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WO2016034113A1 - Encre conductrice a pedot/pss et electrode transparente - Google Patents

Encre conductrice a pedot/pss et electrode transparente Download PDF

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Publication number
WO2016034113A1
WO2016034113A1 PCT/CN2015/088806 CN2015088806W WO2016034113A1 WO 2016034113 A1 WO2016034113 A1 WO 2016034113A1 CN 2015088806 W CN2015088806 W CN 2015088806W WO 2016034113 A1 WO2016034113 A1 WO 2016034113A1
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Prior art keywords
pedot
pss
conductive
conductive ink
ink
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English (en)
Chinese (zh)
Inventor
李大忠
李葰
李元尨
宋立文
陶志刚
李红光
黄心毅
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Priority claimed from CN201410445544.9A external-priority patent/CN104212243B/zh
Priority claimed from CN201410445623.XA external-priority patent/CN104183303B/zh
Application filed by Individual filed Critical Individual
Publication of WO2016034113A1 publication Critical patent/WO2016034113A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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

Definitions

  • the invention relates to a PEDOT/PSS conductive ink and a coating and a related stable transparent coating structure electrode, and belongs to the field of organic optoelectronic applications.
  • Transparent conductive films especially transparent electrodes, play an important role in the display and solar industries.
  • ITO indium tin oxide
  • many research institutions around the world are looking for viable alternatives.
  • materials replacing ITO have been proposed.
  • PEDOT/PSS The conductive polymer poly 3,4-ethylenedioxythiophene-polyvinylbenzenesulfonic acid
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT/PSS is one of the most widely used conductive polymers in the field of optoelectronic components.
  • transparent conductive film made of PEDOT/PSS has the unmatched advantages of traditional ITO materials in the large-scale production and flexible electronics industries.
  • the PEDOT/PSS conductive ink required for the printing film forming process has a certain viscosity, and the thickening agent is often required in the existing high viscosity ink preparation process. Due to the addition of a non-conductive thickener, the conductivity of the transparent conductive film made of the PEDOT/PSS conductive ink is lowered, the haze is increased, and the like;
  • the prepared transparent electrode has excellent electrical, optical and mechanical properties and has been the direction of the industry.
  • researchers have proposed a method for preparing transparent electrodes based on materials such as conductive polymers, carbon nanotubes, graphene, metal grids, and nano-silver wires.
  • the performance of the transparent electrode materials prepared by most of these methods is not comparable to that of ITO transparent electrodes.
  • transparent electrodes prepared based on nano-silver wires have been proved to be the most excellent performance, and they have an electrical property of 100 ⁇ / ⁇ or less while maintaining 90% transmittance. Bend, good adhesion, become a substitute The preferred material for ITO transparent electrodes.
  • Nano silver wire has outstanding performance in many ITO replacement materials, but there are also technical defects that are difficult to avoid. Mainly in the following aspects: (1) organic matter has an advantage in the preparation process of the film-forming device, which requires the transparent electrode material to have a matching energy level, which is also a so-called work function requirement in the industry. In this respect, the nano silver wire material is difficult to interface with other organic functional layer materials; (2) The flatness of the transparent electrode surface has a significant influence on the photoelectric conversion efficiency of the thin film solar cell. Therefore, the evaluation of the quality of the transparent electrode material should not only refer to the transmittance, conductivity, bending, etc., and the surface flatness has become a very important evaluation index for the transparent electrode material.
  • the nano silver wire material is still insufficient;
  • the transparent electrode material is required to have high stability, and the performance of the electrode film such as conductivity and light transmittance is relatively stable as the device is used for a long time.
  • a very critical evaluation indicator for transparent electrode materials is required.
  • PEDOT/PSS has a work function that matches most organic materials, as well as good conductivity and light transmittance, and can be processed by a solution/print process.
  • the conductivity of PEDOT/PSS is difficult to meet the requirements of transparent electrodes for OLED and other components. It takes a long time to make breakthroughs in the use of transparent electrodes alone.
  • the combination of nano-silver wire and PEDOT/PSS can make the properties of the two conductive materials complement each other, that is, while ensuring the conductivity, the problem of energy level matching can be solved, and PEDOT/PSS can also be used for improvement.
