CN107215861A - A kind of carbon material and preparation method thereof, the device for preparing carbon material - Google Patents
A kind of carbon material and preparation method thereof, the device for preparing carbon material Download PDFInfo
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- CN107215861A CN107215861A CN201710425358.2A CN201710425358A CN107215861A CN 107215861 A CN107215861 A CN 107215861A CN 201710425358 A CN201710425358 A CN 201710425358A CN 107215861 A CN107215861 A CN 107215861A
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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
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- 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
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- 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
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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- C01B2204/32—Size or surface area
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- 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
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
Abstract
The present invention relates to a kind of device for being used to prepare carbon material, the device is the container with a receiving space, and the top of the container is for opening and provided with dismountable lid, and the material of the container and lid is high-density graphite.The present invention also provides a kind of method that utilization described device prepares carbon material, and it comprises the following steps：(1) carbon material raw material is provided；(2) the carbon material raw material is placed in the container, and will be equipped with the container of carbon material raw material and carry out high temperature graphitization processing in 1000 degrees Celsius~3800 degrees Celsius, obtain carbon material.The present invention also provides a kind of carbon material.
Description
Technical field
The present invention relates to carbon material, more particularly to a kind of it is used to prepare device, carbon material of carbon material and preparation method thereof.
Background technology
The excellent performance of carbon material such as graphene and CNT, has in handset touch panel, conductive material etc. and widely should
With.Graphene is considered as one of critical material of high performance electrokinetic cell conductive agent.
The preparation method of existing CNT is generally CVD vapour deposition processes, arc process etc..However, this method is made
The CNT produced is defective.
The preparation method of existing graphene is chemistry redox method, mechanical stripping method, CVD vapour deposition processes etc..So
And, the graphene manufactured by those methods is defective.Such as, using chemistry redox method, although the thickness of graphene
Smaller, individual layer rate is high, but graphene can be caused compared with havoc in oxidizing process, produces cavity and introduces other functions
The metal impurities such as group, substantial amounts of element sulphur and iron-cobalt-nickel manganese, and the electrical conductivity of graphene is largely effected on, cause subsequent applications
The performance of battery is damaged when battery.Using mechanical stripping method, although the electrical conductivity of graphene is high, but there is the thickness of graphene
The more shortcoming of the thicker, number of plies is spent, and this method greatest problem is：The raw material used for crystalline flake graphite, expansible graphite or
Person expands worm graphite, when carrying out physical mechanical stripping by methods such as liquid phase or gas phases, and the inside of the raw material is with big
The element sulphur of amount, and residual the impurity such as iron-cobalt-nickel manganese potassium calcium, the content of impurity is significantly exceeded, thus can damage the property of battery
Energy.Using CVD vapour deposition processes, although the characteristics of obtained graphene has the thinner thickness of individual layer or bilayer, electrical conductivity
It is high, but be due to that need to utilize the substrate with substantial amounts of metallic nickel etc., the substrate need to carry out dissolving stripping, cause graphene
Yield is extremely low, it is impossible to as on a large scale into a tonne other application.
The content of the invention
In view of this, it is necessory to provide it is a kind of can be used for prepare on a large scale the excellent carbon material of electric conductivity device,
Preparation method and the excellent carbon material of electric conductivity.
The present invention provides a kind of device for being used to prepare carbon material, and the device is the container with a receiving space, described
The top of container is opening and is provided with dismountable lid, and the material of the container and lid is high-density graphite.
It is preferred that, the inwall of the container coordinates and dismountable the provided with an at least first through hole and with first through hole
One sealing of hole part, the material of the first sealing of hole part is high-density graphite；The lid is provided with least one second through hole and with the
Two through holes coordinate and dismountable second sealing of hole part, and the material of the second sealing of hole part is high-density graphite.
It is preferred that, the high-density graphite is that graphite raw material is passed through into the graphite that high temperature and HIGH PRESSURE TREATMENT are obtained, described
The density of high-density graphite is more than or equal to 1.85g/cm3。
It is preferred that, the graphite raw material is specifically referred to by high temperature graphite raw material is Celsius 2500 degrees Celsius~3000
At a temperature of degree and it is applied in the pressure treatment of 1 atmospheric pressure~3.6 atmospheric pressure.
The present invention also provides a kind of method that utilization said apparatus prepares carbon material, and it comprises the following steps：
(1) carbon material raw material is provided；
(2) the carbon material raw material is placed in the container, and it is Celsius in 1000 to will be equipped with the container of carbon material raw material
~3800 degrees Celsius of progress high temperature graphitization processing of degree, obtain carbon material.
It is preferred that, the time of the processing of high temperature graphitization described in step (2) is 10 hours~1000 hours.
It is preferred that, carbon material raw material described in step (1) is carbon nanometer tube material or graphite raw material.
It is preferred that, the step of also being aoxidized and reduced including a pair of graphite raw materials before step (2) is specially：Will
Graphite raw material is aoxidized, and obtains graphite oxide, then graphite oxide is placed in a saggar and taken the photograph in an inert atmosphere in 1000
Family name is reduced under degree~1100 degree Celsius, wherein the material of the saggar is high-density graphite.
It is preferred that, the saggar includes saggar main body and casket lid, and the top of the saggar main body is opening, the casket lid lid
In the top of saggar main body, wherein,
The saggar main body includes the external cavity of outer casket wall body and the formation of outer casket wall body, and the outer casket wall body lacks provided with one
Mouthful so that external cavity is connected with the external world；
Casket in one is additionally provided with the saggar main body, the interior casket includes the interior sky of interior casket wall body and the formation of interior casket wall body
Chamber, the top of the interior casket is opening, and the internal cavity is connected with external cavity；
The casket lid includes casket caping and casket tegmental wall body, and the casket tegmental wall body is placed in the external cavity of the saggar main body,
The height of the casket tegmental wall body is less than the height of the outer casket wall body.
The present invention also provides the carbon material that a kind of use above method is prepared, the electrical conductivity of the carbon material for 3 ×
104~1 × 106Basic zero defect in S/m, the structure of the carbon material.
Compared with prior art, the material for being used to prepare the device of carbon material is high-density graphite, thus is had
Resistant to elevated temperatures advantage.Particularly when using the device to carry out high temperature graphitization to carbon material raw material, due to the device and instead
It is carbon to answer raw material, thus in the absence of capsule contamination the problem of.And due to device can high temperature resistant, thus in pyrographite
Container is stable during change, and service life is longer.
The effect of the first through hole is so that the inside of device is in communication with the outside, during carbon material is prepared,
The foreign gas produced in raw material can be emitted into the external world.Certainly, the first through hole is set to a kind of preferred mode.First
Through hole can be also not provided with, i.e., be the discharge that foreign gas can be achieved by the microgap between the inwall and lid of the container.
The device it is simple in construction, the method for preparing the device is simple, and raw material is easy to get, cheap, is adapted to large-scale
Commercial application.
When in use, carbon material raw material is put into the device, then carries out high temperature graphitization and obtain carbon material.Relative to
Used in existing method prepare container or substrate for, because the material of the device is high-density graphite, thus avoid drawing
Enter other extra impurity, while the device is as Space, Place is prepared, can be well by the less powder carbon material of density
Raw material is accommodated and Relatively centralized, can large batch of production carbon material.
The principle of the preparation method of the carbon material is：Disorderly arranged carbon atom is set to enter rearrangement and structure turn using heat
The carbon structure of ordered arrangement is deformed into, and the original structure defect in carbon material raw material is effectively repaired.The carbon material
Raw material can be graphite raw material and carbon nanometer tube material.When carbon material raw material is graphite raw material, during high temperature graphitization
Also may be such that graphite raw material laminate graphite the number of plies reduction and obtain the less graphene of the number of plies, in this process, the number of plies compared with
Multiple impact device under the drive of the air-flow of foreign gas that many graphite can be generated during high temperature graphitization formation
Inwall and finally obtain the less graphene of the number of plies.
During existing high temperature graphitization, due to powdery carbon material raw material light weight, easily fly upward and be difficult to height
Warm graphitization forms the carbon material without fault of construction substantially, and graphite raw material is placed in the high-density graphite material system by the application
Into container in, by the way that the container is placed under hot environment, can to graphite raw material carry out high temperature graphitization obtain carbon material.Should
Preparation method, which puts into raw material and collects product, extremely to be facilitated, and be can be achieved to prepare on a large scale, in actual applications, be can be achieved hundred tons
The preparation of rank.Also, in the preparation process, without adding other raw materials, therefore other impurity will not be introduced；Because being not used
Substrate etc., without stripping.The whole preparation process step is simple, and preparation efficiency is high.
The carbon material obtained by the preparation method has advantages below：To carbon material raw material only by high temperature graphitization at
Reason can obtain the carbon material without fault of construction substantially.The basic zero defect of carbon material, thinner thickness, metals content impurity pole
It is low, and with high conductivity.The obtained carbon material can be applied to electrocondution slurry, and be further used for preparing battery.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention for being used to prepare the device of carbon material.
Fig. 2 and Fig. 3 is profile of Fig. 1 described devices in different conditions.
Fig. 4 is the structural representation of saggar of the present invention.
Fig. 5 is the decomposing schematic representation of saggar described in Fig. 4.
Fig. 6 is the structural representation of the saggar main body of saggar described in Fig. 4.
Fig. 7 is the structural representation of the casket lid of saggar described in Fig. 4.
Fig. 8 is transmission electron microscope (TEM) photo for the graphene powder that (1) of the embodiment of the present invention is obtained.
Fig. 9 is the TEM photos for the graphene powder that (2) of the embodiment of the present invention is obtained.
Figure 10 is the TEM photos for the graphene powder that comparative example (1) is obtained.
Figure 11 is the Raman spectrogram for the graphene powder that (1) of the embodiment of the present invention is obtained.
Figure 12 is the Raman spectrogram for the graphene powder that (2) of the embodiment of the present invention is obtained.
Figure 13 is the Raman spectrogram for the graphene powder that comparative example (1) is obtained.
Figure 14 is X-ray diffraction (XRD) figure for the graphene powder that (1) of the embodiment of the present invention is obtained.
