CN107215861B - carbon materials, preparation method thereof and device for preparing carbon materials - Google Patents

carbon materials, preparation method thereof and device for preparing carbon materials Download PDF

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CN107215861B
CN107215861B CN201710425358.2A CN201710425358A CN107215861B CN 107215861 B CN107215861 B CN 107215861B CN 201710425358 A CN201710425358 A CN 201710425358A CN 107215861 B CN107215861 B CN 107215861B
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graphite
container
carbon material
sagger
raw material
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CN107215861A (en
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安军伟
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Wulanchabu Dasheng Graphite New Material Co Ltd
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Wulanchabu Dasheng Graphite New Material Co Ltd
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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
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/30—Purity
    • 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
    • C01B2204/30—Purity
    • 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
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

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Abstract

The invention relates to devices for preparing carbon materials, which are containers with containing spaces, wherein the tops of the containers are provided with openings and are provided with detachable covers, the materials of the containers and the covers are high-density graphite, the invention also provides methods for preparing carbon materials by using the devices, and the methods comprise the following steps of (1) providing carbon material raw materials, (2) placing the carbon material raw materials in the containers, and carrying out high-temperature graphitization treatment on the containers filled with the carbon material raw materials at 1000-3800 ℃ to obtain the carbon materials, and the invention also provides carbon materials.

Description

carbon materials, preparation method thereof and device for preparing carbon materials
Technical Field
The invention relates to a carbon material, in particular to devices for preparing the carbon material, the carbon material and a preparation method thereof.
Background
The carbon material such as graphene and carbon nano tubes has excellent performance, and has wide application in mobile phone touch screens, conductive materials and the like, and the graphene is considered to be of key materials of high-performance conductive agents for power batteries.
The conventional methods for producing carbon nanotubes are typically CVD vapor deposition, arc deposition, etc., however, the carbon nanotubes produced by these methods have drawbacks.
The existing preparation methods of graphene include a chemical oxidation-reduction method, a mechanical stripping method, a CVD vapor deposition method, and the like. However, the graphene manufactured by these methods has drawbacks. For example, by using a chemical oxidation-reduction method, although graphene has a small thickness and a high single-layer rate, graphene is greatly damaged in an oxidation process, a cavity is generated, and other functional groups, a large amount of sulfur elements, iron, cobalt, nickel, manganese and other metal impurities are introduced, so that the conductivity of graphene is greatly affected, and the performance of the battery is damaged when the graphene is subsequently applied to the battery. The mechanical stripping method has the defects of thick graphene and more layers although the graphene has high conductivity, and the method has the following greatest problems: the adopted raw materials are crystalline flake graphite, expandable graphite or expanded worm graphite, when physical and mechanical stripping is carried out by liquid phase or gas phase and other methods, a large amount of sulfur elements and residual impurities such as iron, cobalt, nickel, manganese, potassium, calcium and the like are contained in the raw materials, and the content of the impurities greatly exceeds the standard, so that the performance of the battery is damaged. Although the obtained graphene has the characteristic of thin thickness of a single layer or a double layer and has extremely high conductivity by using a CVD vapor deposition method, since a substrate with a large amount of metallic nickel and the like is used and the substrate needs to be dissolved and peeled, the yield of the graphene is extremely low, and the graphene cannot be used for large-scale ton-level application.
Disclosure of Invention
In view of the above, it is necessary to provide kinds of apparatuses, methods, and materials for mass production of carbon materials having excellent conductivity.
The invention provides a device for preparing carbon material, which is a container with accommodating space, the top of the container is open and is provided with a detachable cover, and the materials of the container and the cover are high-density graphite.
Preferably, the inner wall of the container is provided with at least th through holes and a th hole sealing piece which is matched with the th through holes and can be detached, the th hole sealing piece is made of high-density graphite, the cover is provided with at least second through holes and a second hole sealing piece which is matched with the second through holes and can be detached, and the second hole sealing piece is made of high-density graphite.
Preferably, the high-density graphite is obtained by processing a graphite raw material at high temperature and high pressure, and the density of the high-density graphite is more than or equal to 1.85g/cm3。
Preferably, subjecting the graphite raw material to a high temperature, specifically, subjecting the graphite raw material to a pressure of 1 atm to 3.6 atm at a temperature of 2500 ℃ to 3000 ℃.
The invention also provides methods for preparing carbon material using the above apparatus, comprising the steps of:
(1) providing a carbon material raw material;
(2) and placing the carbon material raw material into the container, and carrying out high-temperature graphitization treatment on the container filled with the carbon material raw material at 1000-3800 ℃ to obtain the carbon material.
Preferably, the time of the high-temperature graphitization treatment in the step (2) is 10 hours to 1000 hours.
Preferably, the carbon material in step (1) is a carbon nanotube material or a graphite material.
Preferably, is further included before the step (2), wherein the step comprises oxidizing the graphite material to obtain graphite oxide, and then placing the graphite oxide in a sagger and reducing the graphite oxide at 1000-1100 ℃ in an inert atmosphere, wherein the sagger is made of high-density graphite.
Preferably, the sagger comprises a sagger body and a sagger cover, the top of the sagger body is an opening, the sagger cover is covered on the top of the sagger body, wherein,
the sagger body comprises an outer box wall body and an outer cavity formed by the outer box wall body, and the outer box wall body is provided with notches, so that the outer cavity is communicated with the outside;
the sagger body is also internally provided with an inner box, the inner box comprises an inner box wall body and an inner cavity formed by the inner box wall body, the top of the inner box is provided with an opening, and the inner cavity is communicated with the outer cavity;
the box cover comprises a box cover top and a box cover wall body, the box cover wall body is arranged in an outer cavity of the box body, and the height of the box cover wall body is smaller than that of the outer box wall body.
The invention also provides carbon materials prepared by the method, wherein the electrical conductivity of the carbon material is 3 x 104～1×106S/m, the structure of the carbon material is substantially free of defects.
Compared with the prior art, the material of the device for preparing the carbon material is high-density graphite, so that the device has the advantage of high temperature resistance. In particular, when the apparatus is used for high-temperature graphitization of a carbon material raw material, since the apparatus and the reaction raw material are both carbon elements, there is no problem of contamination of the vessel. And because the device can resist high temperature, the container is stable in the high-temperature graphitization process, and the service life is longer.
The th through-hole functions to communicate the inside of the apparatus with the outside, and discharge the foreign gas generated from the raw material to the outside during the process of preparing the carbon material, of course, the th through-hole is preferably provided in . the th through-hole may not be provided, that is, the discharge of the foreign gas may be accomplished through a minute gap between the inner wall of the container and the cover.
The device has simple structure, simple method for preparing the device, easily obtained raw materials and low price, and is suitable for large-scale industrial application.
When in use, carbon material raw materials are put into the device and then graphitized at high temperature to obtain the carbon material. Compared with a preparation container or a substrate used in the existing method, the device is made of high-density graphite, so that other additional impurities are avoided, and meanwhile, the device is used as a preparation space, so that powdery carbon material raw materials with low density can be well contained and relatively concentrated, and carbon materials can be produced in large batch.
The principle of the preparation method of the carbon material is as follows: the disordered carbon atoms are rearranged and structurally transformed by heat to form an orderly arranged carbon structure, and original structural defects in the carbon material raw material are effectively repaired. The carbon material raw material can be graphite raw material and carbon nano tube raw material. When the carbon material is a graphite raw material, the number of layers of the layered graphite in the graphite raw material can be reduced in the high-temperature graphitization process to obtain graphene with a small number of layers.
In the existing high-temperature graphitization process, the powdery carbon material raw material is light and easy to fly, so that high-temperature graphitization is difficult to perform to form the carbon material basically without structural defects. The preparation method is extremely convenient for inputting raw materials and collecting products, can realize large-scale preparation, and can realize hundred-ton-level preparation in practical application. In addition, in the preparation process, other raw materials are not required to be added, so that other impurities are not introduced; since no substrate or the like is used, peeling is not required. The whole preparation process has simple steps and high preparation efficiency.
The carbon material obtained by the preparation method has the advantages that the carbon material with basically no structural defects can be obtained by only carrying out high-temperature graphitization treatment on the carbon material raw material, the carbon material is basically free of defects, thin in thickness, extremely low in metal impurity content and high in conductivity, and the obtained carbon material can be applied to conductive paste and further used for preparing batteries in step .
Drawings
FIG. 1 is a schematic structural view of an apparatus for producing a carbon material according to the present invention.
Fig. 2 and 3 are cross-sectional views of the device of fig. 1 in different states.
FIG. 4 is a schematic structural view of the sagger of the present invention.
Fig. 5 is an exploded view of the sagger of fig. 4.
Fig. 6 is a schematic structural view of a sagger body of the sagger of fig. 4.
Fig. 7 is a schematic structural view of a lid of the sagger of fig. 4.
Fig. 8 is a Transmission Electron Microscope (TEM) photograph of the graphene powder obtained in example (1) of the present invention.
Fig. 9 is a TEM photograph of the graphene powder obtained in example (2) of the present invention.
Fig. 10 is a TEM photograph of the graphene powder obtained in comparative example (1).
Fig. 11 is a raman spectrum of the graphene powder obtained in example (1) of the present invention.
Fig. 12 is a raman spectrum of the graphene powder obtained in example (2) of the present invention.
Fig. 13 is a raman spectrum of the graphene powder obtained in comparative example (1).
Fig. 14 is an X-ray diffraction (XRD) pattern of the graphene powder obtained in example (1) of the present invention.
Fig. 15 is an XRD pattern of the graphene powder obtained in example (2) of the present invention.
Fig. 16 is an XRD pattern of the graphene powder obtained in comparative example (1).
FIG. 17 is a SEM photograph of the high purity carbon nanotube obtained in example (3).
FIG. 18 is a TEM photograph of the high-purity carbon nanotube obtained in example (3).
Wherein 1 denotes a container, 2 denotes an th through hole, 3 denotes an th hole sealing member, 4 denotes a lid, 4a denotes a second through hole, 4b denotes a second hole sealing member, 10 denotes a lid, 10a denotes a lid top, 10a1 denotes a top plate, 10a2 denotes a th recess, 10a3 denotes a second recess, 10b denotes a lid wall, 20 denotes a bowl body, 20a denotes an outer bowl wall, 20b denotes a notch, 20c denotes an outer cavity, 30 denotes an inner bowl, 30a denotes an inner cavity, 30b denotes an th baffle, and 30c denotes a second baffle.
The following specific embodiments further illustrate the present invention in conjunction with the above-described figures.
Detailed Description
The apparatus for preparing a carbon material, the carbon material and the method for preparing the same according to the present invention will be further described in with reference to the accompanying drawings.
The present invention provides apparatuses for preparing a carbon material, referring to fig. 1 to 3, the apparatuses are containers 1 having accommodating spaces, and the accommodating spaces of the containers 1 are used at sites for preparing the carbon material.
The shape of the container 1 is not limited as long as it has an accommodating space inside. Specifically, the container 1 may be shaped as a cylinder, a rectangular parallelepiped, or the like. Referring to fig. 1, in the present embodiment, the container 1 is a cylinder, and the cross section thereof is a circle.
Referring to fig. 1, the top of the container 1 is open, and a detachable cover 4 is fitted on the top of the container 1. the cover 4 is provided to facilitate the insertion of materials and the removal of products.
Referring to fig. 2, the inner wall of the container 1 may be provided with at least th through holes 2 and a th hole sealing member 3 detachably engaged with the th through holes 2, the number of the th through holes 2 is not limited, and may be , two, or more, the size of the th through holes 2 and the shape of the opening of the th through holes are not limited, the th through holes 2 are not limited in the specific position of the container 1 as long as the receiving space of the container 1 can communicate with the outside through the th through holes 2, for example, when the container 1 is shaped as a rectangular parallelepiped, the th through holes 2 may be formed in the top, bottom, or side wall of the container 1, and when the container 1 is shaped as a cylinder, the th through holes may be formed in the top or bottom of the container 1.
The th through-hole 2 functions to communicate the inside of the container 1 with the outside, and discharge the foreign gas generated from the raw material to the outside during the process of preparing the carbon material, of course, the th through-hole 2 is preferably , and the th through-hole 2 may not be provided, that is, the discharge of the foreign gas can be realized through the minute gap between the inner wall of the container 1 and the cover 4.
It is understood that when the diameter of the th through hole 2 is large, the th through hole 2 can be used for putting in raw materials and taking out products.
Optionally, the cover 4 may be provided with at least second through holes 4a and a second hole sealing member 4b disposed in cooperation with the second through holes 4a, the second hole sealing member 4b is detachably assembled with the second through holes 4a, the number, shape and size of the second through holes 4a are not limited, the second through holes 4a may be the same as or different from the through holes 2, and the second through holes 4a are disposed to facilitate communication between the accommodating space of the container 1 and the outside.
The detachable assembly of the cover 4 and the container 1, the th hole sealer 3 and the through hole 2, and the second hole sealer 4b and the second through hole 4a may refer to a screw connection, and of course, may refer to other detachable manners, which refer to a state where the two components are bodies from each other or a state where they are separated from each other, the th hole sealer 3 and the second hole sealer 4b may be bolts, etc., the th hole sealer 3 and the th hole sealer 4b and the second through hole 4a, and the cover 4 and the container 1 are assembled, and the containing space of the container 1 is not completely disconnected from the outside, and when the container 1 is placed in a high-temperature heating environment, the air and impurities or gas generated in the preparation process expand and slowly escape through the th hole sealer 2 and the th hole sealer 3, the second through hole sealer 4a and the second hole sealer 4b, and the gap between the top end of the container 1.
In this embodiment, the bottom of the container 1 is provided with the through hole 2 and the hole sealing piece 2a that sets up with the cooperation of through hole 2, the top of the container 1 is the opening, the opening cooperation of the container 1 is provided with lid 4, lid 4 still is provided with second through hole 4a and with the second through hole 4a complex second hole sealing piece 4b, through hole 2 and hole sealing piece 3, second hole sealing piece 4b and second through hole 4a, lid 4 with be all through threaded connection between the container 1, all be equipped with the internal thread portion on the inner wall of container 1, through hole 2, and second through hole 4a, correspondingly, the outer wall of lid 4, hole sealing piece 3, and second hole sealing piece 4b all is equipped with the external screw thread portion corresponding with the internal thread portion.
The container 1, the th hole sealing piece 3 and the second hole sealing piece 4b are all made of high-density graphite, the high-density graphite is obtained by processing a graphite raw material at 2400-3000 ℃ and applying pressure of 1-3.6 atmospheres to obtain the high-density graphite, preferably, the graphite raw material is processed at 2500-2800 ℃ and applying pressure of 3.6 atmospheres to obtain the high-density graphite, the graphite raw material is commercially available and is not described in detail herein, and after the graphite raw material is processed at high temperature and high pressure, a step of turning and milling is further performed to obtain the container 1 with a specific shape.
The device is specially used for in the preparation of the carbon material, can conveniently contain raw materials and prepare the carbon material on a large scale, has simple structure, easy preparation and lower cost, and is beneficial to industrial application.
The present invention also provides methods of making a carbon material using the above apparatus, the method comprising the steps of:
s1, providing a carbon material raw material;
s2, placing the carbon material into the container, and carrying out high-temperature graphitization treatment on the container filled with the carbon material at 900-3800 ℃ to obtain the carbon material.
In step S1, the graphite raw material may be a graphite ore obtained by direct mining, or a powdery substance obtained by purifying and/or pulverizing the graphite ore in step .
In step S2, the high temperature graphitization treatment is based on the principle that the disordered carbon atoms are rearranged and structurally transformed by heat to form an ordered carbon material, and the structural defects are effectively repaired, and the th and second through holes 2 and 4a of the device can be covered with silicon carbide to be sealed in the high temperature graphitization process.
In order to obtain a carbon material having more excellent conductivity, the temperature of the high-temperature graphitization treatment is preferably 900 to 3400 ℃.
The time of the high-temperature graphitization treatment is 10-1000 hours. The time for the high-temperature graphitization treatment is preferably 48 to 1000 hours in view of practical production efficiency.
Specifically, the graphene material obtained in the step S2 is mixed with a solvent such as water, N-methylpyrrolidone, a surfactant, etc. and mechanically exfoliated times or more to obtain a graphene material with fewer layers.
The graphene material can be directly used as a conductive agent or mixed with a solvent to form a conductive paste for further application.
When the carbon material is a graphite material and a graphene material is finally prepared, after the step S1 and before the step S2, a step of oxidizing and reducing the graphite material may be further included.
(a) Oxidizing the graphite raw material to obtain graphite oxide;
(b) placing graphite oxide in a sagger and reducing at 1000-1400 ℃ in an inert atmosphere.
In the step (a), in the oxidation method, concentrated sulfuric acid is used as an intercalation agent (intercalation is performed on graphite), sodium nitrate is used as an intercalation agent auxiliary agent (sodium nitrate has strong oxidizing property in the presence of sulfuric acid), and potassium permanganate is used as a strong oxidizing agent to oxidize graphite into graphite oxide. Then, hydrogen peroxide can be added to remove excessive potassium permanganate, and hydrochloric acid is used to remove sodium ions and sulfate ions, so that pure graphite oxide is obtained.
In step (b), the mechanism by which the graphite oxide is reduced is: under inert atmosphere, the oxygen-containing group chemical bond on the surface of the graphite oxide is broken and broken at high temperature through a high-temperature environment to form micromolecule water and carbon dioxide to escape, and meanwhile, the interlayer spacing between the layers in the graphite oxide is enlarged by a large amount of escaped micromolecules; that is, the graphite oxide having a large number of layers is automatically exfoliated into a carbon material having a small number of layers at the same time as the high-temperature reduction. The carbon material finally prepared in the application refers to graphene with the number of layers being 1-5. The inert atmosphere refers to inert gases such as nitrogen, argon, helium, neon and the like.
The temperature of the reduction is preferably 1000-1100 ℃. The reduction time is 20 minutes to 20 hours, preferably 30 minutes to 12 hours.
The high-temperature reduction and the automatic exfoliation are performed by a sagger having a special structure, the material of which is the same as that of the apparatus for preparing a carbon material, the material of which is high-density graphite, which also takes into consideration the requirement of high-temperature treatment, and also introduces no additional impurities in the reaction, and facilitates the taking and putting of articles from and into the sagger.
Referring to fig. 4 to 7, the sagger includes a sagger lid 10 and a sagger body 20, the top of the sagger body 20 is open, the sagger lid 10 covers the top of the sagger body 20, the sagger body 20 and the sagger lid 10 are independent, the sagger lid 10 is not tightly fixed to the sagger body 20, namely, the sagger lid 10 and the sagger body 20 are not combined into , the sagger lid 10 only covers the top of the sagger body 20 and is used at the same time, because in the preparation process of the graphene, due to the specific design of the sagger, powdery substances such as graphite raw materials and the like in the sagger are basically in the sagger and do not fly to the outside in a large amount, and only a small amount can escape is obtained, and therefore, the sagger lid 10 does not need to be fixed to the sagger body 20, the complexity of the preparation of the sagger is reduced, and the use of the sagger is simpler.
Referring to fig. 6, the sagger body 20 includes an outer casing wall 20a and an outer cavity 20c formed by the outer casing wall 20a, the outer casing wall 20a is provided with notches 20b so that the outer cavity 20c is communicated with the outside, when graphite oxide powder is placed in the sagger body 20 for high temperature reduction, generated water, sulfur dioxide and the like are escaped through the notches 20b on the outer casing wall 20a, and the escaped water, sulfur dioxide and the like also generate an effect of causing reduced graphene to collide with the inner casing wall and the outer casing wall 20a to fall and deposit, thereby increasing the yield of graphene, the shape of the sagger body 20 is not limited, as long as there is outer cavity 20c, the outer casing wall 20a is a plate-shaped structure, may be a flat plate, or a curved plate, and the size and shape of the notches 20b are not limited, as long as the outer cavity 20c can be communicated with the outside.
The saggar body 20 is also provided with inner boxes 30, the inner boxes 30 and the saggar body 20 are molded into bodies, the inner boxes 30 comprise inner box wall bodies and inner cavities 30a formed by the inner box wall bodies, the tops of the inner boxes 30 are open, the inner cavities 30a are communicated with outer cavities 20c, the shapes of the inner boxes 30 can be the same as or different from that of the saggar body 20, the shapes of the inner boxes 30 can be cylinders, cubes and the like, and the inner wall boxes can be planar plate structures or curved plate structures.
When the wall body of the inner box is flatReferring to fig. 5 and 6, the shape of the container body 20 and the inner box 30 is rectangular, and the wall of the inner box can be composed of pairs of baffles 30b and pairs of second baffles 30c, the dimensions of the baffles 30b and the second baffles 30c in the z direction (i.e. vertical direction) are defined as the height H of the baffles 30b3Height H of the second baffle 30c4At this time H3≥H4In the preparation process, the graphite oxide powder is stripped and reduced in an explosive manner to obtain graphene powder, an air-flow mixture formed by the graphene powder and gases such as sulfur dioxide flows, and when the graphene powder meets the inner box wall body, the box cover wall body and the outer box wall body which play a role of blocking, the air-flow mixture collides with the inner box wall body, the box cover wall body and the outer box wall body, so that the gases such as sulfur dioxide are discharged, the graphene powder is deposited, in order to increase the collision probability and times of the air-flow mixture, preferably, the height difference of between the height of the th baffle 30b and the height of the second baffle 30c is provided, and H is H3＞H4。
When the inner case wall is a curved plate structure, inner case notches (not shown) may be formed on the inner case wall.
In the above design, the height difference between the inner casing gap or the th baffle 30b and the second baffle 30c is to facilitate the addition of more obstacles between the inner cavity 30a and the outer cavity 20c, so that the probability and the number of collisions between the airflow mixture formed by the graphene powder and gases such as sulfur dioxide and the like and the inner casing wall and the outer casing wall which have the barrier function are collided and deposited, and the graphene powder is prevented from leaving the sagger along with the airflow, thereby improving the yield of the final graphene powder.
The cartridge cover 10 comprises a cartridge cover top 10a and a flap wall 10 b. The flap wall 10b is disposed within the outer cavity 20c of the sagger body 20. The dimensions of the lid wall 10b and the outer box wall 20a in the vertical z direction are defined as the height H of the lid wall 10b1Height H of outer case wall 20a2. Height H of the container lid wall 10b1Is smaller than the height H of the outer box wall body 20a2The objective of this design is that when the sagger lid 10 is covered on the top of the sagger body 20, the sagger lid wall 10b extends into the outer cavity 20c of the sagger body 20, and the outer cavity 20c is divided into the rd sub-outer cavity 20c1 and the second sub-outer cavity 20 c2. which are communicated with each other, namely, the inner box 30 and the sagger lid wall 10b divide the inner space of the sagger body 20 into three mutually communicated sub-spaces (the inner cavity 30a, the th sub-outer cavity 20c1 and the second sub-outer cavity 20c2), therefore, when the graphite oxide is placed in the sagger body 20, under the effect of high temperature, the graphene powder formed by the reduction of the powdered graphite oxide is deposited by the repeated collision of the inner box wall (i.e. the th baffle 30b and the second baffle 30c), the sagger lid wall 10b and the outer box 20a, and finally, a few layers of graphene material are collected.
Referring to fig. 5 and 7, the lid 10 includes body lid top 10a and lid wall 10 b. the shape and size of the lid 10 is not limited, the dimensions of the lid top 10a in the x-axis and y-axis directions are defined as the length and width of the lid top 10a, the lid wall 10b is disposed near the middle of the lid top 10 a. in particular, referring to fig. 7, the lid top 10a is composed of top plate 10a1 and recess 10a2, the recess 10a2 is formed around the top plate 10a1, i.e., the edge of the top plate 10a1 is recessed inward to form the recess 10a2, i.e., the thickness of the top plate 10a1 around the edge is thinner than the thickness of the middle portion of the top plate 10a1, so that the lid 10 is more stably positioned on the top of the lid body 20 without excessive movement, preferably, the thickness of the second recess 10a 9634 is larger than the thickness of the rectangular top plate 3985 of the lid body 3910 a when the thickness of the rectangular lid 10a in the direction is greater than the thickness of the rectangular lid body 9685,the smallest dimension of the -th recessed part 10a2 in the x-direction and the y-direction is larger than the thickness D of the outer box wall body 20a of the sagger main body 202. The preferred design is to partially extend the top plate 10a1 of the cover 10a into the outer cavity 20c when the graphite oxide is placed in the outer cavity 20c, so as to reduce the area of the gap 20b, thereby ensuring the communication between the outer cavity 20c and the outside, and at the same time, the powdered graphite oxide is confined in the outer cavity 20c, so that more collisions occur between the powdered graphite oxides.
Optionally, referring to fig. 5 and 7, at least a second recess 10 a3. may be formed in the th recess 10a2, and the dimension D of the second recess 10a3 in the thickness direction of the outer cartridge wall 20a1Greater than the thickness D of the outer box wall 20a of the sagger body 202. Specifically, when the sagger body 20 is a rectangular parallelepiped, the length D of the second concave portion 10a3 in the x direction1Greater than the thickness D of the outer box wall 20a of the sagger body 202The second recess 10a3 is used as additional channels for communicating the outer cavity 20c with the outside, thereby facilitating the discharge of small molecule water, carbon dioxide, etc.
In this embodiment, the shape of the sagger body 20 and the shape of the inner box 30 are both rectangular parallelepiped, the height of the th baffle 30b of the inner box 30 is larger than the height of the second baffle 30c, and pairs of second recesses 10a3 are provided in the th recess 10a2 of the box lid 10.
The invention also provides carbon materials obtained by the preparation method, the carbon materials are basically free of defects, have thin thickness and extremely low content of metal impurities and have high electrical conductivity, and the electrical conductivity of the carbon materials is 106And S/m is more than or equal to.
Preferably, the oxidation-reduction step is carried out in a sagger before the graphite starting material is subjected to the graphitization step. The obtained carbon material has more excellent conductivity and higher single-layer rate.
Hereinafter, the explanation will be further made in with reference to specific examples.
