CN109651602A - A kind of preparation method of quick response electrochromism PTBTPA film - Google Patents
A kind of preparation method of quick response electrochromism PTBTPA film Download PDFInfo
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- CN109651602A CN109651602A CN201811517680.9A CN201811517680A CN109651602A CN 109651602 A CN109651602 A CN 109651602A CN 201811517680 A CN201811517680 A CN 201811517680A CN 109651602 A CN109651602 A CN 109651602A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
A kind of preparation method of quick response electrochromism PTBTPA film, with 4, 4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine are monomer, with 1- butyl -3- methyl tetrafluoroborate, 1- butyl -3- methylimidazole fluoroform sulphonate, bis- (trifluoro methylsulfonyl) inferior amine salts of 1- butyl -3- methyl are supporting electrolyte, it is electrolyte using methylene chloride and acetonitrile as the mixed solution of electroanalysis solvent, with gold electrode, platinum electrode, indium tin oxide-coated glass electrode or fluorine-doped tin oxide conductive glass electrode are working electrode, using gold electrode or platinum electrode as auxiliary electrode, using silver/silver chloride electrode as reference electrode；Electrochemical polymerization reaction is carried out using potentiostatic method at room temperature, obtains depositing thin polymer film on the working electrode (s, obtains thin polymer film after eluting the remaining electrolyte of removal polymeric film surface and drying with acetonitrile.At low cost, easy to operate and preparation process of the invention is pollution-free.
Description
Technical field
The present invention relates to a kind of preparation methods of quick response electrochromism PTBTPA film.
Background technique
Generally speaking, Doped ions diffusion property has significant impact, including optics to the optical transition performance of EC polymer
Contrast and switch speed.Since high ionic conductivity, wide electrochemical window and excellent electrochemical stability ionic liquid draw
Extensive interest is played.It has been found that using ionic liquid that can lead to improved electro-chemical activity, photo electric as electrolyte
The configuration of surface of matter and change.In work before, it has already been proven that, compared with conventional electrolysis matter, preparing polymer and EC survey
It can be beneficial to the EC property of enhancing in amount using ionic liquid.
Summary of the invention
The purpose of the present invention is to provide a kind of free of contamination quick response electricity of at low cost, easy to operate and preparation process
The preparation method of mutagens color PTBTPA film.
The present invention adopts the following technical scheme that in order to solve the technical problem
A kind of preparation method of quick response electrochromism PTBTPA film, the preparation method comprises the following steps:
It (1) is single with 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA) in three-electrode cell system
Body, with 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4), 1- butyl -3- methylimidazole fluoroform sulphonate ([BMIM]
OTF), bis- (trifluoro methylsulfonyl) inferior amine salt ([BMIM] TF of 1- butyl -3- methyl2It N is) supporting electrolyte, with methylene chloride and second
Nitrile is that the mixed solution of electroanalysis solvent is electrolyte, with gold electrode, platinum electrode, indium tin oxide-coated glass (ITO) electrode or fluorine
Doped stannum oxide electro-conductive glass (FTO) electrode is working electrode, using gold electrode or platinum electrode as auxiliary electrode, with silver/silver chlorate
Electrode is reference electrode；Electrochemical polymerization reaction is carried out using potentiostatic method at room temperature, obtains depositing on the working electrode (s
Thin polymer film obtains thin polymer film after eluting the remaining electrolyte of removal polymeric film surface and drying with acetonitrile.
(2) spectroelectrochemistry of thin polymer film and electrochromic property test: pass through electrochemical workstation and ultraviolet one
Visible spectrophotometer combination carries out UV absorption test, the test of contrast and the meter of response time to thin polymer film
It calculates；The ITO working electrode for being deposited with thin polymer film is placed in cuvette and is assembled into easy liquid gadget；By right
ITO working electrode applies the ultraviolet-visible absorption spectroscopy that different voltages carry out testing film；It is tested by bipotential step method thin
The dynamic performance of film.
Further, in the step (1), described 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA)
The initial concentration of monomer is 0.75mmol/L；Described supporting electrolyte 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4)
Initial concentration be 0.1mol/L；The methylene chloride and acetonitrile solvent specification is chromatographically pure.
