CN106882796B - Preparation method of three-dimensional graphene structure/high-quality graphene - Google Patents
Preparation method of three-dimensional graphene structure/high-quality graphene Download PDFInfo
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Abstract
The invention provides a preparation method of a three-dimensional graphene structure/high-quality graphene, which comprises the steps of carrying out intercalation treatment on natural crystalline flake graphite or artificial graphite to prepare a graphite interlayer compound; the obtained graphite intercalation compound is subjected to expansion treatment in an expanding agent to obtainTo a high specific surface area three-dimensional graphene structure. And performing ball milling, shearing, high-speed fluid crushing or ultrasonic treatment and the like to obtain the high-quality single-layer and few-layer graphene dispersion liquid. The three-dimensional structure obtained by the invention has more than 1000 m2Specific surface area/g and the lamellar lattice structure remains intact. The graphene lattice structure obtained by mechanical stripping is kept intact, the graphene lattice structure has excellent electrical properties, and the bulk conductivity of the film can reach over 1000S/cm. The graphene material prepared by the invention can be widely applied to the fields of energy storage, composite materials, conductive ink, conductive films and the like. The three-dimensional graphene structure can be directly used as a high-specific-surface-area carbon skeleton, and can be compounded with various materials such as polymers, metal oxides, metal sulfides, carbon nitride and the like to prepare composite materials with various special functionalities.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a preparation method of a three-dimensional graphene structure/high-quality graphene, in particular to a method for obtaining a graphite interlayer compound by using an oxidant and acid as an intercalation agent; expanding the obtained graphite intercalation compound in an expanding agent to obtain a three-dimensional graphene structure; and carrying out physical and mechanical actions such as sanding, ball milling, shearing, ultrasonic and high-speed fluid crushing on the obtained three-dimensional structure to obtain the graphene dispersion liquid.
Background
Carbon element can form a wide variety of substances through different hybridization modes due to its unique electronic structure. Wherein, in sp2Various carbon nanomaterials (including fullerene, carbon nanotube, graphene and the like) existing in a hybrid mode become research hotspots in the field of materials due to excellent electrical, mechanical, thermal and other properties. In order to fully exert the advantages of the carbon material, the carbon material with high specific surface is developedThe deposited carbon material is of critical importance. The carbon material with high specific surface area has more exposed reaction active sites and abundant void structures, and can improve various performances of the carbon material in the application process. For example, when a carbon material having a high specific surface area is applied to the fields of supercapacitors, lithium ion batteries, and the like, the amount of electricity stored per unit volume or unit mass is significantly superior to that of a bulk carbon material.
Since graphene was successfully prepared in 2004 by using an adhesive tape technology, the preparation of a three-dimensional graphene material using a graphene nanosheet layer as a structural unit was widely studied by researchers in various countries. The carbon nano sheet layer can reduce the diffusion distance of ions in the solution, has rich gap structures after being assembled, and is widely applied to the fields of energy storage, catalysis and the like. Mesoporous silicon, calcium oxide and the like are used as template agents, graphene nanosheets grow in holes of the template agents through a chemical vapor deposition method, and the template agents are removed to obtain the three-dimensional graphene material with high specific surface area. However, these methods are expensive, have long routes and are difficult to industrialize. Graphene oxide is the most common precursor for preparing three-dimensional high-specific-surface-area graphene materials. The graphene oxide is prepared by taking graphite as a raw material, and dispersing the graphite in water or a polar organic solvent in an ultrasonic, shearing or oscillating mode after chemical oxidation. Under a certain concentration, the graphene oxide aqueous solution is assembled by hydrothermal or chemical reduction, and a three-dimensional graphene structure with a high specific surface area can be prepared. In addition, the three-dimensional structure can be prepared by standing reduction without stirring or other disturbance in the reduction process of the graphene oxide solution. However, graphene material sheets obtained by the redox method have many defects, and the reduced mechanical, electrical and thermal properties affect the practical application thereof, for example, in energy storage materials, the cycling stability is reduced. Therefore, it is important to develop a graphene three-dimensional structure material with a high specific surface area and a complete lattice structure, which uses a carbon nanosheet layer as a building unit.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned difficulties and providing a method for preparing a three-dimensional graphene structure/high-quality graphene. Graphene III prepared by the methodThe dimensional structure has a dimension of more than 1000 m2The specific surface area is higher than that of a three-dimensional graphene structure assembled by taking graphene oxide as a raw material, the lattice structure of the graphene is complete, and the excellent physical and chemical properties of the carbon material are reserved. And performing mechanical treatment such as sanding, ball milling, shearing, high-speed fluid crushing or ultrasonic treatment on the prepared three-dimensional structure to form stable graphene dispersion liquid. The graphene material prepared by the invention can be applied to the fields of energy storage, catalysis, composite materials and the like, has the advantages of simple operation process, low cost, good controllability and the like, and is suitable for large-scale production and industrial application.