  • the non-uniformity of the surface of the nano-silver wire material coating provides a new solution for mass production of transparent electrodes in the flexible device field in the future.
  • the object (1) of the present invention is to provide a neutralizable PEDOT/PSS conductive ink having low viscosity properties and good environmental resistance, and the solution is to solve the problem of neutralization and viscosity during the reaction.
  • a PEDOT/PSS conductive ink is prepared.
  • the neutral conductive ink can be applied on a large scale by screen printing or the like, and the resulting conductive coating has high transparency and a low haze value.
  • the object (2) of the present invention is to provide a novel transparent electrode of a PEDOT/PSS conductive layer composited with a nanosilver layer and a preparation method thereof. Based on the solution method/printing method, the nano-silver wire conductive layer and the PEDOT/PSS conductive layer or the conductive layer formed by blending the PEDOT/PSS and the nano silver wire are sequentially coated on the transparent substrate layer to form a stacked layer. Electrode structure.
  • the laminated transparent electrode effectively reduces the sheet resistance of the entire transparent electrode film layer; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano silver wire conductive layer, it is isolated from the outside air, thereby avoiding
  • the effect of the PEDOT/PSS conductive layer on the increase of the sheet resistance due to the corrosive action of the acidic PEDOT/PSS and the nano-silver line; and the coating of the PEDOT/PSS conductive layer can also improve the conductivity of the nano-silver conductive layer and the surface during coating. Inhomogeneity.
  • the transparent conductive layer electrode provided by the invention ensures the stability of the transparent electrode in terms of heat resistance and current resistance.
  • the addition of a non-conductive thickener in the PEDOT/PSS dispersion and the effect of neutralizing ions by direct neutralization are avoided, resulting in a film made of the neutral conductive ink.
  • the conductivity, light transmittance, and haze properties are greatly improved; this ion-free neutral PEDOT/PSS material provides a mixture with other types of conductive materials such as nanosilver wires, metal meshes, etc. Possibility to effectively reduce the corrosion of metals due to acidity It is possible to ensure that the conductivity and stability of the resulting conductive coating are not affected.
  • an organic functional additive by appropriately adding an organic functional additive, the environmental resistance of the transparent conductive film, such as stability against water, solvent, and the like, is improved.
  • the PEDOT/PSS conductive inks described above can be prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions.
  • the organic functional additive includes at least one condensate of a guanamine and at least one carbonyl compound as an adhesive.
  • the condensate of guanamine and at least one carbonyl compound, preferably guanamine, is condensed with an aldehyde or a ketone.
  • Suitable aldehydes or ketones are: formaldehyde, acetaldehyde, butyraldehyde, acetone or methyl ethyl ketone.
  • Particularly preferred is formaldehyde;
  • a particularly preferred condensate of guanamine and at least one carbonyl compound is a guanamine-formaldehyde condensate having the structure of formula (I)
  • R 1 represents H or a linear or branched C1 to C8 alkyl group, a phenyl group or a mono-, di-, or tri-substituted phenyl group, preferably H or a linear or branched C1 to C4 alkyl group, a phenyl group, Particularly preferred is H or a methyl group, an ethyl group and a phenyl group.
  • R 2 to R 5 independently of each other represent H or CH 2 -OR 6 , at least one of the groups R 2 to R 5 is not H, and R 6 represents H or a linear or branched C1 to C8 alkyl group, preferably H Or a linear or branched C1-C4 alkyl group, particularly preferably R 2 to R 5 each represent H or CH 2 -OR 6 .
  • such a particularly preferred guanamine-formaldehyde condensate may be a condensation product of the condensate of the formula (I) with each other or with another guanamine.
  • the particularly preferred guanamine-formaldehyde condensate may be partially or fully etherified. Additionally or alternatively, the particularly preferred guanamine-formaldehyde condensate may be modified by reaction with an amine, an aminocarboxylic acid or a sulfite, or by reacting with other compounds reactive with the aldehyde, such as phenols. Or urea co-condensation to modify to improve solubility in water.
  • the content of the condensate of the guanamine and the at least one carbonyl compound in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
  • the PEDOT/PSS conductive inks are prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions.
  • the organic functional additive includes at least one non-aqueous solvent type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone as an adhesive.
