CN111117369A - Polyaniline functionalized graphene conductive ink and preparation method thereof - Google Patents
Polyaniline functionalized graphene conductive ink and preparation method thereof Download PDFInfo
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- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Abstract
The invention discloses polyaniline functionalized graphene conductive ink and a preparation method thereof, wherein a polyaniline functionalized graphene material is prepared by ultrasonic post-in-situ reduction of sulfonated polyaniline and graphene oxide dispersion liquid, and the preparation method utilizes pi-pi interaction between polyaniline and graphene and sulfonic acid groups on the polyaniline to obtain a graphene composite material capable of being stably dispersed in water, so that the problem that a graphene lamellar structure is easy to agglomerate is solved. The conductive ink disclosed by the invention adopts polyaniline functionalized graphene and conductive carbon black as conductive fillers, the water-based resin as a binder and the mixture of water and low-carbon alcohol as a solvent to form a point-surface contact conductive network, so that the conductivity of the conductive ink is improved, and the conductive ink is green, environment-friendly and environment-friendly. Furthermore, after the conductive ink is formed into a film, a conductive film with high conductivity, uniform film formation and strong bending resistance can be obtained, the conductivity is as high as 6.61S/cm, and the conductive ink is expected to be applied to the field of flexible electronic circuit printing.
Description
Technical Field
The invention relates to the field of application of graphene composite materials, in particular to polyaniline functionalized graphene conductive ink and a preparation method thereof.
Background
The conductive ink is a functional ink consisting of conductive filler, solvent, binder and various auxiliaries, and is widely applied to the fields of radio frequency identification, printed circuit boards, electronic screen displays, solar cells, membrane switches and the like. Conductive fillers are key components of conductive inks, which determine the conductive properties of the ink. At present, the widely used conductive ink usually takes metal particles such as nano gold, silver, copper and the like as conductive fillers, and a conductive network is formed through point-point contact among the metal particles so as to realize conductivity. In the preparation process of the nano gold and nano silver conductive ink, a protective agent is often required to be added to limit the growth of metal particles so as to control the particle size of the metal particles, and because the addition of the protective agent can increase the contact resistance and reduce the conductivity of the ink, the protective agent needs to be removed by high-temperature sintering treatment, so that the contact between the metal particles is improved, and the conductivity of the metal particles is improved. However, since the flexible printing support is generally various organic thin films, the heat resistance of the material is poor, and the glass phase transition occurs at high temperature to cause damage, the high temperature sintering step of the gold and silver conductive inks greatly limits their application in flexible printing. Further, gold and silver are precious metals, and the cost of the conductive ink is high by using the gold and silver as conductive fillers, and the conductive ink is not beneficial to large-scale application. Metallic copper is low in cost and is also used as a conductive phase in conductive ink, but compared with gold and silver conductive ink, nano copper particles are poor in conductivity and stability, and are easily oxidized in air, so that the conductivity is further deteriorated. Therefore, it is an important task to develop conductive ink with good conductivity and stability and low cost.
Graphene is a novel two-dimensional carbon nanomaterial with carbon atoms sp2Each carbon atom forms sigma bond with three adjacent carbon atoms and contributes to non-bonded pi electrons, and the pi electrons can freely move in the crystal face of the graphene, so that the graphene has excellent conductivity and the carrier mobility is as high as 2.0 multiplied by 105cm2·V-1·s-1. In addition, the graphene also has excellent light transmittance, and the visible light transmittance can reach 97.7%. Due to the excellent performances of graphene, the conductive ink taking graphene as a conductive filler receives more and more attention, and the graphene conductive ink is expected to be applied to multiple fields such as radio frequency identification, solar cells, flexible electronic circuits and sensors.
However, due to the strong pi-pi interaction between graphene sheets, irreversible agglomeration often occurs, which affects the exertion of excellent physical and chemical properties of graphene, so that graphene agglomeration is effectively prevented, and the preparation of graphene materials with good dispersion property and high conductivity is still a hot spot and a difficult point of current research.
At present, in order to obtain stably dispersed graphene, the graphene is often dispersed in solvents such as N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF), etc., the surface of which can approach the graphene, however, the solvents are toxic and high-boiling organic solvents, and the curing time of the prepared conductive ink is long at normal temperature, so that the wide application of the method in the field of conductive ink is limited. In addition, surfactants such as Sodium Dodecyl Benzene Sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), and the like are added to water to prevent the aggregation of graphene through steric hindrance or electrostatic repulsion, which is also a method for obtaining stably dispersed graphene. However, most surfactants are insulating materials, and the presence of a large amount of surfactant in the conductive ink causes a problem of poor conductivity of the ink.
