CN112408366A - Method for printing and in-situ reduction of graphene - Google Patents
Method for printing and in-situ reduction of graphene Download PDFInfo
- Publication number
- CN112408366A CN112408366A CN202011415542.7A CN202011415542A CN112408366A CN 112408366 A CN112408366 A CN 112408366A CN 202011415542 A CN202011415542 A CN 202011415542A CN 112408366 A CN112408366 A CN 112408366A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- graphene
- ink
- reducing agent
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a method for printing and in-situ reducing graphene. The method is based on a printing technology, patterned printing is carried out on a substrate by using graphene oxide slurry, and a chemical reducing agent is further used to carry out normal-temperature chemical reduction on the pattern in situ, so that a reduced high-conductivity graphene pattern is obtained. According to the method, the graphene oxide pattern does not need to be transferred, the reducing agent is directly printed on the pattern in situ, so that rapid chemical reduction is carried out, the dense stacking of graphene sheet layers and the original precise pattern can be kept in the process, the reduction process is simple, and the reduction effect is good.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a method for printing and in-situ reduction of graphene.
Background
Graphene has gradually become a potential substitute for existing conductors and semiconductors due to its excellent optical and electrical properties. The graphene intrinsic photoelectric magnetic property can be used in electronic components, such as sensors, diodes, photodetectors, radio frequency antennas, terahertz antennas and the like. The preparation method generally comprises three methods: (1) preparing a transparent, patterned graphene monolayer material using a chemical vapor deposition method [ cited patent, CN104023993B to form a patterned graphene layer; CN108545725A a graphene preparation apparatus and a method for patterned graphene growth using the same, (2) dispersing graphene powder to form a slurry, preparing a patterned graphene assembly by coating, printing and other methods [ refer to CN109841426A graphene-based flexible electrode and its preparation method ], (3) dispersing graphene oxide as a precursor to form a slurry, obtaining a patterned graphene oxide assembly by coating, printing and other methods, and then reducing graphene oxide to graphene assembly by chemical reduction, thermal reduction and other methods [ refer to CN106486209A a patterned 3D graphene conductive thin film and its green preparation method and application; CN103236295B a method for preparing a patterned graphene conductive film ].
Among the three methods, (1) graphene prepared by a vapor deposition method has the most complete six-membered carbon ring conjugate structure, and can be used for preparing a high-quality graphene film, but the film has poor shrinkage, the preparation process needs to be carried out on metal substrates such as copper, and after the preparation process is finished, etching transfer is needed, so that the problems of defect introduction, pattern damage and the like are caused, and the preparation cost is extremely high. The patterning of graphene is mainly performed by maskless direct laser writing, masked plasma etching and vapor deposition growth on a pre-patterned metal substrate, and although these techniques provide relatively high resolution graphene patterns, the methods using laser, mask and vacuum increase the process cost, and the above-mentioned several techniques are mostly used for small area manufacturing in the actual production process. (2) By adopting the method for pulping and printing by using the graphene powder, the graphene has large surface energy and is curled and agglomerated, a high-boiling-point polar solvent is required, the graphene cannot be tiled and dispersed in the solvent, and in most cases, an additional surfactant or dispersant is required, so that printed graphene sheets cannot be effectively lapped to form a conductive network, the conductive network is influenced by additives such as the surfactant and the dispersant, and the prepared pattern has poor conductivity. (3) The method for pulping and printing by using the graphene oxide powder is characterized in that the graphene oxide powder can be tiled and dispersed in water due to the existence of polar functional groups, and volatilizes along with water after being printed into a pattern, graphene oxide sheet layers can be densely stacked face to form a better building plane, but a film of the graphene oxide needs to be further reduced, the thermal reduction can be adopted, but the substrate can be damaged due to the fact that the temperature is high (generally, the temperature needs to reach more than 800 ℃), the chemical reduction can also be adopted, but the pattern needs to be soaked by a chemical agent, the film is fluffy and dissolved again due to soaking, and the reduction effect is poor.
Disclosure of Invention
The invention aims to provide a method for printing and reducing graphene in situ. According to the method, the graphene oxide pattern is printed, and the high-conductivity graphene pattern is formed through in-situ chemical reduction, so that the advantages of easy dispersion and easy assembly of graphene oxide into a film are applied, and the reducing agent is printed between graphene oxide thin film layers in situ, so that the graphene oxide is promoted to be fully reduced, and the high-conductivity graphene pattern is finally prepared. This patent preparation process is simple, only needs simple printing apparatus, graphene oxide aqueous slurry, chemical reductant aqueous solution, can directly print the pattern to the target substrate on, practices thrift the raw materials, and the processing procedure is simple, the time is fast, and final off-the-shelf performance is good, need not adopt harsh preparation condition and equipment, does not need operations such as transfer.
The method is based on a printing technology, patterned printing is carried out on a substrate by using graphene oxide slurry, and a chemical reducing agent is further used to carry out normal-temperature chemical reduction on the pattern in situ, so that a reduced high-conductivity graphene pattern is obtained.
The method for reducing graphene in situ provided by the invention comprises the following steps:
1) dispersing graphene oxide and a solvent to obtain graphene oxide ink;
2) uniformly mixing a chemical reducing agent and a solvent to obtain reducing agent ink;
3) setting a system of an ink-jet printer, introducing a printed pattern, injecting the graphene oxide ink obtained in the step 1), adjusting instrument parameters, and starting the instrument to print the graphene oxide ink on a substrate to form the pattern;
4) injecting the reducing agent ink obtained in the step 2) into the other liquid storage tank of the printer in the step 3), adjusting printing parameters of the printer, printing the reducing agent ink on the graphene oxide pattern obtained in the step 3) in situ by using a new head, and then carrying out reduction reaction to complete in-situ reduction of graphene.
In step 1) of the above method, the graphene oxide is graphene having an oxygen-containing functional group; the graphene oxide is prepared by a chemical oxidation method, an electrochemical stripping oxidation method or a mechanical stripping oxidation/acidification method; the methods are all conventionally known methods.
The solvent is a polar solvent; specifically at least one selected from water, low boiling point alcohols and acetone; the low boiling point alcohol is specifically selected from at least one of methanol, ethanol and isopropanol; the solvent preferably necessarily contains water; the volume ratio of the water to other solvents is 6-10: 4-0; preferably, the solvent is pure water; the solvent can be a mixed solution of water and ethanol; the volume ratio of the water to the ethanol is specifically 9: 1;
in the dispersing step, the dispersing method is at least one of mechanical stirring, oscillation and ultrasound; the dispersion methods are all conventional dispersion methods;
in the graphene oxide ink, the dosage ratio of graphene oxide to the solvent is 5-80 mg:1 mL; preferably 10-30 mg:1 mL; more specifically, it may be 10.0 mg: 1.1 mL.
In the step 2), the chemical reducing agent is selected from any one of hydriodic acid and sodium borohydride;
the solvent is a polar solvent; specifically at least one selected from water, low boiling point alcohols and acetone; the low boiling point alcohol is specifically selected from at least one of methanol, ethanol and isopropanol;
in the reducing agent ink, when the reducing agent is hydroiodic acid, the concentration of the hydroiodic acid in the reducing agent ink is 20-60 wt%; preferably 40 to 45 wt%;
when the reducing agent is sodium borohydride, the concentration of the sodium borohydride in the reducing agent ink is 1 wt% -10 wt%; preferably 3 to 5 wt%.
In the step 3), the substrate is a target place for pattern printing; the material of the substrate is at least one of metal and polymer film.
In the step 4), the temperature in the reduction reaction step is room temperature; the time is 20-60 min.
The above steps 1) -3) are suitable for printing thinner patterns.
The method further comprises the following steps: repeating the steps 3) and 4) for several times.
Specifically, the number of times is 2 to 10 times.
The above steps are suitable for printing thicker patterns, and the thickness range is 10nm-300 um.
The invention has the following beneficial effects:
1. the graphene oxide pattern is printed, and reduction is carried out in situ on the pattern, so that the pattern of graphene is obtained by a two-step method, and the preparation path is novel.
2. The pattern is printed by using the graphene oxide, and the characteristics of good dispersion, easy film forming and compact overlapping of the graphene oxide can be applied to construct an initial structure for directionally stacking the sheets.
3. The graphene oxide pattern does not need to be transferred, and a reducing agent is directly printed on the pattern in situ, so that rapid chemical reduction is carried out, and the process can keep compact stacking of graphene sheet layers and maintain original precise patterns. The reduction process is simple and the reduction effect is good.
4. The reduction reaction can be carried out at normal temperature without harsh conditions such as high temperature, vacuum and the like.
5. The method can print multilayer and interlayer graphene oxide-reducing agent-graphene oxide, so that the reducing agent can fully enter the pattern to be fully reduced, and a thicker pattern can be prepared.
6. The prepared graphene pattern has a form that graphene sheets are stacked face to face densely; the prepared graphene pattern has a perfect pattern structure.
7. The operation process is carried out at normal temperature and normal pressure, is simple and quick, and can prepare patterns with any thickness and thickness.
8. The reduction process is sufficient, and the reduced graphene pattern has high electric conductivity and heat conductivity and can be applied to the fields of electronic components such as video antennas, terahertz antennas, sensors, diodes and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a picture of a graphene oxide ink prepared in example 1 of the present invention.
FIG. 2 is a pattern of a restored circuit diagram of an ink jet printed circuit prepared in accordance with example 1 of the present invention.
Fig. 3 is a raman spectrum of the graphene pattern obtained in example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
a normal-temperature reaction in-situ reduction graphene circuit pattern is prepared by the following steps:
(1) graphene oxide and deionized water are used as raw materials, ultrasonic treatment is carried out for 1 hour at 30KHz in a water bath, and graphene oxide ink is prepared, wherein the mass fraction of the graphene oxide is 0.5% (namely the dosage ratio of the graphene oxide to the water is 5.0 mg: 1.0mL), the viscosity is 10cp, and the surface tension is 30 mN/m.
Fig. 1 is a diagram of a graphene oxide ink prepared in example 1 of the present invention, which has stable properties and can be stored and used for a long time.
(2) Soaking the PET flexible substrate in an ethanol solution for cleaning, taking out, wiping the PET flexible substrate with dust-free paper, and drying the PET flexible substrate in a 60 ℃ oven for 30 min.
(3) A liquid storage tank matched with an ink-jet printer (the model is MicroFab Jetlab 4) is washed for 3 times by deionized water, and whether the liquid at the position of a spray head (80 mu m) is uniform and slender liquid or not is observed. When the condition that the spray head has no fiber and ink stain is observed, the prepared graphene oxide solution can be injected into the No. 1 liquid storage tank, the printing parameters of the ink-jet printer are adjusted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. And (3) setting a printing pattern on a computer by using a related graphic processing tool, and printing the graphene oxide on the processed PET flexible substrate by using a No. 1 nozzle through an ink-jet printer after the design is finished, wherein the number of the printed layers is 3. And finally obtaining the required graphene oxide film on the PET film.
(4) Injecting 45% of hydriodic acid aqueous solution into a No. 2 liquid storage tank, repeating the operation on a No. 2 nozzle, printing the hydriodic acid on the graphene oxide film in situ, maintaining the room temperature for 30min, and carrying out in-situ reduction. And drying the pattern at normal temperature to obtain a dried graphene pattern.
FIG. 2 is a schematic diagram of a recovered circuit pattern of an ink-jet printed circuit prepared in example 1 of the present invention.
(5) Performance analysis: when the obtained graphene pattern is subjected to a Raman test, a D peak is at 1335cm & lt-1 & gt, and a G peak is at 1580cm & lt-1 & gt as can be seen from a Raman spectrum shown in FIG. 3. The D peak is a defect peak of graphene, and the integrity of graphene can be calculated by calculating the intensity ratio (ID/IG) of the D peak to the G peak. The smaller the ratio is, the more complete the structure of the graphene is represented, and particularly, when the hydroiodic acid concentration is 15%, the reduced graphene has the smallest resistivity, and the ratio of ID/IG is the smallest, which represents that the reduced graphene has the best integrity at the concentration.
Example 2:
a normal-temperature reaction in-situ reduction thick-layer graphene circuit pattern is prepared by the following steps:
(1) the graphene oxide ink is prepared by using graphene oxide and deionized water as raw materials and an emulsifying machine at the rotating speed of 5000rpm for 30min, wherein the mass fraction of the graphene oxide is 1% (namely the dosage ratio of the graphene oxide to the water is 10.0 mg: 1.0mL), the viscosity is 30cp, and the surface tension is 70 mN/m.
(2) And soaking the PET flexible substrate in pure water for cleaning, taking out and wiping with dust-free paper.
(3) A liquid storage tank matched with an ink-jet printer (the model is MicroFab Jetlab 4) is washed for 3 times by deionized water, and whether the liquid at the position of a spray head (80 mu m) is uniform and slender liquid or not is observed. When the condition that the spray head has no fiber and ink stain is observed, the prepared graphene oxide solution can be injected into the No. 1 liquid storage tank, the printing parameters of the ink-jet printer are adjusted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. A pattern to be printed is designed in advance on a computer by using a related graphic processing tool, and after the design is finished, the graphene oxide is printed on a processed PET flexible substrate by using a No. 1 nozzle through an ink-jet printer, wherein the number of the printed layers is 10. And finally obtaining the required graphene oxide film on the PET film.
(4) Injecting 45% of hydriodic acid aqueous solution into a No. 2 liquid storage tank, repeating the operation on a No. 2 nozzle, printing hydriodic acid on a graphene oxide film in situ, printing 1 layer, maintaining for 30min, and carrying out in-situ reduction.
(5) A No. 1 liquid storage tank is adopted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. The graphene oxide was printed on the original pattern with a number 1 nozzle, the number of layers printed being 10.
(6) And (3) adopting a No. 2 liquid storage tank, repeating the operation on the No. 2 nozzle, printing hydroiodic acid on the graphene oxide film in situ, printing 1 layer, maintaining for 30min, and carrying out in-situ reduction.
(7) A No. 1 liquid storage tank is adopted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. The graphene oxide was printed on the original pattern with a number 1 nozzle, the number of layers printed being 10.
(8) And (3) adopting a No. 2 liquid storage tank, repeating the operation on the No. 2 nozzle, printing hydriodic acid on the graphene oxide film in situ, printing 1 layer, maintaining the room temperature for 30min, and carrying out in-situ reduction. And taking down the pattern, and drying the pattern in an oven at 80 ℃ for 2 hours to obtain a dried graphene pattern.
Example 3:
a graphene pattern subjected to normal-temperature reaction and in-situ reduction comprises the following steps:
(1) graphene oxide and a solvent are used as raw materials, wherein the solvent is a mixed solvent of water and ethanol, and the volume ratio of the water to the ethanol is 9: 1. carrying out ultrasonic treatment on the mixture for 1 hour at 30KHz in a water bath, and preparing the graphene oxide ink at 30 ℃, wherein the mass fraction of the graphene oxide is 1% (namely the dosage ratio of the graphene oxide to the water is 10.0 mg: 1.0mL), the viscosity is 30cp, and the surface tension is 70 mN/m.
(2) A liquid storage tank matched with an ink-jet printer (the model is MicroFab Jetlab 4) is washed for 3 times by deionized water, and whether the liquid at the position of a spray head (80 mu m) is uniform and slender liquid or not is observed. When the condition that the spray head has no fiber and ink stain is observed, the prepared graphene oxide solution can be injected into the No. 1 liquid storage tank, the printing parameters of the ink-jet printer are adjusted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. A pattern to be printed is designed in advance on a computer by using a related graphic processing tool, and after the design is finished, the graphene oxide is printed on a processed PET flexible substrate by using a No. 1 nozzle through an ink-jet printer, wherein the number of the printed layers is 10. And finally obtaining the required graphene oxide film on the PET film.
(3) And (2) injecting a sodium borohydride aqueous solution with the mass fraction of 3% into a No. 2 liquid storage tank, repeating the operation on a No. 2 nozzle, printing sodium borohydride on the graphene oxide film in situ, printing 1 layer, maintaining the room temperature for 20min, and carrying out in-situ reduction.
(4) A No. 1 liquid storage tank is adopted, the step length is 0.05, the frequency is 400Hz, the voltage is 20V, and the printing speed of the spray head is 20 mm/s. The graphene oxide was printed on the original pattern with a number 1 nozzle, the number of layers printed being 10.
(6) And (3) adopting a No. 2 liquid storage tank, repeating the operation on the No. 2 nozzle, printing sodium borohydride on the graphene oxide film in situ, printing 1 layer, maintaining for 30min, and carrying out in-situ reduction. And taking down the pattern, and drying the pattern in an oven at 80 ℃ for 2 hours to obtain a dried graphene pattern.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of reducing graphene in situ, comprising:
1) dispersing graphene oxide and a solvent to obtain graphene oxide ink;
2) uniformly mixing a chemical reducing agent and a solvent to obtain reducing agent ink;
3) setting a system of an ink-jet printer, introducing a printed pattern, injecting the graphene oxide ink obtained in the step 1), adjusting instrument parameters, and starting the instrument to print the graphene oxide ink on a substrate to form the pattern;
4) injecting the reducing agent ink obtained in the step 2) into the other liquid storage tank of the printer in the step 3), adjusting printing parameters of the printer, printing the reducing agent ink on the graphene oxide pattern obtained in the step 3) in situ by using a new head, and then carrying out reduction reaction to complete in-situ reduction of graphene.
2. The method of claim 1, wherein: in the step 1), the graphene oxide is graphene with oxygen-containing functional groups; the graphene oxide is prepared by a chemical oxidation method, an electrochemical stripping oxidation method or a mechanical stripping oxidation/acidification method.
3. The method according to claim 1 or 2, characterized in that: in the step 1), the solvent is a polar solvent; specifically at least one selected from water, low boiling point alcohols and acetone; the low boiling point alcohol is specifically selected from at least one of methanol, ethanol and isopropanol; the solvent preferably necessarily contains water; the volume ratio of the water to other solvents is 6-10: 4-0; preferably, the solvent is pure water; the solvent can be a mixed solution of water and ethanol; the volume ratio of the water to the ethanol is specifically 9: 1.
4. A method according to any one of claims 1 to 3, wherein: in the dispersing step in the step 1), the dispersing method is at least one of mechanical stirring, oscillation and ultrasound;
in the graphene oxide ink, the dosage ratio of graphene oxide to the solvent is 5-80 mg:1 mL; specifically 10-30 mg/1 mL; more specifically, it may be 10.0 mg: 1.1 mL.
5. The method according to any one of claims 1 to 4, wherein: in the step 2), the chemical reducing agent is selected from any one of hydriodic acid and sodium borohydride;
the solvent is a polar solvent; specifically at least one selected from water, low boiling point alcohols and acetone; the low boiling point alcohol is specifically selected from at least one of methanol, ethanol and isopropanol.
6. The method of claim 5, wherein: in the reducing agent ink in the step 2), when the reducing agent is hydroiodic acid, the concentration of the hydroiodic acid in the reducing agent ink is 20-60 wt%; preferably 40 to 45 wt%;
when the reducing agent is sodium borohydride, the concentration of the sodium borohydride in the reducing agent ink is 1 wt% -10 wt%; preferably 3 to 5 wt%.
7. The method according to any one of claims 1 to 6, wherein: in the step 3), the substrate is a target place for pattern printing; the material of the substrate is at least one of metal and polymer film.
8. The method according to any one of claims 1 to 7, wherein: in the step 4), the temperature in the reduction reaction step is room temperature; the time is 20-60 min; specifically 30 min.
9. The method according to any one of claims 1 to 8, wherein: the method further comprises the following steps:
repeating the steps 3) and 4) for several times.
10. The method of claim 9, wherein: the number of times is 2-10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011415542.7A CN112408366A (en) | 2020-12-07 | 2020-12-07 | Method for printing and in-situ reduction of graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011415542.7A CN112408366A (en) | 2020-12-07 | 2020-12-07 | Method for printing and in-situ reduction of graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112408366A true CN112408366A (en) | 2021-02-26 |
Family
ID=74775110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011415542.7A Pending CN112408366A (en) | 2020-12-07 | 2020-12-07 | Method for printing and in-situ reduction of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112408366A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265012A (en) * | 2013-04-26 | 2013-08-28 | 华中科技大学 | Methods for preparing large-area graphene film and large-area graphene composite films |
| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
| CN105694130A (en) * | 2016-04-10 | 2016-06-22 | 北京化工大学 | Preparation method of high-electric-conductivity graphene/natural rubber nano-composite |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
| CN108046241A (en) * | 2017-12-18 | 2018-05-18 | 苏州大学 | A kind of 3D printing surpasses the method for poroelasticity graphene aerogel |
| CN110190265A (en) * | 2019-06-20 | 2019-08-30 | 西北师范大学 | A kind of preparation method of antimony-antimony oxide/redox graphene composite material |
| CN110304621A (en) * | 2018-03-20 | 2019-10-08 | 国家纳米科学中心 | For by the slurry of predetermined pattern redox graphene, application method and obtained graphene film layer |
| CN111446441A (en) * | 2020-04-03 | 2020-07-24 | 浙江工业大学 | Nano-selenium-reduced graphene oxide composite material and preparation and application thereof |
-
2020
- 2020-12-07 CN CN202011415542.7A patent/CN112408366A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
| CN103265012A (en) * | 2013-04-26 | 2013-08-28 | 华中科技大学 | Methods for preparing large-area graphene film and large-area graphene composite films |
| CN105694130A (en) * | 2016-04-10 | 2016-06-22 | 北京化工大学 | Preparation method of high-electric-conductivity graphene/natural rubber nano-composite |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
| CN108046241A (en) * | 2017-12-18 | 2018-05-18 | 苏州大学 | A kind of 3D printing surpasses the method for poroelasticity graphene aerogel |
| CN110304621A (en) * | 2018-03-20 | 2019-10-08 | 国家纳米科学中心 | For by the slurry of predetermined pattern redox graphene, application method and obtained graphene film layer |
| CN110190265A (en) * | 2019-06-20 | 2019-08-30 | 西北师范大学 | A kind of preparation method of antimony-antimony oxide/redox graphene composite material |
| CN111446441A (en) * | 2020-04-03 | 2020-07-24 | 浙江工业大学 | Nano-selenium-reduced graphene oxide composite material and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| KUKJOO KIM ET AL.: "Simultaneous synthesis and patterning of graphene electrodes by reactive inkjet printing", 《CARBON》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2356707B1 (en) | Solution processing method for forming electrical contacts of organic devices | |
| KR101935117B1 (en) | Conductive substrate | |
| KR101651932B1 (en) | Method for manufacturing of conductive metal thin film using carboxylic acid | |
| KR20140093930A (en) | Reduced graphene oxide and method of producing same | |
| JP6042793B2 (en) | Manufacturing method of conductive film, printed wiring board | |
| KR102098448B1 (en) | Method for preparing transparent electrode film | |
| JP2009527076A (en) | Silver organosol ink for conductive line pattern formation | |
| US20150228371A1 (en) | Method for producing electrically conductive thin film, and electrically conductive thin film produced by said method | |
| CN110034388B (en) | Antenna preparation method and antenna with same | |
| KR20130027195A (en) | Fabrication method of graphene films and patterns | |
| CN102610557A (en) | Surface coating method, semiconductor device, and circuit board package | |
| US20210047533A1 (en) | Photonic sintered nanoink, photonic sintering method, and conductive nanostructure | |
| CN105379436A (en) | Method for manufacturing printed circuit board and printed circuit board | |
| CN112408366A (en) | Method for printing and in-situ reduction of graphene | |
| WO2015033823A1 (en) | Production method for conductive film | |
| KR101679144B1 (en) | Composition for forming conductive copper pattern by light sintering including carbon nanostructures, method for preparing conductive copper pattern by light sintering, and electronic device including the conductive copper pattern prepared therefrom | |
| CN113193115B (en) | Suspended carbon nano tube field effect transistor and preparation method thereof | |
| Kaydanova et al. | Direct write contacts for solar cells | |
| JP5543889B2 (en) | Wiring forming method and wiring | |
| CN111128702A (en) | Preparation method of metal electrode | |
| Curtis et al. | Ink jet printed metals and conducting polymers | |
| CN114156368A (en) | Preparation method of electrode of photovoltaic cell | |
| EP3702048B1 (en) | Method for drying polyimide paste and method for producing solar cells capable of highly-efficient photoelectric conversion | |
| CN114031978B (en) | Particle-free conductive ink and preparation method and application thereof | |
| CN106947321B (en) | Ink for manufacturing buffer layer, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210226 |
|
| RJ01 | Rejection of invention patent application after publication |