CN107098338A - A kind of grapheme material and preparation method thereof, the saggar for preparing graphene - Google Patents

A kind of grapheme material and preparation method thereof, the saggar for preparing graphene Download PDF

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Publication number
CN107098338A
CN107098338A CN201710425378.XA CN201710425378A CN107098338A CN 107098338 A CN107098338 A CN 107098338A CN 201710425378 A CN201710425378 A CN 201710425378A CN 107098338 A CN107098338 A CN 107098338A
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saggar
casket
wall body
graphite
main body
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CN107098338B (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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to a kind of saggar for being used to prepare graphene, the material of the saggar is high-density graphite, the saggar includes saggar main body and casket lid, the top of the saggar main body is opening, 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, 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, and the internal cavity is connected with external cavity.The present invention also provides method and grapheme material that a kind of utilization described device prepares grapheme material.

Description

A kind of grapheme material and preparation method thereof, the saggar for preparing graphene
Technical field
The present invention relates to grapheme material, more particularly to it is a kind of be used to preparing the saggar of graphene, grapheme material and its Preparation method.
Background technology
Due to the development of new energy technology particularly electric vehicle engineering, to the high-performance power of high power capacity high power density Battery etc. proposes great demand.As a kind of two-dimension nano materials of high conductivity, graphene is considered as high performance dynamic One of critical material of power battery conductive agent.
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 a kind of casket that can be used for preparing the excellent grapheme material of electric conductivity on a large scale Alms bowl, preparation method and the excellent grapheme material of electric conductivity.
The present invention provides a kind of saggar for being used to prepare graphene, and the saggar includes saggar main body and casket lid, the casket The top of alms bowl 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 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.
It is preferred that, the interior casket wall body is made up of a pair of first baffles and a pair of second baffles, the height of the first baffle Height of the degree more than second baffle.
It is preferred that, the casket caping is made up of a top plate and the first recess, and first recess is formed at the top plate Surrounding, first recess minimum dimension of either direction on the surface of the top plate is all higher than the outer of the saggar main body The thickness of casket wall body.
It is preferred that, at least one second recess is set in first recess, length of second recess in x directions is more than institute State the thickness of the outer casket wall body of saggar main body.
It is preferred that, the material of the saggar is high-density graphite, and the high-density graphite is that graphite raw material is passed through into high temperature Obtained graphite is handled, the density of the high-density graphite is more than or equal to 1.85g/cm3。
It is preferred that, the graphite raw material is specifically referred to graphite raw material 2400 degrees Celsius~3000 by high-temperature process At a temperature of degree Celsius 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 for preparing grapheme material using above-mentioned saggar, and it comprises the following steps：
(1) graphite raw material is provided；
(2) graphite raw material is aoxidized, then the graphite after oxidation is placed in saggar and in an inert atmosphere in 1000 Degree Celsius~1400 degrees Celsius under reduced, obtain grapheme material, wherein the material of the saggar be high-density graphite.
It is preferred that, the time reduced described in step (2) is 20 minutes~20 hours.
It is preferred that, the temperature reduced described in step (2) be 1000 degrees Celsius~1100 degrees Celsius, the reduction when Between be 30 minutes~12 hours.
The present invention also provides the grapheme material that a kind of use above method is prepared, the conductance of the grapheme material Rate is 105More than S/m, the basic zero defect of structure of the grapheme material.
Compared with prior art, the material for being used to prepare the saggar of graphene is high-density graphite, thus is had Resistant to elevated temperatures advantage.
The effect of the breach of the outer casket wall body is so that external cavity is in communication with the outside, and is preparing grapheme material During, can be by the foreign gas produced in raw material such as water, sulfur dioxide (SO2) emissions to the external world.The interior casket, casket tegmental wall body are by institute The inner space for stating saggar main body is divided into three interconnected subspaces (internal cavity, the first sub- exocoel, the second sub- exocoel).Outside The breach of casket wall body, interior casket, casket tegmental wall body, the design of outer casket wall body form the structure of special complexity " labyrinth " formula, favorably In the longer and sinuous gas passage of formation.When being placed in graphite oxide in the internal cavity of the interior casket, in the work of high temperature Under, the graphite oxide of powdery obtains grapheme material, grapheme material and titanium dioxide after the stripping reduction for occurring explosion type The air-flowing type mixture that the gases such as sulphur are formed flows together, when running into the interior casket wall body (i.e. first baffle, that take blocking effect Two baffle plates), casket tegmental wall body and during outer casket wall body, air-flowing type mixture can collide therewith, so that the gas such as sulfur dioxide Body is discharged, and graphene powder is deposited, and greatly improves the recovery rate of grapheme material.
The saggar it is simple in construction, the method for preparing the saggar is simple, and raw material is easy to get, cheap, is adapted to large-scale Commercial application.
When in use, graphite oxide is put into the saggar, then graphite oxide reduce obtaining stone at high temperature Black alkene material.Relative to used in existing method prepare container or substrate for, due to the saggar material be high density Graphite, thus avoid introducing other extra impurity, while the saggar is as Space, Place is prepared, subsequently without such as CVD method The step of stripping group bottom, greatly facilitate the preparation of grapheme material.
During the method for existing use oxidationreduction prepares graphene, entered during due to reduction using hydrazine hydrate Row reduction, there is more defect in the obtained graphene, and impurity content is more；And graphite oxide is placed in institute by the application State in the saggar that high-density graphite material is made, by the way that the saggar is placed under hot environment, high temperature can be carried out to graphite oxide Graphitization obtains grapheme material.The preparation method, which puts into raw material and collects product, extremely to be facilitated, and recovery rate is high, and big rule can be achieved The preparation of mould, in actual applications, can be achieved hundred tonnes of other preparations.Also, in the preparation process, without adding other originals Material, therefore other impurity will not be introduced；Because substrate etc. is not used, without stripping.The whole preparation process step is simple, prepares Efficiency high.
The grapheme material obtained by the preparation method has advantages below：To graphite oxide only by high temperature reduction at Reason can obtain grapheme material, and the basic zero defect of grapheme material, thinner thickness, metals content impurity are extremely low, and With high conductivity.The obtained grapheme 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 saggar of the present invention.
Fig. 2 is the decomposing schematic representation of saggar described in Fig. 1.
Fig. 3 is the structural representation of the saggar main body of saggar described in Fig. 1.
Fig. 4 is the structural representation of the casket lid of saggar described in Fig. 1.
Fig. 5 is transmission electron microscope (TEM) photo for the grapheme material that (1) of the embodiment of the present invention is obtained.
Fig. 6 is the TEM photos for the grapheme material that comparative example (1) is obtained.
Fig. 7 is the Raman spectrogram for the grapheme material that (1) of the embodiment of the present invention is obtained.
Fig. 8 is the Raman spectrogram for the grapheme material that comparative example (1) is obtained.
Fig. 9 is X-ray diffraction (XRD) figure for the grapheme material that (1) of the embodiment of the present invention is obtained.
Figure 10 is the XRD for the grapheme material that comparative example (1) is obtained.
Wherein, 10 casket lid is represented, 10a represents casket caping, and 10a1 represents top plate；10a2 represents the first recess, and 10a3 is represented Second recess, 10b represents casket tegmental wall body, and 20 represent saggar main body, and 20a represents outer casket wall body, 20b indication notch, and 20c represents outer Cavity, 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
Below with reference to accompanying drawing to the saggar, grapheme material and its preparation side provided by the present invention for preparing graphene Method is described further.
The present invention provides a kind of saggar for being used to prepare graphene.Fig. 1 is referred to Fig. 4, the saggar includes casket lid 10 With saggar main body 20.The top of the saggar main body 20 is opening, and the casket lid 10 is placed on the top of saggar main body 20.The casket Alms bowl main body 20 and casket lid 10 be it is separate, the casket lid 10 be not tightly fastened in the saggar main body 20 i.e. both not tie Integrator.The casket lid 10 is only placed on the top of the saggar main body 20 and while using.Because, the graphene system During standby, due to the particular design of saggar, the flour such as graphite raw material in saggar is basic in saggar, and can't be big Amount flies to the external world, and only very small amount is escaped, can be neglected herein.Therefore, casket lid 10 need not be fixed on saggar main body 20, this reduces Complexity prepared by saggar, the use of saggar is also more simple.
Referring to Fig. 3, 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. 2 and Fig. 3, 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, obtain the less grapheme material of the number of plies.
Fig. 2 and Fig. 4 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. 4, 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. 2 and Fig. 4 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 material of the saggar is high-density graphite.The high-density graphite refers to graphite raw material passing through high temperature and height The graphite that pressure processing is obtained.Specifically, at a temperature of 2400 degrees Celsius~3000 degrees Celsius and graphite raw material is applied in into 1 The pressure treatment of atmospheric pressure~3.6 atmospheric pressure, can obtain the high-density graphite.It is preferred that, graphite raw material is taken the photograph 2500 At a temperature of family name degree~2800 degree Celsius and the pressure treatments of 3.6 atmospheric pressure is applied in, can obtain the high-density graphite.Institute State graphite raw material to be commercially available, will not be described here.It is appreciated that by graphite raw material by high temperature and HIGH PRESSURE TREATMENT it Afterwards, the step of also carrying out a turnning and milling, to obtain the saggar with given shape.
Because the material of the saggar is high-density graphite, thus high temperature is can tolerate, and due to preparing graphene material The contained element of material is identical, is carbon, therefore, does not bring extra impurity.For it is existing prepare grapheme material when Dust is easily flown upward without easily by fixed shortcoming, herein described saggar specialized application caused by powdered graphite material density is small In the preparation of grapheme material, it can conveniently accommodate raw material and prepare grapheme material on a large scale.The structure of the device is also simple It is single, easily prepare, cost is relatively low, beneficial to industrial applications.
The present invention also provides a kind of method for preparing grapheme material using above-mentioned saggar.This method comprises the following steps：
There is provided graphite raw material by S1；
S2, is aoxidized to graphite raw material, then the graphite after oxidation is placed in a saggar and in an inert atmosphere in Reduced under 1000 degrees Celsius~1400 degrees Celsius, wherein the material of the saggar is high-density graphite.
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, in the method for the oxidation, intercalator (carrying out intercalation to graphite), sodium nitrate are used as using the concentrated sulfuric acid As intercalation agent aid (sodium nitrate in the presence of sulphuric acid have strong oxidizing property), potassium permanganate is as strong oxidizer by graphite oxygen It is melted into graphite oxide.Afterwards, hydrogen peroxide can be added and remove excessive potassium permanganate, and hydrochloric acid remove sodium ion and sulfate radical from Son, obtains more pure graphite oxide.
The mechanism that the graphite oxide is reduced is：Under inert atmosphere, graphite oxide is caused by the environment of high temperature The oxy radical chemical bond on surface is destroyed and is broken at high temperature, micromolecular water and carbon dioxide effusion is formed, while largely The small molecule of effusion increases the interlamellar spacing between lamella in graphite oxide；I.e. while high temperature reduction, more than the number of plies Graphite oxide, which is automatically also, peels off into the less grapheme material of the number of plies.Herein described grapheme material refers to that the number of plies is 1~5 Graphene.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 grapheme material.This also allows for the requirement of high-temperature process, and And do not introduce extra impurity in the reaction yet, and conveniently pick and place article from the saggar.
Upon step s 2, the step of may also include a mechanical stripping.The mechanical stripping can use solid phase or liquid phase The method of stripping.Specifically, the grapheme material that step S2 is obtained is lived with solvent such as water, 1-METHYLPYRROLIDONE, surface Property the mixing such as agent, by once or repeatedly mechanical stripping, obtain the less grapheme material of the number of plies.Grapheme material passes through machine After tool is peeled off, the number of plies is less, and electric conductivity 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.
The present invention also provides a kind of grapheme material obtained by above-mentioned preparation method.The grapheme material substantially without Defect, thinner thickness, individual layer rate are higher, metals content impurity is extremely low, and with high conductivity.The electricity of the grapheme material Conductance is 105More than S/m.
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 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, obtain grapheme material, wherein the material of the saggar is high density stone Ink.
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 graphene powder obtained to embodiment (1) carries out transmissioning electric mirror test, and test result refers to Fig. 5.
The graphene powder obtained to comparative example (1) carries out transmissioning electric mirror test, and test result refers to Fig. 6.
From Fig. 5, Fig. 6, it is relative with for comparative example (1), Fig. 5 of the graphene powder of embodiment (1) occurs obvious Diffraction fringe, this explanation embodiment (1) graphene powder crystallinity it is more preferable.
The graphene powder obtained to embodiment (1) carries out Raman spectrum test, and test result refers to Fig. 7.
The graphene powder obtained to comparative example (1) carries out Raman spectrum test, and test result refers to Fig. 8.
From Fig. 7~Fig. 8, embodiment (1) is in 1350cm-1Place shows weaker characteristic peak；And compared to contrast For example (1), the intensity of embodiment (1) wants weak many.In 1580cm in embodiment (1)-1With 1350cm-1Two characteristic peaks Strength ratio IG/IdRatio is big compared with the peak intensity ratio of two positions in comparative example (1), and this explanation passes through high temperature graphitization After 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 Fig. 9.
The graphene powder obtained to comparative example (1) carries out XRD tests, and test result refers to Figure 10.
Relative with embodiment (1) from Fig. 9 and Figure 10, the graphene powder that comparative example (1) is obtained is 22 ° at 2 θ angles Wider (interplanar distance is calculated more than 0.35nm according to this feature peak correspondence) of characteristic peak at~26 °, this explanation contrast The piece interlamellar spacing of the graphene prepared in example (1) is bigger.As seen from Figure 10, embodiment (1) is occurred in that at 2 θ angles for 26 ° of position Sharp characteristic peak (interplanar distance is calculated for 0.345nm according to this feature peak correspondence)；And the half-peak breadth d at this feature peak For 0.34nm, the theoretic throat 0.34nm of single-layer graphene is essentially close to.This also illustrates the embodiment of the present application (1) stone Graphene in black alkene powder has graphitization tendency, the reduction of its interlamellar spacing.This is due to the carbon in graphene repair process Atomic rearrangement, and form single-layer graphene, and interaction strong between adjacent two single-layer graphenes, can cause it again Recombining tends to form two layers thicker or multi-layer graphene.
The graphene powder obtained to embodiment (1) carries out the test of specific surface area.The ratio surface of the graphene powder Product is 350g/cm2, this further demonstrates that containing more graphene in graphene powder, it is adapted to further apply.
Further, the grapheme material obtained to embodiment (1) carries out the test of impurity content, the results are shown in Table 1.
Table 1
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
From table 1, embodiment 1) content of impurity is few in the grapheme material, and this further demonstrates the application Grapheme material obtained by the preparation method has fabulous application prospect.
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 saggar for being used to prepare graphene, it is characterised in that the saggar includes saggar main body and casket lid, the saggar The top of 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.
2. the saggar as claimed in claim 1 for being used to prepare graphene, it is characterised in that the interior casket wall body is by a pair first Baffle plate and a pair of second baffle compositions, the height of the first baffle are more than the height of second baffle.
3. the as claimed in claim 1 saggar for being used to prepare graphene, it is characterised in that the casket caping by a top plate and First recess is constituted, and first recess is formed at the surrounding of the top plate, and first recess is on the surface of the top plate The minimum dimension of either direction is all higher than the thickness of the outer casket wall body of the saggar main body.
4. the saggar as claimed in claim 3 for being used to prepare graphene, it is characterised in that set at least one in first recess Second recess, length of second recess in x directions is more than the thickness of the outer casket wall body of the saggar main body.
5. the saggar as claimed in claim 1 for being used to prepare graphene, it is characterised in that the material of the saggar is high density Graphite, the high-density graphite is that graphite raw material is passed through into 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。
6. the saggar as claimed in claim 5 for being used to prepare graphene, 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.
7. a kind of method for preparing grapheme material using the saggar as described in any one of claim 1 to 6, it includes following step Suddenly：
(1) graphite raw material is provided；
(2) graphite raw material is aoxidized, then the graphite after oxidation is placed in saggar and Celsius in 1000 in an inert atmosphere Reduced under~1400 degrees Celsius of degree, obtain grapheme material, wherein the material of the saggar is high-density graphite.
8. the method for grapheme material is prepared using above-mentioned saggar as claimed in claim 7, it is characterised in that in step (2) The time of the reduction is 20 minutes~20 hours.
9. the method for grapheme material is prepared using above-mentioned saggar as claimed in claim 7, it is characterised in that in step (2) Described in the temperature that reduces be 1000 degrees Celsius~1100 degrees Celsius, the time of the reduction is 30 minutes~12 hours.
10. a kind of grapheme material prepared using such as any one of claim 7 to 9 method, it is characterised in that the stone The electrical conductivity of black alkene material is 105More than S/m, the basic zero defect of structure of the grapheme material.
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