CN111392720B - High-concentration graphene oxide solution and preparation method and application thereof - Google Patents
High-concentration graphene oxide solution and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-concentration graphene oxide solution and a preparation method and application thereof, and the preparation method comprises the following steps: preparing a low-concentration graphene oxide solution of 0.1-10 mg/mL; carrying out first refinement on the low-concentration graphene oxide solution; performing concentration treatment on the solution after the first refining to obtain a high-concentration graphene oxide solution; the concentration treatment comprises adding graphene oxide into the solution after the first refinement for second refinement, and adjusting the pH value of the solution after the second refinement to 4-5. The high-concentration graphene oxide solution with good fluidity can be obtained by the specific process, and the graphene macroscopic body with good comprehensive performance can be obtained by utilizing the high-concentration graphene oxide solution, so that the graphene macroscopic body can be applied to multiple fields of energy, biology, environmental protection and the like. The method has low cost and simple process, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of graphene, and particularly relates to a high-concentration graphene oxide solution and a preparation method and application thereof.
Background
The appearance of graphene is an important breakthrough in the field of two-dimensional nanomaterials, has excellent optical, electrical and mechanical properties, is considered to be a revolutionary functional material and structural material in the future, and has important influence in the fields of energy, environment, biomedical treatment, electronic devices, aerospace and the like. Graphene oxide belongs to a quasi-two-dimensional nano material, is an important derivative of graphene, and has rich oxygen-containing functional groups. The graphene oxide has a plurality of excellent physicochemical properties different from those of graphene, and has the advantages of simple preparation process, low cost and very wide application prospect, and is gradually valued by people in recent years. Researches show that the surface of the graphene oxide has good dispersibility in solvents such as water due to the existence of hydrophilic groups such as hydroxyl, carboxyl, epoxy and the like, and is easy to assemble various forms of macroscopic bodies such as graphene oxide paper, graphene oxide fibers, graphene oxide aerogel and the like to be applied to the fields of energy, electronics, environmental protection and the like. The graphene oxide solution with stable dispersion and high concentration is a key raw material for obtaining the graphene oxide macroscopic material.
In practical application of the graphene oxide solution, if the graphene oxide solution is required to exert excellent performance, the concentration of the graphene oxide solution in water or other dispersion systems is important to be increased, and various performances such as morphology, compactness, porosity, mechanical strength, electric conductivity and thermal conductivity of a macroscopic body can be improved. The concentration of the graphene oxide solution sold in the market at present is 0.1-10 mg/mL, and the graphene oxide macroscopic body directly constructed due to the low concentration of the solution has many problems, such as poor mechanical strength of one-dimensional graphene oxide fibers, low thickness of two-dimensional graphene oxide films, low porosity of three-dimensional graphene oxide aerogel and the like. However, the problem of high solution viscosity is encountered during the preparation of high-concentration graphene oxide solution, which is not favorable for improving the performance of the assembly macro-body. Therefore, how to obtain a high-concentration graphene oxide solution becomes a key limiting further application thereof.
At present, research reports on high-concentration graphene dispersions and high-concentration graphene oxide dispersions are available. Chinese patent CN 110330012a discloses a method for preparing graphene dispersion by shearing a layered graphite suspension. However, the raw materials used in the method are expanded graphite or layered graphite and the like which are not subjected to mechanical stripping, and are not graphene oxide raw materials which are provided in the market and have the number of stripped laminas of less than 10; chinese patent CN 109205608A discloses a graphene oxide dispersion with adjustable concentration prepared by placing solvated graphite oxide in a specific solvent and stirring or ultrasonically. However, the method needs to adopt a specific organic solvent, is time-consuming and labor-consuming, and limits the industrial application of the method; chinese patent CN 108862267a discloses a method for concentrating graphene oxide solution by membrane separation technology, but the membrane separation device also relates to a temperature control device, a power device and the like besides membrane and regenerated membrane components, and the equipment components are relatively complex; chinese patent CN 104495807a discloses a high-concentration coupled magnetic moment graphene oxide obtained from graphene oxide with a specific size and hydroxyl group distribution, but the commercially available graphene oxide is mostly prepared by Hummers method, and the oxidation degree and functional group type of graphene oxide are very different from those of graphene oxide with a specific precise structure, and thus there is no universality.