  • the non-aqueous solvent-type polyester adhesive used specifically refers to polyglycol dicarboxylate (n ⁇ 10) and its modifications or diethylene glycol dicarboxylate and its modifications;
  • the alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol;
  • the ether may be diethyl ether, n-propyl ether, n-butyl ether, methyl butyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane.
  • the ketone may be acetone, methyl ethyl ketone, methyl isobutyl ketone or methyl t-butyl ketone;
  • the polymer content in the polyester solution is from 0.5 to 85%, preferably from 25 to 30%;
  • the content of the nonaqueous solvent-type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
  • the above two types of adhesives can also be added at the same time, the weight ratio of the two is 1:10 to 1:1, and the total content is 0.001 to 15% by weight based on the weight of the neutral dispersion respectively. It is preferably 0.1 to 2% by weight.
  • the dispersion liquid of the conductive ink of the invention may be water type or solvent type; the provided adhesive agent can be made of acidic PEDOT/PSS conductive ink, or can be made of ordinary neutralized PEDOT/PSS conductive ink.
  • the latter is to adjust the pH to near-neutral using an alkaline additive in the acidic PEDOT/PSS dispersion, wherein some neutral ions are generated due to the acid-base reaction, and if not removed, the performance of the conductive coating is seriously affected.
  • Neutralization in the polymerization reaction while solving the viscosity characteristics is the core of the PEDOT/PSS conductive ink involved in the present invention.
  • Phosphate ester may be added as a viscosity modifier during the polymerization reaction (may, before, after), and the ester moiety may be methyl, ethyl, propyl, n-butyl, isopropyl, and combinations thereof; 0.0005 to 1% by weight, preferably 0.01 to 0.2% by weight.
  • Neutralizing the reaction solution after the polymerization reaction using a basic additive to adjust the pH to near neutral;
  • the alkaline additive used may be an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, an alkali metal carbonate or a hydrogencarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, carbonic acid.
  • an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide
  • an alkali metal carbonate or a hydrogencarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, carbonic acid.
  • alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonates or hydrogencarbonates such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamines, for example with optionally substituted C1 to C20 a mono-, di- or tri-alkylamine of an alkyl group such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine or dimethylethanolamine, an aromatic amine such as aniline, Diphenylamine, o-diphenylamine, m-diphenylamine or p-diphenylamine.
  • alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonates or hydrogencarbonates such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamines, for example with optionally substituted C1 to C20 a mono-, di- or tri-alkylamine of
  • the alkaline additive is preferably used in the form of a solution, preferably the solvent may be water and/or an alcohol for neutralizing the PEDOT/PSS dispersion.
  • the alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol;
  • the above basic additives are also suitable for the preparation of the above generally neutralized PEDOT/PSS conductive ink.
  • the PEDOT/PSS conductive ink provided by the invention adds the alkaline additive to the PEDOT/PSS dispersion, adjusts the pH value of the system through the pH agent, and the pH ranges from 5.0 to 9.0, preferably the pH ranges from 6.0 to 8.0, more preferably the pH.
  • the value is 6.5 to 7.2;
  • the viscosity ranges from 1 000 to 50 000 mPa ⁇ s, preferably the viscosity ranges from 2 000 to 20 000 mPa ⁇ s; more preferably, the viscosity range is 5 000 to 8 000 mPa ⁇ s;
  • the organic functional additive added in the preparation of the conductive ink includes other organic functional additives such as a conductive enhancer, a surfactant and a leveling agent;
  • a functionalized conductive coating is applied to a substrate such as a composition or laminate.
  • a novel transparent electrode having a neutralized PEDOT/PSS conductive layer, comprising a transparent substrate layer and covering the through A conductive layer on the substrate layer, the conductive layer comprising a nano-silver wire conductive layer overlying the transparent substrate layer, and a neutralized PEDOT/PSS conductive layer overlying the nano-silver wire conductive layer.
