CN109775696A - Semi-dry Process at Room Temperature prepares expanded graphite and wet process removing prepares graphene method - Google Patents
Semi-dry Process at Room Temperature prepares expanded graphite and wet process removing prepares graphene method Download PDFInfo
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- CN109775696A CN109775696A CN201910192940.8A CN201910192940A CN109775696A CN 109775696 A CN109775696 A CN 109775696A CN 201910192940 A CN201910192940 A CN 201910192940A CN 109775696 A CN109775696 A CN 109775696A
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Abstract
Expanded graphite is prepared the present invention provides a kind of Semi-dry Process at Room Temperature and method that wet process removing prepares graphene.The method for preparing expanded graphite may include step: crystalline flake graphite and the concentrated sulfuric acid being mixed, acidifying graphite is obtained, wherein the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid is 1:0.5~25, H in the concentrated sulfuric acid2SO4Mass fraction is 75~98%；Acidifying graphite and swelling agent are mixed, expanded graphite is obtained.The method for preparing graphene is comprising steps of be mixed and stirred for the expanded graphite prepared and water uniformly, to obtain expanded graphite suspension；Alkaline solution is mixed with expanded graphite suspension, obtains the mixed solution that pH is 8~11；Removing dispersion is carried out to mixed solution, obtains graphene suspension.The beneficial effect comprise that process flow is short, it is directly realized by primary expansion at room temperature and obtains expanded graphite, process conditions are easy to control；The graphene-structured of acquisition is more perfect, and piece diameter is big, and electric property is excellent.
Description
Technical field
The present invention relates to field of preparation of graphene, particularly, are related to a kind of Semi-dry Process at Room Temperature and prepare expanded graphite and wet
The method that method removing prepares graphene.
Background technique
Graphene be one kind by carbon atom with sp2Hybridized orbit forms the two-dimentional carbon material that hexangle type is in honeycomb lattice, because
It is led with extra specific surface area, good electric conductivity, mechanical property, thermal property etc. in optical material, energy and material etc.
Domain has broad application prospects.Common graphene preparation method be prepare graphene oxide using improving Hummers method, then
Further reduction prepares redox graphene, and the graphene defect of this method preparation is more, and piece diameter is smaller, and conductivity is lower.
Expanded graphite is also a kind of New Type of Mineral Materials, swollen by intercalation, washing, drying, high temperature by natural flake graphite
Change the loose porous vermiform substance of obtained one kind, also referred to as worm graphite.The expansion multiple of expanded graphite is tens to number
Hundred times, short texture is porous, large specific surface area, has excellent absorption property, good ductility, plasticity and leakproofness
The features such as, it is widely used in the fields such as environmental protection, mechanical, aerospace and new material.Because expanded graphite can further remove system
Standby graphene, causes the extensive concern of scholar in recent years.The bigger, defect using the graphene film diameter prepared of expanded graphite removing
Less, conductivity is higher, this is more advantageous for the industrialized production of graphene.
Currently, expansion stone is prepared after high temperature or microwave treatment mostly using the preparation method that expanded graphite prepares graphene
Ink, then be stripped dispersion obtain graphene, such preparation method be from graphite → expansible graphite → expanded graphite → graphene,
Its preparation process period length, complex process, long flow path, energy consumption is high, and there is the disadvantages of generating intractable acid waste liquid.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to solve above-mentioned one existing in the prior art
Or multiple problems.Expanded graphite is prepared for example, that one of the objects of the present invention is to provide a kind of process flows is short, low energy consumption
Method and the method for preparing graphene.
One aspect of the present invention provides a kind of method for preparing graphene.The method can comprise the following steps that scale
Graphite and the concentrated sulfuric acid are mixed and stirred for uniformly, obtaining acidifying graphite, wherein the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid is 1:
0.5~25, H in the concentrated sulfuric acid2SO4Mass fraction be 75~98%；The acidifying graphite and swelling agent are mixed and stirred for
It is even, obtain expanded graphite；It is mixed and stirred for the expanded graphite and water uniformly, to obtain expanded graphite suspension；Alkalinity is molten
Liquid is mixed with the expanded graphite suspension, obtains the mixed solution that pH is 8~11；Removing point is carried out to the mixed solution
It dissipates, obtains graphene suspension.
