CN109456645B - Surfactant-free graphene composite conductive ink - Google Patents
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Abstract
The invention discloses a surfactant-free graphene composite conductive ink which is prepared by fully mixing and dispersing the following raw material components in parts by weight: 1-50 parts of CB @ rGO conductive filler, 1-15 parts of binder and 1000 parts of alcohol solvent 200 with 1-4 carbon atoms. According to the invention, the problem of dispersion stability of two conductive phases of graphene in the ink dispersion process and the problem of agglomeration of graphene nanosheets are effectively solved by constructing a 'graphene-conductive carbon black-graphene' conductive path, and the problem of contact resistance of a graphene nanomaterial in the process of forming the conductive path is reduced. According to the invention, the composite graphene conductive ink can be stably dispersed for a long time without adding an additional surfactant, and the film annealing temperature can be reduced and the printing adaptability of the ink on various substrates can be improved due to the absence of the insulating surfactant.
Description
Technical Field
The invention belongs to the technical field of graphene application, and particularly relates to surfactant-free graphene composite conductive ink.
Background
The conductive ink is a composite material consisting of conductive filler, a binder, a solvent and various auxiliaries, wherein the conductive filler is a key phase of the performance of the conductive ink. Countless conductive fillers in the conductive ink are uniformly dispersed in the binder and the ink solvent, the liquid conductive ink is in an insulating state, and a printed product obtained by annealing a conductive pattern or a printed film obtained by printing the conductive ink has certain conductivity. The traditional electronic device and energy storage device prepared by photoetching, chemical etching, chemical plating, vacuum deposition and other modes have many defects: expensive metal consumption, complex process, environmental pollution and the like. In the 90 s of the 20 th century, the development of conductive ink was the first to bring about the modern electronic printing technology-printing conductive ink in the traditional silicon-based electronic information technology innovation. Various printing conductive inks such as metallic conductive inks, conductive polymer conductive inks and carbon conductive inks have been rapidly developed as in spring shoots after rain.
Although the conductive silver paste which is researched more mature has excellent conductivity and certain application, silver nanoparticles are easy to migrate and settle, and the metal silver is expensive, so that the wide application of the metal silver is hindered. And the other type of metal conductive ink conductive copper paste as the conductive ink with lower cost greatly limits the application and development of the conductive ink due to the extremely poor oxidation resistance of the copper nanoparticles. In addition, the conductive polymer (represented by PEDOT/PSS) conductive ink has poor stability, low conductivity, and the PEDOT/PSS conductive polymer ink needs to be properly doped and has poor weather resistance. Compared with the various printing conductive ink in the past, the special functional electronic device prepared based on the graphene conductive ink has unique advantages that: corrosion resistance, flexibility, light weight, low cost, environmental protection and the like. With the development of graphene preparation technology, graphene conductive inks have been involved in various fields including: flexible electronic screens, functional sensors, photovoltaic cells, printed microcircuits, and Radio Frequency Identification Devices (RFID), among others. Especially, the RFID which is attracted by the attention at home and abroad is widely applied, and a certain foundation is laid for the flexible electronic era according to the unique advantages of low cost, industrialization, environmental protection and the like of the graphene conductive ink product.
Graphene as a new-generation conductive material has unsurpassed high charge mobility, and Kirill borotin from Columbia university has a charge mobility of 2.5 × 105cm measured from graphene with a complete structure2V · s, which is 100 times as much as single crystal silicon material and whose charge mobility is not affected by temperature. Each carbon atom in the graphene structure provides an unbound pi electron and can freely move on the surface of the graphene crystal, so that the graphene crystal is endowed with ultrahigh electron mobility. Therefore, the graphene is used as a conductive material in energy storage, signal transmission and sensor detectionThe wide application prospect is shown in many fields such as testing and composite materials.
