CN104291327A - Method for preparing graphene by peeling graphite in electrochemical manner by using molten salt - Google Patents
Method for preparing graphene by peeling graphite in electrochemical manner by using molten salt Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene by peeling graphite in an electrochemical manner by using molten salt. The method is characterized by combining an electrochemical method and a solvent method. According to the method, molten salt is used as a peeling medium, and the peeling power is provided by migration of charge particles in the molten salt. According to the technical scheme, the method comprises the following three steps: (1) preparing mixing salt of aluminum chloride, sodium chloride and potassium chloride of appreciate ratio, heating to be 150 DEG C, and keeping the temperature; (2) respectively introducing appreciate current into graphite and an aluminum electrode for electrochemical peeling; and (3) separating the graphene which is obtained by peeling by using the molten salt. The method has the advantages that the graphene defects are small, the equipment requirements are small, the graphene can be rapidly and massively prepared, the industrialization is easy to achieve, and the like.
Description
Technical field
Patent of the present invention relates to a kind of method preparing Graphene, relates to a kind of method adopting molten salt electrochemistry stripping graphite material to prepare Graphene specifically.
Background technology
Graphene is with sp by monolayer carbon atom
2the nano material with hexagonal lattice polynuclear plane of the mode bonding formation of hydridization, belongs to a kind of novel two dimensional crystal material.Graphene has good electroconductibility, thermal conductivity, optical transmission and special mechanical characteristic and electronics property, all has good application prospect in fields such as energy storage, electrically conducting transparent device, matrix material and opto-electronic devices.Therefore, Graphene has become the study hotspot in the multidisciplinary fields such as materialogy, physics and chemistry at present.In industrialization, due to the development of various technology of preparing, the exploitation of graphene product also achieves significant progress in recent years.
The preparation method of Graphene has multiple, totally can be divided into two classes: a class is bottom-to-top method, is obtained by atomic deposition, synthesis; Another kind of is top-to-bottom method, graphite type material is carried out decomposing, peeling off.Bottom-to-top method mainly contains CVD, and the Graphene obtained has the features such as high orientation, high transmission rate, surface-area are large, but due to complex process, cost high, be difficult to marketing.Top-to-bottom method is numerous, has microcomputer stripping method, oxidation reduction process, solvent stripping method, electrochemical process etc.Micromechanics stripping method can prepare high-quality graphene, but there is the deficiency that productive rate is low and cost is high, does not meet industrialization and large-scale production requirement.Oxidation reduction process preparation cost is cheap and easily realize, and stable graphene suspension can be prepared, solve the problem that Graphene not easily disperses, and can the good graphene layer sheet material of quality (Self-Assembled Free-Standing Graphite Oxide Membrane.Adv.Mater. (2009) by the method for solution-air self-assembly, 21,3007-3011), but there is assorted ring and non-carbon functional group in redox Graphene, makes the application of redox Graphene be restricted.Patent of invention " method of the swelling preparing graphite alkene of a kind of electrochemistry " (application number: CN201310659172.5) adopts the method that solvent is peeled off and electrochemistry combines, using sodium perchlorate, aluminum nitrate, water and dimethyl carbonate as electrolytic solution, Graphene can be prepared in a large number, the shortcoming of the method is that the time of electrochemical stripping is longer, and the time that embodiment is taked reaches 48 ~ 72h.
Summary of the invention
For the problems referred to above, the invention provides a kind of graphene preparation method of improvement, utilize aluminum chloride molten salt system as stripping media, charged particle migration in fused salt forms peeling force, make graphite expansion, increase bit interlamellar spacing, makes graphite flake layer thoroughly be separated finally by ultrasonic vibration, obtains Graphene.The present invention can prepare Graphene by rapid, high volume.
The preparation method of Graphene disclosed by the invention is obtained by following steps:
1) sodium-chlor, Repone K drying are mixed according to a certain percentage with aluminum chloride, mixing salt is heated to 150 ~ 180 DEG C, and keeps constant temperature, obtain mineral ion fused salt;
2) graphite is accessed positive source, aluminium sheet access power cathode, is placed in 1) in the middle of the fused salt that obtains;
3) utilize D.C. regulated power supply to 2) in electrode pass into electric current, reach the reaction times chosen, powered-down, now shown in graphite morphology figure as left in Fig. 1;
4) treat that temperature is down to room temperature, to 3) reaction product washes, and make product water pH value of solution for neutral, leave standstill 1h, get suspension;
5) to 4) suspension carries out ultrasonic vibration process 30 ~ 60min, and leave standstill 24 ~ 72h, obtain secondary suspension;
6) to 5) suspension at 60 ~ 120 DEG C of vacuum-drying 12h, obtain Graphene.
Described fused salt is not limited to sodium-chlor, Repone K and aluminum chloride, can use containing aluminum ion (and charged micelle) and replace with fill a prescription fused salt or ionic liquid of good other of graphite wetting property.
Described graphite is not limited to single kind graphite, and the graphite products such as crystalline flake graphite, soft graphite, high conductive graphite can be used to replace.
Described negative electrode is not limited to aluminium electrode, and the other materials that refractory salt corrosion, electroconductibility can be used good replaces.
Described electric current is not limited to unidirectional constant current, can peel off situation regulate size of current, direction according to reality.Size of current is determined by electrode size and setting current density.
The present invention compared with prior art has following characteristics and advantage:
1) this experimental technique is simple, simple to equipment requirements, cost is low, be convenient to scale operation.
2) graphite raw material of this experiment employing is extensive, does not limit to specified raw material.
Accompanying drawing explanation
Fig. 1. left figure is the pattern of graphite after process of the present invention, and right figure is the graphene aqueous solution that the present invention obtains.
Fig. 2. the present invention obtains the stereoscan photograph of Graphene.
Embodiment
Embodiment 1:
1) sodium-chlor, Repone K are mixed with the ratio of aluminum chloride according to 1:1:8, mixing salt is heated to 150 DEG C, and keeps constant temperature, mixing salt is melted completely;
2) utilize tetrafluoroethylene net by fixing for crystalline flake graphite access positive source, aluminium sheet access power cathode, be placed in 1) in the middle of the fused salt that obtains;
3) utilize D.C. regulated power supply to 2) in electrode pass into constant current, current density is 3Adm
-2.When being when reacted 2h, powered-down;
4) treat that temperature is down to room temperature, to 3) reaction product washes, and make product cleaning pH value of solution for neutral, leave standstill 1h, get suspension;
5) to 4) suspension carries out ultrasonic vibration process 60min, and leave standstill 72h, obtain secondary suspension;
6) to 5) suspension 80 DEG C of vacuum-drying 12h, obtain Graphene.
Embodiment 2:
1) sodium-chlor, Repone K are mixed with the ratio of aluminum chloride according to 20:14:66, mixing salt is heated to 150 DEG C, and keeps constant temperature, mixing salt is melted completely;
2) utilize tetrafluoroethylene net by fixing for crystalline flake graphite access positive source, aluminium sheet access power cathode, be placed in 1) in the middle of the fused salt that obtains;
3) utilize D.C. regulated power supply to 2) in electrode pass into constant current, current density is 2Adm
-2.When being when reacted 2h, powered-down;
4) treat that temperature is down to room temperature, to 3) reaction product washes, and make product water pH value of solution for neutral, leave standstill 1h, get suspension;
5) to 4) suspension carries out ultrasonic vibration process 60min, and leave standstill 24h, obtain secondary suspension;
6) to 5) suspension at 100 DEG C of vacuum-drying 10h, obtain Graphene.
Embodiment 3:
1) sodium-chlor, Repone K are mixed with the ratio of aluminum chloride according to 20:14:66, mixing salt is heated to 150 DEG C, and keeps constant temperature, mixing salt is melted completely;
2) using soft graphite as anode, aluminium sheet as negative electrode, be placed in 1) in the middle of the fused salt that obtains;
3) utilize D.C. regulated power supply to 2) in electrode pass into constant current, current density is 3Adm
-2.When being when reacted 2h, powered-down;
4) treat that temperature is down to room temperature, to 3) reaction product washes, and make product water pH value of solution for neutral, leave standstill 1h, get suspension;
5) to 4) suspension carries out ultrasonic vibration process 60min, and leave standstill 24h, obtain secondary suspension;
6) to 5) suspension at 100 DEG C of vacuum-drying 10h, obtain Graphene.
Claims (6)
1. molten salt electrochemistry peels off a method for preparing graphite alkene, and it is characterized in that utilizing fused salt as stripping media, electrode potential provides stripping motivating force, and with the material with graphite features structure for Graphene prepared by raw material, concrete steps are:
1) aluminum chloride, Repone K and sodium-chlor are mixed with certain proportion, be heated to 150 ~ 180 DEG C of constant temperature, salt to be mixed melts completely;
2) graphite raw material is accessed positive source, aluminium sheet access power cathode, pass into suitable electric current, splitting time is 120 ~ 240min;
3) after molten salt electrochemistry is peeled off and terminated, treat that fused salt is down to room temperature, obtain Graphene through washing, standing, ultrasonic, standing, drying and other steps.
2. a kind of molten salt electrochemistry peels off the method for preparing graphite alkene as claimed in claim 1, and it is characterized in that combines electrochemical process and solvent method prepares Graphene, and this method has extraordinary peeling effect to graphite-structure material.
3. preparation method as claimed in claim 1, is characterized in that step 1) in aluminum chloride, Repone K and sodium-chlor blending ratio require that the mass ratio of aluminum chloride is greater than 60 percent.
4. preparation method as claimed in claim 1, is characterized in that step 1) in graphite raw material comprise the material with graphite features structure, as crystalline flake graphite, soft graphite, high starch breeding, doped graphite etc.
5. preparation method as claimed in claim 1, is characterized in that step 2) in aluminium sheet can be replaced by the electro-conductive material of other stable existences in fused salt.
6. preparation method as claimed in claim 1, is characterized in that step 2) in strength of current size be 0.5 ~ 5Adm
-2, electrode size is determined by equipment situation.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
| CN106435632A (en) * | 2016-09-20 | 2017-02-22 | 南昌大学 | Preparation method for boron-doped graphene |
| CN107673338A (en) * | 2017-11-13 | 2018-02-09 | 中南大学 | A kind of method for preparing graphene using discarded graphite electrode |
| CN108134085A (en) * | 2018-01-10 | 2018-06-08 | 福州大学 | The graphite lithium ion battery negative material and preparation method of a kind of surface multi-layer graphite alkylene |
| CN108423661A (en) * | 2018-03-29 | 2018-08-21 | 武汉科技大学 | It is a kind of to derive the graphene that charcoal prepares the method for graphene and its prepares with mesophase pitch |
| CN108675287A (en) * | 2018-07-12 | 2018-10-19 | 西安交通大学 | A method of Anodic stripping prepares graphene in low-temperature molten salt |
| CN110482536A (en) * | 2019-09-25 | 2019-11-22 | 维沃泰克仪器(扬州)有限公司 | A method of graphene microchip is prepared using fused carbonate one-step electrolysis |
| CN111017915A (en) * | 2018-10-10 | 2020-04-17 | 长春工业大学 | Method for preparing graphene from graphite |
| CN111072015A (en) * | 2019-12-20 | 2020-04-28 | 厦门大学 | Preparation method of low-expansion thermal reduction graphene oxide |
| CN112938949A (en) * | 2021-03-04 | 2021-06-11 | 广东邦普循环科技有限公司 | Method for preparing graphene by using waste negative electrode graphite of lithium battery and graphene |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060180477A1 (en) * | 2003-07-14 | 2006-08-17 | Viktor Vasilievich Avdeev | Method for producing oxidised graphite |
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103253654A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene by peeling intercalated graphite through electric field |
| CN103255670A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene paper through utilizing electric field guidance |
| CN103382026A (en) * | 2012-05-02 | 2013-11-06 | 中国科学院上海硅酸盐研究所 | Low-cost mass preparation method of high-quality graphene |
| CN103449410A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Method for preparing graphene |
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| CN104003373A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
-
2014
- 2014-09-24 CN CN201410493509.4A patent/CN104291327A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060180477A1 (en) * | 2003-07-14 | 2006-08-17 | Viktor Vasilievich Avdeev | Method for producing oxidised graphite |
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN103253654A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene by peeling intercalated graphite through electric field |
| CN103255670A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene paper through utilizing electric field guidance |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103382026A (en) * | 2012-05-02 | 2013-11-06 | 中国科学院上海硅酸盐研究所 | Low-cost mass preparation method of high-quality graphene |
| CN103449410A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Method for preparing graphene |
| CN104003373A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
| CN106435632A (en) * | 2016-09-20 | 2017-02-22 | 南昌大学 | Preparation method for boron-doped graphene |
| CN107673338A (en) * | 2017-11-13 | 2018-02-09 | 中南大学 | A kind of method for preparing graphene using discarded graphite electrode |
| CN107673338B (en) * | 2017-11-13 | 2020-06-23 | 中南大学 | Method for preparing graphene by using waste graphite electrode |
| CN108134085A (en) * | 2018-01-10 | 2018-06-08 | 福州大学 | The graphite lithium ion battery negative material and preparation method of a kind of surface multi-layer graphite alkylene |
| CN108423661A (en) * | 2018-03-29 | 2018-08-21 | 武汉科技大学 | It is a kind of to derive the graphene that charcoal prepares the method for graphene and its prepares with mesophase pitch |
| CN108675287A (en) * | 2018-07-12 | 2018-10-19 | 西安交通大学 | A method of Anodic stripping prepares graphene in low-temperature molten salt |
| CN111017915A (en) * | 2018-10-10 | 2020-04-17 | 长春工业大学 | Method for preparing graphene from graphite |
| CN110482536A (en) * | 2019-09-25 | 2019-11-22 | 维沃泰克仪器(扬州)有限公司 | A method of graphene microchip is prepared using fused carbonate one-step electrolysis |
| CN111072015A (en) * | 2019-12-20 | 2020-04-28 | 厦门大学 | Preparation method of low-expansion thermal reduction graphene oxide |
| CN112938949A (en) * | 2021-03-04 | 2021-06-11 | 广东邦普循环科技有限公司 | Method for preparing graphene by using waste negative electrode graphite of lithium battery and graphene |
| WO2022183585A1 (en) * | 2021-03-04 | 2022-09-09 | 广东邦普循环科技有限公司 | Method for preparing graphene by using waste negative electrode graphite of lithium battery and graphene |
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Application publication date: 20150121 |