CN108147402B - Preparation method of high-quality graphene material - Google Patents
Preparation method of high-quality graphene material Download PDFInfo
- Publication number
- CN108147402B CN108147402B CN201810153039.5A CN201810153039A CN108147402B CN 108147402 B CN108147402 B CN 108147402B CN 201810153039 A CN201810153039 A CN 201810153039A CN 108147402 B CN108147402 B CN 108147402B
- Authority
- CN
- China
- Prior art keywords
- graphene
- reaction
- carrying
- ultrasonic
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 138
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002356 single layer Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method of a high-quality graphene material, which comprises the following steps of 1, putting graphene into absolute ethyl alcohol, uniformly stirring, and carrying out ball-milling reaction for 1-2 hours to obtain a graphene alcohol solution; step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder; step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 2-5h, carrying out microwave reaction for 2-4h, and carrying out secondary ultrasonic reaction for 1-4h to obtain a graphene dispersion liquid; step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate; and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 2-4h, carrying out electrolytic reaction for 3-6h, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material. The method solves the problem that the effect of preparing the single-layer graphene by using the N-methylpyrrolidone is poor in the prior art, and simultaneously solves the problems of recycling and removing the N-methylpyrrolidone.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method of a high-quality graphene material.
Background
Graphene is a fully sp-substituted structure2The quasi-two-dimensional crystal material which is composed of hybridized carbon atoms and has the thickness of only a single atomic layer or a plurality of single atomic layers is almost completely transparent, has high heat conductivity coefficient and high electron mobility at normal temperature, is a material with the minimum resistivity in the world, and is also a nano material which is thinnest, but also the hardest in the world. Graphene can be used for developing a thinner new-generation electronic element with higher conducting speed, a transparent touch screen, a high-performance nano electronic device and a photoelectric device, and can also be applied to the fields of gas sensors, composite materials, field emission materials, energy storage and the like. To date, many methods have been developed for the preparation of graphene: micro mechanical separation, graphite oxide reduction, chemical vapor deposition, solvent stripping, and the like. The method adopted at the beginning is a micro-mechanical separation method, the single-layer graphite sheet obtained by the method is relatively complete, but the size of the single-layer graphite cannot be controlled, the method is manually operated, and the thickness is not uniform. The oxidation process of the graphite oxide reduction method usually seriously damages the structure of a graphene lamellar layer, and although the reduction treatment is carried out, various performance indexes of the obtained graphene material still have a large difference with that of high-quality graphene. In addition, the oxidation process of graphite usually requires a large amount of strongly acidic oxidizing agents such as concentrated sulfuric acid, concentrated nitric acid, dichromic acid, potassium permanganate, sodium nitrate, etc.; in the reduction process, high-temperature treatment or use of toxic chemical substances such as hydrazine, dimethylhydrazine and the like is required, so that the energy consumption is high, the efficiency is low, the cost is high and the environment is polluted. The graphene prepared by the chemical vapor deposition method does not show the quantum Hall effect, and how to select a proper linerThe bottom is also a difficult problem, and simultaneously has the defects of higher cost and complex process. The solvent stripping method can prepare high-quality graphene, but liquid-phase ultrasonic stripping usually requires long-time ultrasonic, and the integrity of the graphene is inevitably damaged in some cases even hundreds of hours, so that the performance of the graphene is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a high-quality graphene material, which solves the problem that the effect of preparing single-layer graphene by using N-methylpyrrolidone is poor in the prior art, and also solves the problems of recycling and removing the N-methylpyrrolidone.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a high-quality graphene material comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, uniformly stirring, and carrying out ball milling reaction for 1-2h to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 2-5h, carrying out microwave reaction for 2-4h, and carrying out secondary ultrasonic reaction for 1-4h to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 2-4h, carrying out electrolytic reaction for 3-6h, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material.
The concentration of the graphene in the step 1 in the absolute ethyl alcohol is 20-50 g/L.
The stirring speed in the step 1 is 2000-5000r/min, the pressure of the ball milling reaction is 10-15MPa, and the temperature is 50-70 ℃.
The anhydrous ethanol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 30-50% of the atmospheric pressure, and the temperature is 100-120 ℃.
The concentration of the graphene fine powder in the N-methyl pyrrolidone in the step 3 is 2-5g/L, the ultrasonic frequency of the ultrasonic reaction is 10-20kHz, and the temperature is 80-100 ℃.
