CN109761224A - A kind of method and graphene preparing graphene with graphene oxide - Google Patents
A kind of method and graphene preparing graphene with graphene oxide Download PDFInfo
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- CN109761224A CN109761224A CN201811495431.4A CN201811495431A CN109761224A CN 109761224 A CN109761224 A CN 109761224A CN 201811495431 A CN201811495431 A CN 201811495431A CN 109761224 A CN109761224 A CN 109761224A
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Abstract
The present invention provides a kind of methods and graphene that graphene is prepared with graphene oxide.It is sufficiently reacted the described method includes: the graphene oxide containing oxygen-containing functional group and containing metal impurities and/or nonmetallic inclusion is placed in 30Pa~500Pa and 1250 DEG C or more of environment, obtains graphene.The carbon-to-oxygen ratio of the graphene is 18.0 or more.The present invention prepares graphene under certain temperature, air pressure and time, it takes full advantage of graphene and melts the high feature of boiling point, metal, nonmetallic inclusion in graphene oxide are removed by high temperature, while removing a large amount of oxygen-containing functional groups of institute's band, repairs SP resulted in graphene preparation process3Hydridization defect, graphene impurity content is low, and fault of construction is few, excellent combination property.
Description
Technical field
The present invention relates to technical field of new material preparation, more particularly, are related to a kind of preparing graphite with graphene oxide
The method and graphene of alkene.
Background technique
2004, physicist An Deliehaimu and Constantine the Nuo Woxiao love of graceful Chester university, Britain were first
Single-layer graphene has been isolated from graphite first with mechanical stripping method, and has studied its quasi particle and field-effect characteristic.
The discovery has caused rapidly the research boom of a graphene, in a few years time, the research and application of graphene in the whole world
It is flourished.
The bi-dimensional cellular shape network structure that graphene is made of carbon atom is that one kind can be separated directly from graphite
The plane materiel material come, being made of single layer of carbon atom.The arrangement of carbon atom belongs to compound hex crystal as graphite in graphene
Structure is constituted between each carbon atom and its three most adjacent carbon atom with the mutual stacking of SP2 hybridized orbit on two-dimensional surface
Three σ keys, and a remaining P orbital electron (Π electronics) is formed perpendicular to graphene planes with the Π key of carbon atom around
Delocalization large Π bond.The atom only different there are two types of spatial position on the same atomic plane of graphene.
Structurally, graphene is the basic unit of other all carbon nanomaterials.For example, it can be warped into zero dimension
Fullerene, be curled into one-dimensional carbon nanotube, be stacked to three-dimensional graphite.This unique design feature imparts graphene
The performances such as excellent physics, chemistry and mechanics.
Excellent electric conductivity.Graphene-structured is highly stable.Connection in graphene between each atom is very flexible, when
When stone man external mechanical force, carbon atom face occurs bending and deformation, and makes carbon atom that need not be rearranged to adapt to external force, is also maintained for
Stability in structure.This stable crystal structure makes carbon atom have excellent electric conductivity.Because of the electricity in graphene
When son moves in orbit, it will not be scattered due to lattice defect or introducing foreign atom.In addition, due between carbon atom very
Strong interaction force, therefore, surrounding carbon atom telescopes at normal temperature immediately, electronics is subject in graphene interference nor
It is often small.Its electronic movement velocity can reach the 1/300 of the light velocity, considerably beyond movement velocity of the electronics in general conductor.
Excellent mechanical property.Graphene is the highest substance of mankind's known strength, and also harder than diamond, intensity compares the world
Above best taller upper 100 times of steel or so.Theoretical calculation and experiment detection show the tensile strength and springform of graphene
Amount respectively reaches 125GPa and 1100GPa.
Excellent light transmission.Experiment and notional result show that single-layer graphene only absorbs 2.3% visible light,
That is the light transmittance of visible light is up to 97.7%, and in conjunction with its excellent electric conductivity and mechanical property, graphene can replace oxidation
The conventional conductives thin-film material such as indium tin, fluorine-doped tin oxide can both overcome the brittleness feature of conventional conductive film, can also solve indium money
The problems such as source is short.
These unique performance characteristics make graphene in electronic device (field-effect, radio circuit etc.), optical device (laser
Device, ultrafast electro-optical device etc.), quantum effect device, chemistry, biosensor, composite material, energy storage material and device
Have wide practical use in terms of (supercapacitor, lithium ion battery, fuel cell etc.) field.
Currently, the graphene preparation method of mainstream has mechanical stripping method, oxidation-reduction method, epitaxial growth method, chemical vapor
Sedimentation etc., wherein oxidation-reduction method due to its is low in cost, production equipment is simple, single yield is maximum, in gas producing formation manifold,
The advantages that lateral dimension is uniform becomes industrialized production most popular method.But the graphene prepared with the method, due to being inserted in oxidation
During layer, the crystal structure of its own is easily broken, and is caused graphene internal flaw to increase, is significantly influenced
The performance of graphene；On the other hand, using the graphene of oxidation-reduction method production there is also a large amount of metals, nonmetallic inclusion,
This also further affects large-scale development and the application of graphene.
Summary of the invention
It is above-mentioned existing in the prior art it is an object of the present invention to solving for the deficiencies in the prior art
One or more problems.For example, one of the objects of the present invention is to provide a kind of fault of construction is few, the graphite of excellent combination property
Alkene.
To achieve the goals above, an aspect of of the present present invention provides a kind of side that graphene is prepared with graphene oxide
Method, the method may include following steps: by the oxygen containing oxygen-containing functional group and containing metal impurities and/or nonmetallic inclusion
Graphite alkene, which is placed in 30Pa~500Pa and 1250 DEG C or more of environment, sufficiently to react, and obtains graphene.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the metal is miscellaneous
Matter is one of iron, manganese, potassium and sodium or a variety of, and the nonmetallic inclusion is one or both of sulphur, silicon.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the oxygen-containing official
Can roll into a ball may include one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the oxidation stone
The carbon-to-oxygen ratio of black alkene can be between 0.5~2.0, and the carbon-to-oxygen ratio of the graphene can be 18.0 or more.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the oxidation stone
Heating time of the black alkene in the environment can be 60min~600min.
It is described to aoxidize in an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide
The step that graphene is placed in the environment may include that graphene oxide is laid in carrier, then is placed in the environment,
The carrier is for graphite carrier or in the container for being coated with graphite linings with graphene oxide contact surface.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the environment
Air pressure can be 60Pa~100Pa, and the temperature of the environment can be 1700 DEG C~2500 DEG C.
In an exemplary embodiment of the method for the invention for preparing graphene with graphene oxide, the environment
Air pressure can be 85Pa~95Pa, and the temperature of the environment can be 1700 DEG C~2200 DEG C.
Another aspect provides a kind of graphene, the graphene is by above-described with graphene oxide system
The method of standby graphene is prepared.
Compared with prior art, the beneficial effect comprise that the present invention utilizes high-temperature vacuum in certain temperature, gas
Graphene is prepared under pressure and time, the high feature of the molten boiling point of graphene is taken full advantage of and is made a return journey under vacuum conditions by high temperature
Except metal, the nonmetallic inclusion in graphene, while a large amount of oxygen-containing functional groups of graphene oxide institute band are removed, repairs oxidation stone
Black alkene during the preparation process caused by SP3Hydridization defect.The graphene impurity content being prepared is low, and fault of construction is few, comprehensive
Conjunction is had excellent performance.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 shows the SEM electron microscopic picture of the graphene oxide of an illustrative embodiment of the invention；
Fig. 2 shows the BET adsorption desorption curves of the graphene oxide of an illustrative embodiment of the invention；
The 60min that handles under the conditions of 2200 DEG C/93Pa that Fig. 3 shows an illustrative embodiment of the invention is prepared
Graphene SEM electron microscopic picture；
The 60min that handles under the conditions of 2200 DEG C/93Pa that Fig. 4 shows an illustrative embodiment of the invention is prepared
Graphene BET adsorption desorption curve；
The 180min that handles under the conditions of 2200 DEG C/93Pa that Fig. 5 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 180min that handles under the conditions of 2200 DEG C/93Pa that Fig. 6 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived；
The 300min that handles under the conditions of 2200 DEG C/93Pa that Fig. 7 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 300min that handles under the conditions of 2200 DEG C/93Pa that Fig. 8 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived；
The 300min that handles under the conditions of 1689 DEG C/93Pa that Fig. 9 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 300min that handles under the conditions of 1689 DEG C/93Pa that Figure 10 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived；
The 300min that handles under the conditions of 2500 DEG C/93Pa that Figure 11 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 300min that handles under the conditions of 2500 DEG C/93Pa that Figure 12 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived；
The 300min that handles under the conditions of 2200 DEG C/65Pa that Figure 13 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 300min that handles under the conditions of 2200 DEG C/65Pa that Figure 14 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived；
The 300min that handles under the conditions of 2200 DEG C/83Pa that Figure 15 shows an illustrative embodiment of the invention is prepared into
The graphene SEM electron microscopic picture arrived；
The 300min that handles under the conditions of 2200 DEG C/83Pa that Figure 16 shows an illustrative embodiment of the invention is prepared into
The graphene BET adsorption desorption curve arrived.
Specific embodiment
Hereinafter, will be described in detail in conjunction with attached drawing and exemplary embodiment a kind of graphene according to the present invention and its
Preparation method.
Specifically, in the existing preparation process for preparing graphene oxide, such as using Hummers graphite oxide is prepared
Alkene, preparation product in contain comparable metal and/or nonmetallic inclusion, cause preparation graphene it is impure.Also,
In existing graphene preparation process, in particular with graphene prepared by oxide-reduction method, it will lead in graphene and contain
Have a large amount of metal and/or nonmetallic inclusion, and during aoxidizing intercalation, the crystal structure of graphene itself be easy to by
It destroys, the internal flaw that will lead to graphene increases, and can significantly influence the performance of graphene.The present invention utilizes graphene
The molten boiling point difference for containing impurity with it controls temperature, pressure and reaction time appropriate in vacuum environment,
While effectively removing impurity, the SP3 fault of construction in graphene oxide can be repaired and remove its oxygen-containing functional group, and then made
It is standby to obtain the higher high-quality graphene of purity.Temperature range appropriate can make the SP in graphene oxide3Fault of construction is able to
It repairs, then is aided with vacuum condition, can remove a large amount of oxygen-containing functional groups of graphene oxide institute band, to form graphene, and can
Metal and/or nonmetallic inclusion are removed from graphene oxide in the form of a vapor, and then it is higher excellent that purity is prepared
Matter graphene.Moreover, the effect of vacuum condition can also reduce the fusing point and boiling point of impurity, in turn in high-temperature heating process
Requirement of the preparation process to temperature is reduced, to achieve the effect that energy conservation and cost squeeze.
Fig. 1 shows the SEM electron microscopic picture of the graphene oxide of an illustrative embodiment of the invention；Fig. 2 shows this
Invent the BET adsorption desorption curve of the graphene oxide of an exemplary embodiment；Fig. 3 shows an example of the present invention implementation
The graphene SEM electron microscopic picture for handling 60min under the conditions of 2200 DEG C/93Pa and being prepared of example；Fig. 4 shows the present invention one
The graphene BET adsorption desorption curve for handling 60min under the conditions of 2200 DEG C/93Pa and being prepared of a exemplary embodiment；Fig. 5
Show the graphene for handling 180min under the conditions of 2200 DEG C/93Pa and being prepared of an illustrative embodiment of the invention
SEM electron microscopic picture；Fig. 6 shows processing 180min system under the conditions of 2200 DEG C/93Pa of an illustrative embodiment of the invention
Standby obtained graphene BET adsorption desorption curve；Fig. 7 show an illustrative embodiment of the invention in 2200 DEG C/93Pa item
The graphene SEM electron microscopic picture that 300min is prepared is handled under part；Fig. 8 show an illustrative embodiment of the invention
The graphene BET adsorption desorption curve that 300min is prepared is handled under the conditions of 2200 DEG C/93Pa；Fig. 9 shows the present invention one
The graphene SEM electron microscopic picture for handling 300min under the conditions of 1689 DEG C/93Pa and being prepared of exemplary embodiment；Figure 10 shows
The graphene BET for handling 300min under the conditions of 1689 DEG C/93Pa and being prepared of an illustrative embodiment of the invention is gone out
Adsorption desorption curve；Figure 11 shows processing 300min system under the conditions of 2500 DEG C/93Pa of an illustrative embodiment of the invention
Standby obtained graphene SEM electron microscopic picture；Figure 12 show an illustrative embodiment of the invention in 2500 DEG C/93Pa condition
The graphene BET adsorption desorption curve that lower processing 300min is prepared；Figure 13 shows an illustrative embodiment of the invention
The graphene SEM electron microscopic picture that 300min is prepared is handled under the conditions of 2200 DEG C/65Pa；Figure 14 shows the present invention one
The graphene BET adsorption desorption curve for handling 300min under the conditions of 2200 DEG C/65Pa and being prepared of exemplary embodiment；Figure 15
Show the graphene for handling 300min under the conditions of 2200 DEG C/83Pa and being prepared of an illustrative embodiment of the invention
SEM electron microscopic picture；Figure 16 shows processing 300min system under the conditions of 2200 DEG C/83Pa of an illustrative embodiment of the invention
Standby obtained graphene BET adsorption desorption curve.
An aspect of of the present present invention provides a kind of graphene preparation method, at one of graphene preparation method of the invention
In exemplary embodiment, the preparation method may include by the graphene oxide containing metal impurities and/or nonmetallic inclusion
It is placed in vacuum environment, heating is at air pressure 30Pa~500Pa, 1250 DEG C of conditions above of temperature to remove oxygen-containing functional group
And impurity, obtain few, with high purity, good combination property the graphene of fault of construction.
In the present embodiment, the metal impurities may include the combination of one or more of iron, manganese, potassium, sodium etc..It is described
Nonmetallic inclusion may include one of impurity such as sulphur, silicon or two kinds of combinations.
More than, the metal impurities and nonmetallic inclusion contained in graphene oxide are with gaseous under vacuum environment
Form is volatilized away.At high temperature, normal atmosphere is depressed, such as under 2000 DEG C or so of hot conditions, can achieve oxidation
The fusing point and boiling point of the metal impurities and nonmetallic inclusion that contain in graphene, to be separated from graphene oxide.Further,
Under certain vacuum degree, the fusing point and boiling point of metal impurities and nonmetallic inclusion can be reduced further, be set through the invention
The temperature and vacuum degree set are easy to the metal impurities and nonmetallic inclusion contained in removal graphene oxide.Oxygen of the invention
The type of the metal and nonmetallic inclusion that contain in graphite alkene is not limited to above-described impurity, other can be in height of the invention
The impurity that can be volatilized under temperature and vacuum environment.
In the present embodiment, further, the air pressure of the environment can be 60Pa~100Pa, further, environment
Air pressure can be 65Pa~100Pa.Under the ambient pressure that is arranged of the present invention, the fusing point for the impurity that graphene oxide contains and
Boiling point is lower, it is easier to volatilization removal.Further, the temperature of the environment can be 1250 DEG C~2500 DEG C, more into one
Step, the temperature of the environment can be 1250 DEG C~2200 DEG C.Environment temperature of the invention, which is arranged, to be advantageous in that, if warm
Degree is lower than 1250 DEG C, and the volatilization for being unfavorable for impurity is gone out, and the fusing point and boiling point of certain impurity may be not achieved.Preferably, it is arranged
Temperature be not higher than 2500 DEG C.If the temperature being arranged is higher than 2500 DEG C, temperature too it is high may loss to stove it is serious, energy
Consume larger, higher cost.For example, temperature can be 2200 DEG C, it is advantageous since 2200 DEG C be carbon material graphitization temperature, and also
In the self-defect for repairing graphene oxide.
In the present embodiment, heating time of the graphene oxide under vacuum environment can be 60min~600min.
Above-mentioned heating time, which is arranged, to be advantageous in that, if heating time is lower than 60min, the heating time of possible graphene oxide is not
It is enough, it cannot adequately remove impurity；Heating time is higher than 600min, and heating time is too long, and energy consumption consumption is too big.Preferably, add
The hot time is 120min~300min.
In the present embodiment, the oxygen-containing functional group in the graphene oxide includes carboxyl, hydroxyl, carbonyl, ehter bond and ring
One of oxygroup is a variety of.Above-mentioned oxygen-containing functional group can be decomposed into two under the high temperature and air pressure conditions that the present invention is arranged
Carbonoxide and water can effectively remove the oxygen-containing functional group in graphene oxide.Theoretically speaking in 1000 DEG C of temperature and
Functional group can be removed under vacuum environment of the invention, but since the temperature of impurity removal is higher, present invention setting
Temperature should be higher than 1250 DEG C.The SEM electron microscopic picture of the graphene oxide is as shown in Figure 1, BET adsorption desorption curve such as Fig. 2
It is shown.Certainly, oxygen-containing functional group of the invention is without being limited thereto, can be decomposed at temperature and air pressure of the invention carbon dioxide and
Water.
In the present embodiment, the graphene oxide can be made by following steps: first with low-temperature oxidation intercalation
To graphite oxidation intercalation and be separated into slurry, then by freeze-drying graphene oxide is prepared, then 500 DEG C~
600 DEG C, such as in 500 DEG C of processing graphene oxides.However, it is to be understood that the preparation method of the graphene oxide is simultaneously
It is not limited to this.
In the present embodiment, such as graphene oxide is placed directly in the equipment of high-temperature vacuum (for example, being placed in high-temperature vacuum
In furnace), it will cause graphene oxide and contacted with the direct of equipment, be likely to result in graphene oxide and polluted by other impurities, dropped
The low graphene purity that it is prepared.It is preferred, therefore, that graphene oxide can be placed in carrier, then it is placed in again
It, in this way can be to avoid adhesion of the graphene in high temperature dedoping step with furnace wall, between graphene in vacuum environment
Adhesion, and because of graphene reduced performance caused by adhesion (for example, the number of plies increase etc.), and can be to avoid to furnace wall
Attachment etc..In order to avoid carrier impacts graphene purity, and since the fusing point of graphite is up to 3652 DEG C, much higher than normal
See the molten boiling point of metal impurities and nonmetallic inclusion, and in treatment process, it will not be introduced because of carrier medium in graphene
His element impurity.Therefore, it is possible to use graphite carrier or surface be coated with graphite linings container, for example, graphite alms bowl.When
The right container must be container resistant to high temperature.But the present invention is not limited to this, other molten boilings also can be selected in the carrier medium
Point higher carrier medium, such as tungsten foil, tantalum carbide carrier or hafnium carbide carrier etc..
More than, graphene oxide can select the mode of tiling to be placed in the carrier.It is advantageous in that, is put down using tiling
Paving can make the heating surface area of graphene oxide bigger, be conducive to sufficiently removal impurity, while in a certain amount of feelings of graphene oxide
Under condition, tiles and produce the bigger graphene of area.
In the present embodiment, vacuum high temperature furnace can be selected to carry out high-temperature vacuum processing to graphene oxide.For example, described
Vacuum high temperature furnace can select purifying furnace.
In the present embodiment, before high-temperature vacuum processing, the carbon-to-oxygen ratio that contains in the graphene oxide can 0.5~
Between 2.0.Carbon-to-oxygen ratio highest can achieve 2 (C:O=2:1).After method high-temperature vacuum processing of the invention, in graphene
Carbon-to-oxygen ratio can be improved to 18 or more, for example, can achieve 20.Oxygen element mostlys come from the oxygen-containing official in graphene oxide
It can roll into a ball, oxygen content is lower, shows that the performance for the graphene that the quantity of oxygen-containing functional group is fewer, is prepared is better.
In the present embodiment, ferro element and manganese element content can achieve less than 65ppm in the graphene.Further
, iron content can achieve less than 50ppm, and further, iron content can achieve less than 20ppm.Aoxidize stone
The time that black alkene reacts in vacuum environment is longer, and impurity content is lower.It is prepared in the existing method for preparing stone alkene
Generally all in 2000ppm or more, preparation method of the invention can be reduced effectively in graphene the content of obtained graphene
The impurity iron contained can be preferably used in as lithium ion battery conductive additive.The specific surface area of graphene can reach
To 58m2/ g or more.Further, the specific surface area of graphene can achieve 100m2/ g or more.Conductivity can be 900S/cm
~1500S/cm.For raw material graphene oxide, the conductivity of graphene oxide is substantially in 0.1S/cm~20S/cm, warp
After crossing reaction, the graphene conductive rate being prepared can achieve 900S/cm~1500S/cm, there is significant increase.
Another aspect provides a kind of graphenes.In an exemplary embodiment of graphene of the invention
In, the graphene can be prepared by above-mentioned graphene preparation method.The carbon-to-oxygen ratio that the graphene contains can be
18.0 or more.
The above exemplary embodiments for a better understanding of the present invention carry out further it below with reference to specific example
Explanation.
Example 1
A kind of graphene preparation method, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is laid in graphite alms bowl, and by the carrier
It is put into vacuum high temperature furnace.
S2: vacuum high temperature furnace is evacuated to negative pressure 93Pa.
S3: it is 2200 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 60min.
Obtain graphene after the completion of above-mentioned three step, taking-up carrier to be cooled to room temperature, the Fe element for measuring graphene is miscellaneous
Matter content is 45.5ppm.According to BET adsorption desorption song calculate specific surface area be 206.3m2/g.Compared with existing graphene, this hair
The graphene purity of bright preparation is higher.The SEM electron microscopic picture of the graphene of preparation is as shown in figure 3, BET adsorption desorption curve such as Fig. 4
It is shown.
Example 2
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is placed in graphite alms bowl carrier, and by the load
Body is put into purifying furnace.
S2: the purifying furnace is evacuated to negative pressure 93Pa.
S3: it is 2200 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 180min.
Obtain graphene after the completion of above-mentioned three step, taking-up carrier to be cooled to room temperature, the Fe element for measuring graphene is miscellaneous
Matter content is 34.3ppm.According to BET adsorption desorption song calculate specific surface area be 194.8m2/g.Compared with existing graphene, now make
Standby graphene purity is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in figure 5, BET adsorption desorption curve such as Fig. 6 institute
Show.
Example 3
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is laid in graphite alms bowl carrier, and will be described
Carrier is put into vacuum high temperature furnace.
S2: the vacuum high temperature furnace is evacuated to negative pressure 93Pa.
S3: it is 2200 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 300min.
Graphene is obtained after the completion of above-mentioned three step, carrier is taken out after being cooled to room temperature, measures the Fe element of graphene
Impurity content is 11.6ppm.According to BET adsorption desorption song calculate specific surface area be 134.4m2/ g, it is existing compared with existing graphene
The graphene purity of preparation is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in fig. 7, BET adsorption desorption curve such as Fig. 8
It is shown.
Example 4
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is placed in graphite alms bowl carrier, and by the load
Body is put into vacuum high temperature furnace.
S2: the vacuum high temperature furnace is evacuated to negative pressure 93Pa.
S3: it is 1689 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 300min.
Graphene is obtained after the completion of above-mentioned three step, carrier is taken out after being cooled to room temperature, measures the Fe element of graphene
Impurity content is 60.5ppm.According to BET adsorption desorption song calculate specific surface area be 125.7m2/g.It is existing compared with existing graphene
The graphene purity of preparation is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in figure 9, BET adsorption desorption curve such as Figure 10
It is shown.
Example 5
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is placed in graphite alms bowl carrier, and by the load
Body is put into vacuum high temperature furnace.
S2: the vacuum high temperature furnace is evacuated to negative pressure 93Pa.
S3: it is 2500 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 300min.
Graphene is obtained after the completion of above-mentioned three step, carrier is taken out after being cooled to room temperature, measures the Fe element of graphene
Impurity content is 1.51ppm.According to BET adsorption desorption song calculate specific surface area be 58.96m2/g.It is existing compared with existing graphene
The graphene purity of preparation is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in figure 11, and BET adsorption desorption curve is as schemed
Shown in 12.
Example 6
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide containing impurity such as iron, manganese, potassium, sodium, silicon is placed in carrier, and the carrier is put into
In vacuum high temperature furnace.
S2: the vacuum high temperature furnace is evacuated to negative pressure 65Pa.
S3: it is 2200 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 300min.
Graphene is obtained after the completion of above-mentioned three step, carrier is taken out after being cooled to room temperature, measures the Fe element of graphene
Impurity content is 13.7ppm.According to BET adsorption desorption song calculate specific surface area be 75.5m2/g.Compared with existing graphene, now make
Standby graphene purity is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in figure 13, BET adsorption desorption curve such as Figure 14
It is shown.
Example 7
A kind of preparation method of graphene, comprising the following steps:
S1: the graphene oxide of the impurity such as iron content, manganese, potassium, sodium, silicon is placed in carrier, and the carrier is put into height
In warm vacuum drying oven.
S2: the vacuum high temperature furnace is evacuated to negative pressure 83Pa.
S3: it is 2200 DEG C by the temperature setting of the vacuum high temperature furnace, and heats 300min.
Graphene is obtained after the completion of above-mentioned three step, carrier is taken out after being cooled to room temperature, measures the Fe element of graphene
Impurity content is 12.3ppm.According to BET adsorption desorption song calculate specific surface area be 126.2m2/g.It is existing compared with existing graphene
The graphene purity of preparation is higher.The SEM electron microscopic picture of the graphene now prepared is as shown in figure 15, and BET adsorption desorption curve is as schemed
Shown in 16.
The summary sheet of technological parameter and results of measuring is as shown in the table in above-mentioned example 1~7:
As can be seen from the above table, comparative examples 1,2,3, in reasonable negative pressure, heating temperature and within the scope of heating time,
When negative pressure is identical with heating temperature, heating time is longer, and Fe elemental impurity levels are lower.In view of continuous heating 300min,
It can be made that impurity content is very low, the very high graphene of purity if extending heating time again may greatly increase system
Standby cost.Therefore 120~300min is chosen to be preferable heating time section by the present invention.
Comparative examples 3,4,5, in reasonable negative pressure, heating temperature and within the scope of heating time, when negative pressure and heating time
When identical, heating temperature is higher, and Fe elemental impurity levels are lower.In view of heating temperature remains 2200 DEG C, can be made
Impurity content is very low, the very high graphene of purity, if improving heating temperature again, although graphene can also be further increased
Purity, but heating temperature is further increased, it correspondingly needs to improve the power requirement of vacuum high temperature furnace, increases preparation cost.Cause
This, the present invention can be chosen to be preferable heating temperature section for 1700 DEG C~2200 DEG C.