Disclosure of Invention
Based on this, the present invention aims to overcome the disadvantages in the prior art, and provides a preparation method of polyaniline-functionalized graphene, which comprises the following steps:
step S1: dissolving sulfonated polyaniline in graphene oxide dispersion liquid, and reacting to obtain polyaniline/graphene oxide dispersion liquid;
step S2: and carrying out in-situ reduction on the polyaniline/graphene oxide dispersion solution by using a reducing agent to prepare polyaniline functionalized graphene.
Compared with the prior art, the sulfonated polyaniline and graphene oxide dispersion liquid are subjected to ultrasonic in-situ reduction to prepare polyaniline functionalized graphene, the pi-pi interaction between polyaniline and graphene and the sulfonic acid group on the polyaniline are utilized to obtain the graphene composite material capable of being stably dispersed in water, and the problem that the graphene lamellar structure is easy to agglomerate is solved.
Further, the reducing agent in step S2 is one or more of hydrazine hydrate, sodium borohydride, ascorbic acid, and hydroiodic acid. Hydrazine hydrate, sodium borohydride, ascorbic acid and hydroiodic acid have low toxicity, and are used as reducing agents, easy to operate and treat and suitable for industrial scale.
Further, the mass ratio of the graphene oxide to the sulfonated polyaniline to the reducing agent is 1: 0.5-2: 2-20. The sulfonated polyaniline and graphene oxide dispersion liquid is subjected to ultrasonic treatment and then subjected to in-situ reduction to prepare polyaniline functionalized graphene, so that the agglomeration of graphene can be effectively prevented, and the dispersion performance of graphene is improved.
Further, the graphene oxide is prepared by taking graphite powder as a raw material and adopting an improved Hummers method. The improved Hummers method has short reaction time and high safety.
Further, the sulfonated polyaniline is prepared by adopting a chlorosulfonic acid sulfonated polyaniline method. The method has the advantages of less waste acid generated by sulfonating chlorosulfonic acid, less product dissolution loss, mild reaction conditions, simple separation process and suitability for sulfonation reaction with high pi value.
The invention also aims to provide a preparation method of the polyaniline functionalized graphene conductive ink, which comprises the following steps:
step A: mixing polyaniline functionalized graphene and conductive carbon black to form a conductive filler, and mixing the conductive filler with a certain amount of binder and solvent for pretreatment to prepare a conductive ink premix;
and B: grinding the conductive ink premix prepared in the step A to prepare polyaniline functionalized graphene conductive ink;
wherein, the polyaniline-functionalized graphene in the step a is prepared by the method for preparing polyaniline-functionalized graphene in any one of claims 1 to 5.
Compared with the prior art, the sulfonated polyaniline and graphene oxide dispersion liquid is subjected to ultrasonic in-situ reduction to prepare polyaniline functionalized graphene, the polyaniline functionalized graphene is mixed with conductive carbon black to form a conductive filler, a conductive network in point-surface contact is formed in conductive ink, and the conductivity of the conductive ink is improved.
Further, the mass ratio of the polyaniline functionalized graphene to the carbon black is 1: 0.2-4. The conductive ink forms a conductive network in point-surface contact, so that the conductivity of the conductive ink is improved.
Furthermore, in the polyaniline functionalized graphene conductive ink, the mass fractions of the conductive filler, the solvent and the binder are 5-20%, 50-80% and 10-30%.
Further, the binder is one or more of waterborne acrylic resin, waterborne polyurethane, waterborne epoxy resin and waterborne silica gel. The conductive ink takes the water-based resin as the adhesive, so that the use of toxic volatile organic compounds in the oily conductive ink is avoided, and the prepared conductive ink is green and environment-friendly.
Further, the solvent is one or more of deionized water, ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, butanediol and the like. The conductive ink takes the mixed solution of deionized water and low-carbon alcohol as a solvent, so that the use of toxic volatile organic compounds in the oily conductive ink is avoided, and the prepared conductive ink is green, environment-friendly and environment-friendly.
Drawings
Fig. 1 is a flow chart of preparation of polyaniline functionalized graphene conductive ink according to the present invention.
Fig. 2 is an SEM image of the polyaniline-functionalized graphene composite material prepared in example 1.
Fig. 3 is an SEM image of the graphite conductive material prepared in comparative example 1.
Fig. 4 is a graph comparing a polyaniline-functionalized graphene dispersion and a graphene dispersion without polyaniline functionalization after standing for 2 months, respectively.
Fig. 5 is a fourier infrared spectrum of polyaniline functionalized graphene (rGO/SPANI), Graphene Oxide (GO), Sulfonated Polyaniline (SPANI) prepared in example 1, and reduced graphene (rGO) prepared in comparative example 1.
