEDOT in comparative example 1 of the present invention.
Fig. 5 shows transmitance-time graph of ZnO nanotube/array-PEDOT composite material in the embodiment of the present invention 7.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
In the present invention, preparation method is then conventional method unless otherwise specified.Raw material used is equal unless otherwise instructed
It can be obtained from disclosed commercial sources, the percentage is mass percent unless otherwise specified.
ZnO nano-rod array is with reference to Guang-Wei She etc. in document (APPLIED PHYSICS in the present invention
LETTERS 92,053111) described in method.
Embodiment 1
A kind of preparation of electrochromic material, includes the following steps:
1) platinized platinum is polished through the sand paper of 2000 mesh, is cleaned with dichromic acid mixed liquor, rinsed with deionized water, dehydrated alcohol
Completely, as to electrode；
Saturated calomel electrode deionized water, ethanol are clean, as reference electrode；
Ito glass passes through acetone, dehydrated alcohol, each ultrasound 15min of deionized water, and drying is used as working electrode.
2) it weighs 0.0932g zinc acetate to be dissolved in 100mL deionized water, is configured to the zinc acetate solution of 5.0mmol/L；
It weighs 1.4910g potassium chloride to be dissolved in 100mL deionized water, is made into the Klorvess Liquid of 0.2mol/L；
Above-mentioned zinc acetate solution and each 17.5mL mixing of Klorvess Liquid are taken, acetic acid zinc concentration is 2.5mmol/L after mixing,
Potassium chloride concentration is 0.1mol/L, and three electrode groups in step (1) are got togather as reaction solution and be put into reaction solution by mixed liquor
In, solution is heated to 85 DEG C.The first voltage response 10s of application -1.3V.vs.SCE, then apply the voltage of -1.0V.vs.SCE
2000s is reacted, ZnO nano-rod array is made.Fig. 1 shows the stereoscan photograph of ZnO nano-rod array in the present embodiment, scanning
1.2 μm, diameter 350nm of electric microscopic observation length, array is neat, intensive.
3) by step 2) working electrode take out, to the ZnO nano-rod array being attached in ito glass substrate successively into
Row dehydrated alcohol and deionized water cleaning, it is spare after drying.
4) 1) electrode group in is installed, has the ito glass of ZnO nano-rod array as work using growth obtained in 3)
Electrode.
5) electrolyte 35mL is measured, the electrolyte is the water containing paratoluenesulfonic acid sodium salt He (3,4- dioxoethyl) thiophene
Solution, it is 0.1mol/L that wherein paratoluenesulfonic acid sodium salt and (3,4- dioxoethyl) thiophene, which are the concentration of (EDOT),；
4) it is put into after three electrode groups in are got togather, is passed through argon gas, applies the voltage response 40s of 1.0V.vs.SCE.It is sweeping
The thickness for retouching the compound PEDOT of observed under electron microscope is about 1.5 μm.Section, surface are observed by scanning electron microscope
Thickness has certain fluctuating.
6) working electrode in step 5) is taken out, the composite materials being attached to above successively through dehydrated alcohol and is gone
Ionized water cleaning, drying obtain electrochromic material.
Electrochromic material obtained is tested for the property:
Using three-electrode system, it is used as using clean platinum filament to electrode, using the Ag/AgCl of cleaning as reference electrode, with
Compound after cleaning, drying is as working electrode, with lithium perchlorate (the i.e. LiClO of 0.1mol/L4) solution as electrolyte,
It is combined into test device.Ultraviolet-uisible spectrophotometer and electrochemical workstation are combined.Electrochemical workstation is using timing electricity
Stream method, ultraviolet-uisible spectrophotometer use TimeScan, the three-electrode system newly assembled are put into ultraviolet specrophotometer,
Two methods and contrast with test material.It when fading completely, fades, the transmitance difference of coloring process is contrast, survey
The contrast value of examination is 18.73%.
Embodiment 2
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
In step 2) in the preparation of ZnO nano-rod array, ZnO is made in the voltage response 100s of application -1.0V.vs.SCE
Nanometer stick array.0.10 μm of nanorod length is observed under scanning electron microscope, 0.10 μm of diameter, is arranged sparse.
Apply the voltage response 40s of 1.0V.vs.SCE in step 5).1.40 μm of the thickness average out to of the PEDOT of growth leads to
Electron microscope observation section is over-scanned, there is certain fluctuating on surface.
