CN111533122A - Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof - Google Patents
Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000003682 fluorination reaction Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
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- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
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- 229910052754 neon Inorganic materials 0.000 claims description 2
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- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
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- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- 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
- C01B2204/26—Mechanical properties
Abstract
The invention belongs to the technical field of nano materials, and discloses a fluorinated graphene macroscopic assembly, a graphene macroscopic assembly and a preparation method thereof. The preparation method of the fluorinated graphene macroscopic assembly provided by the invention is simple to operate, low in energy consumption and low in cost, and is beneficial to industrial production, the prepared fluorinated graphene macroscopic assembly has better mechanical strength and dielectric property, and the graphene macroscopic assembly prepared by high-temperature defluorination of the fluorinated graphene macroscopic assembly has good conductivity. The preparation method is suitable for preparing fluorinated graphene macroscopic assemblies and graphene macroscopic assemblies.
Description
Technical Field
The invention belongs to the technical field of nano materials, and relates to a carbon-based nano material, in particular to a fluorinated graphene macroscopic assembly and a preparation method thereof, and a graphene macroscopic assembly.
Background
Graphene has excellent mechanical and physicochemical properties, and is one of the most important new materials in the 21 st century. At present, graphene has been successfully applied to various fields including energy, catalysis, lubrication, electronics, electricity, and communication. However, graphene-based materials are going from the laboratory to large-scale practical applications, and face a key problem: graphene nanoplatelets are difficult to form macroscopic assemblies with excellent properties quickly, orderly and densely. In the prior art, a simple and convenient vacuum filtration is usually adopted to prepare the graphene film, but the forming mode of the vacuum filtration is time-consuming and energy-consuming, and simultaneously a large amount of solvent is needed for assistance, and the thickness of the prepared graphene film is generally less than 30 microns, so that a structural material with a certain thickness cannot be obtained. Therefore, a direct molding technique is needed to rapidly construct a graphene-based self-assembly with high compactness and high quality in a large scale, so as to promote the large-scale application of the graphene material.
Compared with graphene, the fluorinated graphene has the characteristics of high functionalization density and adjustable energy gap, and also has excellent thermal stability, chemical reactivity, photoelectric property and biological application property, so that the fluorinated graphene is also applied to various fields. Conversion of graphene to fluorinated grapheneAt the same time sp will also be2Conversion of carbon skeleton to sp3The carbon skeleton enables the out-of-plane rigidity of the fluorinated graphene to be superior to that of the graphene, so that the fluorinated graphene nanosheets are difficult to bend under the action of external force and can be orderly and tightly self-assembled layer by layer. Since fluorinated graphene has better self-lubricating capability and out-of-plane rigidity, compared with graphene, a macroscopic assembly can be prepared by compression molding, and a preparation process of the macroscopic assembly of fluorinated graphene is not disclosed in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of fluorinated graphene and a graphene macroscopic assembly, wherein the fluorinated graphene prepared by direct high-temperature constant-temperature fluorination has larger self-lubricating capability and surface-to-surface rigidity compared with graphene, so that the fluorinated graphene can be directly subjected to compression molding;
another object of the present invention is to provide a fluorinated graphene macroscopic assembly prepared by the above method, which has better dielectric properties;
the invention also provides a graphene macroscopic assembly, and the graphene macroscopic assembly can be obtained by performing high-temperature defluorination treatment on the fluorinated graphene macroscopic assembly.
In order to achieve the purpose, the technical method comprises the following steps:
a preparation method of a fluorinated graphene macroscopic assembly body comprises the steps of carrying out fluorination reaction on graphene to obtain fluorinated graphene, and then carrying out compression molding to obtain the fluorinated graphene macroscopic assembly body.
As a limitation: before the fluorination reaction, introducing nitrogen into the reaction device, extracting gas in the reaction device, performing nitrogen replacement for 2-5 times to ensure that the pressure of the reaction device is less than or equal to 100Pa, then heating the temperature in the reaction device to 250 ℃ and introducing fluorination reaction mixed gas into the reaction device at the speed of 0.1-6L/min, wherein the mass of the graphene is 1000mg and the volume of the fluorination reaction mixed gas is 6-20L.
As a further limitation: the fluorination reaction mixed gas is a combination of an inactive gas and 2-30% of fluorine gas by volume fraction, or a combination of the inactive gas, 5-20% of oxygen gas and 2-30% of fluorine gas by volume fraction.
