CN105862071B - A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture - Google Patents
A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture Download PDFInfo
- Publication number
- CN105862071B CN105862071B CN201610238909.XA CN201610238909A CN105862071B CN 105862071 B CN105862071 B CN 105862071B CN 201610238909 A CN201610238909 A CN 201610238909A CN 105862071 B CN105862071 B CN 105862071B
- Authority
- CN
- China
- Prior art keywords
- poly
- agar
- film
- nano particle
- rthylene dioxythiophene
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Abstract
The invention discloses a kind of aperture it is controllable poly- (3, 4- ethene dioxythiophenes) film preparation method, first prepare the different agar nano particle of grain size, it is coated onto working electrode surface, recycle electrochemical polymerization, polyase 13 on the working electrode (s, 4- ethene dioxythiophene monomers, poly- (3 are obtained in electrode surface, 4- ethene dioxythiophenes)/agar nano particle laminated film, then by poly- (3, 4- ethene dioxythiophenes)/agar nano particle laminated film from electrode surface remove, it immerses and removes agar nano particle in hot water, obtain porous poly- (3, 4- ethene dioxythiophenes) film.Poly- (3,4-rthylene dioxythiophene) membrane pore size disclosed by the invention is controllable, has excellent mechanical property and electric property, and the preparation method of poly- (3,4-rthylene dioxythiophene) film is simple, is not necessarily to complex device, organic solvent is not needed, it is environmentally safe.
Description
Technical field
The present invention relates to a kind of preparation methods of controllable poly- (3,4-rthylene dioxythiophene) film in aperture, belong to polymer
Field of functional materials.
Background technology
Poly- (3,4-rthylene dioxythiophene) is a kind of conducting polymer, its molecular structure determine it have electric conductivity it is high,
The advantages that chemical stability is good, high temperature resistant, light transmission is high has been applied in solar cell, transparent conductive film, photoelectric device
Equal fields.The synthetic method of poly- (3,4- ethene dioxythiophenes) can be divided into chemical oxidation method and electrochemical polymerization.Chemistry
Method for oxidation is that oxidant is utilized in dicyandiamide solution, such as persulfate or trivalent iron salt, causes 3,4-rthylene dioxythiophene list
Body carries out oxidation polymerization, obtains powdered poly- (3,4-rthylene dioxythiophene).Electrochemical polymerization method uses three-electrode system (work
Make electrode, to electrode and reference electrode), allow 3,4-rthylene dioxythiophene monomer in working electrode table under DC Electric Field
Oxidation polymerization occurs for face, obtains conductive polymer film.
The conducting polymer thin film with diverse microcosmic structure is prepared, and the microstructure for regulating and controlling film is current conductive poly-
Close one of the important topic in object field.Once it had been reported that and poly- (3,4-rthylene dioxythiophene) film is directly prepared for using spin-coating method,
Also it has been reported that using modification Langmuir-Blodget (LB) embrane methods through 3,4- ethene dioxythiophenes monomer in LB film hydrophilic groups
It polymerize between group, is prepared for poly- (3,4- ethene dioxythiophenes) film.But these methods are difficult poly- (the 3,4- ethylene dioxy thiophenes of control
Pheno) film microstructure.Chinese invention patent application CN101445618 discloses a kind of poly- (3,4- ethylene two of self-supporting
Oxygen thiophene) porous membrane preparation method.The invention is using organic solvent by organic dyestuff from poly- (3,4-rthylene dioxythiophene)
It is extracted in film, to obtain poly- (3,4-rthylene dioxythiophene) porous membrane, the above method needs to use organic dyestuff
With organic solvent, there is larger pollution to environment, and is only capable of regulating and controlling poly- (3,4- ethylene by the sweep speed of cyclic voltammetry
Dioxy thiophene) porous membrane aperture, then it is more that cannot polyaniline be regulated and controled for electrochemical method for synthesizing such as constant current or constant potentials
The aperture of hole film.Therefore it is necessary to which a kind of environmentally protective method of exploitation prepares controllable poly- (3, the 4- ethylene two in aperture
Oxygen thiophene) film.
