CN108516542B - Preparation method of high-fluorine-content nano fluorinated graphene - Google Patents
Preparation method of high-fluorine-content nano fluorinated graphene Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- C01B2204/00—Structure or properties of graphene
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Abstract
The invention relates to the technical field of nano materials, and discloses a preparation method of high-fluorine-content nano fluorinated graphene, which comprises the steps of firstly adopting fluorine gas as a fluorine source in step 1, wherein the fluorine gas has strong reaction activity and can etch the graphene, so that chemical crushing is realized, the particle size of the graphene is reduced, the low-fluorine-content nano fluorinated graphene with nano size is effectively prepared, secondly, the particle size of the fluorinated graphene is further reduced through ultrasonic dispersion and high-energy ball milling in steps 2 and 3, and finally, the fluorine content in the high-fluorine-content nano fluorinated graphene powder is finally ensured through the high-temperature fluorination reaction of fluorine-containing gas in step 4; through reasonably designed reaction steps, the finally prepared nano fluorinated graphene powder with high fluorine content and nano-scale particle size has the structural size of less than 100 nm.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of high-fluorine-content nano fluorinated graphene.
Background
The fluorinated graphene serving as a novel derivative of graphene not only maintains the high-strength performance of graphene, but also brings novel interface and physicochemical properties such as surface energy reduction, hydrophobicity enhancement, band gap broadening and the like due to the introduction of fluorine atoms. Meanwhile, the fluorinated graphene is high-temperature resistant, stable in chemical property, similar to polytetrafluoroethylene in property, and called as two-dimensional Teflon. The fluorinated graphene has the characteristics of reduced surface energy, enhanced hydrophobicity, high temperature resistance, stable chemical property and the like, can be used as a tunnel barrier or a high-quality insulator or barrier material, can also be used for light-emitting diodes and displays, can be used in the fields of interfaces, novel nano electronic devices, lubricating materials, battery electrode materials, hydrophobic and oleophobic agents, nuclear reactor materials and the like, particularly used under the conditions of high speed, high pressure and high temperature, has better effect, can be widely applied to high-speed airplanes, carrier rockets, missiles, tanks, automobiles and the like as lubricants, and has wide application prospects in the fields of water resistance, oil resistance, coatings and the like. The horizontal lamellar of the fluorinated graphene generally reaches the micron level, so that the fluorinated graphene is limited in part of application fields, and the fluorinated graphene needs to be subjected to nanocrystallization to prepare the fluorinated graphene material with a three-dimensional nanocrystallization structure.
Chinese patent publication No. CN201510753302.0 discloses a method for preparing nano graphite fluoride, which comprises the following steps: the nano graphite is put into a reaction kettle and reacts for 5 to 70 hours in the mixed gas environment of fluorine and nitrogen with the fluorine volume concentration of 50 to 100 percent under the condition that the temperature is 300 to 500 ℃, and the nano graphite fluoride with the fluorine-carbon ratio of 0.1 to 1.47 is obtained. The method has the advantages of high reaction efficiency, safe reaction and low cost, can obtain the nano graphite fluoride with the fluorine-carbon ratio of 1.47 at most, and is suitable for industrial production. The process is of no practical significance, the traditional nano graphite is prepared by a mechanical grinding method, the nano level can not be achieved at all, and the micron level is the limit which can be achieved by grinding.
Disclosure of Invention
The invention aims to provide a preparation method of high-fluorine-content nano fluorinated graphene, which aims to solve the problem that the high-fluorine-content nano fluorinated graphene with a nano size cannot be prepared by the existing physical mechanical ball milling method.
In order to achieve the technical purpose and achieve the technical effect, the invention discloses a preparation method of nano fluorinated graphene with high fluorine content, which comprises the following steps:
step 1: putting graphene as a carbon source into fluorination equipment, introducing fluorine gas, and carrying out high-temperature fluorination to prepare fluorinated graphene with low fluorine content;
and 2, step: adding a liquid phase solvent into the low fluorine content fluorinated graphene obtained in the step 1, uniformly mixing, transferring to a ball milling tank of a planetary ball mill, and carrying out ball milling to obtain fluorinated graphene slurry;
and step 3: adding the liquid phase solvent into the fluorinated graphene slurry obtained in the step 2 again, uniformly mixing, performing ultrasonic separation to obtain a fluorinated graphene dispersion solution, and performing spray drying to obtain low-fluorine-content nano fluorinated graphene powder;
and 4, step 4: and (3) putting the low-fluorine-content nano fluorinated graphene powder obtained in the step (3) into fluorination equipment, introducing fluorine-containing gas, and carrying out high-temperature fluorination to obtain the high-fluorine-content nano fluorinated graphene powder.
