CN114408907A - Carbon black-based graphene and preparation method and application thereof - Google Patents
Carbon black-based graphene and preparation method and application thereof Download PDFInfo
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- 239000006229 carbon black Substances 0.000 title claims abstract description 187
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004202 carbamide Substances 0.000 claims abstract description 45
- -1 polyethylene Polymers 0.000 claims abstract description 45
- 238000005087 graphitization Methods 0.000 claims abstract description 39
- 239000004698 Polyethylene Substances 0.000 claims abstract description 35
- 229920000573 polyethylene Polymers 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 238000009830 intercalation Methods 0.000 claims abstract description 23
- 230000002687 intercalation Effects 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 46
- 150000004706 metal oxides Chemical group 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
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- 229910052742 iron Inorganic materials 0.000 description 5
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 239000002699 waste material Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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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
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
Abstract
The invention discloses carbon black-based graphene and a preparation method and application thereof. The preparation method of the carbon black-based graphene comprises the following steps: s1, carrying out catalytic graphitization treatment on the carbon black to obtain graphitized carbon black; s2, adding urea into the graphitized carbon black, grinding to enable the graphitized carbon black to be stripped and form an intercalation compound with the urea; the mass ratio of the graphitized carbon black to the urea is (3-10) to 1; s3, calcining the intercalation compound at the temperature of 300-500 ℃ to form the carbon black-based graphene. The preparation method is simple to operate, can reduce the preparation cost of the graphene, and is beneficial to large-scale production of the graphene. The prepared carbon black-based graphene has good dispersibility in polyethylene and high reinforcement, and the resistance of the high polymer material can be greatly reduced by the carbon black-based graphene with a low dosage.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to carbon black-based graphene and a preparation method and application thereof.
Background
The graphene is sp2The new material which is formed by tightly stacking hybridized and connected carbon atoms into a single-layer two-dimensional honeycomb lattice structure has the advantages of large specific surface area, excellent conductivity, high flexibility and the like, and is widely applied to conductivityPolymer materials, energy storage and conversion, electronic devices, sensors, biomedicine and other fields.
At present, the raw materials for preparing graphene mainly comprise natural graphite and carbon-containing gas (CH)4、C2H4Etc.) or a carbon-containing organic oligomer. However, the natural graphite has high impurity content and complex components, needs additional purification steps, is complex in purification steps, increases the preparation cost of the graphene, and is not beneficial to large-scale production of the graphene. The method for preparing graphene by using carbon-containing gas or carbon-containing organic oligomer mostly adopts a vapor deposition method, but has the problems of low graphene yield, raw material waste and the like, and can also increase the preparation cost of graphene, thereby being beneficial to large-scale production of graphene.
The carbon black has the advantages of high carbon content, high purity, low impurity content and the like, and no report of preparing the graphene by taking the carbon black as a raw material is found at present, so that the application provides the method for preparing the carbon black-based graphene by taking the carbon black as the raw material.
Disclosure of Invention
In order to reduce the preparation cost of graphene and facilitate large-scale production of graphene, the application provides carbon black-based graphene and a preparation method and application thereof.
In a first aspect, the present application provides a method for preparing carbon black-based graphene, which is implemented by adopting the following technical scheme:
a preparation method of carbon black-based graphene comprises the following steps:
s1, carrying out catalytic graphitization treatment on the carbon black to obtain graphitized carbon black;
s2, adding urea into the graphitized carbon black, grinding to enable the graphitized carbon black to be stripped and form an intercalation compound with the urea; the mass ratio of the graphitized carbon black to the urea is (3-10) to 1;
s3, calcining the intercalation compound at the temperature of 300-500 ℃ to form the carbon black-based graphene.
By adopting the technical scheme, the carbon content of the carbon black is increased after the carbon black is subjected to catalytic graphitization treatment, and urea molecules easily enter the sheet layer of the graphitized carbon black to form a graphitized carbon black stacking body under the auxiliary action of mechanical grinding, so that the graphitized carbon black is partially stripped, and the particle size of the graphitized carbon black is reduced.
The mass ratio of the graphitized carbon black to the urea is controlled to be (3-10):1, and the urea mainly exists between layers of the graphitized carbon black and can play an effective intercalation role; when heated at high temperature, urea is rapidly decomposed to generate a large amount of ammonia gas and carbon dioxide, and the urea decomposition further expands the graphitized carbon black subjected to grinding treatment and is further stripped to form ultrathin oligo-layer graphene.