The invention provides a preparation method of a three-dimensional graphene structure/high-quality graphene, which comprises the following specific steps:
(1) carrying out intercalation treatment on raw material graphite in an intercalation agent to enable the intercalation agent to enter graphite interlayers so as to prepare a graphite interlayer compound;
(2) putting the graphite intercalation compound obtained in the step (1) into an expanding agent, stirring for fifteen minutes, standing for 1-48 hours to ensure that the expanding agent fully enters the graphite intercalation, decomposing to release gas between the layers, increasing the interlayer spacing of graphene, and separating graphene sheets to form a three-dimensional graphene structure body with ultrahigh specific surface area;
(3) and (3) treating the three-dimensional graphene structure obtained in the step (2) in a treating agent by any one mode or a combination mode of ultrasonic, sand grinding, ball milling, high-speed fluid crushing or shearing to obtain a graphene dispersion liquid.
In the invention, the raw material graphite is natural crystalline flake graphite or artificial graphite.
In the invention, the intercalation agent in the step (1) is composed of acid and oxidant, the acid is any one of sulfuric acid, phosphoric acid or nitric acid, and the oxidant is one or the combination of sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, potassium ferrate, potassium dichromate, chromium trioxide or hydrogen peroxide. The purpose of intercalation is to weaken the van der waals forces between graphite platelets and to introduce small amounts of oxygen-containing functional groups. The intercalation agent species listed above may be selected from one of them for intercalation, and may be any combination therebetween, but is not limited thereto.
In the invention, the adding amount of the oxidant in the step (1) is 0.1-20 times of the mass of the raw material graphite; the addition amount of the acid is 10-100 times of the mass of the raw material graphite.
In the invention, the expanding agent in the step (2) is composed of an acid and an oxidant, wherein the acid is any one of sulfuric acid or phosphoric acid, and the oxidant is one of sulfur trioxide, hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate or a combination of the sulfur trioxide, the hydrogen peroxide, the ammonium persulfate, the potassium persulfate and the sodium persulfate. In the expanding agent, an oxidant and acid enter graphite interlayers, and the oxidant is decomposed between the graphite interlayers to release gas. The gas generation overcomes the van der waals forces between the graphite layers, causing the graphite to expand.
In the invention, the addition amount of the oxidant in the step (2) is 0.1-20 times of that of the raw material graphite, and the acid dosage is 10-200 times of that of the raw material graphite.
In the invention, the ultrasonic power is controlled to be 50-5000W during the ultrasonic treatment in the step (3), and the ultrasonic time is 15 min-5 h; the rotation speed of the sand mill is controlled to be 150-1600rpm during sanding, and the sanding time is controlled to be 0.5-12 h; the rotating speed of the ball mill is controlled to be 150-; the control pressure is 10-150 MPa when the high-speed fluid is crushed, and the flow rate is as follows: 300-40000L/h; the shearing rate is controlled to be 1000-30000 rpm, and the shearing time is controlled to be 0.5-10 h.