Further, the fluorine-containing gas in step 4 is a mixed gas containing 20% fluorine gas or nitrogen trifluoride gas.
Further, the preparation method in step 1 specifically comprises the following steps: after fluorine gas is introduced, the pressure is kept between 80 and 95KPa, and the reaction is carried out for 8 to 16 hours at the temperature of 450 and 500 ℃.
Further, the high-temperature fluorination in the step 4 is carried out at the holding pressure of 100-120KPa and the reaction is carried out for 8-16h at the temperature of 650-700 ℃.
Further, the liquid phase solvent in step 2 or step 3 is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, tetramethylurea, N-methylacetamide, acetamide, pyrrole, pyridine, tetrahydrofuran, chloroform, ethanol, propanol, isobutanol, acetonitrile, acetone, dimethyl sulfoxide, γ -butyrolactone, and 1, 3-dimethyl-2-imidazo-ketone.
Further, the ball milling method in the step 2 is at a rotation speed of 300-.
Further, the ultrasonic separation in step 3 specifically comprises: and carrying out ultrasonic treatment for 12-36h at the ultrasonic frequency of 20-100kHz to obtain the fluorinated graphene dispersion liquid.
By adopting the scheme, the invention has the following beneficial effects: according to the method, through the optimized design of the steps, firstly, fluorine gas is adopted as a fluorine source in the step 1, the fluorine gas has strong reaction activity and can etch the graphene, so that chemical crushing is realized, the particle size of the graphene is reduced, the reaction contact area is increased, and the nanocrystallization of the fluorinated graphene is effectively ensured, secondly, through the ultrasonic dispersion and the high-energy ball milling in the steps 2 and 3, the particle size of the graphene is further reduced, the dispersion degree of the graphene is improved, and finally, through the high-temperature fluorination reaction again in the step 4, the fluorine content in the high-fluorine-content nano fluorinated graphene powder is finally ensured. The result shows that the method can obtain the fluorinated graphene with high fluorine content and nano-particle size.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
Step 1: putting 50g of graphene into fluorination equipment, introducing fluorine gas, keeping the pressure at 95KPa, and reacting for 12h at the temperature of 450-500 ℃.
Step 2: weighing 100g of the fluorinated graphene with low fluorine content prepared in the first step, adding 500mL of N-methyl pyrrolidone, transferring to a ball milling tank of a planetary ball mill, and carrying out ball milling for 5h at the rotating speed of 600r/min to obtain fluorinated graphene slurry.
And step 3: and (3) transferring the fluorinated graphene slurry prepared in the step (2) into a plastic bottle, adding 200mL of N-methyl pyrrolidone, performing ultrasonic separation for 24h under the condition of 50kHz to obtain a fluorinated graphene dispersion solution, and performing spray drying to obtain the low-fluorine-content nano fluorinated graphene powder.
And 4, step 4: and (3) putting 50g of the low-fluorine-content nano fluorinated graphene powder prepared in the third step into fluorination equipment, introducing mixed gas containing 20% fluorine gas, keeping the pressure at 100-120KPa, and reacting for 16h at the temperature of 650-700 ℃ to obtain the high-fluorine-content nano fluorinated graphene powder.
Taking the high-fluorine-content nano fluorinated graphene powder obtained in the embodiment 1 as a detection object, and performing element content measurement and particle size characterization on the detection object; the element content determination method comprises the following steps: the samples were dispersed on aluminum foil sheets and fixed, and C, F elements were added to the samples and normalized for the two element content. The specific experimental method for particle size characterization adopts a corresponding standard detection method of GB/T29022-.
TABLE 1 elemental content measurement results Table
Table 2 table of particle size characterization results
| Sample Name | Result of detection Result |
| High fluorine content nano fluorinated graphene powder | 63.5 nm |
As shown in table 1, the fluorine content in the high-fluorine-content nano fluorinated graphene powder is 65.3% which is higher than that of the fluorinated graphene or fluorinated graphite product prepared by the conventional method after the high-fluorine-content nano fluorinated graphene powder is characterized by element content measurement.
As shown in tables 1 and 2, after the particle size characterization of the high-fluorine-content nano fluorinated graphene powder by the particle size analyzer, the average particle size of the high-fluorine-content nano fluorinated graphene powder is 63.5nm after the high-fluorine-content nano fluorinated graphene powder is uniformly dispersed in an aqueous solution, and the particle size reaches the nanoscale.