  • the transparent substrate layer is selected from transparent materials: glass, glass resin, fluoropolymer, silicone, polyolefin, polyether hydrocarbon, PET, PEN, PMMA, and copolymer or composition of PC, PI and combinations thereof. Or laminate, etc.;
  • the conductive layer has a thickness of 50 to 300 nm;
  • the neutralized PEDOT/PSS conductive layer constituting the above is made of a neutralized PEDOT/PSS conductive ink:
  • the nano silver wire conductive ink used in the present invention has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 ⁇ m, and a nano silver wire diameter of 5 to 300 nm;
  • a preparation method for a neutralized PEDOT transparent stable electrode comprising the following steps:
  • a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire is cured to form a polymer conductive layer.
  • the present invention has the following beneficial effects:
  • the transparent electrode having a neutralized PEDOT/PSS composite conductive layer has a sheet resistance of 10 to 150 ⁇ / ⁇ and a light transmittance of 85 to 91% at a wavelength of 550 nm, thereby obtaining high conductivity and high. Transmittance; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano-silver wire conductive layer to isolate it from the outside air, and avoiding corrosion due to contact with silver nanowires with acidic PEDOT/PSS The effect of increasing the sheet resistance is to significantly improve the stability of the transparent electrode in terms of heat resistance and current resistance.
  • the transparent electrode film having the neutralized PEDOT/PSS composite conductive layer of the present invention has the advantages of high conductivity, good light transmittance, simple manufacturing process, weather resistance and current resistance, and can be used for organic solar cells and organic light-emitting. Diode or touch display and medical devices, capacitors and other fields.
  • Figure 1 is a schematic cross-sectional view showing the structure of the present invention
  • Figure 2 shows the stability of transparent electrodes made of different conductive materials at different temperatures.
  • Figure 3 is a scanning electron microscope image (SEM) of a transparent electrode made of different conductive materials.
  • Examples 1 to 5 and Comparative Examples 1 and 2 are preparations of a neutralized PEDOT/PSS dispersion based on the above polymerization process.
  • Example 1 After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 2 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
  • Example 1 After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 5 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
  • Example 2 After completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 2 hours, and after the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, 2-amino-2-methyl-1-propanol was added thereto. After the pH meter monitors the pH to near neutral, the viscosity is measured by a rotary viscometer;
  • Example 2 After the completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 5 hours, and the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, and 2-amino-2-methyl-1-propanol was added thereto. After the pH meter is adjusted to monitor the pH to near neutral, the viscosity is measured by a rotary viscometer;
  • Table 1 Viscosity and pH of PEDOT/PSS dispersions in Examples 1 to 5 and Comparative Examples 1 and 2.
  • Example 2 0.5 4500 7.5
  • Example 3 1 2354 7.6
  • Example 4 2 4672 8.0
  • Example 5 5 4736 7.8 Comparative example 1 2 25 7.5 Comparative example 2 5 33 7.6
  • the difference between the operation of the examples and the comparative example is that in the embodiment, the alkali is first added to adjust the pH value, and then aged for different time (0.5 hour, 1 hour, 2 hours, 5 hours), and then treated by anion-cation exchange resin.
  • the comparison ratio is first aged for different time (2 hours, 5 hours), and then treated by anion-cation exchange resin, and then alkali is added to adjust the pH.
  • the viscosity of the neutralized PEDOT/PSS dispersion prepared in Examples 1, 3, 4 and 5 increased with the aging time, and the viscosity after 2 hours of aging time Basically stable; and in Example 2, triethyl phosphate was added as a material, and after 0.5 hours of aging, the viscosity was nearly stable (substantially the same as the viscosity values in Examples 4 and 5); prepared in Comparative Examples 1 and 2.
  • the viscosity of the neutralized PEDOT/PSS dispersion does not change with the aging time, and is a low-viscosity dispersion. In the coating process such as screen printing, it is necessary to add a thickener to the desired viscosity before use.
  • Examples 6 to 10 are based on the neutralized PEDOT/PSS dispersion prepared in Example 4, and an adhesive, a surfactant, and a conductivity enhancer are added to prepare a neutralized PEDOT/PSS conductive ink; 3-7 is a neutralized PEDOT/PSS conductive ink prepared on the basis of Comparative Example 1 and a commercially available PH500 product by adding a thickener, an adhesive, a surfactant, and a conductive reinforcing agent.
  • Benzoin amine-formaldehyde resin WH-03 and adipic acid diethylene glycol polyester methyl ethyl ketone solution SJS-2 or polyethylene glycol dicaprate isopropanol solution SJS- used in the examples and comparative examples 3 are all synthetically produced by Shanghai Synthetic Resin Research Institute.
