CN103451670B - A kind of Electrochemical preparation method of Graphene - Google Patents
A kind of Electrochemical preparation method of Graphene Download PDFInfo
- Publication number
- CN103451670B CN103451670B CN201310411276.4A CN201310411276A CN103451670B CN 103451670 B CN103451670 B CN 103451670B CN 201310411276 A CN201310411276 A CN 201310411276A CN 103451670 B CN103451670 B CN 103451670B
- Authority
- CN
- China
- Prior art keywords
- graphite
- graphene
- solution
- dimethyl formamide
- electrolytic solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
A kind of electrochemical preparation method of grapheme material, 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-methylimidazolium hydrogen sulphate salt as electrolytic solution, impose 3.1 ~ 6.0V voltage, separately win high level expansion graphite in anode and cathode; Corresponding electrolytic solution is added by 100:1 ~ 30:1 again in expanded graphite, grinding 3 ~ 6h, then proceed in acetone and dimethyl formamide mixed solution, the volume ratio of acetone and dimethyl formamide is 1.1:1 ~ 3:1,13000rpm is centrifugal, precipitation proceeds to dimethyl formamide, and 2000 ~ 10000rpm is centrifugal, obtains upper solution and is stable graphene solution.The grapheme material preparation process gentleness that the present invention produces is simple and easy, and defectiveness cures phenomenon, and product Graphene defect is few, and quality is high.
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 obtaining grapheme material with new processing mode.
Background technology
Graphene, a kind of two-dimensional atomic crystal material of carbon atom close-packed arrays formation of individual layer.2004 by the people such as scientist Geim A K by adhesive tape repeatedly exfoliated graphite obtain plumbago single slice.Before Graphene is found, theoretical and experimentally all think perfect two-dirnentional structure all cannot under non-zero absolute temperature stable existence, therefore the discovery of Graphene causes global concern, and its discoverer obtains 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 of Graphene; Three-dimensional graphite can be regarded as and formed through piling up by Graphene.Although Graphene only has the thickness of a carbon atom, and be one the thinnest in known materials, taller 100 times of the iron and steel that its hardness ratio is best in the world.Electroconductibility is also best in current known materials, and the movement velocity of electronics reaches 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.These superior performances and special two-dirnentional structure make Graphene have fine development prospect.
Due to quantum effect and the excellent chemical property of Graphene uniqueness, when the electronics in Graphene moves in track, or foreign atom can not be introduced and scattering occurs because of lattice imperfection.Because its interatomic force is very strong, even if carbon atom telescopes at normal temperatures, the interference that the electronics in Graphene is subject to is also very little.Be with a wide range of applications in electron device and transistor, photon sensor, matrix material, solar cell, ultracapacitor, hydrogen storage material etc.As the New Type of Carbon sill storing 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 Graphene monolithic and forms a thin layer, thus reach high Charge Storage level, add electrical capacity.This can significantly in improvement shop and the efficiency of hybrid vehicles and performance.
The preparation method of Graphene, mainly contains numerous preparation methods such as mechanically peel method, crystal epitaxy method, chemistry redox method, chemical Vapor deposition process, electrochemical stripping at present.
Patent US7824651B2 describes a kind of method obtaining the Graphene be dispersed in tensio-active agent based on supersound process graphite flake.The method, by adding dispersion agent sodium lauryl sulphate (SDS), ultrasonic 2h, obtains the graphite suspension of stable dispersion; In patent US2798878, use chemical oxidization method, carry out the process of low temperature Strong oxdiative by adding potassium permanganate, the vitriol oil, SODIUMNITRATE etc. to pyrolytic graphite, obtain graphite oxide, supersound process obtains the method for graphene oxide; In patent CN102275908A, disclose a kind of Hummers method traditional by improvement, obtain being oxidized sufficient graphene oxide colloidal solution, add reductive agent, reacting by heating through ultrasonic preparation, process obtains the Graphene colloidal solution disperseed in organic solvent.
At present, the method using chemistry redox to obtain Graphene is the most general with widely, namely prolongs and has held Hummers oxidation style, then obtain graphene oxide through ultrasonic disperse, and last reductive agent reduction, obtains Graphene.But this method uses strong oxidizer and severe corrosive acid, introduce a large amount of defect, and experimentation is complicated, tediously long consuming time in graphene product.
The present invention, uses simple electrochemical method to obtain high-quality graphene sheet from negative and positive the two poles of the earth graphite in proton simultaneously, and cures phenomenon from the graphene film defectiveness that negative electrode obtains, and experiment condition is gentle, and cost is low, consuming time short.
Summary of the invention
The Graphene defect that the object of the invention is to prepare for prior art is many, and the deficiency of the complicated tediously long or apparatus expensive of process, provides 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.
An electrochemical preparation method for 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-methylimidazolium hydrogen sulphate salt as electrolytic solution, impose 3.1 ~ 6.0V voltage, separately win high level expansion graphite in anode and cathode.
2) by 1) in the expanded graphite of step, corresponding electrolytic solution is added by 100:1 ~ 30:1, grinding 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) described in Graphite Electrodes be height pyrolytic graphite sheet or Graphite Powder 99 is pressed into graphite flake, then pressure is wrapped in stainless (steel) wire.
The present invention carries out graphite preexpanding simultaneously and carries out grinding again and obtain graphene film from negative and positive the two poles of the earth, thus charge stripping efficiency and productive rate high, and from the graphene film that negative electrode obtains, because there is cathodic reduction reaction, therefore defectiveness cures phenomenon, product Graphene defect is few, and quality is high.Adopt low voltage, reaction conditions is gentle.
Accompanying drawing explanation
Fig. 1 is the Raman figure of Graphene prepared by the present invention.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in more detail.
Embodiment 1
Adopt straight pressing 20mg Graphite Powder 99 to be pressed into graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Raman figure as shown in Figure 1, anode and cathode is self-control graphite flake electrode, and electrolytic solution is 1-methylimidazolium hydrogen sulphate salt, continues to impose 4V voltage 5 hours.Anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add 0.2ml1-methylimidazolium hydrogen sulphate salt, grind 3 hours.Proceeded to by this gelatinous mixture in mixed solvent acetone and DMF (V:V=2:1), high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Proceeded to by settling in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is obtained graphene solution, in lead.
As Fig. 1 Raman figure, in figure, a is the Graphene that negative electrode obtains, and in figure, b is the Graphene that anode obtains, and in figure, c is graphite powder, the graphene film defectiveness that negative electrode obtains as seen from the figure cures phenomenon, and is also only introduce a small amount of defect compared to most of oxidation reduction process anode graphite alkene.
Embodiment 2
Raman figure as shown in Figure 1, anode and cathode is 20mg height pyrolytic graphite sheet, and electrolytic solution is 1-butyl-3-methylimidazolium hydrogen sulphate salt, continues to impose 5v voltage 5 hours.Anode and cathode expanded graphite is proceeded to respectively in two agate mortars, add 0.3ml1-butyl-3-methylimidazolium hydrogen sulphate salt, grind 3 hours.Proceeded to by this gelatinous mixture in mixed solvent acetone and DMF (V:V=1.5:1), high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Proceeded to by settling in 50ml DMF, the centrifugal 5min of 5000rmp, supernatant liquor is obtained graphene solution, gray.
Embodiment 3
Adopt straight pressing 20mg Graphite Powder 99 to be pressed into graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Raman figure 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.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.Proceeded to by this gelatinous mixture in mixed solvent acetone and DMF (V:V=2.5:1), high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Proceeded to by settling in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is obtained graphene solution, gray.
Embodiment 4
Adopt straight pressing 20mg Graphite Powder 99 to be pressed into graphite flake (8mm X 6 mm), then pressure is wrapped in stainless (steel) wire.Raman figure 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.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.Proceeded to by this gelatinous mixture in mixed solvent acetone and DMF (V:V=3:1), high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Proceeded to by settling in 50ml DMF, the centrifugal 5min of 10000rmp, supernatant liquor is obtained graphene solution, slightly gray.
Embodiment 5
Raman figure as shown in Figure 1, anode and cathode is 20mg height pyrolytic graphite sheet, and electrolytic solution is N-Methyl pyrrolidone hydrosulfate, continues to impose 5V voltage 6.5 hours.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.Proceeded to by this gelatinous mixture in mixed solvent acetone and DMF (V:V=2:1), high speed centrifugation washs 3 times to remove, and rotating speed is 13000rmp, each time 10min.Proceeded to by settling in 50ml DMF, the centrifugal 5min of 2000rmp, supernatant liquor is obtained graphene solution, in lead.
Claims (2)
1. an electrochemical preparation method for grapheme material, is characterized in that comprising 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-methylimidazolium hydrogen sulphate salt as electrolytic solution, impose 3.1 ~ 6.0V voltage, separately win high level expansion graphite in anode and cathode;
2) by 1) in the expanded graphite of step, be that 100:1 ~ 30:1 adds corresponding electrolytic solution by graphite quality and electrolytic solution volume ratio, grinding 3 ~ 6h, then proceed in acetone and dimethyl formamide mixed solution, the volume ratio of acetone and dimethyl formamide is that 1.1:1 ~ 3:1,13000rpm are 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 for height pyrolytic graphite sheet or Graphite Powder 99 to be pressed into graphite flake, then pressure is wrapped in stainless (steel) wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310411276.4A CN103451670B (en) | 2013-09-11 | 2013-09-11 | A kind of Electrochemical preparation method of Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310411276.4A CN103451670B (en) | 2013-09-11 | 2013-09-11 | A kind of Electrochemical preparation method of Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103451670A CN103451670A (en) | 2013-12-18 |
| CN103451670B true CN103451670B (en) | 2015-09-23 |
Family
ID=49734490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310411276.4A Expired - Fee Related CN103451670B (en) | 2013-09-11 | 2013-09-11 | A kind of Electrochemical preparation method of Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103451670B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017171682A2 (en) | 2016-03-28 | 2017-10-05 | Sahin Yücel | A method in order to generate graphene based electrode |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088261B (en) * | 2014-05-14 | 2017-10-20 | 国能纳米科技有限公司 | The 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 |
| CN105152164B (en) * | 2015-08-21 | 2017-06-16 | 合肥工业大学 | A kind of preparation method of graphene platelet |
| GB201517784D0 (en) * | 2015-10-08 | 2015-11-25 | Univ Manchester | Production of graphene |
| US20180072573A1 (en) * | 2016-09-14 | 2018-03-15 | Alpha Metals, Inc. | Production of 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 |
| 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 |
| CN109873116B (en) * | 2019-02-28 | 2022-04-22 | 华南理工大学 | Worm graphite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-09-11 CN CN201310411276.4A patent/CN103451670B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017171682A2 (en) | 2016-03-28 | 2017-10-05 | Sahin Yücel | A method in order to generate graphene based electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103451670A (en) | 2013-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103451670B (en) | A kind of Electrochemical preparation method of Graphene | |
| Yang et al. | New insight to the role of edges and heteroatoms in nanocarbons for oxygen reduction reaction | |
| Cao et al. | Room temperature oxidation of Ti3C2 MXene for supercapacitor electrodes | |
| Zhao et al. | MnO2/graphene/nickel foam composite as high performance supercapacitor electrode via a facile electrochemical deposition strategy | |
| Mishra et al. | One-step solvothermal synthesis of carnation flower-like SnS2 as superior electrodes for supercapacitor applications | |
| Kuang et al. | Tunable synthesis of hierarchical NiCo2O4 nanosheets-decorated Cu/CuOx nanowires architectures for asymmetric electrochemical capacitors | |
| Wu et al. | Electrochemical exfoliation of graphene and graphene-analogous 2D nanosheets | |
| Lai et al. | Preparation of supercapacitor electrodes through selection of graphene surface functionalities | |
| Zhang et al. | Electrochemical reduction of graphene oxide films: Preparation, characterization and their electrochemical properties | |
| Liu et al. | A general green strategy for fabricating metal nanoparticles/polyoxometalate/graphene tri-component nanohybrids: enhanced electrocatalytic properties | |
| Li et al. | Graphdiyne/graphene/graphdiyne sandwiched carbonaceous anode for potassium-ion batteries | |
| CN103466608B (en) | A kind of ball milling preparation method of Graphene | |
| Wang et al. | Co3S4/NCNTs: a catalyst for oxygen evolution reaction | |
| Hao et al. | Face-to-face self-assembly graphene/MnO2 nanocomposites for supercapacitor applications using electrochemically exfoliated graphene | |
| Bindumadhavan et al. | Silver nanoparticles embedded boron-doped reduced graphene oxide as anode material for high performance lithium ion battery | |
| CN104174422B (en) | High nitrogen doped Graphene and fullerene selenizing molybdenum hollow ball nano composite material and preparation method thereof | |
| Nonaka et al. | Crumpled graphene decorated with manganese ferrite nanoparticles for hydrogen peroxide sensing and electrochemical supercapacitors | |
| Zhao et al. | Preparation and application of porous nitrogen-doped graphene obtained by co-pyrolysis of lignosulfonate and graphene oxide | |
| Zeng et al. | Facile synthesis of graphene@ NiO/MoO3 composite nanosheet arrays for high-performance supercapacitors | |
| Cheng et al. | The supercapacitive behavior and excellent cycle stability of graphene/MnO2 composite prepared by an electrostatic self-assembly process | |
| Lv et al. | Ultrafine nanoparticles assembled Mo2C nanoplates as promising anode materials for sodium ion batteries with excellent performance | |
| Zhang et al. | Highly defective graphite for scalable synthesis of nitrogen doped holey graphene with high volumetric capacitance | |
| Yang et al. | Reduced graphene oxide/carbon nanotube composites as electrochemical energy storage electrode applications | |
| He et al. | Superior pseudocapacitive performance and mechanism of self-assembled MnO2/MXene films as positive electrodes for flexible supercapacitors | |
| Kim et al. | Surface-modified reduced graphene oxide electrodes for capacitors by ionic liquids and their electrochemical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150923 Termination date: 20190911 |