Example 2
Step 1: putting 50g of graphene into fluorination equipment, introducing fluorine gas, keeping the pressure at 80KPa, and reacting for 8h at 450 ℃.
Step 2: weighing 100g of the low-fluorine-content nano fluorinated graphene obtained in the step 1, mixing the low-fluorine-content nano fluorinated graphene with 500mL of liquid phase solvent, transferring the mixture to a ball milling tank of a planetary ball mill after uniform mixing, and performing ball milling for 2 hours at a rotating speed of 300r/min to obtain fluorinated graphene slurry.
And 3, transferring the fluorinated graphene slurry obtained in the step 2 into a plastic bottle, adding a liquid phase solvent for mixing, transferring the mixture into an ultrasonic separator after uniform mixing, performing ultrasonic treatment for 1h at the ultrasonic frequency of 20kHz to obtain a fluorinated graphene dispersion liquid, and performing spray drying on the fluorinated graphene dispersion liquid to obtain the low-fluorine-content nano fluorinated graphene powder.
And 4, weighing 50g of the low-fluorine-content nano fluorinated graphene powder obtained in the step 3, putting the low-fluorine-content nano fluorinated graphene powder into fluorination equipment, introducing mixed gas containing 20% of fluorine gas, keeping the pressure at 100KPa, reacting for 8 hours at 650 ℃ to obtain high-fluorine-content nano fluorinated graphene powder, wherein the F content is 61.5%, the C content is 38.5% and the average particle size is 86.64nm according to the method of the example 1.
Wherein, the liquid phase solvent in the steps 2 and 3 is a mixture of N-methylpyrrolidone and N, N-dimethylformamide.
Example 3
Step 1: putting 50g of graphene into fluorination equipment, introducing fluorine gas, keeping the pressure at 90KPa, and reacting for 12h at 485 ℃.
And 2, step: weighing 100g of the low-fluorine-content nano fluorinated graphene obtained in the step 1, mixing the low-fluorine-content nano fluorinated graphene with 2000mL of liquid-phase solvent, uniformly mixing, transferring to a ball milling tank of a planetary ball mill, and carrying out ball milling for 12h at a rotating speed of 500r/min to obtain fluorinated graphene slurry.
And 3, step 3: and (3) transferring the graphene fluoride slurry obtained in the step (2) into a plastic bottle, adding a liquid phase solvent for mixing, after uniform mixing, transferring into an ultrasonic separator, carrying out ultrasonic treatment for 12 hours at an ultrasonic frequency of 60kHz to obtain a graphene fluoride dispersion liquid, and carrying out spray drying on the graphene fluoride dispersion liquid to obtain the low-fluorine-content nano graphene fluoride powder.
And 4, step 4: weighing 50g of the low-fluorine-content nano fluorinated graphene powder obtained in the step 3, putting the low-fluorine-content nano fluorinated graphene powder into fluorination equipment, introducing mixed gas containing 20% of fluorine gas, keeping the pressure at 110KPa, reacting for 12 hours at 675 ℃ to obtain high-fluorine-content nano fluorinated graphene powder, wherein the F content is 62.8%, the C content is 37.2% and the average particle size is 82.3nm according to the method of the example 1.
Wherein, the liquid phase solvent in the steps 2 and 3 is a mixture of ethanol and isobutanol.
Example 4
Step 1: putting 50g of graphene into fluorination equipment, introducing fluorine gas, keeping the pressure at 90KPa, and reacting for 12h at 450 ℃.
Step 2: weighing 100g of the low-fluorine-content nano fluorinated graphene obtained in the step 1, mixing the low-fluorine-content nano fluorinated graphene with 1000mL of liquid phase solvent, uniformly mixing, transferring to a ball milling tank of a planetary ball mill, and performing ball milling for 24 hours at a rotating speed of 600r/min to obtain fluorinated graphene slurry.
And step 3: and (3) adding a liquid phase solvent into the fluorinated graphene slurry obtained in the step (2), uniformly mixing, transferring into an ultrasonic separator in a plastic bottle, carrying out ultrasonic treatment for 24 hours at an ultrasonic frequency of 60kHz to obtain a fluorinated graphene dispersion liquid, and carrying out spray drying on the fluorinated graphene dispersion liquid to obtain the low-fluorine-content nano fluorinated graphene powder.
And 4, step 4: weighing 50g of the low-fluorine-content nano fluorinated graphene powder obtained in the step 3, putting the low-fluorine-content nano fluorinated graphene powder into fluorination equipment, introducing nitrogen trifluoride-containing gas, keeping the pressure at 100KPa, reacting for 12 hours at 685 ℃ to obtain high-fluorine-content nano fluorinated graphene powder, wherein the F content is 63.8%, the C content is 36.2% and the average particle size is 78.6nm according to the method in the example 1.
