CN116947033A - High-resilience graphite foam/carbon nano tube composite material and preparation method thereof - Google Patents
High-resilience graphite foam/carbon nano tube composite material 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 164
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 74
- 239000010439 graphite Substances 0.000 title claims abstract description 74
- 239000006260 foam Substances 0.000 title claims abstract description 71
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930192474 thiophene Natural products 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 230000005587 bubbling Effects 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000001307 helium Substances 0.000 claims abstract description 3
- 229910052734 helium Inorganic materials 0.000 claims abstract description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004090 dissolution Methods 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007906 compression Methods 0.000 abstract description 20
- 230000006835 compression Effects 0.000 abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 229910052786 argon Inorganic materials 0.000 description 15
- 238000005229 chemical vapour deposition Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000007667 floating Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 ethylene, propylene, benzene Chemical class 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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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
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a high-resilience graphite foam/carbon nano tube composite material and a preparation method thereof, wherein the method comprises the following steps: placing graphite foam into reaction equipment, dissolving ferrocene and thiophene into a solvent to serve as a reaction carbon source, and heating the reaction equipment to 800-1000 ℃ in helium or inert gas atmosphere; introducing a mixed gas of hydrogen and inert gas, and bubbling a reaction carbon source into reaction equipment from the mixed gas at a constant speed to react to obtain the graphite foam/carbon nano tube composite material. The method has extremely simple procedure and shorter reaction time, and particularly compared with the condition that the rebound quantity of a single graphite foam is less than 50% in 15% compression ratio, the graphite foam/carbon nano tube composite material has higher rebound quantity of 70% -90% in 15% compression ratio, and can reach more than 90% after 20 times of circulation in 15% compression ratio, and the rebound performance is greatly improved.
Description
Technical Field
The invention relates to the technical field of preparation of carbon nanotube materials, in particular to a high-resilience graphite foam/carbon nanotube composite material and a preparation method thereof.
Background
Carbon Nanotubes (CNTs) are seamless hollow nanoscale tubes formed by winding single-layer or multi-layer graphene sheets around a central axis according to a certain helix angle. The carbon nanotube as one-dimensional nanometer material has light weight, perfect hexagonal structure connection, many abnormal mechanical, electrical and chemical properties, such as extremely high strength, extremely high toughness and good electric and heat conductivity.
Currently, the preparation process of carbon nanotubes mainly includes Chemical Vapor Deposition (CVD), arc discharge, laser ablation, combustion flame, electrolysis, and the like.
The arc discharge method is simple and quick, the prepared carbon nano tube is straight, the crystallinity is high, but the yield is not high, and fullerene, graphite particles, amorphous carbon and other carbon particles are deposited on the cathode besides the carbon nano tube. And because the arc temperature is as high as 3000-3700 ℃, the formed carbon nanotubes can be sintered into a whole and sintered into a bundle, and a plurality of amorphous carbon impurities exist in the bundle, so that a plurality of defects are caused. The arc process is currently mainly used for producing single-walled carbon nanotubes. The selection of proper catalyst combination and content is one of the main directions of the research of preparing single-wall carbon nano tubes by an arc method.
The laser ablation method is a simple and effective new method for preparing the carbon nano tube. The former generates high temperature by arc discharge, and the latter generates high temperature by laser evaporation, compared with the arc method. The morphology of the obtained carbon nanotubes was similar to that obtained by the arc method, but the carbon nanotubes were of higher quality and no amorphous carbon appeared. The method is easy for continuous production, but the prepared carbon nano tube has low purity, is easy to tangle, and requires an expensive laser with high cost.
Chemical Vapor Deposition (CVD) is a widely used method in which hydrocarbons (e.g., methane, ethylene, propylene, benzene, etc.) or carbon-containing oxides (e.g., CO) are cracked into carbon atoms under the catalysis of a catalyst, and the carbon atoms adhere to the surfaces of the catalyst particles under the action of the catalyst to form carbon nanotubes. The method has the advantages of simple operation, easier control of technological parameters, relatively lower growth temperature, low cost and large yield, and can be used for large-scale production. However, since the carbon nanotubes prepared therefrom contain many impurities and the carbon nanotubes are entangled into micro-sized large clusters, further purification and dispersion treatment are required.
Floating catalytic method (FCCVD) is used as one of chemical vapor deposition, and is characterized by that it adopts organic metal compound such as ferrocene, etc. as catalyst, and is dissolved in hydrocarbon solution such as benzene, the catalyst is fed into reactor together with hydrocarbon solution, and the catalyst granules are formed by using carrier gas (such as H) 2 ) In (a) and (b) are provided. The floating catalysis method can improve the catalysis efficiency of the metal catalyst and prolong the service life of the catalyst, so that the density and the length of the grown carbon nano tube are greatly increased, and the continuous preparation can be realized.
Graphite Foam (GF), which is a representative of porous carbon materials, has many other types of materials that do not possess particular physicochemical properties such as low density, high strength, high electrical and thermal conductivity, good thermal stability, high adsorptivity, and high specific surface area due to its unique three-dimensional porous structure and excellent properties. However, at the same time, the graphite foam has some disadvantages, such as poor rebound performance, and if the rebound performance of the graphite foam can be improved, the application field of the graphite foam can be further expanded, and the application value of the graphite foam can be improved.
Disclosure of Invention
In order to improve the rebound resilience of the graphite foam, the invention introduces carbon nano tubes into the graphite foam. The carbon nano tube grows in the pore wall of the graphite foam, more nano-level micropores can be formed in the graphite foam pores by utilizing the one-dimensional structure of the carbon nano tube in a crossing way, and a network structure which is connected with each other is constructed, so that the carbon nano tube can rebound rapidly due to the compressibility of the network structure in the compression process of the graphite foam, and a very high rebound quantity is obtained.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a high-resilience graphite foam/carbon nano tube composite material comprises the following steps of
Placing graphite foam into reaction equipment, dissolving ferrocene and thiophene into a solvent to serve as a reaction carbon source, and heating the reaction equipment to 800-1000 ℃ in helium or inert gas atmosphere;
introducing a mixed gas of hydrogen and inert gas, and bubbling a reaction carbon source into reaction equipment from the mixed gas at a constant speed to react to obtain the graphite foam/carbon nano tube composite material.
Further, the concentration of the ferrocene after dissolution is 1-9g/L.
Further, the concentration of the thiophene after dissolution is 0-10ml/L (not 0).
Further, the flow rate of the mixed gas is 0.1-0.2L/min.
Further, the temperature rising rate of the reaction equipment is 0-10 ℃/min (not 0).
Further, the reaction equipment is a horizontal tube furnace.
Further, the reaction time is 1-5h.
Further, in the mixed gas of the hydrogen and the inert gas, the inert gas is hydrogen= (0.25-4) 1 according to the volume ratio.
Further, the solvent includes cyclohexane or n-hexane.
Based on the same technical conception, the invention also provides a high-resilience graphite foam/carbon nano tube composite material which is prepared by the preparation method.
Compared with the prior art, the invention has the following positive effects:
according to the invention, a floating catalysis method is adopted, cyclohexane is used as a carbon source, ferrocene is used as a catalyst precursor, thiophene is used as an additive to promote the growth of carbon nanotubes, the temperature is raised to 800-1000 ℃ at a heating rate of 10 ℃/min, the temperature is kept for 1-5h, the graphite foam/carbon nanotube composite material is obtained, the process is extremely simple, the reaction time is shorter, and especially compared with the condition that the rebound quantity of a single graphite foam is less than 50% in 15% compression ratio, the graphite foam/carbon nanotube composite material has higher rebound quantity of 70% -90% in 15% compression ratio, and can reach more than 90% after 20 times of circulation in 15% compression ratio, so that the rebound quantity can be greatly improved. And secondly, the invention uses the horizontal tube furnace reaction equipment, and the outlet is provided with the tail gas recovery device, so that the invention is environment-friendly and saves cost.
Therefore, the invention has the characteristics of simple process, low equipment cost, environmental protection, excellent rebound resilience performance and good cycle performance of the prepared composite material.
Drawings
FIG. 1 is a graph showing the cycle resilience performance of the graphite foam/carbon nanotube composite material prepared in example 1;
FIG. 2 is a graph showing the cycle resilience performance of the graphite foam/carbon nanotube composite material prepared in example 2;
FIG. 3 is a graph showing the cycle resilience performance of the graphite foam/carbon nanotube composite material prepared in example 3;
FIG. 4 is a graph of the cyclic resilience of a graphite foam;
FIG. 5 is an electron microscope scan of the composite materials prepared in example 4 and comparative example 1;
FIG. 6 is a graph showing the recycling elastic energy of the composite materials prepared in example 4 and comparative example 1.
Detailed Description
The invention is further described below in connection with the drawings and the detailed description, without limiting the scope thereof.
Example 1
A preparation method of a high-resilience graphite foam/carbon nano tube composite material. The preparation method of the embodiment comprises the following specific steps:
step one: graphite foam was placed in a constant temperature zone of a horizontal tube furnace reaction apparatus, analytically pure ferrocene (concentration 1g/L after dissolution) and analytically pure thiophene (concentration 5ml/L after dissolution) were dissolved in cyclohexane as a reaction carbon source, and the horizontal tube furnace reaction apparatus was heated to a reaction temperature of 850 ℃ at a heating rate of 10 ℃/min under an argon atmosphere.
Step two: introducing mixed gas of hydrogen and argon, wherein the volume ratio of the argon to the hydrogen is 2:1, the flow rate of the mixed gas is 0.1L/min, bubbling the reacted carbon source into a constant temperature area of a horizontal tube furnace from the mixed gas of the hydrogen and the argon at a constant speed for reaction, and preserving heat for 1h to finally obtain the graphite foam/carbon nano tube composite material.
The graphite foam/carbon nanotube composite material prepared in this example has a cyclic resilience performance as shown in fig. 1, and the compression amount per time is 15%.
Example 2
A preparation method of a high-resilience graphite foam/carbon nano tube composite material under cyclic compression. The preparation method of the embodiment comprises the following specific steps:
step one: graphite foam was placed in a constant temperature zone of a horizontal tube furnace reaction apparatus, analytically pure ferrocene (concentration 5g/L after dissolution) and analytically pure thiophene (concentration 1ml/L after dissolution) were dissolved in cyclohexane as a reaction carbon source, and the horizontal tube furnace reaction apparatus was heated to a reaction temperature of 950 ℃ at a heating rate of 10 ℃/min under an argon atmosphere.
Step two: introducing mixed gas of hydrogen and argon, wherein the volume ratio of the argon to the hydrogen is=3:1, the flow rate of the mixed gas is 0.2L/min, bubbling the mixed gas of the hydrogen and the argon into a constant temperature area of a horizontal tube furnace for reaction at a constant speed, and preserving heat for 5 hours to finally obtain the graphite foam/carbon nano tube composite material.
The graphite foam/carbon nanotube composite material prepared in this example has a cyclic resilience performance as shown in fig. 2, and the compression amount per time is 15%.
Example 3
A preparation method of a graphite foam/carbon nano tube composite material. The preparation method of the embodiment comprises the following specific steps:
step one: graphite foam was placed in a constant temperature zone of a horizontal tube furnace reaction apparatus, analytically pure ferrocene (concentration 7g/L after dissolution) and analytically pure thiophene (concentration 10ml/L after dissolution) were dissolved in n-hexane as a reaction carbon source, and the horizontal tube furnace reaction apparatus was heated to a reaction temperature of 900 ℃ at a heating rate of 2 ℃/min under an argon atmosphere.
Step two: introducing mixed gas of hydrogen and argon, wherein the volume ratio of the argon to the hydrogen is=4:1, the flow rate of the mixed gas is 0.15L/min, bubbling the reaction carbon source into a constant temperature area of a horizontal tube furnace from the mixed gas of the hydrogen and the argon at a constant speed for reaction, and preserving heat for 3 hours to finally obtain the graphite foam/carbon nano tube composite material.
The graphite foam/carbon nanotube composite material prepared in this example has a cyclic resilience performance as shown in fig. 3, and the compression amount per time is 15%.
Example 4
A preparation method of a graphite foam/carbon nano tube composite material. The preparation method of the embodiment comprises the following specific steps:
step one: graphite foam was placed in a constant temperature zone of a horizontal tube furnace reaction apparatus, analytically pure ferrocene (concentration 9g/L after dissolution) and analytically pure thiophene (concentration 4ml/L after dissolution) were dissolved in cyclohexane as a reaction carbon source, and the horizontal tube furnace reaction apparatus was heated to a reaction temperature of 1000 ℃ at a heating rate of 8 ℃/min under an argon atmosphere.
Step two: introducing mixed gas of hydrogen and argon, wherein the volume ratio of the argon to the hydrogen is=1:1, the flow rate of the mixed gas is 0.12L/min, bubbling the reaction carbon source into a constant temperature area of a horizontal tube furnace from the mixed gas of the hydrogen and the argon at a constant speed for reaction, and preserving heat for 2 hours to finally obtain the graphite foam/carbon nano tube composite material.
Example 5
A preparation method of a graphite foam/carbon nano tube composite material. The preparation method of the embodiment comprises the following specific steps:
step one: graphite foam was placed in a constant temperature zone of a horizontal tube furnace reaction apparatus, analytically pure ferrocene (concentration 3g/L after dissolution) and analytically pure thiophene (concentration 8ml/L after dissolution) were dissolved in cyclohexane as a reaction carbon source, and the horizontal tube furnace reaction apparatus was heated to a reaction temperature of 800 ℃ at a heating rate of 5 ℃/min under an argon atmosphere.
Step two: introducing mixed gas of hydrogen and argon, wherein the volume ratio of the argon to the hydrogen is=0.25:1, the flow rate of the mixed gas is 0.18L/min, bubbling a reaction carbon source into a constant temperature zone of a horizontal tube furnace from the mixed gas of the hydrogen and the argon at a constant speed for reaction, and preserving the heat for 4 hours to finally obtain the graphite foam/carbon nano tube composite material.
FIG. 4 is a graph of 15% compression cycle resilience performance of a single graphite foam material, with a single graphite foam material initially compressed, less than 50% rebound at 15% compression, and less than 5 cycles of compression, with almost no rebound. In order to improve the rebound resilience performance, the invention synthesizes the graphite foam/carbon nano tube composite material by adopting a floating catalysis method, and referring to figures 1-3, the extremely high rebound resilience of 70% -90% can be realized under 15% compression, and the rebound resilience of 90% can be still reached after 20 times of circulation under 15% compression, wherein 15% compression is based on the thickness of the material after the last compression rebound. Secondly, the length and the density of the carbon nano tube prepared by the traditional chemical vapor deposition technology are limited, and the invention can greatly improve the length and the density of the carbon nano tube by adopting a floating catalysis method, has shorter reaction time, and is very beneficial to industrial production.
Comparative example 1
Preparing a graphite foam/carbon nano tube composite material by adopting a common chemical vapor deposition method, namely placing the graphite foam into a chemical vapor deposition reaction tube furnace, introducing hydrogen, taking methane as a precursor in a hydrogen atmosphere, performing chemical vapor deposition reaction for 30min, and cooling to obtain the graphite foam/carbon nano tube composite material.
The materials prepared in example 4 and comparative example 1 were subjected to electron microscopy, and the results are shown in fig. 5, in which,
FIG. a is a 150 XSEM image of a graphite foam/carbon nanotube composite material prepared in example 4 (FCCVD method);
FIG. b is a 500 XSEM image of a graphite foam/carbon nanotube composite material prepared in example 4 (FCCVD method);
FIG. c is a 110 SEM image of a graphite foam/carbon nanocomposite tube material prepared according to comparative example 1 (CVD method);
FIG. d is a 500-fold SEM image of a graphite foam/carbon nanocomposite tube material prepared in comparative example 1 (CVD process);
as can be seen from the figure, the cell structure of the graphite foam of example 4 is filled with a large number of carbon nanotubes, the cell structure is substantially encapsulated, and as can be seen from the enlarged SEM image, the cell structure is substantially invisible. Although a certain amount of carbon nanotubes grew in the graphite foam of comparative example 1, the cell structure of the graphite foam was clearly seen, and it can also be seen from the enlarged SEM image that the cell structure was not completely covered with carbon nanotubes. Therefore, if the graphite foam/carbon nano tube composite material is prepared by adopting the CVD method, the growth effect of the carbon nano tube is not ideal, the growth amount is small, the length and the density are small, and the effect of improving the elasticity is limited.
FIG. 6 is a graph showing the recycling elastic energy curves of the materials prepared in example 4 and comparative example 1 at 15% compression; it can be seen that the composite material prepared in example 4 has significantly higher compression resilience than the material of comparative example 1 for the first few times, and that the composite material prepared in example 4 has better rebound performance after 10 cycles.
In conclusion, the specific embodiment has the characteristics of simple process, low production cost and environmental friendliness, and the prepared graphite foam/carbon nano tube composite material has excellent rebound resilience.
The foregoing description of the embodiments of the present invention is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the foregoing embodiments according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a high-resilience graphite foam/carbon nano tube composite material is characterized by comprising the steps of placing graphite foam in reaction equipment, dissolving ferrocene and thiophene in a solvent to serve as a reaction carbon source, and heating the reaction equipment to 800-1000 ℃ in helium or inert gas atmosphere;
introducing a mixed gas of hydrogen and inert gas, and bubbling a reaction carbon source into reaction equipment from the mixed gas at a constant speed to react to obtain the graphite foam/carbon nano tube composite material.
2. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the concentration of ferrocene after dissolution is 1-9g/L.
3. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the concentration of the thiophene after dissolution is 0-10ml/L.
4. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the flow rate of the mixed gas is 0.1-0.2L/min.
5. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the reaction equipment has a heating rate of 0-10 ℃/min.
6. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the reaction equipment is a horizontal tube furnace.
7. The method for preparing a high resilience graphite foam/carbon nanotube composite material according to claim 1, wherein the reaction time is 1 to 5 hours.
8. The preparation method of the high-resilience graphite foam/carbon nano tube composite material according to claim 1, wherein the volume ratio of the inert gas to the hydrogen= (0.25-4) 1 in the mixed gas of the hydrogen and the inert gas.
9. The method of claim 1, wherein the solvent comprises cyclohexane or n-hexane.
10. A high resilience graphite foam/carbon nanotube composite material, characterized by being prepared by the preparation method according to any one of claims 1 to 9.
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