Electrochromic material obtained is tested for the property:
Method and step is 10.16% with embodiment 1, the contrast of test.
Embodiment 3
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
In step 2) in the preparation of ZnO nano-rod array, ZnO is made in the voltage response 4000s of application -1.0V.vs.SCE
Nanometer stick array.1.50 μm of length, diameter 400nm are observed under scanning electron microscope, array is neat, intensive.
Apply the voltage response 40s of 1.0V.vs.SCE in step 5).1.60 μm of the thickness average out to of the PEDOT of growth leads to
Electron microscope observation section is over-scanned, there is certain fluctuating on surface.
Electrochromic material obtained is tested for the property:
Method and step is 12.55% with embodiment 1, the contrast of test.
Embodiment 4
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
In step 2) in the preparation of ZnO nano-rod array, ZnO is made in the voltage response 1000s of application -1.0V.vs.SCE
Nanometer stick array.1.0 μm of length, diameter 280nm are observed under scanning electron microscope, array is neat, intensive.
Apply the voltage response 40s of 1.0V.vs.SCE in step 5).1.50 μm of the thickness average out to of the PEDOT of growth leads to
Electron microscope observation section is over-scanned, there is certain fluctuating on surface.
Electrochromic material obtained is tested for the property:
Method and step is 15.62% with embodiment 1, the contrast of test.
Embodiment 5
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
Apply the voltage response 100s of 0.8V.vs.SCE in step 5).1.30 μm of the thickness average out to of the PEDOT of growth,
Section is observed by scanning electron microscope, there is certain fluctuating on surface.
Electrochromic material obtained is tested for the property:
Method and step is 16.92% with embodiment 1, the contrast of test.
Embodiment 6
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
Apply the voltage response 300s of 1.5V.vs.SCE in step 5).2.50 μm of the thickness average out to of the PEDOT of growth.
Electrochromic material obtained is tested for the property:
Method and step is 15.38% with embodiment 1, the contrast of test.
Embodiment 7
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
The ZnO nano-rod array in step 3) is first subjected to alkaline etching in step 4):
It prepares pH and is 13.4 NaOH aqueous slkali, and be heated to 85 DEG C, growth in step 3) is had into ZnO nano-rod array
Ito glass immerses the aqueous slkali, carries out the alkaline etching of 30min, to the ZnO nano array after etching by dehydrated alcohol and go from
Sub- water cleaning, it is spare after drying.It is 1.20 μm, mean outside diameter 345nm that observation, which obtains length, under a scanning electron microscope, erosion
The inner cavity mean inside diameter carved is the ZnO nanotube/array of 312nm.
There is the ito glass of ZnO nanotube/array as working electrode using growth made from this step.
Fig. 2 shows the stereoscan photographs of ZnO nanotube/array in the present embodiment.
Fig. 3 shows the stereoscan photograph of ZnO nanotube/array-PEDOT composite material in the present embodiment, passes through scanning electricity
The micro- sem observation section of son, there is certain fluctuating on surface.
Fig. 5 shows transmitance-time graph of ZnO nanotube/array-PEDOT composite material in the embodiment of the present invention.Table
It shows in coloured state and colour fading state cyclic process, the variation of transmitance, highest transmitance is colour fading state transmitance, minimum transmission
Rate is coloured state transmitance, their difference is the value of contrast.
Electrochromic material obtained is tested for the property:
Method and step is 37.62% with embodiment 1, the contrast of test.
The electrochromic material of the embodiment has obtained optimal application effect.
Embodiment 8
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
The time 5min of alkaline etching in step 4).It is 1.22 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 350nm, and the inner cavity mean inside diameter etched is the ZnO nanotube/array of 265nm.
Electrochromic material obtained is tested for the property:
Method and step is 28.26% with embodiment 1, the contrast of test.
Embodiment 9
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
The time 15min of alkaline etching in step 4).It is 1.22 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 348nm, and the inner cavity mean radius etched is the nano-tube array of 280nm.
Electrochromic material obtained is tested for the property:
Method and step is 31.26% with embodiment 1, the contrast of test.
Embodiment 10
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
75 DEG C of the temperature of alkaline etching in step 4).It is 1.22 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 350nm, and the inner cavity mean inside diameter etched is the nano-tube array of 300nm.
Electrochromic material obtained is tested for the property:
Method and step is 35.61% with embodiment 1, the contrast of test.