At present, the preparation method of the graphene conductive ink mainly comprises the steps of preparing the graphene conductive ink by a liquid-phase stripping method and preparing the graphene conductive ink by an oxidation reduction method. The liquid phase exfoliation method is mainly embodied by using the surface energy (E) between graphene and an organic solvents) The mechanism that exists between the difference and the interlayer force of graphene: i.e., the lower the difference in surface energy, the smaller the van der Waals interaction between graphene layers, where graphene surface energy (E)s-G≈70.0mJ·m-2) And dimethylformamide surface energy (DMF) (E)S-DMF≈65.0 mJ·m-2) With N-methylpyrrolidone surface energy (NMP) (E)s-NMP≈68.2mJ·m-2) Are closer together. Therefore, the liquid phase stripping method mainly utilizes the solvent to carry out rapid shear stripping on the natural graphite to obtain the graphene conductive filler and prepare the graphene conductive ink. However, the method has low preparation efficiency, large graphene sheet layer distribution, different sheet diameters, and large toxicity of DMF and NMP solvents, which makes the method unsuitable for commercial application. Recently, reports of preparing graphene conductive ink by stripping graphene materials with a mixed solvent liquid phase are also presented, and the mixed solvent with surface energy similar to that of graphene is obtained by regulating and controlling the ratio of green solvent ethanol to water, and then the graphene is obtained by stripping. The method is relatively simple in process, toxic and harmful solvents are avoided, however, the dispersion problem of graphene or the addition of an excessively insulated surfactant can prevent the application of the liquid phase stripping method in the field of conductive ink. The graphene conductive ink prepared by the oxidation stripping method solves the problem of dispersion of the graphene conductive ink, GO is directly dispersed in the conductive ink as a conductive precursor, and then the water-based high-stability dispersed green conductive ink can be obtained, however, a conductive film printed by the GO conductive ink needs further post-treatment to obtain a material with certain conductive performance, the post-treatment comprises thermal reduction treatment or chemical reduction treatment and rolling treatment, and various post-treatment methods damage the reduced graphene oxide film to a certain degree. And the rGO film prepared by the GO conductive ink has high brittleness and poor flexibility. The preparation method of two types of graphene conductive ink for researching fire heat at present depends onThe defects are obvious, so that if the use of a toxic solvent with a high boiling point and an insulating surfactant can be avoided, the preparation of the graphene conductive ink which has the advantages of safe and environment-friendly solvent, no surfactant, high stable dispersion, high conductivity and capability of printing a flexible film can promote the development of the next-generation flexible electronic device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a surfactant-free graphene composite conductive ink.
The technical scheme of the invention is as follows:
the surfactant-free graphene composite conductive ink is prepared by fully mixing and dispersing the following raw material components in parts by weight:
1-50 parts by weight of CB @ rGO conductive filler
1-15 parts of binder
Alcohol solvent with 1-4 carbon atoms 200-;
the CB @ rGO conductive filler is prepared by mixing graphene oxide and carbon black and then reducing the mixture by ethylene glycol and p-phenylenediamine.
In a preferred embodiment of the present invention, the CB @ rGO conductive filler is prepared by a process comprising the steps of:
(1) mixing graphene oxide, carbon black and water, and performing ultrasonic treatment to obtain a GO/CB dispersion liquid;
(2) carrying out freeze drying treatment on the GO/CB dispersion liquid to obtain a GO interlayer CB conductive precursor;
(3) mixing a GO interlayer CB conductive precursor, ethylene glycol and p-phenylenediamine, and then reducing for 1-24h at 70-100 ℃ in a hot water bath;
(4) and (4) washing the material obtained in the step (3) by using an alcoholic solution to obtain the CB @ rGO conductive filler.
Further preferably, the mass ratio of the graphene oxide to the carbon black to the water is 1-10: 100-1000.
Further preferably, the mass ratio of the GO interlayer CB conductive precursor to the ethylene glycol to the p-phenylenediamine is 1-10: 10-1000: 1-100.
Further preferably, the carbon black is at least one of acetylene black, furnace black, gas black, channel black and lamp black.