Fig. 6 is a raman spectrum of polyaniline functionalized graphene (rGO/SPANI), Graphene Oxide (GO), Sulfonated Polyaniline (SPANI) prepared in example 1 and reduced graphene (rGO) prepared in comparative example 1.
FIG. 7 is a graph showing the conductivity of cured conductive films of the conductive inks prepared in examples 1 to 5 and comparative example 1 of the present invention.
Detailed Description
Referring to fig. 1, a flow chart of a method for preparing polyaniline-functionalized graphene conductive ink according to the present invention is shown, the method includes the following steps:
(1) preparation of graphene oxide
Methods for preparing graphene include Hummers method, Brodie method, Staudenmaier method, and modified Hummers method. Graphite or graphene is used as a preparation raw material. Among them, the Brodie method and Staudenmaier method use potassium chlorate (KClO) as an oxidant although the oxidation degree is high3) Fuming HNO3Unsafe factors exist in the reaction process, and ClO is also generated2、NO2、N2O4And the like. The Hummers method and the modified Hummers method have short reaction time and high safety, so that the preparation of graphene oxide by the two methods has been long. In this embodiment, the modified Hummers method is preferably used to prepare graphene oxide.
Specifically, the steps for preparing graphite oxide in this example are: firstly, weighing potassium persulfate and phosphorus pentoxide, adding the potassium persulfate and the phosphorus pentoxide into concentrated sulfuric acid, uniformly stirring, adding graphite powder, fully reacting to prepare pre-oxidized graphite, filtering, washing and drying the pre-oxidized graphite; then adding sodium nitrate and pre-oxidized graphite into concentrated sulfuric acid in an ice water bath, stirring uniformly, and slowly adding potassium permanganate to react fully; then slowly adding deionized water into the reaction solution, stirring, reacting for a period of time, and then adding deionized water and hydrogen peroxide again to prepare a khaki mixed solution; and finally, washing the mixed solution for 2-3 times by using a hydrochloric acid solution, then washing the mixed solution to be neutral by using deionized water, dialyzing and purifying the prepared product, and then carrying out ultrasonic treatment to obtain the graphene oxide dispersion liquid.
(2) Preparation of sulfonated polyaniline
Sulfonated polyaniline is a derivative obtained by linking a sulfonic acid group to a benzene ring chain of polyaniline. The preparation method comprises a m-aminobenzene sulfonic acid and aniline monomer copolymerization method, a fuming sulfuric acid sulfonated polyaniline method and a chlorosulfonic acid sulfonated polyaniline method. The chlorosulfonic acid sulfonated polyaniline method is preferred in the embodiment, and specifically, the steps for preparing the sulfonated polyaniline in the embodiment are as follows:
step 2-1: mixing an aniline solution dissolved in hydrochloric acid with an ammonium persulfate solution dissolved in deionized water, cooling, stirring, fully reacting, filtering, washing the precipitate with deionized water for 2-3 times, and drying to obtain Polyaniline (PANI) powder;
step 2-2: and (3) dispersing the PANI powder prepared in the step (2-1) into 1, 2-dichloroethane to prepare PANI dispersion liquid, dropwise adding chlorosulfonic acid solution dissolved in the 1, 2-dichloroethane into the PANI dispersion liquid, and fully reacting to obtain a solid product. Dispersing the prepared solid product in deionized water, heating for full reaction, then rotationally evaporating water, washing the precipitated solid with acetone, and drying to obtain sulfonated polyaniline;
(3) preparation of polyaniline functionalized graphene
Step 3-1: dissolving the sulfonated polyaniline prepared in the step (2) into the graphene oxide dispersion liquid prepared in the step (1), and performing ultrasonic reaction to obtain a polyaniline graphene oxide dispersion liquid;
step 3-2: adding a reducing agent into the polyaniline graphene oxide dispersion liquid, performing reflux reaction to obtain polyaniline functionalized graphene dispersion liquid, washing, and freeze-drying to obtain polyaniline functionalized graphene solid.
Specifically, the mass ratio of the graphene oxide, the sulfonated polyaniline and the reducing agent in the step 3-1 is 1: 0.5-2: 2-20; in the step 3-2, the reducing agent is one or more of hydrazine hydrate, sodium borohydride, ascorbic acid and hydroiodic acid.
(4) Preparation of polyaniline functionalized graphene conductive ink
Step 4-1: firstly, weighing 5-20% of conductive filler, 50-80% of solvent and 10-30% of binder according to a proportion; the weighed components are mixed and stirred and then placed in an ultrasonic cleaning agent for ultrasonic treatment to prepare the conductive ink premix, wherein the ultrasonic power is 200-400W, the time is 20-60 minutes, the stirring speed is 150-400 rpm, and the time is 30-360 minutes.