Further, in the step (1), the working electrode is preferably indium tin oxide-coated glass electrode；It is described
Auxiliary electrode be preferably platinum electrode；The reference electrode is preferably biliquid direct type silver/silver chloride electrode；The biliquid connects
Type silver/silver chloride electrode is that the first liquid connects with the potassium chloride solution of 3moL/L, with electrolyte of the present invention for the second liquid
It connects.
In the step (1), the constant potential polymerization are as follows: in above-mentioned electrolyte environment, voltage is chosen for 1.2V,
Polymerizeing electricity is preferably 0.04C, and polymerization terminates, and 50~70s of dedoping, obtains polymer after eluting under -0.6V negative potential
Film.
In the step (1), the thin polymer film elution, drying course concrete operations are as follows: use eluent methylene chloride
The thin polymer film of deposition on the working electrode (s；Dry 4~8h is placed in 60~80 DEG C of vacuum ovens again to get product.
In the step (2), the different voltage range of the described application be 0~1.3V (preferably 0V, 0.6V, 0.7V,
0.8V、0.9V、1.0V、1.1V、1.2V、1.3V)。
In the step (2), the bipotential step method are as follows: the electrochromism handoff response between 0V to 1.4V,
The voltage step time is 5s.
The present invention characterizes the structure of resulting polymers film by infrared spectroscopy, it was demonstrated that the shape of the thin polymer film
At.
Compared with prior art, the beneficial effects of the present invention are:
(1) by obtaining the different electrochromism PTBTPA thin polymer film of response speed with different ionic liquids.
(2) by obtaining the pattern PTBTPA thin polymer film different with film thickness with different ionic liquids, to obtain
Obtain the different thin polymer film of contrast.
(3) present invention is at low cost, easy to operate, and preparation process is pollution-free, meets Green Chemistry, protects the ecology of environment
Theory.
Detailed description of the invention
Fig. 1 is the surface sweeping electron microscope of PTBTPA film prepared by embodiment 1.
Fig. 2 is the surface sweeping electron microscope of PTBTPA film prepared by embodiment 2.
Fig. 3 is the surface sweeping electron microscope of PTBTPA film prepared by embodiment 3.
Fig. 4 is the infrared spectrogram of PTBTPA film prepared by embodiment 1.
Fig. 5 is the uv absorption spectra of PTBTPA film prepared by embodiment 1.
Fig. 6 is optical contrast of the PTBTPA film of the preparation of embodiment 1 at 1100nm wavelength.
Fig. 7 is response time test chart of the PTBTPA film of the preparation of embodiment 1 at 1100nm wavelength.
Specific embodiment
The present invention will be further described with reference to the accompanying drawing.
Referring to Fig.1~Fig. 7, a kind of preparation method of quick response electrochromism PTBTPA film, the preparation method packet
Include following steps:
It (1) is single with 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA) in three-electrode cell system
Body, with 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4), 1- butyl -3- methylimidazole fluoroform sulphonate ([BMIM]
OTF), bis- (trifluoro methylsulfonyl) inferior amine salt ([BMIM] TF of 1- butyl -3- methyl2It N is) supporting electrolyte, with methylene chloride and second
Nitrile is that the mixed solution of electroanalysis solvent is electrolyte, with gold electrode, platinum electrode, indium tin oxide-coated glass (ITO) electrode or fluorine
Doped stannum oxide electro-conductive glass (FTO) electrode is working electrode, using gold electrode or platinum electrode as auxiliary electrode, with silver/silver chlorate
Electrode is reference electrode；Electrochemical polymerization reaction is carried out using potentiostatic method at room temperature, obtains depositing on the working electrode (s
Thin polymer film obtains thin polymer film after eluting the remaining electrolyte of removal polymeric film surface and drying with acetonitrile.
(2) spectroelectrochemistry of thin polymer film and electrochromic property test: pass through electrochemical workstation and ultraviolet one
Visible spectrophotometer combination carries out UV absorption test, the test of contrast and the meter of response time to thin polymer film
It calculates；The ITO working electrode for being deposited with thin polymer film is placed in cuvette and is assembled into easy liquid gadget；By right
ITO working electrode applies the ultraviolet-visible absorption spectroscopy that different voltages carry out testing film；It is tested by bipotential step method thin
The dynamic performance of film.
In the step (1), described 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA) monomers it is initial
Concentration is 0.75mmol/L；Described supporting electrolyte 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4) initial concentration
For 0.1mol/L；The methylene chloride and acetonitrile solvent specification is chromatographically pure.