Figure 15 is the XRD for the graphene powder that (2) of the embodiment of the present invention is obtained.
Figure 16 is the XRD for the graphene powder that comparative example (1) is obtained.
Figure 17 is the stereoscan photograph for high-purity CNT that embodiment (3) is obtained.
Figure 18 is the TEM photos for high-purity CNT that embodiment (3) is obtained.
Wherein, 1 container is represented, 2 represent first through hole, and 3 represent the first sealing of hole part, and 4 represent lid, and 4a represents that second leads to
Hole, 4b represents the second sealing of hole part, and 10 represent casket lid, and 10a represents casket caping, and 10a1 represents top plate；10a2 represents the first recess,
10a3 represents the second recess, and 10b represents casket tegmental wall body, and 20 represent saggar main bodys, and 20a represents outer casket wall body, 20b indication notch,
20c represents external cavity, and 30 represent interior casket, and 30a represents internal cavity, and 30b represents first baffle, and 30c represents second baffle.
Specific examples below will further illustrate the present invention with reference to above-mentioned accompanying drawing.
Embodiment
The device provided by the present invention for preparing carbon material, carbon material and preparation method thereof are made below with reference to accompanying drawing
Further illustrate.
The present invention provides a kind of device for being used to prepare carbon material.Fig. 1 to Fig. 3 is referred to, the device is to be accommodated with one
The container 1 in space.The receiving space of the container 1 is used for the place for preparing carbon material.
The shape of the container 1 is not limited, as long as it is internal with receiving space.Specifically, the container 1
Shape can be cylinder, cuboid etc..Referring to Fig. 1, in the present embodiment, the container 1 is shaped as cylinder, its cross section
Be shaped as circle.
Referring to Fig. 1, the top of the container 1 is opening, and coordinate dismountable provided with one at the top of the container 1
Lid 4.The setting purpose of the lid 4 is, can conveniently be put into raw material and take out product.
Referring to Fig. 2, the inwall of the container 1 can be provided with an at least first through hole 2, and coordinate with first through hole 2 and
Dismountable first sealing of hole part 3.The quantity of the first through hole 2 is not limited, and can be one, two or multiple.Described first
The pore size of through hole 2 and the hole shape of the first through hole are not limited.The first through hole 2 is in the container 1
Particular location is not limited, and is connected as long as the receiving space of the container 1 can be realized by the first through hole 2 with the external world
.For example, when being shaped as cuboid of the container 1, the first through hole 2 can be in top, the bottom of the container 1
Or on the wall of side；When the container 1 is when being shaped as cylinder, the first through hole can be at the top or bottom of the container 1.
The effect of the first through hole 2 is so that the inside of container 1 is in communication with the outside, and is preparing the process of carbon material
In, the foreign gas produced in raw material can be emitted into the external world.Certainly, the first through hole 2 is set to a kind of preferred mode.
First through hole 2 can be also not provided with, i.e., be that foreign gas can be achieved by the microgap between the inwall and lid 4 of the container 1
Discharge.
It is understood that when the aperture of the first through hole 2 is larger, the first through hole 2 can also be used for being put into original
Material and taking-up product.
Optionally, it can be equipped with the lid 4 provided with least one second through hole 4a and with the second through hole 4a
The second sealing of hole part 4b.The second sealing of hole part 4b and the second through hole 4a is that dismountable mode is assembled.The second through hole 4a
Quantity, form and dimension be not construed as limiting, the second through hole 4a can be identical with first through hole 2, can also differ.It is described
Second through hole 4a's is provided in, and facilitates the receiving space of the container 1 to be in communication with the outside.
Between the lid 4 and the container 1, the first sealing of hole part 3 and first through hole 2 and the second sealing of hole part 4b
It can refer to the second through hole 4a dismountable assembling mode and be connected through a screw thread.Certainly, other dismountable modes can also be referred to.
Dismountable mode, refers between two parts may be either the state for becoming mutually integral, or the shape being separated from each other
State.The first sealing of hole part 3 and the second sealing of hole part 4b can be bolt etc..The first sealing of hole part 3 and first through hole 2, described the
After being assembled between two sealing of hole part 4b and the second through hole 4a and the lid 4 and the container 1, the receiving of the container 1 is empty
Between do not connected completely not with the external world, in the environment of the container 1 is placed in high-temperature heating, the air of the receiving space with
And the impurity or gas produced in preparation process can be expanded and by the sealing of hole part 3 of first through hole 2 and first, the second through hole
Gap between 4a and the top and lid 4 of the second sealing of hole part 4b and container 1 and slowly escape.
In the present embodiment, the bottom of the container 1 is equipped with provided with a first through hole 2 and with first through hole 2
First sealing of hole part 2a, the top of the container 1 is to be equipped with lid 4, the lid 4 at opening, the opening of the container 1
Be additionally provided with one second through hole 4a and with the second through hole 4a coordinate the second sealing of hole part 4b, the sealing of hole part 3 of first through hole 2 and first,
It is to be connected through a screw thread between the second sealing of hole part 4b and the second through hole 4a, the lid 4 and the container 1, described
Internal thread part is equipped with container 1, the through hole 4a of first through hole 2 and second inwall, accordingly, in the lid 4, the first envelope
The sealing of hole part 4b of orifice 3 and second outer wall is equipped with the external thread part corresponding with internal thread part.
The container 1, the first sealing of hole part 3, the second sealing of hole part 4b material are high-density graphite.The high-density graphite
Refer to graphite raw material passing through the graphite that high temperature and HIGH PRESSURE TREATMENT are obtained.Specifically, by graphite raw material 2400 degrees Celsius~
At a temperature of 3000 degrees Celsius and the pressure treatment of 1 atmospheric pressure~3.6 atmospheric pressure is applied in, can obtain the high density stone
Ink.It is preferred that, graphite raw material at a temperature of 2500 degrees Celsius~2800 degrees Celsius and is applied in the pressure of 3.6 atmospheric pressure
Processing, can obtain the high-density graphite.The graphite raw material is commercially available, and will not be described here.It is appreciated that inciting somebody to action
Graphite raw material is after high temperature and HIGH PRESSURE TREATMENT, the step of also carrying out a turnning and milling, to obtain the container 1 with given shape.
Because the material of described device is high-density graphite, thus high temperature is can tolerate, and by with preparing carbon material institute
It is identical containing element, it is carbon, therefore, does not bring extra impurity.For it is existing prepare carbon material when powdered graphite
Dust is easily flown upward without easily by fixed shortcoming, herein described device is specifically applied to carbon material caused by material density is small
Preparation, can conveniently accommodate raw material and prepare carbon material on a large scale.The structure of the device is also simple, easily prepares, cost
It is relatively low, beneficial to industrial applications.
The present invention also provides a kind of method that utilization said apparatus prepares carbon material.This method comprises the following steps：
There is provided carbon material raw material by S1；
S2, the carbon material raw material is placed in the container, and will be equipped with the container of carbon material raw material in 900 degrees Celsius
~3800 degrees Celsius of progress high temperature graphitization processing, obtain carbon material.
In step sl, the graphite ore that the graphite raw material can obtain directly to dig up mine, or graphite ore is entered
One step is purified and/or crushed obtained flour.It is existing skill that graphite ore, which is purified, and/or smashed
Art, therefore not to repeat here.
In step s 2, the principle of the high temperature graphitization processing is：Disorderly arranged carbon atom is weighed using heat
Row and structure change the carbon material to form ordered arrangement, and its fault of construction is effectively repaired.In the pyrographite
Diamond dust can be covered during change at the through hole 4a of first through hole 2 and second of described device to be closed.
In order to obtain the carbon material that electric conductivity is more excellent, the temperature of the high temperature graphitization processing is preferably 900 degrees Celsius
~3400 degrees Celsius.
The time of the high temperature graphitization processing is 10 hours~1000 hours.In view of actual production efficiency, the height
The time of warm graphitization processing is preferably 48 hours~1000 hours.
When the carbon material raw material is graphite raw material, and when finally preparing grapheme material, upon step s 2, also
The step of may include a mechanical stripping.The method that the mechanical stripping can be peeled off using solid phase or liquid phase.Specifically, by step
The grapheme material that S2 is obtained is mixed with solvent such as water, 1-METHYLPYRROLIDONE, surfactant etc., by once or many
Secondary mechanical stripping, obtains the less grapheme material of the number of plies.Grapheme material passes through after mechanical stripping, and the number of plies is less, conductive
Property is more excellent.
The grapheme material can be directly used as conductive agent, or be mixed to form electrocondution slurry with solvent and further should
With.
When the carbon material raw material is graphite raw material, and when finally preparing grapheme material, walked after step S1
Before rapid S2, the step of a pair of graphite raw materials are aoxidized and reduced may also include.It is specific as follows：
(a) graphite raw material is aoxidized, obtains graphite oxide；
(b) graphite oxide is placed in a saggar and gone back in an inert atmosphere in 1000 degrees Celsius~1400 degrees Celsius
It is former.
In step (a), in the method for the oxidation, intercalator (carrying out intercalation to graphite), nitric acid are used as using the concentrated sulfuric acid
Sodium is as intercalation agent aid (sodium nitrate in the presence of sulphuric acid have strong oxidizing property), and potassium permanganate is as strong oxidizer by graphite
It is oxidized to graphite oxide.Afterwards, hydrogen peroxide can be added and remove excessive potassium permanganate, and hydrochloric acid removes sodium ion and sulfate radical
Ion, obtains more pure graphite oxide.
In step (b), the mechanism that the graphite oxide is reduced is：Under inert atmosphere, pass through the environment of high temperature
So that the oxy radical chemical bond on graphite oxide surface is destroyed and is broken at high temperature, micromolecular water and carbon dioxide ease are formed
Go out, while the small molecule largely escaped increases the interlamellar spacing between lamella in graphite oxide；I.e. while high temperature reduction, institute
State the graphite oxide more than the number of plies and be automatically also and peel off into the less carbon material of the number of plies.The carbon finally prepared in the application
Material refers to the graphene that the number of plies is 1~5.The inert atmosphere refers to the inert gases such as nitrogen, argon gas, helium, neon.
The temperature of the reduction is preferably 1000 degrees Celsius~1100 degrees Celsius.The time of the reduction is 20 minutes~20
Hour, it is preferably, 30 minutes~12 hours.
The high temperature reduction and the step of automatically strip realized by a saggar with special construction.The saggar
Material it is identical with the material of the device for preparing carbon material.The material of the saggar is high-density graphite.This is also
In view of the requirement of high-temperature process, and do not introduce extra impurity in the reaction yet, and conveniently picked and placeed from the saggar
Article.
Fig. 4 is referred to Fig. 7, the saggar includes casket lid 10 and saggar main body 20.The top of the saggar main body 20 is
Opening, the casket lid 10 is placed on the top of saggar main body 20.The saggar main body 20 is separate, the casket lid with casket lid 10
10 be not tightly fastened in the saggar main body 20 i.e. the two be not combined into one.The casket lid 10 is only placed on the saggar
The top of main body 20 and use simultaneously.Because, in the graphene preparation process, due to the particular design of saggar, in saggar
The flour such as graphite raw material it is basic in saggar, and can't largely fly to the external world, only very small amount is escaped, and can be neglected herein
Slightly.Therefore, casket lid 10 need not be fixed on saggar main body 20, this reduces complexity prepared by saggar, and the use of saggar is also more
To be simple.
Referring to Fig. 6, the saggar main body 20 includes the external cavity of outer casket wall body 20a and outer casket wall body 20a formation
20c.The outer casket wall body 20a is provided with a breach 20b so that external cavity 20c is connected with the external world.Put when by graphite oxide powder
When high temperature reduction is carried out in the saggar main body 20, water, sulfur dioxide of generation etc. can be via on the outer casket wall body 20a
Breach 20b and escape.Can also be produced while water, sulfur dioxide etc. are escaped the graphene that obtains reduction and interior casket wall body and
Outer casket wall body 20a collides and fallen the effect of deposition, and lifts the recovery rate of graphene.The shape of the saggar main body 20 is not
Limit, as long as there is an external cavity 20c.The outer casket wall body 20a is a platy structure, can be the plate of plane, or curved surface
Plate.The size and shape of the breach 20b is not limited, as long as the external cavity 20c can be in communication with the outside.
Casket 30 in one are additionally provided with the saggar main body 20.The interior casket 30 is formed in one with the saggar main body 20.
The interior casket 30 includes the internal cavity 30a of interior casket wall body and the formation of interior casket wall body.The top of the interior casket 30 is opening.It is described
Internal cavity 30a is connected with external cavity 20c.The shape of the interior casket 30 can be identical with the shape of the saggar main body 20, also may be used
Differ.The shape of the interior casket 30 can be cylinder, cube etc..The interior casket wall body can be the plate construction of plane,
It can be the plate construction of curved surface.
When the plate construction that the interior casket wall body is plane, Fig. 5 and Fig. 6, the saggar main body 20 and interior casket are referred to
30 shape is cuboid, and the interior casket wall body can be made up of a pair of first baffle 30b and a pair of second baffle 30c.It is fixed
The justice first baffle 30b and second baffle 30c is respectively the first baffle in the size of z directions (i.e. vertical direction)
30b height H3, institute second baffle 30c height H4, now H3≥H4.In preparation process, graphite oxide powder explodes
Graphene powder, the air-flowing type mixture one that the gas such as graphene powder and sulfur dioxide is formed are obtained after the stripping reduction of formula
Flowing is played, when running into the interior casket wall body, casket tegmental wall body and the outer casket wall body that take blocking effect, air-flowing type mixture can be sent out therewith
Raw collision, so that the gas such as sulfur dioxide is discharged, graphene powder is deposited.Occur to increase air-flowing type mixture
The probability and number of times of collision, it is preferred that there is a height between first baffle 30b height and second baffle 30c height
Difference, H3＞ H4。
When that can be provided with casket breach in one on the plate construction that the interior casket wall body is curved surface, the interior casket wall body, (figure is not
Show).
In above-mentioned design, the difference in height between interior the casket breach or first baffle 30b and second baffle 30c
It is for being beneficial to set up more obstruction between internal cavity 30a and external cavity 20c, makes the gas such as graphene powder and sulfur dioxide
The probability of the collision of air-flowing type mixture and the interior casket wall body and outer casket wall body that take blocking effect that body is formed is sent out with number of times
Life is collided and deposited, and avoids graphene powder from all leaving saggar with air-flow, so as to improve the yield of final graphene powder.
In other words, the saggar is designed to such complexity, be in order to increase gas circulation passage length, change air-flow discharge side
To mixed airflow and interior casket wall body, casket tegmental wall body and outer casket that the gas such as raising graphene powder and sulfur dioxide is formed
The collision probability of wall body, changes the flow direction of graphene powder in air-flow, causes the sinking of more graphene powders to deposit, carry
The yield of high graphene powder.