Invention content
The present invention is to overcome above-mentioned shortcoming, and it is an object of the present invention to provide a kind of poly- (3, the 4- ethylene dioxies of aperture controllably
Thiophene) film preparation method.Poly- (3,4-rthylene dioxythiophene) membrane pore size disclosed by the invention is controllable, has excellent power
Performance and electric property are learned, and the preparation method of poly- (3,4-rthylene dioxythiophene) film is simple, is not necessarily to complex device, is not required to
Organic solvent is wanted, it is environmentally safe.
To achieve the goals above, the technical scheme is that：A kind of poly- (3,4- ethylene dioxy thiophenes that aperture is controllable
Pheno) film preparation method, include the following steps：
1) agar dissolving is configured to the aqueous solution of a concentration of 0.1-10% mass fractions, takes aqueous agar solution 3mL, fat
Sour sugar ester 2g, peanut oil 45mL are centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) the agar nano particle 0.1-0.5g that step 1) obtains is taken to be added in 20mL water, after stirring 5-10 minutes, by work
It is immersed 5 minutes as electrode, then takes out working electrode, dried at 50 DEG C；
3) the 3,4-rthylene dioxythiophene monomer of 1-3mmol, 1-5mmol supporting electrolytes are dispersed in the water of 50mL,
It is placed in one by reference electrode, to electrode and working electrode, carries out electrochemistry formated under nitrogen protection；
4) laminated film for poly- (the 3,4-rthylene dioxythiophene)/agar nano particle for obtaining step 3) is from working electrode
Sur-face peeling immerses 1-4 hours in 90-95 DEG C of hot water and removes agar nano particle, obtains porous poly- (3,4- ethylene dioxy thiophenes
Pheno) film.
By said program, the supporting electrolyte is for neopelex, dodecyl sodium sulfate or to toluene sulphur
Sour sodium.
By said program, the reference electrode is saturated calomel electrode, is platinized platinum to electrode, and working electrode is ITO conductive
Glass, stainless steel substrates, platinized platinum or gold plaque.
By said program, the electrochemistry formated uses galvanostatic method, Faradaic current 2-5mA/cm2, polymerization time is
10-30 minutes；Or potentiostatic method, working electrode potential 1.3V, polymerization time are 10-30 minutes.
Compared with prior art, the present invention has following prominent effect：
1) agar causes poly- (3,4-rthylene dioxythiophene) film to have different microstructures as soft template；2) will
The electrochemical polymerization of 3,4-rthylene dioxythiophene is on the working electrode that agar nano particle is contained on surface, then by agar nanometer
The dissolving abjection of grain in the hot water, obtains porous poly- (3,4-rthylene dioxythiophene) film；3) by selecting various concentration
Aqueous agar solution can prepare the agar nano particle with different-grain diameter, and then it is thin to regulate and control poly- (3,4-rthylene dioxythiophene)
The aperture of film；4) poly- (3,4- ethene dioxythiophenes) film has good mechanical property and electric property, and (tensile strength is
4.5-7.8MPa conductivity 0.2-3.7S/cm)；5) preparation method is simple, is not necessarily to complex device, does not need organic solvent, right
Environmental nonpollution.
Specific implementation mode
In order to better understand the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1：
1) it configures agar dissolving to aqueous solution of the concentration 4%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, peanut
Oily 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) the agar nano particle 0.15g that step 1) obtains is taken to be added in 20mL water, stirring is after ten minutes, conductive by ITO
Glass working electrode is immersed 5 minutes, then takes out ITO electro-conductive glass working electrodes, is dried at 50 DEG C；
3) 3,4- ethene dioxythiophenes monomer, the 1mmol neopelexes of 1mmol are dispersed in the water of 50mL
In, saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and ITO electro-conductive glass working electrodes, adopt at room temperature
Electrochemistry formated, working electrode potential 1.3V are carried out with potentiostatic method, polymerization time is 20 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) is conductive from ITO
Glass working electrode surface is removed, and is immersed 1 hour in 95 DEG C of hot water and is removed agar nano particle, obtaining average pore size is about
Poly- (3,4- ethene dioxythiophenes) film of 175nm.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 6.1MPa, electricity
Conductance is 1.1S/cm.