As a further limitation: the inactive gas is at least one of helium, neon, argon, krypton, xenon, radon, nitrogen and carbon dioxide.
As another limitation: the pressure of the fluorination reaction is 10-120KPa, and the reaction time is 1-3 h; the temperature for compression molding is normal temperature, the pressure is 5-50MPa, and the pressure maintaining time is 5-40 min.
The invention also provides a fluorinated graphene macroscopic assembly prepared by the method.
As a limitation: the compression strength of the fluorinated graphene macroscopic assembly is 8-102MPa, the dielectric constant is 1.2-3 under the condition of 5MHz frequency, and the dielectric loss is 0.001-0.1.
The invention also provides a preparation method of the graphene macroscopic assembly, and the graphene macroscopic assembly is obtained after the fluorinated graphene macroscopic assembly is defluorinated at high temperature.
As a limitation: the high temperature is 1500-3500 ℃.
The graphene macroscopic assembly provided by the invention has the conductivity of 104-10×104S/m。
Due to the adoption of the scheme, compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the fluorinated graphene macroscopic assembly, the fluorination reaction is carried out by firstly heating to the set temperature and then filling the fluorination reaction mixed gas, compared with the traditional fluorination reaction in which the temperature is gradually raised from room temperature after filling fluorine gas/nitrogen gas, more C-F covalent bonds vertical to the plane are introduced into the graphene plane, and the prepared fluorinated graphene has larger interlayer spacing and thus has stronger self-lubricating capability; in addition, the fluorinated graphene prepared by the method can be directly molded under a normal temperature condition to prepare a fluorinated graphene macroscopic assembly, and the method is simple to operate, low in energy consumption and low in cost, and is beneficial to industrial production;
(2) the fluorinated graphene macroscopic assembly provided by the invention has an interlocking structure of nacreous layers formed by closely arranging the layers, so that the compressive strength of the fluorinated graphene macroscopic assembly is up to 102MPa, and meanwhile, the fluorinated graphene macroscopic assembly has a dielectric constant of 1.2, dielectric loss of 0.001 and good dielectric property under the condition of frequency of 5 MHz;
(3) the fluorinated graphene macroscopic assembly provided by the invention is applied to preparation of the graphene macroscopic assembly, and the conductivity of the prepared graphene macroscopic assembly can reach 105S/m, and has good conductivity.
The preparation method is suitable for preparing fluorinated graphene macroscopic assemblies and graphene macroscopic assemblies.
Drawings
The invention is described in further detail below with reference to the figures and the embodiments.
Fig. 1 is a schematic diagram of a process for preparing fluorinated graphene macroscopic assemblies according to embodiments 1 to 8 of the present invention;
FIG. 2 is a fluorinated graphene macroscopic assembly of examples 1-8 of the present invention;
FIG. 3 is a graph showing the coefficient of friction of fluorinated graphene of example 6 of the present invention and graphene of comparative example 3;
fig. 4(a-d) is a graph showing the results of characterizing the degree of bending of the graphene of comparative example 3 in example 9 of the present invention;
FIG. 4(e-h) is a graph showing the bending degree characterization results of fluorinated graphene in example 6 of the present invention;
FIG. 5 is a graph of the dielectric constant characterization results of fluorinated graphene macroscopic assemblies of example 6 according to the present invention;
FIG. 6 is a graph of the dielectric loss characterization results of fluorinated graphene macroscopic assemblies according to example 6 of the present invention;
fig. 7 is a graph of a conductive property characterization result of the graphene macroscopic assembly of example 6 of the present invention;
FIG. 8 is a schematic diagram of a process for preparing fluorinated porous graphene based on C-F bonds at defects in comparative example 1 according to example 9 of the present invention;
fig. 9 is a schematic diagram of a process for preparing a graphene macroscopic assembly of comparative example 3 according to example 9 of the present invention;
fig. 10 is an XRD spectrum of comparative example 4 temperature-rising fluorination and fluorinated graphene of example 6 of the present invention, example 9.
Detailed Description
The present invention is further described with reference to the following examples, but it will be understood by those skilled in the art that the present invention is not intended to be exhaustive and that the present invention provides only some examples, but is not limited to the following examples, and any modifications and variations based on the specific examples of the present invention are within the scope of the claims.
