CN112048219A - Water-based high-conductivity graphene printing ink and preparation method thereof - Google Patents
Water-based high-conductivity graphene printing ink and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based high-conductivity graphene ink and a preparation method thereof. The preparation method comprises the following steps: firstly, carrying out surface treatment on graphene oxide by using an oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at the surface defect of the graphene oxide to obtain the graphene oxide with a surface defect-free structure; treating the graphene oxide with a reducing agent under second ultrasonic conditions and microwave conditions in sequence to reduce the oxidized functional groups on the surface of the graphene oxide to form reduced graphene oxide; and mixing the reduced graphene oxide with water-based resin, conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink. According to the invention, carbon-carbon bonds at the graphene defects are broken under the combined action of the oxidant and the ultrasound, and the broken graphene oxide with no defects on the surface is further reduced by using the reducing agent under the conditions of ultrasound and microwave to obtain the reduced graphene oxide with excellent conductivity.
Description
Technical Field
The invention particularly relates to water-based high-conductivity graphene ink and a preparation method thereof, and belongs to the technical field of ink.
Background
In recent years, as people demand lighter, thinner, more flexible and more efficient electronic products, the requirements for the conductive circuit in the electronic device are more and more strict. The traditional conductive ink adopts conductive carbon black or conductive graphite as a filler, the ink is low in price but poor in conductivity of a circuit, and like the metal ink taking silver powder as the conductive filler, the metal ink is good in conductivity but high in cost, complex in production process, poor in stability and the like.
Graphene is a two-dimensional carbon nanomaterial which is formed by forming hexagonal honeycomb lattices by sp2 hybridized orbitals of carbon atoms, so that the unique structure endows the graphene with excellent physicochemical characteristics, such as ultrahigh electron mobility, high thermal conductivity, high Young modulus and the like; at present, the most used method for preparing graphene is a redox method, but the graphene prepared by the method has two problems, the first redox graphene is difficult to disperse and can be used only by a special dispersion process; the surface of the second redox graphene has more defects and an incomplete two-dimensional structure, so that the conductivity of the second redox graphene is far from the theoretical value.
Disclosure of Invention
The invention mainly aims to provide a water-based high-conductivity graphene ink and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of water-based high-conductivity graphene ink, which comprises the following steps:
firstly, carrying out surface treatment on graphene oxide by using an oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at the surface defect of the graphene oxide and obtain the graphene oxide with a defect-free surface;
reducing the graphene oxide subjected to surface treatment by using a reducing agent under second ultrasonic conditions and microwave conditions in sequence, so that oxidized functional groups on the surface of the graphene oxide are reduced to form reduced graphene oxide;
and mixing the reduced graphene oxide with water-based resin, conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
Further, the preparation method specifically comprises the following steps: mixing a first mixed system containing graphene oxide and aqueous resin with an oxidant to form a second mixed system, and subjecting the graphene oxide to surface treatment by the oxidant under a first ultrasonic condition so as to break defects on the surface of the graphene oxide and obtain graphene oxide with a defect-free surface structure;
mixing the second mixed system with a reducing agent to form a third mixed system, and sequentially enabling the reducing agent and the graphene oxide subjected to surface treatment to perform reduction reaction under a second ultrasonic condition and a microwave condition to reduce the graphene oxide in the third mixed system to reduced graphene oxide,
and mixing the third mixed system with conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
The embodiment of the invention also provides the water-based high-conductivity graphene ink obtained by the preparation method.