3,6,7, in reasonable negative pressure, heating temperature and within the scope of heating time, when heated between and heating temperature phase
Meanwhile negative pressure is bigger, Fe elemental impurity levels are lower.In view of impurity content can be made under conditions of negative pressure 100Pa
Very low, the very high grapheme material of purity, if improving level of vacuum again, although it is pure to further increase graphene
Degree, may improve the air-tightness requirement and power requirement to vacuum high temperature furnace, and increase preparation cost.Therefore the present invention will
60Pa~100Pa is chosen to be preferable negative pressure value.
The BET of the BET adsorption desorption curve of graphene made from above-mentioned 7 examples and graphene oxide shown in Fig. 2 is inhaled
Desorption curve compares, and the specific surface area of grapheme material made from above-mentioned 7 examples compares the specific surface area of graphene oxide
It is substantially reduced, it should be understood that, main reason is that functional group's (predominantly oxygen-containing functional group) in graphene oxide is gone
It removes, reduces specific surface area.
The grapheme material impurity content that above-mentioned 7 examples provide is few, structure is high-quality, with high purity.Based on above-mentioned example 3,
5,6,7, perhaps the technological parameter of example 1,2,4 is slightly adjusted for example, increasing the temperature of reaction or increasing in reaction environment
In reaction time, it is≤high-quality the graphene of 20ppm that Fe elemental impurity levels, which can be prepared,.This graphene is used as and leads
Electric additive is in battery/capacitor energy storage material using can have a good application prospect.The reason is that, on the one hand due to gold
It is few to belong to impurity (Fe) content, advantageously reduces self-discharge phenomenon；On the other hand, due to the reparation of graphene-structured defect, also can
Greatly improve the multiplying power and cycle performance of battery/capacitor.
Based on above-mentioned 7 examples, its technological parameter is slightly adjusted, for example, in the control reaction time, can be prepared ratio
Surface area can be more than 100m2/ g, for example, specific surface area can achieve 100-500m2/ g, conductivity are 900S/cm~1100S/
The high-quality graphene of cm.
In conclusion the present invention prepares graphene under certain temperature section and time using vacuum high-temperature, make full use of
Graphene melts the high feature of boiling point and under vacuum conditions removes metal, the nonmetallic inclusion in graphene by high temperature,
Remove a large amount of oxygen-containing functional groups of graphene institute band simultaneously, repair graphene oxide during the preparation process caused by SP3Hydridization
Defect, the graphene impurity content being prepared is low, and fault of construction is few, excellent combination property.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (9)
1. a kind of method for preparing graphene with graphene oxide, which is characterized in that the described method comprises the following steps:
Graphene oxide containing oxygen-containing functional group and containing metal impurities and/or nonmetallic inclusion is placed in 30Pa~500Pa
It is sufficiently reacted in 1250 DEG C or more of environment, obtains graphene.
2. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the metal impurities
For one of iron, manganese, potassium and sodium or a variety of, the nonmetallic inclusion is one or both of sulphur, silicon.
3. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the oxygen-containing function
Group includes one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of.
4. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the graphite oxide
The carbon-to-oxygen ratio of alkene is between 0.5~2.0, and the carbon-to-oxygen ratio of the graphene is 18.0 or more.
5. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the graphite oxide
Heating time of the alkene in the environment is 60min~600min.
6. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that described to aoxidize stone
The step that black alkene is placed in the environment includes that graphene oxide is laid in carrier, then is placed in the environment, the load
Body is for graphite carrier or in the container for being coated with graphite linings with graphene oxide contact surface.
7. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the gas of the environment
Pressure is 60Pa~100Pa, and the temperature of the environment is 1700 DEG C~2500 DEG C.
8. the method according to claim 1 for preparing graphene with graphene oxide, which is characterized in that the gas of the environment
Pressure is 85Pa~95Pa, and the temperature of the environment is 1700 DEG C~2200 DEG C.
9. a kind of graphene, which is characterized in that graphene graphene system as described in any one of claim 1 to 8
Preparation Method is prepared.
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