The microwave power of the microwave reaction in the step 3 is 500-1000W, the temperature is 100-130 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 60-70kHz, and the temperature is 130-150 ℃.
The centrifugation speed in the step 4 is 4000-7000 r/min.
The volume ratio of the added amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1-1.4.
The ultrasonic frequency of the ultrasonic dispersion in the step 5 is 20-50kHz, and the temperature is 40-50 ℃.
The voltage of the electrolytic reaction in the step 5 is 5-12V, and the current density is 10-300mA/cm2And the drying temperature is 50-80 ℃.
Step 1, placing graphene into absolute ethyl alcohol to form a dispersion system, and meanwhile, playing a role of an auxiliary solvent, increasing the temperature conduction effect and the temperature uniformity in the ball milling process, ensuring the uniformity of ball milling, and obtaining graphene fine powder with stable particle size and fine particles.
And 2, removing water in the graphene in a reduced pressure distillation mode to form graphene fine powder with uniform particle size, and preventing aggregation of graphene particles.
3, putting the graphene fine powder into N-methyl pyrrolidone, dispersing graphene in an ultrasonic mode to form a good dispersion system, and then heating the whole body through a microwave reaction, wherein gaps in graphene particles are continuously enlarged to form a good gap structure; the secondary ultrasonic reaction can be used for stripping the graphene with the gaps for the second time, and further crushing and dispersing the graphene fine powder to obtain a graphene dispersion system.
And 4, carrying out centrifugal dispersion on the graphene dispersion liquid, separating graphene from N-methyl pyrrolidone through high-speed rotation of a centrifugal machine to form a liquid state and a solid state, and obtaining graphene precipitate with N-methyl pyrrolidone.
Step 5, putting the graphene precipitate with the N-methyl pyrrolidone into methanol, dispersing the N-methyl pyrrolidone in the methanol under the ultrasonic dispersion condition, and dispersing the graphene precipitate into the methanol to form a good dispersion system; the methanol has a good conductive effect, a good electrolyte system can be formed, the N-methyl pyrrolidone is uniformly dispersed and exposed in multiple areas in an electrolytic reaction to form a rapid degradation effect, and meanwhile, the N-methyl pyrrolidone on the surface of the graphene is rapidly degraded; due to the fact that graphene and N-methyl pyrrolidone are good in insolubility in methanol, gaps can be filled with the methanol under the ultrasonic dispersion condition, a good uniform dispersion effect is achieved, meanwhile, the most comprehensive degradation is achieved under the electrolysis condition, and the well-dispersed graphene material is obtained.
From the above description, it can be seen that the present invention has the following advantages:
1. the method solves the problem that the effect of preparing the single-layer graphene by using the N-methylpyrrolidone is poor in the prior art, and simultaneously solves the problems of recycling and removing the N-methylpyrrolidone.
2. The method adopts an ultrasonic-microwave-secondary ultrasonic mode, so that the problem that long-time ultrasonic is needed for liquid phase ultrasonic stripping can be solved, the integrity of the graphene can be protected to the maximum extent, and the stable performance of the graphene can be ensured.
3. The invention adopts the alternate reaction of ultrasound and microwave, which can greatly reduce the reaction time and improve the reaction rate, and simultaneously, the continuous reaction can greatly improve the yield, thus being convenient for industrialized continuous production.
4. According to the invention, the graphene precipitate is placed in methanol for ultrasonic dispersion to obtain a good dispersion system, so that the methanol is completely permeated, and simultaneously, N-methyl pyrrolidone is converted into carbon dioxide and water in an electrolysis mode to obtain a well-dispersed graphene material.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of a high-quality graphene material comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, stirring uniformly, and performing ball milling reaction for 1h to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 2 hours, carrying out microwave reaction for 2 hours, and carrying out secondary ultrasonic reaction for 1 hour to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 2 hours, carrying out electrolytic reaction for 3 hours, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material.
The concentration of the graphene in the step 1 in the absolute ethyl alcohol is 20 g/L.
The stirring speed in the step 1 is 2000r/min, the pressure of the ball milling reaction is 10MPa, and the temperature is 50 ℃.
The absolute ethyl alcohol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 30 percent of the atmospheric pressure, and the temperature is 100 ℃.
The concentration of the graphene fine powder in the N-methyl pyrrolidone in the step 3 is 2g/L, the ultrasonic frequency of the ultrasonic reaction is 10kHz, and the temperature is 80 ℃.
