CN106315568B - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN106315568B CN106315568B CN201610706925.7A CN201610706925A CN106315568B CN 106315568 B CN106315568 B CN 106315568B CN 201610706925 A CN201610706925 A CN 201610706925A CN 106315568 B CN106315568 B CN 106315568B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The present invention relates to a kind of preparation methods of graphene, include the following steps；(1) biological material is pre-processed, obtains pretreated biological material, the biological material includes one or more of stalk, rice husk, peanut shell, bark；(2) preprocessing biomass in metallic catalyst and the step (1) is mixed, is loaded, obtain the biological material that load has catalyst；(3) in the means of deposition for thering is the biological material of catalyst to mix with the load that the step (2) obtains foaming agent, and being coated in CVD reactor.(4) it is passed through protective gas in the CVD reactor in the step (3), keeps the temperature 5-20h at 600-1000 DEG C, obtains graphene；Compared with prior art, preparation method no pollution to the environment provided by the invention, and using biological material as carbon source, it is at low cost, it is easy to accomplish the industrialized production of graphene.
Description
Technical field
The invention belongs to carbon material technical field more particularly to a kind of preparation methods of graphene.
Background technique
2004, two scientists of Univ Manchester UK had found graphene using the method that micromechanics is removed,
And Nobel Prize in physics was obtained in 2010.Graphene is a kind of single atomic thickness and the carbon atom with sp2 bond
Slab construction theoretically there is perfect hexagonal reticulated structure, excellent electronic stability, thermal conductivity, optical property, power is presented
Learn performance etc..Since graphene was discovered, since its excellent performance and huge market application prospect have caused physics
With the research boom in the fields such as material science.It is also most hard nano material that graphene, which is most thin at present, is provided simultaneously with light transmission
The performance that numerous common materials such as property is good, thermal coefficient is high, electron mobility is high, resistivity is low, mechanical strength is high do not have, not
To be expected in numerous necks such as electrode, battery, transistor, touch screen, solar energy, sensor, super light material, medical treatment, sea water desalination
Domain is widely applied, and is one of most promising advanced material.However there is presently no effective methods can volume production high quality graphite
Alkene.
In order to allow outstanding grapheme material to realize industrialized production and application, must just develop one kind can give birth on a large scale
It produces and the number of plies and the controllable preparation method of size.The preparation method of graphene has mechanical stripping method, epitaxial growth method, oxidation at present
Reduction method, ultrasonic stripping method, organic synthesis method, solvent-thermal method etc..In these methods, mechanical stripping method and epitaxial growth legal system
Standby efficiency is very low, it is difficult to meet large-scale needs.Oxidation-reduction method prepares the low in cost and easy of grapheme material powder
It realizes, but a large amount of waste liquid can be generated, environment is caused seriously to pollute, limits the extensive industrialized development of graphene.
These methods are all using graphite ore as former material, and this mineral resources are not recyclable regeneratives, are unfavorable for the big rule of graphene
Mould production.
Biological material is a kind of natural reproducible resource, and no pollution to the environment has high in modern chemical industry
Potential using value, yield is huge, but application market is not wide, and chemically component analysis can be seen that, in biological material
Phosphorus content be about 60%, have huge prospect in terms of preparing carbon material.
China Patent Publication No. 103466613A discloses a kind of method for preparing graphene as raw material using lignin.The party
Porcelain example boat equipped with lignin and catalyst is put into hinge tube furnace by method first, is at the uniform velocity passed through inert protective gas,
Sample is heated to from room temperature by target temperature with constant heating rate in furnace simultaneously, and is kept under target temperature, to sample
When product temperature degree is down to room temperature, sample is taken out, to get graphene after deionized water washing, vacuum filtration, low temperature drying.This
The preparation process of invention is easy, and gained quality of graphene is excellent, and yield is considerable.However, this method is sintered using anaerobic, sintering
Temperature reaches 1500 DEG C, and the high requirements on the equipment, equipment preparation cost improves, it is impossible to be applied to large-scale production.
China Patent Publication No. 103935986A discloses a kind of side that graphene is prepared with biological carbon source material high yield
Method is added in acid solution after including the following steps: biological carbon source material microwave treatment, then is washed, is dried, and obtains pre-
The biological carbon source material of processing；Pretreated biological carbon source material is mixed with catalyst, is deposited in 600-1600 DEG C, protective gas
In lower calcining 1-12h, the graphene is obtained after cooling.This method significantly reduces production cost, realizes graphene
Large-scale industrial production.However, some noble metal catalysts have been arrived in use in this method, not only cost is improved, preparation
Graphene area is small, and it is poor to crystallize, and is unfavorable for the industrialized development of graphene.
According to above-mentioned, although mechanically repeatedly grinding obtains graphene, due to being answered by grinding pressure
The effect of power, grinding, which is hit, causes certain destruction to graphite lattice, since grinding applies pressure to graphite, to the graphite of removing
Huge impact force is generated, this impact force can make graphene layer generate fault of construction, easily cause graphene layer structural lattice
Defect reduces the size of graphene after removing, so that graphene product crystalline size obtained is small, it is difficult to obtain large-size high-quality
Measure graphene, either mechanical ball milling or mechanical Gas grinding are to sacrifice graphene size and lattice is complete
Whole property；In addition, the crunch of abrasive media will lead to graphite linings structure become it is even closer will lead to instead peeling effect drop
It is low, cause milling time length, cost very high；Furthermore the graphene of grinding production at present belongs to intermittent, carries out to graphite
While removing, the graphene removed can not be filtered out in time, thus be difficult to carry out the volume production of continuous-stable, and be easy
Pollute environment, it is difficult to realize graphene industrialized production.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation methods of graphene, and the present invention is with biological material
Raw material, from a wealth of sources, renewable, no pollution to the environment is at low cost, can be easily achieved the industrialized production of graphene.
The technical scheme to solve the above technical problems is that
A kind of preparation method of graphene, comprising the following steps:
(1) biological material is pre-processed, obtains pretreated biological material, the biological material includes straw
One or more of stalk, rice husk, peanut shell, bark；
(2) preprocessing biomass in metallic catalyst and the step (1) is mixed, is loaded, obtaining load has
The biological material of catalyst；
(3) there is the biological material of catalyst to mix with the load that the step (2) obtains foaming agent, and be coated on and change
It learns in the means of deposition in gas-phase deposition reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), at 600-1000 DEG C
5-20h is kept the temperature, graphene is obtained.
Compared with prior art, the beneficial effects of the present invention are:
Preparation method provided by the invention does not use strong acid, no pollution to the environment, and the present invention with biological material
For carbon source, raw material cost is low and is easy to get for carbon source, solves the problems, such as at high cost, realizes graphene industrialized production,
The present invention pre-processes biomass, on the one hand can remove the impurity such as cell wall in biological material, retains in biomass
Pectin, hemicellulose, cellulose；On the other hand the polyphosphazene polymer reduced in biological material is right, is being catalyzed biomass
It under agent effect, is easier to be catalyzed, while catalytic pyrolysis occurs for biomass in the reactor, and biological material is made to be easier to obtain thickness
For 0.3-5nm；The graphene that radial dimension is 10-20 μm.
Based on the above technical solution, the present invention can also be improved as follows.
Preferably, the step (1) specifically includes the following steps:
After biomass cleaning, screening, it is crushed to 50-300 mesh, using aqueous slkali soaking 5-10min, filtering, drying
Obtain pretreated biological material.
Preferably, the aqueous slkali is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide.
Preferably, the metallic catalyst include cesium salt, aluminium isopropoxide, manganese dioxide, antimony oxide, in stannous chloride
One or more.
Preferably, the mass ratio of the metallic catalyst and the biological material in the step (1) in the step (2) is
(0.01-30): 1.
Preferably, the foaming agent includes azodicarbonamide, 4,4 '-oxobenzenesulfonyl hydrazide, unifor, 4,
One or more of 4 '-disulfonyl hydrazides, dinitrosopentamethylene tetramine.
Preferably, the mass ratio of the foaming agent and the biological material in the step (1) is (1-10): 1.
Preferably, the step (4) specifically includes the following steps:
20-40MPa is pressurized to the rate of pressurization of 0.1-0.6MPa/s in CVD reactor, with 5-20
DEG C/heating rate of min is warming up to 600-1000 DEG C.
The present invention provides a kind of graphene, is prepared according to preparation method described in above-mentioned technical proposal；
The graphene with a thickness of 0.3-5nm；
The radial dimension of the graphene is 10-20 μm.
The present invention provides a kind of preparation method of graphene, comprising the following steps: (1) is located biological material in advance
Reason, obtains pretreated biological material, the biological material includes one of stalk, rice husk, peanut shell, bark or several
Kind；(2) preprocessing biomass in metallic catalyst and the step (1) is mixed, is loaded, obtaining load has catalyst
Biological material；(3) there is the biological material of catalyst to mix with the load that the step (2) obtains foaming agent, and apply
It is overlying in the means of deposition in CVD reactor.(4) in the CVD reactor in the step (3)
It is passed through protective gas, 5-20h is kept the temperature at 600-1000 DEG C, obtains graphene.
The present invention prepares graphene and the prior art preparation graphene table of comparisons
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
(1) in parts by weight, by after the cleaning of 1 part of stalk, screening, 50 mesh are crushed to, using soaking with sodium hydroxide 5min,
It filters, be dried to obtain pretreated stalk material；
(2) in parts by weight, the pretreated straw in 0.01 part of cesium salt and the step (1) is mixed, is loaded, is obtained
There is the stalk material of cesium salt to load；
(3) in parts by weight, the load that 1 part of azodicarbonamide and the step (2) obtain is had to the stalk material of cesium salt
Material mixing, and in the means of deposition being coated in CVD reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), in chemical vapor deposition
20MPa is pressurized to the rate of pressurization of 0.1MPa/s in reactor, is warming up to 600 DEG C with the heating rate of 5 DEG C/min, heat preservation
5h obtains graphene.
Graphite is removed to form thickness in 0.3-5nm, the large scale area graphite alkene that radial dimension is 10-20 μm.
Embodiment 2
(1) in parts by weight, by after 10 parts of peanut shell cleanings, screenings, 200 mesh is crushed to, are impregnated using calcium hydroxide
10min is filtered, is dried to obtain pretreated peanut shell material；
(2) in parts by weight, the pretreatment peanut shell in 1 part of manganese dioxide and the step (1) is mixed, is born
It carries, obtains the peanut shell material that load has manganese dioxide；
(3) in parts by weight, the load that 5 parts of unifor and the step (2) obtain is had to the flower of manganese dioxide
Raw shell material mixing, and in the means of deposition being coated in CVD reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), in chemical vapor deposition
30MPa is pressurized to the rate of pressurization of 0.3MPa/s in reactor, is warming up to 800 DEG C with the heating rate of 10 DEG C/min, heat preservation
10h obtains graphene.
Graphite is removed to form thickness in 0.3-5nm, the large scale area graphite alkene that radial dimension is 10-20 μm.
Embodiment 3
(1) in parts by weight, by after 100 parts of bark cleanings, screenings, 300 mesh is crushed to, are impregnated using calcium hydroxide
10min is filtered, is dried to obtain pretreated tree bark materials；
(2) in parts by weight, the pretreatment bark in 10 parts of stannous chlorides and the step (1) is mixed, is loaded,
Obtain the tree bark materials that load has stannous chloride；
(3) in parts by weight, the load that 100 parts of dinitrosopentamethylene tetramines and the step (2) obtain there is into chlorine
Change cuprous tree bark materials mixing, and in the means of deposition being coated in CVD reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), in chemical vapor deposition
40MPa is pressurized to the rate of pressurization of 0.6MPa/s in reactor, is warming up to 1000 DEG C with the heating rate of 20 DEG C/min, heat preservation
20h obtains graphene.
Graphite is removed to form thickness in 0.3-5nm, the large scale area graphite alkene that radial dimension is 10-20 μm.
Comparative example 1
(1) in parts by weight, by after 50 parts of rice husk cleanings, screenings, 10 mesh is crushed to, are impregnated using calcium hydroxide
1min is filtered, is dried to obtain pretreated rice hull material；
(2) in parts by weight, the pretreatment rice husk in 5 parts of antimony oxides and the step (1) is mixed, is born
It carries, obtains the rice hull material that load has antimony oxide；
(3) in parts by weight, by 100 part 4, the load that 4 '-oxobenzenesulfonyl hydrazide are obtained with the step (2) has three oxygen
Change the rice hull material mixing of two antimony, and in the means of deposition being coated in CVD reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), in chemical vapor deposition
10MPa is pressurized to the rate of pressurization of 0.01MPa/s in reactor, is warming up to 300 DEG C with the heating rate of 2 DEG C/min, heat preservation
1h obtains graphene.
Graphite is removed to form thickness in 20-50nm, the large scale area graphite alkene that radial dimension is 1-5 μm.
Comparative example 2
(1) in parts by weight, by after 30 parts of stalk cleanings, screenings, 400 mesh is crushed to, are impregnated using potassium hydroxide
20min is filtered, is dried to obtain pretreated stalk material；
(2) in parts by weight, the pretreated straw in 3 parts of aluminium isopropoxides and the step (1) is mixed, is loaded,
Obtain the stalk material that load has aluminium isopropoxide；
(3) in parts by weight, the load that 60 parts of unifor and the step (2) obtain is had to the straw of aluminium isopropoxide
The mixing of stalk material, and in the means of deposition being coated in CVD reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), in chemical vapor deposition
60MPa is pressurized to the rate of pressurization of 2MPa/s in reactor, is warming up to 2000 DEG C with the heating rate of 50 DEG C/min, heat preservation
30h obtains graphene.
Graphite is removed to form thickness in 20-50nm, the large scale area graphite alkene that radial dimension is 1-5 μm.
By above embodiments with preparation method provided by the invention it can be seen from comparative example using biological material as carbon
Graphene is prepared in source, and not only biomass source is extensive, and at low cost, renewable, and no pollution to the environment is conducive to graphite
Alkene industrialized production, and obtained graphene thickness is low, radial big, the application field of the graphene made is wider.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of preparation method of graphene, which comprises the following steps:
(1) biological material is pre-processed, obtains pretreated biological material, the biological material include stalk,
One or more of rice husk, peanut shell, bark；
(2) preprocessing biomass in metallic catalyst and the step (1) is mixed, is loaded, obtaining load has catalysis
The biological material of agent；
(3) there is the biological material of catalyst to mix with the load that the step (2) obtains foaming agent, and be coated on chemical gas
In means of deposition in phase deposition reactor；
(4) it is passed through protective gas in the CVD reactor in the step (3), is kept the temperature at 600-1000 DEG C
5-20h obtains graphene；
The step (1) specifically includes the following steps:
After biomass cleaning, screening, it is crushed to 50-300 mesh, using aqueous slkali soaking 5-10min, filters, be dried to obtain
Pretreated biological material；
The aqueous slkali is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide；
The metallic catalyst includes one of cesium salt, aluminium isopropoxide, manganese dioxide, antimony oxide, stannous chloride or several
Kind；
The mass ratio of the biological material in metallic catalyst and the step (1) in the step (2) is (0.01-30):
1；
The foaming agent includes azodicarbonamide, 4,4 '-oxobenzenesulfonyl hydrazide, unifor, 4,4 '-disulfonyls
One or more of hydrazine, dinitrosopentamethylene tetramine；
The mass ratio of biological material in the foaming agent and the step (1) is (1-10): 1；
The step (4) specifically includes the following steps:
20-40MPa is pressurized to the rate of pressurization of 0.1-0.6MPa/s in CVD reactor, with 5-20 DEG C/min
Heating rate be warming up to 600-1000 DEG C.
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| CN109809749B (en) * | 2019-04-02 | 2021-09-03 | 四川聚创石墨烯科技有限公司 | Construction method of graphene cement-based composite material |
| CN110357077A (en) * | 2019-07-23 | 2019-10-22 | 路英军 | A kind of biomass graphene preparation method |
| CN110395720A (en) * | 2019-09-03 | 2019-11-01 | 王志朋 | The method for preparing vertical graphene film as raw material using biomass |
| CN112299768B (en) * | 2020-11-13 | 2022-05-03 | 西安建筑科技大学 | Graphene functionalized cement-based material and preparation method thereof |
| CN116060002A (en) * | 2023-02-24 | 2023-05-05 | 中国科学院生态环境研究中心 | Graphene-loaded metal monoatomic composite material, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318878A (en) * | 2013-06-27 | 2013-09-25 | 江南石墨烯研究院 | Preparation method and application of large size and shape ratio graphene microsheet |
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104386684A (en) * | 2014-12-16 | 2015-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene and graphene |
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104591176A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
-
2016
- 2016-08-23 CN CN201610706925.7A patent/CN106315568B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318878A (en) * | 2013-06-27 | 2013-09-25 | 江南石墨烯研究院 | Preparation method and application of large size and shape ratio graphene microsheet |
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104386684A (en) * | 2014-12-16 | 2015-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene and graphene |
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104591176A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023031589A1 (en) * | 2021-09-01 | 2023-03-09 | Grown Graphene Limited | Method for preparing a carbon nanomaterial |
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