In the step (1), the working electrode is preferably indium tin oxide-coated glass electrode；The auxiliary electrode
Preferably platinum electrode；The reference electrode is preferably biliquid direct type silver/silver chloride electrode；The biliquid direct type silver/chlorination
Silver electrode is that the first liquid connects with the potassium chloride solution of 3moL/L, is that the second liquid connects with electrolyte of the present invention.
In the step (1), the constant potential polymerization are as follows: in above-mentioned electrolyte environment, voltage is chosen for 1.2V,
Polymerizeing electricity is preferably 0.04C, and polymerization terminates, and 50~70s of dedoping, obtains polymer after eluting under -0.6V negative potential
Film.
In the step (1), the thin polymer film elution, drying course concrete operations are as follows: use eluent methylene chloride
The thin polymer film of deposition on the working electrode (s；Dry 4~8h is placed in 60~80 DEG C of vacuum ovens again to get product.
In the step (2), the different voltage range of the described application be 0~1.3V (preferably 0V, 0.6V, 0.7V,
0.8V、0.9V、1.0V、1.1V、1.2V、1.3V)。
In the step (2), the bipotential step method are as follows: the electrochromism handoff response between 0V to 1.4V,
The voltage step time is 5s.
Embodiment 1
A kind of preparation method of quick response electrochromism PTBTPA film, the preparation method comprises the following steps:
(1) a kind of preparation method of quick response electrochromism PTBTPA film, the preparation method comprises the following steps:
In three-electrode cell system, with TBTPA (0.05535g, 0.75mmol) for monomer, with [BMIM] BF4(2.26g,
It 0.01mol) is supporting electrolyte, CH2Cl2: ACN (70ml:30ml volume ratio) solution, be configured to monomer concentration 0.75mmol/L,
The mixed solution 100mL of supporting electrolyte concentration 0.1mol/L is electrolyte, using ITO electro-conductive glass as working electrode, with platinum electricity
Extremely auxiliary electrode, using silver/silver chloride electrode as reference electrode.Electrochemical polymerization is carried out using potentiostatic method 1.2V at room temperature
Reaction polymerize electricity 0.04C, then dedoping 50s under negative potential -0.6V again, obtains one layer and be deposited on ITO working electrode
Orange thin polymer film elutes the remaining electrolyte of removal polymeric film surface with acetonitrile and in 60 DEG C of vacuum drying environment
PTBTPA film is obtained after drying 5h.By its surface microscopic topographic of sem test, as shown in Figure 1.
(2) the PTBTPA film being attached on ito glass prepared by previous step is put into three-electrode cell, with [BMIM]
BF4 (2.26g, 0.01mol) is supporting electrolyte, and CH2Cl2:ACN (70ml:30ml volume ratio) solution is configured to support electrolysis
The mixed solution 100mL of matter concentration 0.1mol/L is electrolyte, and wherein working electrode is the ito glass with PTBTPA film,
It is platinum filament to electrode, reference electrode is silver-silver chloride electrode.Using electrochemical workstation and ultraviolet spectrometer joint technology, electricity
Chem workstation is set as potentiostatic electrolysis, and ultraviolet spectra is set as ultravioletvisible absorption, and scanning range is 1100~
300nm.Finally obtained data are as shown in Figure 6；In order to detect the response speed and contrast of PTBTPA film, we are using electricity
Chem workstation and ultraviolet spectrometer joint technology, electrochemical workstation are set as more potential step methods: initial potential 0V,
Termination current potential is 1.4V, and potential pulse width is 5s, sweep time 200s；Ultraviolet spectra is set as spectrum dynamics, wavelength
1100nm is respectively set.Finally obtained data are as shown in Figure 7.
Embodiment 2
A kind of preparation method of quick response electrochromism PTBTPA film, the preparation method comprises the following steps:
(1) in three-electrode cell system, with TBTPA (0.05535g, 0.75mmol) for monomer, with [BMIM] OTF
(4.19g, 0.01mol) is supporting electrolyte, CH2Cl2: ACN (70ml:30ml volume ratio) solution is configured to monomer concentration
0.75mmol/L, supporting electrolyte concentration 0.1mol/L mixed solution 100mL be electrolyte, using ITO electro-conductive glass as work
Electrode, using platinum electrode as auxiliary electrode, using silver/silver chloride electrode as reference electrode.At room temperature using potentiostatic method 1.2V into
Row electrochemical polymerization reaction, polymerize electricity 0.04C, then dedoping 50s under negative potential -0.6V again, obtains one layer and be deposited on ITO
Orange thin polymer film on working electrode, it is with the remaining electrolyte of acetonitrile elution removal polymeric film surface and true at 60 DEG C
PTBTPA film is obtained after drying 5h in empty dry environment.By its surface microscopic topographic of sem test, as shown in Figure 2.