Step 4-2: and ball-milling the conductive ink premix to prepare the uniform graphene composite conductive ink, wherein the milling process is a planetary ball milling method, the rotating speed is 150-.
Specifically, the conductive filler in the embodiment is a mixture of the polyaniline functionalized graphene prepared in the step (3) and conductive carbon black in a mass ratio of 1: 0.2-4; the binder is one or more of waterborne acrylic resin, waterborne polyurethane, waterborne epoxy resin and waterborne silica gel; the solvent is one or more of deionized water, ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, butanediol, etc. The binder in this embodiment is preferably an aqueous acrylic resin, and the solvent is preferably a mixed solvent of deionized water, ethylene glycol, and isopropyl alcohol.
In order to further verify the performance of the polyaniline-functionalized graphene composite material, a step (5) is added for representing a conductivity map of the cured conductive film of the polyaniline-functionalized graphene composite material film.
(5) Preparation of polyaniline functionalized graphene composite conductive ink film
And coating the conductive ink on the glossy photographic paper by using a bar coating method, and curing for 30 minutes in a constant-temperature air-blast oven at 80 ℃ to obtain the polyaniline functionalized graphene composite conductive ink film.
Compared with the prior art, the sulfonated polyaniline and graphene oxide dispersion liquid are subjected to ultrasonic in-situ reduction to prepare polyaniline functionalized graphene, and the graphene composite material capable of being stably dispersed in water is obtained by utilizing pi-pi interaction between polyaniline and graphene and sulfonic acid groups on the polyaniline, so that the problem that a graphene lamellar structure is easy to agglomerate is solved; according to the invention, polyaniline functionalized graphene and conductive carbon black are mixed to form a conductive filler, and a conductive network in point-surface contact is formed in the conductive ink, so that the conductivity of the conductive ink is improved. The polyaniline functionalized graphene conductive ink prepared by the invention takes water-based resin as an adhesive and takes a mixed solution of deionized water and low carbon alcohol as a solvent, so that the use of toxic volatile organic compounds in oily conductive ink is avoided, the prepared conductive ink is green and environment-friendly, and after the polyaniline functionalized graphene composite conductive ink prepared by the invention is coated and cured on a paper-based material, a conductive film with good conductivity, uniform film formation and good bending resistance can be obtained, and the polyaniline functionalized graphene composite conductive ink is expected to be used for printing of flexible electronic circuits.
The polyaniline functionalized graphene conductive ink and the preparation method thereof according to the present invention are further illustrated by the following specific examples.
Example 1
(1) Preparation of graphene oxide
Firstly, 2.5g of potassium persulfate and 2.5g of phosphorus pentoxide are weighed and added into 18mL of concentrated sulfuric acid at 80 ℃, 3g of graphite powder is added after uniform stirring, the reaction is carried out for 4.5 hours to prepare pre-oxidized graphite, and the obtained pre-oxidized graphite is filtered, washed and dried overnight. Then, 1g of sodium nitrate and 1g of pre-oxidized graphite are added into 60mL of concentrated sulfuric acid in an ice-water bath, after the mixture is uniformly stirred, 6g of potassium permanganate is slowly added, the mixture is stirred for 15 minutes, the temperature is increased to 35 ℃, and then the reaction is carried out for 2 hours. After the reaction, 120mL of deionized water was slowly added to the reaction solution, and stirred at 80 ℃ for 30 minutes, and then 365mL of deionized water and 10mL of 30% hydrogen peroxide were sequentially added to obtain a khaki mixed solution. And finally, washing the mixed solution for three times by using a 1:10 HCl solution, washing the mixed solution to be neutral by using deionized water, purifying the obtained product by using a dialysis method, and performing ultrasonic treatment to obtain the graphene oxide dispersion liquid.