The intercalation compound is a urea intercalation graphitized carbon black compound, the calcination temperature of the intercalation compound is controlled to be 300-500 ℃, urea can be thoroughly decomposed, the stripping effect and the volume expansion rate of the graphitized carbon black are improved, and the loss on ignition of the graphitized carbon black in the calcination process can be reduced.
The preparation method of the carbon black-based graphene is simple to operate, the yield of the prepared carbon black-based graphene is high, and the problem of raw material waste is basically solved; the carbon black is used as a raw material, the carbon black has the advantages of wide material source, high carbon content, high purity, low impurity content and the like, a purification step is not needed, the preparation cost of the graphene can be reduced, and the large-scale production of the graphene is facilitated; the carbon black is subjected to catalytic graphitization treatment, and is subjected to grinding intercalation and thermal expansion to prepare a carbon black-based graphene material, meanwhile, the carbon black has a nano microcrystalline structure, and the prepared carbon black-based graphene material is thin in sheet layer and is flexibly curled to form a thin yarn-shaped irregular structure. The carbon black-based graphene has good dispersibility in polyethylene and high reinforcement, and the resistance of the high polymer material can be greatly reduced by the carbon black-based graphene with a low dosage.
Preferably, the mass ratio of the graphitized carbon black to the urea is 3.33: 1.
Preferably, the grinding is performed by ball milling with zirconia balls at the rotation speed of 450-550 rpm; the zirconia ball is formed by mixing a zirconia ball with the diameter of 5mm, a zirconia ball with the diameter of 3mm and a zirconia ball with the diameter of 1mm according to the mass ratio of 2:5: 3.
More preferably, the grinding is performed by ball milling with zirconia balls at the rotating speed of 500 rpm; the zirconia ball is formed by mixing a zirconia ball with the diameter of 5mm, a zirconia ball with the diameter of 3mm and a zirconia ball with the diameter of 1mm according to the mass ratio of 2:5: 3.
According to the method, the graphitized carbon black is partially stripped before calcination by adopting ball milling to form a urea intercalation graphitized carbon black compound, the ball milling rotating speed is controlled to be 500rpm, the diameter of a zirconia ball is controlled to be 5mm, and the mass ratio of the zirconia ball with the diameter of 5mm to the zirconia ball with the diameter of 1mm is controlled to be 2:5:3, so that the urea intercalation graphitized carbon black compound is favorably formed, the stability of the urea intercalation graphitized carbon black compound is improved, and the further stripping in subsequent calcination is favorably carried out to form carbon black-based graphene.
Preferably, the calcination temperature of the intercalated composite is 450 ℃.
Preferably, the step of S1 is:
mixing the catalyst and the carbon black according to the mass ratio (0.5-5) of 100, grinding, carrying out catalytic graphitization treatment for 1-5h in the nitrogen atmosphere at 1500-2500 ℃, and cooling to obtain the graphitized carbon black.
The mass ratio of the catalyst to the carbon black is controlled to be (0.5-5):100, the catalytic effect is good, the graphitization degree of the carbon black can be improved, and the graphitization treatment temperature can be reduced.
The temperature for catalytic graphitization is controlled to be 1500-2500 ℃, the graphitization degree of the carbon black is higher, the resistivity of the polyethylene/carbon black-based graphene compound can be reduced, and meanwhile, the required energy consumption is lower, so that the large-scale production of the carbon black-based graphene is facilitated.
According to the method, the catalytic graphitization treatment time is controlled to be 1-5h, the graphitization degree of the carbon black is high, the resistivity of the polyethylene/carbon black-based graphene compound can be reduced, the required energy consumption is low, the economic value is high, and the large-scale production of the carbon black-based graphene is facilitated.
Preferably, the time of the catalytic graphitization treatment is 2.5 h.
Preferably, the temperature of the catalytic graphitization treatment is 2300 ℃.
Preferably, the mass ratio of the carbon black to the catalyst is 100: 4.
In the application, the carbon black is selected from one or more of carbon black N330, carbon black N660 and carbon black N774.
In the present application, the catalyst is an iron-containing catalyst and/or a titanium-containing catalyst.
Preferably, the catalyst is an iron-containing catalyst.
In the application, the decomposition temperature of the iron-containing catalyst is lower than that of the titanium-containing catalyst, iron and carbon form an iron carbide intermediate to form a chain reaction, graphitization is realized at a lower temperature, iron volatilizes at a lower temperature, metal oxide residues are less, and the quality of catalytic graphitization is improved.
In a second aspect, the present application provides a carbon black-based graphene, which is implemented by using the following technical scheme:
the carbon black-based graphene is prepared by the method, and is an few-layer graphene.
In a third aspect, the present application provides an application of carbon black-based graphene, which is implemented by using the following technical scheme:
use of carbon black-based graphene for a polyethylene/carbon black-based graphene composite, the polyethylene/carbon black-based graphene composite comprising polyethylene and carbon black-based graphene.
Preferably, the mass ratio of the carbon black-based graphene to the polyethylene is 1 (10-30); more preferably, the mass ratio of the carbon black-based graphene to the polyethylene is 1: 10.
The carbon black-based graphene prepared by the application has good dispersibility in polyethylene and a strong reinforcing effect, and can greatly reduce the resistance of polyethylene/carbon black-based graphene compound under a lower addition amount.
In summary, the present application has the following beneficial effects:
1. according to the preparation method of the carbon black-based graphene, the carbon black is subjected to catalytic graphitization treatment, and the carbon black-based graphene material is prepared through grinding intercalation and thermally induced expansion, so that the operation is simple, the yield of the prepared carbon black-based graphene is high, and the problem of raw material waste is basically avoided; the carbon black is used as a raw material, the carbon black has the advantages of wide material source, high carbon content, high purity, low impurity content and the like, a purification step is not needed, the preparation cost of the graphene can be reduced, and the large-scale production of the graphene is facilitated; meanwhile, the carbon black has a nano microcrystalline structure, and the carbon black is subjected to graphitization treatment, grinding intercalation and expansion stripping treatment to prepare the carbon black-based few-layer graphene material more easily, so that the resistance of the high polymer material can be greatly reduced by the carbon black-based graphene with a lower dosage.
2. The mass ratio of the graphitized carbon black to the urea is controlled to be (3-10):1, and the urea mainly exists between layers of the graphitized carbon black and can play an effective intercalation role; when heated at high temperature, urea is rapidly decomposed to generate a large amount of ammonia gas and carbon dioxide, and the graphitized carbon black is further expanded and further stripped to form ultrathin few-layer graphene by the decomposition of the urea.
3. According to the method, the calcination temperature of the intercalation compound is controlled to be 300-500 ℃, so that urea can be thoroughly decomposed, the stripping effect and the volume expansion rate of the graphitized carbon black are improved, and the loss on ignition of the graphitized carbon black in the calcination process can be reduced.
4. The mass ratio of the catalyst to the carbon black is controlled to be (0.5-5):100, the catalytic effect is good, the graphitization degree of the carbon black can be improved, and the graphitization treatment temperature can be reduced.
5. The temperature for catalytic graphitization is controlled to be 1500-2500 ℃, the catalytic graphitization treatment time is 1-5h, the graphitization degree of the carbon black is high, the resistivity of the polyethylene/carbon black-based graphene compound can be reduced, the required energy consumption is low, and the large-scale production of the carbon black-based graphene is facilitated.
6. The carbon black-based graphene prepared by the application has good dispersibility in polyethylene and a strong reinforcing effect, and can greatly reduce the resistance of polyethylene/carbon black-based graphene compound under a lower addition amount.
Drawings
FIG. 1 is an XRD pattern of the graphitized carbon black prepared in example 7;
FIG. 2 is an SEM image of the graphitized carbon black prepared in example 7;
fig. 3 is a TEM image of carbon black-based graphene prepared in example 15.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the present application are all commercially available;
wherein, the carbon black N330 and the carbon black N660 are purchased from Hebei ink Yu chemical Co., Ltd;
polyethylene, under the designation MB9500, was purchased from Shanghai super cyclone chemical technology, Inc.
Examples
Examples 1 to 16 provide a method for producing carbon black-based graphene, and example 1 is described below.
The preparation method of carbon black-based graphene provided in embodiment 1 includes the following steps:
s1, mixing 100g of carbon black N330 and 0.5g of ferric oxide uniformly, fully grinding uniformly, carrying out catalytic graphitization treatment at 1500 ℃ for 4h in a nitrogen atmosphere, and cooling to room temperature to obtain graphitized carbon black;
s2, adding 20g of urea into the graphitized carbon black prepared in the step 60g S1, uniformly mixing, and performing ball milling for 1h to form an intercalation compound; the specific operation of the ball milling is that zirconia balls with the diameter of 5mm, zirconia balls with the diameter of 3mm and zirconia balls with the diameter of 1mm are mixed according to the mass ratio of 2:5:3 and then are put into a ball mill, and the rotating speed of the ball mill is controlled to be 500 rpm;
s3, placing the intercalation compound prepared in the step S2 into a crucible (the loading capacity of the intercalation compound is lower than 1/3 of the capacity of the crucible), covering a crucible cover (not sealing), calcining for 1h at 300 ℃ in the air atmosphere, and cooling to room temperature to obtain the carbon black-based graphene.
Examples 2 to 4 differ from example 1 in the kind and quality of the catalyst used in the step S1, and are shown in Table 1.
TABLE 1 types and quality of catalysts in examples 1-4S1
| Examples | Example 1 | Example 2 | Example 3 | Example 4 |
| Kind of catalyst | Ferric oxide | Ferric oxide | Ferric oxide | Titanium dioxide |
| Quality of the catalyst | 0.5g | 5g | 4g | 4g |
| Mass ratio of carbon black to catalyst | 100:0.5 | 100:5 | 100:4 | 100:4 |
Examples 5 to 9, which are different from example 3 in the temperature and time of the catalytic graphitization treatment in the step S1, are shown in table 2.
TABLE 2 temperature and time for catalytic graphitization treatment in examples 3, 5-9S1 procedure
| Examples | Example 3 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| Temperature of | 1500℃ | 2500℃ | 2300℃ | 2300℃ | 2300℃ | 2500℃ |
| Time | 5h | 1h | 1h | 2.5h | 4h | 2.5h |
Example 10 was different from example 1 in that the mass of the catalyst was 0.3g, the temperature of the catalytic graphitization treatment was 2800 ℃, and the time of the catalytic graphitization treatment was 4 hours.
Example 11 differs from example 2 in that the mass of the catalyst was 6 g.
Examples 12 to 13 differ from example 7 in the quality of urea in the step S2, as shown in table 3.
TABLE 3 quality of urea in examples 7, 12-13S2
| Examples | Example 7 | Example 12 | Example 13 |
| Quality of urea | 20g | 6g | 18g |
| Mass ratio of graphitized carbon black to urea | 3:1 | 10:1 | 3.33:1 |
Examples 14 to 15 differ from example 13 in the calcination temperature in the step S3, as shown in Table 4.
TABLE 4 calcination temperatures in examples 13-15S3
| Examples | Example 13 | Example 14 | Example 15 |
| Calcination temperature | 300℃ | 500℃ | 450℃ |
Example 16 is different from example 15 in that carbon black N660 is substituted for carbon black N330 and the like.
Comparative example
Comparative examples 1-2, which differ from example 1 in the quality of urea in the step S2, are shown in table 5.
TABLE 5 quality of urea in comparative examples 1-2S2
| Comparative example | Comparative example 1 | Comparative example 2 |
| Quality of urea | 30g | 3g |
| Mass ratio of graphitized carbon black to urea | 2:1 | 20:1 |
Comparative examples 3 to 4, which are different from example 1 in the calcination temperature in the step of S3, are shown in table 6.
TABLE 6 calcination temperatures in comparative examples 3-4S3
| Comparative example | Comparative example 3 | Comparative example 4 |
| Calcination temperature | 200℃ | 600℃ |
Application example
Application examples 1 to 16 provide a polyethylene/carbon black-based graphene composite, and the following description will take application example 1 as an example.
The preparation steps of the polyethylene/carbon black-based graphene composite provided in application example 1 are as follows:
uniformly mixing the carbon black-based graphene prepared in the example 1 with polyethylene according to the mass ratio of 1:10 to obtain a polyethylene/carbon black-based graphene compound.
Application examples 2 to 16 are different from application example 1 in the source of carbon black-based graphene, and are specifically shown in table 7.
Table 7 sources of application examples 1-16 carbon black based graphene
Comparative application
Application comparative examples 1 to 4 are different from application example 1 in that the carbon black-based graphene is derived from a different source, as shown in table 8.
Table 8 sources of carbon black based graphene using comparative examples 1-4
| Comparative application | Application comparative example 1 | Comparative application example 2 | Comparative application example 3 | Application comparative example 4 |
| Sources of carbon black-based graphene | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
Application comparative example 5 is different from application example 1 in that carbon black-based graphene and the like are replaced by carbon black N330.
Application comparative example 6, a polyethylene/conductive carbon black composite was prepared by the steps of:
and uniformly mixing the commercially available conductive carbon black and polyethylene according to the mass ratio of 3:5 to obtain the polyethylene/conductive carbon black compound.
Comparative application example 7 was different from comparative application example 6 in that the mass ratio of conductive carbon black to polyethylene was 1: 10.
Performance test
1. Metal oxide residue: whether metal oxide (ferric oxide or titanium dioxide) remains on the surfaces of the carbon black-based graphene described in examples 1 to 16 and comparative examples 1 to 4 is detected by a fluorescence analysis method, if the metal oxide residues are detected, the carbon black-based graphene is classified into 1 to 5 grades according to the relative content of the metal oxide, wherein the 1 grade represents that the relative content of the metal oxide is 0.01 to 0.02 wt%, the 2 grade represents that the relative content of the metal oxide is 0.02 to 0.04 wt% and is not equal to 0.02 wt%, the 3 grade represents that the relative content of the metal oxide is 0.04 to 0.07 wt% and is not equal to 0.04 wt%, the 4 grade represents that the relative content of the metal oxide is 0.07 to 0.1 wt% and is not equal to 0.07 wt%, and the 5 grade represents that the relative content of the metal oxide is more than 0.1 wt%, respectively, and the test results are shown in table 9.
TABLE 9 Metal oxide residue test results
2. Resistance: the polyethylene/carbon black-based graphene compound described in application examples 1-16, the polyethylene/carbon black-based graphene compound described in application comparative examples 1-4, and the polyethylene/carbon black compound described in application comparative examples 5-7 were pressed into test pieces with a diameter of 20mm, and the resistance value at 90 ℃ was measured by using a cable shielding layer resistivity tester according to the national standard GB11017-89 test method, and the test results are shown in Table 10.
TABLE 10 resistance test data
| Sample (I) | Resistance (omega cm) | Sample (I) | Resistance (omega cm) |
| Application example 1 | 2315 | Application example 13 | 1270 |
| Application example 2 | 1872 | Application example 14 | 885 |
| Application example 3 | 1865 | Application example 15 | 893 |
| Application example 4 | 2240 | Application example 16 | 895 |
| Application example 5 | 1297 | Application comparative example 1 | 2388 |
| Application example 6 | 1306 | Comparative application example 2 | 2870 |
| Application example 7 | 1278 | Comparative application example 3 | 3028 |
| Application example 8 | 1274 | Application comparative example 4 | 2104 |
| Application example 9 | 1272 | Comparative application example 5 | 5690 |
| Application example 10 | 1921 | Comparative application example 6 | 3580 |
| Application example 11 | 1865 | Application comparative example 7 | 4950 |
| Application example 12 | 1458 | / | / |
The following test data for tables 9 and 10 illustrate the present application in detail.
Compared with the experimental data of application example 1 and application comparative examples 5-7, the carbon black-based graphene prepared by the method has good dispersibility in polyethylene and strong reinforcing effect, and the resistance of the polyethylene/carbon black-based graphene compound can be greatly reduced by the carbon black-based graphene at a lower addition amount.
Comparing the experimental data of application example 1 and application comparative examples 1-2, it can be seen that the resistance of the polyethylene/carbon black-based graphene composite of application example 1 is lower than the resistance of the polyethylene/carbon black-based graphene composite of application comparative examples 1-2. The mass ratio of the graphitized carbon black to the urea in the application comparative example 2 is more than 10:1, the dosage of the urea is too small, and the urea is difficult to effectively intercalate and generate sufficient gas expansion pressure; the mass ratio of the graphitized carbon black to the urea in the application comparative example 1 is less than 3:1, the amount of the urea is too much, the urea not only exists between layers of the graphitized carbon black, but also a large amount of the urea is accumulated on the outer surface of the graphitized carbon black, and the urea accumulated on the outer surface of the graphitized carbon black can cause decomposition of ineffective gas when being heated at high temperature, which is not beneficial to expanding and stripping of graphitized carbon black sheets.