Embodiment 11
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
95 DEG C of the temperature of alkaline etching in step 4).It is 1.18 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 340nm, and the inner cavity mean inside diameter etched is the nano-tube array of 328nm.
Electrochromic material obtained is tested for the property:
Method and step is 34.83% with embodiment 1, the contrast of test.
Embodiment 12
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
The pH of alkaline etching is 11.2 in step 4).It is 1.22 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 350nm, and the inner cavity mean inside diameter etched is the nano-tube array of 302nm.
Electrochromic material obtained is tested for the property:
Method and step is 32.52% with embodiment 1, the contrast of test.
Embodiment 13
A kind of preparation of electrochromic material, step with embodiment 7, the difference is that:
The pH of alkaline etching is 12.8 in step 4).It is 1.22 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 350nm, and the inner cavity mean inside diameter etched is the nano-tube array of 309nm.
Electrochromic material obtained is tested for the property:
Method and step is 33.54% with embodiment 1, the contrast of test.
The result of 7~embodiment of embodiment 13 is summarized to table 1: such as being drawn a conclusion as can be drawn from Table 1: similarly being lost
Carve temperature, in the case of same pH, different etching periods compare (7~embodiment of embodiment 9), at etching period 30 minutes, material
Expect performance more preferably；Same pH, same etching period, different temperatures compare (embodiment 7, embodiment 10, embodiment 11), lose
When carving 85 DEG C of temperature, material property is more preferably；Compare (embodiment 7, implementation in same etch temperature, same etching period, difference pH
Example 12, embodiment 13), when pH is 13.4, material property is more preferably.But generally, for same ZnO nanorod, using this
Different etching condition in invention can get preferable material property performance although having certain influence to material property.
Table 1: the influence of etching temperature, time, pH to electrochromism result
| Temperature (DEG C) | Etching period (minute) | pH | Contrast | |
| Embodiment 7 | 85 | 30 | 13.4 | 37.62% |
| Embodiment 8 | 85 | 5 | 13.4 | 28.26% |
| Embodiment 9 | 85 | 15 | 13.4 | 31.26% |
| Embodiment 10 | 75 | 30 | 13.4 | 35.61% |
| Embodiment 11 | 95 | 30 | 13.4 | 34.83% |
| Embodiment 12 | 85 | 30 | 11.2 | 32.52% |
| Embodiment 13 | 85 | 30 | 12.8 | 33.54% |
Embodiment 14
A kind of preparation of electrochromic material, step prepare nanometer stick array with embodiment 4, the difference is that: then
Nanometer rods are etched according to the step of embodiment 7.It is 1.0 μm that observation, which obtains length, under a scanning electron microscope, average
Overall diameter is 280nm, and the inner cavity mean inside diameter etched is the nano-tube array of 240nm.
Electrochromic material obtained is tested for the property:
Method and step is 19.38% with embodiment 1, the contrast of test.
Embodiment 14 and embodiment 4 are compared, the ZnO nanorod of electrochemical growth on ito glass is etched into ZnO and is received
Electrochemical growth PEDOT, the electronic color-changing performance of material are better than the electrochemical growth ZnO nano on ito glass again after mitron
After stick, Direct Electrochemistry grows the material property of PEDOT.
Comparative example 1
A kind of preparation of electrochromic material, step with embodiment 1, the difference is that:
Without step 2)~step 4), directly using ito glass as working electrode in step 5), on ito glass surface
PEDOT is grown, pure PEDOT is prepared.Observing the thickness of PEDOT under a scanning electron microscope is about 140nm, passes through scanning electron
Micro- sem observation section, and surface relative relief is smaller.
Fig. 4 shows transmitance-time graph of PEDOT in this comparative example 1: representing coloured state and colour fading state is circulated throughout
Cheng Zhong, the variation of transmitance, highest transmitance are colour fading state transmitance, and minimum transmitance is coloured state transmitance, they
Difference is the value of contrast.
Electrochromic material obtained is tested for the property:
Method and step is 4.69% with embodiment 1, the contrast of test.
