CN103451670A - Electrochemical preparation method of graphene - Google Patents
Electrochemical preparation method of graphene Download PDFInfo
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- CN103451670A CN103451670A CN2013104112764A CN201310411276A CN103451670A CN 103451670 A CN103451670 A CN 103451670A CN 2013104112764 A CN2013104112764 A CN 2013104112764A CN 201310411276 A CN201310411276 A CN 201310411276A CN 103451670 A CN103451670 A CN 103451670A
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Abstract
The invention provides an electrochemical preparation method of a graphene material. The preparation method comprises the following steps: using graphite electrodes as negative and positive electrodes respectively and one or more of 1-butyl-3-methylimidazolium dihydrogenphosphate, N-methyl pyrrolidone hydrosulfate, N-methyl pyrrolidone dihydrogenphosphate and 1-methylimidazolium hydrosulfate as an electrolyte, applying voltage of 3.1-6.0V, and obtaining highly expanded graphite at the negative and positive electrodes respectively; then adding the corresponding electrolyte to the expanded graphite according to (100:1)-(30:1), grinding for 3-6 hours, then transferring the expanded graphite to acetone and dimethyl formamide mixed liquor, carrying out centrifugation at 13000rpm, transferring the precipitate to dimethyl formamide, and carrying out centrifugation at 2000-10000rpm, thus obtaining a supernatant, namely a stable graphene solution, wherein the volume ratio of acetone to dimethyl formamide is (1.1:1)-(3:1). The preparation method has the beneficial effects that the preparation process of the graphene material produced by the preparation method is mild and simple and has a defect cure phenomenon, and the product graphene has few defects and high quality.
Description
Technical field
What the present invention relates to is a kind of method of preparing grapheme material relevant with technical field of nano material, is specifically related to a kind of method that obtains grapheme material with new processing mode.
Background technology
Graphene, the two-dimentional atomic crystal material that a kind of carbon atom close-packed arrays of individual layer forms.Within 2004, by people such as scientist Geim A K, pass through the adhesive tape plumbago single slice that exfoliated graphite obtains repeatedly.Before Graphene is found, theoretical and experimentally all think perfect two-dirnentional structure all can't be under non-zero absolute temperature stable existence, so the discovery of Graphene caused global concern, its discoverer has obtained the Nobel Prize in physics of 2010 simultaneously.
In fact, Graphene is the composition unit of other dimension carbon-based materials.The soccerballene of zero dimension can be regarded as the reunion of particular graphite alkene shape and forms; The carbon nanotube of one dimension can be regarded as the curling structure formed of Graphene; Three-dimensional graphite can be regarded as by Graphene and forms through piling up.Although Graphene only has the thickness of a carbon atom, and be the thinnest a kind of in known materials, its hardness ratio is taller 100 times of best iron and steel in the world.Electroconductibility is also best in current known materials, and the movement velocity of electronics has reached 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.The performance that these are superior and special two-dirnentional structure make Graphene have fine development prospect.
Due to the quantum effect of Graphene uniqueness and excellent chemical property, when the electronics in Graphene moves in track, can or not introduce foreign atom because of lattice imperfection scattering occurs.Because reactive force between its atom is very strong, though at normal temperatures on every side carbon atom telescope, the interference that the electronics in Graphene is subject to is also very little.At aspects such as electron device and transistor, photon sensor, matrix material, solar cell, ultracapacitor, hydrogen storage materials, be with a wide range of applications.As storing the New Type of Carbon sill of electric charge in ultracapacitor, the theoretical specific surface area of Graphene can reach 2630m
2/ g, this means that positive and negative charge ions a large amount of in electrolytic solution can be stored in a thin layer of formation in the Graphene monolithic, thereby reach high Charge Storage level, increased electrical capacity.This is significantly in the improvement shop and efficiency and the performance of hybrid vehicles.
The preparation method of Graphene, mainly contain numerous preparation methods such as mechanically peel method, crystal epitaxy method, chemistry redox method, chemical Vapor deposition process, electrochemical stripping at present.
Patent US7824651B2 has described a kind of method that obtains being dispersed in the Graphene in tensio-active agent based on the supersound process graphite flake.The method is by adding dispersion agent sodium lauryl sulphate (SDS), and ultrasonic 2h obtains the graphite suspension of stable dispersion; In patent US2798878, use chemical oxidization method, by adding potassium permanganate, the vitriol oil, SODIUMNITRATE etc., pyrolytic graphite is carried out to the strong oxide treatment of low temperature, obtain graphite oxide, supersound process obtains the method for graphene oxide; In patent CN102275908A, disclose a kind of Hummers method traditional by improvement, through the ultrasonic sufficient graphene oxide colloidal solution of oxidation for preparing, added reductive agent, reacting by heating, process and obtain being dispersed in the Graphene colloidal solution in organic solvent.
At present, the method for using chemistry redox to obtain Graphene is the most general with widely, prolongs and has held the Hummers oxidation style, then obtained graphene oxide through ultrasonic dispersion, and last reductive agent reduction, obtain Graphene.But this method is used strong oxidizer and severe corrosive acid, introduced a large amount of defects in the Graphene product, and experimentation is complicated, tediously long consuming time.
The present invention uses simple electrochemical method to obtain the high-quality graphene sheet from negative and positive the two poles of the earth graphite in proton simultaneously, and the graphene film defectiveness obtained from negative electrode healing phenomenon, the experiment condition gentleness, and cost is low, consuming time short.
Summary of the invention
The Graphene defect that the objective of the invention is to prepare for prior art is many, and the deficiency of the complicated tediously long or apparatus expensive of process, provide a kind of cost low, high quality, the preparation method of the grapheme material that process is simple to operation.
The present invention is achieved by the following technical solutions.
A kind of electrochemical preparation method of grapheme material comprises the following steps:
1) Graphite Electrodes is divided as anodic-cathodic, using one or more in 1-butyl-3-Methylimidazole dihydrogen phosphate, N-Methyl pyrrolidone hydrosulfate, N-Methyl pyrrolidone dihydrogen phosphate, 1-Methylimidazole hydrosulfate as electrolytic solution, impose 3.1 ~ 6.0V voltage, in anode and cathode, separately win high level expansion fossil China ink.
2) by 1) in the expanded graphite of step, add corresponding electrolytic solution by 100:1～30:1, grind 3 ~ 6h, then proceed in acetone and dimethyl formamide (DMF) (V:V=1.1:1 ~ 3:1) mixed solution, 13000rpm is centrifugal, precipitation proceeds to DMF, and 2000 ~ 10000rpm is centrifugal, obtains upper solution and is stable graphene solution.
Step 1) Graphite Electrodes described in is for height pyrolytic graphite sheet or Graphite Powder 99 is pressed into to graphite flake, then pressure is wrapped in stainless (steel) wire.
The present invention carries out the pre-expansion of graphite simultaneously and grinds the acquisition graphene film again from negative and positive the two poles of the earth, therefore charge stripping efficiency and productive rate are high, and the graphene film obtained from negative electrode, because cathodic reduction reaction is arranged, therefore defectiveness is cured phenomenon, product Graphene defect is few, and quality is high.Adopt low voltage, the reaction conditions gentleness.
The accompanying drawing explanation
Fig. 1 is the Raman figure of the Graphene for preparing of the present invention.
Embodiment
Below in conjunction with accompanying drawing, with embodiment, the present invention is described in more detail.
Example 1
Adopt straight pressing that the 20mg Graphite Powder 99 is pressed into to graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Experimental equipment as shown in Figure 1, anode and cathode is self-control graphite flake electrode, and electrolytic solution is 1-Methylimidazole hydrosulfate, continues to impose 4V voltage 5 hours.The anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add 0.2ml1-Methylimidazole hydrosulfate, grind 3 hours.This gelatinous mixture is proceeded in mixed solvent acetone and DMF (V:V=2:1), and high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Settling is proceeded in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is the graphene solution made, and is lead.
As Fig. 1 Raman figure, figure a is the Graphene that negative electrode makes, and figure b is the Graphene that anode makes, and figure c is the Graphite Powder 99 raw material, the graphene film defectiveness that negative electrode obtains is as seen from the figure cured phenomenon, and is only also to introduce a small amount of defect than most of oxidation reduction process anode graphite alkene.
Example 2
Experimental equipment as shown in Figure 1, anode and cathode is 20mg height pyrolytic graphite sheet, and electrolytic solution is 1-butyl-3-Methylimidazole hydrosulfate, continues to impose 5v voltage 5 hours.The anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add 0.3ml1-butyl-3-Methylimidazole hydrosulfate, grind 3 hours.This gelatinous mixture is proceeded in mixed solvent acetone and DMF (V:V=1.5:1), and high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Settling is proceeded in 50ml DMF, the centrifugal 5min of 5000rmp, supernatant liquor is the graphene solution made, gray.
Example 3
Adopt straight pressing that the 20mg Graphite Powder 99 is pressed into to graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Experimental equipment as shown in Figure 1, anode and cathode is self-control graphite flake electrode, and electrolytic solution is 1-butyl-3-Methylimidazole dihydrogen phosphate, continues to impose 6V voltage 4.5 hours.The anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add the above-mentioned 1-butyl of 0.5ml-3-Methylimidazole dihydrogen phosphate, grind 6 hours.This gelatinous mixture is proceeded in mixed solvent acetone and DMF (V:V=2.5:1), and high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Settling is proceeded in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is the graphene solution made, gray.
Example 4
Adopt straight pressing that the 20mg Graphite Powder 99 is pressed into to graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Experimental equipment as shown in Figure 1, anode and cathode is self-control graphite flake electrode, and electrolytic solution is N-Methyl pyrrolidone hydrosulfate and 1-butyl-3-Methylimidazole dihydrogen phosphate, continues to impose 3.1V voltage 8 hours.The anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add the above-mentioned N-Methyl pyrrolidone hydrosulfate of 0.3ml and 1-butyl-3-Methylimidazole dihydrogen phosphate, grind 2.5 hours.This gelatinous mixture is proceeded in mixed solvent acetone and DMF (V:V=3:1), and high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Settling is proceeded in 50ml DMF, the centrifugal 5min of 10000rmp, supernatant liquor is the graphene solution made, slightly gray.
Example 5
Experimental equipment as shown in Figure 1, anode and cathode is 20mg height pyrolytic graphite sheet, and electrolytic solution is the N-Methyl pyrrolidone hydrosulfate, continues to impose 5V voltage 6.5 hours.The anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add the above-mentioned N-Methyl pyrrolidone hydrosulfate of 0.4ml, grind 5 hours.This gelatinous mixture is proceeded in mixed solvent acetone and DMF (V:V=2:1), and high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Settling is proceeded in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is the graphene solution made, and is lead.
Claims (2)
1. the electrochemical preparation method of a grapheme material is characterized in that comprising the following steps:
Graphite Electrodes is divided as anodic-cathodic, using one or more in 1-butyl-3-Methylimidazole dihydrogen phosphate, N-Methyl pyrrolidone hydrosulfate, N-Methyl pyrrolidone dihydrogen phosphate, 1-Methylimidazole hydrosulfate as electrolytic solution, impose 3.1 ~ 6.0V voltage, in anode and cathode, separately win high level expansion fossil China ink;
By 1) in the expanded graphite of step, add corresponding electrolytic solution by 100:1～30:1, grind 3 ~ 6h, then proceed in acetone and dimethyl formamide mixed solution, the volume ratio of acetone and dimethyl formamide is 1.1:1 ~ 3:1, and 13000rpm is centrifugal, and precipitation proceeds to dimethyl formamide, 2000 ~ 10000rpm is centrifugal, obtains upper solution and is stable graphene solution.
2. the electrochemical preparation method of grapheme material as claimed in claim 1, is characterized in that: step 1) described in Graphite Electrodes be height pyrolytic graphite sheet or Graphite Powder 99 is pressed into to graphite flake, then press and be wrapped in stainless (steel) wire.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088261A (en) * | 2014-05-14 | 2015-11-25 | 国能纳米科技有限公司 | Preparation method of graphene |
| CN105152164A (en) * | 2015-08-21 | 2015-12-16 | 合肥工业大学 | Preparation method of graphene sheet |
| CN106894039A (en) * | 2017-03-25 | 2017-06-27 | 哈尔滨摆渡新材料有限公司 | A kind of method and device for preparing Graphene |
| CN107032339A (en) * | 2017-06-20 | 2017-08-11 | 成都新柯力化工科技有限公司 | It is a kind of based on the electrostatic repulsion method that continuously stripping prepares graphene |
| CN108349727A (en) * | 2015-10-08 | 2018-07-31 | 曼彻斯特大学 | The production of graphene |
| CN109844183A (en) * | 2016-09-14 | 2019-06-04 | 爱法组装材料公司 | The manufacture of graphene |
| CN109873116A (en) * | 2019-02-28 | 2019-06-11 | 华南理工大学 | A kind of worm graphite and preparation method thereof |
| US10787746B2 (en) | 2014-10-13 | 2020-09-29 | Haibo Xu | Graphene oxide prepared by electrochemically oxidizing and cutting end face of carbon-based three-dimensional material and method therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR201603935A2 (en) | 2016-03-28 | 2017-10-23 | Yuecel Sahin | A METHOD FOR PRODUCING GRAFEN BASED ELECTRODE |
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| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103183332A (en) * | 2011-12-27 | 2013-07-03 | 财团法人工业技术研究院 | Method for forming graphene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103183332A (en) * | 2011-12-27 | 2013-07-03 | 财团法人工业技术研究院 | Method for forming graphene |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088261A (en) * | 2014-05-14 | 2015-11-25 | 国能纳米科技有限公司 | Preparation method of graphene |
| US10787746B2 (en) | 2014-10-13 | 2020-09-29 | Haibo Xu | Graphene oxide prepared by electrochemically oxidizing and cutting end face of carbon-based three-dimensional material and method therefor |
| CN105152164A (en) * | 2015-08-21 | 2015-12-16 | 合肥工业大学 | Preparation method of graphene sheet |
| CN105152164B (en) * | 2015-08-21 | 2017-06-16 | 合肥工业大学 | A kind of preparation method of graphene platelet |
| CN108349727A (en) * | 2015-10-08 | 2018-07-31 | 曼彻斯特大学 | The production of graphene |
| CN109844183A (en) * | 2016-09-14 | 2019-06-04 | 爱法组装材料公司 | The manufacture of graphene |
| CN106894039A (en) * | 2017-03-25 | 2017-06-27 | 哈尔滨摆渡新材料有限公司 | A kind of method and device for preparing Graphene |
| CN106894039B (en) * | 2017-03-25 | 2019-06-04 | 哈尔滨摆渡新材料有限公司 | A kind of method and device preparing graphene |
| CN107032339A (en) * | 2017-06-20 | 2017-08-11 | 成都新柯力化工科技有限公司 | It is a kind of based on the electrostatic repulsion method that continuously stripping prepares graphene |
| CN107032339B (en) * | 2017-06-20 | 2018-03-20 | 成都新柯力化工科技有限公司 | It is a kind of based on the electrostatic repulsion method that continuously stripping prepares graphene |
| CN109873116A (en) * | 2019-02-28 | 2019-06-11 | 华南理工大学 | A kind of worm graphite and preparation method thereof |
| CN109873116B (en) * | 2019-02-28 | 2022-04-22 | 华南理工大学 | Worm graphite and preparation method thereof |
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