WO2018171317A1 - 一种pedot:pss@离子液体凝胶复合自支撑柔性透明电极的制备方法 - Google Patents
一种pedot:pss@离子液体凝胶复合自支撑柔性透明电极的制备方法 Download PDFInfo
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- WO2018171317A1 WO2018171317A1 PCT/CN2018/072963 CN2018072963W WO2018171317A1 WO 2018171317 A1 WO2018171317 A1 WO 2018171317A1 CN 2018072963 W CN2018072963 W CN 2018072963W WO 2018171317 A1 WO2018171317 A1 WO 2018171317A1
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- WIPO (PCT)
- Prior art keywords
- ionic liquid
- pedot
- pss
- transparent electrode
- liquid
- Prior art date
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- 229920000144 PEDOT:PSS Polymers 0.000 title claims abstract description 146
- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 92
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 81
- 229920000831 ionic polymer Polymers 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 22
- -1 N-vinylpyridine tetrafluoroborate Chemical compound 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 12
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- SDTAXUVLXYGRNE-UHFFFAOYSA-O bis(trifluoromethylsulfonyl)azanide;3-methyl-1h-imidazol-3-ium Chemical compound C[N+]=1C=CNC=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F SDTAXUVLXYGRNE-UHFFFAOYSA-O 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 4
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- UVQPDGXQIPNYNU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-2h-imidazole Chemical compound CCN1CN(C=C)C=C1 UVQPDGXQIPNYNU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000009881 electrostatic interaction Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 13
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 10
- 230000005693 optoelectronics Effects 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 2
- ALDIECUKIYBNLB-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-ethenylimidazol-1-ium Chemical compound CCCC[N+]=1C=CN(C=C)C=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F ALDIECUKIYBNLB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DBNWBEGCONIRGQ-UHFFFAOYSA-N 1,1-diphenylpropan-2-one Chemical compound C=1C=CC=CC=1C(C(=O)C)C1=CC=CC=C1 DBNWBEGCONIRGQ-UHFFFAOYSA-N 0.000 description 1
- XXZFCJVFXKCILB-UHFFFAOYSA-N 1-methylpyrrolidine;hydrobromide Chemical compound [Br-].C[NH+]1CCCC1 XXZFCJVFXKCILB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GSGPKPPQAOUFFT-UHFFFAOYSA-M [Br-].C(=C)[N+]1(CCCCC1)C Chemical compound [Br-].C(=C)[N+]1(CCCCC1)C GSGPKPPQAOUFFT-UHFFFAOYSA-M 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Definitions
- the invention belongs to the field of preparation and application of electronic devices, and relates to a method for preparing a high performance flexible transparent electrode by using a PEDOT:PSS film and an ionic liquid gel.
- Flexible transparent electrodes play an important role in the development of the electronics and optoelectronics industry, and are optoelectronic functional materials that are indispensable for the preparation of numerous electronic and optoelectronic components.
- flexible transparent electrodes are mainly prepared by chemical vapor deposition, sol-gel method, vacuum evaporation deposition, etc. on a transparent organic polymer substrate (Reference: J. A. Lewis et al. Science, 323, 1590-1593 (2009); R. B. Kaner et al. Science, 335, 1326-1330 (2012); D. B. Janes et al. Nature Nanotech, 2, 378-384 (2007); Y. Cui et al. Nature Nanotech, 8, 421-425 (2013)).
- the flexible transparent electrode material prepared by these methods has a limitation of the substrate, and it is necessary to consider the adhesion between the conductive layer and the substrate. If subjected to very large mechanical deformation, it is prone to defect fracture, partial peeling, etc., which is greatly reduced.
- the conductive properties of the flexible transparent electrode severely limit further applications.
- a self-supporting conductive film (Reference: D. A. Mengistie, C. H. Chen, K. M. Boopathi, F. W. Pranoto, L. J. Li, C. W. Chu, ACS Appl. Mater. Interfaces 7, 94-100 (2015); Z. F. Li, G. Q. Ma, R. Ge, F. Qin, X. Y.
- the existing transparent electrode technology has high cost, complicated process, scarce raw materials, and the transparent electrode is easy to rupture and fall off with the substrate.
- a method for preparing a PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode comprising the following steps:
- Preparation of a transparent polyionic liquid film coating an ionic liquid prepolymer on a substrate, and photopolymerizing the ionic liquid prepolymer on the surface of the substrate to obtain a polyionic liquid film;
- the transparent PEDOT:PSS film prepared in the step 1) is prepared, the transparent PEDOT:PSS film prepared in the step 1) is combined with the ionic liquid prepolymerization liquid by electrostatic action, and the ionic liquid prepolymerization liquid is initiated by light or heat.