In the invention, the treating agent is one or more of N, N-dimethylformamide, N-methyl pyrrolidone, o-dichlorobenzene, dimethyl sulfoxide, toluene, tert-butyl alcohol, isopropanol or a mixed solvent of ethanol and water, or is an aqueous solution containing a coagent, wherein the coagent is any one of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, linear alkyl benzene sulfonate, alpha-alkenyl sodium sulfonate, fatty alcohol polyoxyethylene ether sodium sulfate, lauryl sodium sulfate, alkylphenol polyoxyethylene ether, alkylolamide, fatty alcohol polyoxyethylene ether, lauryl dimethyl betaine, hexadecyl dimethyl ammonium chloride, sodium hydroxide, a nonionic organic fluorine surfactant or polyether modified polyorganosiloxane and the like.
According to the invention, the specific surface area of the prepared three-dimensional graphene structure/high-quality graphene can reach 1000 m2More than g, the graphene lamellar crystal structure is kept intact, and the yield is close to 100%; the obtained three-dimensional graphene structure can be completely peeled off through the actions of sanding, ball milling, ultrasonic, high-speed fluid crushing, shearing and the like, and a stable graphene dispersion liquid is formed in an organic solvent or a surfactant aqueous solution. The obtained graphene has the number of layers of 1-10, the yield can reach 100%, the graphite lattice integrity is high, and the conductivity can reach more than 1000S/cm.
Aiming at the defects in the prior art, the inventor provides the technical scheme of the invention through long-term practice and research, the scheme can realize the efficient, low-cost and large-scale preparation of the three-dimensional graphene structure/high-quality graphene, solves the key problem of large-scale preparation of the three-dimensional graphene structure and the high-quality graphene dispersion liquid, and provides an effective way for realizing the practical application of the graphene in various fields (such as energy storage materials, composite materials, catalysis, conductive films and heat dissipation films).
Compared with the prior art, the invention has the following advantages:
(1) the artificial graphite or natural flake graphite is used as a raw material, so that the raw material source is wide and the cost is low.
(2) The method has mild operation conditions, does not relate to the oxidation-reduction process of graphite, does not need to use a strong reducing agent with high toxicity, does not need to use pure hydrogen to reduce at high temperature, and avoids the danger of explosion.
(3) According to the invention, graphite is not required to be completely oxidized into graphene oxide, and then the three-dimensional graphene is obtained by assembling, but is directly obtained by using graphite as a raw material in an expansion mode, so that the process for preparing the graphene three-dimensional structure is greatly simplified, and the quality of the graphene three-dimensional structure is remarkably improved. The three-dimensional graphene structure prepared by the method has high specific surface area and low oxidation degree, and is favorable for further surface modification and formation of composite materials with other materials.
(4) The preparation method of the graphene dispersion liquid has the characteristics of high yield, high quality and low energy consumption.
Drawings
Fig. 1 is a scanning electron microscope image of a three-dimensional graphene structure.
Fig. 2 is a raman spectrum of graphite, the three-dimensional graphene structures obtained in examples 1 and 16.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after said combination of steps or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the steps, and is not intended to limit the order of arrangement of each method or the scope of the implementation of the invention, and changes or modifications in the relative relationship thereof, without substantial technical changes, should also be considered as the scope of the implementation of the invention.
Example 1
(1) 90 ml of concentrated sulfuric acid (98%) is slowly added into 30 ml of concentrated nitric acid (65%) under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter 150 micrometers, carbon content higher than 95%) is added into the reaction solution, and the mixture is stirred for 24 hours under the condition of room temperature. And then, filtering to remove the reaction liquid, wherein the obtained solid is the graphite intercalation compound.
(2) 240 ml of concentrated sulfuric acid (98%) is slowly added into 60 ml of hydrogen peroxide (30%) under the condition of ice-water bath, and after cooling, the mixed solution is transferred into water bath at 40 ℃. Then, adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 48 hours, filtering and washing to obtain a three-dimensional graphene structure with a specific surface area of 1360 m2In terms of/g, the yield is 100%. Fig. 1 shows the scanning electron microscope results and fig. 2 the corresponding raman spectra.