(2) Preparation of sulfonated polyaniline
Step 2-1: respectively dissolving 9.3g of aniline in 100mL of 1M HCl, dissolving 28.6g of ammonium persulfate in 80mL of deionized water, cooling the two solutions to 0 ℃, mixing and stirring for 12 hours to fully react to prepare green precipitates; after the reaction is finished, washing the green precipitate with deionized water for 2-3 times, and drying to obtain Polyaniline (PANI) powder;
step 2-2: dispersing 2.0g of PANI powder prepared in the step 2-1 into 50mL of 1, 2-dichloroethane to prepare PANI dispersion liquid, then weighing 3.63g of chlorosulfonic acid to dissolve into 5mL of 1, 2-dichloroethane to prepare chlorosulfonic acid dispersion liquid, dropwise adding the chlorosulfonic acid dispersion liquid into the PANI dispersion liquid, and reacting for 5 hours to obtain a solid product; then, dispersing the prepared solid product in 200mL of deionized water, heating to 100 ℃, and reacting for 5 hours; finally, after the reaction is finished, the water content is evaporated in a rotating mode, and the precipitated solid is washed and dried by acetone to obtain sulfonated polyaniline;
(3) preparation of polyaniline functionalized graphene
Step 3-1: dissolving 100mg of sulfonated polyaniline prepared in the step (2) in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL prepared in the step (1), and performing ultrasonic reaction for 1 hour to prepare polyaniline graphene oxide dispersion liquid;
step 3-2: adding 1mL of hydrazine hydrate into the polyaniline graphene oxide dispersion liquid prepared in the step 3-1, refluxing for 12 hours at 95 ℃, obtaining polyaniline functionalized graphene dispersion liquid after reflux reaction, and washing and freeze-drying the polyaniline functionalized graphene dispersion liquid to obtain polyaniline functionalized graphene solid.
(4) Preparation of polyaniline functionalized graphene conductive ink
Step 4-1: the raw materials are weighed according to the mixture ratio of 12 percent of conductive filler, 20 percent of water-based resin and 68 percent of solvent by mass. The conductive filler is a mixture of the polyaniline functionalized graphene prepared in the step (3) and conductive carbon black in a mass ratio of 2:1, the water-based resin is water-based acrylic resin, and the solvent is a mixed solvent of deionized water, ethylene glycol and isopropanol in a volume ratio of 5:3: 2.
Step 4-2: accurately weighing the components in proportion, mixing and stirring the weighed components at the rotating speed of 300rpm for 30min, and placing the mixture in an ultrasonic cleaning machine for 400W ultrasonic treatment for 30min to obtain a conductive ink premix; and ball-milling the pre-mixture for 6 hours at the rotating speed of 350rpm by using a planetary ball mill to obtain the uniform graphene composite conductive ink.
(5) Preparation of polyaniline functionalized graphene composite conductive ink film
And coating the conductive ink on the glossy photographic paper by using a bar coating method, and curing for 30 minutes in a constant-temperature air-blast oven at 80 ℃ to obtain the polyaniline functionalized graphene composite conductive ink film.
Example 2
In this embodiment, step (1), step (2), step (4) and step (5) are completely the same as in embodiment 1, and are not described herein again. The preparation method of the polyaniline-functionalized graphene conductive ink of the embodiment differs from that of the embodiment 1 as follows:
(3) preparation of polyaniline functionalized graphene
Step 3-1: dissolving 100mg of sulfonated polyaniline prepared in the step (2) in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL prepared in the step (1), and performing ultrasonic reaction for 1 hour to prepare polyaniline graphene oxide dispersion liquid;
step 3-2: adding 1g of ascorbic acid into the polyaniline graphene oxide dispersion liquid prepared in the step 3-1, refluxing for 8 hours at 60 ℃, obtaining polyaniline functionalized graphene dispersion liquid after reflux reaction, and washing and freeze-drying the polyaniline functionalized graphene dispersion liquid to obtain polyaniline functionalized graphene solid.
Example 3
In this embodiment, step (1), step (2), step (4) and step (5) are completely the same as in embodiment 1, and are not described herein again. The preparation method of the polyaniline-functionalized graphene conductive ink of the embodiment differs from that of the embodiment 1 as follows:
(4) preparation of polyaniline functionalized graphene
Step 3-1: dissolving 100mg of sulfonated polyaniline prepared in the step (2) in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL prepared in the step (1), and performing ultrasonic reaction for 1 hour to prepare polyaniline graphene oxide dispersion liquid;
step 3-2: adding 1g of sodium borohydride into the polyaniline graphene oxide dispersion liquid prepared in the step 3-1, refluxing for 10 hours at 100 ℃, obtaining polyaniline functionalized graphene dispersion liquid after reflux reaction, and washing and freeze-drying the polyaniline functionalized graphene dispersion liquid to obtain polyaniline functionalized graphene solid.
Example 4
In this embodiment, step (1), step (2) and step (5) are completely the same as embodiment 1, and are not described herein again. The preparation method of the polyaniline-functionalized graphene conductive ink of the embodiment differs from that of the embodiment 1 as follows:
(5) preparation of polyaniline functionalized graphene
Step 3-1: dissolving 100mg of sulfonated polyaniline prepared in the step (2) in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL prepared in the step (1), and performing ultrasonic reaction for 1 hour to prepare polyaniline graphene oxide dispersion liquid;
step 3-2: adding 0.7mL of hydrazine hydrate into the polyaniline graphene oxide dispersion liquid prepared in the step 3-1, refluxing for 12 hours at 95 ℃, obtaining polyaniline functionalized graphene dispersion liquid after reflux reaction, and washing and freeze-drying the polyaniline functionalized graphene dispersion liquid to obtain polyaniline functionalized graphene solid.