The microwave power of the microwave reaction in the step 3 is 500W, the temperature is 100 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 60kHz, and the temperature is 130 ℃.
The centrifugal speed in the step 4 is 4000 r/min.
The volume ratio of the added amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1.
The ultrasonic frequency of the ultrasonic dispersion in the step 5 is 20kHz, and the temperature is 40 ℃.
The voltage of the electrolytic reaction in the step 5 is 5V, and the current density is 10mA/cm2And the drying temperature is 50 ℃.
Example 2
A preparation method of a high-quality graphene material comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, stirring uniformly, and performing ball milling reaction for 2 hours to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 5 hours, carrying out microwave reaction for 4 hours, and carrying out secondary ultrasonic reaction for 4 hours to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 4 hours, carrying out electrolytic reaction for 6 hours, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material.
The concentration of the graphene in the step 1 in the absolute ethyl alcohol is 50 g/L.
The stirring speed in the step 1 is 5000r/min, the pressure of the ball milling reaction is 15MPa, and the temperature is 70 ℃.
The absolute ethyl alcohol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 30-50% of the atmospheric pressure, and the temperature is 120 ℃.
The concentration of the graphene fine powder in the step 3 in the N-methyl pyrrolidone is 5g/L, the ultrasonic frequency of the ultrasonic reaction is 20kHz, and the temperature is 100 ℃.
The microwave power of the microwave reaction in the step 3 is 1000W, the temperature is 130 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 70kHz, and the temperature is 150 ℃.
The centrifugation speed in the step 4 is 7000 r/min.
The volume ratio of the added amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1.4.
The ultrasonic frequency of the ultrasonic dispersion in the step 5 is 50kHz, and the temperature is 50 ℃.
The voltage of the electrolytic reaction in the step 5 is 12V, and the current density is 300mA/cm2And the drying temperature is 80 ℃.
Example 3
A preparation method of a high-quality graphene material comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, stirring uniformly, and performing ball milling reaction for 2 hours to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 3 hours, carrying out microwave reaction for 4 hours, and carrying out secondary ultrasonic reaction for 2 hours to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 3 hours, carrying out electrolytic reaction for 4 hours, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material.
The concentration of the graphene in the step 1 in the absolute ethyl alcohol is 30 g/L.
The stirring speed in the step 1 is 3000r/min, the pressure of the ball milling reaction is 12MPa, and the temperature is 60 ℃.
The absolute ethyl alcohol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 40% of the atmospheric pressure, and the temperature is 110 ℃.
The concentration of the graphene fine powder in the step 3 in the N-methyl pyrrolidone is 3g/L, the ultrasonic frequency of the ultrasonic reaction is 15kHz, and the temperature is 90 ℃.
The microwave power of the microwave reaction in the step 3 is 700W, the temperature is 110 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 65kHz, and the temperature is 140 ℃.
The centrifugation speed in the step 4 is 5000 r/min.
The volume ratio of the added amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1.2.
The ultrasonic frequency of the ultrasonic dispersion in the step 5 is 30kHz, and the temperature is 45 ℃.
The voltage of the electrolytic reaction in the step 5 is 8V, and the current density is 100mA/cm2And the drying temperature is 60 ℃.
Example 4
A preparation method of a high-quality graphene material comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, stirring uniformly, and performing ball milling reaction for 2 hours to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 4 hours, carrying out microwave reaction for 3 hours, and carrying out secondary ultrasonic reaction for 3 hours to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
and 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 3 hours, carrying out electrolytic reaction for 5 hours, and carrying out centrifugal filtration and drying to obtain the high-quality graphene material.
The concentration of the graphene in the step 1 in the absolute ethyl alcohol is 40 g/L.
The stirring speed in the step 1 is 4000r/min, the pressure of the ball milling reaction is 13MPa, and the temperature is 65 ℃.
The absolute ethyl alcohol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 45% of the atmospheric pressure, and the temperature is 115 ℃.
The concentration of the graphene fine powder in the step 3 in N-methyl pyrrolidone is 4g/L, the ultrasonic frequency of the ultrasonic reaction is 18kHz, and the temperature is 95 ℃.
The microwave power of the microwave reaction in the step 3 is 800W, the temperature is 120 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 65kHz, and the temperature is 145 ℃.
The centrifugation speed in the step 4 is 6000 r/min.
The volume ratio of the added amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1.3.
The ultrasonic frequency of the ultrasonic dispersion in the step 5 is 40kHz, and the temperature is 45 ℃.