(3) 0.1g of the wet three-dimensional graphene structure was placed in 100 mL of N-methylpyrrolidone and sonicated in a water bath for 30 min to give a black suspension containing single and few layers of graphene with an exfoliation yield of about 100%.
Example 2
(1) 660 ml of concentrated sulfuric acid (98%) is slowly added into 220 ml of concentrated nitric acid (65%) under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter 150 microns, carbon content higher than 95%) is added into the reaction solution, and the mixture is stirred for 24 hours under the condition of room temperature. And then, filtering to remove the reaction liquid, wherein the obtained solid is the graphite intercalation compound.
(2) 240 ml of concentrated sulfuric acid (98%) is slowly added into 60 ml of hydrogen peroxide (30%) under the condition of ice-water bath, and after cooling, the mixed solution is transferred into water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring at room temperature for 15 minutes, standing and expanding for 24 hours, washing, and filtering to obtain the three-dimensional graphene structure. Specific surface area 1250 m2In terms of/g, the yield is 100%.
(3) And (3) placing 0.1g of wet three-dimensional graphene structure body in 100 mL of N-methylpyrrolidone, and performing ultrasonic treatment for 30 min by using a probe with 35% output power to obtain single-layer graphene and few-layer graphene, wherein the yield is about 100%.
Example 3
(1) 90 ml of concentrated sulfuric acid (98%) is slowly added into 30 ml of concentrated nitric acid (65%) under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter 500 micrometers, carbon content higher than 95%) is added into the reaction solution, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 540 ml of concentrated sulfuric acid (98%) is slowly added to 135 ml of hydrogen peroxide (30%) under the condition of ice-water bath, and after cooling, the mixed solution is transferred into water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 3 hours, washing and filtering to obtain the three-dimensional graphene structure. Specific surface area of 1320 m2In terms of/g, the yield is 100%.
(3) 0.1g of the wet three-dimensional graphene structure was placed in 100 mL of N-methylpyrrolidone and sheared at 18000 rpm for 1 hour to obtain single-layer and few-layer graphene with a yield of about 100%.
Example 4
(1) Under the condition of ice-water bath, slowly adding 90 ml of concentrated sulfuric acid (98%) into 30 ml of concentrated nitric acid (65%), uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 500 micrometers, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel, wherein the obtained solid is the graphite intercalation compound.
(2) And (2) adding 0.3 g of ammonium persulfate into 300 ml of sulfuric acid, adding the graphite intercalation compound obtained in the step (1) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing and expanding for 1 hour, washing, and filtering until the filtrate is neutral to obtain the three-dimensional graphene structure. Specific surface area 1250 m2In terms of/g, the yield is 100%.
(3) And (3) replacing water with the wet three-dimensional graphene structure by using N-methyl pyrrolidone, placing the filtered wet material in a ball milling tank, and carrying out ball milling for 5 hours at 300 rpm. Adding N-methyl pyrrolidone into the ball-milled materials to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding N-methyl pyrrolidone, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Example 5
(1) Under the condition of ice-water bath, slowly adding 90 ml of sulfuric acid into 30 ml of nitric acid, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) And (2) adding 0.3 g of ammonium persulfate into 20 ml of sulfuric acid, adding the graphite intercalation compound obtained in the step (1) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing and expanding for 3 hours, washing, and filtering until the filtrate is neutral to obtain the three-dimensional graphene structure. Specific surface area 1300 m2In terms of/g, the yield is 100%.