Further preferably, the carbon black has a particle diameter of 10 to 200nm and an initial conductivity of 5 to 200S/m.
More preferably, the graphene oxide is prepared by a traditional Hummers method, and the graphene oxide is prepared by taking crystalline flake graphite as a raw material and KMnO4And concentrated sulfuric acid is used as a strong oxidant to carry out oxidation intercalation on the original flake graphite.
Still more preferably, the binder is at least one of polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropylmethylcellulose, and nitrocellulose.
Still more preferably, the alcohol solvent is at least one of ethanol, ethylene glycol, glycerol, isopropanol and n-butanol.
The invention has the beneficial effects that:
1. according to the invention, the problem of dispersion stability of two conductive phases of graphene in the ink dispersion process and the problem of agglomeration of graphene nanosheets are effectively solved by constructing a 'graphene-conductive carbon black-graphene' conductive path, and the problem of contact resistance of a graphene nanomaterial in the process of forming the conductive path is reduced.
2. According to the invention, the composite graphene conductive ink can be stably dispersed for a long time without adding an additional surfactant, and the film annealing temperature can be reduced and the printing adaptability of the ink on various substrates can be improved due to the absence of the insulating surfactant.
3. The alcohol solvent of the invention has various selectivity, and comprises ethylene glycol, glycerol, isopropanol, n-butanol and the like. The conductive ink with different viscosities can be obtained by selecting the solvents with different viscosities, so that the graphene conductive ink is suitable for various printing modes (such as drop coating, spin coating, ink-jet printing, screen printing and the like).
4. The reducing agent p-phenylenediamine simultaneously has the functions of reducing GO and dispersing the conductive filler, a pi-pi conjugated effect is formed between an oxidation product (OPPD) of the p-phenylenediamine after the reaction is finished and the rGO nano sheet, and the OPPD with a water-based functional group can effectively form a stable dispersion system with the conductive filler CB @ rGO. The conductive ink disclosed by the invention has the advantages of no surfactant addition, high stable dispersion, high conductivity, excellent printing adaptability, excellent flexible conductive film and the like, and is expected to be applied to printing of various flexible electronic devices.
Drawings
FIG. 1 is a schematic diagram of the principle of preparing a surfactant-free graphene composite conductive ink according to the present invention;
FIG. 2 is a comparative picture of the dispersion performance of the surfactant-free graphene composite conductive ink (20mg/mL) according to the present invention, which is obtained by performing a dispersion performance test using different solvents as dispersion solutions and standing for two months;
fig. 3 is a graph showing the results of conductivity tests of the surfactant-free graphene composite conductive ink of the present invention, wherein (a) is a graph showing the comparison of the results of conductivity tests of conductive films prepared in cases 1 and 2 of the present invention at different graphene/carbon black ratios, and (b) is a graph showing the comparison of the results of conductivity tests of conductive films prepared in example 1 of the present invention by different processing methods;
fig. 4 is a graph showing the test results of the surfactant-free graphene composite conductive ink of the present invention, wherein (a) the graphene composite conductive thin film obtained by printing the prepared ink of examples 1 and 2 of the present invention on a paper substrate is connected to a conductive path, so that a bulb in the circuit can emit light; (b) and (3) a flexibility test chart of the graphene composite conductive film and the pure carbon black conductive film.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Accurately weighing the following raw materials in parts by mass: 1 part of graphene oxide and 1 part of acetylene black, dispersing and stripping Graphene Oxide (GO) nanosheets and intercalating carbon black particles (CB) into the graphene oxide nanosheets by high-frequency ultrasonic treatment to obtain a stable graphene oxide/carbon black (GO/CB) dispersion liquid;
(2) carrying out freeze drying treatment on the obtained GO/CB dispersion liquid to obtain a CB interlayer GO conductive precursor;
(3) accurately weighing the following raw materials in parts by mass: 0.5 part/5 part of p-phenylenediamine (PPD), 1 part of precursor material and 100 parts of ethylene glycol, mixing, performing high-frequency ultrasonic treatment for 1min, and then performing constant-temperature 80 ℃ water bath treatment on the obtained dispersion to obtain the CB @ rGO coating structure material. The redundant p-phenylenediamine and free carbon black particles are removed through filtering, water washing and centrifugal operation, so that the conductive filler with low reduction degree (LCB @ rGO) and high reduction degree (HCB @ rGO) is obtained, and the preparation principle of the conductive filler is shown in figure 2.