The casket lid 10 includes casket caping 10a and casket tegmental wall body 10b.The casket tegmental wall body 10b is placed in the saggar main body
In 20 external cavity 20c.It is respectively described to define the size of the casket tegmental wall body 10b and outer casket wall body 20a in vertical z directions
Casket tegmental wall body 10b height H1, outer casket wall body 20a height H2.The height H of the casket tegmental wall body 10b1Less than the outer casket wall
Body 20a height H2, the purpose of this design is, described when the casket lid 10 to be placed on to the top of the saggar main body 20
Casket tegmental wall body 10b is stretched into the external cavity 20c of the saggar main body 20, and by the external cavity 20c point for be interconnected the
The one sub- sub- exocoel 20c2 of exocoel 20c1 and second.This is specifically designed, i.e., in casket 30, casket tegmental wall body 10b by the saggar main body
20 inner space is divided into three interconnected subspaces (internal cavity 30a, the first sub- exocoel 20c1, the second sub- exocoel
20c2), therefore when being placed in graphite oxide in the saggar main body 20, in the presence of high temperature, the graphite oxide of powdery exists
The graphene powder formed after reducing, can be by interior casket wall body (i.e. first baffle 30b, second baffle 30c), casket tegmental wall body
10b, outer casket wall body 20a collision repeatedly and deposit, the less grapheme material of the number of plies for finally receiving more.
Fig. 5 and Fig. 7 are referred to, the casket lid 10 includes the casket caping 10a and casket tegmental wall body 10b of one.The casket lid
10 form and dimension is not limited.Define the length that sizes of the casket caping 10a in x-axis and y-axis direction is casket caping 10a
Degree and width.The casket tegmental wall body 10b is located at the close medium position of the casket caping 10a.Specifically, referring to Fig. 7, described
Casket caping 10a is made up of a top plate 10a1 and the first recess 10a2.The first recess 10a2 is formed at the top plate 10a1
Surrounding, i.e., described top plate 10a1 edge surrounding caves inward to form the first recess 10a2, i.e., described top plate 10a1's
The thickness of edge surrounding is comparatively stablized in favor of casket lid 10 compared with the thinner thickness of top plate 10a1 center section and is located at saggar
Above main body 20, excessive movement does not occur.It is preferred that, the first recess 10a2 takes up an official post on the surface of the top plate 10a1
The minimum dimension in one direction is all higher than the outer casket wall body 20a of the saggar main body 20 thickness.When being shaped as the casket lid 10
During rectangular plate-like, minimum dimensions of the first recess 10a2 in x directions and y directions is all higher than the outer casket of the saggar main body 20
Wall body 20a thickness D2.The purpose of this decision design is, when graphite oxide is placed in external cavity 20c, the casket caping
10a top plate 10a1 can be stretched into partly in the external cavity 20c, and reduces the area of the breach 20b as far as possible, and then is being ensured
While the external cavity 20c is connected with the external world, powdery graphite oxide is restricted in the external cavity 20c, powdery oxidation
More collisions occur between graphite.
Optionally, Fig. 5 and Fig. 7 is referred to, at least one second recess 10a3 can be set in the first recess 10a2.Described
Dimension Ds of the two recess 10a3 on outer casket wall body 20a thickness direction1More than the outer casket wall body 20a of the saggar main body 20
Thickness D2.Specifically, when the saggar main body 20 is cuboid, length Ds of the second recess 10a3 in x directions1More than institute
State the outer casket wall body 20a of saggar main body 20 thickness D2.The effect of the second recess 10a3 is, is used as the external cavity
The extra passage that 20c is connected with the external world, and beneficial to the discharge of micromolecular water, carbon dioxide etc..
In the present embodiment, the shape of the saggar main body 20 and interior casket 30 is cuboid, the first gear of the interior casket 30
Plate 30b height is more than second baffle 30c height, and a pair of second recesses are set in the first recess 10a2 of the casket lid 10
10a3。
The present invention also provides a kind of carbon material obtained by above-mentioned preparation method.The basic zero defect of carbon material, thickness
Spend relatively thin, metals content impurity extremely low, and with high conductivity.The electrical conductivity of the carbon material is 106More than S/m.
It is preferred that, oxidationreduction step is carried out in saggar before graphite raw material carries out graphitization step.What this was obtained
Carbon material has more excellent electrical conductivity and individual layer rate is higher.
Hereinafter, it will further illustrate in conjunction with specific embodiments.
Embodiment (1)
(1) graphite raw material is provided, the graphite raw material is graphite ore by purification, crushing；
(2) graphite raw material is placed in the container being made up of high-density graphite, and will be equipped with the container of graphite raw material and carried out
High temperature graphitization processing, specifically, be stepped up temperature, 7 days heating-up times, finally stablize 3400 degrees Celsius 15 days, subsequent 7
Its time fast cooling obtains graphene powder to 25 degrees Celsius.
Embodiment (2)
(1) graphite raw material is provided, the graphite raw material is graphite ore by purification, crushing；
(2) graphite raw material is aoxidized, then the graphite after oxidation is placed in a saggar and in an inert atmosphere in
Reduced under 1000 degrees Celsius~1050 degrees Celsius, wherein the material of the saggar is high-density graphite；
(3) graphite after reduction is placed in the container being made up of high-density graphite, and will be equipped with the graphite after reduction
Container carries out high temperature graphitization processing, specifically, being stepped up temperature, 7 days heating-up times, finally stablizes at 3400 degree Celsius 15
My god, subsequent 7 day time fast cooling obtains graphene powder to 25 degrees Celsius.
