CN115651313A - Preparation method of carbon composite material - Google Patents
Preparation method of carbon composite material Download PDFInfo
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- CN115651313A CN115651313A CN202211373646.5A CN202211373646A CN115651313A CN 115651313 A CN115651313 A CN 115651313A CN 202211373646 A CN202211373646 A CN 202211373646A CN 115651313 A CN115651313 A CN 115651313A
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Abstract
The invention relates to a preparation method of a carbon composite material, belonging to the field of preparation of carbon composite materials, wherein a carbon material is used as a dispersion phase, and the carbon material adopts at least one of graphene, graphene oxide, graphene nanoplatelets prepared by a mechanical stripping method or carbon tube powder; enabling the dispersion liquid to pass through the filter element structure for a period of time according to a certain flow rate, and enabling the filter element to achieve preset weight gain; taking down the filter element, cutting the filter material layer, taking the filter material layer and crushing the filter material layer to obtain a mixture; then extruding and granulating or performing heat treatment to obtain the carbon composite material, wherein the structural form of the carbon composite material can be functional master batches or porous carbon composite materials; the invention can solve the problem of dispersion uniformity of carbon materials such as graphene, carbon tube powder and the like in a dispersion medium, and simultaneously can avoid the influence of impurity introduction on the performance of the composite material, and the method has the advantages of simple process and strong operability.
Description
Technical Field
The invention relates to the technical field of preparation of carbon composite materials, in particular to a preparation method of a carbon composite material.
Background
In the prior art, the preparation method of the carbon composite material generally comprises the following steps: carbon materials such as graphene and carbon tube powder are used as a dispersion phase, resin and the like are used as a dispersion medium, the carbon materials are dispersed in the dispersion medium to obtain a uniformly dispersed dispersion system, and then the dispersion system is prepared by granulation or other composite modes.
The prior art has the following technical problems: since the microstructure of the graphene and carbon tube powder is in an agglomerated state, the graphene and carbon tube powder is extremely easy to agglomerate in a dispersion medium, so that the dispersion uniformity is poor, and the preparation of the composite material is affected subsequently. Therefore, the greatest bottleneck restricting the application of graphene and carbon tube powder is dispersibility. In order to solve the problem of uneven dispersion, the prior art has the following solutions: an auxiliary dispersing agent is added in a dispersing system or carbon materials such as graphene and the like are subjected to surface treatment, but the two methods easily cause the introduction of impurities, influence the performance of the prepared composite material, and the preparation process is often complex.
Therefore, there is a need to develop a method that can solve the problem of dispersion uniformity of carbon materials such as graphene and carbon tube powder in a dispersion medium, and can avoid impurities from being introduced to affect the performance of the composite material.
Disclosure of Invention
The invention provides a preparation method of a carbon composite material aiming at the problems in the prior art, which can solve the problem of dispersion uniformity of carbon materials such as graphene, carbon tube powder and the like in a dispersion medium, and can avoid the influence of impurity introduction on the performance of the composite material, and has simple process method and strong operability.
The technical scheme for solving the technical problems is as follows: a preparation method of a carbon composite material takes a carbon material as a dispersion phase, wherein the carbon material adopts at least one of graphene, graphene oxide, graphene nanoplatelets prepared by a mechanical stripping method or carbon tube powder, and is characterized by comprising the following steps:
a. dispersing a carbon material in a liquid dispersion medium to prepare a dispersion liquid;
b. enabling the dispersion liquid to pass through the filter element structure for a period of time according to a certain flow rate, and enabling the filter element to achieve preset weight gain;
c. b, taking down the filter element obtained in the step b, cutting a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A;
d. and (3) preparing the carbon composite material by extruding and granulating or performing heat treatment on the mixture A, wherein the structural form of the carbon composite material can be functional master batches, and can also be a porous carbon composite material.
Further, the dispersion medium adopts one or a mixture of more than two of water, DMF, NMP, methanol and ethyl acetate.
Furthermore, the filter element adopts a melt-blown filter element, and the material of a filter material layer of the filter element is polypropylene, polyvinyl chloride or polyurethane.