(4) Accurately weighing the following raw materials in parts by mass: 5 parts of CB @ rGO conductive filler, 1 part of water-based acrylic resin and 100 parts of ethylene glycol are mixed, and the mixed liquid is subjected to high-frequency ultrasonic treatment to obtain the graphene composite conductive ink.
(5) The conductive ink is spin-coated on the glass slide by a spin coating method, and the glass slide is placed in a constant-temperature air blast oven at 80 ℃ to be heated and dried, so that the composite graphene conductive graphene film is obtained, and a film conductive path is formed, as shown in fig. 2.
(6) Various characterization tests including four-probe resistance test and Scanning Electron Microscope (SEM) are carried out on the obtained conductive filler and conductive film, and the performance test and characterization are shown in figures 1, 2, 3 and 4.
Example 2
(1) Accurately weighing the following raw materials in parts by mass: graphene oxide 1 part, acetylene black 4 parts/2 parts/1 part/0.5 part/0.25 part (M)GO/MCB4/1, 2/1, 1/1, 1/2 and 1/4), dispersing and stripping Graphene Oxide (GO) nanosheets and intercalating carbon black particles (CB) into the graphene oxide nanosheets by high-frequency ultrasonic treatment to obtain a stable graphene oxide/carbon black (GO/CB) dispersion liquid;
(2) carrying out freeze drying treatment on the obtained GO/CB dispersion liquid to obtain a CB interlayer GO conductive precursor;
(3) accurately weighing the following raw materials in parts by mass: 5 parts of p-phenylenediamine (PPD) and precursor material (M)GO/MCB4/1, 2/1, 1/1, 1/2 and 1/4) and 100 parts of ethylene glycol, mixing, performing high-frequency ultrasound for 1min, and performing water bath treatment on the obtained dispersion at constant temperature of 80 ℃ to obtain the CB @ rGO coated structural material. Through filtering and water washingRemoving redundant p-phenylenediamine and free carbon black particles through centrifugal operation to obtain the HCB @ rGO conductive filler with high reduction degree;
(4) accurately weighing the following raw materials in parts by mass: CB @ rGO (M)GO/MCa(4/1, 2/1, 1/1, 1/2, 1/4) each 5 parts of conductive filler, 1 part of aqueous acrylic resin, and 100 parts of ethylene glycol were mixed, and the mixture was subjected to high-frequency ultrasonic treatment to obtain (M)GO/MCB4/1, 2/1, 1/1, 1/2 and 1/4) five parts of graphene composite conductive ink;
(5) spin-coating conductive ink on a glass slide by a spin-coating method, and placing the glass slide in a constant-temperature air-blast oven at 80 ℃ for heating and drying to obtain a graphene composite conductive graphene film;
(6) various characterization tests are carried out on the obtained conductive filler and the conductive film (except four probe resistance tests, CB @ rGO conductive filler (M) is utilizedGO/MCB4/1, 2/1, 1/1, 1/2, 1/4) sample resistance testing, the remaining performance tests used CB @ rGO conductive filler (M)GO/MCB1/1) materials), including four-probe resistance testing, SEM performance testing and characterization, as shown in figures 1, 2, 3, 4;
as shown in fig. 1, according to a schematic diagram of preparation of the graphene composite conductive ink in embodiment 1 of the present invention, a conductive filler conductive precursor obtained by a cold-dry method is a CB intercalated GO structure, and in a process of reduction of the precursor, the structure can prevent aggregation of graphene due to reduction of surface free energy, and in a reduction process, an excess rGO nanosheet is coated on the surface of the precursor due to reduction of surface energy to form a complete structure (CB @ rGO) in which the graphene wraps a carbon black particle intercalation. The graphene composite conductive ink in fig. 2 can be stably dispersed in ethylene glycol, glycerol, n-butanol, isopropanol, DMF and NMP for a long time. The electrical resistivity of the RACB @ rGO conductive film in the figure 3 reaches 5091S/m, and the obtained conductive film has excellent conductivity. As shown in fig. 4(a), various patterns and bending resistance tests obtained by printing the graphene composite conductive film are shown, and (b) 85% of conductivity of the graphene composite conductive film is still retained after the graphene composite conductive film is folded for thousands of times, while the conductivity of the common carbon black conductive ink is lost after the graphene composite conductive film is folded for 200 times due to the damage of a conductive path.