- PEDOT PSS film surface cross-linking polymerization, water washing, heating, to obtain PEDOT: PSS@ ionic liquid gel composite self-supporting flexible transparent electrode;
- the PEDOT:PSS solution is spin-coated onto the polyionic liquid film for polymerization, rinsed with water, and heated to obtain PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode.
- a transparent PEDOT:PSS film is prepared by spin coating.
- the ionic liquid prepolymerization liquid comprises an ionic liquid containing a polymerizable group and an ionic liquid containing a group capable of electrostatic attraction with PEDOT:PSS;
- the ionic liquid containing a polymerizable group is an ionic liquid monomer containing a vinyl double bond, specifically an imidazole ionic liquid, a pyridine ionic liquid, a quaternary ammonium salt ionic liquid, a quaternary phosphonium salt ionic liquid, pyrrolidine One or more of an ionic liquid and a piperidine ionic liquid;
- the ionic liquid containing a polymerizable group is a polyionic liquid containing a crosslinkable group as a functional polyionic liquid, specifically a polyionic liquid macromolecule containing a carboxyl group, a hydroxyl group, an amino group or a nitrile group;
- the ionic liquid containing a group which can be electrostatically attracted to PEDOT:PSS is an imidazole-based cationic ionic liquid or a dinitrileamine salt anionic ionic liquid.
- the imidazole ionic liquid is 1-vinyl-3-ethylimidazolidinitrileamine salt;
- the pyridine ionic liquid is N-vinylpyridine tetrafluoroborate;
- the quaternary ammonium salt ionic liquid is tributyl a vinyl ammonium (trifluoromethanesulfonyl)imide salt;
- the quaternary phosphonium salt ionic liquid is tributyl vinyl bromide;
- the pyrrolidine ionic liquid is N-vinyl-N-methylpyrrolidine bromide;
- the piperidine ionic liquid is N-vinyl-N-methyl piperidinium bromide;
- Polyionic liquid macromolecules containing a carboxyl group, a hydroxyl group, an amino group or a nitrile group are poly(1-vinyl-3-carboxyethylimidazolium nitrate), poly(1-vinyl-3-hydroxyethylimidazolium tetrafluoroborate) Salt), poly(1-vinyl-3-aminopropylimidazolium nitrate) or poly(1-vinyl-3-ethylimidazolidinitrileamine salt);
- the imidazole cationic ionic liquid is N-methylimidazolium hydrogensulfate or N-methylimidazolium bis(trifluoromethanesulfonyl)imide salt;
- the dinitrileamine salt anionic ionic liquid is 1-vinyl-3-ethylimidazole Dinitrileamine salt or 1-ethyl-3-ethylimidazolidinitrileamine salt.
- the ionic liquid prepolymer further comprises a monomer initiator, which is benzoin ethyl ether, diphenyl ethyl ketone, benzophenone, potassium persulfate, ammonium persulfate, peroxidation.
- a monomer initiator which is benzoin ethyl ether, diphenyl ethyl ketone, benzophenone, potassium persulfate, ammonium persulfate, peroxidation.
- a monomer initiator which is benzoin ethyl ether, diphenyl ethyl ketone, benzophenone, potassium persulfate, ammonium persulfate, peroxidation.
- benzoyl di-tert-butyl peroxide, azobisisobutyronitrile
- the mass ratio of the ionic liquid polymer monomer in the monomer initiator/ionic liquid prepolymer is 1/1000-20/1000.
- the ionic liquid prepolymer further comprises a crosslinking agent, and the crosslinking agent is N, N-methylene bis acrylamide, polyethylene glycol dimethacrylate, glutaraldehyde, chlorine One or more of an aqueous calcium solution and a diisocyanate;
- the mass ratio of the ionic liquid polymer monomer in the crosslinker/ionic liquid prepolymer is 1/1000-50/1000.
- the photoinitiated wavelength is from 250 nm to 420 nm.
- the thermally induced heating temperature is 70-90 oC.
- the invention also provides a self-supporting flexible transparent electrode prepared by the above preparation method, which improves the self-supporting property and transparency of the composite transparent electrode by a chemically crosslinked ionic liquid gel network structure.
- the transparent PEDOT:PSS film formed in the step 1) of the invention has the property of superionic liquid, and the electrostatically charged ionic liquid prepolymer forms a uniform thin layer on the surface of the PEDOT:PSS by electrostatic action.
- the ionic liquid prepolymerization liquid in the above step 2) in the present invention has both a polymerization crosslinking function and an electrostatic action.
- the transparent ionic liquid film formed in the step 2) of the present invention causes the PEDOT:PSS to form a uniform thin layer by electrostatic action.
- the PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode of the invention can be used for preparing flexible display screens, such as mobile phones, computer monitors, watches, and visualization glasses. It can also be used to prepare flexible organic light emitting diodes and solar cells.
- the PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode overcomes the high cost, complicated process, scarce raw materials, and easy cracking and falling off of the transparent electrode with the transparent electrode technology.
- the present invention can adjust the thickness of the transparent electrode and thereby regulate the resistance of the transparent electrode.
- the method of the invention is simple in operation, easy to control, simple in equipment required, and capable of mass production.
- the transparent electrode is particularly suitable for preparing a screen of a visible electronic device, a wearable electronic device, a flexible organic light emitting diode, a flexible solar cell, an organic electric device. Illuminating panel.
- FIG. 1 is a schematic view showing the structure of a PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode of the present invention.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used in the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the mass ratio of ethylimidazole dinitrileamine salt and N-methylimidazolium hydrogensulfate/potassium persulfate/N,N-methylenebisacrylamide is 1000/10/10) coated to step (1)
- a composite PEDOT:PSS film was obtained.
- the PEDOT:PSS film in step (2) is heated at 80oC for 10 min, rinsed several times with distilled water, and heated at 120oC for 10 min to obtain PEDOT:PSS@polyionic liquid composite flexible transparent electrode with excellent conductivity and stability.
- Fig. 1 it can be seen from Fig. 1 that the ionic liquid gel and the PEDOT:PSS form a self-supporting composite flexible transparent electrode by electrostatic action.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89% and a sheet resistance of 100 ⁇ /sq, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used in the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the mass ratio of ethylimidazole dinitrileamine salt and N-methylimidazolium hydrogensulfate/potassium persulfate/N,N-methylenebisacrylamide is 1000/10/10) coated to step (1)
- a composite PEDOT:PSS film was obtained.
- the PEDOT:PSS film in step (2) is heated at 80oC for 10 min, rinsed several times with distilled water, and heated at 120oC for 10 min to obtain PEDOT:PSS@polyionic liquid composite flexible transparent electrode with excellent conductivity and stability.
- Fig. 1 it can be seen from Fig. 1 that the ionic liquid gel and the PEDOT:PSS form a self-supporting composite flexible transparent electrode by electrostatic action.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89% and a sheet resistance of 100 ⁇ /sq, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used in the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the film was applied onto a transparent PEDOT:PSS film formed in the step (1) to obtain a composite PEDOT:PSS film.
- the PEDOT:PSS film in step (2) was irradiated for 1 h under 255 nm ultraviolet light, rinsed several times with distilled water, and heated at 120 °C for 10 min to obtain PEDOT:PSS@polyionic liquid composite flexible transparent electrode with excellent conductivity and stability. .
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89% and a sheet resistance of 100 ⁇ /sq, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used in the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the PEDOT:PSS film in step (2) was heated at 80 °C for 10 min, rinsed several times with distilled water, and heated at 120 °C for 10 min to obtain PEDOT:PSS@polyionic liquid composite flexible transparent electrode with excellent conductivity and stability.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used in the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the mass ratio of phosphine bromide and 1-ethyl-3-ethylimidazolidinitrileamine salt/benzoyl peroxide/polyethylene glycol dimethacrylate is 1000/10/10) coated to step (1)
- a composite PEDOT:PSS film was obtained.
- the PEDOT:PSS film in step (2) was irradiated for 1 h under 255 nm ultraviolet light, rinsed several times with distilled water, and heated at 120 °C for 10 min to obtain PEDOT:PSS@polyionic liquid composite flexible transparent electrode with excellent conductivity and stability. .
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used to prepare a PEDOT:PSS@P[VBIm][NTf 2 ] composite transparent electrode in the next step.
- the PEDOT:PSS film in step (2) was heated at 80 °C for 10 min, rinsed several times with distilled water, and heated at 120 °C for 10 min to obtain PEDOT:PSS@P[VBIm][NTf 2 ] composite flexible transparent with excellent conductivity and stability. electrode.
- the PEDOT:PSS@P[VBIm][NTf 2 ] composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto a glass slide to form a PEDOT:PSS film, which was used to prepare a PEDOT:PSS@P[VBIm][NTf 2 ] composite transparent electrode in the next step.
- the PEDOT:PSS film in step (2) was irradiated for 1 h under 255 nm ultraviolet light, rinsed several times with distilled water, and heated at 120 °C for 10 min to obtain PEDOT:PSS@P[VBIm][NTf 2 with excellent conductivity and stability.
- PEDOT prepared above: PSS @ P [VBIm] [ NTf 2] of the composite light transmittance of the transparent electrode is greater than 89%, can be used to prepare a flexible touch and flexible solar cell device.
- the PEDOT:PSS solution was spin-coated onto the transparent polyionic liquid film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@polyionic liquid composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89% and a sheet resistance of 100 ⁇ /sq, and can be used for preparing a flexible touch device and a flexible solar cell.
- the polyionic liquid film was formed by irradiating with nm light for 1 h, and the polyionic liquid film was used for the next step to prepare a PEDOT:PSS@polyionic liquid composite transparent electrode.
- the PEDOT:PSS solution was spin-coated onto the transparent polyionic liquid film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@polyionic liquid composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89% and a sheet resistance of 100 ⁇ /sq, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto the transparent polyionic liquid film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@polyionic liquid composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto the transparent polyionic liquid film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@polyionic liquid composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@polyionic liquid composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto the transparent P[VBIm][NTf 2 ] film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@P[VBIm][NTf 2 ] composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@P[VBIm][NTf 2 ] composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS solution was spin-coated onto the transparent P[VBIm][NTf 2 ] film formed in the step (1) to obtain a composite film.
- the composite film in the step (2) was washed several times with distilled water and heated at 120 ° C for 10 min to obtain a PEDOT:PSS@P[VBIm][NTf 2 ] composite flexible transparent electrode excellent in electrical conductivity and stability.
- the PEDOT:PSS@P[VBIm][NTf 2 ] composite transparent electrode prepared above has a light transmittance of more than 89%, and can be used for preparing a flexible touch device and a flexible solar cell.
- the PEDOT:PSS@ionic liquid gel composite self-supporting flexible transparent electrode obtained by the invention does not damage or the conductivity decreases after one thousand bending cycle test, and passes through 0 -100 oC temperature heating, 0-30
- the bar vacuum environment has no effect on its performance, and the resulting conductive layer is stable in nature.
Abstract
本发明涉及一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,所述制备方法将导电高分子PEDOT:PSS和离子液体单体通过静电作用复合,在光、热条件下聚合交联得到PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极。本发明提供的复合柔性透明电极稳定性好、力学性能优异,克服了现有柔性透明电极与基底间的脱落、断裂等问题,具有制备过程简单、成本低、稳定、柔性好的特点,该透明电极适用于制备可穿戴电子设备、柔性触屏、柔性太阳能电池、柔性有机EL面板。
Description
本发明属于电子器件制备与应用领域,涉及利用PEDOT:PSS薄膜与离子液体凝胶复合制备高性能柔性透明电极的方法。
柔性透明电极在电子与光电子产业的发展中占有举足轻重的地位,是制备众多电子与光电子元器件不可缺少的光电功能材料。目前,柔性透明电极主要是通过在透明有机聚合物基底上通过化学气相沉积、溶胶-凝胶法、真空蒸发沉积等方法制备(参考文献:J. A. Lewis et al. Science, 323,
1590-1593 (2009); R. B. Kaner et al. Science, 335, 1326-1330 (2012); D. B.
Janes et al. Nature Nanotech, 2, 378-384 (2007); Y. Cui et al. Nature Nanotech,
8, 421-425 (2013))。然而,通过这些方法制备出的柔性透明电极材料都有基底的限制,需要考虑导电层与基底间的粘附作用,如果受到非常大的机械变形,容易发生缺陷断裂,部分剥落等情况,大幅降低柔性透明电极的导电性能,严重限制进一步应用。为了解决这个问题,自支撑的导电膜(参考文献:D. A.
Mengistie, C. H. Chen, K. M. Boopathi, F. W. Pranoto, L. J. Li, C. W. Chu, ACS
Appl. Mater. Interfaces 7, 94-100 (2015); Z. F. Li, G. Q. Ma, R. Ge, F. Qin, X.
Y. Dong, W. Meng, T. F. Liu, J. H. Tong, F. Y. Jiang, Y. F. Zhou, K. Li, X.
Min, K. F. Huo, Y. H. Zhou, Angew. Chem. Int. Ed. 55, 979-982 (2016))将提供一个新的机遇。然而,制作同时具有高光学透明度和低方块电阻的自支撑薄膜仍然是一个巨大的挑战。
现有透明电极技术中成本高,工艺复杂,原料稀缺,透明电极容易与基底破裂和脱落
为达到上述目的,本发明采用了如下的技术方案:
一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,所述方法包括以下步骤:
1)在基底上制备透明PEDOT:PSS薄膜或制备透明聚离子液体薄膜;
透明聚离子液体薄膜的制备:在基底上涂布离子液体预聚液,用光或热引发离子液体预聚液在基底表面交联聚合得到聚离子液体薄膜;
2)当步骤1)所制备的是透明PEDOT:PSS薄膜时,将步骤1)制备的透明PEDOT:PSS薄膜与离子液体预聚液通过静电作用复合,用光或热引发离子液体预聚液在PEDOT:PSS薄膜表面交联聚合,经水冲洗,加热,得到PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极;
当步骤1)所制备的是透明聚离子液体薄膜时,将PEDOT:PSS溶液旋涂到聚离子液体薄膜上聚合,经水冲洗,加热,得到PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极。
优选地,在所述步骤1)中,通过旋涂制备透明的PEDOT:PSS薄膜。
优选地,所述离子液体预聚液包括含有可聚合基团的离子液体以及含有可与PEDOT:PSS进行静电吸引的基团的离子液体;
其中,含有可聚合基团的离子液体为含乙烯基双键的离子液体单体,具体为咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季磷盐类离子液体、吡咯烷类离子液体和哌啶类离子液体中的一种或多种;
或者,含有可聚合基团的离子液体为含有可交联基团的聚离子液体为功能性聚离子液体,具体为含羧基、羟基、氨基或腈基的聚离子液体大分子;
含有可与PEDOT:PSS进行静电吸引的基团的离子液体为咪唑类阳离子离子液体或二腈胺盐阴离子离子液体。
进一步优选地,咪唑类离子液体为1-乙烯基-3-乙基咪唑二腈胺盐;吡啶类离子液体为N-乙烯基吡啶四氟硼酸盐;季铵盐类离子液体为三丁基乙烯基铵(三氟甲烷磺酰)亚胺盐;季磷盐类离子液体为三丁基乙烯基溴化膦;吡咯烷类离子液体为N-乙烯基-N-甲基吡咯烷溴盐;哌啶类离子液体为N-乙烯基-N-甲基哌啶溴盐;
含羧基、羟基、氨基或腈基的聚离子液体大分子为聚(1-乙烯基-3-羧乙基咪唑硝酸盐)、聚(1-乙烯基-3-羟乙基咪唑四氟硼酸盐)、聚(1-乙烯基-3-胺丙基咪唑硝酸盐)或聚(1-乙烯基-3-乙基咪唑二腈胺盐);
咪唑类阳离子离子液体为N-甲基咪唑硫酸氢盐或N-甲基咪唑双(三氟甲烷磺酰)亚胺盐;二腈胺盐阴离子离子液体为1-乙烯基-3-乙基咪唑二腈胺盐或1-乙基-3-乙基咪唑二腈胺盐。
优选地,所述离子液体预聚液中还包括单体引发剂,所述的单体引发剂是安息香乙醚、二苯基乙酮、二苯甲酮、过硫酸钾、过硫酸铵、过氧化苯甲酰、过氧化二叔丁基、偶氮二异丁腈中的一种或多种;
单体引发剂/离子液体预聚液中离子液体聚合物单体的质量比例是1/1000-20/1000。
优选地,所述离子液体预聚液中还包括交联剂,所述的交联剂是N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、戊二醛、氯化钙水溶液、二异氰酸酯中的一种或多种;
交联剂/离子液体预聚液中离子液体聚合物单体的质量比例是1/1000-50/1000。
优选地,所述的光引发的波长为250 nm-420 nm。
优选地,所述的热引发的加热温度是70-90 ºC。
本发明还提供了采用上述的制备方法所制备的自支撑柔性透明电极,该电极通过化学交联的离子液体凝胶网络结构提高复合透明电极的自支撑性能及透明度。
本发明步骤1)形成的透明PEDOT:PSS薄膜具有超亲离子液体的性质,含有静电荷的离子液体预聚液通过静电作用在PEDOT:PSS表面形成均一的薄层。
本发明中的上述步骤2)中的离子液体预聚液同时具有聚合交联功能和静电作用。
本发明步骤2)形成的透明离子液体薄膜通过静电作用,使PEDOT:PSS形成均一的薄层。
本发明PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的应用,制备的复合柔性透明电极可用于制备柔性显示屏,比如手机、电脑显示器、手表、可视化眼镜等。也可用于制备柔性有机发光二极管、太阳能电池。
本发明提供的PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极,克服了现有透明电极技术中成本高,工艺复杂,原料稀缺,透明电极容易与基底破裂和脱落等。通过控制PEDOT:PSS溶液的稀释浓度,本发明可以调节透明电极的厚度,进而调控透明电极的电阻。本发明的方法操作简便、易于控制、所需设备简单、能够大规模生产,该透明电极尤其适用于制备可视电子设备的屏幕、可穿戴电子设备、柔性有机发光二极管、柔性太阳能电池、有机电致发光面板。
图1是本发明的PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的结构示意图。
实施例1
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与离子液体预聚液的静电作用
将含1-乙烯基-3-乙基咪唑二腈胺盐、N-甲基咪唑硫酸氢盐、过硫酸钾、N,N-亚甲基双丙烯酰胺的溶液(1-乙烯基-3-乙基咪唑二腈胺盐和N-甲基咪唑硫酸氢盐/过硫酸钾/N,N-亚甲基双丙烯酰胺的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在80ºC加热10 min,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极,结构如图1所示,从图1可以看出离子液体凝胶与PEDOT:PSS通过静电作用形成自支撑的复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,方块电阻为100 Ω/sq,可用于制备柔性触控器件和柔性太阳能电池。
实施例1
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与离子液体预聚液的静电作用
将含1-乙烯基-3-乙基咪唑二腈胺盐、N-甲基咪唑硫酸氢盐、过硫酸钾、N,N-亚甲基双丙烯酰胺的溶液(1-乙烯基-3-乙基咪唑二腈胺盐和N-甲基咪唑硫酸氢盐/过硫酸钾/N,N-亚甲基双丙烯酰胺的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在80ºC加热10 min,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极,结构如图1所示,从图1可以看出离子液体凝胶与PEDOT:PSS通过静电作用形成自支撑的复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,方块电阻为100 Ω/sq,可用于制备柔性触控器件和柔性太阳能电池。
实施例2
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与离子液体预聚液的静电作用
将含N-乙烯基吡啶四氟硼酸盐、N-甲基咪唑双(三氟甲烷磺酰)亚胺盐、二苯甲酮、 N,N-亚甲基双丙烯酰胺的溶液(N-乙烯基吡啶四氟硼酸盐和N-甲基咪唑双(三氟甲烷磺酰)亚胺盐/过硫酸钾/N,N-亚甲基双丙烯酰胺的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3) PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在255 nm紫外光下照射1 h,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,方块电阻为100 Ω/sq,可用于制备柔性触控器件和柔性太阳能电池。
实施例3
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与离子液体预聚液的静电作用
将含三丁基乙烯基铵(三氟甲烷磺酰)亚胺盐、1-乙烯基-3-乙基咪唑二腈胺盐、过氧化苯甲酰、聚乙二醇二甲基丙烯酸酯的溶液(三丁基乙烯基铵(三氟甲烷磺酰)亚胺盐和1-乙烯基-3-乙基咪唑二腈胺盐/过氧化苯甲酰/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在80ºC加热10 min,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例4
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与离子液体预聚液的静电作用
将含三丁基乙烯基溴化膦、1-乙基-3-乙基咪唑二腈胺盐、过氧化二叔丁基、聚乙二醇二甲基丙烯酸酯的溶液(三丁基乙烯基溴化膦和1-乙基-3-乙基咪唑二腈胺盐/过氧化苯甲酰/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3) PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在255 nm紫外光下照射1 h,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例5
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@P[VBIm][NTf
2]复合透明电极。
(2)PEDOT:PSS与[VBIm][NTf
2]预聚液的静电作用
将含N-乙烯基-N-甲基吡咯烷溴盐、N-甲基咪唑硫酸氢盐、过氧化苯甲酰、聚乙二醇二甲基丙烯酸酯的溶液(N-乙烯基-N-甲基吡咯烷溴盐和N-甲基咪唑硫酸氢盐/过氧化苯甲酰/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3)PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在80ºC加热10 min,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@P[VBIm][NTf
2]复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例6
(1)透明PEDOT:PSS薄膜的制备方法
将PEDOT:PSS溶液旋涂到玻璃片上,形成PEDOT:PSS薄膜,此PEDOT:PSS薄膜用于下一步制备PEDOT:PSS@P[VBIm][NTf
2]复合透明电极。
(2)PEDOT:PSS与[VBIm][NTf
2]预聚液的静电作用
将含N-乙烯基-N-甲基哌啶溴盐、N-甲基咪唑双(三氟甲烷磺酰)亚胺盐、过氧化苯甲酰、聚乙二醇二甲基丙烯酸酯的溶液(N-乙烯基-N-甲基哌啶溴盐和N-甲基咪唑双(三氟甲烷磺酰)亚胺盐/过氧化苯甲酰/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/10)涂布到步骤(1)形成的透明PEDOT:PSS薄膜上,得到复合PEDOT:PSS薄膜。
(3)PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的制备
将步骤(2)中的PEDOT:PSS薄膜在255 nm紫外光下照射1 h,蒸馏水冲洗数次,120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@P[VBIm][NTf
2]复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例7
(1)透明聚离子液体薄膜的制备方法
将含聚(1-乙烯基-3-羧乙基咪唑硝酸盐)、1-乙烯基-3-乙基咪唑二腈胺盐、过硫酸铵、N,N-亚甲基双丙烯酰胺的溶液(聚(1-乙烯基-3-羧乙基咪唑硝酸盐)和1-乙烯基-3-乙基咪唑二腈胺盐/过硫酸钾/N,N-亚甲基双丙烯酰胺的质量比例是1000/10/10)涂布到玻璃片上,在80ºC加热10 min,形成聚离子液体薄膜,此聚离子液体薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与聚离子液体的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明聚离子液体薄膜上,得到复合薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,方块电阻为100 Ω/sq,可用于制备柔性触控器件和柔性太阳能电池。
实施例8
(1)透明聚离子液体薄膜的制备方法
将含聚(1-乙烯基-3-羟乙基咪唑四氟硼酸盐)、1-乙基-3-乙基咪唑二腈胺盐、二苯基乙酮、氯化钙的溶液(聚(1-乙烯基-3-羟乙基咪唑四氟硼酸盐)和1-乙基-3-乙基咪唑二腈胺盐/过硫酸钾/氯化钙的质量比例是1000/20/20)涂布到玻璃片上,在255
nm紫外光下照射1 h,形成聚离子液体薄膜,此聚离子液体薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与聚离子液体的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明聚离子液体薄膜上,得到复合薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,方块电阻为100 Ω/sq,可用于制备柔性触控器件和柔性太阳能电池。
实施例9
(1)透明聚离子液体薄膜的制备方法
将含聚(1-乙烯基-3-胺丙基咪唑硝酸盐)、N-甲基咪唑硫酸氢盐、安息香乙醚、戊二醛的溶液(聚(1-乙烯基-3-胺丙基咪唑硝酸盐)和N-甲基咪唑硫酸氢盐/过氧化苯甲酰/过硫酸钾/戊二醛的质量比例是1000/10/10)涂布到玻璃片上,在70ºC加热10 min,形成聚离子液体薄膜,此聚离子液体薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与聚离子液体的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明聚离子液体薄膜上,得到复合薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例10
(1)透明聚离子液体薄膜的制备方法
将含聚(1-乙烯基-3-乙基咪唑二腈胺盐)、1-乙烯基-3-乙基咪唑二腈胺盐、偶氮二异丁腈、二异氰酸酯的溶液(聚(1-乙烯基-3-乙基咪唑二腈胺盐)和1-乙烯基-3-乙基咪唑二腈胺盐/过氧化苯甲酰/二异氰酸酯的质量比例是1000/1/1)涂布到玻璃片上,在255
nm紫外光下照射1 h,形成聚离子液体薄膜,此聚离子液体薄膜用于下一步制备PEDOT:PSS@聚离子液体复合透明电极。
(2)PEDOT:PSS与聚离子液体的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明聚离子液体薄膜上,得到复合薄膜。
(3)PEDOT:PSS@聚离子液体复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@聚离子液体复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@聚离子液体复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例11
(1)透明P[VBIm][NTf
2]薄膜的制备方法
将含1-乙烯基-3-丁基咪唑双(三氟甲烷磺酰)亚胺盐、1-乙基-3-乙基咪唑二腈胺盐、过氧化苯甲酰、聚乙二醇二甲基丙烯酸酯的溶液(1-乙烯基-3-丁基咪唑双(三氟甲烷磺酰)亚胺盐和1-乙基-3-乙基咪唑二腈胺盐/过氧化苯甲酰/过硫酸钾/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/50)涂布到玻璃片上,在90ºC加热10 min,形成P[VBIm][NTf
2]薄膜,此P[VBIm][NTf
2]薄膜用于下一步制备PEDOT:PSS@P[VBIm][NTf
2]复合透明电极。
(2)PEDOT:PSS与P[VBIm][NTf
2]的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明P[VBIm][NTf
2]薄膜上,得到复合薄膜。
(3)PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@P[VBIm][NTf
2]复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
实施例12
(1)透明P[VBIm][NTf
2]薄膜的制备方法