Comparing the experimental data of application example 1 and application comparative examples 3 to 4, it can be seen that the resistance of the polyethylene/carbon black-based graphene composite corresponding to application example 1 is lower than the resistance of the polyethylene/carbon black-based graphene composite corresponding to application comparative examples 3 to 4. The calcination temperature of the intercalation compound in the application comparative example 3 is lower than 300 ℃, the calcination temperature is too low, the urea is not completely decomposed, and the generated ammonia gas and carbon dioxide are less, so that the stripping effect of the graphitized carbon black is poor, and the volume expansion rate of the graphitized carbon black is also lower; the calcination temperature of the intercalation compound in the application comparative example 4 is higher than 500 ℃, the calcination temperature is too high, the loss on ignition of the graphitized carbon black in the calcination process is high, the yield of the carbon black-based graphene can be reduced, the urea is thoroughly decomposed early, the stripping effect and the expansion rate of the graphitized carbon black can not be improved basically, the energy consumption is high, and the large-scale production of the carbon black-based graphene is not facilitated.
Comparing the experimental data of application example 1 and application examples 10 to 11, it can be seen that in example 12, the mass ratio of the catalyst to the carbon black is greater than 5:100, the amount of the catalyst is too high, the metal oxide remains on the surface of the carbon black-based graphene, the graphitization degree of the carbon black is slightly improved but the influence is small, the resistance of the polyethylene/carbon black-based graphene composite is slightly reduced but the reduction is limited, but from the economic viewpoint, the preparation cost of the carbon black-based graphene can be increased, and the mass production of the carbon black-based graphene is not facilitated; in example 10, the mass ratio of the catalyst to the carbon black is less than 0.5:100, the catalyst dosage is too low, the carbon black graphitization catalysis effect is weak, the catalytic graphitization treatment temperature needs to be more than 2800 ℃, the energy consumption is high, the preparation cost of the carbon black-based graphene is increased from the economic viewpoint, and the large-scale production of the carbon black-based graphene is not facilitated.
Compared with the experimental data of application examples 3 or 4 and application examples 5-9, the carbon black catalytic graphitization treatment temperature is from 1500 ℃ to 2300 ℃, the catalytic graphitization degree can be obviously improved, the resistivity is reduced, the metal oxide residue is reduced, the temperature is further increased to 2500 ℃, the resistivity is slightly reduced but tends to be stable, and the economic value is low. The temperature is lower, and the graphitization degree is lower. The resistance is high and metal oxide remains after being treated for 5 hours at 1500 ℃. The heat preservation time of the carbon black catalytic graphitization treatment is prolonged, so that the graphitization degree of the carbon black can be improved, the time is further prolonged, the resistivity is slightly reduced but is not changed greatly, and the economic value is not great.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of carbon black-based graphene is characterized by comprising the following steps:
s1, carrying out catalytic graphitization treatment on the carbon black to obtain graphitized carbon black;
s2, adding urea into the graphitized carbon black, grinding to enable the graphitized carbon black to be stripped and form an intercalation compound with the urea; the mass ratio of the graphitized carbon black to the urea is (3-10) to 1;
s3, calcining the intercalation compound at the temperature of 300-500 ℃ to form the carbon black-based graphene.
2. The method for preparing carbon black-based graphene according to claim 1, wherein the mass ratio of the graphitized carbon black to the urea is 3.33: 1.
3. The method for preparing carbon black-based graphene according to claim 1 or 2, wherein the grinding is performed by ball milling using zirconia balls at a rotation speed of 450-; the zirconia ball is formed by mixing a zirconia ball with the diameter of 5mm, a zirconia ball with the diameter of 3mm and a zirconia ball with the diameter of 1mm according to the mass ratio of 2:5: 3.
4. The method of claim 1, wherein the intercalated compound is calcined at a temperature of 450 ℃.
5. The method for preparing carbon black-based graphene according to claim 1, wherein the step of S1 is:
mixing the catalyst and the carbon black according to the mass ratio (0.5-5) of 100, grinding, carrying out catalytic graphitization treatment for 1-5h in the nitrogen atmosphere at 1500-2500 ℃, and cooling to obtain the graphitized carbon black.
6. The method for preparing carbon black-based graphene according to claim 5, wherein the time for the catalytic graphitization treatment is 2.5 h.
7. The method for preparing carbon black-based graphene according to claim 5, wherein the temperature of the catalytic graphitization treatment is 2300 ℃.
8. The method for preparing carbon black-based graphene according to claim 5, wherein the mass ratio of the carbon black to the catalyst is 100: 4.
9. Carbon black-based graphene prepared according to any one of claims 1 to 8, wherein the carbon black-based graphene is an oligo-layer graphene.
10. A polyethylene/carbon black-based graphene composite, comprising polyethylene and the carbon black-based graphene prepared according to the method of any one of claims 1 to 8.
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