In summary, the surfactant-free graphene composite conductive ink disclosed by the invention can realize long-term stable dispersion without adding an additional surfactant. Because of no insulating surfactant, the annealing temperature of the film can be reduced, and the printing adaptability of the printing ink on various substrates can be improved. The conductive ink has various solvent selectivity, including ethylene glycol, glycerol, isopropanol, n-butanol, DMF, NMP, etc. The conductive ink with different viscosities can be obtained by selecting the solvents with different viscosities, so that the graphene conductive ink is suitable for various printing modes (such as drop coating, spin coating, ink-jet printing, screen printing and the like). The invention also constructs a 'graphene-conductive carbon black-graphene' conductive path, solves the agglomeration problem of the graphene material in the reduction process and reduces the contact resistance problem of the graphene nano material in the formation of the conductive path. Meanwhile, a stable dispersion system is formed between the conductive filler CB @ rGO and the OPPD through a pi-pi conjugated effect formed between a water-based p-phenylenediamine oxidation product (OPPD) and the rGO nano sheet. The conductive ink disclosed by the invention has the advantages of no surfactant addition, high stable dispersion, high conductivity, excellent printing adaptability, excellent flexible conductive film and the like, and is expected to be applied to printing of various flexible electronic devices.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
the surfactant-free graphene composite conductive ink is prepared by fully mixing and dispersing the following raw material components in parts by weight:
1-50 parts by weight of CB @ rGO conductive filler
1-15 parts of binder
Alcohol solvent with 1-4 carbon atoms 200-;
the CB @ rGO conductive filler is prepared by mixing graphene oxide and carbon black and then reducing the mixture by ethylene glycol and p-phenylenediamine.
The preparation method of the CB @ rGO conductive filler comprises the following steps:
(1) mixing graphene oxide, carbon black and water, and performing ultrasonic treatment to obtain a GO/CB dispersion liquid;
(2) carrying out freeze drying treatment on the GO/CB dispersion liquid to obtain a GO interlayer CB conductive precursor;
(3) mixing a GO interlayer CB conductive precursor, ethylene glycol and p-phenylenediamine, and then reducing for 1-48h in a hot water bath at 20-200 ℃;
(4) and (4) washing the material obtained in the step (3) by using an alcoholic solution to obtain the CB @ rGO conductive filler.
The mass ratio of the graphene oxide to the carbon black to the water is 1-10: 100-1000. The mass ratio of the GO interlayer CB conductive precursor to the ethylene glycol to the p-phenylenediamine is 1-10: 10-1000: 1-100. The carbon black is at least one of acetylene black, furnace black, gas black, channel black and lamp black. The particle diameter of the carbon black is 10-200nm, and the initial conductivity is 5-200S/m.