Embodiment (3)
(1) provide carbon nanometer tube material, wherein carbon nanometer tube material contain a certain amount of metal (iron, cobalt, nickel, manganese, calcium, zinc,
Aluminium, chromium, cadmium, the total content of copper are more than or equal to 100ppm)；
(2) carbon nanometer tube material is placed in the container being made up of high-density graphite, and will be equipped with carbon nanometer tube material
Container carries out high temperature graphitization processing, specifically, being stepped up temperature, 7 days heating-up times, finally stablizes at 3400 degree Celsius 15
My god, subsequent 7 day time fast cooling obtains high-purity CNT to 25 degrees Celsius.
Comparative example (1)
In order to better illustrate the advantage of the grapheme material obtained by herein described method, the application is also provided a pair
Ratio (1).The comparative example (1) provides a kind of preparation method of grapheme material.
Specially：Using Hummers methods, the graphite raw material GC325 (325 mesh) of purification will be crushed by the concentrated sulfuric acid, nitric acid
The processing such as sodium, potassium permanganate, has obtained graphite oxide powder；Then graphite oxide powder is placed in a common chemical gaseous phase
Peeled off in the tube furnace of deposition, obtained graphene powder.
The preparation process of the comparative example (1) is carried out not in herein described container and saggar.
The graphene powder obtained to embodiment (1) carries out transmissioning electric mirror test, and test result refers to Fig. 8.
The graphene powder obtained to embodiment (2) carries out transmissioning electric mirror test, and test result refers to Fig. 9.
The graphene powder obtained to comparative example (1) carries out transmissioning electric mirror test, and test result refers to Figure 10.
From Fig. 8 to Figure 10, it is relative with for comparative example (1), Fig. 8 of the graphene powder of embodiment (1) and (2) and
Occurs obvious diffraction fringe in Fig. 9, the crystallinity of the graphene powder of this explanation embodiment (1) and (2) is more preferable.
The graphene powder obtained to embodiment (1) carries out Raman spectrum test, and test result refers to Figure 11.
The graphene powder obtained to embodiment (2) carries out Raman spectrum test, and test result refers to Figure 12.
The graphene powder obtained to comparative example (1) carries out Raman spectrum test, and test result refers to Figure 13.
From Figure 11~Figure 13, embodiment (2) is in 1350cm-1Place shows weaker characteristic peak；And compared to pair
For ratio (1), the intensity of embodiment (2) wants weak many.In 1580cm in embodiment (1) and (2)-1With 1350cm-1Two
The strength ratio I of characteristic peakG/IdPeak intensity ratio of the ratio compared with two positions in comparative example (1) is big, and this explanation is through too high
After warm graphitization processing, the original fault of construction of grapheme material is repaired.
The graphene powder obtained to embodiment (1) carries out XRD tests, and test result refers to Figure 14.
The graphene powder obtained to embodiment (2) carries out XRD tests, and test result refers to Figure 15.
The graphene powder obtained to comparative example (1) carries out XRD tests, and test result refers to Figure 16.
It is relative with embodiment (1) and embodiment (2) from Figure 14~Figure 16, the graphene powder that comparative example (1) is obtained
It is wider (interplanar distance is calculated more than 0.35nm according to this feature peak correspondence) of the characteristic peak at 22 °~26 ° at 2 θ angles,
The piece interlamellar spacing of the graphene prepared in this explanation comparative example (1) is bigger.From Figure 14 and Figure 15, embodiment (1) and implementation
Example (2) occurs in that (calculate interplanar distance according to this feature peak correspondence is sharp characteristic peak at 2 θ angles for 26 ° of position
0.345nm)；And the half-peak breadth d at this feature peak is 0.34nm, is essentially close to the theoretic throat 0.34nm of single-layer graphene.
This also illustrates the graphene in the embodiment of the present application (1) and embodiment (2) described graphene powder has graphitization tendency, its
The reduction of interlamellar spacing.This is due to the carbon atom rearrangement in graphene repair process, and the defect on graphene sheet layer is carried out
Sufficient reparation, becomes the perfect graphene crystal of individual layer, and strong mutual between adjacent two single-layer graphenes
Effect, can cause it is recombined to tend to form two layers thicker or multi-layer graphene or thicker graphite flake again.
The graphene powder that is obtained to embodiment (1), embodiment (2) carries out the test of specific surface area, test result see
Table 1.
Table 1
| Specific surface area (m2/g) | |
| Embodiment (1) | 21~100 |
| Embodiment (2) | 350 |
From table 1, the specific surface area for the graphene powder that the embodiment (1), embodiment (2) are obtained is larger, and this enters
One step, which is confirmed, contains more a small number of layer graphenes in graphene powder, be adapted to further apply.
Further, the graphene powder obtained to embodiment (2) carries out the test of impurity content, 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 |
The content of impurity is few in table 2, embodiment (2) described graphene powder, and this further demonstrates this Shen
Graphene powder that please be obtained by the preparation method has fabulous application prospect.