(2) the PTBTPA film being attached on ito glass prepared by previous step is put into three-electrode cell, with [BMIM]
OTF (4.19g, 0.01mol) is supporting electrolyte, CH2Cl2: ACN (70ml:30ml volume ratio) solution is configured to support electrolysis
The mixed solution 100mL of matter concentration 0.1mol/L is electrolyte, and wherein working electrode is the ito glass with PTBTPA film,
It is platinum filament to electrode, reference electrode is silver-silver chloride electrode.Using electrochemical workstation and ultraviolet spectrometer joint technology, electricity
Chem workstation is set as potentiostatic electrolysis, and ultraviolet spectra is set as ultravioletvisible absorption, and scanning range is 1100~
300nm；In order to detect the response speed and contrast of PTBTPA film, we are joined using electrochemical workstation and ultraviolet spectrometer
With technology, electrochemical workstation is set as more potential step methods: initial potential 0V, and termination current potential is 1.4V, potential pulse
Width is 5s, sweep time 200s；Ultraviolet spectra is set as spectrum dynamics, and 1100nm is respectively set in wavelength.
Embodiment 3
A kind of preparation method of quick response electrochromism PTBTPA film, the preparation method comprises the following steps:
(1) in three-electrode cell system, with TBTPA (0.05535g, 0.75mmol) for monomer, with ([BMIM]
OTF) (2.88g, 0.01mol) is supporting electrolyte, CH2Cl2: ACN (70ml:30ml volume ratio) solution is configured to monomer concentration
0.75mmol/L, supporting electrolyte concentration 0.1mol/L mixed solution 100mL be electrolyte, using ITO electro-conductive glass as work
Electrode, using platinum electrode as auxiliary electrode, using silver/silver chloride electrode as reference electrode.At room temperature using potentiostatic method 1.2V into
Row electrochemical polymerization reaction, polymerize electricity 0.04C, then dedoping 50s under negative potential -0.6V again, obtains one layer and be deposited on ITO
Orange thin polymer film on working electrode, it is with the remaining electrolyte of acetonitrile elution removal polymeric film surface and true at 60 DEG C
PTBTPA film is obtained after drying 5h in empty dry environment.By its surface microscopic topographic of sem test, as shown in Figure 3.
(2) the PTBTPA film being attached on ito glass prepared by previous step is put into three-electrode cell, with
([BMIM] OTF) (2.88g, 0.01mol) is supporting electrolyte, CH2Cl2: ACN (70ml:30ml volume ratio) solution is configured to
The mixed solution 100mL of supporting electrolyte concentration 0.1mol/L is electrolyte, and wherein working electrode is with PTBTPA film
Ito glass is platinum filament to electrode, and reference electrode is silver-silver chloride electrode.It is combined using electrochemical workstation and ultraviolet spectrometer
Technology, electrochemical workstation are set as potentiostatic electrolysis, and ultraviolet spectra is set as ultravioletvisible absorption, scanning range 1100
~300nm；In order to detect the response speed and contrast of PTBTPA film, we use electrochemical workstation and ultraviolet spectrometer
Joint technology, electrochemical workstation are set as more potential step methods: initial potential 0V, and termination current potential is 1.4V, current potential arteries and veins
Rushing width is 5s, sweep time 200s；Ultraviolet spectra is set as spectrum dynamics, and 1100nm is respectively set in wavelength.
Claims (8)
1. a kind of preparation method of quick response electrochromism PTBTPA film, which is characterized in that the preparation method include with
Lower step:
(1) in three-electrode cell system, with 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA) for monomer,
With 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4), 1- butyl -3- methylimidazole fluoroform sulphonate ([BMIM]
OTF), bis- (trifluoro methylsulfonyl) inferior amine salt ([BMIM] TF of 1- butyl -3- methyl2It N is) supporting electrolyte, with methylene chloride and second
Nitrile is that the mixed solution of electroanalysis solvent is electrolyte, with gold electrode, platinum electrode, indium tin oxide-coated glass (ITO) electrode or fluorine
Doped stannum oxide electro-conductive glass (FTO) electrode is working electrode, using gold electrode or platinum electrode as auxiliary electrode, with silver/silver chlorate
Electrode is reference electrode；Electrochemical polymerization reaction is carried out using potentiostatic method at room temperature, obtains depositing on the working electrode (s
Thin polymer film obtains thin polymer film after eluting the remaining electrolyte of removal polymeric film surface and drying with acetonitrile.