The graphene oxide is prepared by a traditional Hummers method, and is prepared by taking crystalline flake graphite as a raw material and KMnO4And concentrated sulfuric acid is used as a strong oxidant to carry out oxidation intercalation on the original flake graphite. The binder is at least one of polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropyl methyl cellulose and nitrocellulose. The alcohol solvent is at least one of ethanol, ethylene glycol, glycerol, isopropanol and n-butanol.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. The surfactant-free graphene composite conductive ink is characterized in that: the material is prepared by fully mixing and dispersing the following raw material components in parts by weight:
1-50 parts by weight of CB @ rGO conductive filler,
1 to 15 parts by weight of a binder,
alcohol solvent with 1-4 carbon atoms 200-;
the CB @ rGO conductive filler is prepared by mixing graphene oxide and carbon black and then reducing the mixture by ethylene glycol and p-phenylenediamine, and the preparation method comprises the following steps:
(1) mixing graphene oxide, carbon black and water, and performing ultrasonic treatment to obtain a GO/CB dispersion liquid;
(2) carrying out freeze drying treatment on the GO/CB dispersion liquid to obtain a GO interlayer CB conductive precursor;
(3) mixing a GO interlayer CB conductive precursor, ethylene glycol and p-phenylenediamine, and then reducing for 1-24h at 70-100 ℃ in a hot water bath;
(4) washing the material obtained in the step (3) through an alcoholic solution to obtain the CB @ rGO conductive filler;
the mass ratio of the graphene oxide to the carbon black to the water is 1-10: 100-1000;
the particle diameter of the carbon black is 10-200nm, and the initial conductivity is 5-200S/m.
2. The surfactant-free graphene composite conductive ink according to claim 1, wherein: the mass ratio of the GO interlayer CB conductive precursor to the ethylene glycol to the p-phenylenediamine is 1-10: 10-1000: 1-100.
3. The surfactant-free graphene composite conductive ink according to claim 1, wherein: the carbon black is at least one of acetylene black, furnace black, gas black, channel black and lamp black.
4. The surfactant-free graphene composite conductive ink according to any one of claims 1 to 3, wherein: the graphene oxide is prepared by a traditional Hummers method, and is prepared by taking crystalline flake graphite as a raw material and KMnO4And concentrated sulfuric acid is used as a strong oxidant to carry out oxidation intercalation on the original flake graphite.
5. The surfactant-free graphene composite conductive ink according to any one of claims 1 to 3, wherein: the binder is at least one of polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropyl methyl cellulose and nitrocellulose.
6. The surfactant-free graphene composite conductive ink according to any one of claims 1 to 3, wherein: the alcohol solvent is at least one of ethanol, ethylene glycol, glycerol, isopropanol and n-butanol.
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| CN111004546A (en) * | 2019-11-28 | 2020-04-14 | 华瑞墨石丹阳有限公司 | Graphite nanosheet conductive ink and preparation method and application thereof |
| CN111117369B (en) * | 2020-02-05 | 2022-11-15 | 广州特种承压设备检测研究院 | Polyaniline functionalized graphene conductive ink and preparation method thereof |
| CN111432509B (en) * | 2020-04-15 | 2022-02-11 | 广东康烯科技有限公司 | Titanium quantum dot doped graphene-based electric heating plate and electric heating device |
| CN111899990B (en) * | 2020-08-07 | 2021-09-28 | 北京化工大学 | Large-area continuous flexible self-supporting electrode and preparation method and application thereof |
| CN112011228B (en) * | 2020-08-31 | 2022-01-07 | 上海电力大学 | Conductive film coating for improving oxidation resistance of copper plate and preparation method thereof |
| CN112500741B (en) * | 2020-10-29 | 2024-04-19 | 宁波石墨烯创新中心有限公司 | Graphene composite conductive ink and preparation method and application thereof |
| CN113249762A (en) * | 2021-05-28 | 2021-08-13 | 黑龙江科技大学 | Preparation method of graphene high-temperature heating aluminum plate |
| CN114235902A (en) * | 2021-11-15 | 2022-03-25 | 湖北亿纬动力有限公司 | Method for testing dispersion stability of carbon black |
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