Wherein, the liquid phase solvent in the steps 2 and 3 is a mixture of acetone and acetamide.
Example 5
Step 1: putting 50g of graphene into fluorination equipment, introducing fluorine gas, keeping the pressure at 95KPa, and reacting for 16h at 500 ℃.
Step 2: weighing 100g of the low-fluorine-content nano fluorinated graphene obtained in the step 1, mixing the low-fluorine-content nano fluorinated graphene with 3000mL of liquid-phase solvent, uniformly mixing, transferring to a ball milling tank of a planetary ball mill, and performing ball milling for 48 hours at the rotating speed of 800r/min to obtain fluorinated graphene slurry.
And step 3: and (3) adding a liquid phase solvent into the fluorinated graphene slurry obtained in the step (2), uniformly mixing, transferring into an ultrasonic separator in a plastic bottle, carrying out ultrasonic treatment for 120 hours at an ultrasonic frequency of 100kHz to obtain a fluorinated graphene dispersion liquid, and carrying out spray drying on the fluorinated graphene dispersion liquid to obtain the low-fluorine-content nano fluorinated graphene powder.
And 4, step 4: and (3) weighing 50g of the low-fluorine-content nano fluorinated graphene powder obtained in the step (3), putting into fluorination equipment, introducing nitrogen trifluoride-containing gas, keeping the pressure at 120KPa, reacting for 16h at 700 ℃ to obtain high-fluorine-content nano fluorinated graphene powder, wherein the F content is 65.3%, the C content is 34.7% and the average particle size is 63.5nm according to the method in the example 1.
Wherein, the liquid phase solvent in the steps 2 and 3 is a mixture of acetone and dimethyl sulfoxide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (6)
1. A preparation method of nano fluorinated graphene with high fluorine content is characterized by comprising the following steps:
Step 1: placing graphene as a carbon source into fluorination equipment, introducing fluorine gas, keeping the pressure at 80-95KPa, reacting for 8-16h at the temperature of 450-500 ℃, and performing high-temperature fluorination to prepare fluorinated graphene with low fluorine content;
step 2: adding a liquid phase solvent into the low fluorine content fluorinated graphene obtained in the step 1, uniformly mixing, transferring to a ball milling tank of a planetary ball mill, and carrying out ball milling to obtain fluorinated graphene slurry;
and step 3: adding the liquid phase solvent into the fluorinated graphene slurry obtained in the step 2 again, uniformly mixing, performing ultrasonic separation to obtain a fluorinated graphene dispersion solution, and performing spray drying to obtain low-fluorine-content nano fluorinated graphene powder;
and 4, step 4: and (3) putting the low-fluorine-content nano fluorinated graphene powder obtained in the step (3) into fluorination equipment, introducing fluorine-containing gas, and carrying out high-temperature fluorination to obtain the high-fluorine-content nano fluorinated graphene powder.
2. The method for preparing nano fluorinated graphene with high fluorine content according to claim 1, wherein the method comprises the following steps: the fluorine-containing gas in step 4 is a mixed gas containing 20% fluorine gas or nitrogen trifluoride gas.
3. The method for preparing nano fluorinated graphene with high fluorine content according to claim 1 or 2, wherein the method comprises the following steps: the high-temperature fluorination pressure of 100-120KPa in the step 4 is reacted for 8-16h at the temperature of 650-700 ℃.
4. The method for preparing nano fluorinated graphene with high fluorine content according to claim 1 or 2, wherein the method comprises the following steps: the liquid phase solvent in step 2 or step 3 is one or more of N-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, N-methylacetamide, acetamide, pyrrole, pyridine, tetrahydrofuran, trichloromethane, ethanol, propanol, isobutanol, acetonitrile, acetone, dimethyl sulfoxide, gamma-butyrolactone, and 1, 3-dimethyl-2-imidazo-ketone.
5. The method for preparing nano fluorinated graphene with high fluorine content according to claim 1 or 2, wherein the method comprises the following steps: the ball milling method in the step 2 is that the rotating speed is 300-.
6. The method for preparing nano fluorinated graphene with high fluorine content according to claim 1 or 2, wherein the method comprises the following steps: the ultrasonic separation in the step 3 specifically comprises the following steps: and carrying out ultrasonic treatment for 12-36h at the ultrasonic frequency of 20-100kHz to obtain the fluorinated graphene dispersion liquid.
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