Examples 1-8 fluorinated graphene macroscopic assemblies and methods of making the same
Embodiments 1 to 8 are respectively a fluorinated graphene macroscopic assembly, and a preparation method and an application thereof, a schematic diagram of a preparation process thereof is shown in fig. 1, various parameters for preparing the fluorinated graphene macroscopic assembly are shown in table 1, and a prepared fluorinated graphene macroscopic assembly is shown in fig. 2.
The preparation method of the fluorinated graphene macroscopic assembly of example 1 is performed according to the following steps:
1) putting graphene into a fluorination reaction kettle, introducing nitrogen into the reaction kettle, and pumping out gas until the pressure in the reaction kettle is 100Pa, so as to finish the nitrogen replacement for three times;
2) introducing mixed gas of nitrogen and fluorine gas into the reaction kettle at the speed of 0.2L/min until the pressure in the reaction kettle reaches 10KPa, and reacting at 190 ℃ for 1h to obtain fluorinated graphene;
3) and carrying out compression molding on the prepared fluorinated graphene at normal temperature under the pressure of 20MPa, and maintaining the pressure for 30min to obtain the fluorinated graphene macroscopic assembly.
And (3) performing high-temperature defluorination on the fluorinated graphene macroscopic assembly of the embodiment 1 at the temperature of 2200 ℃ to obtain the graphene macroscopic assembly.
Examples 2 to 8 relate to a method for preparing each of fluorinated graphene macro-assemblies and a method for preparing each of the graphene macro-assemblies, which are substantially the same as those in example 1, except that parameters are different. The preparation parameters and performance indexes of the fluorinated graphene macroscopic assemblies of examples 1 to 8, and the preparation method and performance indexes of the graphene macroscopic assemblies are shown in table 1.
TABLE 1 preparation parameters and performance indexes of fluorinated graphene macroscopic assemblies, and preparation method and performance indexes of graphene macroscopic assemblies
Referring to fig. 5 and 6, the dielectric constant and the dielectric loss of the fluorinated graphene macroscopic assembly of example 6 under the condition of 5MHz are 1.8 and 0.01, respectively, and the dielectric performance is better, and referring to fig. 7, the conductivity of the graphene macroscopic assembly of example 6 can be found to be 5.5 × 104S/m, and has good conductivity.
As can be seen from Table 1, the fluorinated graphene macroscopic assemblies prepared in examples 1 to 8 have a compressive strength of 8 to 102MPa, a dielectric constant of 1.2 to 3, a dielectric loss of 0.001 to 0.1 and good dielectric properties under a frequency of 5 MHz; the prepared graphene macroscopic assembly has the conductivity of 104-10×104S/m, and has good conductivity.
Example 9 fluorinated graphene macroscopic Assembly and comparative example 1 thereof
1) Putting the porous graphene into a fluorination reaction kettle, introducing nitrogen into the reaction kettle, and pumping out the gas until the pressure in the reaction kettle is 100Pa, so as to finish the nitrogen replacement for three times;
2) introducing a mixed gas of nitrogen and fluorine gas with volume fraction of 5% into the reaction kettle at a speed of 0.2L/min until the pressure in the reaction kettle reaches 120KPa, and reacting at 240 ℃ for 1h to obtain the fluorinated porous graphene;
3) and (3) carrying out compression molding on the prepared fluorinated porous graphene at normal temperature under the pressure of 20MPa, and keeping the pressure for 30min to obtain the fluorinated porous graphene macroscopic assembly, wherein the schematic diagram of the preparation process is shown in FIG. 8.
Comparative example 2
And (3) carrying out compression molding on the graphite fluoride at normal temperature under the pressure of 20MPa, and maintaining the pressure for 30min to obtain the graphite fluoride macroscopic assembly.
Comparative example 3
And (3) carrying out compression molding on the graphene at normal temperature under the pressure of 20MPa, and keeping the pressure for 30min to obtain the graphene macroscopic assembly, wherein the schematic diagram of the preparation process is shown in FIG. 9.
Comparative example 4
1) Introducing mixed gas of fluorine gas and nitrogen gas into a reaction kettle at room temperature, heating the reaction kettle to 240 ℃, and preparing fluorinated graphene through fluorination;
2) and carrying out compression molding on the prepared fluorinated graphene at normal temperature under the pressure of 20MPa, and keeping the pressure for 30 min.