  • the PEDOT/PSS conductive inks prepared in Examples 6 to 10 and Comparative Examples 3 to 7 were made of a 100 ⁇ m high transparent PET film (Dongli) as a substrate (light transmittance > 92.0%, haze ⁇ 0.5%).
  • a wet film thickness of 20 ⁇ m was applied to the bar, and cured at 135 ° C for 5 minutes to prepare a transparent conductive film, and the relevant performance data was tested (Table 2).
  • the four-probe resistance meter was used to test the resistance of the coating sheet; the transmittance and haze were tested according to the standard GB/T 2410-2008; the pencil hardness was tested according to GB/T6739-2006; the coating adhesion test was GB. /T9286-1998 (Hundred Grid Knife) experimental test;
  • the film made of conductive ink with Benzene guanamine-formaldehyde resin WH-03 has higher pencil hardness, but the haze is too large.
  • WH-03 is mixed with SJS-2SJS-3. After that, the obtained performance data of the conductive ink is optimized in all aspects; and the conductive ink after adjusting the viscosity by adding TT-615 as a thickener, the sheet resistance and the haze value of the film are large.
  • the resistance of the transparent conductive film coating to the solvent was measured by rubbing the cotton wool ball infiltrated with different solvents at a pressure of 1 kg for 10 times.
  • Table 3 Solvent resistance of transparent conductive film coatings prepared in Examples 6 to 10 and Comparative Examples 3 to 7
  • the stabilized PEDOT/PSS conductive layer electrode of the present invention comprises a transparent substrate layer 1 and a transparent electrode layer, and the transparent electrode layer covers the transparent substrate layer 1 and has a thickness of 25 ⁇ 1000 nm, comprising a nano-silver wire conductive layer 2 coated on the substrate layer 1, and a neutral PEDOT/PSS polymer conductive layer coated on the surface of the nano-silver wire conductive layer 2 or blended with the nano-silver wire
  • the polymer conductive layer 3 is formed later.
  • the transparent substrate layer 1 is made of a transparent material such as glass, PET, PEN, PMMA or PI as a substrate material.
  • the nano silver wire conductive layer 2 is formed by coating a nano silver wire conductive ink on a transparent substrate layer.
  • the nano silver wire conductive ink has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 ⁇ m, a nano silver wire diameter of 5 to 300 nm, and a polymer conductive layer 3 of a nano silver wire.
  • the unique laminated structure of the neutral PEDOT/PSS conductive polymer layer and the nano silver wire conductive layer greatly reduces the sheet resistance of the transparent electrode conductive layer while maintaining good light transmittance, haze and the like. It is worth mentioning that the transparent electrode made of this structure also has very stable environmental resistance such as heat resistance, solvent resistance and current resistance.
  • a method for preparing a stable PEDOT/PSS conductive layer electrode using the above structure comprising the steps of:
  • a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire, and the polymer conductive layer 3 is formed by curing optimization.
  • the substrate material is subjected to surface pretreatment as the transparent substrate layer 1.
  • the optical PET film was selected as the substrate material, and the surface was cleaned before use, and ultrasonic cleaning was carried out in the ultrasonic cleaning bath for 10 minutes with washing liquid, deionized water, isopropyl alcohol and deionized water, and then dried in a nitrogen stream.
  • a nano-silver wire conductive layer 2 is prepared by coating on the transparent substrate layer 1.
  • the nano silver wire conductive ink is selected as the material, and the nano silver wire conductive ink (XFNANO Agnws-60nm/20 ⁇ m isopropanol solvent, solid content 5%, Nanjing Xianfeng nanometer) is adopted by a roll coating process. Material Technology Co., Ltd.) was coated on the surface of the transparent substrate layer 1 with a wet film thickness of 12 ⁇ m. After coating, the coating was dried at 150 ° C for 5 minutes to prepare a nano-silver wire conductive layer 2.
  • the nano silver wire conductive ink XFNANO Agnws-60nm/20 ⁇ m isopropanol solvent, solid content 5%, Nanjing Xianfeng nanometer
  • a neutral PEDOT/PSS polymer conductive layer 3 is coated on the nano silver wire conductive layer 2.