An exemplary embodiment according to the present invention, the crystalline flake graphite cannot pass through 170 meshes, the crystalline flake graphite
Phosphorus content 85% or more.
An exemplary embodiment according to the present invention, the swelling agent may include hydrogen peroxide or Peracetic acid.
An exemplary embodiment according to the present invention, it is described to be mixed and stirred for uniformly walking with swelling agent by acidifying graphite
Suddenly can include: the swelling agent is slowly added into the acidifying graphite, is stirred evenly, is then stood at room temperature so that acid
Graphite is expanded to expanded graphite.
An exemplary embodiment according to the present invention, the obtained expanded graphite are vermiform, the expanded graphite
Length can be 1.0~4.5mm, allowance for expansion can be 100~200ml/g.
An exemplary embodiment according to the present invention, the alkaline solution may include NaOH solution or ammonium hydroxide.
An exemplary embodiment according to the present invention, the method, which may further comprise the step of:, is obtaining the expanded graphite
Later, the expanded graphite is washed.
An exemplary embodiment according to the present invention, the method may further comprise the step of: the graphene suspension
Centrifugation purification is carried out, the graphene dispersing solution refined.
Another aspect of the present invention also provides a kind of method that Semi-dry Process at Room Temperature prepares expanded graphite.The method may include
Following steps: crystalline flake graphite and the concentrated sulfuric acid are mixed and stirred for uniformly, to obtain acidifying graphite, wherein crystalline flake graphite and the concentrated sulfuric acid
Mass volume ratio be 1:0.5~25, H in the concentrated sulfuric acid2SO4Mass fraction be 75~98%；By the acidifying graphite and expansion
Agent is mixed and stirred for uniformly, obtaining expanded graphite.
In an exemplary embodiment of the present invention, the method also includes steps: washing the expanded graphite.
Compared with prior art, beneficial effects of the present invention can include: process flow is short, can not swollen graphite preparation process,
High-temperature expansion process and corresponding process procedure are directly realized by primary expansion at room temperature and obtain expanded graphite, reacted
Cheng Wenhe, process conditions are easy to control；Generated acid solution processing is easy in expanded graphite preparation process, and no pernicious gas generates；
Graphene-structured extent of the destruction obtained is low, and defect is few, and structure is more perfect, and piece diameter is big, and electric property is excellent, it is easier to push away
Wide application.
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 scanning electron microscope (SEM) photograph for the acid expanded graphite that example 1 is prepared；
Fig. 2 shows the figures for the graphene dispersing solution that example 1 is prepared；
Fig. 3 shows the scanning electron microscope (SEM) photograph for the acid expanded graphite that example 2 is prepared；
Fig. 4 shows the figure for the graphene dispersing solution that example 2 is prepared；
Fig. 5 shows the scanning electron microscope (SEM) photograph for the acid expanded graphite that example 3 is prepared；
Fig. 6 shows the figure for the graphene dispersing solution that example 3 is prepared.
Specific embodiment
Hereinafter, Semi-dry Process at Room Temperature preparation expansion of the invention will be described in detail in conjunction with attached drawing and exemplary embodiment
The method of graphite and graphene method is prepared by removing.
Common to have using the technique that expanded graphite prepares graphene: graphite is processed into expansible graphite, may expand stone
Expanded graphite is obtained after the heated expansion process of ink, graphene can be obtained after being stripped in expanded graphite.The present invention is directed to the technique
Preparation process period length existing for process, complex process, long flow path, energy consumption is high, and exists and generate intractable acid waste liquid etc.
Disadvantage, proposes that a kind of Semi-dry Process at Room Temperature prepares the method for expanded graphite and directly wet process removing prepares high conductivity graphite
The method of alkene, this method simple process, low energy consumption, with short production cycle and environmentally friendly.