Therefore, the high-concentration graphene oxide solution and the preparation method thereof are an important technical means for expanding the application prospect.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The present invention is directed to overcome at least one of the above drawbacks of the prior art, and provides a high-concentration graphene oxide solution, a preparation method and an application thereof, so as to solve the problems that the existing graphene oxide solution is difficult to increase the concentration, or is restricted by the problem of high solution viscosity during the preparation of the high-concentration graphene oxide solution, and is not favorable for improving the performance of the assembled macroscopic body of the graphene oxide solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a high-concentration graphene oxide solution, which comprises the following steps: preparing a low-concentration graphene oxide solution of 0.1-10 mg/mL; carrying out first refinement on the low-concentration graphene oxide solution; performing concentration treatment on the solution after the first refining to obtain a high-concentration graphene oxide solution; the concentration treatment comprises adding graphene oxide into the solution after the first refinement for second refinement, and adjusting the pH value of the solution after the second refinement to 4-5.
According to an embodiment of the invention, the method further comprises the step of performing concentration treatment on the solution after the first refining for multiple times in a circulating manner to obtain a high-concentration graphene oxide solution with the concentration of more than 100mg/mL and the viscosity of less than 1500 mPas.
According to one embodiment of the present invention, each of the first and second refinements independently includes sequentially performing a primary refinement in which graphene oxide D90 is <5 μm in a solution and a secondary refinement in which graphene oxide D90 is <1 μm in a solution.
According to one embodiment of the present invention, the primary refining apparatus is selected from one or more of an ultrasonic cell crusher, a sand mill and an emulsifying machine, and the secondary refining apparatus is selected from one or more of a high-pressure homogenizer and a microfluidizer.
According to one embodiment of the invention, when the preliminary refining equipment is an ultrasonic cell crusher, the ultrasonic power is 800W-1200W, and the processing time is 60 min-90 min; when the primary refining equipment is a sand mill, the rotating speed of the sand mill is 3000-5000 rpm, and the processing time is 60-90 min; when the primary refining equipment is an emulsifying machine, the shearing rotating speed of the emulsifying agent is 10000 rpm-30000 rpm, and the processing time is 10 min-30 min; the processing pressure of the secondary refining is 1000 bar-1500 bar, and the processing flow rate is 0.3 s/mL-0.5 s/mL.
According to an embodiment of the present invention, the adjusting the pH of the solution after the second refinement includes: and adding one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide into the solution after the second refining, and stirring for 1-2 h.
According to one embodiment of the present invention, the graphene oxide solution is an aqueous graphene oxide solution, and the aqueous graphene oxide solution includes a dispersant selected from one or more of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and gamma-aminopropyltriethoxysilane.
According to an embodiment of the invention, in the concentration treatment, the adding of the graphene oxide includes adding graphene oxide powder and/or adding a graphene oxide solution, and when the graphene oxide solution is added, the concentration of the added graphene oxide solution is greater than 10 mg/mL.
The invention also provides a high-concentration graphene oxide solution, which is prepared by adopting the preparation method.
The invention also provides application of the high-concentration graphene oxide solution in preparation of a graphene oxide macroscopic body.
According to the technical scheme, the invention has the beneficial effects that:
according to the invention, the high-concentration graphene oxide solution with good fluidity is obtained through a specific process, and the graphene macroscopic body with good comprehensive performance can be further obtained by adopting the high-concentration graphene oxide solution, so that the graphene oxide macroscopic body can be applied to multiple fields of energy, biology, environmental protection and the like. The method has low cost and simple process, and is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a flow chart of a process for preparing a high concentration graphene oxide solution according to an embodiment of the present invention;
fig. 2 is a scanning electron microscope cross-sectional view of the high-concentration graphene oxide film in example 2.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a high-concentration graphene oxide solution, which comprises the following steps: preparing a low-concentration graphene oxide solution of 0.1-10 mg/mL; carrying out first refinement on the low-concentration graphene oxide solution; performing concentration treatment on the solution after the first refining to obtain a high-concentration graphene oxide solution; the concentration treatment comprises adding graphene oxide into the solution after the first refinement for second refinement, and adjusting the pH value of the solution after the second refinement to 4-5.