The voltage of the electrolytic reaction in the step 5 is 10V, and the current density is 200mA/cm2And the drying temperature is 70 ℃.
Performance detection
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Number of graphene layers | 3 | 5 | 4 | 3 |
| Graphene sheet diameter | 2.3μm | 2.5μm | 1.4μm | 1.7μm |
| Electrical conductivity of | 4200S/m | 4300S/m | 4900S/m | 5000S/m |
In summary, the invention has the following advantages:
1. the method solves the problem that the effect of preparing the single-layer graphene by using the N-methylpyrrolidone is poor in the prior art, and simultaneously solves the problems of recycling and removing the N-methylpyrrolidone.
2. The method adopts an ultrasonic-microwave-secondary ultrasonic mode, so that the problem that long-time ultrasonic is needed for liquid phase ultrasonic stripping can be solved, the integrity of the graphene can be protected to the maximum extent, and the stable performance of the graphene can be ensured.
3. The invention adopts the alternate reaction of ultrasound and microwave, which can greatly reduce the reaction time and improve the reaction rate, and simultaneously, the continuous reaction can greatly improve the yield, thus being convenient for industrialized continuous production.
4. According to the invention, the graphene precipitate is placed in methanol for ultrasonic dispersion to obtain a good dispersion system, so that the methanol is completely permeated, and simultaneously, N-methyl pyrrolidone is converted into carbon dioxide and water in an electrolysis mode to obtain a well-dispersed graphene material.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (1)
1. A preparation method of a high-quality graphene material is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, putting graphene into absolute ethyl alcohol, uniformly stirring, and carrying out ball milling reaction for 1-2h to obtain graphene alcohol solution;
step 2, putting the graphene alcohol solution into a reaction kettle, and removing absolute ethyl alcohol to obtain graphene fine powder;
step 3, adding the graphene fine powder into N-methyl pyrrolidone, carrying out ultrasonic reaction for 2-5h, carrying out microwave reaction for 2-4h, and carrying out secondary ultrasonic reaction for 1-4h to obtain a graphene dispersion liquid;
step 4, adding the graphene dispersion liquid into a centrifuge for rapid centrifugation to obtain graphene precipitate;
step 5, placing the graphene precipitate into methanol for ultrasonic dispersion for 2-4h, carrying out electrolytic reaction for 3-6h, and carrying out centrifugal filtration and drying to obtain a high-quality graphene material;
the concentration of the graphene in the absolute ethyl alcohol in the step 1 is 20-50g/L, the stirring speed is 2000-5000r/min, the pressure of the ball-milling reaction is 10-15MPa, and the temperature is 50-70 ℃;
the anhydrous ethanol removal in the step 2 adopts a reduced pressure distillation method, the pressure is 30-50% of the atmospheric pressure, and the temperature is 100-120 ℃;
the concentration of the graphene fine powder in the N-methyl pyrrolidone in the step 3 is 2-5g/L, the ultrasonic frequency of the ultrasonic reaction is 10-20kHz, the temperature is 80-100 ℃, the microwave power of the microwave reaction is 500-1000W, the temperature is 100-130 ℃, the ultrasonic frequency of the secondary ultrasonic reaction is 60-70kHz, and the temperature is 130-150 ℃;
the centrifugal speed in the step 4 is 4000-7000 r/min;
the volume ratio of the addition amount of the methanol to the N-methyl pyrrolidone in the step 5 is 1-1.4; the ultrasonic frequency of the ultrasonic dispersion in the step 5 is 20-50kHz, and the temperature is 40-50 ℃; the voltage of the electrolytic reaction in the step 5 is 5-12V, and the current density is 10-300mA/cm2And the drying temperature is 50-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810153039.5A CN108147402B (en) | 2018-02-21 | 2018-02-21 | Preparation method of high-quality graphene material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810153039.5A CN108147402B (en) | 2018-02-21 | 2018-02-21 | Preparation method of high-quality graphene material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108147402A CN108147402A (en) | 2018-06-12 |
| CN108147402B true CN108147402B (en) | 2021-06-25 |
Family
ID=62457381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810153039.5A Active CN108147402B (en) | 2018-02-21 | 2018-02-21 | Preparation method of high-quality graphene material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108147402B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017916A (en) * | 2020-01-07 | 2020-04-17 | 南开大学 | Preparation method of graphene with controllable layer number |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101459617B1 (en) * | 2013-05-03 | 2014-11-10 | 전남대학교산학협력단 | Graphene solutions with high colloidal stability and method for producing the same |