Conclusion: only electrochemical growth PEDOT is as electrochromic material in ITO substrate, right in electrochromic applications
Only have 4.69% than degree, and uses method of the invention, the first electrochemical growth ZnO nanorod on ITO, then electrochemical growth
PEDOT can be such that its contrast in electrochromic applications improves to 16.92%, more preferably, the first electrochemical growth on ITO
ZnO nanorod, then after being etched and forming ZnO nanotube/, then electrochemical growth PEDOT, it can make it in electrochromic applications
Contrast improve to 37.62%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of electrochromic material, which is characterized in that the electrochromic material is poly- (3, the 4- dioxy second of ZnO nano array-
Base) thiophene composite；Poly- (3,4- dioxoethyl) thiophene composite of ZnO nano array-includes ZnO nano array layer
With poly- (3,4- dioxoethyl) the thiophene material layer for being formed in ZnO nano array layer surface.
2. electrochromic material according to claim 1, which is characterized in that the electrochromic material is by substrate
The upper ZnO nano array formed perpendicular to substrate, in uniform compound poly- (3,4- dioxoethyl) the thiophene system in ZnO nano array surface
?.
3. electrochromic material according to claim 1, which is characterized in that the ZnO nano array layer is ZnO nanorod
Array layer or ZnO nanotube/array layer.
4. electrochromic material according to claim 3, which is characterized in that ZnO nano in the ZnO nano-rod array layer
The length of stick is 0.1~1.5 μm；The mean outside diameter of ZnO nanorod is 100~400nm in the ZnO nano-rod array layer.
5. electrochromic material according to claim 3, which is characterized in that ZnO nano in the ZnO nanotube/array layer
The length of pipe is 0.1~1.5 μm；The mean outside diameter of ZnO nanotube/is 100~400nm in the ZnO nanotube/array layer；Institute
The mean inside diameter for stating ZnO nanotube/in ZnO nanotube/array layer is 240~328nm.
6. electrochromic material according to claim 1, which is characterized in that poly- (3,4- dioxoethyl) the thiophene material
Layer with a thickness of 1.3~2.5 μm.
7. a kind of preparation method of the electrochromic material as described in any one of claim 1~6 claim, feature exist
In including the following steps:
1) ZnO nano array perpendicular to substrate is formed on the substrate；
2) poly- (3,4- dioxoethyl) thiophene polymeric is grown in by ZnO nano array made from step 1) using electrochemical method
The electrochromic material is made in surface.
8. preparation method according to claim 7, which is characterized in that be formed on the substrate described in step 1) perpendicular to base
The specific steps of the ZnO nano array at bottom include: using electrochemical method in substrate growth of vertical in the ZnO nanorod of substrate
Array.
9. preparation method according to claim 7, which is characterized in that be formed on the substrate described in step 1) perpendicular to base
The specific steps of the ZnO nano array at bottom include: using electrochemical method in substrate growth of vertical in the ZnO nanorod of substrate
Array；ZnO nano-rod array obtained is performed etching, ZnO nanotube/array is made.
10. a kind of electrochromic material answering in electrochromism field as described in any one of claim 1~6 claim
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810004358.XA CN109988551B (en) | 2018-01-03 | 2018-01-03 | Electrochromic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810004358.XA CN109988551B (en) | 2018-01-03 | 2018-01-03 | Electrochromic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109988551A true CN109988551A (en) | 2019-07-09 |
| CN109988551B CN109988551B (en) | 2022-07-01 |
Family
ID=67128398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810004358.XA Active CN109988551B (en) | 2018-01-03 | 2018-01-03 | Electrochromic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109988551B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115128878A (en) * | 2021-03-25 | 2022-09-30 | 中国科学院上海硅酸盐研究所 | Flexible electrochromic device based on in-situ zinc oxide nano-rod and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456579A (en) * | 2008-12-05 | 2009-06-17 | 天津大学 | Method for synthesizing zinc oxide nano tube array by low-temperature hydrothermal method |
| CN102266775A (en) * | 2011-06-09 | 2011-12-07 | 中国科学院理化技术研究所 | Photo-catalytic material based on zinc oxide nanometer linear array modified with cuprous oxide quantum dots, and preparation method and application thereof |
| CN104164698A (en) * | 2014-07-25 | 2014-11-26 | 中国科学院理化技术研究所 | Method for enhancing monocrystal zinc oxide nanorod surface enhanced Raman scattering signals |