Compared with the prior art, the invention has the advantages that:
the preparation method of the water-based high-conductivity graphene ink provided by the embodiment of the invention is simple in process flow and easy to operate;
according to the preparation method of the water-based high-conductivity graphene ink, provided by the embodiment of the invention, the surface of graphene oxide is ultrasonically crushed by using an oxidant, so that carbon-carbon bonds at the defects of the graphene are broken under the combined action of the oxidant and ultrasound, the graphene oxide is cut along the defects by using scissors, and the crushed graphene oxide is further reduced by using a reducing agent under the conditions of ultrasound and microwave to obtain reduced graphene oxide with excellent conductivity;
according to the preparation method of the water-based high-conductivity graphene ink provided by the embodiment of the invention, the graphene oxide has excellent dispersibility in water, and the whole process is an in-situ reduction reaction in the presence of water-based resin, so that the problem of difficulty in dispersing the reduced graphene oxide is solved;
according to the preparation method of the water-based high-conductivity graphene ink provided by the embodiment of the invention, the prepared water-based graphene ink has the advantages of high conductivity and stable dispersion, the requirements of the ink industry and the defect of difficult dispersion of reduced graphene oxide are overcome, and the water-based high-conductivity graphene ink has a huge market prospect.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the description of the embodiment or the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram illustrating the principle of the graphene oxide sheared by the oxidant under the action of ultrasound in an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of a structure of graphene oxide after graphene oxide is sheared by an oxidant in an exemplary embodiment of the invention;
fig. 3 is a schematic structural diagram of reduced graphene oxide with fewer defects on the surface, which is obtained by subjecting graphene oxide sheared by an oxidant to a reducing agent (e.g., ammonia water) and microwave treatment in an exemplary embodiment of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The invention provides a preparation method of water-based high-conductivity graphene printing ink, which mainly comprises the following steps:
1) carrying out surface defect-free structuring treatment on graphene oxide by using an oxidant under an ultrasonic condition;
2) reducing graphene oxide by using a reducing agent under ultrasonic conditions and microwave conditions to obtain reduced graphene oxide so as to reduce functional groups on the surface of the graphene oxide and recover the conductivity of the graphene oxide;
3) and blending the reduced graphene oxide with water-based resin, conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent, and passing through three rollers to obtain the final graphene water-based conductive ink, wherein the roller spacing of the three rollers is 0.01-0.2 mm, and the rotating speed ratio of the rollers of the three rollers grinder (front: the method comprises the following steps: then) the ratio of the grinding time to the grinding time is 1:3:9, the rotation speed of a middle roller is 50-100 r/min, and the grinding times are 3-5.
The method comprises the steps of blending the water-based resin and the graphene oxide, adding a proper amount of oxidant, and enabling the surface defects of the graphene oxide to be fractured under the ultrasonic condition, wherein the ultrasonic condition can accelerate the fracturing process, adding a proper amount of reducing agent after a period of time, and continuing ultrasonic treatment. In the process, the aqueous resin plays a role in connection and support in the whole system, so that the graphene oxide is less agglomerated in an alkaline environment and in a reduction process.
According to the preparation method of the water-based high-conductivity graphene ink, the oxidant can play a scissor-like role to cut the defects on the surface of the graphene oxide, the oxygen-containing functional groups on the surface of the graphene oxide can be removed through the reduction effect of the reducing agent and the microwave effect, so that the originally non-conductive graphene oxide has conductivity, the prepared water-based ink has excellent conductivity due to the fact that the graphene in the interior has a complete lamellar structure, and meanwhile, the problem that the graphene oxide is not easy to disperse can be solved through in-situ reduction of the graphene oxide in water-based resin.
The embodiment of the invention provides a preparation method of water-based high-conductivity graphene ink, which comprises the following steps:
firstly, carrying out surface treatment on graphene oxide by using an oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at the surface defect of the graphene oxide and obtain the graphene oxide with a defect-free structure on the surface;
reducing the graphene oxide subjected to surface treatment by using a reducing agent under second ultrasonic conditions and microwave conditions in sequence, so that oxidized functional groups on the surface of the graphene oxide are reduced to form reduced graphene oxide;
and mixing the reduced graphene oxide with water-based resin, conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
Further, the ultrasonic power of the first ultrasonic condition is 1-5KW, and the reaction time of the graphene oxide and the oxidant under the first ultrasonic condition is 30-120 min.
Further, the mass ratio of the oxidant to the graphene oxide is 1-10: 100.