(3) And (3) replacing water with the wet three-dimensional graphene structure by using N-methyl pyrrolidone, placing the filtered wet material in a ball milling tank, and sanding for 6 hours at 500 rpm. Adding N-methylpyrrolidone into the sand-milled material to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out supernatant, adding N-methylpyrrolidone, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting supernatant until the supernatant is colorless
Example 6
(1) 90 ml of sulfuric acid is slowly added into 30 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter is 150 microns, and carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring at room temperature for 15 minutes, standing and expanding for 3 hours, filtering, and washing with water to obtain the three-dimensional graphene structure. Specific surface area of 1320 m2In terms of/g, the yield is 100%.
(3) Putting 0.1g of wet three-dimensional graphene structure body into 100 mL of ethanol and water mixed solution, performing water bath ultrasonic treatment for 30 min to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out supernatant, adding ethanol and water mixed solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting supernatant until the supernatant is colorless.
Example 7
(1) 660 ml of sulfuric acid is slowly added into 220 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. Then, adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 3 hours, and washingAnd washing and filtering to obtain the three-dimensional graphene structure. Specific surface area 1230 m2In terms of/g, the yield is 100%.
(3) Putting 0.1g of wet three-dimensional graphene structure body into 100 mL of mixed solution of ethanol and water, performing ultrasonic treatment for 30 min by using a 35% output power probe to obtain black suspension, centrifuging for 15 min at 12000 rpm, pouring out supernatant, adding the mixed solution of ethanol and water, centrifuging for 30 min at 1000 rpm, repeatedly centrifuging, and collecting supernatant until the supernatant is colorless.
Example 8
(1) 90 ml of sulfuric acid is slowly added into 30 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter is 150 microns, and carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 540 ml of sulfuric acid was slowly added to 135 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a 40 ℃ water bath. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 3 hours, washing and filtering to obtain the three-dimensional graphene structure. Specific surface area 1050 m2In terms of/g, the yield is 100%.
(3) Placing 0.1g of wet three-dimensional graphene structure body in 100 mL of mixed liquid of ethanol and water, shearing for 1h at 18000 rpm to obtain black suspension, centrifuging for 15 min at 12000 rpm, pouring out supernatant, adding mixed liquid of ethanol and water, centrifuging for 30 min at 1000 rpm, repeatedly centrifuging, and collecting supernatant until the supernatant is colorless.
Example 9
(1) Under the condition of ice-water bath, slowly adding 90 ml of sulfuric acid into 30 ml of nitric acid, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 0.3 g of ammonium persulfate was added to 20 ml of sulfuric acid, andand (3) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at 35 ℃, standing and expanding for 3 hours, washing and filtering until the filtrate is neutral, thus obtaining the three-dimensional graphene structure. Specific surface area 1250 m2In terms of/g, the yield is 100%.
(3) And ball-milling the wet three-dimensional graphene structure for 5 hours at 300 rpm. Adding a mixed solution of ethanol and water into the ball-milled materials to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out a supernatant, adding a mixed solution of ethanol and water, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Example 9
(1) Under the condition of ice-water bath, slowly adding 90 ml of sulfuric acid into 30 ml of nitric acid, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) Adding 0.3 g of ammonium persulfate into 20 ml of sulfuric acid, adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at 35 ℃, standing and expanding for 3 hours, washing and filtering until the filtrate is neutral to obtain a three-dimensional graphene structure with the specific surface area of 1100 m2In terms of/g, the yield is 100%.
(3) And (3) sanding the wet three-dimensional graphene structure for 2 hours at 800 rpm. Adding a mixed solution of ethanol and water into the sanded material to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out a supernatant, adding a mixed solution of ethanol and water, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Example 11
(1) 90 ml of sulfuric acid is slowly added into 30 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter is 150 microns, and carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring at room temperature for 15 minutes, standing and expanding for 3 hours, filtering, and washing with water to obtain the three-dimensional graphene structure. Specific surface area 1200 m2In terms of/g, the yield is 100%.