Further, an extruder is adopted for extrusion granulation in the step d, wherein the temperature interval of the extruder is as follows: the temperature of the conveying section is 140-150 ℃, and the temperatures of the melting section, the mixing section, the exhaust section and the homogenizing section are all 180-200 ℃.
Further, the mixture is mixed with an activating agent before the heat treatment in the step d, and the heat treatment process is carried out under the conditions of inert atmosphere and the temperature of 700-1100 ℃.
Further, the activating agent adopts KOH, naOH and ZnCl 2 、CaCO 3 And MgO.
The beneficial effects of the invention are: the method comprises the steps of preparing easily aggregated carbon materials such as graphene, graphene oxide, carbon nanotubes and graphene nanoplatelets by a mechanical stripping method into dispersion liquid, ensuring monodispersity of the dispersion liquid, enabling the dispersion liquid to slowly pass through a melt-blown filter element, intercepting the carbon materials by the interception effect of melt-blown filter element fibers, enabling the carbon materials to be uniformly adsorbed on filter element fibers (as shown in figure 1), realizing the micro-scale combination of the easily aggregated carbon materials and polymer fibers, and crushing a filter layer after combination to further obtain a more uniform mixture; the content of the carbon material in the composite material can be controlled by controlling the concentration of the dispersion liquid and the speed of the dispersion liquid passing through the filter element; the mixture is further processed to obtain the composite material with uniform phase.
Drawings
Fig. 1 is an SEM image of a graphene oxide/polypropylene fiber composite material prepared in example 1 of the present invention.
FIG. 2 is a picture of the functional masterbatch prepared in example 1 of the present invention;
fig. 3 is an SEM image of the graphene/porous carbon composite material prepared in example 5 of the present invention.
Fig. 4 is an SEM image of the graphene/porous carbon composite material prepared in comparative example 2 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The preparation method of this example includes the following steps:
a. dispersing graphene oxide in water to prepare a dispersion liquid with the concentration of 0.5%;
b. enabling the dispersion liquid to pass through the filter element structure for 2 hours at the flow speed of 1L/h, wherein the filter material layer of the used filter element is made of polypropylene melt-blown fibers; calculating the weight increment delta M of the filter element to be 25.3g, wherein the mass ratio of the graphene oxide to the polypropylene filter layer is 1:9.8. wherein Δ M = M2-M1, M1 is the original weight (dry weight) of the filter element, and M2 is the weight of the dispersion after treatment and drying by the filter element;
c. b, taking down the filter element obtained in the step b, cutting off a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A, wherein an SEM picture of the mixture A is shown in figure 1, and uniformly mixing the mixture A in a mixer;
d. and (3) performing melt extrusion granulation on the mixture A through an extruder, wherein the appearance of the obtained master batch is shown in figure 2, and the temperature interval of the extruder is as follows: the temperature of the conveying section is 150 ℃, and the temperatures of the melting section, the mixing section, the exhaust section and the homogenizing section are all 200 ℃.
Example 2
The preparation method of this example includes the following steps:
a. dispersing graphene in NMP to prepare a dispersion liquid with the concentration of 1%;
b. enabling the dispersion liquid to pass through a filter element structure for 2 hours according to the volume of 0.5L/h, wherein the material of a filter material layer of the used filter element is polyurethane melt-blown fiber; calculating the weight gain Δ M =27.8g of the filter element; at the moment, the mass ratio of the graphene to the polyurethane filter layer is 1:8.6.
c. b, taking down the filter element obtained in the step b, cutting a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A, and uniformly mixing the mixture A in a mixer;
d. and (3) performing melt extrusion granulation on the mixture A through an extruder, wherein the temperature interval of the extruder is as follows: the temperature of the conveying section is 140 ℃, and the temperatures of the melting section, the mixing section, the exhaust section and the homogenizing section are all 180 ℃.