| CN104692374A (en) * | 2015-03-17 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Preparation method of high-concentration graphene dispersion |
| CN104772064A (en) * | 2015-03-31 | 2015-07-15 | 山东玉皇新能源科技有限公司 | Method for preparing grapheme dispersion liquid |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN107352531A (en) * | 2017-08-04 | 2017-11-17 | 湖南国盛石墨科技有限公司 | A kind of method that micro crystal graphite prepares graphene |
-
2018
- 2018-02-21 CN CN201810153039.5A patent/CN108147402B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101459617B1 (en) * | 2013-05-03 | 2014-11-10 | 전남대학교산학협력단 | Graphene solutions with high colloidal stability and method for producing the same |
| CN104692374A (en) * | 2015-03-17 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Preparation method of high-concentration graphene dispersion |
| CN104772064A (en) * | 2015-03-31 | 2015-07-15 | 山东玉皇新能源科技有限公司 | Method for preparing grapheme dispersion liquid |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN107352531A (en) * | 2017-08-04 | 2017-11-17 | 湖南国盛石墨科技有限公司 | A kind of method that micro crystal graphite prepares graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108147402A (en) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | A facile, high‐yield, and freeze‐and‐thaw‐assisted approach to fabricate MXene with plentiful wrinkles and its application in on‐chip micro‐supercapacitors | |
| Wang et al. | Graphene wrapped MXene via plasma exfoliation for all-solid-state flexible supercapacitors | |
| Xie et al. | Advances in microwave-assisted production of reduced graphene oxide | |
| JP6634162B2 (en) | Continuous Preparation of Graphene Oxide Nanoplatelets | |
| Zhang et al. | Preparing graphene from anode graphite of spent lithium-ion batteries | |
| EP3056469B1 (en) | Production method for graphene | |
| CN105883781B (en) | A kind of preparation method of large area redox graphene film | |
| CN104556018B (en) | A kind of preparation method of high-quality graphene conductive film | |
| CN104556017B (en) | A kind of magnanimity preparation method of high-quality graphene | |
| CN105186004B (en) | A kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application | |
| US20110286147A1 (en) | Electrode material and capacitor | |
| TW201536676A (en) | Preparation method of graphene and dispersed composition of graphene | |
| CN108423663A (en) | A kind of method that electrochemistry prepares ultra-thin graphene nanometer sheet | |
| CN102956864A (en) | Preparation method of nitrogen-doped graphene electrode | |
| CN108147402B (en) | Preparation method of high-quality graphene material | |
| Bhargava et al. | Superior dielectric properties and bandgap modulation in hydrothermally grown Gr/MgO nanocomposite | |
| Chen et al. | Growth of single-crystal α-MnO2 nanorods on multi-walled carbon nanotubes | |
| CN106206051A (en) | A kind of Graphene modified activated carbon and application thereof | |
| CN111559743A (en) | Preparation method and application of graphene powder | |
| JP2011195432A (en) | Method for producing flaky graphite and flaky graphite | |
| KR20180074102A (en) | High purity reduced graphene oxide and manufacturing method thereof | |
| CN115536018A (en) | Graphene oxide slurry, heat-conducting film and preparation method | |
| CN104916459A (en) | Preparation method of highly-oriented graphene film for supercapacitor | |
| CN105744817A (en) | Preparation method for highly-oriented electromagnetic shielding membrane by assembling graphene and metal layer by layer | |
| CN106379890B (en) | Graphene flower, forming method thereof and composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210603 Address after: 341000 south of Ouxiang road and east of shangou Avenue, shangou Industrial Park, Yudu County, Ganzhou City, Jiangxi Province Applicant after: Jiangxi Zhongjuhong New Material Technology Co.,Ltd. Address before: 213169 No.3, xinqiaotou, dongyanghu village, co construction village committee, Xueyan Town, Wujin District, Changzhou City, Jiangsu Province Applicant before: Wu Yaliang |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180612 Assignee: Jiangxi Wanglai Technology Co.,Ltd. Assignor: Jiangxi Zhongjuhong New Material Technology Co.,Ltd. Contract record no.: X2023980044075 Denomination of invention: A Preparation Method for High Quality Graphene Materials Granted publication date: 20210625 License type: Common License Record date: 20231020 |