  • a neutral PEDOT/PSS conductive ink was prepared as in Example 10.
  • a blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink is coated on the nano silver wire conductive layer 2 to form a polymer conductive layer 3.
  • the preparation process of the neutral PEDOT/PSS conductive ink preparation is also the same as that of the embodiment 11;
  • a blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink was printed on the surface of the nano silver wire conductive layer 2, and the process liquid was the same as in Example 11, thereby completing the entire stable PEDOT/PSS conduction. Layer electrode.
  • the Heraeus PEDOT/PSS CLEVIOS TM PH1000 dispersion was selected as the comparative experimental material, and the following four comparative conductive layer electrodes were designed and fabricated at different temperatures (90, 120, 150, 180, The stability of the surface resistance of each conductive layer electrode was tested at 210 ° C):
  • the nano-silver wire conductive ink was coated into a conductive layer electrode according to the method of Example 11, and the surface resistance curve with temperature was tested (the block line AgNW in Fig. 2) );
  • the nano silver wire conductive ink was coated into a nano silver wire conductive layer according to the method of Example 11, and then coated on the conductive layer to prepare PH1000 to be electrically conductive.
  • Example 11 The conductive layer electrode prepared in Example 11 was tested for the surface resistance as a function of temperature (upper triangle line AgNW/Neutral-pH PEDOT in Fig. 2);
  • the conductive layer prepared by the composite of nano-silver wire and PH1000 shows that the square resistance decreases sharply and the conductivity decreases sharply after the temperature rises to 150 ° C.
  • the conductive film which is made of neutral PEDOT/PSS conductive ink and nano silver wire is used. Its sheet resistance is very stable with temperature changes.
  • the conductive layer made of nano silver wire, PH1000 and neutral PEDOT/PSS conductive ink alone has stable performance with temperature change. Therefore, the PEDOT/PSS conductive ink after neutral treatment is used in combination with a metallic conductive material such as a nano silver wire.
  • the PH1000 product shows good compatibility and stability.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne des procédés de préparation pour une encre conductrice à PEDOT/PSS, un revêtement conducteur et une électrode enrobée. Le procédé de préparation de l'encre conductrice comprend les étapes suivantes: l'obtention d'une dispersion de PEDOT/PSS avec une viscosité d'encre neutre, suivie de l'ajout d'au moins un condensat formé par de la guanamine et au moins un composé carbonyle et/ou une solution de polyester à solvant non aqueux en tant qu'adhésif dans la dispersion avec la viscosité d'encre et l'ajout d'autres additifs fonctionnels pour obtenir l'encre conductrice à PEDOT/PSS. Sur un substrat transparent (1), un revêtement conducteur à base de nanofils d'argent (2) est revêtu sur la première couche, et un revêtement d'encre conductrice à PEDOT/PSS (3) ou un revêtement conducteur (3) formé par le mélange d'une encre conductrice à PEDOT/PSS neutralisée ou une encre conductrice à nanofils d'argent est revêtu sur la seconde couche, de manière à former une électrode enrobée en une structure stratifiée. Une telle électrode peut être utilisée dans des domaines tels que des cellules solaires organiques, des diodes électroluminescentes organiques ou des écrans à affichage tactile et des dispositifs médicaux et des condensateurs.
PCT/CN2015/088806 2014-09-03 2015-09-02 Encre conductrice a pedot/pss et electrode transparente Ceased WO2016034113A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201410445544.9A CN104212243B (zh) 2014-09-03 2014-09-03 一种pedot/pss导电油墨及涂层的制备方法
CN201410445623.XA CN104183303B (zh) 2014-09-03 2014-09-03 一种稳定的pedot/pss导电层电极及其制备方法
CN201410445544.9 2014-09-03
CN201410445623.X 2014-09-03

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CN106313794A (zh) * 2016-10-13 2017-01-11 衡山县佳诚新材料有限公司 一种复合隔热调光玻璃及其制备方法
CN110338781A (zh) * 2019-07-23 2019-10-18 广西师范大学 一种非金属柔性干电极及其制备方法
US11513410B2 (en) 2017-05-10 2022-11-29 National Institute For Materials Science Electrochromic device using organic/metal hybrid polymer and method for producing same

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