Referring to fig. 3, the fluorinated graphene of example 6 has a friction coefficient of 0.09, and the graphene of comparative example 3 has a friction coefficient of 0.19, and thus it can be seen that the fluorinated graphene has a better self-lubricating ability than graphene; referring to fig. 4(a-d), graphene is prone to wrinkle and even bend, indicating that its out-of-plane stiffness is small, resulting in poor layer-by-layer stacking of graphene sheets in direct compression molding: referring to fig. 4(e-h), fluorinated graphene is not prone to wrinkle or even bend, indicating that its out-of-plane stiffness is large, so its lamellae are well stacked layer by layer in direct compression molding;
comparative examples 1, 2, 3 and 4 are shown in table 2 for compressive strength comparison with example 1:
TABLE 2 comparative data on compressive Strength
| Group of | Compressive Strength (MPa) |
| Practice ofExample 6 | 102 |
| Comparative example 1 | 1 |
| Comparative example 2 | 5 |
| Comparative example 3 | 0 |
| Comparative example 4 | 30 |
As can be seen from Table 2, the compressive strength of the fluorinated porous graphene in comparative example 1 is 1MPa, and direct molding cannot be realized, which indicates that the introduced C-F bond cannot promote fluorination intercalation at the defect; the compression strength of the graphite fluoride of the comparative example 2 is 5MPa, and direct molding cannot be realized, which shows that the two-dimensional material characteristic is the premise of realizing direct molding; the compressive strength of the original graphene of comparative example 3 is 0MPa, indicating that the original graphene with poor self-lubricating ability and small out-of-plane stiffness cannot be directly compression molded; the compression strength of the fluorinated graphene assembly prepared by temperature-rising fluorination in the comparative example 4 is slightly 30MPa, which is obviously lower than the compression strength of 102MPa of the fluorinated graphene assembly in the example 6, as shown in fig. 10, it is shown that more C-F bonds vertical to the graphene plane can be introduced by direct constant-temperature fluorination, the interlayer spacing is larger, the self-lubricating capability is better, and the direct molding is facilitated; in summary, direct graphene formation requires the introduction of C-F covalent bonds perpendicular to the plane.
Claims (10)
1. A preparation method of a fluorinated graphene macroscopic assembly is characterized in that the fluorinated graphene is subjected to fluorination reaction to prepare fluorinated graphene, and then compression molding is carried out to obtain the fluorinated graphene macroscopic assembly.
2. The method as claimed in claim 1, wherein before the fluorination reaction, nitrogen is introduced into the reaction apparatus and the gas in the reaction apparatus is extracted, the nitrogen is substituted for 2-5 times to make the pressure of the reaction apparatus less than or equal to 100Pa, then the temperature in the reaction apparatus is raised to 160-250 ℃, and then the mixed gas of the fluorination reaction is introduced into the reaction apparatus at a speed of 0.1-6L/min, wherein the mass of the graphene is 100-1000mg, and the volume of the mixed gas of the fluorination reaction is 6-20L.
3. The method of claim 2, wherein the fluorination reaction gas mixture is a combination of an inert gas and 2-30 vol% fluorine gas, or a combination of an inert gas, 5-20 vol% oxygen gas and 2-30 vol% fluorine gas.
4. The method of claim 3, wherein the non-reactive gas is at least one of helium, neon, argon, krypton, xenon, radon, nitrogen, and carbon dioxide.
5. The method for preparing the fluorinated graphene macroscopic assembly according to any one of claims 1 to 4, wherein the pressure of the fluorination reaction is 10 to 120KPa, and the reaction time is 1 to 3 h; the temperature for compression molding is normal temperature, the pressure is 5-50MPa, and the pressure maintaining time is 5-40 min.
6. Fluorinated graphene macroscopic assembly, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. The fluorinated graphene macroscopic assembly of claim 6, wherein the compressive strength of the fluorinated graphene macroscopic assembly is 8 to 102MPa, the dielectric constant is 1.2 to 3 and the dielectric loss is 0.001 to 0.1 at a frequency of 5 MHz.
8. A preparation method of a graphene macroscopic assembly, which is characterized in that the fluorinated graphene macroscopic assembly of claim 6 or 7 is defluorinated at a high temperature to obtain the graphene macroscopic assembly.
9. The method of preparing a graphene macroscopic assembly according to claim 8, wherein the high temperature is 1500 ℃ to 3500 ℃.
10. A graphene macroscopic assembly, characterized in that, it is prepared by the preparation method of claim 8 or 9, and the prepared graphene macroscopic assembly has an electrical conductivity of 104-10×104S/m。
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