2. a kind of preparation method of quick response electrochromism PTBTPA film as described in claim 1, which is characterized in that institute
It is further comprising the steps of to state preparation method:
(2) spectroelectrochemistry of thin polymer film and electrochromic property test: visible with ultraviolet one by electrochemical workstation
Spectrophotometer combination carries out UV absorption test, the test of contrast and the calculating of response time to thin polymer film；It will
The ITO working electrode for being deposited with thin polymer film, which is placed in cuvette, is assembled into easy liquid gadget；By working ITO
Electrode applies the ultraviolet-visible absorption spectroscopy that different voltages carry out testing film；By bipotential step method come the power of testing film
Learn performance.
3. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In, in the step (1), the initial concentration of described 4,4 ', 4 "-three [4- (2- bithiophene base) phenyl] amine (TBTPA) monomers
For 0.75mmol/L；Described supporting electrolyte 1- butyl -3- methyl tetrafluoroborate ([BMIM] BF4) initial concentration be
0.1mol/L；The methylene chloride and acetonitrile solvent specification is chromatographically pure.
4. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In in the step (1), the working electrode is indium tin oxide-coated glass electrode；The auxiliary electrode is platinum electrode；
The reference electrode is biliquid direct type silver/silver chloride electrode；The biliquid direct type silver/silver chloride electrode is with the chlorine of 3moL/L
Changing aqueous solutions of potassium is that the first liquid connects, and is that the second liquid connects with the electrolyte.
5. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In, in the step (1), the constant potential polymerization are as follows: in above-mentioned electrolyte environment, voltage is chosen for 1.2V, polymerization
Electricity is 0.04C, and polymerization terminates, and 50~70s of dedoping, obtains thin polymer film after eluting under -0.6V negative potential.
6. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In, in the step (1), the thin polymer film elution, drying course operation are as follows: be deposited on work with eluent methylene chloride
Thin polymer film on electrode；Dry 4~8h is placed in 60~80 DEG C of vacuum ovens again to get product.
7. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In in the step (2), the different voltage range of the application is 0~1.3V.
8. a kind of preparation method of quick response electrochromism PTBTPA film as claimed in claim 1 or 2, feature exist
In, in the step (2), the bipotential step method are as follows: the electrochromism handoff response between 0V to 1.4V, voltage steps
The jump time is 5s.
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| CN111072930A (en) * | 2019-11-20 | 2020-04-28 | 浙江工业大学 | Fluorine-containing thiophene derivative polymer film PEDOT-F, and preparation method and application thereof |
| CN111635143A (en) * | 2020-06-02 | 2020-09-08 | 东华大学 | Method for preparing porphyrin-based polymer electrochromic film through electrodeposition |
| CN112755733A (en) * | 2020-12-04 | 2021-05-07 | 北京理工大学 | Electropolymerization prepared self-supporting ILs @ CMP film for improving CO2/CH4Method of separating properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110592609B (en) * | 2019-08-30 | 2021-02-02 | 浙江工业大学 | Method for improving cycling stability of polymer electrochromic film |
| CN111072930A (en) * | 2019-11-20 | 2020-04-28 | 浙江工业大学 | Fluorine-containing thiophene derivative polymer film PEDOT-F, and preparation method and application thereof |
| CN111072930B (en) * | 2019-11-20 | 2022-05-24 | 浙江工业大学 | Fluorine-containing thiophene derivative polymer film PEDOT-F, and preparation method and application thereof |
| CN111635143A (en) * | 2020-06-02 | 2020-09-08 | 东华大学 | Method for preparing porphyrin-based polymer electrochromic film through electrodeposition |
| CN112755733A (en) * | 2020-12-04 | 2021-05-07 | 北京理工大学 | Electropolymerization prepared self-supporting ILs @ CMP film for improving CO2/CH4Method of separating properties |
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Application publication date: 20190419 |