| CN105018918A (en) * | 2015-06-30 | 2015-11-04 | 长安大学 | Growth method for ZnO nanotube array |
-
2018
- 2018-01-03 CN CN201810004358.XA patent/CN109988551B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456579A (en) * | 2008-12-05 | 2009-06-17 | 天津大学 | Method for synthesizing zinc oxide nano tube array by low-temperature hydrothermal method |
| CN102266775A (en) * | 2011-06-09 | 2011-12-07 | 中国科学院理化技术研究所 | Photo-catalytic material based on zinc oxide nanometer linear array modified with cuprous oxide quantum dots, and preparation method and application thereof |
| CN104164698A (en) * | 2014-07-25 | 2014-11-26 | 中国科学院理化技术研究所 | Method for enhancing monocrystal zinc oxide nanorod surface enhanced Raman scattering signals |
| CN105018918A (en) * | 2015-06-30 | 2015-11-04 | 长安大学 | Growth method for ZnO nanotube array |
Non-Patent Citations (2)
| Title |
|---|
| MOVAFFAQ KATEB ET AL.: "Fast switching and high contrast electrochromic device based on PEDOT nanotube grown on ZnO nanowires", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
| MOVAFFAQ KATEB ET AL.: "ZnO–PEDOT core–shell nanowires:An ultrafast,high contrast and transparent electrochromic display", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115128878A (en) * | 2021-03-25 | 2022-09-30 | 中国科学院上海硅酸盐研究所 | Flexible electrochromic device based on in-situ zinc oxide nano-rod and preparation method thereof |
| CN115128878B (en) * | 2021-03-25 | 2023-12-08 | 中国科学院上海硅酸盐研究所 | Flexible electrochromic device based on in-situ zinc oxide nanorods and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109988551B (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shi et al. | Structure modulated amorphous/crystalline WO3 nanoporous arrays with superior electrochromic energy storage performance | |
| CN103469272B (en) | Tungsten trioxide/polyanilinecore-shell core-shell nanowire array radiochromic film and preparation method thereof | |
| Li et al. | Self-seeded growth of nest-like hydrated tungsten trioxide film directly on FTO substrate for highly enhanced electrochromic performance | |
| Sakthivel et al. | Electrochemical synthesis of poly (3, 4-ethylenedioxythiophene) on terbium hexacyanoferrate for sensitive determination of tartrazine | |
| Wang et al. | A new electrodeposition approach for preparing polyoxometalates-based electrochromic smart windows | |
| CN103996549B (en) | A kind of preparation method of cellulose nano-fibrous electrochromism ultracapacitor | |
| CN106563442B (en) | A kind of preparation method and applications of ultra-thin two water tungstic trioxide nano-slice | |
| Wu et al. | Electrochromic properties of nanostructured tungsten oxide films prepared by surfactant-assisted sol–gel process | |
| CN103903870A (en) | Super capacitor capable of changing colors and being stretched and manufacturing method thereof | |
| CN104788022B (en) | The application of flake nano silver electrochomeric films | |
| CN101214932A (en) | Method for preparing nanometer tin selenide | |
| CN106540673A (en) | A kind of three-dimensional TiO2The synthetic method of/ZnO heterojunction array | |
| CN112111119A (en) | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof | |
| CN112239590A (en) | High-performance polylactic acid nano composite material and preparation method thereof | |
| CN108298832A (en) | Tungsten oxide electrochomeric films and preparation method thereof with EO-1 hyperion adjustable range | |
| Wang et al. | High optical switching speed and flexible electrochromic display based on WO3 nanoparticles with ZnO nanorod arrays’ supported electrode | |
| Liu et al. | Transparent, smooth, and sustainable cellulose-derived conductive film applied for the flexible electronic device | |
| Vankova et al. | WO 3 nanorolls self-assembled as thin films by hydrothermal synthesis | |
| CN104311798A (en) | Preparation method of conductive polymer film having inverse opal structure | |
| CN109988551A (en) | A kind of electrochromic material and its preparation method and application | |
| Dewan et al. | Multi-shelled NiO hollow microspheres as bifunctional materials for electrochromic smart window and non-enzymatic glucose sensor | |
| CN112552896A (en) | Electrochromic conductive polymer composite film and device preparation method | |
| CN101492536B (en) | Nano-polyaniline material with morphology inheritance and electrochemical preparation method | |
| Tao et al. | Preparation of Co doped NiO thin films with excellent switching time and coloring efficiency through sol-gel spin coating | |
| CN107188236B (en) | A kind of preparation method of tungsten oxide nanometer band structure electrochomeric films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |