CN104412335B - Utilize mixed electrode of nano silver wire and Graphene and preparation method thereof - Google Patents
Utilize mixed electrode of nano silver wire and Graphene and preparation method thereof Download PDFInfo
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- CN104412335B CN104412335B CN201380035160.3A CN201380035160A CN104412335B CN 104412335 B CN104412335 B CN 104412335B CN 201380035160 A CN201380035160 A CN 201380035160A CN 104412335 B CN104412335 B CN 104412335B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 113
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 239000002070 nanowire Substances 0.000 claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- -1 polyethylene terephthalate Polymers 0.000 claims description 14
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- 239000003638 chemical reducing agent Substances 0.000 claims description 10
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- 229940124024 weight reducing agent Drugs 0.000 claims description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
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- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940067157 phenylhydrazine Drugs 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 21
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical group O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000011112 polyethylene naphthalate Substances 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002042 Silver nanowire Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 229920002678 cellulose Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XGDBOJRURXXJBF-UHFFFAOYSA-M fluoroindium Chemical compound [In]F XGDBOJRURXXJBF-UHFFFAOYSA-M 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- NOVHEGOWZNFVGT-UHFFFAOYSA-N hydrazine Chemical compound NN.NN NOVHEGOWZNFVGT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000003828 vacuum filtration 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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention relates to the use of mixed electrode of nano silver wire and Graphene and preparation method thereof, in detail, relate to providing the technology of following mixed electrode and preparation method thereof: above-mentioned mixed electrode includes silver nanoparticle gauze and Graphene, thus the light transmittance of above-mentioned mixed electrode is high, above-mentioned mixed electrode has the sheet resistance of raising, electrocatalytic reaction and flexibility.
Description
Technical field
The present invention relates to the use of mixed electrode of nano silver wire and Graphene and preparation method thereof, in detail, relate to carrying
Technology for following mixed electrode and preparation method thereof: above-mentioned mixed electrode includes silver nanoparticle gauze and Graphene,
Thus the light transmittance of above-mentioned mixed electrode is high, above-mentioned mixed electrode has sheet resistance and the flexibility of raising.
Background technology
In display device or solaode, make light transmission and transmit image and the transparency electrode of electric current occurs is core
Heart parts.At present, using most is tin indium oxide (indium tin oxide；ITO) as transparency electrode purposes.
But, the usage amount of tin indium oxide is significantly increased year by year, and the reserves of corresponding tcrude ore are the abundantest, thus in advance
Meter corresponding tcrude ore soon can be exhausted, and the price of the tin indium oxide of costliness becomes the biggest problem.Further, when make by
During the transparency electrode bending prepared such as the oxide of tin indium oxide, there is slight crack or broken in sull, therefore,
There is the problem that the sheet resistance (sheet resistance) of transparency electrode increases, and exist and be difficult to be applicable to flexible electrical
The shortcoming of sub-device.Therefore, the transparency electrode of problem as above is can solve the problem that in the urgent need to exploitation.
Apply at American Chemical Society's nanometer (ACS Nano, 2010,4,2955)) in propose use nano silver wire system
There is the problem that the particle of insulating properties occurs having in the surface of nano silver wire in standby transparency electrode.Conventional use has
The flexible electrode of the nano silver wire of the sheet resistance similar with oxide-based transparency electrode is because of in the nanometer being layered on top of each other
The non-conductive portion that exists between line and need high critical concentration, therefore, only by nano silver wire film shape purely
The electrode become is difficult to be applicable to display or solaode.
It is known that, it is possible to diameter and length by regulation nano wire successfully change the critical dense of silver nanoparticle gauze
Degree.The nano wire with the structure mutually crossed has a structure of sparse thin separation, thus there is electricity cannot be whole
The problem flowed equably in individual face.Further, thin film or the coating with the structure that nano silver wire is layered on top of each other exist
The shortcoming with insulating property (properties), accordingly, there exist asking of the electrical property needed for cannot having electronic equipment or catalysis characteristics
Topic.
Can be used alone nano silver wire and there is the sheet resistance similar with conventional transparency electrode, but, because of shape
Become the silver oxide insulating particle on the surface of nano silver wire that the problem that sheet resistance increases occurs during using.
Further, in the structure of silver nanoparticle gauze, there is the Dead space generated because nano silver wire mutually crosses
, therefore there is the insulating space that electronics cannot be made to pass through, thus in order to have high conductance in (uncovered area)
Rate and need the critical concentration of high nano silver wire, cause the making of electronic equipment or electrode used for solar batteries to exist
Problem, the net of nano silver wire the thin film formed has high rough surface group, thus exists and cause electronic installation short
The problem on road.
Further, in utilizing CNT just to carry out to the research preparing electrode, but, CNT the electricity prepared
Extremely very sensitive to moisture, if absorbing moisture, sheet resistance can be significantly increased, and in order to prevent this phenomenon, and exists
The problem needing to carry out external application.Further, different from nano silver wire, the structure of CNT is sinuate, because of
And it is difficult to avoid that the coacervation occurring mutually being wound around serious CNT.
The work function of electrode is one of most important factor in the electronic device.In transparent conductive electrode, use stone
Ink alkene is electron transmission ability and the catalysis characteristics of Graphene of Graphene as the purpose of work function Auto-regulator.
The resistance of the touch screen electrode used in smart mobile phone or touch screen is 100-500 Ω/sq, such as solar energy
The resistance of electrode used in the photoelectronic device of battery is 10～30 Ω/sq, even if with the low burning of resistance
Thing.Generally, utilize the tin indium oxide that absorbance is more than 90% (indium tin oxide) in 550nm or
Person's absorbance is less than tin indium oxide but is fluorine-doped tin oxide (FTO, the fluorine-doped tin of more than 80%
Oxide) as electrode material.
But, these electrode materials are unstable in acid or alkali, and ion is prone to polymeric membrane diffusion and permeates,
Absorbance near infrared range is low, and fluorine-doped tin oxide exists the leakage of current, curved because of the defect in structure
Problem broken during folding.
Further, the comparative electrode of solaode generally uses electrocatalytic reaction (electrocatalytic activity)
Outstanding platinum, but there is expensive problem in platinum.
Therefore, the exploitation of photoelectron device must develop that chemical stability is outstanding, flatness is outstanding, absorbance is high
The new electrode materials of high conductivity, have been carried out much about use CNT, graphite, conductivity macromolecule,
White carbon blacks etc. substitute the research of the electrode material of platinum, tin indium oxide, fluorine-doped tin oxide etc..
After 2004 find, the Graphene performance with a Rotating fields of graphite with two-dimensional shapes can be answered
For the outstanding characteristic of following photoelectron device, therefore Graphene is just being carried out a lot of correlational study.Especially,
Graphene be band gap be the quasiconductor of 0eV, the conduction band of Graphene and valence band (valence band) contact with each other,
Thus there is the character of uniqueness, and, the work function (4.42eV) of Graphene and the Fluorin doped as transparency electrode
Stannum oxide (4.40eV) is close, carries out because of the highest electrical conductivity of Graphene and cheap processing probability
Electrode and the applied research of optoelectronic areas.
In dye-sensitized solar cell or organic solar batteries, utilize in a large number by fluorine-doped tin oxide or
The transparency electrode of tin indium oxide coating, but the roughness of electrode is fatefulue to the performance of photoelectron device.Fluorine
The electric short circuit of solaode can be caused in the coarse surface of doped stannum oxide electrode, it is therefore expected that surface is very
Smooth graphene film can the probability of replacement fluorine doped stannum oxide the highest.Further, substrate applies Fluorin doped
The operation of stannum oxide is extremely complex, uses expensive evaporation or sputtering process, therefore, causes Fluorin doped to aoxidize
The price of tin electrode rises, thus needs the exploitation can the technology of replacement fluorine doped stannum oxide.
So far, according to the content of Graphene, the electrical conductivity of transparent graphene composite is 10-3～1S/cm degree,
Thus it is not used as the electrode material of photoelectron device.
Summary of the invention
The technical problem to be solved in the present invention
It is an object of the invention to, it is provided that following mixed electrode and preparation method thereof: above-mentioned mixed electrode includes silver
Nanowire mesh and Graphene, thus the light transmittance of above-mentioned mixed electrode is high, above-mentioned mixed electrode has the surface of raising
Resistance, electrocatalytic reaction and flexibility.
Technical scheme
In order to reach above-mentioned purpose, the mixed electrode of one embodiment of the invention is characterised by, including substrate, silver
Nano wire and graphene film.
On the other hand, in order to reach above-mentioned purpose, the spy of the preparation method of the mixed electrode of one embodiment of the invention
Levy and be, including: the step of silver coating nano wire on substrate；And it is being coated with the substrate of above-mentioned nano silver wire
The step of upper coating solution-type Graphene.
Further, in order to reach above-mentioned purpose, the feature of the preparation method of the mixed electrode of another embodiment of the present invention
It is, including: the step of silver coating nano wire on substrate；The substrate being coated with above-mentioned nano silver wire applies
The step of lysotype graphene oxide；And make the step that above-mentioned graphene oxide reduces.
Beneficial effect
The mixed electrode of the present invention has light transmittance height and has the sheet resistance of raising and the effect of flexibility.
Further, the hot stability of the chemistry of the mixed electrode of the present invention is outstanding, it is possible to be applicable to the dye sensitization type sun
The electrode of the various electronic equipments such as energy battery.
Detailed description of the invention
Hereinafter, mixed electrode of the present invention and preparation method thereof is described in detail.
Mixed electrode
The present invention provides the mixed electrode including substrate, nano silver wire and graphene film.
Wherein, as long as aforesaid substrate is transparent and has the material of flexibility and does not the most limit, especially, aforesaid substrate
Be preferably selected from polyethylene terephthalate (PET, Polyethylene Terephthalate), polyether sulfone (PES,
Poly Ether Sulfone), polymethyl methacrylate (PMMA, Poly Methyl Methacrylate), poly-carbon
Acid esters (PC, Poly Carbonate), PEN (PEN, Polyethylene Naphthalate),
In cyclic olefine copolymer (COC, Cyclic Olefin Copolymer), polyimides (PI, Poly Imide)
More than one.
Preferably, a length of 5 μm of the above-mentioned nano silver wire included by the mixed electrode of the present invention～150 μm and vertical
Horizontal ratio is 200～2500:1.The sheet resistance of the effect length electrode of nano silver wire and light transmittance, therefore, upper
State the length of nano silver wire less than in the case of 5 μm, need further amounts of nano silver wire, and, along with silver nanoparticle
The quantity of the contact point that line and nano silver wire mutually cross and generate increases, and what final generation sheet resistance increased asks
Topic.In the case of the length of nano silver wire is more than 150 μm, the repeatability that there is sheet resistance declines, processes
Property deteriorate problem.
Preferably, the concentration of the above-mentioned nano silver wire included by the mixed electrode of the present invention is 1.0～10mg/mL.
The concentration of nano silver wire is the factor of light transmittance and the sheet resistance affecting electrode, therefore, at above-mentioned nano silver wire
Concentration, less than in the case of 1.0mg/mL, causes coating uniformity to decline because the viscosity of nano silver wire solution is too low,
In the case of the concentration of nano silver wire is more than 10mg/mL, exists because viscosity is too high and be difficult to asking of coating
Topic.
Preferably, Graphene used in the preparation process of the mixed electrode of the present invention or graphene oxide solution
Concentration is 0.5～5.0mg/mL.In the case of the concentration of graphene solution is less than 0.5mg/mL, in order to obtain
Required sheet resistance and need to make nozzle repeatedly come and go while being coated or carrying out repeating to apply, therefore deposit
Needing the problem of the coating time grown very much, in the case of the concentration of graphene solution is more than 5.0mg/mL, point
Dissipate graphene film stacking more than 10 layers and thickening situation is more, thus exist surface roughness height, light transmittance
The problem declined.
And, it is preferable that the thickness of the graphene film of coating is 1～100nm.Thickness at graphene film is more than
In the case of 100nm, use can be limited because the surface roughness of coating is high for electrode applications.
The mixed electrode of the present invention be sheet resistance be the electrode of 10～500 Ω/sq, electrical conductivity is outstanding, and light transmittance is
70～92%, transparent such that it is able to being effectively used in dye-sensitized solar cell etc. needs the electronics of the transparency
Equipment and solaode etc..
The preparation method of mixed electrode
The present invention provides the preparation method of a kind of mixed electrode, the preparation method of above-mentioned mixed electrode to include: at substrate
The step of upper silver coating nano wire；And on the substrate being coated with above-mentioned nano silver wire, apply solution-type Graphene
Step.
Further, according to another embodiment of the present invention, it is provided that the preparation method of a kind of mixed electrode, above-mentioned mixing electricity
The preparation method of pole includes: the step of silver coating nano wire on substrate；At the substrate being coated with above-mentioned nano silver wire
The step of upper coating lysotype graphene oxide；And make the step that above-mentioned graphene oxide reduces.
Wherein, as long as aforesaid substrate is transparent and has the material of flexibility and does not the most limit, especially, aforesaid substrate
It is preferably selected from polyethylene terephthalate (PET), polyether sulfone (PES), polymethyl methacrylate
(PMMA), Merlon (PC), PEN (PEN), cyclic olefine copolymer (COC),
More than one in polyimides (PI).
Preferably, a length of 5 μm of the above-mentioned nano silver wire included by the mixed electrode of the present invention～150 μm and vertical
Horizontal ratio is 200～2500:1.The sheet resistance of the effect length electrode of nano silver wire and light transmittance, therefore, upper
State the length of nano silver wire less than in the case of 5 μm, need further amounts of nano silver wire, and, along with silver nanoparticle
The quantity of the contact point that line and nano silver wire mutually cross and generate increases, and what final generation sheet resistance increased asks
Topic.In the case of the length of nano silver wire is more than 150 μm, the repeatability that there is sheet resistance declines, processes
Property deteriorate problem.
Preferably, the concentration of the above-mentioned nano silver wire included by the mixed electrode of the present invention is 1.0～10mg/mL.
The concentration of nano silver wire is the factor of light transmittance and the sheet resistance affecting electrode, therefore, at above-mentioned nano silver wire
Concentration, less than in the case of 1.0mg/mL, causes coating uniformity to decline because the viscosity of nano silver wire solution is too low,
In the case of the concentration of nano silver wire is more than 10mg/mL, exists because viscosity is too high and be difficult to asking of coating
Topic.
Preferably, Graphene used in the preparation process of the mixed electrode of the present invention or graphene oxide solution
Concentration is 0.5～5.0mg/mL.In the case of the concentration of graphene solution is less than 0.5mg/mL, in order to obtain
Required sheet resistance and need to make nozzle repeatedly come and go while being coated or carrying out repeating to apply, therefore deposit
Needing the problem of the coating time grown very much, in the case of the concentration of graphene solution is more than 5.0mg/mL, point
Dissipate graphene film stacking more than 10 layers and thickening situation is more, thus exist surface roughness height, light transmittance
The problem declined.
And, it is preferable that the thickness of the graphene film of coating is 1～100nm.Thickness big at graphene film
In the case of 100nm, use can be limited because the surface roughness of coating is high for electrode applications.
The substrate be coated with nano wire applies method or the coating lysotype graphene oxide of solution-type Graphene
Method can utilize the multiple methods such as vacuum filtration process, spurt method, ink-jet method, spin-coating method.
In utilizing the preparation method of the present invention of reduction process, method of reducing can be divided into 1) utilize reducing agent molten
Liquid processes the method for graphene oxide；And 2) utilize volatile reducing-agent steam to process graphene oxide
Two kinds of methods such as method.
Wherein, as long as the material that above-mentioned reductant solution can make graphene oxide reduce the most does not limits, but
Preferably, above-mentioned reductant solution is selected from hydrazine, thionyl chloride (thionyl chloride) and the one of sodium borohydride
More than Zhong.
On the other hand, the boiling point of above-mentioned reducing agent steam is 10～200 DEG C, it is preferable that above-mentioned reducing agent steam is
Selected from hydrazine monohydrate, sodium borohydride, hydroquinone, dimethylhydrazine, phenylhydrazine, ethylenediamine more than one.
Hereinafter, by specific embodiment, mixed electrode of the present invention and preparation method thereof is illustrated.
Preparation example
(1) preparation of nano silver wire
As in ACS Nano (American Chemical Society's nanometer, 2010,4 (5), 2955)) in introduce method, use many
Unit's alcohol regulates diameter and length, thus synthesis of silver nano-wire.
Specifically, by polyvinylpyrrolidone (PVP) and the potassium bromide (KBr) of 84.032mmol of 6.010mmol
Put into the round-bottomed flask of ethylene glycol (EG) equipped with 20mL, and synthesize.
For thermostabilization, the temperature of 170 DEG C while 800rpm (revolutions per minute) stirring mixture
After lower heating one hour, add the AgCl powder of 0.349mmol, thus generate initial stage Ag and crystallize (seed).
After five minutes, the silver nitrate solution in the ethylene glycol of 1.295mmol is titrated ten minutes with 1mL/min, and
Utilize within 1 hour, make nano silver wire grow completely.
By mixture instantaneous cooling to about 5 DEG C, and maintain 50 minutes at room temperature.Use water and acetone, utilize continuously
Dispersion-precipitation circulation purify product.After the dispersions of 15 times-precipitation circulation, most nanoparticle exists
Removed during pouring (decantation) container into.
The by-product at initial stage is nano wire, nanometer rods, nanocube.In order to remove nanocube, nanometer rods
And other nanoparticles, and employ polycarbonate membrane filter.Nano silver wire on polycarbonate membrane is devoted
Dichloromethane makes Merlon dissolve, and thus obtains elongated nano wire.The nano wire block of cohesion can easily divide
Dissipating in multi-solvents, the ultrasound wave of short time is the most abundant.In order to control the length of nano silver wire, change polyethylene
Ketopyrrolidine (PVP) and AgNO3Ratio.
(2) preparation of graphene oxide
It is known that Graphene has carbon atom by the two dimension structure that formed of covalent bond, and there is unique character
Strong catalysis activity (catalytic activity).The preparation method of graphene film makes highly oriented pyrolytic graphite
(HOPG, highly ordered pyrolytic graphite) repeatedly peel off (peeling) carry out interlaminar separation and
The method etc. that the mechanical methods being prepared and the chemical by carbon element aoxidize and prepare.
In an embodiment of the present invention, utilize easily prepared top-down solution operation to make graphite oxidation and sharp
Graphene is prepared with the graphene oxide thus prepared.The preparation method of graphene oxide is as follows.
Graphite as the material that sets out of Graphene employs the flake graphite purchased from Bay Carbon Co., and utilizes
Hummers (Xiu Mosi) method prepares graphene oxide.
Process cause graphite by bronsted lowry acids and bases bronsted lowry and prepare graphene oxide, utilize sulphuric acid and potassium permanganate (KMnO4)
To import oxide between graphite flake, and pH regulator is become use after neutrality.
Potassium sulfate is utilized under nitrogen flowing methanol to be purified.3-aminopropyltriethoxysilane
(APTES), concentrated hydrochloric acid equal solvent and reagent purchased from aldrich (Aldrich) company, purify.
Graphite (2g) is put into the flask of 500ml, and places 10 minutes in sulphuric acid (50ml) ice container.
Add potassium permanganate (6g) to its mixing liquid, add a small amount of (noting less than 25 DEG C) every time.Afterwards, exist
React two hours at a temperature of 35 DEG C.After the reaction of two hours, interpolation distilled water (92ml) is the most anti-
Answer 15 minutes.
Then add distilled water (280ml) and hydrogen peroxide (10ml) reacts 10 minutes then,.Then, add
After distilled water (900ml) and hydrochloric acid (100ml) react 30 minutes, distilled water is utilized to clean, until it becomes pH7,
And be dried in vacuum drier.By the ultrasound wave operation of 60W, graphite is carried out at least 3 hours
Interlaminar separation.High purity oxygen functionalized graphene is obtained from the upper solution separated by evaporization process.
Although the graphene oxide obtained by above operation is non-conductive material, but through reduction process just
Graphene can be become, and there is transport properties.The reactive group comprising the oxygen being present in graphene oxide gives hydrophilic
Property base give the characteristic that dissolves easily in water, therefore, when preparing Graphene, produce and can in industry a large amount of
Usability aspect is extremely important.In an embodiment of the present invention, employ to improve the purity of graphene oxide
Centrifugal separation, freeze-dried method obtain high-purity graphene oxide.
(3) preparation of mixed electrode and the reduction of graphene oxide
In an embodiment of the present invention, in order to utilize solution based processes to employ spin coating work to prepare Graphene electrodes
Sequence.
In order to utilize spin coating operation to form uniform graphene oxide film on substrate, and graphene oxide is made to disperse
And regulate the concentration etc. of spin coating rotating speed and graphene oxide, and purged by non-reactive gas, thus obtain
Thin film.
While changing the experiment factor of spincoating conditions etc., utilize scanning microscope or atomic force microscope to observe oxygen
The dispersity of functionalized graphene and the size variation of graphene oxide, the optimal spin coating needed for thus electrode is prepared in selection
Condition.Further, in the present invention, after graphene oxide be impregnated in hydrazine solution, utilize spin-coating method to be coated on silver
On nanowire mesh, thus prepare mixed electrode.
It is spun in the graphene oxide on nano silver wire and is attached with a lot of epoxy radicals, hydroxyl, carboxyl etc., therefore,
Having electrical insulating property, therefore itself is not used as electrode material.Need graphene oxide is converted to Graphene knot
The reduction process of structure, uses following reduction process.
The graphene oxide solution being stably scattered in water is spun on the substrate being coated with nano silver wire, and
After carrying out the chemical heat treatment of 10 minutes at a temperature of 150 DEG C, hydrazine gas is utilized to reduce.Graphite oxide
High sheet resistance (the ＞ 10 of alkene10Ω/sq) by reduction process in the mixed electrode of nano wire and Graphene
Drop to 100 Ω/sq value below.
(4) mixed electrode is applicable to dye-sensitized solar cell
The mixed electrode utilizing nano silver wire and the Graphene obtained in the present invention comes replacement fluorine doped stannum oxide or oxygen
Change indium stannum and prepare dye-sensitized solar cell as electrode.
The present invention can substitute indium tin oxide material exhausted within the more than ten years, it is possible to is infinitely applied to solar-electricity
The multiple optoelectronic areas such as pond, touch screen.Further, utilize prepared by the nano silver wire of solution-type and Graphene is mixed
Composite electrode utilizes abundant carbon resource and nano silver wire, therefore compared with tin indium oxide or fluorine-doped tin oxide, and preparation
Low cost, occurs when bending compared with crack increases sheet resistance with tin indium oxide or fluorine-doped tin oxide,
After bending experiment repeatedly, surface electrode does not the most almost change, and therefore has and can be applicable to flexible apparatus
Advantage.
<embodiment 1>
The graphene solution of reduction is applied on the net to prepare mixed electrode at nano silver wire.
Specifically, utilize Mei Yueer (Meyor) bar that diameter is about 35nm and length is about the Yin Na of 30 μm
Rice noodle solution is coated on polyethylene terephthalate (PET) base material, and is dried nano silver wire film.
Graphene oxide be impregnated in hydrazine solution to be reduced into Graphene.With the rotating speed of 1000rpm by molten for the Graphene of reduction
Liquid is spun on nano silver wire nethike embrane.The thickness of the graphene film of external application (overcoat) can be by regulation rotating speed
Change.When rotating speed is 1000rpm, sheet resistance reaches 165 Ω/sq, and light transmittance reaches 81%.
In the nano silver wire with the web frame mutually crossed, nano wire cannot cover a part of region of base material,
Thus form " inactive area (the uncovered area) " with non-conducting character.Cannot cover as above
Covering the region overlay graphene film of whole base material, thus, transparency electrode has electrical connectivity on the whole.
<embodiment 2>
Utilize method same as in Example 1, but be prepared by the order changing layer.I.e. first coating reduction on base material
Graphene, and silver coating nano wire thereon.
<embodiment 3>
Utilize (in-situ) reducing process in situ that the graphene oxide being externally applied on nano silver wire is prepared as mixing electricity
Pole.
Specifically, on polyethylene terephthalate (PET) base material, utilize Mei Yueer (Meyor) bar
After the nano silver wire solution of diameter about 35nm and length about 30 μm is carried out nano silver wire coating, at it
On with 1000rpm spin coating graphene oxide.Utilize the mixed film that hydrazine (hydrazine) steam treated is dried.Institute
The sheet resistance obtained is 150 Ω/sq, and light transmittance is 84%.Nano silver wire-graphene oxide mixed structure is exposed
In hydrazine steam, then realizing (in-situ) graphene oxide reduction in situ, meanwhile, hydrazine steam makes to be present in silver
The silver salt reduction of nano wire.
<comparative example 1>
The preparation method of nano silver wire electrode is as follows.
Use polyol process (polyol method) to synthesize diameter and be about 35nm and length is about the silver of 30 μm
Nano wire.For PET substrate, utilize 3-aminopropyltriethoxysilane
(APTES) process, and utilize the power of 50W to carry out oxygen plasma process.Preparation concentration is
The nano silver wire dispersion liquid of 5mg/mL.Mei Yueer (Meyor) bar is utilized to be coated on poly-by nano silver wire solution
On ethylene glycol terephthalate substrate, it is dried 10～30 minutes at a temperature of 150 DEG C.The table of nano silver wire film
Surface resistance is 175 Ω/sq, and the light transmittance at the wavelength of 550nm is about 83%.
<comparative example 2>
Combined silver nano wire and the preparation method of the electrode of water-soluble fibre used in embodiment 1 are as follows.
Use water-soluble cellulose (such as, hydroxypropyl methyl cellulose (HPMC), methylcellulose, ethoxy
Cellulose etc.) as viscosity modifier, use xanthan gum (Xanthan gum) as surfactant, use
Polyvinyl alcohol is as processing aid.Viscosity modifier plays raising coating processability but does not affect the property of silver nanoparticle gauze
The effect of matter.
<comparative example 3>
The mixed electrode that preparation is formed by single wall carbon nano tube and Graphene.As remembered in US2007/0284557
The content carried, admixed graphite alkene and CNT apply the mixed transparent electrode formed by graphene-carbon nano tube.
The diameter of the single wall carbon nano tube used is about 6nm, and length is about 200nm.Used in this comparative example
Graphene be and the graphite alkenes mentioned at PNAS (National Academy of Sciences, vol.102, No.30 (2005))
As simple layer or multi-layer graphene.Owing to single wall carbon nano tube is between graphene film and graphene film, because of
And the loose contact between graphene film, the quantity of the contact that graphene film contacts with each other increases, therefore, and surface electricity
Resistance up to 2000 Ω/about sq, light transmittance is 80%.
Compared with the electrode formed by CNT and Graphene, nano silver wire and Graphene the mixed transparent formed
Electrode has better connectivity and lower sheet resistance value.
<comparative example 4>
In the transparency electrode utilizing salt acid vapour to eliminate to be present in the metal-oxide on surface of nano silver wire, deposit
Be nano silver wire surface metal impurities over time through and make sheet resistance sharply increase.As
Described in the conventional patent of US2008/0286447A1, use include having of N and S to protect nano silver wire
The preservative (such as, fragrance triazole, imidazoles, thiazole) of machine thing.(receive at Nanoscale Research Letters
Rice research news flash, 2011,6,75) propose and utilize salt acid vapour to make a return journey the metal oxygen on surface of desilver nanostructure
Compound can reduce sheet resistance.In US2011/0024159, ammonia is utilized to clean from unreacted AgNO3
The silver halide (Silver halide) obtained and other by-products.Ammonia can be with insoluble silver salt Composite,
Utilize water to eventually clean.Hydrazine steam is effective to the reduction of silver graphene oxide.
Evaluate
The structure transitivity arranging comparative example and embodiment obtains table 1 below and table 2.
Table 1
Table 2
(◎: the most outstanding, zero: outstanding, ×: bad)
Understand with reference to table 1 and table 2, embodiment 1 to embodiment 3 and comparative example 1, comparative example 2, comparative example 4
Comparing, electro catalytic activity is outstanding, and, compared with Example 3, ageing stability is outstanding.
Above, the specific embodiment of the present invention is illustrated, but, without departing from the scope of the present invention can
Enough carry out various deformation.Therefore, the scope of the present invention is not limited to embodiment described, but wants according to invention
Depending on asking protection domain and equivalent thereof to substitute.
As it has been described above, illustrate the present invention with reference to limited embodiment and accompanying drawing, but, the invention is not limited in
Above-described embodiment, one skilled in the art of the present invention can carry out multiple amendment based on as above record
And deformation.Therefore, the thought of the present invention should define according to the claimed scope of invention, and should be interpreted that invention
The equivalent of claimed scope or equivalent variations belong to the thought range of the present invention.
Claims (11)
1. a transparent mixed electrode, it is characterised in that
Including substrate, nano silver wire and graphene film；
A length of 5 μm of described nano silver wire～150 μm, and aspect ratio is 200～2500:1, concentration is
1.0～10mg/mL,
Described graphene film by the solution-type Graphene that concentration is 0.5～5.0mg/mL or concentration be 0.5～
The lysotype graphene oxide of 5.0mg/mL is formed, and the thickness of described graphene film is 1nm～100nm,
The sheet resistance of described transparent mixed electrode is 10～500 Ω/sq.
Transparent mixed electrode the most according to claim 1, it is characterised in that described substrate is for selected from poly-
Ethylene glycol terephthalate, polyether sulfone, polymethyl methacrylate, Merlon, cyclic olefine copolymer,
More than one in PEN and polyimides.
Transparent mixed electrode the most according to claim 1, it is characterised in that described transparent mixed electrode
Light transmittance be 70～94%.
4. the preparation method of a transparent mixed electrode, it is characterised in that including:
The step of silver coating nano wire on substrate, and
The substrate being coated with described nano silver wire applies solution-type Graphene and forms the step of graphene film
Suddenly；
A length of 5 μm of described nano silver wire～150 μm, and aspect ratio is 200～2500:1, concentration is
1.0～10mg/mL,
The concentration of described solution-type Graphene is 0.5～5.0mg/mL,
The thickness of described graphene film is 1nm～100nm,
The sheet resistance of described transparent mixed electrode is 10～500 Ω/sq.
The preparation method of transparent mixed electrode the most according to claim 4, it is characterised in that described base
Plate is selected from polyethylene terephthalate, polyether sulfone, polymethyl methacrylate, Merlon, ring
More than one in olefin copolymer, PEN and polyimides.
6. the preparation method of a transparent mixed electrode, it is characterised in that including:
The step of silver coating nano wire on substrate,
The substrate being coated with described nano silver wire applies the step of lysotype graphene oxide, and
The reduction of described graphene oxide is made to form the step of graphene film；
A length of 5 μm of described nano silver wire～150 μm, and aspect ratio is 200～2500:1, concentration is
1.0～10mg/mL,
The concentration of described lysotype graphene oxide is 0.5～5.0mg/mL,
The thickness of described graphene film is 1nm～100nm,
The sheet resistance of described transparent mixed electrode is 10～500 Ω/sq.
The preparation method of transparent mixed electrode the most according to claim 6, it is characterised in that described also
Former is to utilize reductant solution to process graphene oxide.
The preparation method of transparent mixed electrode the most according to claim 7, it is characterised in that described also
Former agent solution is selected from more than one of hydrazine, thionyl chloride and sodium borohydride.
The preparation method of transparent mixed electrode the most according to claim 6, it is characterised in that described also
Former is to utilize volatile reducing-agent steam to process graphene oxide.
The preparation method of transparent mixed electrode the most according to claim 9, it is characterised in that described
The boiling point of reducing agent steam is 10～200 DEG C, described reducing agent steam be selected from hydrazine monohydrate, sodium borohydride,
Hydroquinone, dimethylhydrazine, phenylhydrazine, ethylenediamine more than one.
The preparation method of 11. transparent mixed electrodes according to claim 6, it is characterised in that described
Substrate be selected from polyethylene terephthalate, polyether sulfone, polymethyl methacrylate, Merlon,
More than one in cyclic olefine copolymer, PEN and polyimides.
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| PCT/KR2013/002868 WO2013165101A1 (en) | 2012-04-30 | 2013-04-05 | Hybrid electrode using silver nanowires and graphene, and preparation method thereof |
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| KR101536627B1 (en) * | 2013-04-30 | 2015-07-14 | 한국교통대학교산학협력단 | METHOD OF MANUFACTURING HYBRID ELECTRODE USING Ag NANOWIRE AND GRAPHENE |
| US9337149B2 (en) | 2014-07-29 | 2016-05-10 | Samsung Electronics Co, Ltd. | Semiconductor devices and methods of fabricating the same |
| KR101627422B1 (en) * | 2014-09-30 | 2016-06-03 | 한양대학교 산학협력단 | Transparent electrode by metal nanowire with graphene oxide using complex light source with full range wavelenth and fabrication method of thereof |
| CN104492677A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method for transparent electric coating for graphene protection |
| CN106180749B (en) * | 2016-07-23 | 2018-07-17 | 常州大学 | It is a kind of doping big L/D ratio nano-silver thread graphene preparation method and its application in terms of preparing conducting resinl |
| KR101976611B1 (en) * | 2016-11-24 | 2019-05-10 | 한국화학연구원 | Graphene laminated structure and method for manufacturing the same |
| CN107673328A (en) * | 2017-09-27 | 2018-02-09 | 郴州博太超细石墨股份有限公司 | A kind of graphene/nano silver line nesa coating and its preparation method and application |
| CN107768023A (en) * | 2017-09-27 | 2018-03-06 | 林荣铨 | There is composite construction conducting film of high adhesion force and preparation method thereof based on graphene |
| CN107910128B (en) * | 2017-10-13 | 2020-01-21 | 哈尔滨工业大学深圳研究生院 | Method for improving mechanical property of flexible device by graphene oxide self-assembled composite silver nanowire |
| CN108517048B (en) * | 2018-04-28 | 2020-12-25 | 吉林建筑大学 | Silver nanowire grid-reduced graphene oxide composite electrode and preparation method thereof |
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| CN112652721B (en) * | 2020-12-22 | 2022-11-01 | 中国科学院长春应用化学研究所 | Silver nanowire composite electrode with low resistance, high transmittance and low roughness, and preparation method and application thereof |
| CN117374135B (en) * | 2023-12-04 | 2024-03-22 | 广东省载诚新材料有限公司 | Metal oxide composite conductive film and application thereof in preparation of heterojunction solar cell |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101365649A (en) * | 2006-03-13 | 2009-02-11 | 株式会社尼康 | Process for production of carbon nanotube aggregates, carbon nanotube aggregates, catalyst particle dispersion membrane, electron emitters, and field emission displays |
| WO2011016889A2 (en) * | 2009-05-22 | 2011-02-10 | William Marsh Rice University | Highly oxidized graphene oxide and methods for production thereof |
| CN102270524A (en) * | 2010-05-21 | 2011-12-07 | 中国科学院福建物质结构研究所 | Silver nano-wire transparent conducting film based on thermoplastic transparent polymer and preparation method thereof |
Family Cites Families (2)
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| WO2011016889A2 (en) * | 2009-05-22 | 2011-02-10 | William Marsh Rice University | Highly oxidized graphene oxide and methods for production thereof |
| CN102270524A (en) * | 2010-05-21 | 2011-12-07 | 中国科学院福建物质结构研究所 | Silver nano-wire transparent conducting film based on thermoplastic transparent polymer and preparation method thereof |
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