(4) Preparation of polyaniline functionalized graphene conductive ink
Step 4-1: the raw materials are weighed according to the mixture ratio of 10 percent of conductive filler, 22 percent of water-based resin and 68 percent of solvent by mass. The conductive filler is a mixture of the polyaniline functionalized graphene prepared in the step (3) and conductive carbon black according to the mass ratio of 1:1, the water-based resin is water-based acrylic resin, and the solvent is a mixed solvent of deionized water, ethylene glycol and isopropanol according to the volume ratio of 5:4: 1.
Step 4-2: accurately weighing the components in proportion, mixing and stirring the weighed components at the rotating speed of 300rpm for 30min, and placing the mixture in an ultrasonic cleaning machine for 400W ultrasonic treatment for 20min to obtain a conductive ink premix; and (3) ball-milling the premix for 4 hours at the rotating speed of 350rpm by using a planetary ball mill to obtain the uniform graphene composite conductive ink.
Example 5
In this embodiment, step (1), step (2) and step (5) are completely the same as embodiment 1, and are not described herein again. The preparation method of the polyaniline-functionalized graphene conductive ink of the embodiment differs from that of the embodiment 1 as follows:
(6) preparation of polyaniline functionalized graphene
Step 3-1: dissolving 200mg of sulfonated polyaniline prepared in the step (2) in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL prepared in the step (1), and performing ultrasonic reaction for 1 hour to prepare polyaniline graphene oxide dispersion liquid;
step 3-2: adding 1mL of hydrazine hydrate into the polyaniline graphene oxide dispersion liquid prepared in the step 3-1, refluxing for 12 hours at 95 ℃, obtaining polyaniline functionalized graphene dispersion liquid after reflux reaction, and washing and freeze-drying the polyaniline functionalized graphene dispersion liquid to obtain polyaniline functionalized graphene solid.
(4) Preparation of polyaniline functionalized graphene conductive ink
Step 4-1: the raw materials are weighed according to the mixture ratio of 15 percent of conductive filler, 28 percent of water-based resin and 57 percent of solvent by mass. The conductive filler is a mixture of the polyaniline functionalized graphene prepared in the step (3) and conductive carbon black according to the mass ratio of 1:2, the water-based resin is water-based acrylic resin, and the solvent is a mixed solvent of deionized water, ethylene glycol and isopropanol according to the volume ratio of 6:3: 1.
Step 4-2: accurately weighing the components in proportion, mixing and stirring the weighed components at the rotating speed of 400rpm for 60min, and placing the mixture in an ultrasonic cleaning machine for 400W ultrasonic treatment for 60min to obtain a conductive ink premix; and (3) ball-milling the premix for 8 hours at the rotating speed of 350rpm by using a planetary ball mill to obtain the uniform graphene composite conductive ink.
Comparative example 1
The comparative example is to prepare the graphene conductive ink, wherein the preparation method of the graphene oxide is completely the same as that of example 1, and is not described herein again. The method comprises the following specific steps:
(1) preparing graphene oxide: same as example 1
(2) Preparation of graphene
200mg of sodium dodecyl benzene sulfonate is weighed and dissolved in 20mL of graphene oxide dispersion liquid with the concentration of 5mg/mL, and ultrasonic dispersion is carried out for 1 hour. Adding 1mL of hydrazine hydrate, carrying out reflux reaction at 95 ℃ for 12h to obtain a graphene dispersion solution, and washing, freezing and drying to obtain a reduced graphene oxide solid.
(3) Preparation of graphene conductive ink
Step A: the raw materials are weighed according to the mixture ratio of 12 percent of conductive filler, 20 percent of water-based resin and 68 percent of solvent by mass. The conductive filler is a mixture of graphene and conductive carbon black according to the mass ratio of 1:1, the water-based resin is water-based acrylic resin, and the solvent is a mixed solvent of deionized water, ethylene glycol and isopropanol according to the volume ratio of 5:3: 2.
And B: accurately weighing the components in proportion, mixing and stirring the components at the rotating speed of 300rpm for 30min, and putting the components in an ultrasonic cleaning machine for 400W ultrasonic treatment for 30min to obtain the conductive ink premix. And ball-milling the pre-mixture for 6 hours at the rotating speed of 350rpm by using a planetary ball mill to obtain uniform graphene conductive ink.
(4) Preparation of graphene conductive ink film
And coating the conductive ink on the glossy photographic paper by using a bar coating method, and curing for 30 minutes in a constant-temperature air-blast oven at 80 ℃ to obtain the graphene conductive ink film.