Embodiment 2：
1) it configures agar dissolving to aqueous solution of the concentration 6%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, peanut
Oily 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) it takes the agar nano particle 0.3g that step 1) obtains to be added in 20mL water, stirs after five minutes, by stainless steel substrates work
It is immersed 5 minutes as electrode, then takes out stainless steel substrates working electrode, dried at 50 DEG C；
3) the 3,4-rthylene dioxythiophene monomer of 2mmol, 4mmol dodecyl sodium sulfates are dispersed in the water of 50mL,
Saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and stainless steel substrates working electrode, use permanent electricity at room temperature
Stream method carries out electrochemistry formated, Faradaic current 5mA/cm2, polymerization time is 25 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) is from stainless steel substrates
Working electrode surface is removed, and is immersed 2 hours in 92 DEG C of hot water and is removed agar nano particle, it is about 214nm's to obtain average pore size
Poly- (3,4- ethene dioxythiophenes) film.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 5.8MPa, and conductivity is
0.7S/cm。
Embodiment 3：
1) it configures agar dissolving to aqueous solution of the concentration 0.5%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, flower
Oil generation 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) it takes the agar nano particle 0.4g that step 1) obtains to be added in 20mL water, after stirring 8 minutes, working electrode is soaked
Enter wherein 5 minutes, then take out gold plaque working electrode, is dried at 50 DEG C；
3) the 3,4-rthylene dioxythiophene monomer of 2mmol, 4mmol paratoluenesulfonic acid sodium salts are dispersed in the water of 50mL, it will
Saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and gold plaque working electrode, at room temperature use galvanostatic method into
Row electrochemistry formated, Faradaic current 3mA/cm2, polymerization time is 30 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) works from gold plaque
Electrode surface is removed, and is immersed 1.5 hours in 94 DEG C of hot water and is removed agar nano particle, and it is about the poly- of 91nm to obtain average pore size
(3,4- ethene dioxythiophenes) film.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 6.8MPa, and conductivity is
2.2S/cm。
Embodiment 4：
1) it configures agar dissolving to aqueous solution of the concentration 1%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, peanut
Oily 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) it takes the agar nano particle 0.15g that step 1) obtains to be added in 20mL water, after stirring 6 minutes, platinized platinum is worked
Electrode is immersed 5 minutes, then takes out platinized platinum working electrode, is dried at 50 DEG C；
3) 3,4- ethene dioxythiophenes monomer, the 4.5mmol neopelexes of 1.5mmol are dispersed in 50mL's
In water, saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and platinized platinum working electrode, use permanent electricity at room temperature
Position method carries out electrochemistry formated, working electrode potential 1.3V, and polymerization time is 30 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) is from platinum plate electrode
Sur-face peeling immerses 1 hour in 95 DEG C of hot water and removes agar nano particle, obtains poly- (3, the 4- second that average pore size is about 112nm
Alkene dioxy thiophene) film.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 4.5-7.8MPa, conductivity 0.2-
3.7S/cm。
Embodiment 5：
1) it configures agar dissolving to aqueous solution of the concentration 8%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, peanut
Oily 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) it takes the agar nano particle 0.3g that step 1) obtains to be added in 20mL water, stirs after ten minutes, by ITO conduction glass
Glass working electrode is immersed 5 minutes, then takes out ITO electro-conductive glass working electrodes, is dried at 50 DEG C；
3) 3,4- ethene dioxythiophenes monomer, the 4mmol dodecyl sodium sulfates of 2.5mmol are dispersed in the water of 50mL
In, saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and ITO electro-conductive glass working electrodes, adopt at room temperature
Electrochemistry formated, Faradaic current 3.5mA/cm are carried out with galvanostatic method2, polymerization time is 25 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) is conductive from ITO
Glass working electrode surface is removed, and is immersed 3 hours in 90 DEG C of hot water and is removed agar nano particle, obtaining average pore size is about
Poly- (3,4- ethene dioxythiophenes) film of 346nm.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 4.7MPa, electricity
Conductance is 0.3S/cm.