One aspect of the present invention provides a kind of method that Semi-dry Process at Room Temperature prepares expanded graphite.
In an exemplary embodiment of the present invention, the method that the Semi-dry Process at Room Temperature prepares expanded graphite may include with
Lower step:
S01: crystalline flake graphite and the concentrated sulfuric acid are mixed and stirred for uniformly, to obtain acidifying graphite, sulfuric acid system there can be graphite
Slight special adsorption, acidifying graphite are the graphite that slight sulfuric acid intercalation has occurred.Wherein, graphite is placed in concentrated sulfuric acid environment
In, one is to provide reaction medium, second is that carrying out intercalation to graphite.For example, crystalline flake graphite can be placed in container, then thereto
The concentrated sulfuric acid is added and stirs evenly and carries out pre-acidified processing, obtains acidifying graphite.Wherein, the mass body of crystalline flake graphite and the concentrated sulfuric acid
Product can be 1:0.5~1:25, such as 1:10 than (ratio i.e. between the quality of crystalline flake graphite and the volume of the concentrated sulfuric acid)；The concentrated sulfuric acid
Middle H2SO4Mass fraction be 75% or more, such as 98%.The crystalline flake graphite cannot be by 170 meshes, according to can lead to
The crystalline flake graphite of 170 sieves is crossed, then expansion multiple (i.e. the expansion multiple of expanded graphite) can decrease, and expansion effect is bad.Squama
The piece diameter of piece graphite is bigger, and expansion multiple is higher；Further, in order to make expansion after expanded graphite expansion multiple it is more equal
One, crystalline flake graphite can pass through 80 meshes and cannot pass through 170 meshes.The phosphorus content of the crystalline flake graphite is 85% or more, example
Such as 85~99%, if the phosphorus content of crystalline flake graphite is too low, impurity can consume more polyacid and swelling agent, influence expansion effect.
S02: it is mixed and stirred for acidifying graphite and swelling agent uniformly, to obtain expanded graphite.For example, can be slow by swelling agent
It is added in acidifying graphite and stirs evenly, intercalation expansion is carried out to acidifying graphite, directly obtains expanded graphite.Wherein, scale stone
The mass volume ratio (ratio i.e. between the quality of crystalline flake graphite and the volume of swelling agent) of ink and swelling agent can be 1:0.1~1:
5, such as 1:2.Swelling agent may include hydrogen peroxide or can be further hydrogen peroxide, crystalline flake graphite and hydrogen peroxide for Peracetic acid
Mass volume ratio can be 1:0.5~1:5.
In above-mentioned step, the purpose of acidization that crystalline flake graphite is mixed with sulfuric acid is that crystalline flake graphite edge occurs to insert
Layer so that sulfuric acid is inserted into interlayer, and then continues to spread, but the intercalation of sulfuric acid and crystalline flake graphite spontaneous can not carry out,
Therefore need to be added auxiliary oxidizing agent, i.e. swelling agent.
The proportion of hydrogen peroxide and the concentrated sulfuric acid is to influence the key factor of allowance for expansion in the present invention, when the amount of hydrogen peroxide compares
Hour, the oxidisability of mixed liquor is weaker, and the edge of crystalline flake graphite is not easy to be opened, and sulfuric acid enters the channel of graphite layers
It is few, the amount of being finally inserted into is affected, thus allowance for expansion is smaller.When there are many amount of hydrogen peroxide, although improving the driving of reaction
Power, but the concentration of the concentrated sulfuric acid is reduced, so that sulfuric acid is decreased in the insertion of interlayer and diffusivity, allowance for expansion is still smaller.
In the present embodiment, impurity inside graphite is typically all some silicate minerals such as quartz, mica, and sulfuric acid can be with
It reacts, and then cleans therewith.
In the present embodiment, the method may further comprise the step of: washing expanded graphite, remaining in expanded graphite to remove
The concentrated sulfuric acid and swelling agent.