The performance of the polyaniline-functionalized graphene composite material prepared in the above embodiment and the performance of the graphene conductive material prepared in comparative example 1 are characterized as follows:
SEM image of scanning electron microscope
Referring to fig. 2 and 3, fig. 2 is an SEM image of the polyaniline-functionalized graphene composite material prepared in example 1, and fig. 3 is an SEM image of the graphite conductive material prepared in comparative example 1. As can be seen from the figure, the graphene in comparative example 1 is directly prepared by reducing graphene oxide in the presence of a surfactant, and the obtained graphene dispersion liquid has poor uniformity. Referring to fig. 4, fig. 4 is a comparison graph of the polyaniline-functionalized graphene dispersion solution and the graphene dispersion solution without polyaniline functionalization after standing for 2 months, and it can be seen that the polyaniline-functionalized graphene dispersion solution can still be stably and uniformly dispersed, and the graphene dispersion solution without polyaniline-functionalization is significantly layered, indicating that graphene is seriously agglomerated.
(II) Fourier infrared spectrogram
Referring to fig. 5, fig. 5 is a graph of fourier infrared spectra of polyaniline functionalized graphene (rGO/SPANI), Graphene Oxide (GO), Sulfonated Polyaniline (SPANI) prepared in example 1 and reduced graphene (rGO) prepared in comparative example 1. As can be seen from the figure, Graphene Oxide (GO) is 3440cm-1A strong broad peak is nearby, which corresponds to the stretching vibration peak of alcoholic hydroxyl (C-OH), and is further 1630cm-1And 1100cm-1There are also two peaks near, corresponding to the stretching vibration peaks of carbonyl (C ═ O) and epoxy (C-O-C), respectively, and these oxygen-containing groups are all generated by Hummers method under the action of strong oxidant concentrated sulfuric acid and potassium permanganate when GO is prepared. The peaks also appear in the infrared spectrum of reduced graphene oxide (rGO) obtained by direct reduction of hydrazine hydrate, but the intensity of the peaks is obviously weakened compared with that of GO, which shows that the reduction reaction of hydrazine hydrate can reduce oxygen-containing groups in GO, recover the lattice structure of graphene and is beneficial to the improvement of the electrical properties of graphene. The infrared spectrum of Sulfonated Polyaniline (SPANI) shows that SPANI also has absorption peaks near the oxygen-containing group peak, wherein 3000-3400cm-1The wide peak corresponds to N-H stretching vibration peak, C-N stretching vibration and C-H stretching vibration peak on benzene ring, vibration peak of benzene ring skeleton is near 1600cm-1, 1130cm-1The vicinity is a bending vibration peak outside the C-H plane of the benzene ring. Thus, the graphene/sulfonated polyaniline (rGO/SPANI) composite was found to be 3440cm-1、1630cm-1And 1100cm-1The infrared peak intensity is the superposition of the characteristic peaks of rGO and SPANI. From the figure, it can be seen that the overlap, rGO/SPANI, is 3440cm-1Has a peak similar to rGO strength of 1630cm-1Peak at a weaker level thanThe rGO is presumed to have fewer alcohol hydroxyl groups and carbonyl groups on graphene in the rGO/SPANI composite material than the rGO, and the SPANI composite material is shown to promote the removal of oxygen-containing groups in the GO, so that the graphene has better structural and electrical properties.
(III) Raman Spectroscopy
Please refer to fig. 6, which is a raman spectrum of the polyaniline functionalized graphene (rGO/SPANI), Graphene Oxide (GO), Sulfonated Polyaniline (SPANI) prepared in example 1 and reduced graphene (rGO) prepared in comparative example 1. As can be seen from the figure, the Raman spectra of GO, rGO and rGO/SPANI all have characteristic peaks D and G of the graphene material, which are respectively located at 1350cm-1And 1580cm-1Nearby. The two peaks represent disordered vibrations of graphene and sp in graphene2The in-plane vibration of the hybridized carbon atoms, and therefore the relative intensities (ID/IG) of these two peaks can be used to characterize the lattice defects and the degree of disordering of graphene. The ID/IG values in the GO, rGO and rGO/SPANI spectra were calculated to be 1.36, 1.00 and 0.8, respectively. Since the raman spectrum of the SPANI has peaks near the D peak and the G peak, it also contributes to the peak intensity at the D peak and the G peak in rGO/SPANI, and if the influence of these portions is subtracted, the ID/IG ratio of the graphene should be lower than 0.8. Therefore, after reduction by hydrazine hydrate, the disordering degree of the graphene structure is reduced, the ID/IG value of rGO/SPANI in the three materials is the minimum, the disordering degree of the graphene structure is the minimum, the interaction between SPANI and GO is beneficial to removing oxygen-containing groups in GO, and the lattice defect in the graphene structure is reduced, which is consistent with the conclusion of infrared spectroscopy. The characterization results show that the compounding of the graphene and the sulfonated polyaniline is beneficial to uniform and stable dispersion of graphene in an aqueous solution and inhibition of aggregation of a graphene lamellar structure, and is also beneficial to restoration of the structure in the reduction process of graphene oxide, so that a graphene material with better performance is obtained.