Embodiment 6：
1) it configures agar dissolving to aqueous solution of the concentration 0.2%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, flower
Oil generation 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) the agar nano particle 0.25g that step 1) obtains is taken to be added in 20mL water, after stirring 7 minutes, by stainless steel substrates
Working electrode is immersed 5 minutes, then takes out stainless steel substrates working electrode, is dried at 50 DEG C；
3) the 3,4-rthylene dioxythiophene monomer of 2mmol, 5mmol paratoluenesulfonic acid sodium salts are dispersed in the water of 50mL, it will
Saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and stainless steel substrates working electrode, use constant potential at room temperature
Method carries out electrochemistry formated, working electrode potential 1.3V, and polymerization time is 30 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) is from stainless steel substrates
Working electrode surface is removed, and is immersed 1.5 hours in 93 DEG C of hot water and is removed agar nano particle, it is about 65nm's to obtain average pore size
Poly- (3,4- ethene dioxythiophenes) film.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 7.5MPa, and conductivity is
3.4S/cm。
Embodiment 7：
1) it configures agar dissolving to aqueous solution of the concentration 3%, takes aqueous agar solution 3mL, sucrose fatty acid ester 2g, peanut
Oily 45mL is centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) the agar nano particle 0.2g that step 1) obtains is taken to be added in 20mL water, after stirring 8 minutes, by ITO conduction glass
Glass working electrode is immersed 5 minutes, then takes out ITO electro-conductive glass working electrodes, is dried at 50 DEG C；
3) 3,4- ethene dioxythiophenes monomer, the 3.5mmol neopelexes of 1.5mmol are dispersed in 50mL's
In water, saturated calomel electrode reference electrode, platinized platinum are placed in one to electrode and gold plaque working electrode, use permanent electricity at room temperature
Stream method carries out electrochemistry formated, Faradaic current 4.5mA/cm2, polymerization time is 30 minutes；
4) laminated film for poly- (3,4- the ethene dioxythiophenes)/agar nano particle for obtaining step 3) works from gold plaque
Electrode surface remove, immerse 90 DEG C of hot water in 2 hours remove agar nano particle, obtain average pore size be about 160nm it is poly- (3,
4- ethene dioxythiophenes) film.The tensile strength of poly- (3,4-rthylene dioxythiophene) film is 6.2MPa, conductivity 1.3S/
cm。
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of the technological parameter (such as temperature, time) of the present invention,
Interval value can realize the present invention, embodiment numerous to list herein.
Claims (4)
1. a kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture, includes the following steps：
1) agar dissolving is configured to the aqueous solution of a concentration of 0.1-10% mass fractions, takes aqueous agar solution 3mL, aliphatic acid sugar
Ester 2g, peanut oil 45mL are centrifugally separating to obtain agar nano particle after 60 DEG C are uniformly mixed；
2) the agar nano particle 0.1-0.5g that step 1) obtains is taken to be added in 20mL water, after stirring 5-10 minutes, by work electricity
Pole is immersed 5 minutes, then takes out working electrode, is dried at 50 DEG C；
3) the 3,4-rthylene dioxythiophene monomer of 1-3mmol, 1-5mmol supporting electrolytes are dispersed in the water of 50mL, will be joined
It is placed in one than electrode, to electrode and working electrode, carries out electrochemistry formated under nitrogen protection；
4) laminated film for poly- (the 3,4-rthylene dioxythiophene)/agar nano particle for obtaining step 3) is from working electrode surface
Stripping immerses 1-4 hours in 90-95 DEG C of hot water and removes agar nano particle, obtains porous poly- (3,4-rthylene dioxythiophene)
Film.
2. the preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture according to claim 1, feature
It is：The supporting electrolyte is neopelex, dodecyl sodium sulfate or paratoluenesulfonic acid sodium salt.
3. the preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture according to claim 1, feature
It is：The reference electrode be saturated calomel electrode, to electrode be platinized platinum, working electrode be ITO electro-conductive glass, stainless steel substrates,
Platinized platinum or gold plaque.
