CN106006613A - Method for preparing graphene - Google Patents
Method for preparing graphene Download PDFInfo
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- CN106006613A CN106006613A CN201610346996.0A CN201610346996A CN106006613A CN 106006613 A CN106006613 A CN 106006613A CN 201610346996 A CN201610346996 A CN 201610346996A CN 106006613 A CN106006613 A CN 106006613A
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- graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Abstract
The invention relates to a method for preparing graphene. The method comprises the concrete processes that one or several substances which are easily evaporated, sublimated and decomposed at high temperature of halogen, hydrochloric acid, hydrogen bromide, hydrogen iodide, ammonium nitrate, zinc chloride, ferric chloride, ammonium carbonate, sodium carbonate, potassium carbonate or ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate and the like are used as an intercalation agent; firstly, raw materials such as exfoliated graphite, layered graphite and carbon paper for preparing the graphene are pretreated; the pretreated raw materials are subjected to electrochemical oxidation at a certain voltage to obtain a precursor in an oxidation state; the oxidized materials are further subjected to blasting stripping under the ultrasound and stirring effects; flaky oxidized graphene is obtained; the oxidized graphene subjected to heat treatment is reduced into the graphene. The method has the advantages that the operation is simple; the preparation is convenient; high-quality graphene or oxidized graphene can be prepared in a large scale; the method can be used for solving the problems of high cost, low product quality, operation complexity, great pollution and the like of the existing graphene preparation technology.
Description
Technical field
The present invention relates to field of graphene, more particularly, to a kind of method preparing Graphene on a large scale.
Background technology
Owing to having electric-conductivity heat-conductivity high, high light transmittance, high-specific surface area and excellent mechanical performances and pliability, Graphene, as a kind of new carbon, enjoyed people to pay close attention in the last few years.According to the content of " made in China (2025) ", Graphene will be expected the fields such as the conductive heat conducting material in lithium ion battery used for electric vehicle, ocean engineering anticorrosion, flexible electronic device and optical electrical field and is used widely in future.But, preparing high-quality Graphene remains the difficult problem that current industrial quarters is faced on a large scale.
The method producing Graphene substantially can be divided into four kinds:
1, mechanical stripping method
Mechanical stripping method i.e. utilizes mechanical force to be peeled away by graphene sheet layer, and this method can prepare high-quality graphene, but can not meet the production requirement of industrialization, scale, and the method is only used for laboratory at present and prepares a small amount of single-layer graphene.Ball-milling method is similar to the principle of this method, but ball-milling method is the longest, and is readily incorporated impurity.
2, chemical vapour deposition technique
Vapour deposition process needs the substrate using metal material as deposition, forms Graphene in solid substrate surface, and this method needs to carry out under conditions of high temperature, and production cost is high, and Graphene separates more difficulty with substrate.
3, epitaxial growth method
SiC epitaxy can get monolayer or the ideal Graphene of minority layer, but relatively costly.Monocrystal SiC expensive, and when using the method, power consumption is relatively big, causes production cost the highest, and reaction condition is the harshest, be the most also difficult to large area and prepare.
4, oxidation-reduction method
Oxidation-reduction method is the most ripe at academia, is typically all based on Hummer method.This method is with low cost, but this method strong acid and oxidizing species reaction generate graphene oxide, graphene sheet layer can be caused in oxidizing process to generate substantial amounts of defect, thus cause Graphene attribute to become, and this method uses strong acid and oxidizing species also can cause serious environmental pollution.
As can be seen here, in current Graphene production method, have that production cost is high, efficiency low with environmental pollution etc. problem, therefore, be produced on a large scale in the urgent need to exploitation one, with low cost and eco-friendly high-quality graphene preparation method.
Summary of the invention
The present invention is to overcome at least one defect (not enough) described in above-mentioned prior art, it is provided that a kind of efficient, can the scale method of preparing Graphene, and be a kind of with low cost, preparation method of environment amenable high-quality graphene
For solving above-mentioned technical problem, technical scheme is as follows:
A kind of method preparing Graphene, use intercalator that raw material is carried out intercalation pretreatment, electrochemical oxidation method raw material pretreated to intercalation is utilized to aoxidize, recycle ultrasonic and stirring and carry out further blasting stripping, through high-temperature heat treatment, graphene oxide is reduced again, during adding thermal reduction, there is volatilization or decompose in intercalator, Graphene is carried out stripping again；Finally give high-quality graphene powder；The method utilizing the present invention, before not by graphene oxide high temperature reduction, it is possible to obtains high-quality graphene oxide.
Wherein intercalator is volatile labile reagent, and this intercalator simultaneously works as the effect of conduction when electroxidation；Raw material is expanded graphite, lamellar graphite or carbon paper.
Preferably, one or more during described intercalator is halogen, hydrochloric acid, hydrogen bromide, hydrogen iodide, ammonium nitrate, zinc chloride, iron chloride, ammonium carbonate, sodium carbonate, potassium carbonate or ammonium hydrogen carbonate, sodium bicarbonate, potassium bicarbonate solution；The solubility scope of this intercalator is 2wt%-80wt%.
Preferably, the time of described intercalator pretreatment is 2min-48h.
Preferably, the oxidation voltage of described electrochemical oxidation method is 2V-50V, and oxidization time is 1min-2h.
Preferably, described to utilize ultrasonic and stirring time be 5min to 24h, ultrasonic with in the range of when stirring, solution temperature maintains 0 DEG C-100 DEG C.
Preferably, through high-temperature heat treatment, graphene oxide is reduced, it is in high vacuum environment or in noble gas (nitrogen, argon etc.) atmosphere by graphene oxide reduction, when high temperature reduction, intercalator can volatilize (evaporate or distil) or decompose, obtaining into graphene powder, its temperature is 200 DEG C-900 DEG C, and the time is 5min-5h.
Compared with prior art, technical solution of the present invention provides the benefit that:
There is while intercalator in the present invention effect of conductive agent, the ion of conduction was provided in the electrochemical oxidation stage.
Intercalator in the present invention evaporates when the later stage heats/distils/decomposes, on the one hand can reduce the amount that intercalator remains in Graphene, and on the other hand intercalator can recycle completely, and whole production process meets the requirement of environmental protection.
The present invention is present in the intercalator of graphite layers and can remove at heat treatment stages, therefore can ensure that the highly purified graphene product of acquisition.
The present invention there is repeatedly Graphene stripping process, including intercalator pretreatment stage, electrochemical oxidation stage, ultrasonic stripping bench and heat treatment stages.Both the method having included physics, also includes chemical stripping method.
Graphene in the present invention is through repeatedly expansion process, and its extent of exfoliation, productivity and uniformity are the highest.
High-quality graphene oxide can be obtained before the heat treatment stages of the present invention.
If the heat treatment process of the present invention uses argon or in vacuum or be heat treatment in airtight environment, ensure that the lamellar structure that Graphene is the most complete the most to the full extent, therefore can obtain highly purified Graphene.
If the heat treatment process of the present invention employs nitrogen as protective gas, then just can introduce nitrating in Graphene, thus improve structure and the character such as electricity, mechanics of Graphene.
Accompanying drawing explanation
Fig. 1 is the graphene sheet layer structural representation finally preparing gained.
Detailed description of the invention
Accompanying drawing being merely cited for property explanation, it is impossible to be interpreted as the restriction to this patent；In order to the present embodiment is more preferably described, some parts of accompanying drawing have omission, zoom in or out, and do not represent the size of actual product；
To those skilled in the art, in accompanying drawing, some known features and explanation thereof may will be understood by omission.With embodiment, technical scheme is described further below in conjunction with the accompanying drawings.
Embodiment 1
With the ammonium chloride solution of 30%wt as intercalator, with expanded graphite as raw material, pretreatment time is 6 hours；The voltage of electrochemical oxidation is 10V, and oxidization time is 30 minutes；Carrying out supersound process subsequently, the time is 30 minutes, obtains the dispersion liquid of graphene oxide, is filtrated to get graphene oxide powder, uses freeze-drying to be dried, and in the atmosphere of argon shield, 500 DEG C of heat treatments 1 hour, obtain graphene powder.
In the present embodiment gained graphene powder, the number of plies of graphene film is 3 to 10 layers, and average thickness is 3.4 nanometers, average platelet a size of 5.3 microns, good crystallinity, ash ＜ 0.1%.
Embodiment 2
With the ammonium chloride solution of 30%wt as intercalator, with expanded graphite as raw material, pretreatment time is 6 hours；The voltage of electrochemical oxidation is 10V, and oxidization time is 30 minutes；Carrying out supersound process subsequently, the time is 30 minutes, obtains the dispersion liquid of graphene oxide, is filtrated to get graphene oxide powder, uses freeze-drying to be dried, and in the atmosphere of nitrogen protection, 500 DEG C of heat treatments 1 hour, obtain graphene powder.
In the present embodiment gained graphene powder, the number of plies of graphene film is 3 to 8 layers, and average thickness is 2.9 nanometers, average platelet a size of 5.1 microns, ash ＜ 0.1%.
Embodiment 3
With the ammonium nitrate solution of 50%wt as intercalator, with carbon paper as raw material, pretreatment time is 30 minutes；The voltage of electrochemical oxidation is 15V, and oxidization time is 30 minutes；Carrying out supersound process subsequently, the time is 30 minutes, obtains the dispersion liquid of graphene oxide, is filtrated to get graphene oxide powder, uses freeze-drying to be dried, and in the atmosphere of argon shield, 500 DEG C of heat treatments 2 hours, obtain graphene powder.
In the present embodiment gained graphene powder, the number of plies of graphene film is 2 to 5 layers, and average thickness is 1.9 nanometers, average platelet a size of 5.5 microns, ash ＜ 0.1%.
Embodiment 4
With the ammonium nitrate solution of 50wt% as intercalator, with lamellar graphite as raw material, pretreatment time is 2 hours；The voltage of electrochemical oxidation is 10V, and oxidization time is 45 minutes；Carrying out supersound process subsequently, the time is 90 minutes, obtains the dispersion liquid of graphene oxide, is filtrated to get graphene oxide powder, uses freeze-drying to be dried, and in the atmosphere of argon shield, 500 DEG C of heat treatments 1 hour, obtain graphene powder.
In the present embodiment gained graphene powder, the number of plies of graphene film is 4 to 8 layers, and average thickness is 3.7 nanometers, average platelet a size of 5.7 microns, good crystallinity, ash ＜ 0.1%.
Embodiment 5
With the bromine+10wt% sal volatile of 10wt% as intercalator, with expanded graphite as raw material, pretreatment time is 8 hours；The voltage of electrochemical oxidation is 5V, and oxidization time is 60 minutes；Carrying out supersound process subsequently, the time is 60 minutes, obtains the dispersion liquid of graphene oxide, is filtrated to get graphene oxide powder, uses freeze-drying to be dried, and in the atmosphere of argon shield, 500 DEG C of heat treatments 2 hours, obtain graphene powder.
In the present embodiment gained graphene powder, the number of plies of graphene film is 2 to 10 layers, and average thickness is 2.6 nanometers, average platelet a size of 4.8 microns, good crystallinity, ash ＜ 0.1%.
The corresponding same or analogous parts of same or analogous label；
Described in accompanying drawing, position relationship is used for the explanation of being merely cited for property, it is impossible to be interpreted as the restriction to this patent；
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also cannot all of embodiment be given exhaustive.All any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, within should be included in the protection domain of the claims in the present invention.
Claims (6)
1. the method preparing Graphene, it is characterized in that, use intercalator that raw material is carried out intercalation pretreatment, electrochemical oxidation method raw material pretreated to intercalation is utilized to aoxidize, recycle ultrasonic and stirring and carry out further blasting stripping, then through high-temperature heat treatment, graphene oxide is reduced, during adding thermal reduction, there is volatilization or decompose in intercalator, Graphene is carried out stripping again；Finally give graphene powder；
Wherein raw material is expanded graphite, lamellar graphite or carbon paper.
The method preparing Graphene the most according to claim 1, it is characterized in that, described intercalator is one or more in halogen, hydrochloric acid, hydrogen bromide, hydrogen iodide, ammonium nitrate, zinc chloride, iron chloride, ammonium carbonate, sodium carbonate, potassium carbonate or ammonium hydrogen carbonate, sodium bicarbonate, potassium bicarbonate solution；The solubility scope of this intercalator is 2wt%-80wt%.
The method preparing Graphene the most according to claim 1, it is characterised in that the time of described intercalator pretreatment is 2min-48h.
The method preparing Graphene the most according to claim 1, it is characterised in that the oxidation voltage of described electrochemical oxidation method is 2V-50V, oxidization time is 1min-2h.
The method preparing Graphene the most according to claim 1, it is characterised in that described to utilize ultrasonic and stirring time be 5min to 24h, ultrasonic with in the range of when stirring, temperature maintains 0 DEG C-100 DEG C.
The method preparing Graphene the most according to claim 1, it is characterized in that, through high-temperature heat treatment, graphene oxide is reduced, it is in high vacuum environment or in atmosphere of inert gases, graphene oxide to be reduced, there is volatilization or decompose in intercalator therein, obtaining into graphene powder, its temperature is 200 DEG C-900 DEG C, and the time is 5min-5h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU173850U1 (en) * | 2017-03-24 | 2017-09-14 | Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" | DEVICE FOR ELECTROCHEMICAL PROCESSING OF GRAPHITE NANOPLATES |
| CN109796010A (en) * | 2019-03-29 | 2019-05-24 | 翁夏翔 | A kind of method that low-temperature molten salt prepares multi-layer graphene |
| CN110229304A (en) * | 2019-07-09 | 2019-09-13 | 兰州大学 | A kind of fire-retardant graphene polyurethane composite foam material and preparation method thereof |
| CN110451497A (en) * | 2019-08-26 | 2019-11-15 | 上海利物盛纳米科技有限公司 | A kind of method of quick free from admixture redox graphene |
| CN112744814A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Graphite modification method, modified graphite prepared by method, application of modified graphite, hydrocarbon oxidation method and volatile organic compound removal method |
| CN113816371A (en) * | 2021-09-25 | 2021-12-21 | 凯盛石墨碳材料有限公司 | Method for preparing expandable graphite by freeze-drying |
| CN114107889A (en) * | 2021-11-11 | 2022-03-01 | 杭州四马化工科技有限公司 | Metal foil demoulding method |
| CN115159514A (en) * | 2022-07-19 | 2022-10-11 | 中钢集团南京新材料研究院有限公司 | Method for electrochemically preparing graphene, graphene with high specific surface area and related products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU173850U1 (en) * | 2017-03-24 | 2017-09-14 | Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" | DEVICE FOR ELECTROCHEMICAL PROCESSING OF GRAPHITE NANOPLATES |
| CN109796010A (en) * | 2019-03-29 | 2019-05-24 | 翁夏翔 | A kind of method that low-temperature molten salt prepares multi-layer graphene |
| CN110229304A (en) * | 2019-07-09 | 2019-09-13 | 兰州大学 | A kind of fire-retardant graphene polyurethane composite foam material and preparation method thereof |
| CN110451497A (en) * | 2019-08-26 | 2019-11-15 | 上海利物盛纳米科技有限公司 | A kind of method of quick free from admixture redox graphene |
| CN112744814A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Graphite modification method, modified graphite prepared by method, application of modified graphite, hydrocarbon oxidation method and volatile organic compound removal method |
| CN112744814B (en) * | 2019-10-30 | 2023-04-07 | 中国石油化工股份有限公司 | Graphite modification method, modified graphite prepared by method, application of modified graphite, hydrocarbon oxidation method and volatile organic compound removal method |
| CN113816371A (en) * | 2021-09-25 | 2021-12-21 | 凯盛石墨碳材料有限公司 | Method for preparing expandable graphite by freeze-drying |
| CN113816371B (en) * | 2021-09-25 | 2023-09-08 | 凯盛石墨碳材料有限公司 | Method for preparing expandable graphite through freeze-drying |
| CN114107889A (en) * | 2021-11-11 | 2022-03-01 | 杭州四马化工科技有限公司 | Metal foil demoulding method |
| CN115159514A (en) * | 2022-07-19 | 2022-10-11 | 中钢集团南京新材料研究院有限公司 | Method for electrochemically preparing graphene, graphene with high specific surface area and related products |
| CN115159514B (en) * | 2022-07-19 | 2023-10-13 | 中钢集团南京新材料研究院有限公司 | Method for electrochemically preparing graphene, high specific surface area graphene and related products |
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Application publication date: 20161012 |