将含1-乙烯基-3-丁基咪唑双(三氟甲烷磺酰)亚胺盐、N-甲基咪唑硫酸氢盐、过氧化苯甲酰、聚乙二醇二甲基丙烯酸酯的溶液(1-乙烯基-3-丁基咪唑双(三氟甲烷磺酰)亚胺盐和N-甲基咪唑硫酸氢盐/过氧化苯甲酰/聚乙二醇二甲基丙烯酸酯的质量比例是1000/10/10)涂布到玻璃片上,在420nm紫外光下照射1 h,形成P[VBIm][NTf
2]薄膜,此P[VBIm][NTf
2]薄膜用于下一步制备PEDOT:PSS@P[VBIm][NTf
2]复合透明电极。
(2)PEDOT:PSS与P[VBIm][NTf
2]的静电作用
将PEDOT:PSS溶液旋涂到步骤(1)形成的透明P[VBIm][NTf
2]薄膜上,得到复合薄膜。
(3)PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的制备
将步骤(2)中的复合薄膜用蒸馏水冲洗数次,在120ºC加热10 min,得到导电性能和稳定性优异的PEDOT:PSS@P[VBIm][NTf
2]复合柔性透明电极。
(4)复合离子液体凝胶透明电极的应用
上述制备的PEDOT:PSS@P[VBIm][NTf
2]复合透明电极的透光率大于89%,可用于制备柔性触控器件和柔性太阳能电池。
本发明得到的PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极经过一千次弯曲循环测试不会损坏或者导电性下降,且经过0
-100 ºC温度加热、0-30
bar真空度环境对其性能无影响,生成的导电层性质稳定。
Claims (9)
- 一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,所述方法包括以下步骤:1)在基底上制备透明PEDOT:PSS薄膜或制备透明聚离子液体薄膜;透明聚离子液体薄膜的制备:在基底上涂布离子液体预聚液,用光或热引发离子液体预聚液在基底表面交联聚合得到聚离子液体薄膜;2)当步骤1)所制备的是透明PEDOT:PSS薄膜时,将步骤1)制备的透明PEDOT:PSS薄膜与离子液体预聚液通过静电作用复合,用光或热引发离子液体预聚液在PEDOT:PSS薄膜表面交联聚合,经水冲洗,加热,得到PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极;当步骤1)所制备的是透明聚离子液体薄膜时,将PEDOT:PSS溶液旋涂到聚离子液体薄膜上聚合,经水冲洗,加热,得到PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,在所述步骤1)中,通过旋涂制备透明的PEDOT:PSS薄膜。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,所述离子液体预聚液包括含有可聚合基团的离子液体以及含有可与PEDOT:PSS进行静电吸引的基团的离子液体;其中,含有可聚合基团的离子液体为含乙烯基双键的离子液体单体,具体为咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季磷盐类离子液体、吡咯烷类离子液体和哌啶类离子液体中的一种或多种;或者,含有可聚合基团的离子液体为含有可交联基团的聚离子液体为功能性聚离子液体,具体为含羧基、羟基、氨基或腈基的聚离子液体大分子;含有可与PEDOT:PSS进行静电吸引的基团的离子液体为咪唑类阳离子离子液体或二腈胺盐阴离子离子液体。
- 根据权利要求3所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,咪唑类离子液体为1-乙烯基-3-乙基咪唑二腈胺盐;吡啶类离子液体为N-乙烯基吡啶四氟硼酸盐;季铵盐类离子液体为三丁基乙烯基铵(三氟甲烷磺酰)亚胺盐;季磷盐类离子液体为三丁基乙烯基溴化膦;吡咯烷类离子液体为N-乙烯基-N-甲基吡咯烷溴盐;哌啶类离子液体为N-乙烯基-N-甲基哌啶溴盐;含羧基、羟基、氨基或腈基的聚离子液体大分子为聚(1-乙烯基-3-羧乙基咪唑硝酸盐)、聚(1-乙烯基-3-羟乙基咪唑四氟硼酸盐)、聚(1-乙烯基-3-胺丙基咪唑硝酸盐)或聚(1-乙烯基-3-乙基咪唑二腈胺盐);咪唑类阳离子离子液体为N-甲基咪唑硫酸氢盐或N-甲基咪唑双(三氟甲烷磺酰)亚胺盐;二腈胺盐阴离子离子液体为1-乙烯基-3-乙基咪唑二腈胺盐或1-乙基-3-乙基咪唑二腈胺盐。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,所述离子液体预聚液中还包括单体引发剂,所述的单体引发剂是安息香乙醚、二苯基乙酮、二苯甲酮、过硫酸钾、过硫酸铵、过氧化苯甲酰、过氧化二叔丁基、偶氮二异丁腈中的一种或多种;单体引发剂/离子液体预聚液中离子液体聚合物单体的质量比例是1/1000-20/1000。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,所述离子液体预聚液中还包括交联剂,所述的交联剂是N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、戊二醛、氯化钙水溶液、二异氰酸酯中的一种或多种;交联剂/离子液体预聚液中离子液体聚合物单体的质量比例是1/1000-50/1000。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,所述的光引发的波长为250 nm-420 nm。
- 根据权利要求1所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法,其特征在于,所述的热引发的加热温度是70-90 ºC。
- 权利要求1-8任一项所述的一种PEDOT:PSS@离子液体凝胶复合自支撑柔性透明电极的制备方法所制备的自支撑柔性透明电极。
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