(IV) four Probe resistance test and conductivity calculation
Please refer to fig. 7, which is a graph showing the conductivity of the cured conductive films of the conductive inks prepared in examples 1-5 and comparative example 1 of the present invention. As can be seen from the figure, the conductive ink using polyaniline functionalized graphene as the conductive filler component has better conductivity, and particularly, the conductivity of example 1 can reach 6.61S/cm, which is about 2 times higher than that of the graphene conductive film without polyaniline functionalization in comparative example 1. The result shows that when the polyaniline functionalized graphene is used as the conductive ink filler, the excellent performance of the graphene two-dimensional nano material can be better exerted, a good point-surface conductive path is formed with conductive carbon black, and the conductivity of the conductive film is improved.
Compared with the prior art, the sulfonated polyaniline and the graphene are compounded to obtain the polyaniline functionalized graphene, so that the dispersion performance of the graphene in water can be effectively improved, the stable graphene-water dispersion liquid is obtained, and the problem that the performance is deteriorated because the graphene lamellar structure is easy to agglomerate is effectively solved. Mixing polyaniline functionalized graphene and carbon black to serve as a conductive filler, forming a conductive network in a point-surface contact mode, using water-based acrylic resin, water-based polyurethane, water-based epoxy resin, water-based silica gel and the like as binders, using a mixture of deionized water and low-carbon alcohols such as ethylene glycol, isopropanol and the like as solvents, and preparing the polyaniline functionalized graphene water-based conductive ink through stirring, ultrasonic treatment and grinding processes. The conductive ink has the characteristics of uniform and stable dispersion, mild post-treatment conditions, high conductivity, good printing adaptability and the like, and is expected to be applied to the field of printing of flexible electronic devices.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The preparation method of polyaniline functionalized graphene is characterized by comprising the following steps:
step S1: dissolving sulfonated polyaniline in graphene oxide dispersion liquid, and reacting to obtain polyaniline/graphene oxide dispersion liquid;
step S2: and carrying out in-situ reduction on the polyaniline/graphene oxide dispersion solution by using a reducing agent to prepare polyaniline functionalized graphene.
2. The method of claim 1, wherein the method comprises the following steps: the reducing agent in step S2 is one or more of hydrazine hydrate, sodium borohydride, ascorbic acid, and hydroiodic acid.
3. The method of claim 2, wherein the method comprises the following steps: the mass ratio of the graphene oxide to the sulfonated polyaniline to the reducing agent is 1: 0.5-2: 2-20.
4. The method of claim 3, wherein the method comprises the following steps: the graphene oxide is prepared by taking graphite powder as a raw material and adopting an improved Hummers method.
5. The method of claim 4, wherein the method comprises the following steps: the sulfonated polyaniline is prepared by adopting a chlorosulfonic acid sulfonated polyaniline method.
6. A preparation method of polyaniline functionalized graphene conductive ink is characterized by comprising the following steps:
step A: mixing polyaniline functionalized graphene and conductive carbon black to form a conductive filler, and mixing the conductive filler with a certain amount of binder and solvent for pretreatment to prepare a conductive ink premix;
and B: grinding the conductive ink premix prepared in the step A to prepare polyaniline functionalized graphene conductive ink;
wherein, the polyaniline-functionalized graphene in the step a is prepared by the method for preparing polyaniline-functionalized graphene in any one of claims 1 to 5.
7. The method for preparing polyaniline functionalized graphene conductive ink as described in claim 6, wherein: the mass ratio of the polyaniline functionalized graphene to the carbon black is 1: 0.2-4.
8. The method for preparing polyaniline functionalized graphene conductive ink as described in claim 7, wherein: in the polyaniline functionalized graphene conductive ink, the mass fractions of conductive filler, solvent and binder are 5-20%, 50-80% and 10-30%.
9. The method for preparing polyaniline functionalized graphene conductive ink as described in claim 8, wherein: the binder is one or more of waterborne acrylic resin, waterborne polyurethane, waterborne epoxy resin and waterborne silica gel.
10. The method for preparing polyaniline functionalized graphene conductive ink as described in claim 9, wherein: the solvent is one or more of deionized water, ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, butanediol, etc.
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