In the present embodiment, the expanded graphite obtained is wormlike porous material, and pore size distribution range is 10~100 μm；
The expansion multiple of expanded graphite can be 100~200 times, and resistivity can be 1 × 10-6~1 × 10-4Ω·cm；The length of expanded graphite
Degree can be 1.0mm~4.5mm, such as 1.5mm, 3mm or 4.0mm etc.；100~200ml/g of allowance for expansion of expanded graphite, such as
150±30ml/g。
Another aspect of the present invention also provides a kind of method that wet process removing prepares graphene.
Expanded graphite can be prepared graphene, such as a upper exemplary embodiment by the preparation method as raw material
In the expanded graphite prepared.
The preparation method can also be using crystalline flake graphite as raw material, to prepare graphene.
In another exemplary embodiment of the invention, the preparation method may include and a upper exemplary embodiment
Identical S01, S02 step of expanded graphite is prepared in addition to this to further comprise the steps of:
S03: it is mixed and stirred for expanded graphite and water uniformly, to obtain expanded graphite suspension.Expanded graphite suspension
Concentration can be 0.01~0.3mg/ml, such as 0.2 ± 0.05mg/ml.Wherein, if the concentration of expanded graphite suspension is too low,
Graphene yield can reduce, if excessive concentration, splitting time can be more long.
S04: alkaline solution is mixed with expanded graphite suspension, obtains the mixed solution that pH is 8~11.Alkaline solution can
For NaOH solution or ammonium hydroxide.PH control is in above range, then mixed solution has preferable dispersibility and stability, if pH is not
In above range, sinking can be assembled by standing a period of time graphene, be superimposed as thick-layer graphite flake again between lamella.
S05: removing dispersion is carried out to the mixed solution, obtains graphene suspension.It is stirred for example, high speed dispersion can be used
It mixes machine, homogenizer or ultrasonic dispersing machine and carries out dispersion removing.Wherein, removing dispersion process can be not necessarily to dispersing agent, at low cost.
In the present embodiment, the method, which may further comprise the step of:, isolates graphene from the graphene suspension.
In the present embodiment, the method also includes steps: the graphene suspension being carried out centrifugation purification, obtains essence
The graphene dispersing solution of system.Wherein, centrifugation purification can be carried out by centrifuge, and centrifugation time can be 5~10 minutes, and revolving speed is
5000~12000 revs/min.In centrifugal process, impurity is because density is big, eventually by centrifugation to centrifugation bottom of the tube, Ke Yishi
Now clean again.
In the present embodiment, the method may further comprise the step of: isolates graphene, example from the graphene dispersing solution
Such as filtering.
In the present embodiment, graphene-structured extent of the destruction obtained is low, and structure is more perfect, and piece diameter is big, electrical property
Can be excellent, graphene film diameter can be 1~150 μm in graphene dispersing solution, such as 100 μm, the conductivity of graphene can for 2.0 ×
102~1.5 × 105S/m, such as 1.0 × 105S/m.The concentration of the graphene dispersing solution is 0.2~20gL-1, such as
10g·L-1。
Expansion reaction process of the invention is mild, and used swelling agent will not generate oxidation to graphite, removes preparation
Graphene-structured extent of the destruction is low, and structure is more perfect, and conductivity is higher.
In the present embodiment, the expanded graphite obtained is wormlike porous material, and pore size distribution range is 10~100 μm；
The expansion multiple of expanded graphite can be 100~200 times, and resistivity can be 1 × 10-6~1 × 10-4Ω·cm；The length of expanded graphite
Degree can be 1.5mm~5.5mm, such as 1.8mm, 3mm or 4.8mm etc.；100~200ml/g of allowance for expansion of expanded graphite, such as
150±30ml/g。
In further exemplary embodiment of the invention, adopts the following technical scheme that and utilize natural flaky graphite room
Semidry method prepares expanded graphite, and then the method for directly wet process removing preparation high-electroconductivity graphene under the conditions of temperature, can specifically wrap
Include following steps:
(1) take phosphorus content be greater than 85%, piece diameter be+170 mesh~-80 mesh crystalline flake graphite (can by 80 meshes, no
170 meshes can be passed through) it is placed in acid tolerance response device, it is 1:0.5~1:25 by the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid
It weighs a certain amount of concentrated sulfuric acid to be added in the acid tolerance response device, after agitated mixing, obtains acidifying graphite.
(2) swelling agent is added slowly to stir evenly in acidifying graphite described in step (1), acidifying graphite is carried out slotting
Layer expansion, directly obtains acid expanded graphite (i.e. expanded graphite).
(3) industrial water is added in the acid tolerance response device for filling acid expanded graphite described in step (2), is stirred
Acid expanded graphite suspension (expanded graphite suspension) is obtained after uniformly.
(4) alkaline solution is added in acid expanded graphite suspension described in step (3), adjustment pH value to 8~11,
It is stripped decentralized processing 1~obtain crude graphene suspension for 24 hours.
(5) crude graphene suspension is centrifuged off impurities at bottom, obtains washed graphite alkene dispersion liquid.
In the present embodiment, the concentrated sulfuric acid used can be technical grade or the pure grade of analysis.
In the present embodiment, swelling agent used is hydrogen peroxide in above-mentioned steps (2), used hydrogen peroxide be technical grade or
Analyze pure grade.The step includes the following steps: A) by hydrogen peroxide by the mass volume ratio of crystalline flake graphite and hydrogen peroxide be 1:0.1~
The amount of 1:5 is slowly added dropwise into acidifying graphite；B it) stirs evenly, standing 2~12h makes its Self-expanding；It is swollen to obtain " worm " shape
Swollen graphite, length can be 1.0mm~4.5mm, 100~200ml/g of allowance for expansion.
In the present embodiment, the concentration of acid expanded graphite suspension described in above-mentioned steps (3) is 0.01~0.3mg/
ml。
Use the above method prepare acid expanded graphite for wormlike porous material, pore size distribution range can be 10~
100 μm, expansion multiple can be 100~200 times, and resistivity can be 1 × 10-6~1 × 10-4Ω·cm；Prepared graphene point
Graphene film diameter can be 1~150 μm in dispersion liquid, such as 90 ± 20 μm, the conductivity of graphene can be 2.5 × 102~1.8 ×
105S/m。
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
The method for preparing expanded graphite and then directly wet process removing preparation High conductivity graphene with natural flaky graphite,
It comprises the following steps that
(1) prepare expanded graphite: choosing phosphorus content is 85%, and granularity is that the natural flaky graphite of 170 purposes is raw material, is claimed
1g crystalline flake graphite is measured into acid tolerance response device, adds sulfuric acid for 1:1.5 according to the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid
Enter into graphite, is uniformly mixed through magnetic agitation；It is slow according to the amount that the mass volume ratio of crystalline flake graphite and hydrogen peroxide is 1:0.5
It is added dropwise in acidifying graphite and stirs evenly, stand reaction 2h, obtain acid expanded graphite, expansion rate 150ml/g.
(2) it prepares graphene: being slowly added to tap water in oxytropism expanded graphite, then aqueous slkali is slowly added dropwise thereto,
Until pH=8, to acid expanded graphite suspension obtained, using high speed dispersion homogenizer under 6000 revs/min of revolving speed,
Removing 30 minutes, obtains crude graphene suspension；Then supercentrifuge is used again, under conditions of 12000 revs/min, from
The heart 5 minutes, obtain washed graphite alkene dispersion liquid.
Fig. 1 is the scanning electron microscope (SEM) photograph for the acid expanded graphite that this example 1 is prepared, and expanded graphite is in vermiform, worm
Length about 1.5mm；The shooting condition of Fig. 1 is: EHT (i.e. acceleration voltage)=15.00kV, WD (operating distance)=8.4mm,
Signal A=SE2 (type photodetector), Mag=100X (amplifying 100 times).Fig. 2 is the graphene that this example 1 is prepared
The photo of dispersion liquid, dispersion liquid are in black, are uniformly dispersed, and graphene film diameter is greater than 60 μm and accounts for 75% (i.e. piece diameter is big in graphene
In 60 μm account for 75%), graphene conductivity is 1.36 × 104S/m。
Example 2
It is specific the preparation method is as follows:
(1) prepare expanded graphite: choosing phosphorus content is 90%, and granularity is that the natural flaky graphite of 120 purposes is raw material, is claimed
1g crystalline flake graphite is measured into acid tolerance response device, sulfuric acid is added for 1:2 according to the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid
Into graphite, it is uniformly mixed through magnetic agitation；It is slowly added dropwise according to the amount that the mass volume ratio of crystalline flake graphite and hydrogen peroxide is 1:2
It is stirred evenly into acidifying graphite, stands reaction 4h, obtain acid expanded graphite.
(2) it prepares graphene: being slowly added to tap water in oxytropism expanded graphite, then aqueous slkali is slowly added dropwise thereto,
Until pH=9 using high speed dispersion homogenizer under 6000 revs/min of revolving speed, removes 30 points to acid expanded graphite suspension
Clock obtains crude graphene suspension；Then supercentrifuge is used again, under conditions of 10000 revs/min, is centrifuged 8 minutes,
Obtain washed graphite alkene dispersion liquid.
As shown in figure 3, the scanning electron microscope (SEM) photograph for the acid expanded graphite being prepared for this example 2, expanded graphite is in worm
Shape, length about 2.2mm；The shooting condition of Fig. 3 is: EHT=15.00kV, WD (operating distance)=7.4mm, Signal A=
SE2, Mag=100X (amplify 100 times).Fig. 4 is the photo for the graphene dispersing solution that this example 2 is prepared, and dispersion liquid is in
Black is uniformly dispersed, wherein graphene film diameter accounts for 72% greater than 80 μm, and graphene conductivity is 6.7 × 104S/m。
Example 3
It is specific the preparation method is as follows:
(1) prepare expanded graphite: choosing phosphorus content is 99%, and granularity is that the natural flaky graphite of 80 purposes is raw material, is claimed
1g crystalline flake graphite is measured into acid tolerance response device, adds sulfuric acid for 1:2.5 according to the mass volume ratio of crystalline flake graphite and the concentrated sulfuric acid
Enter into graphite, is uniformly mixed through magnetic agitation；It is slowly dripped according to the amount that the mass volume ratio of crystalline flake graphite and hydrogen peroxide is 1:5
It adds in acidifying graphite and stirs evenly, stand reaction 1.5h, obtain acid expanded graphite.
(2) it prepares graphene: being slowly added to tap water in oxytropism expanded graphite, then aqueous slkali is slowly added dropwise thereto,
Until pH=11, to acid expanded graphite suspension, using high speed dispersion homogenizer under 6000 revs/min of revolving speed, removing 30
Minute, obtain crude graphene suspension；Then supercentrifuge is used again, under conditions of 5000 revs/min, is centrifuged 10 points
Clock obtains washed graphite alkene dispersion liquid.
Fig. 5 is the scanning electron microscope (SEM) photograph for the acid expanded graphite that this example 3 is prepared, and expanded graphite is in vermiform, length
About 3.8mm；The shooting condition of Fig. 5 is: EHT=10.00kV, WD (operating distance)=11.2mm, Signal A=SE2, Mag=
30X (amplifies 30 times).Fig. 6 is the photo for the graphene dispersing solution that this example 3 is prepared, and dispersion liquid is in black, and dispersion is equal
Even, graphene film diameter is greater than 95 μm and accounts for 65%, and graphene conductivity is 1.45 × 105S/m。
In conclusion the advantages of of the invention method for preparing expanded graphite and graphene, includes:
(1) prior art will first prepare expansible graphite and then high-temperature expansion, and required process is more, and required time is that number is small
When, and the present invention only needs a step and expansion can be realized at room temperature, it can not swollen graphite preparation process, high-temperature expansion process
And corresponding process procedure, time generally can be completed in 10min~1h, process flow is short, and reaction process is mild, technique item
Part is easy to control, and production energy consumption is low, and preparation cost is low.
(2) generated acid solution processing is easy in expanded graphite preparation process, and no pernicious gas generates.
(3) graphene-structured extent of the destruction obtained is low, and structure is more perfect, and piece diameter is big, and electric property is excellent, graphite
Ene product piece diameter is up to 150 μm, and even more greatly, conductivity is up to 1.5 × 105S/m；
(4) can be removed in production process raw material impurity (for example, acidization and centrifugal process can remove it is miscellaneous
Matter), relatively low to ingredient requirement, preparation cost is low.
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 (10)
1. a kind of method for preparing graphene, which is characterized in that the described method comprises the following steps:
Crystalline flake graphite and the concentrated sulfuric acid are mixed and stirred for uniformly, to obtain acidifying graphite, wherein the quality of crystalline flake graphite and the concentrated sulfuric acid
Volume ratio is 1:0.5~25, H in the concentrated sulfuric acid2SO4Mass fraction be 75~98%；
It is mixed and stirred for the acidifying graphite and swelling agent uniformly, to obtain expanded graphite；
It is mixed and stirred for the expanded graphite and water uniformly, to obtain expanded graphite suspension；
Alkaline solution is mixed with the expanded graphite suspension, obtains the mixed solution that pH is 8~11；
Removing dispersion is carried out to the mixed solution, obtains graphene suspension.
2. the method according to claim 1 for preparing graphene, which is characterized in that the crystalline flake graphite cannot pass through 170
Mesh, the phosphorus content of the crystalline flake graphite is 85% or more.
3. the method according to claim 1 for preparing graphene, which is characterized in that the swelling agent includes hydrogen peroxide or mistake
Fluoroacetic acid.
4. the method according to claim 1 for preparing graphene, which is characterized in that described to mix acidifying graphite and swelling agent
Merging the step of stirring evenly includes:
The swelling agent is slowly added into the acidifying graphite, is stirred evenly, is then stood at room temperature so that acidification stone
Ink is expanded to expanded graphite.
5. the method according to claim 1 for preparing graphene, which is characterized in that the obtained expanded graphite is worm
Shape, the length of the expanded graphite are 1.0~4.5mm, and allowance for expansion is 100~200ml/g.
6. the method according to claim 1 for preparing graphene, which is characterized in that the alkaline solution includes NaOH solution
Or ammonium hydroxide.
7. the method according to claim 1 for preparing graphene, which is characterized in that the method also includes steps:
To after the expanded graphite, the expanded graphite is washed.
8. the method according to claim 1 for preparing graphene, which is characterized in that the method also includes steps:
The graphene suspension is subjected to centrifugation purification, the graphene dispersing solution refined.
9. a kind of method that Semi-dry Process at Room Temperature prepares expanded graphite, which is characterized in that the described method comprises the following steps:
Crystalline flake graphite and the concentrated sulfuric acid are mixed and stirred for uniformly, to obtain acidifying graphite, wherein the quality of crystalline flake graphite and the concentrated sulfuric acid
Volume ratio is 1:0.5~25, H in the concentrated sulfuric acid2SO4Mass fraction be 75~98%；
It is mixed and stirred for the acidifying graphite and swelling agent uniformly, to obtain expanded graphite.
10. the method that Semi-dry Process at Room Temperature according to claim 9 prepares expanded graphite, which is characterized in that the method is also
Comprising steps of washing the expanded graphite.
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| CN110117005A (en) * | 2019-06-13 | 2019-08-13 | 青岛科技大学 | A method of reaction prepares bulking filler from pressuring expansion technology |
| CN111234537A (en) * | 2020-02-24 | 2020-06-05 | 哈尔滨理工大学 | Graphene anti-dripping flame-retardant synergist and preparation method thereof |
| CN115072712A (en) * | 2022-06-21 | 2022-09-20 | 西南科技大学 | Graphene with large sheet diameter and high conductivity and preparation method thereof |
| CN115959657A (en) * | 2023-03-16 | 2023-04-14 | 清华大学 | Natural graphite-based heat dissipation film and preparation method thereof |
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