Example (1)
(1) Providing a graphite raw material, wherein the graphite raw material is obtained by purifying and crushing graphite ores;
(2) placing a graphite raw material in a container made of high-density graphite, carrying out high-temperature graphitization treatment on the container filled with the graphite raw material, specifically, gradually raising the temperature, raising the temperature for 7 days, finally stabilizing at 3400 ℃ for 15 days, and then rapidly cooling to 25 ℃ within 7 days to obtain graphene powder.
Example (2)
(1) Providing a graphite raw material, wherein the graphite raw material is obtained by purifying and crushing graphite ores;
(2) oxidizing a graphite raw material, placing the oxidized graphite in an sagger, and reducing at 1000-1050 ℃ in an inert atmosphere, wherein the sagger is made of high-density graphite;
(3) placing the reduced graphite in a container made of high-density graphite, carrying out high-temperature graphitization treatment on the container filled with the reduced graphite, specifically, gradually raising the temperature for 7 days, stabilizing at 3400 ℃ for 15 days, and then rapidly cooling to 25 ℃ for 7 days to obtain graphene powder.
Example (3)
(1) Providing a carbon nanotube raw material, wherein the carbon nanotube raw material contains quantitative metals (the total content of iron, cobalt, nickel, manganese, calcium, zinc, aluminum, chromium, cadmium and copper elements is more than or equal to 100 ppm);
(2) placing a carbon nano tube raw material in a container made of high-density graphite, carrying out high-temperature graphitization treatment on the container filled with the carbon nano tube raw material, specifically, gradually raising the temperature for 7 days, stabilizing at 3400 ℃ for 15 days, and then rapidly cooling to 25 ℃ within 7 days to obtain the high-purity carbon nano tube.
COMPARATIVE EXAMPLE (1)
To better illustrate the advantages of the graphene materials obtained by the methods described herein, the present application also provides comparative example (1). this comparative example (1) provides a preparation method of graphene materials.
Specifically, a pulverized and purified graphite raw material GC325(325 mesh) is treated by concentrated sulfuric acid, sodium nitrate, potassium permanganate and the like by using a Hummers method to obtain graphite oxide powder, and then the graphite oxide powder is put into common tube furnaces for chemical vapor deposition to be stripped to obtain graphene powder.
The preparation of this comparative example (1) was not carried out in the container and in the sagger described in the present application.
The graphene powder obtained in example (1) is subjected to a transmission electron microscope test, and the test result refers to fig. 8.
The graphene powder obtained in example (2) is subjected to a transmission electron microscope test, and the test result refers to fig. 9.
The graphene powder obtained in comparative example (1) is subjected to a transmission electron microscope test, and the test result refers to fig. 10.
As can be seen from fig. 8 to 10, the diffraction fringes appeared in fig. 8 and 9 of the graphene powders of examples (1) and (2) compared to the comparative example (1), which indicates that the crystallinity of the graphene powders of examples (1) and (2) is better.
The graphene powder obtained in example (1) was subjected to raman spectroscopy, and the results of the raman spectroscopy are shown in fig. 11.
The graphene powder obtained in example (2) is subjected to raman spectroscopy, and the test results are shown in fig. 12.
The graphene powder obtained in comparative example (1) was subjected to raman spectroscopy, and the test results are shown in fig. 13.
As can be seen from FIGS. 11 to 13, the thickness of the sample (2) is 1350cm-1A relatively weak characteristic peak is presented; and the strength of example (2) was much weaker than that of comparative example (1). At 1580cm in examples (1) and (2)-1And 1350cm-1Is the ratio of the intensities of the two characteristic peaks IG/IdThe ratio is larger than the peak intensity ratio of the two positions in the comparative example (1), which shows that the original structural defects of the graphene material are repaired after the high-temperature graphitization treatment.
XRD test was performed on the graphene powder obtained in example (1), and the test result is shown in fig. 14.
XRD test was performed on the graphene powder obtained in example (2), and the test result is shown in fig. 15.
XRD test was performed on the graphene powder obtained in comparative example (1), and the test result is shown in fig. 16.
As can be seen from fig. 14 to 16, the graphene powder obtained in comparative example (1) has a wider characteristic peak at a2 θ angle of 22 ° to 26 ° (a interplanar spacing calculated from the characteristic peak correspondence is greater than 0.35nm) as compared to example (1) and example (2), which indicates that the graphene prepared in comparative example (1) has a larger lamella spacing. As can be seen from fig. 14 and 15, in both examples (1) and (2), a sharp characteristic peak (0.345 nm as calculated from the characteristic peak) appears at a position where the 2 θ angle is 26 °; and the half-peak width d of the characteristic peak is 0.34nm, which is basically close to the theoretical thickness of 0.34nm of single-layer graphene. This also indicates that the graphene in the graphene powder described in examples (1) and (2) of the present application is prone to graphitization and the interlayer distance thereof is reduced. The defects on the graphene sheet layers are fully repaired due to the rearrangement of carbon atoms in the graphene repairing process to form a single-layer perfect graphene crystal, and the strong interaction between two adjacent single-layer graphene leads the graphene to be recombined to form thicker two or more layers of graphene or thicker graphite sheets.
The specific surface area of the graphene powder obtained in example (1) and example (2) was measured, and the results are shown in table 1.
TABLE 1
Specific surface area (m)2/g)
Example (1) 21～100
Example (2) 350
As can be seen from table 1, the graphene powders obtained in the examples (1) and (2) have large specific surface areas, and it is confirmed that the graphene powder contains a large number of few layers of graphene at step , and is suitable for the application at step .
Further , the graphene powder obtained in example (2) was tested for impurity content, and the results are shown in Table 2.
TABLE 2
Impurity element Al As Ca Cd Co Cr
Content (ppm) 0.001 0.033 37.225 0.001 0.004 0.001
Impurity element Cu Fe Ge Hg Mn Mo
Content (ppm) 0.037 5.67 0.001 0.001 0.082 0.157
Impurity element Ni Pb Sb Si Sn S
Content (ppm) 0.401 0.036 0.001 3.624 0.003 53
As can be seen from table 2, the content of impurities in the graphene powder described in example (2) is very low, which further verifies that the graphene powder obtained by the preparation method described in the present application has excellent application prospects.
The morphology of the high purity carbon nanotubes obtained in example (3) was measured, and the results are shown in FIGS. 17 and 18. As can be seen from fig. 17 and 18, the structure of the high-purity carbon nanotube after the high-temperature graphitization treatment has no obvious defects basically, and is relatively smooth.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.

Claims (6)

  1. A method for preparing carbon materials, comprising the steps of:
    (1) providing a graphite raw material;
    (2) placing the graphite raw material in an container, and carrying out high-temperature graphitization treatment on the container filled with the graphite raw material at 1000-3800 ℃ to obtain a carbon material, wherein the material of the container is high-density graphite;
    , oxidizing and reducing the graphite raw material to obtain graphite oxide, placing the graphite oxide in a saggar, and reducing the graphite oxide in an inert atmosphere at 1000-1100 ℃, wherein the saggar is made of high-density graphite, the saggar comprises a saggar body and a saggar cover, the top of the saggar body is provided with an opening, and the saggar cover covers the top of the saggar body,
    the sagger body comprises an outer box wall body and an outer cavity formed by the outer box wall body, and the outer box wall body is provided with notches, so that the outer cavity is communicated with the outside;
    the sagger body is also internally provided with an inner box, the inner box comprises an inner box wall body and an inner cavity formed by the inner box wall body, the top of the inner box is provided with an opening, and the inner cavity is communicated with the outer cavity;
    the box cover comprises a box cover top and a box cover wall body, the box cover wall body is arranged in an outer cavity of the box body, and the height of the box cover wall body is smaller than that of the outer box wall body.
  2. 2. The method for producing a carbon material as claimed in claim 1, wherein the time of the high-temperature graphitization treatment in the step (2) is 10 to 1000 hours.
  3. 3. The method for producing a carbon material as claimed in claim 1, wherein the container is open at the top and is provided with a detachable lid, and the lid is made of high-density graphite.
  4. 4. The method for preparing a carbon material as claimed in claim 3, wherein the inner wall of the container is provided with at least th through holes and th hole sealing pieces which are matched with and detachable from th through holes, the material of the th hole sealing pieces is high-density graphite, the cover is provided with at least second through holes and second hole sealing pieces which are matched with and detachable from the second through holes, and the material of the second hole sealing pieces is high-density graphite.
  5. 5. The method for producing a carbon material according to claim 3, wherein the high-density graphite is graphite obtained by subjecting a graphite raw material to a high-temperature treatment, and the density of the high-density graphite is 1.85g/cm or more3。
  6. 6. The method for producing a carbon material according to claim 5, wherein the method for producing the high-density graphite comprises: and treating the graphite raw material at 2400-3000 ℃ under the pressure of 1-3.6 atmospheres to obtain the high-density graphite.
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