CN106629676A - Alkaline-electrolyte-based graphene preparation method - Google Patents
Alkaline-electrolyte-based graphene preparation method Download PDFInfo
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- CN106629676A CN106629676A CN201610865166.9A CN201610865166A CN106629676A CN 106629676 A CN106629676 A CN 106629676A CN 201610865166 A CN201610865166 A CN 201610865166A CN 106629676 A CN106629676 A CN 106629676A
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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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses an alkaline-electrolyte-based graphene preparation method, and mainly aims to solve problems about use of acidic pollutants in the prior art. The method comprises the following steps: optimizing and selecting an alkaline solution as an electrolyte, adopting a graphite electrode formed by rolling as an anode, and adopting an inert metal electrode as a cathode; applying a positive direct current voltage between the cathode and the anode, intercalating and stripping the graphite electrode by virtue of the action of an electrolytic ion and an electric field, collecting a graphene precursor in a solution after a reaction process is ended, and performing repeated washing, ultrasonic treatment and drying on the graphene precursor to finally obtain pure thin-layer graphene. Compared with a conventional graphene preparation method, the preparation method has the characteristics of simplicity for operation, safety, high efficiency, environment friendliness, structural integrity and high performance of a graphene product, and the like, and is suitable for implement mass production of graphene.
Description
Technical field
The invention belongs to technical field of graphene preparation, and in particular to one kind by electrochemical stripping, rapidly and efficiently and
The method for contamination-freely preparing Graphene.
Background technology
2004, the Andre Geim of Univ Manchester UK taught and be by mechanically pulling off highly directional with his colleagues
The method of pyrolytic graphite (HOPG) has prepared first monolayer or few layer graphite, i.e., " Graphene ", and obtain promise in 2010
Bel's PHYSICS.Nobel Prize committee member will be considered that the significant contribution of the discovery is mainly manifested in three aspects：1) prepare first
Monoatomic layer two-dimensional material " Graphene " is gone out, having overthrown two-dimentional monoatomic layer crystal can not possibly stably deposit under non-absolute zero
Judgement；2) method for proposing observation Graphene first；3) find that Graphene has abnormal quantum hall effect etc. special
Physical effect and performance, be generally considered can final substituted for silicon, so as to cause the revolution again of electronics industry, and be numerous
Closest to the material of application in ' star ' material.Hereafter, the excellent mechanical property of Graphene, thermal property, electrical properties and light
Learn unique physical and chemical performance such as property to be also found quickly, become one of international natural science applied study hotspot.
It is generally believed that prepared by the extensive of Graphene, high-quality, low cost and environmental protection is to restrict its wide variety of " bottle
Neck ".So far, the preparation method of graphite alkene is reported out that relatively conventional method has in succession：Mechanical stripping method,
Epitaxial growth method, chemical vapour deposition technique (CVD), oxidation-reduction method, electrochemical stripping method etc..Wherein, be by mechanically pulling off or
The Graphene that epitaxial growth is obtained has higher crystal mass, but yield is extremely limited；CVD is to prepare graphene film
Good method, with quality of forming film it is high, area is big the features such as, but synthesis temperature is high, substrate requirements are harsh, need subsequent transfer etc.
Shortcoming limits further applying for the method.It is based on the oxidation-reduction method of Hummers, Brodie and Staudenmaier method
A kind of achievable large-scale low-cost preparation method for generally adopting at present, but the introducing of strong acid and strong oxidizer can destroy graphite
The intrinsic structure of alkene, causes product defect to increase, and performance is greatly reduced；Further, since the method is in a large number using strong acid and strong oxygen
Agent, its environmental issue in industrialization preparation is frequently subjected to the restriction and restriction of governments and laws regulation, it is considered to be a kind of
Fall behind and superseded technology.
