CN106395805B - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN106395805B CN106395805B CN201611078239.6A CN201611078239A CN106395805B CN 106395805 B CN106395805 B CN 106395805B CN 201611078239 A CN201611078239 A CN 201611078239A CN 106395805 B CN106395805 B CN 106395805B
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Abstract
A kind of preparation method of graphene, includes the following steps：It is to electrode with platinized platinum in three-electrode system, copper foil is working electrode, and graphene oxide solution is electrolyte, carries out electro-deposition；The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；Using dilute sulfuric acid as electrolyte, the copper foil of the graphene oxide that deposited partial reduction connects cathode, and platinized platinum connects anode, carries out electrochemical reduction, obtains the graphene film of self-supporting.The method that the preparation method of above-mentioned graphene utilizes electrochemistry, only only used the reagents such as dilute sulfuric acid, does not need strong corrosive, highly toxic reducing agent, will not introduce impurity functional group, environmentally protective；It is simple and easy to get using copper foil as working electrode, it can also reuse, greatly reduce experimental cost；Experimental period is short, can be rapidly and efficiently prepare graphene film；It is carried out under normal temperature and pressure, does not need atmosphere protection, experimental facilities is simple, further reduced experimental cost, improves operability.
Description
Technical field
The present invention relates to grapheme material field more particularly to a kind of preparation methods of graphene.
Background technology
Graphene is a kind of two dimensional surface material with hexagonal structure being made of carbon atom.Unique knot of graphene
Structure feature makes it with good electricity, calorifics and mechanical property, and is widely used in sensor field, energy storage and novel
Display field, field of semiconductor materials and biomedical sector.
The preparation method of graphene includes mainly mechanical stripping method, liquid phase stripping method, oxidation-reduction method, electrochemical stripping method
With chemical vapour deposition technique etc..Wherein, it is most to be expected to heavy industrialization to prepare redox graphene using graphene oxide
One of method of production.Currently, the reducing agent of common reduced graphene mainly has a hydrazine hydrate, and sodium borohydride, metal hydride,
Hydroiodic acid, glucose and vitamin C etc..But these reducing agents are mostly toxic, it is expensive, and much restoring
The perfect hexagonal structure that graphene is destroyed in journey, introduces additional functionality.Alternatively, it is in reduction, reducing agent is used
Amount is very big, and reduction cycle is long, complicated for operation.
Invention content
In consideration of it, it is necessary to provide it is a kind of efficiently, low consumption, environmentally protective, easy to operate extensive prepare graphene
The preparation method of graphene.
A kind of preparation method of graphene, includes the following steps：
It is to electrode with platinized platinum in three-electrode system, copper foil is working electrode, and graphene oxide solution is electrolyte,
Carry out electro-deposition；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using dilute sulfuric acid as electrolyte, the copper foil of the graphene oxide that deposited partial reduction connects cathode, and platinized platinum connects just
Pole carries out electrochemical reduction, obtains the graphene film of self-supporting.
The graphene oxide solution is prepared with the following method in one of the embodiments,：By graphene oxide powder
End and deionized water are uniformly mixed, and obtain graphene oxide solution.
A concentration of 1mg/mL~3mg/mL of the graphene oxide solution in one of the embodiments,.
The size of the copper foil is 1cm × 8cm in one of the embodiments, wherein is immersed in the graphene oxide
Area in solution is 1cm2~4cm2。
The time of the electro-deposition is 10min~30min in one of the embodiments,.
The voltage of the electro-deposition is 3V~5V in one of the embodiments,.
A concentration of 0.1M~0.5M of the dilute sulfuric acid in one of the embodiments,.
The time of the electrochemical reduction is 10min~30min, current density 2mA/ in one of the embodiments,
cm2~10mA/cm2。
The method that the preparation method of above-mentioned graphene utilizes electrochemistry, only only used dilute sulfuric acid in the entire experiment process
Equal reagents, do not need conventional strong corrosive, highly toxic reducing agent, and impurity function will not be introduced in reduction process
Group, it is environmentally protective；It is simple and easy to get using copper foil as working electrode, it can also reuse, greatly reduce experimental cost；
Experimental period is short, can be rapidly and efficiently prepare graphene film；There is no a particular/special requirement to experimental situation, under normal temperature and pressure
It carries out, does not also need atmosphere protection, and experimental facilities is simple, further reduced experimental cost, improve operability.
Description of the drawings
Fig. 1 is the preparation method flow chart of the graphene of an embodiment.
Fig. 2 is the infrared spectrogram of graphene prepared by embodiment 1 to embodiment 5.
Specific implementation mode
In order to make the objectives, technical solutions, and advantages of the present invention be more clear, with reference to the accompanying drawings and embodiments, to this hair
It is bright to be further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting.
Referring to Fig. 1, the preparation method of the graphene of an embodiment, includes the following steps：
S10, in three-electrode system, be to electrode with platinized platinum, copper foil is working electrode, and graphene oxide solution is electrolysis
Liquid carries out electro-deposition.
In three-electrode system, using mercury electrode as reference electrode.
In one embodiment, graphene oxide solution is prepared with the following method：By graphene oxide powder and go from
Sub- water is uniformly mixed, and obtains graphene oxide solution.A concentration of 1mg/mL~3mg/mL of graphene oxide solution.
In one embodiment, the dosage of graphene oxide solution can be 100mL.
In one embodiment, it is to electrode with the platinized platinum of 3cm × 3cm.The size of copper foil can be 1cm × 8cm,
In, the area being immersed in graphene oxide solution is 1cm2-4cm2.Specifically, utilizing 3 × 3cm2Platinum plate electrode be to electricity
Pole, 1 × 8cm2Copper foil be working electrode, connect the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, face
Area is 2cm2。
In one embodiment, the time of electro-deposition can be 10min~30min.The voltage of electro-deposition can be 3V~
5V.After S10, graphene oxide is uniformly deposited on copper foil surface.
S20, taking-up deposited the copper foil of the graphene oxide of partial reduction, and room temperature air-dries.
S30, using dilute sulfuric acid as electrolyte, the copper foil that deposited the graphene oxide of partial reduction connects cathode, and platinized platinum connects just
Pole carries out electrochemical reduction, obtains the graphene film of self-supporting.
The concentration of dilute sulfuric acid can be 0.1M~0.5M.
The time of electrochemical reduction can be 10min~30min, and current density can be 2mA/cm2~10mA/cm2。
The preparation method of above-mentioned graphene, the thickness of the graphene film being prepared is at 2 μm~4 μm, sheet resistance
For 1K Ω/sq~6K Ω/sq.
The preparation method of above-mentioned graphene also has atmosphere not have particular/special requirement temperature and pressure, is at normal temperatures and pressures
It can be achieved, the C/O ratios for the graphene being prepared are high, and quality is good.
Compared with prior art, the advantages of preparation method of above-mentioned graphene, is：
(1) compared with prior art, the method that the preparation method of above-mentioned graphene utilizes electrochemistry, in whole experiment process
In only only used the reagents such as dilute sulfuric acid, do not need conventional strong corrosive, highly toxic reducing agent, and in reduction process
Impurity functional group will not be introduced, it is environmentally protective；
(2) preparation method of above-mentioned graphene has used copper foil as working electrode in reduction, not only to a certain degree
On can be with the reduction of catalytic graphite alkene, and the electrode is simple and easy to get, can also reuse, greatly reduce experimental cost；
(3) principle and method of electrochemistry is utilized in the preparation method of above-mentioned graphene, effectively eliminates graphite oxide
Oxygen-containing functional group in alkene obtains the Flexible graphene film of high conductivity and thermal conductivity；
(4) preparation method of above-mentioned graphene, experimental period is short, can be rapidly and efficiently prepare graphene film；
(5) preparation method of above-mentioned graphene does not have particular/special requirement to experimental situation, can be carried out under normal temperature and pressure, not yet
Atmosphere protection is needed, and experimental facilities is simple, further reduced experimental cost, improves operability.
It is specific embodiment part below.
Embodiment 1
The graphene solution for configuring 3mg/mL, utilizes 3 × 3cm2Platinum plate electrode be to electrode, 1 × 8cm2Copper foil be work
Make electrode, connects the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, facing area 2cm2, under 5V voltages
Electro-deposition 10 minutes；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using the dilution heat of sulfuric acid of 0.1M as electrolyte, connect using the copper foil for the graphene oxide that deposited partial reduction negative
Pole, platinized platinum connect anode, are 3mA/cm in current density2Lower electrochemical reduction 20 minutes.
Performance test:
Sheet resistance is:5.32KΩ/sq.
Embodiment 2
The graphene solution for configuring 2mg/mL, utilizes 3 × 3cm2Platinum plate electrode be to electrode, 1 × 8cm2Copper foil be work
Make electrode, connects the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, facing area 1cm2, under 3V voltages
Electro-deposition 20 minutes；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using the dilution heat of sulfuric acid of 0.5M as electrolyte, connect using the copper foil for the graphene oxide that deposited partial reduction negative
Pole, platinized platinum connect anode, are 5mA/cm in current density2Lower electrochemical reduction 10 minutes.
Performance test:
Sheet resistance is:3.19KΩ/sq.
Embodiment 3
The graphene solution for configuring 1mg/mL, utilizes 3 × 3cm2Platinum plate electrode be to electrode, 1 × 8cm2Copper foil be work
Make electrode, connects the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, facing area 2cm2, under 3V voltages
Electro-deposition 15 minutes；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using the dilution heat of sulfuric acid of 0.5M as electrolyte, connect using the copper foil for the graphene oxide that deposited partial reduction negative
Pole, platinized platinum connect anode, are 10mA/cm in current density2Lower electrochemical reduction 30 minutes.
Performance test:
Sheet resistance is:2.5KΩ/sq.
Embodiment 4
The graphene solution for configuring 3mg/mL, utilizes 3 × 3cm2Platinum plate electrode be to electrode, 1 × 8cm2Copper foil be work
Make electrode, connects the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, facing area 4cm2, under 3V voltages
Electro-deposition 30 minutes；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using the dilution heat of sulfuric acid of 0.3M as electrolyte, connect using the copper foil for the graphene oxide that deposited partial reduction negative
Pole, platinized platinum connect anode,；It is 2mA/cm in current density2Lower electrochemical reduction 15 minutes.
Performance test:
Sheet resistance is:6.17KΩ/sq.
Embodiment 5
The graphene solution for configuring 2mg/mL, utilizes 3 × 3cm2Platinum plate electrode be to electrode, 1 × 8cm2Copper foil be work
Make electrode, connects the cathode and anode of constant pressure source respectively；Wherein two electrode spacings are 2cm, facing area 2cm2, under 3V voltages
Electro-deposition 10 minutes；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using the dilution heat of sulfuric acid of 0.5M as electrolyte, connect using the copper foil for the graphene oxide that deposited partial reduction negative
Pole, platinized platinum connect anode, are 3mA/cm in current density2Lower electrochemical reduction 15 minutes.
Performance test:
Sheet resistance is:1.25KΩ/sq.
The infrared spectrum of embodiment 1 to graphene prepared by embodiment 5 is as shown in Figure 2.Wherein, number 1~5 respectively represents
The infrared spectrum curve for the graphene that embodiment 1 is prepared to embodiment 5.
It the above is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without departing from the principles of the invention, several improvements and modifications can also be made, these improvements and modifications also should be regarded as this hair
Bright protection domain.
Claims (6)
1. a kind of preparation method of graphene, which is characterized in that include the following steps：
It is to electrode with platinized platinum in three-electrode system, copper foil is working electrode, and graphene oxide solution is electrolyte, is carried out
Electro-deposition；
The copper foil for the graphene oxide that deposited partial reduction is taken out, room temperature air-dries；
Using dilute sulfuric acid as electrolyte, the copper foil of the graphene oxide that deposited partial reduction connects cathode, and platinized platinum connects anode, into
Row electrochemical reduction obtains the graphene film of self-supporting；
A concentration of 0.1M~0.5M of the dilute sulfuric acid；
The time of the electrochemical reduction is 10min~30min, current density 2mA/cm2~10mA/cm2。
2. the preparation method of graphene as described in claim 1, which is characterized in that the graphene oxide solution is using as follows
It is prepared by method：Graphene oxide powder and deionized water are uniformly mixed, graphene oxide solution is obtained.
3. the preparation method of graphene as claimed in claim 2, which is characterized in that the graphene oxide solution it is a concentration of
1mg/mL~3mg/mL.
4. the preparation method of graphene as described in claim 1, which is characterized in that the size of the copper foil is 1cm × 8cm,
Wherein, the area being immersed in the graphene oxide solution is 1cm2~4cm2。
5. the preparation method of graphene as described in claim 1, which is characterized in that the time of the electro-deposition be 10min~
30min。
6. the preparation method of graphene as described in claim 1, which is characterized in that the voltage of the electro-deposition is 3V~5V.
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| CN107354497B (en) * | 2017-06-23 | 2019-05-03 | 河海大学 | A kind of graphene surface processing raising corrosion proof method of copper magnesium alloy |
| CN108706571A (en) * | 2018-06-06 | 2018-10-26 | 丽水学院 | Method for the splicing of fragment graphene oxide |
| CN112645313B (en) * | 2021-01-16 | 2022-05-27 | 大连理工大学 | Method for electrochemically rapidly preparing graphene-based monatomic catalyst in batch and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN102061504A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for synthesizing graphene-containing composite thin film material |
| CN102930991A (en) * | 2012-11-08 | 2013-02-13 | 南京师范大学 | Electrochemistry one-step method for preparing graphene/polyaniline conductive composites |
| US20140076721A1 (en) * | 2012-09-14 | 2014-03-20 | International Business Machines Corporation | Electrochemical etching apparatus |
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| CN102061504A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for synthesizing graphene-containing composite thin film material |
| US20140076721A1 (en) * | 2012-09-14 | 2014-03-20 | International Business Machines Corporation | Electrochemical etching apparatus |
| CN102930991A (en) * | 2012-11-08 | 2013-02-13 | 南京师范大学 | Electrochemistry one-step method for preparing graphene/polyaniline conductive composites |
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| Large-Area, Conductive and Flexible Reduced GrapheneOxide (RGO) Membrane Fabricated by Electrophoretic Deposition(EPD);Mei Wang et al;;《Appl. Mater. Interface》;20140116;第6卷;第1747-1753页 * |
| Three-dimensional porous graphene-based composite materials: electrochemical synthesis and application;Kaiwu Chen et al;;《Journal of Materials Chemistry》;20120815;第22卷;第20968–20976页 * |
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Effective date of registration: 20200807 Address after: Room 2309, 23 / F, block B, Guanggu international, Jiayuan Road, Donghu New Technology Development Zone, Wuhan City, Hubei Province Patentee after: Wuhan shaiyang HVAC Equipment Co.,Ltd. Address before: 1068 No. 518055 Guangdong city in Shenzhen Province, Nanshan District City Xili University School Avenue Patentee before: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY CHINESE ACADEMY OF SCIENCES |