(3) Placing 0.1g of wet three-dimensional graphene structure body in 100 mL of 0.5 mg/mL polyvinylpyrrolidone aqueous solution, performing water bath ultrasonic treatment for 30 min to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out a supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Example 12
(1) 660 ml of sulfuric acid is slowly added into 220 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 3 hours, washing and filtering to obtain the three-dimensional graphene structure. Specific surface area 1250 m2In terms of/g, the yield is 100%.
(3) Putting 0.1g of wet three-dimensional graphene structure body into 100 mL of 0.5 mg/mL of polyvinylpyrrolidone aqueous solution, performing ultrasonic treatment for 30 min by using a 35% output power probe to obtain a black suspension, centrifuging for 15 min at 12000 rpm, pouring out a supernatant, adding 0.5 mg/mL of polyvinylpyrrolidone aqueous solution, centrifuging for 30 min at 1000 rpm, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Example 13
(1) 90 ml of sulfuric acid is slowly added into 30 ml of nitric acid under the condition of ice-water bath, after uniform mixing, 3 g of crystalline flake graphite (particle diameter is 150 microns, and carbon content is higher than 95%) is added into the reaction liquid, and the mixture is stirred for 24 hours under the condition of room temperature. And then, carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 540 ml of sulfuric acid was slowly added to 135 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a 40 ℃ water bath. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring for 15 minutes at room temperature, standing and expanding for 3 hours, washing and filtering to obtain the three-dimensional graphene structure. Specific surface area 1150 m2In terms of/g, the yield is 100%.
(3) Placing 0.1g of wet three-dimensional graphene structure body in 100 mL of 0.5 mg/mL polyvinylpyrrolidone aqueous solution, shearing at 18000 rpm for 1h to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out a supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Example 14
(1) Under the condition of ice-water bath, slowly adding 90 ml of sulfuric acid into 30 ml of nitric acid, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) And (2) adding 0.3 g of ammonium persulfate into 20 ml of sulfuric acid, adding the graphite intercalation compound obtained in the step (1) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing and expanding for 3 hours, washing, and filtering until the filtrate is neutral to obtain the three-dimensional graphene structure. Specific surface area 1010 m2More than g.
(3) And adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the wet three-dimensional graphene structure, and carrying out ball milling for 5h under the condition of 300 rpm. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the ball-milled material to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Example 15
(1) Under the condition of ice-water bath, slowly adding 90 ml of sulfuric acid into 30 ml of nitric acid, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the reaction liquid, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction liquid by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) And (2) adding 0.3 g of ammonium persulfate into 20 ml of sulfuric acid, adding the graphite intercalation compound obtained in the step (1) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing and expanding for 3 hours, washing, and filtering until the filtrate is neutral to obtain the three-dimensional graphene structure. Specific surface area 910 m2More than g.
(3) And adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the wet three-dimensional graphene structure, and sanding for 4 hours at 600 rpm. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the sanded material to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Example 16
(1) Slowly adding 3 g of potassium dichromate into 100 ml of concentrated sulfuric acid under the condition of ice-water bath, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 micrometers, and the carbon content is higher than 95%) into a reaction solution, stirring for 24 hours at room temperature, and then carrying out suction filtration on the reaction solution by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) And (2) adding 0.3 g of ammonium persulfate into 20 ml of sulfuric acid, adding the graphite intercalation compound obtained in the step (1) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing and expanding for 3 hours, washing, and filtering until the filtrate is neutral to obtain the three-dimensional graphene structure. Specific surface area 1020 m2(ii) in terms of/g. The corresponding raman spectrum is given in figure 2.
(3) And adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the wet three-dimensional graphene structure, and sanding for 4 hours at 600 rpm. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the sanded material to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Example 17
(1) Under the condition of ice-water bath, 18 g of chromium trioxide is slowly added into 100 ml of sulfuric acid, after uniform mixing, 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) is added into the reaction liquid, after stirring for 24 hours at room temperature, the reaction liquid is filtered by a sand core funnel, and the obtained solid is the graphite intercalation compound.