Fig. 1 is a flow chart of a preparation process of a high-concentration graphene oxide solution according to an embodiment of the present invention. The method for preparing the high-concentration graphene oxide solution will be specifically described below with reference to fig. 1.
Firstly, preparing a low-concentration graphene oxide solution of 0.1-10 mg/mL, and carrying out first refinement on the low-concentration graphene oxide solution to prepare the low-concentration low-viscosity graphene oxide solution. Generally, the viscosity of the graphene oxide solution after the first refinement is less than 800mPa · s.
The first refinement comprises primary refinement and secondary refinement which are sequentially performed. The lamellar structure of the graphene is primarily crushed through primary refinement, so that the graphene oxide D90 in the solution is smaller than 5 mu m, and then secondary refinement with higher crushing degree is carried out, namely ultramicro refinement, so that the graphene oxide D90 in the graphene oxide solution is smaller than 1 mu m. The thinning process can break a large-sheet structure of graphene oxide, on one hand, the uniformity of the size of graphene oxide sheets is ensured, on the other hand, the size of the graphene oxide sheets is reduced, the number of functional groups at the edges of the graphene oxide sheets is increased, namely the ionization degree of the functional groups, so that the viscosity of the solution can be reduced, and the subsequent continuous addition of the graphene oxide is facilitated to improve the concentration of the solution.
In some embodiments, the primary refining apparatus is selected from one or more of an ultrasonic cell disruptor, a sand mill, and an emulsifying machine, and the secondary refining apparatus is selected from one or more of a high pressure homogenizer and a microfluidizer.
For example, when the preliminary refining equipment is an ultrasonic cell disruptor, the ultrasonic power is 800W-1200W, such as 800W, 950W, 980W, 1035W, 1126W, 1200W and the like, and the treatment time is 60 min-90 min, such as 60min, 63min, 68min, 72min, 78min, 83min, 89min and the like; when the preliminary refining equipment is a sand mill, the rotation speed of the sand mill is 3000 rpm-5000 rpm, such as 3000rpm, 3200rpm, 3400rpm, 3800rpm, 4200rpm, 4700rpm, 5000rpm and the like, and the treatment time is 60 min-90 min, such as 61min, 66min, 75min, 76min, 80min, 83min, 90min and the like; when the primary refining equipment is an emulsifying machine, the shearing rotation speed of the emulsifying agent is 10000 rpm-30000 rpm, such as 10000rpm, 12000rpm, 15000rpm, 23000rpm, 26000rpm, 28000rpm, 30000rpm and the like, and the processing time is 10 min-30 min, such as 10min, 12min, 15min, 20min, 24min, 27min, 30min and the like.
When the secondary refining equipment is a high-pressure homogenizer, the treatment pressure is 1000 bar-1500 bar, such as 1000bar, 1300bar, 1350bar, 1420bar, 1460bar, 1470bar, 1500bar and the like, and the treatment flow rate is 0.3 s/mL-0.5 s/mL, such as 0.3s/mL, 0.34s/mL, 0.36s/mL, 0.38s/mL and the like. When the secondary refining equipment is a micro-jet homogenizer, the treatment pressure is 1000 bar-1500 bar, such as 1000bar, 1110bar, 1250bar, 1270bar, 1360bar, 1480bar, 1500bar and the like, and the treatment flow rate is 0.3 s/mL-0.5 s/mL, such as 0.31s/mL, 0.33s/mL, 0.37s/mL, 0.38s/mL and the like.
And then, performing concentration treatment on the solution after the first thinning to obtain a high-concentration graphene oxide solution. Wherein, the concentration treatment comprises the following steps: and adding graphene oxide into the solution after the first refinement for second refinement, and adjusting the pH value of the solution after the second refinement to 4-5.
Specifically, the viscosity of the graphene oxide solution after the first refinement is reduced, and graphene oxide is added on the basis, so that the concentration of the graphene oxide solution is increased. The problem of solution viscosity increase can be introduced while the concentration of the graphene oxide solution is increased, so that the solution needs to be refined for the second time, namely, the primary refining and secondary refining processes are carried out again, and the purpose of reducing the solution viscosity is achieved.