Pattern test has been carried out to high-purity CNT that embodiment (3) is obtained, Figure 17 and Figure 18 is as a result seen.By Figure 17 and
Figure 18 is visible, and basic no significant defect in the structure of high-purity CNT after high temperature graphitization processing, structure is relatively smooth.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of device for being used to prepare carbon material, it is characterised in that the device is the container with a receiving space, the appearance
The top of device is opening and is provided with dismountable lid, and the material of the container and lid is high-density graphite.
2. the device as claimed in claim 1 for being used to prepare carbon material, it is characterised in that the inwall of the container is provided with least
One first through hole and coordinate and dismountable first sealing of hole part with first through hole, the material of the first sealing of hole part is high density
Graphite；The lid coordinates and dismountable second sealing of hole part provided with least one second through hole and with the second through hole, and described the
The material of two sealing of hole parts is high-density graphite.
3. the device as claimed in claim 1 for being used to prepare carbon material, it is characterised in that the high-density graphite is by graphite
Raw material passes through the graphite that high-temperature process is obtained, and the density of the high-density graphite is more than or equal to 1.85g/cm3。
4. the device as claimed in claim 3 for being used to prepare carbon material, it is characterised in that the graphite raw material is passed through into high temperature
Processing specifically refers to graphite raw material at a temperature of 2400 degrees Celsius~3000 degrees Celsius and is applied in 1 atmospheric pressure~3.6
The pressure treatment of individual atmospheric pressure.
5. a kind of method for preparing carbon material using such as any one of Claims 1-4 described device, it comprises the following steps：
(1) carbon material raw material is provided；
(2) the carbon material raw material is placed in the container, and will be equipped with the container of carbon material raw material in 1000 degrees Celsius~
3800 degrees Celsius of progress high temperature graphitization processing, obtain carbon material.
6. the method for preparing carbon material using said apparatus as claimed in claim 5, it is characterised in that described in step (1)
Carbon material raw material is carbon nanometer tube material or graphite raw material.
7. the method for preparing carbon material using said apparatus as claimed in claim 5, it is characterised in that described in step (2)
The time of high temperature graphitization processing is 10 hours~1000 hours.
8. the method for preparing carbon material using said apparatus as claimed in claim 6, it is characterised in that before step (2)
The step of also being aoxidized and reduced including a pair of graphite raw materials, be specially：Graphite raw material is aoxidized, obtains aoxidizing stone
Ink, then graphite oxide is placed in a saggar and reduced in an inert atmosphere under 1000 degrees Celsius~1100 degrees Celsius,
The material of wherein described saggar is high-density graphite.
9. the method for preparing carbon material using said apparatus as claimed in claim 8, it is characterised in that the saggar includes casket
Alms bowl main body and casket lid, the top of the saggar main body is opening, and the casket lid is placed on the top of saggar main body, wherein,
The saggar main body includes the external cavity of outer casket wall body and the formation of outer casket wall body, and the outer casket wall body is provided with a breach,
So that external cavity is connected with the external world；
Casket in one is additionally provided with the saggar main body, the interior casket includes the internal cavity of interior casket wall body and the formation of interior casket wall body,
The top of the interior casket is opening, and the internal cavity is connected with external cavity；
The casket lid includes casket caping and casket tegmental wall body, and the casket tegmental wall body is placed in the external cavity of the saggar main body, described
The height of casket tegmental wall body is less than the height of the outer casket wall body.
10. a kind of carbon material prepared using such as any one of claim 5 to 9 method, it is characterised in that the carbon material
Electrical conductivity be 3 × 104~1 × 106S/m, the basic zero defect of structure of the carbon material.
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| CN111573661A (en) * | 2020-06-04 | 2020-08-25 | 内蒙古中科四维热管理材料有限公司 | Preparation method and equipment of graphene slurry |
| CN111661839A (en) * | 2020-06-04 | 2020-09-15 | 内蒙古中科四维热管理材料有限公司 | Preparation method and equipment of graphene slurry and method for preparing heat dissipation film by using graphene slurry |
| CN114525427A (en) * | 2020-11-06 | 2022-05-24 | 湖南七点钟文化科技有限公司 | Tin-based alloy material, preparation method thereof, high-resistance film and preparation method thereof |
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| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
| CN104528693A (en) * | 2009-05-26 | 2015-04-22 | 创业发展联盟技术有限公司 | Carbon material and method for producing the same |
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| CN104528693A (en) * | 2009-05-26 | 2015-04-22 | 创业发展联盟技术有限公司 | Carbon material and method for producing the same |
| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111573661A (en) * | 2020-06-04 | 2020-08-25 | 内蒙古中科四维热管理材料有限公司 | Preparation method and equipment of graphene slurry |
| CN111661839A (en) * | 2020-06-04 | 2020-09-15 | 内蒙古中科四维热管理材料有限公司 | Preparation method and equipment of graphene slurry and method for preparing heat dissipation film by using graphene slurry |
| CN114525427A (en) * | 2020-11-06 | 2022-05-24 | 湖南七点钟文化科技有限公司 | Tin-based alloy material, preparation method thereof, high-resistance film and preparation method thereof |
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