CN203728584U - Device for preparing graphene paper based on glow plasma positive column - Google Patents

Device for preparing graphene paper based on glow plasma positive column Download PDF

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Publication number
CN203728584U
CN203728584U CN201420063297.1U CN201420063297U CN203728584U CN 203728584 U CN203728584 U CN 203728584U CN 201420063297 U CN201420063297 U CN 201420063297U CN 203728584 U CN203728584 U CN 203728584U
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China
Prior art keywords
paper
graphene
substrate table
positive column
chip bench
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Expired - Lifetime
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CN201420063297.1U
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Chinese (zh)
Inventor
薄拯
岑可法
严建华
池涌
李晓东
祝伟光
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The utility model discloses a device for preparing graphene paper based on a glow plasma positive column. The device comprises a substrate table, a quartz sleeve, a quartz tube, a conical electrode, a high-voltage negative power supply and a helium-gas gas source, wherein the substrate table, the quartz sleeve and the conical electrode are arranged in the quartz tube; the substrate table can horizontally move in the quartz tube; the substrate table is embedded into the quartz sleeve; the conical tip surface of the conical electrode faces towards the substrate table; the conical electrode is connected with the high-voltage negative power supply; the substrate table is grounded; one end of the quartz tube is open, and the other end of the quartz tube is connected with the helium-gas gas source. In a preparation process, the graphene oxide paper is fixed on the substrate table, and glow discharge plasmas with a positive column are formed between the graphene oxide paper and the conical electrode by virtue of high voltage. The device disclosed by the utility model can realize rapid preparation of the graphene paper under the normal pressure, is simple in arrangement and process, environmental friendly, and high in energy utilization rate, has large-scale amplification application potential, and is beneficial to promoting the graphene paper to be widely applied in a plurality of fields.

Description

Prepare the device of Graphene paper based on glow plasma positive column
Technical field
The utility model belongs to plasma body and nano material preparing technical field, relates in particular to a kind of device of preparing Graphene paper based on glow plasma positive column.
Background technology
Graphene is a kind of by sp 2the two-dimensional nano material that hydridization carbon atom is arranged with hexagonal lattice, since 2004 find first, has caused very big interest and extensive concern with its peculiar performance.The flexible flexible materials that Graphene paper is made up of multi-disc Graphene, has good electroconductibility, large specific surface area and good mechanical property, has broad application prospects in stored energy field.For example, Graphene paper can be as collapsible ultracapacitor energy storage material without binding agent and conductive agent in the situation that.
At present, the preparation method of Graphene paper mainly contains chemical reduction method (Haiqun Chen etc., Adv. Mater., 2008,20,3557 – 3561; H. Shin etc., Adv. Funct. Mater, 2009,19,1987-1992) and hot reducing method (H. C. Schniepp etc., Journal of Physical Chemistry B, 2006,110,8535-8539; Y. Zhu etc., ACS Nano, 2010,4,1227-1233; Patent CN 101901640 A).Wherein, chemical reduction method has the potentiality of scale operation Graphene paper, but conventional reductive agent is as hydrazine or sodium borohydride, has chemical toxicity or explosivity, easily causes environmental pollution and is detrimental to health.Meanwhile, due to the use of reductive agent, easily in Graphene paper, mix impurity.Compared with chemical reduction method, hot reducing method, without reductive agent, is realized removal and the reduction of graphene oxide paper surface oxygen functional group by high temperature, and reaction environment is dried and does not exist the problem of introducing impurity.But the reaction process of hot reducing method needs certain high temperature conventionally, can cause loss and the waste of energy in heating and cooling background gas.
Plasma body, as the 4th kind of form of material, is a kind of energy transformation and effective powerful tool of utilizing.Have and utilize multiple plasma source to carry out the report that redox graphene is prepared Graphene at present.For example: microwave plasma source (Y. Zhu etc., Carbon, 2010,48,2118-2122; Z. Li etc., Journal of Materials Chemistry, 2010,20,4781-4783; Patent CN 102107870 A; Patent CN 102139873A), radio-frequency inductance coupling plasma (Q. Wang etc., Applied Physics Letters, 2012,101) and electron beam plasma body (M. Baraket etc., Carbon, 2010,48,3382-3390) etc.In order to realize the abundant acceleration of higher electron mean free path with electron gain, above-mentioned plasma deoxidization process need to be carried out conventionally in the environment of low pressure or vacuum, and this has increased complicacy and the preparation cost of equipment to a great extent.
Summary of the invention
The purpose of this utility model is to overcome the deficiencies in the prior art, and a kind of device of preparing Graphene paper based on glow plasma positive column is provided.
The device of preparing Graphene paper based on glow plasma positive column comprises: chip bench, quartz socket tube, silica tube, tapered electrode, high pressure negative electricity power supply and helium source of the gas; Chip bench, quartz socket tube and tapered electrode are arranged in silica tube; Chip bench can translation in silica tube; Chip bench embeds quartz socket tube; Tapered electrode cone-tip surface is to chip bench; Tapered electrode is connected with high pressure negative electricity power supply, chip bench ground connection; Silica tube one end opening, the other end is connected with helium source of the gas.
Preferably, the material of described chip bench is conducting metal or graphite.
Preferably, between described quartz socket tube and silica tube, there is gap.
Preferably, the material of described tapered electrode is conducting metal.
The beneficial effect that the utility model compared with prior art has:
1) this device can be realized the fast restore of graphene oxide paper in 2 seconds ~ 5 seconds, and device and process are simple, possessed the potentiality of extensive amplification application.
2), than chemical reduction method, this device is without adding reductive agent, to human body and environment all without potential negative impact.
3), than chemical reduction method, this device carries out under drying conditions, can in product, not introduce impurity.
4) than hot reducing method, this installs without heating, utilizes high-energy electron in plasma body to realize the reduction of graphene oxide paper, has higher energy utilization efficiency.
5) than microwave plasma, radio-frequency inductance coupling plasma and electron beam plasma deoxidization method, this device can carry out under condition of normal pressure, has avoided low pressure condition required complex appts and operating device.
Brief description of the drawings
Fig. 1 is device schematic diagram of the present utility model.
In figure, chip bench 1, quartz socket tube 2, silica tube 3, tapered electrode 4, high pressure negative electricity power supply 5, helium source of the gas 6, negative glow 7, positive column 8.
Graphene paper scanning electron microscope (SEM) figure that Fig. 2 obtains for the utility model embodiment 1.
The graphene oxide paper that Fig. 3 obtains for the utility model embodiment 1 and X-ray diffraction (XRD) spectrogram of Graphene paper.
The graphene oxide paper that Fig. 4 obtains for the utility model embodiment 1 and X-ray electronic energy (XPS) spectrogram of Graphene paper.
The graphene oxide paper that Fig. 5 obtains for the present embodiment 1 and the infrared spectra (FTIR) of Graphene paper detect figure.
The graphene oxide paper that Fig. 6 obtains for the present embodiment 1 and ultraviolet-visible light (UV-Vis) spectrogram of Graphene paper.
Embodiment
Below in conjunction with accompanying drawing, the utility model is described in further detail.
As shown in Figure 1, the device of preparing Graphene paper based on glow plasma positive column comprises: comprise chip bench 1, quartz socket tube 2, silica tube 3, tapered electrode 4, high pressure negative electricity power supply 5 and helium source of the gas 6; Chip bench 1, quartz socket tube 2 and tapered electrode 4 are arranged in silica tube 3; Chip bench 1 can be in the interior translation of silica tube 3; Chip bench 1 embeds quartz socket tube 2, and the graphene oxide paper on chip bench 1 surface is fixed by quartz socket tube 2; Tapered electrode 4 cone-tip surfaces are to graphene oxide paper; Tapered electrode 4 is connected with high pressure negative electricity power supply 5, chip bench 1 ground connection; Silica tube 3 one end openings, the other end is connected with helium source of the gas 6.
Material selection conducting metal or the graphite of chip bench,, wherein there is gap between quartz socket tube and silica tube in the material selection conducting metal of tapered electrode.
The method of preparing Graphene paper based on glow plasma positive column is as follows:
1), graphene oxide paper is placed on to chip bench surface, adopt quartz socket tube to be fixed, graphene oxide paper and tapered electrode are set, and to bore sharp distance be 6 centimetres ~ 8 centimetres.
2), open helium source of the gas, in silica tube, pass into helium, wherein helium gas flow is 1 liter/min ~ 3 liters/min, continue 10 minutes.
3), keep helium gas flow constant, open high pressure negative electricity power supply, adjust voltage to 10 kilovolt ~ 15 kilovolts, between graphene oxide paper and tapered electrode cone point, produce glow discharge plasma, form negative glow, then translation chip bench, it is 10.8 centimetres ~ 15 centimetres that adjustment graphene oxide paper and tapered electrode 4 are bored sharp distance, in keeping negative glow to exist, form positive column between graphene oxide paper and tapered electrode cone point.
4), keep helium gas flow and voltage constant, continuous discharge 2 seconds ~ 5 seconds.
5), close high pressure negative electricity power supply, close helium source of the gas, obtain Graphene paper.
Below in conjunction with specific embodiment, the utility model is further elaborated, but the utility model is not limited to following examples.
Embodiment 1
1. the vitriol oil that is 98% by natural graphite and mass concentration at room temperature evenly mixes, wherein the ratio of the vitriol oil and natural graphite is 25 milliliters: 1 gram, under condition of ice bath, add potassium permanganate, wherein the quality of potassium permanganate is 3.5 times of natural graphite, in magnetic stirring apparatus, uniform stirring 30 minutes, is heated to 35 by gained mixture oc and in magnetic stirring apparatus uniform stirring 2 hours, add deionized water and hydrogen peroxide, wherein the ratio of deionized water and natural graphite is 100 milliliters: 1 gram, the ratio of hydrogen peroxide and natural graphite is 8 milliliters: 1 gram, gained mixed solution carries out clean by whizzer, finally by vacuum drying oven 35 othe dry graphite oxide powder that obtains under C condition.Deionized water is added to obtained graphite oxide powder, wherein the ratio of graphite oxide powder and deionized water is 0.3 milligram: 1 milliliter, within 2 hours, obtain the dispersion liquid of graphene oxide in deionized water by 300 watts of supersound process, the dispersion liquid of acquisition is carried out to 24 hours vacuum filtrations by the millipore filtration of 0.22 micron pore size, finally seasoning 6 hours in air, obtains graphene oxide paper at microporous membrane surface.
2. graphene oxide paper is placed on to chip bench 1 surface, adopts quartz socket tube 2 to be fixed, block by quartz socket tube 2 the graphene oxide paper that is placed on chip bench 1 surface.Chip bench 1, quartz socket tube 2 and tapered electrode 4 are arranged in silica tube 3, and tapered electrode 4 cone-tip surfaces are to chip bench 1.Tapered electrode 4 is connected with high pressure negative electricity power supply 5.By chip bench 1 ground connection.Silica tube 3 one end openings, the other end is connected with helium source of the gas 6.
3. graphene oxide paper and tapered electrode 4 are set, and to bore sharp distance be 6 centimetres, opens helium source of the gas 6, in silica tube 3, passes into helium, and wherein helium gas flow is 1 liter/min, continues 10 minutes.Keep helium gas flow constant, open high pressure negative electricity power supply 5, adjust voltage to 10 kilovolt, bore and between point, produce glow discharge plasma at graphene oxide paper and tapered electrode 4, form negative glow 7, then translation chip bench 1, it is 10.8 centimetres that adjustment graphene oxide paper and tapered electrode 4 are bored sharp distance, when graphene oxide paper and tapered electrode 4 are bored and kept negative glow 7 to exist between point, form positive column 8.Keep helium gas flow and voltage constant, continuous discharge 2 seconds.Close high pressure negative electricity power supply 5, close helium source of the gas 6, obtain Graphene paper.
By above-mentioned steps, can realize the reduction of graphene oxide paper, obtain the flexible soft graphite alkene of sheet paper.Figure 2 shows that Graphene paper scanning electron microscope (SEM) figure that the utility model embodiment 1 obtains, embody typical Graphene paper appearance structure.Figure 3 shows that graphene oxide paper that the utility model embodiment 1 obtains and X-ray diffraction (XRD) spectrogram of Graphene paper.The peak value institute corresponding angle of graphene oxide paper and Graphene paper is respectively 10.2 degree and 22.7 degree, and corresponding graphene layer spacing is respectively 0.87nm and 0.39nm, the elimination that reduces to have confirmed oxygenated functional group of interlamellar spacing.The graphene oxide paper that Fig. 4 obtains for the utility model embodiment 1 and X-ray electronic energy (XPS) spectrogram of Graphene paper.By reduction, the C/O atomic ratio of Graphene paper is 7.6:1, is significantly higher than the 2.2:1 of Graphene paper.The graphene oxide paper that Fig. 5 obtains for the present embodiment 1 and the infrared spectra (FTIR) of Graphene paper detect figure.Graphene oxide paper is at 1738cm -1, 3413cm -1, 1383cm -1, 1228cm -1and 1054cm -1there is significant characteristic peak Deng position, shown the existence of the oxygenated functional groups such as C=O, O-H, C-O, after reduction, these characteristic peaks in the infrared spectrogram of Graphene paper or disappearance or intensity significantly reduce, confirmed reduction effect.The graphene oxide paper that Fig. 6 obtains for the present embodiment 1 and ultraviolet-visible light (UV-Vis) spectrogram of Graphene paper.The 264nm that the wavelength that characteristic peak is corresponding moves to Graphene paper from the 230nm of graphene oxide paper, has confirmed reduction effect.
Embodiment 2
Repeat embodiment 1, its difference is only: it is 7 centimetres that initial setting up graphene oxide paper and tapered electrode 4 are bored sharp distance, helium gas flow is 2 liters/min, the voltage of negative electricity high pressure is 12 kilovolts, after translation chip bench 1, it is 12 centimetres that adjustment graphene oxide paper and tapered electrode 4 are bored sharp distance, continuous discharge 3.5 seconds.By above-mentioned steps, can obtain C/O atomic ratio is the Graphene paper of 5.4:1.
Embodiment 3
Repeat embodiment 1, its difference is only: it is 8 centimetres that initial setting up graphene oxide paper and tapered electrode 4 are bored sharp distance, helium gas flow is 3 liters/min, the voltage of negative electricity high pressure is 15 kilovolts, after translation chip bench 1, it is 15 centimetres that adjustment graphene oxide paper and tapered electrode 4 are bored sharp distance, continuous discharge 5 seconds.By above-mentioned steps, can obtain C/O atomic ratio is the Graphene paper of 6.1:1.
Obviously, above-described embodiment of the present utility model is only for the utility model example is described, but not is the restriction to embodiment of the present utility model or enforcement material.In fact, along with the increase of service voltage, can corresponding increase interelectrode distance obtain the atmospheric pressure glow discharge plasma with positive column, embodiment can not enumerate at this.Allly belong to apparent variation or the still row in protection domain of the present utility model of variation that the technical solution of the utility model amplifies.

Claims (4)

1. the device of preparing Graphene paper based on glow plasma positive column, is characterized in that: comprise chip bench, quartz socket tube, silica tube, tapered electrode, high pressure negative electricity power supply and helium source of the gas; Chip bench, quartz socket tube and tapered electrode are arranged in silica tube; Chip bench can translation in silica tube; Chip bench embeds quartz socket tube; Tapered electrode cone-tip surface is to chip bench; Tapered electrode is connected with high pressure negative electricity power supply, chip bench ground connection; Silica tube one end opening, the other end is connected with helium source of the gas.
2. the device of preparing Graphene paper based on glow plasma positive column according to claim 1, is characterized in that: the material of described chip bench is conducting metal or graphite.
3. the device of preparing Graphene paper based on glow plasma positive column according to claim 1, is characterized in that: between described quartz socket tube and silica tube, have gap.
4. the device of preparing Graphene paper based on glow plasma positive column according to claim 1, is characterized in that: the material of described tapered electrode is conducting metal.
CN201420063297.1U 2014-02-12 2014-02-12 Device for preparing graphene paper based on glow plasma positive column Expired - Lifetime CN203728584U (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103818899A (en) * 2014-02-12 2014-05-28 浙江大学 Device and method for preparing graphene paper based on glow plasma positive column area
CN104671237A (en) * 2015-02-04 2015-06-03 浙江大学 Device and method for preparing graphene film on basis of plasma
CN113003567A (en) * 2021-05-06 2021-06-22 哈尔滨工程大学 Device and method for reducing graphene oxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103818899A (en) * 2014-02-12 2014-05-28 浙江大学 Device and method for preparing graphene paper based on glow plasma positive column area
CN103818899B (en) * 2014-02-12 2015-07-29 浙江大学 A kind of apparatus and method preparing graphene paper based on glow plasma positive column
CN104671237A (en) * 2015-02-04 2015-06-03 浙江大学 Device and method for preparing graphene film on basis of plasma
CN113003567A (en) * 2021-05-06 2021-06-22 哈尔滨工程大学 Device and method for reducing graphene oxide
CN113003567B (en) * 2021-05-06 2022-12-13 哈尔滨工程大学 Device and method for reducing graphene oxide

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Granted publication date: 20140723