In addition, after the second refining treatment, the pH value of the solution after the second refining treatment needs to be adjusted to 4-5, so that strong sheet-to-sheet repulsive force caused by problems of carboxyl protonation and the like is reduced, the compatibility of the graphene oxide in the solution is improved, and the high-concentration graphene oxide solution with good fluidity is further obtained. The method for adjusting the pH value comprises the following steps: and (3) dropwise adding one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide into the solution after the second refining, and fully stirring the solution for 1-2 h after dropwise adding.
In some embodiments, the method further includes performing concentration treatment on the solution after the first refinement for multiple cycles, that is, repeatedly performing operations of adding graphene oxide, performing the second refinement, and adjusting the pH value of the solution, so as to facilitate dissolving more graphene oxide and obtain a graphene oxide solution with a higher concentration. Generally, the concentration of the obtained high-concentration graphene oxide solution is more than 100mg/mL, and the viscosity is less than 1500 mPas.
When graphene oxide is added, graphene oxide powder can be optionally added, and a graphene oxide solution can also be added. Generally, when the graphene oxide powder is added, the dosage is based on the principle of small-amount and multiple-cycle addition. When the graphene oxide solution is added, the concentration of the added graphene oxide solution is ensured to be more than 10 mg/mL.
In some embodiments, the graphene oxide solution is an aqueous graphene oxide solution, the aqueous graphene oxide solution includes a dispersant, the dispersant includes a surfactant or a silane coupling agent, and the like, for example, the surfactant may be sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, and the like, and the silane coupling agent may be γ - (2, 3-epoxypropoxy) propyltrimethoxysilane (KH-560), γ -aminopropyltriethoxysilane (KH-550), and the like.
In summary, the high-concentration graphene oxide solution with good fluidity can be obtained by the method, and the high-concentration graphene oxide solution can be assembled in different forms to prepare graphene oxide macrosomes, for example, graphene oxide fibers, graphene oxide paper, graphene oxide aerogel and the like are applied to multiple fields of energy, biology, environmental protection and the like, and various performance indexes of the graphene oxide macrosomes, such as mechanical strength, specific surface area, porosity and the like, can be improved. The high-concentration graphene oxide solution disclosed by the invention is low in preparation cost, simple in method and suitable for large-scale industrial production.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) 2g of graphene oxide and 500mL of deionized water are taken, and the graphene oxide is prepared into a 4mg/mL graphene oxide aqueous solution with the viscosity of 561 mPas and the pH of 1.3.
2) And (3) treating the graphene oxide aqueous solution for 10min under the condition that the rotation speed of an emulsifying machine is 10000rpm, and treating for 10min under the conditions that the pressure of a high-pressure homogenizer is 1000bar and the flow rate is 0.5s/mL to obtain the graphene oxide solution with the viscosity of 279mPa & s.
3) To the above graphene oxide aqueous solution, 25g of graphene oxide was added to obtain a graphene oxide aqueous solution having a viscosity of 3300mPa · s. And (3) treating the graphene oxide aqueous solution for 20min under the condition that the rotation speed of an emulsifying machine is 15000rpm, and treating for 20min under the conditions that the pressure of a high-pressure homogenizer is 1200bar and the flow rate is 0.5 s/mL. Further, sodium hydroxide was slowly added dropwise to the graphene oxide solution, and the mixture was sufficiently stirred for 1 hour until the pH of the graphene oxide solution was 4, to obtain a graphene oxide solution with a viscosity decreased by 732mPa · s.
4) And continuously adding 25g of graphene oxide into the graphene oxide solution, wherein the viscosity of the graphene oxide solution is increased to 4375mPa & s. Treating at 15000rpm for 20min, and treating at 1200bar and 0.5s/mL for 20 min. Further, ammonia water is slowly dripped into the graphene oxide solution, and the mixture is fully stirred for 2 hours until the pH value of the graphene oxide solution is 4, so that the graphene oxide solution with the viscosity reduced to 1087mPa & s and the concentration as high as 104mg/mL is obtained.