Further, the oxidant includes any one or a combination of two or more of double oxidation, sodium hypochlorite, ozone and potassium permanganate, but is not limited thereto.
Further, the ultrasonic power of the second ultrasonic condition is 1-5KW, and the reaction time of the oxidized graphene subjected to surface treatment and the reducing agent under the second ultrasonic condition is 30-120 min; the microwave power is 1-2KW, and the reaction time under the microwave condition is 5-30 min.
Further, the mass ratio of the reducing agent to the graphene oxide is 1-10: 100.
The oxidant includes any one or a combination of more than two of ammonia water, sodium borohydride, hydrazine hydrate and ascorbic acid, but is not limited thereto.
Further, the solid mass ratio of the graphene oxide to the aqueous resin is 1-10: 100; preferably, the aqueous resin includes any one or a combination of two or more of acrylic resin, epoxy resin, phenolic resin and polyurethane resin, but is not limited thereto.
Further, the sheet diameter of the graphene oxide is 0.1-10 μm, and the mass ratio of carbon element to oxygen element in the graphene oxide is 1-2: 1.
further, the solid mass ratio of the conductive carbon black to the water-based resin is 30-100: 100.
Further, the conductive carbon black includes any one or a combination of two or more of conductive furnace carbon black, superconducting furnace carbon black, and super conductive furnace carbon black, but is not limited thereto.
Further, the mass of the dispersing agent, the flatting agent and the defoaming agent is 0.3-2 wt% of the total mass of the graphene water-based ink.
Further, the dispersant includes any one or a combination of two or more of BYK310, BYK190, cyanote 6208, and SN5040, but is not limited thereto.
Further, the defoaming agent comprises any one or a combination of more than two of BYK-A555, BYK-R605, BYK-515 and BYK-530, but is not limited to the above.
Further, the leveling agent includes any one or a combination of two or more of BYK-333, BYK-346, and BYK-381, but is not limited thereto.
Further, the preparation method specifically comprises the following steps:
mixing a first mixed system containing graphene oxide and an aqueous resin with an oxidant to form a second mixed system, and subjecting the graphene oxide to surface treatment by the oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at surface defects of the graphene oxide to obtain graphene oxide with a defect-free surface structure;
mixing the second mixed system with a reducing agent to form a third mixed system, and sequentially enabling the reducing agent and the graphene oxide subjected to surface treatment to perform reduction reaction under a second ultrasonic condition and a microwave condition to reduce the graphene oxide in the third mixed system to reduced graphene oxide,
and mixing the third mixed system with conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
Further, the preparation method specifically comprises the following steps: firstly, the reducing agent and the graphene oxide after surface treatment are subjected to reduction reaction under a second ultrasonic condition, and then the reducing agent and the graphene oxide after surface treatment are further subjected to reduction reaction under a microwave condition, so that oxygen-containing functional groups on the surface of the graphene oxide are reduced to form reduced graphene oxide.
Further, the preparation method also comprises the following steps: and removing excessive reducing agent and oxidizing agent in the third mixed system under the microwave.
The embodiment of the invention also provides the water-based high-conductivity graphene ink obtained by the preparation method.
In some more specific embodiments, a method for preparing a novel aqueous highly conductive graphene ink includes:
1) under the condition of room temperature, firstly carrying out ultrasonic treatment on the graphene oxide/water-based resin mixed solution and hydrogen peroxide or other oxidants for 30-120min under a first ultrasonic condition of 1-5KW so as to break carbon-carbon bonds at the surface defect of the graphene oxide and obtain the graphene oxide with a defect-free structure on the surface, wherein the ultrasonic power under the first ultrasonic condition is;
2) carrying out ultrasonic treatment on the mixed solution (containing aqueous resin, graphene oxide and possibly residual oxidant) reacted in the step 1) and reducing agents such as ammonia water for 30-120min under a second ultrasonic condition of 1-5KW, and then carrying out microwave treatment for 5-30min under a microwave condition of 1-2KW so as to reduce the graphene oxide in the mixed solution, wherein the residual oxidizing agents and reducing agents in the mixed solution can be removed through the microwave treatment;
3) and finally, mixing the mixed solution obtained after the reaction in the step 2) with conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent, and grinding by three rollers to obtain the graphene water-based ink.
The technical solution, the implementation process and the principle thereof will be further explained with reference to the specific embodiments as follows.
Example 1
A preparation method of novel water-based high-conductivity graphene ink can comprise the following steps:
step one, shearing and reducing graphene oxide: under the condition of room temperature, dissolving 100g of graphene oxide with the sheet diameter of 0.1 mu m and the carbon/oxygen mass ratio of 1 in 20kg of aqueous acrylic resin with the solid content of 50%, ultrasonically stirring for 30min to completely disperse the graphene oxide, adding 1g of hydrogen peroxide, ultrasonically stirring for 30min, adding 1g of ammonia water, continuously ultrasonically stirring for 30min, then moving to a microwave device, and treating for 10min under the microwave condition with the power of 2KW to obtain an in-situ reduced graphene oxide/resin mixed solution;
step two, preparing the water-based graphene ink: taking 1kg of the in-situ reduced graphene oxide/water-based acrylic resin mixed solution obtained in the first step, sequentially adding 300g of conductive furnace carbon black, 10g of BYK310, 10g of BYK-A555 and 10g of BYK-333, stirring and mixing to form water-based high-conductivity graphene ink, adjusting the roller spacing of a three-roller machine to 0.1mm, and rolling the water-based high-conductivity graphene ink for 3 times by the three-roller machine;
step three, testing the performance of the water-based graphene ink: and (3) printing the water-based high-conductivity graphene ink prepared in the second step on a PET (polyethylene terephthalate) film by adopting screen printing, drying to prepare a conductive membrane, and testing to obtain the sheet resistance, the thickness and the corresponding resistivity of the obtained conductive membrane, wherein the results are shown in Table 1.
Example 2
Step one, shearing and reducing graphene oxide: under the condition of room temperature, 1000g of graphene oxide with the sheet diameter of 0.1 mu m and the carbon/oxygen mass ratio of 1 is dissolved in 20kg of aqueous acrylic resin with the solid content of 50 percent, the mixture is ultrasonically stirred for 30min to completely disperse the graphene oxide, 50g of hydrogen peroxide is added, after the mixture is ultrasonically stirred for 30min, 50g of ammonia water is added, the mixture is continuously ultrasonically stirred for 30min, and then the mixture is moved to a microwave device to be treated for 30min under the microwave condition with the power of 3KW, so that in-situ reduction graphene oxide/aqueous acrylic resin mixed solution is obtained;
step two, preparing the water-based graphene ink: taking 1kg of the in-situ reduced graphene oxide/water-based acrylic resin mixed solution obtained in the first step, sequentially adding 300g of conductive furnace carbon black, 10g of BYK310, 10g of BYK-A555 and 10g of BYK-333, stirring and mixing to form water-based high-conductivity graphene ink, adjusting the roller spacing of a three-roller machine to 0.05mm, and rolling the water-based high-conductivity graphene ink for 3 times by the three-roller machine;
step three, testing the performance of the water-based graphene ink: and (3) printing the water-based high-conductivity graphene ink prepared in the second step on a PET (polyethylene terephthalate) film through screen printing, drying to prepare a conductive membrane, and testing to obtain the sheet resistance, the thickness and the corresponding resistivity of the obtained conductive membrane, wherein the results are shown in Table 1.
Example 3
Step one, shearing and reducing graphene oxide: under the condition of room temperature, dissolving 100g of graphene oxide with the sheet diameter of 10 microns and the carbon/oxygen mass ratio of 1.5 in 20kg of aqueous acrylic resin with the solid content of 50%, ultrasonically stirring for 30min to completely disperse the graphene oxide, adding 10g of hydrogen peroxide, ultrasonically stirring for 30min, adding 10g of ammonia water, continuously ultrasonically stirring for 30min, then moving to a microwave device, and treating for 10min under the microwave condition with the power of 2KW to obtain an in-situ reduced graphene oxide/aqueous acrylic resin mixed solution;
step two, preparing the water-based graphene ink: and (3) taking 1kg of the in-situ reduced graphene oxide/water-based acrylic resin mixed solution obtained in the first step, sequentially adding 300g of conductive furnace carbon black, 10g of BYK310, 10g of BYK-A555 and 10g of BYK-333, stirring and mixing to form the water-based high-conductivity graphene ink, adjusting the roller spacing of a three-roller machine to 0.1mm, and rolling the water-based high-conductivity graphene ink for 3 times by the three-roller machine.
Step three, testing the performance of the water-based graphene ink: printing ink on a PET film through screen printing, drying to prepare a conductive film, and testing to obtain the sheet resistance, the thickness and the corresponding resistivity of the obtained conductive film, wherein the results are shown in Table 1.
Example 4
Step one, shearing and reducing graphene oxide: under the condition of room temperature, 500g of graphene oxide with the sheet diameter of 10 microns and the carbon/oxygen mass ratio of 1 is dissolved in 20kg of aqueous epoxy resin with the solid content of 50%, the mixture is ultrasonically stirred for 30min, 30g of hydrogen peroxide is added, 30g of ammonia water is added after the mixture is ultrasonically stirred for 30min, the mixture is continuously ultrasonically stirred for 30min, then the mixture is moved to a microwave device, and the mixture is treated for 30min under the microwave condition with the power of 2KW, so that in-situ reduction graphene oxide/aqueous epoxy resin mixed solution is obtained;
step two, preparing the water-based graphene ink: and (3) taking 1kg of the in-situ reduced graphene oxide/water-based epoxy resin mixed solution obtained in the first step, sequentially adding 300g of conductive furnace carbon black, 10g of BYK310, 10g of BYK-A555 and 10g of BYK-333, stirring and mixing to form the water-based high-conductivity graphene ink, adjusting the roller spacing of a three-roller machine to 0.1mm, and rolling the water-based high-conductivity graphene ink for 3 times by the three-roller machine.
Step three, testing the performance of the water-based graphene ink: printing ink on a PET film through screen printing, drying to prepare a conductive film, and testing to obtain the sheet resistance, the thickness and the corresponding resistivity of the obtained conductive film, wherein the results are shown in Table 1.
Example 5
Step one, shearing and reducing graphene oxide: under the condition of room temperature, 500g of graphene oxide with the sheet diameter of 5 microns and the carbon/oxygen mass ratio of 2 is dissolved in 20kg of aqueous acrylic resin with the solid content of 50%, the graphene oxide is stirred for 30min by ultrasound so as to be completely dispersed, 20g of hydrogen peroxide is added, 20g of ammonia water is added after the graphene oxide is stirred for 30min by ultrasound, the mixture is continuously stirred for 30min by ultrasound, then the mixture is moved to a microwave device, and the mixture is treated for 10min under the microwave condition with the power of 2KW so as to obtain in-situ reduction graphene oxide/aqueous acrylic resin mixed solution;
step two, preparing the water-based graphene ink: taking 1kg of the in-situ reduced graphene oxide/water-based acrylic resin mixed solution obtained in the first step, sequentially adding 300g of conductive furnace carbon black, then adding 15g of BYK310, 15g of BYK-A555 and 15g of BYK-333, stirring and mixing to form water-based high-conductivity graphene ink, adjusting the roller spacing of a three-roller machine to 0.1mm, and rolling the water-based high-conductivity graphene ink for 4 times by the three-roller machine;
step three, testing the performance of the water-based graphene ink: printing ink on a PET film through screen printing, drying to prepare a conductive film, and testing to obtain the sheet resistance, the thickness and the corresponding resistivity of the obtained conductive film, wherein the results are shown in Table 1.
Comparative example 1
The scheme of comparative example 1 is substantially the same as that of example 1 except that comparative example 1 does not add an oxidizing agent and a reducing agent, and the performance parameters of the conductive film obtained in comparative example 1 are shown in table 1.
Comparative example 2
The scheme of comparative example 2 is substantially the same as that of example 1 except that no oxidizing agent is added to comparative example 2 and the performance parameters of the conductive film obtained in comparative example 2 are shown in table 1.
Comparative example 3
The scheme of comparative example 3 is substantially the same as that of example 1 except that comparative example 3 omits the process of microwave treatment and the performance parameters of the conductive film obtained in comparative example 3 are shown in table 1.
Comparative example 4
The scheme of comparative example 4 is substantially the same as that of example 1, except that no graphene oxide is added in comparative example 4, and the performance parameters of the conductive membrane obtained in comparative example 4 are shown in table 1.
Comparative example 5
The scheme of comparative example 5 is substantially the same as that of example 1, except that comparative example 5 uses commercially available reduced graphene oxide and the performance parameters of the conductive film obtained in comparative example 5 are shown in table 1.
Table 1 shows the performance test of the three-splint substrate of the graphene table tennis bat obtained in examples 1 to 5 and comparative examples 1 to 5
As can be seen from the test data shown in table 1, since graphene oxide is not conductive and is a two-dimensional lamellar material, conductive carbon black is wrapped in the graphene oxide during the drying process, so that the conductive performance of the conductive ink is greatly reduced; the preparation method of the novel water-based high-conductivity graphene ink provided by the embodiment of the invention can greatly improve the conductivity of the conductive ink, and the conductivity of the reduced graphene oxide with a surface defect-free structure obtained by oxidizing/ultrasonic shearing and reducing the graphene oxide is also larger than that of the untreated graphene oxide.
Specifically, referring to fig. 1-3, a carbon-carbon bond at a defect of graphene oxide is broken under the combined action of an oxidant and ultrasound, which is similar to a method of shearing graphene oxide along the defect by a scissors, so as to obtain graphene oxide without a defect structure, and ammonia water, other reducing agents and microwaves can remove oxygen-containing functional groups on the surface of the graphene oxide without a defect structure, so that the graphene oxide which is originally non-conductive is reduced and has conductivity, and the reactions are performed in aqueous resin, and the method for in-situ reducing the graphene oxide to obtain the reduced graphene oxide can solve the problem that the reduced graphene oxide is not easily dispersed. And the in-situ reduced graphene oxide obtained by the method has a complete lamellar structure and has a good mixing effect with resin, so that the water-based ink prepared by the embodiment has excellent conductivity.
According to the invention, the surface of graphene oxide is ultrasonically crushed by using an oxidant, so that carbon-carbon bonds at the defect part of the graphene are broken under the combined action of the oxidant and the ultrasound, the graphene oxide is cut along the defect part similarly to a scissor, and meanwhile, the crushed graphene oxide is further reduced by using a reducing agent under the conditions of ultrasound and microwave to obtain the reduced graphene oxide with excellent conductivity, so that the problem of difficult dispersion of the reduced graphene oxide is solved by utilizing the characteristic that the graphene oxide has excellent dispersibility in water and enabling the whole process to generate in-situ reaction under a water-based resin matrix, and finally, the reduced graphene oxide/water-based resin is mixed with conductive carbon black and other auxiliary agents to prepare the water-based graphene ink; the water-based graphene ink prepared by the invention has the advantages of high conductivity and stable dispersion, solves the requirements of the ink industry and the defect of difficult dispersion of reduced graphene oxide, and has great market prospect.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. Furthermore, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. In addition, where the term "about" is used before a quantity, the present teachings also include the particular quantity itself unless specifically stated otherwise.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of water-based high-conductivity graphene ink is characterized by comprising the following steps:
firstly, carrying out surface treatment on graphene oxide by using an oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at the surface defect of the graphene oxide and obtain the graphene oxide with a defect-free structure on the surface;
reducing the graphene oxide subjected to surface treatment by using a reducing agent under second ultrasonic conditions and microwave conditions in sequence, so that oxidized functional groups on the surface of the graphene oxide are reduced to form reduced graphene oxide;
and mixing the reduced graphene oxide with water-based resin, conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
2. The method of claim 1, wherein: the ultrasonic power of the first ultrasonic condition is 1-5KW, and the reaction time of the graphene oxide and the oxidant under the first ultrasonic condition is 30-120 min.
3. The production method according to claim 1 or 2, characterized in that: the mass ratio of the oxidant to the graphene oxide is 1-10: 100; preferably, the oxidant comprises any one or a combination of more than two of double oxidation, sodium hypochlorite, ozone and potassium permanganate.
4. The method of claim 1, wherein: the ultrasonic power of the second ultrasonic condition is 1-5KW, and the reaction time of the graphene oxide subjected to surface treatment and the reducing agent under the second ultrasonic condition is 30-120 min; the microwave power is 1-2KW, and the reaction time under the microwave condition is 5-30 min.
5. The production method according to claim 1 or 4, characterized in that: the mass ratio of the reducing agent to the graphene oxide is 1-10: 100; preferably, the oxidizing agent comprises any one or a combination of more than two of ammonia water, sodium borohydride, hydrazine hydrate and ascorbic acid.
6. The method of claim 1, wherein: the solid mass ratio of the graphene oxide to the aqueous resin is 1-10: 100; preferably, the aqueous resin comprises any one or a combination of more than two of acrylic resin, aqueous epoxy resin, aqueous phenolic resin and aqueous polyurethane resin; preferably, the sheet diameter of the graphene oxide is 0.1-10 μm, and the mass ratio of carbon element to oxygen element in the graphene oxide is 1-2: 1.
7. the method of claim 1, wherein: the solid mass ratio of the conductive carbon black to the water-based resin is 30-100: 100; preferably, the conductive carbon black comprises any one or a combination of two or more of conductive furnace carbon black, superconducting furnace carbon black and special conductive furnace carbon black; preferably, the mass of the dispersing agent, the flatting agent and the defoaming agent is 0.3-2 wt% of the total mass of the graphene water-based ink; preferably, the dispersant comprises any one or the combination of more than two of BYK310, BYK190, Cyanote 6208 and SN 5040; the defoaming agent comprises any one or the combination of more than two of BYK-A555, BYK-R605, BYK-515 and BYK-530; the leveling agent comprises any one or the combination of more than two of BYK-333, BYK-346 and BYK-381.
8. The method according to claim 1, comprising:
mixing a first mixed system containing graphene oxide and an aqueous resin with an oxidant to form a second mixed system, and subjecting the graphene oxide to surface treatment by the oxidant under a first ultrasonic condition so as to break carbon-carbon bonds at surface defects of the graphene oxide to obtain graphene oxide with a defect-free surface structure;
mixing the second mixed system with a reducing agent to form a third mixed system, and sequentially enabling the reducing agent and the graphene oxide subjected to surface treatment to perform reduction reaction under a second ultrasonic condition and a microwave condition to reduce the graphene oxide in the third mixed system to reduced graphene oxide,
and mixing the third mixed system with conductive carbon black, a dispersing agent, a flatting agent and a defoaming agent to prepare the graphene water-based ink.
9. The method according to claim 8, comprising: firstly, under a second ultrasonic condition, reducing the reducing agent and the graphene oxide subjected to surface treatment to perform a reduction reaction, and then, under a microwave condition, further performing a reduction reaction on the reducing agent and the graphene oxide subjected to surface treatment to reduce oxygen-containing functional groups on the surface of the graphene oxide to form reduced graphene oxide; preferably, the preparation method further comprises the following steps: and removing excessive reducing agent and oxidizing agent in the third mixed system under the microwave.
10. The aqueous highly conductive graphene ink obtained by the production method according to any one of claims 1 to 9.
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