Example 3
The preparation method of the embodiment comprises the following steps:
a. dispersing the carbon nano tube in DMF to prepare a dispersion liquid with the concentration of 2 percent;
b. enabling the dispersion liquid to pass through the filter element structure for 1h at the flow speed of 0.5L/h, wherein the filter material layer of the used filter element is polyvinyl chloride melt-blown fiber; calculating the weight gain Δ M =30.1g of the filter element; at the moment, the mass ratio of the carbon nano tube to the polyvinyl chloride filter layer is 1:8.1.
c. b, taking down the filter element obtained in the step b, cutting a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A, and uniformly mixing the mixture A in a mixer;
d. and (2) performing melt extrusion granulation on the mixture A through an extruder, wherein the temperature interval of the extruder is as follows: the temperature of the conveying section is 150 ℃, and the temperatures of the melting section, the mixing section, the exhaust section and the homogenizing section are all 180 ℃.
Example 4
The preparation method of this example includes the following steps:
a. dispersing graphene nanoplatelets prepared by a mechanical stripping method in methanol to prepare a dispersion liquid with the concentration of 1%;
b. the dispersion liquid passes through the filter element structure for 2 hours according to the volume ratio of 2L/h, and the filter material layer of the used filter element is polypropylene melt-blown fiber; calculating the weight gain Δ M =32.2g of the filter element; at the moment, the mass ratio of the graphene microchip to the polypropylene filter layer by the mechanical stripping method is 1:9.3.
c. b, taking down the filter element obtained in the step b, cutting a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A;
d. the mixture A is mixed with an activator ZnCl 2 、CaCO 3 Mixing the materials according to the mass ratio of 1.
Example 5
The preparation method of this example includes the following steps:
a. dispersing graphene oxide in ethyl acetate to prepare a dispersion liquid with the concentration of 1%;
b. the dispersion liquid passes through the filter element structure for 3 hours according to the volume ratio of 1L/h, and the filter material layer of the used filter element is polyvinyl chloride melt-blown fiber; calculating the weight gain delta M =29.6g of the filter element; at the moment, the mass ratio of the graphene oxide to the polypropylene filter layer is 1:10.2.
c. taking down the filter element obtained in the step b, cutting a filter material layer, taking the filter material layer and crushing the filter material layer to obtain a mixture A;
d. and mixing the mixture A with an activating agent KOH according to the mass ratio of 1:2, and carrying out heat treatment for 3h under the temperature condition of 700 ℃ in an inert atmosphere to obtain the graphene/porous carbon composite material, wherein an SEM image of the graphene/porous carbon composite material is shown in FIG. 3.
Example 6
The preparation method of the embodiment comprises the following steps:
a. dispersing the carbon nano tube in water to prepare a dispersion liquid with the concentration of 0.5 percent;
b. enabling the dispersion liquid to pass through a filter element structure for 2 hours according to the volume ratio of 0.5L/h, wherein a filter material layer of the used filter element is polyurethane melt-blown fiber; calculating the weight gain Δ M =22.7g of the filter element; at the moment, the mass ratio of the carbon nano tube to the polypropylene filter layer is 1:12.3.
c. b, taking down the filter element obtained in the step b, cutting a filter material layer of the filter element, taking the filter material layer and crushing the filter material layer to obtain a mixture A;
d. and mixing the mixture A with activating agents NaOH and MgO according to the mass ratio of 1.
Comparative example 1
The preparation method of comparative example 1 includes the following steps: and (3) weighing the graphene oxide powder and the pure polypropylene master batch according to the mass ratio of 1.
Comparative example 2
The preparation method of the present comparative example 2 includes the steps of: according to the mass ratio of the graphene oxide to the polyvinyl chloride filter layer of 1:10.2 weighing the graphene oxide powder and the pure polyvinyl chloride master batch, dry-mixing and uniformly mixing, and then preparing the graphene/porous carbon composite material according to the step d of the embodiment 5, wherein an SEM picture is shown in figure 4.
Next, the surface resistance and mechanical property tests (10 sample bars are respectively tested, and the average value is the test result) are performed on the functional master batches obtained in examples 1 to 3 and comparative example 1, and the average deviation of each property is calculated; the porous carbon composites obtained in examples 4 to 6 and comparative example 2 were subjected to a specific surface area (BET) test, a conductivity test, a specific capacity of a supercapacitor, and a 4hr rate discharge test of a lead-carbon battery. The test results are shown in Table 1.