And pouring the graphene oxide solution into a container, and putting the container into a vacuum oven for 1min under the conditions that the temperature of the vacuum oven is room temperature and the vacuum degree is less than 267 Pa. And taking out the watch glass, and gently removing the holes on the surface of the graphene oxide aqueous solution by using a glass rod.Repeating the steps for multiple times until the solution is taken out, wherein no depression appears on the surface of the graphene oxide solution. Coating the treated graphene oxide solution on a PET substrate by a scraper, drying at room temperature, and peeling to obtain the graphene oxide solution with the thickness of 200 mu m, smooth surface, high orientation of microstructure and density of 2.1g/cm3And the high-flexibility graphene oxide film can be repeatedly folded for more than 5000 times.
Example 2
1) 5g of graphene oxide and 500mL of polyvinyl alcohol are taken, the graphene oxide is prepared into a 10mg/mL graphene oxide solution, the viscosity is 452mPa · s, and the pH of the solution is 1.4.
2) And (3) treating the graphene oxide solution in a cell ultrasonic crusher for 1h, wherein the treatment power is 1000W. And (3) treating for 20min under the conditions that the pressure of the micro-jet homogenizer is 1500bar and the flow rate is 0.3s/mL to obtain a graphene oxide solution with the viscosity of 239mPa & s.
3) 30g of graphene oxide was added to the graphene oxide solution to obtain a graphene oxide solution having a viscosity of 4077mPa · s. The solution is processed in a cell ultrasonic crusher for 1h with the processing power of 1000W, and is continuously processed in a sand mill for 1h with the rotating speed of 4000 rpm. The treatment is continued for 30min under the conditions of 1500bar pressure and 0.3s/mL flow rate of the microfluidizer. Further, sodium hydroxide was slowly added dropwise to the graphene oxide solution, and the mixture was sufficiently stirred for 2 hours until the pH of the graphene oxide solution was 4.5, and the viscosity of the graphite oxide solution was reduced to 788mPa · s.
4) And continuously adding 20g of graphene oxide into the graphene oxide solution to obtain a graphene oxide solution with the viscosity of 4854 mPas. The solution is processed in a cell ultrasonic crusher for 1h with the processing power of 1000W, and is continuously processed in a sand mill for 1h with the rotating speed of 4000 rpm. The treatment was continued in a microfluidizer for 20min at a treatment pressure of 1500bar and a flow rate of 0.3 s/mL. Further, a sodium bicarbonate solution is slowly dripped into the graphene oxide solution, and the mixture is fully stirred for 2 hours until the pH of the graphene oxide solution is 4.1, the viscosity of the graphene oxide solution is reduced to 1323mPa & s, and the concentration of the graphene oxide solution is as high as 110 mg/mL.
Pouring the graphene oxide solution into a containerAnd (4) keeping the vacuum oven at room temperature and the vacuum degree of less than 267Pa for 2 min. And taking out the watch glass, and gently removing the holes on the surface of the graphene oxide aqueous solution by using a glass rod. Repeating the steps for multiple times until the solution is taken out, wherein no depression appears on the surface of the graphene oxide solution. Coating the treated graphene oxide solution on a PET substrate by a scraper, drying in a blast oven for 24h, and peeling to obtain a 380-micron-thick film with smooth surface, high orientation of microstructure and density of 2.3g/cm3And the graphene oxide film with high flexibility can be repeatedly folded for more than 5000 times. Fig. 2 is a scanning electron microscope cross-sectional view of the high-concentration graphene oxide film in example 2, and it can be seen from fig. 2 that the microstructure of the graphene oxide film has a high degree of orientation.
Example 3
1) Adding 3g of graphene oxide into 500mL of deionized water, and preparing the graphene oxide into a 6mg/mL graphene oxide solution with the viscosity of 743mPa & s and the pH of 1.1.
2) And (3) treating the graphene oxide solution for 15min under the condition that the rotation speed of an emulsifying machine is 10000rpm, and treating for 10min under the conditions that the pressure of a high-pressure homogenizer is 1200bar and the flow rate is 0.5 s/mL. A graphene oxide solution having a viscosity of 459mPa · s was obtained.
3) 25g of graphene oxide was added to the graphene oxide aqueous solution to obtain a graphene oxide aqueous solution having a viscosity of 3790mPa · s. And (3) treating the graphene oxide aqueous solution for 20min under the condition that the rotation speed of an emulsifying machine is 15000rpm, and treating for 20min under the conditions that the pressure of a high-pressure homogenizer is 1200bar and the flow rate is 0.5 s/mL. Further, ammonia water was slowly added dropwise to the graphene oxide solution, and the mixture was sufficiently stirred for 2 hours until the pH of the graphene oxide solution was 4.7, to obtain a graphene oxide aqueous solution with a viscosity reduced to 735mPa · s.
4) 25g of graphene oxide was further added to the graphene oxide aqueous solution, and the viscosity of the graphene oxide aqueous solution was increased to 3491mPa · s. Treating at 15000rpm for 20min, and treating at 1200bar and 0.5s/mL for 20 min. Further, ammonia water is slowly dripped into the graphene oxide solution, and the mixture is fully stirred for 2 hours until the pH value of the graphene oxide solution is 4.3, so that the graphene oxide solution with the viscosity reduced to 1321mPa & s and the concentration as high as 106mg/mL is obtained.
Carrying out vacuum filtration on the high-concentration graphene oxide solution to obtain an independently supported flexible graphene oxide film, wherein the thickness of the graphene oxide film can be 500 mu m, and the graphene oxide film has higher compaction density which can reach 2.5g/cm3。
In conclusion, the high-concentration graphene oxide solution with good fluidity is obtained by a specific method, and the high-concentration graphene oxide solution can be used for further obtaining a graphene macroscopic body with good comprehensive performance and can be applied to multiple fields of energy, biology, environmental protection and the like. The method has low cost and simple process, and is suitable for large-scale industrial production.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (8)
1. A preparation method of a high-concentration graphene oxide solution is characterized by comprising the following steps:
preparing a low-concentration graphene oxide solution of 0.1-10 mg/mL;
carrying out first refinement on the low-concentration graphene oxide solution; and
performing concentration treatment on the solution after the first refinement to obtain the high-concentration graphene oxide solution;
wherein the concentration treatment comprises adding graphene oxide into the solution after the first refinement for second refinement, and adjusting the pH value of the solution after the second refinement to 4-5,
the method also comprises the step of carrying out the concentration adding treatment on the solution after the first thinning for multiple times to obtain a high-concentration graphene oxide solution with the concentration of more than 100mg/mL and the viscosity of less than 1500mPa & s,
wherein the first refining and the second refining respectively and independently comprise primary refining and secondary refining in sequence, the graphene oxide D90 in the solution after the primary refining is less than 5 μm, and the graphene oxide D90 in the solution after the secondary refining is less than 1 μm.
2. The preparation method according to claim 1, wherein the primary refining apparatus is selected from one or more of an ultrasonic cell crusher, a sand mill and an emulsifying machine, and the secondary refining apparatus is selected from one or more of a high-pressure homogenizer and a microfluidizer.
3. The preparation method according to claim 2, wherein when the preliminary fining equipment is an ultrasonic cell disruptor, the ultrasonic power is 800W-1200W, and the treatment time is 60 min-90 min; when the preliminary refining equipment is a sand mill, the rotating speed of the sand mill is 3000-5000 rpm, and the processing time is 60-90 min; when the preliminary refining equipment is an emulsifying machine, the shearing rotation speed of the emulsifying machine is 10000 rpm-30000 rpm, and the processing time is 10 min-30 min; the processing pressure of the secondary refining is 1000 bar-1500 bar, and the processing flow rate is 0.3 s/mL-0.5 s/mL.
4. The method according to claim 1, wherein the adjusting the pH of the solution after the second refinement comprises: and adding one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide into the solution after the second refining, and stirring for 1-2 h.
5. The preparation method according to claim 1, wherein the graphene oxide solution is an aqueous graphene oxide solution, and a dispersant is included in the aqueous graphene oxide solution, and the dispersant is selected from one or more of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
6. The preparation method according to claim 1, wherein in the concentration treatment, the adding of the graphene oxide comprises adding graphene oxide powder and/or adding a graphene oxide solution, and the concentration of the added graphene oxide solution is greater than 10mg/mL when the graphene oxide solution is added.
7. A high-concentration graphene oxide solution obtained by the preparation method of any one of claims 1 to 6.
8. Use of the high concentration graphene oxide solution according to claim 7 for the preparation of graphene oxide macrosomes.
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