Recently, electrochemical stripping method because it is simple, quick, safety and environmental protection and the advantage such as can in a large number prepare and cause greatly
Ground concern.The principle of the method is, as anode, electricity to be carried out to it in liquid phase environment using high purity graphite (or graphite paper) electrode
Chemical stripping obtains Graphene.But what electrolyte system relatively conventional at present was still selected is acid solution (such as sulphuric acid, phosphorus
Acid etc.), toxic and harmful can be produced in preparation process, to environment.For example, Chinese Academy of Sciences Suzhou nanometer Liu Li
Big grade proposes from the aqueous sulfuric acid that concentration is 3-18mol/L as electrolyte, can be efficiently peeled off and prepare Graphene.But
Sulphuric acid belongs in itself a kind of strong acid, and SO can be produced in preparation process2Deng gas, therefore there are still certain environmental issue.
Zhong Yiliang of South China Science ＆ Engineering University etc. is with diammonium phosphate (NH4)2HPO4Make electrolyte, it is found that graphite anode can adsorb phosphoric acid
Simultaneously there is electroxidation expansion stripping in radical ion, but the product reunion for obtaining is more serious, and lamella is uneven, particularly phosphoric acid based sols
There is also problem of environmental pollution.
Therefore, it is current international Research Emphasis that prepared by the non-acid (anacidity or weak acid) of Graphene.If can be by electricity
Solution liquid is changed to alkaline solution system, will thoroughly solve the environmental issue in Graphene preparation process, for realizing the green of Graphene
Color industrialized production is extremely important.
The content of the invention
Present invention aims to the environmental issue that prior art is present, proposes one kind using alkaline solution as electricity
Solution liquid, realizes Graphene environmental protection, fast and efficiently electrochemical stripping preparation method.The method is simple with taking less, operating
Single, environmentally friendly the features such as, Graphene products pure, lamella is relatively thin, structural integrity, is particularly suitable for extensive industry metaplasia
Produce.
The technical solution used in the present invention is specific as follows：
A kind of graphene preparation method based on alkaline electrolyte, comprises the following steps：The carbon content to be formed is rolled with Jing
>=99% graphite electrode as anode, using inert metal electrode as negative electrode, by negative electrode and anode with the spacing of 25-100mm
In being inserted in parallel into alkaline electrolyte, then the forward dc voltage of 1-10V is imposed, energization 0.5-5h stops collecting solution after being powered
In solid, then solid is washed repeatedly and ultrasound is to be gone the removal of impurity, then be transferred into being dried in 60 DEG C of baking oven
10 hours, obtain pure Graphene.
Described alkaline electrolyte be NaOH aqueous solutions, KOH aqueous solutions, ammonia or any several mixed liquor in them,
The concentration of electrolyte is 1-10mol/L in described alkaline electrolyte.
Being shaped as described graphite electrode is bar-shaped, banding or lamellar.
Described graphite electrode is high purity graphite paper or high purity graphite rod.
Described inert metal electrode is copper, silver, platinum, gold, titanium, lead or any several alloy in them.
A kind of Graphene, is prepared by the above-mentioned graphene preparation method based on alkaline electrolyte.
Application of the above-mentioned Graphene in chemical field.
The present invention has advantages below and beneficial effect：
(1) Graphene prepared by the present invention, peeling effect is obvious, products pure, structural integrity.
(2) compared with existing preparation method, the electrolyte adopts alkaline system, and any pollutant are not related in preparation process
The participation and generation of matter, is a kind of environmental protection, preparation method rapidly and efficiently, is that the mass industrialized production of Graphene is carried
A kind of new method and new approaches are supplied, with important and wide using value.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of the graphite ene product under low power in the embodiment of the present invention 1.
Fig. 2 is scanning electron microscope (SEM) figure of the graphite ene product under high power in the embodiment of the present invention 1.
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) figure of the graphite ene product under low power in the embodiment of the present invention 1.
Fig. 4 is high-resolution-ration transmission electric-lens (HRTEM) figure of the graphite ene product under high power in the embodiment of the present invention 1.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples, but is not therefore limited the present invention to described
Scope of embodiments within.
Embodiment 1
Using the NaOH aqueous solutions of 1mol/L as electrolyte, with high purity graphite paper (space difficult to understand, I levels, the phosphorus content of general commercial
>=99%) as anode, the platinized platinum using size as 1mm*2mm is used as negative electrode.By above-mentioned negative electrode and anode with anomaly between 50mm
Row is inserted in electrolyte, then imposes the forward dc voltage of 3.5V, starts electrochemical stripping.Graphite paper electrode is in electrolytic ion
In the presence of electric field, lamellar structure is opened, and is gradually cracked into thin graphene.After 1 hour to be energised, stripping process is completed,
The product of superjacent will be floated over by collected by suction, it is repeatedly washed and ultrasound is to go the removal of impurity,
It is then transferred to be dried 10 hours in 60 DEG C of baking oven, finally gives pure graphite ene product.
Graphene edge curling, the fold for preparing is can be seen that by Fig. 1 and Fig. 2 substantially, with typical Graphene
Pattern.Graphene can be seen that by Fig. 3 and Fig. 4 and present fluffy and transparent gauze-like；High-resolution-ration transmission electric-lens (HRTEM)
Picture shows that the number of plies of the Graphene sample is two-layer.
Embodiment 2
Using the KOH aqueous solutions of 6mol/L as electrolyte, with the high purity graphite rod of general commercial (space difficult to understand, a diameter of 10mm,
Phosphorus content >=99%) as anode, using platinum electrode as negative electrode.Above-mentioned negative electrode and anode are inserted in parallel into the spacing of 25mm
In electrolyte, then the forward dc voltage of 5V is imposed, start electrochemical stripping.Effect of the graphite electrode in electrolytic ion and electric field
Under, lamellar structure is opened, and is gradually cracked into thin graphene.3 hours to be energised, stripping process was completed, and will float over superjacent
Product got up by collected by suction, it is repeatedly washed and ultrasound to go the removal of impurity, be then transferred to 60 DEG C
Dry 10 hours in baking oven, finally give pure graphite ene product.
Embodiment 3
Using the ammonia of 10mol/L as electrolyte, with the high purity graphite paper of general commercial (space difficult to understand, I levels, phosphorus content >=
99%) as anode, the platinized platinum using size as 2mm*2mm is used as negative electrode.Above-mentioned negative electrode is parallel with the spacing of 100mm with anode
In being inserted into electrolyte, then the forward dc voltage of 10V is imposed, start electrochemical stripping.Graphite electrode is in electrolytic ion and electricity
In the presence of, lamellar structure is opened, and is gradually cracked into thin graphene.After 5 hours to be energised, stripping process is completed, will be floating
Got up by collected by suction in the product of superjacent, it is repeatedly washed and ultrasound is to go the removal of impurity, then turned
Move on in 60 DEG C of baking oven and dry 10 hours, finally give pure graphite ene product.
Embodiment 4
With the NaOH/KOH (mass ratioes 1 of 1mol/L:1) mixed aqueous solution is electrolyte, with the high purity graphite of general commercial
Paper (space difficult to understand, I levels, phosphorus content >=and 99%) as anode, the platinized platinum using size as 1mm*2mm is used as negative electrode.By above-mentioned negative electrode and
Anode is inserted in parallel in electrolyte with the spacing of 50mm, then imposes the forward dc voltage of 3.5V, starts electrochemical stripping.Stone
Electrode ink in the presence of electrolytic ion and electric field, open, and is gradually cracked into thin graphene by lamellar structure.To be energised 1.5 is little
Shi Hou, stripping process is completed, and will float over the product of superjacent by collected by suction, and it is repeatedly washed
With ultrasound to go the removal of impurity, it is then transferred to be dried 10 hours in 60 DEG C of baking oven, finally gives pure graphite ene product.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of graphene preparation method based on alkaline electrolyte, it is characterised in that comprise the following steps：Roll to be formed with Jing
Carbon content >=99% graphite electrode as anode, using inert metal electrode as negative electrode, by negative electrode and anode with 25-100
The spacing of mm is inserted in parallel in alkaline electrolyte, then imposes the forward dc voltage of 1-10 V, energization 0.5-5 h, stops being powered
The solid in solution is collected afterwards, then solid is washed repeatedly and ultrasound is to go the removal of impurity, then be transferred into 60 DEG C
Dry 10 hours in baking oven, obtain pure Graphene.
2. the graphene preparation method based on alkaline electrolyte according to claim 1, it is characterised in that：Described alkalescence
Electrolyte is NaOH aqueous solutions, KOH aqueous solutions, ammonia or any several mixed liquor in them, in described alkaline electrolyte
The concentration of electrolyte is 1-10 mol/L.
3. the graphene preparation method based on alkaline electrolyte according to claim 1, it is characterised in that：Described graphite
Being shaped as electrode is bar-shaped, banding or lamellar.
4. the graphene preparation method based on alkaline electrolyte according to claim 1, it is characterised in that：Described graphite
Electrode is high purity graphite paper or high purity graphite rod.
5. the graphene preparation method based on alkaline electrolyte according to claim 1, it is characterised in that：Described inertia
Metal electrode is copper, silver, platinum, gold, titanium, lead or any several alloy in them.
6. a kind of Graphene, it is characterised in that：The graphite based on alkaline electrolyte by described in claim requires any one of 1-5
Alkene preparation method is prepared.
7. application of the Graphene described in claim 6 in chemical field.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037666A (en) * | 2018-08-02 | 2018-12-18 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109205600A (en) * | 2017-07-07 | 2019-01-15 | 哈尔滨摆渡新材料有限公司 | A kind of device and method preparing graphene using galvanized wire |
| CN109485032A (en) * | 2018-11-28 | 2019-03-19 | 河南大学 | A method of preparing high-quality graphene quantum dot or big lamella graphene oxide |
| CN110133069A (en) * | 2019-04-16 | 2019-08-16 | 上海工程技术大学 | Surface graphene graphite base carbon material and its preparation method and application |
| CN110371961A (en) * | 2019-08-20 | 2019-10-25 | 中钢集团南京新材料研究院有限公司 | A kind of method of electrolytic preparation high intrinsic degree graphene |
| CN111924832A (en) * | 2020-09-23 | 2020-11-13 | 广西师范大学 | Device and method for producing graphene by electrochemically stripping graphite from electrode array |
| CN112225206A (en) * | 2020-10-20 | 2021-01-15 | 陕西理工大学 | Method for preparing water-soluble graphene by electric field driving of double graphite electrodes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205600A (en) * | 2017-07-07 | 2019-01-15 | 哈尔滨摆渡新材料有限公司 | A kind of device and method preparing graphene using galvanized wire |
| CN109037666A (en) * | 2018-08-02 | 2018-12-18 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109037666B (en) * | 2018-08-02 | 2020-08-07 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109485032A (en) * | 2018-11-28 | 2019-03-19 | 河南大学 | A method of preparing high-quality graphene quantum dot or big lamella graphene oxide |
| CN110133069A (en) * | 2019-04-16 | 2019-08-16 | 上海工程技术大学 | Surface graphene graphite base carbon material and its preparation method and application |
| CN110371961A (en) * | 2019-08-20 | 2019-10-25 | 中钢集团南京新材料研究院有限公司 | A kind of method of electrolytic preparation high intrinsic degree graphene |
| CN111924832A (en) * | 2020-09-23 | 2020-11-13 | 广西师范大学 | Device and method for producing graphene by electrochemically stripping graphite from electrode array |
| CN112225206A (en) * | 2020-10-20 | 2021-01-15 | 陕西理工大学 | Method for preparing water-soluble graphene by electric field driving of double graphite electrodes |
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