The surface resistance test method refers to the following steps: GB/T15662-1995 test method for volume resistivity of conductive and antistatic plastics GBT15662-1995 test method for volume resistivity of conductive and antistatic plastics;
the mechanical property test method refers to: GBT 1843-2008 plastic cantilever beam impact strength;
test reference for porous carbon material: measuring the pore volume specific surface area by a GB/T7702.20-2008 coal granular activated carbon test method; the conductivity adopts a four-probe powder conductivity tester; the specific capacity of the super capacitor is tested by a blue light tester at a sweep speed of 1 mV/s; and (4) detecting the 4hr discharge rate of the lead-carbon battery by referring to the GB/T36280-2018 lead-carbon battery for power energy storage.
TABLE 1
As can be seen from the data in Table 1, in the examples 1 to 3, compared with the comparative example 1, the parallelism of the limit test results of the surface resistance and the notch impact strength of each sample strip in the examples is better, and the average deviation is obviously smaller than that of the comparative example, which shows that the two composite materials obtained in the examples are more uniform, and the dispersion uniformity of the dispersion phase obtained by adopting the method is obviously improved. Examples 4 to 6 have higher electrical conductivity than comparative example 2, which shows that the carbon material has a significant effect of improving the electrical conductivity of the porous carbon material when the carbon material is doped into the bulk phase of the porous carbon material. As can be seen by comparing with fig. 3 and 4, in the composite material prepared in comparative example 2, two phases of the lamellar graphene and the porous carbon in the microstructure exist separately, and the composite material in the microscale is not formed, whereas in the graphene/porous carbon composite material prepared in example 5, the graphene in the lamellar structure is inserted into the porous material, which is beneficial to greatly improve the uniformity of the dispersion of the carbon material in the porous carbon material.
Claims (8)
1. A preparation method of a carbon composite material takes a carbon material as a dispersion phase, wherein the carbon material adopts at least one of graphene, graphene oxide, graphene nanoplatelets prepared by a mechanical stripping method or carbon tube powder, and is characterized by comprising the following steps:
a. dispersing a carbon material in a liquid dispersion medium to prepare a dispersion liquid;
b. passing the dispersion through a filter element arrangement;
c. b, taking the filter material layer of the filter element obtained in the step b, and crushing to obtain a mixture A;
d. and (3) preparing the mixture A into the carbon composite material by extrusion granulation or heat treatment.
2. The method for producing a carbon composite material according to claim 1, wherein the dispersion medium is one or a mixture of two or more of water, DMF, NMP, methanol, and ethyl acetate.
3. The method for preparing the carbon composite material according to claim 1, wherein the filter element is a melt-blown filter element, and a filter material layer of the filter element is made of polypropylene, polyvinyl chloride or polyurethane.
4. The method for preparing the carbon composite material according to claim 1, wherein an extruder is used for the extrusion granulation in the step d, wherein the temperature interval of the extruder is as follows: the temperature of the conveying section is 140-150 ℃, and the temperatures of the melting section, the mixing section, the exhaust section and the homogenizing section are all 180-200 ℃.
5. The method of claim 1, wherein the mixture is mixed with an activator prior to the heat treatment in step d.
6. The method for producing a carbon composite material according to claim 5, wherein the activator is KOH, naOH, or ZnCl 2 、CaCO 3 And MgO or a mixture of two or more thereof.
7. The method of preparing a carbon composite according to claim 1 or 5, wherein the heat treatment process in the step d is performed under an inert atmosphere.
8. The method for preparing a carbon composite material according to claim 1 or 5, wherein the heat treatment temperature in the step d is 700 to 1100 ℃.
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Patent Citations (6)
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| CN102807737A (en) * | 2012-08-07 | 2012-12-05 | 上海交通大学 | Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material |
| CN105366658A (en) * | 2015-11-13 | 2016-03-02 | 哈尔滨工程大学 | Method for preparing porous carbon for super capacitor by waste plastic carbonization |
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