(2) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring at room temperature for 15 minutes, standing and expanding for 10 hours, washing, and filtering to obtain the three-dimensional graphene structure. Specific surface area 1160 m2In terms of/g, the yield is 100%.
(3) And adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the wet three-dimensional graphene structure, and sanding for 4 hours at 600 rpm. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the sanded material to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Example 18
(1) Slowly adding 3 g of potassium permanganate into a mixed solution of 80 ml of concentrated sulfuric acid and 20 ml of concentrated phosphoric acid under the ice-water bath condition, uniformly mixing, adding 3 g of crystalline flake graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into a reaction solution, stirring for 24 hours at room temperature, and carrying out suction filtration on the reaction solution by using a sand core funnel to obtain a solid, namely the graphite intercalation compound.
(2) 250 ml of sulfuric acid was slowly added to 50 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. And (2) adding the graphite intercalation compound in the step (1) into the mixed solution, stirring at room temperature for 15 minutes, standing and expanding for 6 hours, washing, and filtering to obtain the three-dimensional graphene structure. Specific surface area 1210 m2In terms of/g, the yield is 100%.
(3) And adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the wet three-dimensional graphene structure, and carrying out ball milling for 5h under the condition of 300 rpm. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the ball-milled material to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Comparative example 1
(1) 240 ml of sulfuric acid was slowly added to 60 ml of hydrogen peroxide in an ice-water bath, and after cooling, the mixture was transferred to a water bath at 40 ℃. Then, 1g of raw material graphite (particle diameter 150 microns, carbon content higher than 95%) is added into the mixed solution, stirred for 15 minutes at room temperature, then kept stand and expanded for 3 hours, washed and filtered until the filtrate is neutral, and the product is obtained. The graphite expands, and the specific surface area is 241 m2/g。
(2) Placing 0.1g of the product in the medium-wet state of (1) in 100 mL of N-methylpyrrolidone, performing water bath ultrasonic treatment for 30 min to obtain a black suspension, centrifuging at 12000 rpm for 15 min, pouring out a supernatant, adding the N-methylpyrrolidone, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Comparative example 2
(1) Adding 30 g of sodium persulfate into 300 ml of sulfuric acid, adding 3 g of raw material graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing for expansion for 6 hours, washing, and filtering until the filtrate is neutral to obtain the product. The graphite expands and has a specific surface area of 60 m2/g。
(2) And (2) placing 0.1g of the wet product in the step (1) in 100 mL of N-methylpyrrolidone, performing probe ultrasound for 30 min under 35% output power to obtain a black suspension, centrifuging for 15 min at 12000 rpm, pouring out a supernatant, adding N-methylpyrrolidone, centrifuging for 30 min at 1000 rpm, repeatedly centrifuging, and collecting a supernatant until the supernatant is colorless.
Comparative example 3
(1) Adding 30 g of potassium persulfate into 300 ml of sulfuric acid, adding 3 g of raw material graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the mixed solution, stirring at 35 ℃ for 15 minutes, standing for expansion for 6 hours, washing, and filtering until the filtrate is neutral to obtain the product. The graphite expands and has a specific surface area of 64 m2/g。
(2) And (3) replacing the product in the step (1) with water in the product in the N-methylpyrrolidone (1), placing the filtered wet material in a ball milling tank, and carrying out ball milling for 5 hours at 300 rpm. Adding N-methyl pyrrolidone into the ball-milled materials to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding N-methyl pyrrolidone, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Comparative example 4
(1) Adding 30 g of ammonium persulfate into 300 ml of sulfuric acid, adding 3 g of raw material graphite (the particle diameter is 150 microns, and the carbon content is higher than 95%) into the mixed solution, stirring for 15 minutes at 35 ℃, standing and expanding for 6 hours, washing, and filtering until the filtrate is neutral to obtain the product. The graphite expands and has a specific surface area of 67 m2/g。
(2) 0.1g of the wet product obtained in step (1) was added with 0.5 mg/mL of an aqueous polyvinylpyrrolidone solution and sanded at 600rpm for 4 hours. Adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution into the sanded material to obtain black suspension, centrifuging at 12000 rpm for 15 min, pouring out the supernatant, adding 0.5 mg/mL polyvinylpyrrolidone aqueous solution, centrifuging at 1000 rpm for 30 min, repeatedly centrifuging, and collecting the supernatant until the supernatant is colorless.
Claims (4)
1. A preparation method of a three-dimensional graphene structure/high-quality graphene is characterized by comprising the following specific steps:
(1) carrying out intercalation treatment on raw material graphite in an intercalation agent to enable the intercalation agent to enter graphite interlayers so as to prepare a graphite interlayer compound; the intercalation agent in the step (1) consists of acid and oxidant, wherein the acid is any one of sulfuric acid, phosphoric acid or nitric acid, and the oxidant is one of or the combination of sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, potassium dichromate, chromium trioxide or hydrogen peroxide; the adding amount of the oxidant in the step (1) is 0.1-20 times of the mass of the raw material graphite; the adding amount of the acid is 10-100 times of the mass of the raw material graphite;
(2) putting the graphite intercalation compound obtained in the step (1) into an expanding agent, stirring for fifteen minutes, standing for 1-48 hours to ensure that the expanding agent fully enters the graphite intercalation, decomposing to release gas between the layers, increasing the interlayer spacing of graphene, and separating graphene sheets to form a three-dimensional graphene structure body with ultrahigh specific surface area; the expanding agent in the step (2) consists of acid and oxidant, wherein the acid is any one of sulfuric acid or phosphoric acid, and the oxidant is one of sulfur trioxide, hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate or a combination of the sulfur trioxide, the hydrogen peroxide, the ammonium persulfate, the potassium persulfate and the sodium persulfate; in the step (2), the addition amount of the oxidant is 0.1-20 times of that of the raw material graphite, and the acid dosage is 10-200 times of that of the raw material graphite;
(3) and (3) treating the three-dimensional graphene structure obtained in the step (2) in a treating agent by any one mode or a combination mode of ultrasonic, sand grinding, ball milling, high-speed fluid crushing or shearing to obtain a graphene dispersion liquid.
2. The method for preparing a three-dimensional graphene structure/high-quality graphene according to claim 1, wherein the raw material graphite is natural flake graphite or artificial graphite.
3. The method for preparing a three-dimensional graphene structure/high-quality graphene according to claim 1, wherein in the step (3), the ultrasonic power is controlled to be 50-5000W during ultrasonic treatment, and the ultrasonic time is 15 min-5 h; the rotation speed of the sand mill is controlled to be 150-1600rpm during sanding, and the sanding time is controlled to be 0.5-12 h; the rotating speed of the ball mill is controlled to be 150-; the control pressure is 10-150 MPa when the high-speed fluid is crushed, and the flow rate is as follows: 300-40000L/h; the shearing rate is controlled to be 1000-30000 rpm, and the shearing time is controlled to be 0.5-10 h.
4. The method for preparing three-dimensional graphene structure/high-quality graphene according to claim 1, it is characterized in that the treating agent adopts one or more of N, N-dimethylformamide, N-methylpyrrolidone, o-dichlorobenzene, dimethyl sulfoxide, toluene, tertiary butanol, isopropanol or mixed solvent of ethanol and water, or the water solution contains a coagent, wherein the coagent is any one of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, linear alkyl benzene sodium sulfonate, alpha-alkenyl sodium sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate, lauryl sodium sulfate, alkylphenol polyoxyethylene, alkylolamide, fatty alcohol-polyoxyethylene ether, dodecyl dimethyl betaine, hexadecyl dimethyl ammonium chloride, sodium hydroxide, a nonionic organic fluorine surfactant or polyether modified polysiloxane.
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| CN111204747B (en) * | 2019-10-28 | 2022-01-18 | 杭州电子科技大学 | Preparation method of three-dimensional graphene material |
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