4. the preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture according to claim 1, feature
It is：The electrochemistry formated uses galvanostatic method, Faradaic current 2-5mA/cm2, polymerization time is 10-30 minutes；Or it is permanent
Potentiometry, working electrode potential 1.3V, polymerization time are 10-30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610238909.XA CN105862071B (en) | 2016-04-15 | 2016-04-15 | A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610238909.XA CN105862071B (en) | 2016-04-15 | 2016-04-15 | A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105862071A CN105862071A (en) | 2016-08-17 |
| CN105862071B true CN105862071B (en) | 2018-11-06 |
Family
ID=56633360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610238909.XA Expired - Fee Related CN105862071B (en) | 2016-04-15 | 2016-04-15 | A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105862071B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10140666C2 (en) * | 2001-08-24 | 2003-08-21 | Univ Braunschweig Tech | Process for producing a conductive structured polymer film and use of the process |
| KR100993848B1 (en) * | 2006-12-30 | 2010-11-11 | 고려대학교 산학협력단 | Polythiophene based polymer nano material and method for controlling the properties of photoluminesence and conductivity of the same |
| KR20090029982A (en) * | 2007-09-19 | 2009-03-24 | 삼성전자주식회사 | Method for preparing electrochromic polymer nanotube and electrochromic device utilizing the same |
| KR20090085788A (en) * | 2008-02-05 | 2009-08-10 | 고려대학교 산학협력단 | Poly (3,4-ethylenedioxythiophene)(pedot) nanowires for organic photoelectric device, method for cotrolling the properties of photoluminescence |
| CN101418214B (en) * | 2008-12-08 | 2012-05-02 | 浙江大学 | Electrochromic material and preparation method thereof |
| CN101445618B (en) * | 2009-01-06 | 2011-03-23 | 武汉工程大学 | A preparation method of self-supporting poly (3, 4- ethylenedioxythiophene) porous membrane |
| CN101781094A (en) * | 2009-01-16 | 2010-07-21 | 中国科学院理化技术研究所 | Method for directly preparing poly (3,4) dioxoethyl-thiophene film on surface of conductive glass |
| CN102020832B (en) * | 2010-11-25 | 2012-08-29 | 武汉大学 | Conductive poly 3,4-ethylene dioxy thiophene film and preparation method thereof |
| CN102321235B (en) * | 2011-06-28 | 2013-04-17 | 四川大学 | Preparation method of poly-3,4-ethylene dioxythiophene and compound arrays thereof |
-
2016
- 2016-04-15 CN CN201610238909.XA patent/CN105862071B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105862071A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105218864B (en) | A kind of Electrochromic composite material and device preparation method based on nano-cellulose | |
| CN105887126B (en) | It is poly-（3,4 ethylenedioxy thiophenes）Nano wire film and its synthetic method and application | |
| CN107610817B (en) | A kind of LBL self-assembly silver nanowires flexible conductive film | |
| CN111074258B (en) | Method for blackening copper foil and recovering primary color at room temperature | |
| CN106543415B (en) | Thin polymer film and the preparation method and application thereof based on intersection construction conjugated molecule | |
| CN102629684A (en) | Polyaniline-graphene composite film and its preparation method, cells and e-books | |
| CN105428080A (en) | Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof | |
| CN104311798A (en) | Preparation method of conductive polymer film having inverse opal structure | |
| CN108286054A (en) | A kind of diaphragm of electrolyzer and methods for using them of electrolysis carbon dioxide carbon monoxide | |
| CN105424786A (en) | Method for preparation of peroxide polyaniline/beta-cyclodextrin composite film modified electrode and electrochemical recognition of tryptophan enantiomers | |
| CN108927019A (en) | A kind of preparation method of block copolymer film and the salt error power generation film of functional pore membrane hydridization | |
| CN107382095A (en) | Color-variable, stable circulation PANI electrochomeric films preparation method | |
| CN107895812A (en) | A kind of solid electrolyte film preparation method based on the macromolecule modified gelatin polymer of natural polysaccharide | |
| CN101445618B (en) | A preparation method of self-supporting poly (3, 4- ethylenedioxythiophene) porous membrane | |
| CN105506726B (en) | A kind of in-situ electrochemistry preparation of silver-colored nano thin-film | |
| CN108490051A (en) | A kind of flexible miniature is from driving gas at normal temperature sensor and preparation method thereof | |
| CN101492536B (en) | Nano-polyaniline material with morphology inheritance and electrochemical preparation method | |
| CN105862071B (en) | A kind of preparation method of controllable poly- (3,4-rthylene dioxythiophene) film in aperture | |
| CN110824804B (en) | Flexible electrochromic film and preparation method thereof | |
| CN105036566A (en) | Preparation method of electrochromic film of anodic oxidation TiO2 nanotube array | |
| WO2013019101A1 (en) | Composite electrode with in-situ polymerized polyaniline and preparation method thereof | |
| CN101445617B (en) | A preparation method of self-supporting polyaniline porous membrane | |
| CN105713226A (en) | Preparation method of polyaniline film with controllable pore sizes | |
| CN103545050A (en) | Method and product for establishing conductive hydrogel ultrathin membrane by using layered assembly and electrochemical technology | |
| CN107603160B (en) | Conductive polymer hydrogel composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181106 Termination date: 20210415 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |