CN102560437B - Device and method for fast preparing large-area vertically aligned graphene - Google Patents
Device and method for fast preparing large-area vertically aligned graphene Download PDFInfo
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- CN102560437B CN102560437B CN 201110457518 CN201110457518A CN102560437B CN 102560437 B CN102560437 B CN 102560437B CN 201110457518 CN201110457518 CN 201110457518 CN 201110457518 A CN201110457518 A CN 201110457518A CN 102560437 B CN102560437 B CN 102560437B
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Abstract
The invention discloses a device and method for fast preparing large-area vertically aligned graphene. The device comprises a heating furnace, a multicone electrode, a high-voltage negative power source, a quartz tube, a substrate, a ceramic insulator and an electric translation platform, wherein the multicone electrode, the substrate and the ceramic insulator are arranged in the quartz tube, the quartz tube is placed in the heating furnace; the substrate faces to the cone tip of the multicone electrode; the substrate is connected with the electric translation platform; and the substrate is earthed and the multicone electrode is connected with the high-voltage negative power source. The preparation process comprises the following four steps: heating the substrate; performing translation on the substrate and discharging with the gas among the multicone electrode; reducing the substrate; and cooling the substrate. By adopting the device and the method, the one-step atmospheric fast large-area growth of vertically aligned graphene can be realized on the surface of the substrate and no catalyst or adhesive is required. The obtained graphene nanoplate is nearly perpendicular to the surface of the substrate and is especially suitable for being used in field emission, nanoscale plasmas, supercapacitors, secondary batteries and the like.
Description
Technical field
The invention belongs to the nano material preparing technical field, relate in particular to a kind of quick preparation devices and methods therefor of vertical orientated Graphene on a large scale.
Background technology
Graphene (graphene) be by carbon atom according to
Sp 2The hexangle type that hybridized orbital forms is the two dimensional crystal structure of honeycomb lattice, and thickness only is the monolayer carbon atomic diameter.Because its unique two-dirnentional structure and excellent crystal quality, Graphene has huge specific surface area (2630 m
2g
-1), simultaneously at electroconductibility (electronic mobility 20000 cm
2V
-1s
-1), thermal conductivity (thermal conductivity 5300 Wm
-1k
-1), mechanics of machinery intensity (breakdown point 42 Nm
-1) etc. the aspect all show very excellent characteristic.The people such as the extra large nurse of Univ Manchester UK in 2004 (Geim A.) and Nuo Woxiaoluofu (Novoselov K.) first Graphene is separated from graphite (
Novoselov KS, Geim AK, et al. Science, 2004; 306:666-669).Excellent properties and huge applications potentiality based on this novel nano-material shows have obtained Nobel Prize in physics in 2010 in double harness.
Number of patent application is the multiple preparation method who discloses grapheme material in the patent documents such as 201110093737.9,201110048734.3,201110060953.3, but the Graphene that obtains all is parallel direction with substrate, and namely multi-layer graphene is stacked on substrate surface.Yet some application processes of Graphene require Graphene vertically to be grown in substrate surface.For example: when adopting Graphene as the ultracapacitor active material (
Miller JR, Outlaw RA, et al. Science, 2010; 329:1637-1639), only have when the edge surface of Graphene the surface of Graphene fully to be applied to ion storage during to the direction of motion of ion.Similarly application also comprises: field emission, field ionization, lithium ion battery, support of the catalyst etc.Above-mentioned application all requires Graphene vertically to be grown in substrate surface, with realization the edge of graphene nano level thickness and huge specific surface area is taken full advantage of.
According to literature search, the most using plasma of present vertical orientated Graphene strengthens chemical vapour deposition (plasma-enhanced chemical vapor deposition, PECVD) technology prepares under low pressure or vacuum condition, for example: microwave plasma source, 133 Pa(
Wu YH, Qiao PW, et al. Advanced Materials, 2002; 14:64-67); The radio-frequency inductance coupling plasma source, 12 Pa(
Wang JJ, Zhu MY, et al. Applied Physics Letters, 2007; 90:123107), radio frequency capacitively coupled plasma source, 13.3 Pa(
Hiramatsu M, Shiji K, et al. Applied Physics Letters, 2004; 84:4708-4710) etc.Above-mentioned plasma body gas phase strengthens the desired low pressure of chemical vapor deposition processes or vacuum, has had a strong impact on the speed of growth and the growth area of Graphene, has hindered the extensive preparation and application of this high-quality nano material.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of quick preparation devices and methods therefor of vertical orientated Graphene on a large scale is provided.
Fast preparation on a large scale the device of vertical orientated Graphene comprise process furnace, bore electrode more, high pressure negative electricity power supply, silica tube, substrate, ceramics insulator and motorized precision translation stage; Many cone electrodes, substrate and insulating ceramic body are arranged in the silica tube, and silica tube is placed in the process furnace; Basal surface is to many cones electrode cone point; Substrate links to each other with motorized precision translation stage; Substrate ground connection is bored electrode more and is linked to each other with high pressure negative electricity power supply.
Described many cone electrodes are two to be embedded with upper conical electrod-array, and the adjacent conical electrode is parallel, between adopt ceramics insulator to be separated by, spacing is 1～10 millimeter.
The tapering of the single tapered electrode in described many cone electrodes is 1:3～1:20.
Each tapered electrode in described many cone electrodes all adopts independently high pressure negative electricity power supply 3 power supplies.
Substrate is 1～20 millimeter with the spacing of many cone electrode cone points.
Described base material be in gold and silver, copper, aluminium, iron, stainless steel, silicon and the carbon one or more.
Fast the step of the method for vertical orientated Graphene is as follows on a large scale in preparation:
1) opens process furnace, in normal pressure hydrogen and rare gas element mixed atmosphere, substrate is heated to 600～900
oC;
2) keep furnace temperature of heating furnace constant, opening high pressure negative electricity power supply, adjusting service voltage is 1～6 kilovolt, take substrate as anode, take many cones electrode as negative electrode, 600～900
oProduce plasma body and continuous discharge in C normal pressure rare gas element, hydrocarbon polymer and the steam mixed atmosphere, discharging current is 0.1～2 milliampere;
3) in discharge process, keep furnace temperature of heating furnace constant, substrate with the speed translation of 0.01～1 mm/second, in the translation process, keeps substrate and many cone interelectrode distances constant under the driving of motorized precision translation stage, and be 30 seconds～1 hour discharge time;
4) after discharge finishes, keep furnace temperature of heating furnace constant, substrate is reduced in hydrogen atmosphere;
5) after reduction finishes, close process furnace, substrate is cooled to room temperature in hydrogen and inert gas atmosphere, and obtains vertical orientated Graphene on substrate 5 surfaces.
In described rare gas element, hydrocarbon polymer and the steam mixed atmosphere, the volume percent of rare gas element and hydrocarbon polymer is 0.01～100:1, and steam relative humidity is 5～100%.
Described rare gas element is argon gas or helium.
Described hydrocarbon polymer is one or more in methane, ethane, ethene and the acetylene.
The beneficial effect that the present invention compared with prior art has:
1) by this method, can realize that Graphene is in the vertical growth on multiple conductive substrates surface.The nanometer sheet that obtains is comprised of about 1～7 layer graphene, about 1～10 nanometer of total thickness, and about 0.355 nanometer of graphene layer spacing, the direction of growth is approximately perpendicular to substrate.
2) than graphene preparation methods such as tape stripping method, graphite oxide reduction method, silicon carbide epitaxial growth methods, the Graphene of this method preparation is particularly useful for the application such as field emission, nano level plasma body, support of the catalyst and energy storage approximately perpendicular to substrate.
3) this method can realize under normal pressure, therefore can finish the primary crystallization of Graphene about 10～30 seconds, can prepare lateral dimension and highly about about 0.5～2 micron Graphene about 3～5 minutes; Than the plasma enhanced chemical vapor deposition method that has now under low pressure or the vacuum condition, can high 1～2 order of magnitude on the speed of growth.This Fast Growth has reduced the consumption of gas precursor, and the consumption of heat energy and electric energy, has reduced production cost.
4) many cones electrode of this method employing provides possibility for vertical orientated Graphene in suprabasil Large-Area-Uniform growth, can realize the big area batch production of vertical orientated Graphene.
5) this method is removed substrate and is required conduction and anti-900
oOutside the above high temperature of C, without other particular requirement, therefore can realize based on the actual application requirements the single step preparation of vertical orientated Graphene in multiple substrate.
6) undope extra catalyzer and tackiness agent of the material that obtains can directly apply to multiple physical and chemical process.
Based on the above-mentioned advantage of this method, can promote quickly this high-quality nano material of Graphene in the widespread use of industry member by this method, and can produce huge economic benefits.
Description of drawings
Fig. 1 is the fast preparation apparatus structure synoptic diagram of vertical orientated Graphene on a large scale.
Among the figure, process furnace 1, bore electrode 2, high pressure negative electricity power supply 3, silica tube 4, substrate 5, stupalith 6, motorized precision translation stage 7 more.
Fig. 2 is that the embodiment of the invention 1 is at the stereoscan photograph of the vertical orientated grapheme material of stainless steel surface preparation.
Fig. 3 is that the embodiment of the invention 1 is at the high-resolution-ration transmission electric-lens photo of the vertical orientated grapheme material of stainless steel surface preparation.
Fig. 4 is that the embodiment of the invention 2 is at the stereoscan photograph of the vertical orientated grapheme material of irregular porous carbon film surface preparation.
Embodiment
As shown in Figure 1, fast preparation on a large scale the device of vertical orientated Graphene comprise process furnace 1, bore electrode 2 more, high pressure negative electricity power supply 3, silica tube 4, substrate 5, ceramics insulator 6 and motorized precision translation stage 7; Many cone electrodes 2, substrate 5 and insulating ceramic body 6 are arranged in the silica tube 4, and silica tube 4 is placed in the process furnace 1; Substrate 5 is in the face of many cone electrode 2 cone points; Substrate 5 links to each other with motorized precision translation stage 7; Substrate 5 ground connection are bored electrode 2 more and are linked to each other with high pressure negative electricity power supply 3.
Described many cone electrodes 2 are two to be embedded with upper conical electrod-array, and the adjacent conical electrode is parallel, between adopt ceramics insulator 6 to be separated by, spacing is 1～10 millimeter.
The tapering of the single tapered electrode in described many cone electrodes 2 is 1:3～1:20.
Each tapered electrode in described many cone electrodes 2 all adopts independent high pressure negative electricity power supply 3 power supplies.
Described base material be in gold and silver, copper, aluminium, iron, stainless steel, silicon and the carbon one or more.
Fast the step of the method for vertical orientated Graphene is as follows on a large scale in preparation:
1) opens process furnace 1, in normal pressure hydrogen and rare gas element mixed atmosphere, substrate 5 is heated to 600～900
oC;
2) keep process furnace 1 furnace temperature constant, opening high pressure negative electricity power supply 3, adjusting service voltage is 1～6 kilovolt, take substrate 5 as anode, take many cones electrode 2 as negative electrode, 600～900
oProduce plasma body and continuous discharge in C normal pressure rare gas element, hydrocarbon polymer and the steam mixed atmosphere, discharging current is 0.1～2 milliampere;
3) in discharge process, keep process furnace 1 furnace temperature constant, substrate 5 with the speed translation of 0.01～1 mm/second, in the translation process, keeps substrate 5 and many cone electrode 2 spacings constant under the driving of motorized precision translation stage 8, and be 30 seconds～1 hour discharge time;
4) after discharge finishes, keep process furnace 1 furnace temperature constant, substrate 5 is reduced in hydrogen atmosphere;
5) after reduction finishes, close process furnace 1, substrate 5 is cooled to room temperature in hydrogen and inert gas atmosphere, and obtains vertical orientated Graphene on substrate 5 surfaces.
In described rare gas element, hydrocarbon polymer and the steam mixed atmosphere, the volume percent of rare gas element and hydrocarbon polymer is 0.01～100:1, and steam relative humidity is 5～100%.
Described rare gas element is argon gas or helium.
Described hydrocarbon polymer is one or more in methane, ethane, ethene and the acetylene.
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.
1. bore electrode 2 more and be comprised of the array that comprises three tapered electrodes, the adjacent conical electrode is parallel, between adopt ceramics insulator 6 to be separated by, spacing is 10 millimeters, the tapering of boring the single tapered electrode in the electrode 2 is 1:10 more.Each tapered electrode in many cone electrodes 2 all adopts independent high pressure negative electricity power supply 3 power supplies.
2. selecting the stainless steel substrates of 0.025 millimeter of thickness is substrate 5.Substrate 5 is in the face of many cone electrode 2 cone points, and spacing is 20 millimeters.Substrate 5 ground connection.
3. substrate 5, bore electrode 2 and ceramics insulator 6 is positioned in the silica tube 4, silica tube 4 is placed in the process furnace 1 more.
4. substrate 5 links to each other with motorized precision translation stage 7.
5. in silica tube 4, pass into hydrogen and argon gas mixed gas (total flux: 2000 ml/min; Volume ratio: 1:1), and be heated to 700 by process furnace 1
oC.
6. keeping 700
oUnder the prerequisite of C heating, close hydrogen and argon gas mixed gas, pass into simultaneously argon gas, methane and steam mixed gas.Mixed gas total flux 1500 ml/min, argon gas and methane volume ratio are 10:1.Steam is by the methane bubbling, and adjustment mixed gas relative humidity is 38.5%.Opening high pressure negative electricity power supply 3, adjusting service voltage is 4.6 kilovolts, forms plasma body between many cone electrodes 2 and substrate 5.In the discharge process, substrate 5 translation under the driving of motorized precision translation stage 7, translatory velocity is 0.01 mm/second.In the translation process, the spacings that keep substrate 5 and many cone electrodes 2 cone points be 10 millimeters constant.Discharge sustain is closed high-voltage power supply 3 after 5 minutes.
7. close argon gas, methane and steam mixed gas, pass into simultaneously hydrogen, hydrogen flowing quantity is 1500 ml/min, keeps furnace temperature 700
oC reduces, 30 minutes time length.
8. pass into hydrogen and argon gas mixed gas (total flux: 2000 ml/min; Volume ratio: 1:1).Close process furnace 1, naturally cooling.When temperature is lower than 50
oDuring C, close hydrogen and argon gas mixed gas, take out sample, can obtain vertical orientated Graphene on substrate 5 surfaces.
By above-mentioned steps, can be at the vertical orientated graphene nano lamella of stainless steel-based basal surface uniform fold one deck.Figure 2 shows that the vertical orientated grapheme material stereoscan photograph of stainless steel surface.As shown in Figure 2, graphene nanometer sheet is grown in stainless steel-based basal surface along the near vertical direction, every about 300 nanometers of graphene nanometer sheet height, about 750 nanometers of lateral length.Figure 3 shows that the vertical orientated grapheme material high-resolution-ration transmission electric-lens photo of stainless steel surface.As shown in Figure 3, every about 2 nanometers of nanometer sheet total thickness are comprised of 1～7 layer graphene, about 0.355 nanometer of interfloor distance.
Embodiment 2
By above-mentioned steps, can cover the vertical orientated graphene nano lamella of one deck at irregular porous carbon film surface uniform.Figure 3 shows that the vertical orientated grapheme material stereoscan photograph on irregular carbon film surface.As shown in Figure 3, graphene nanometer sheet is grown in irregular carbon film surface, every about 100 nanometers of graphene nanometer sheet height, about 200 nanometers of lateral length along the near vertical direction.
By above-mentioned steps, can cover the vertical orientated graphene nano lamella of one deck at goldleaf.
By above-mentioned steps, can cover the vertical orientated graphene nano lamella of one deck at the silver strip surface uniform.
By above-mentioned steps, can be at the vertical orientated graphene nano lamella of aluminium foil surface uniform fold one deck.
Embodiment 6
Obviously, the above embodiment of the present invention only is for example of the present invention is described, but not is to embodiments of the present invention or implements the restriction of material.In fact, present method may be implemented in multiple conduction and ability 900
oThe material of the above high temperature of C can't give exhaustive at this.Allly belong to apparent variation or the change that technical scheme of the present invention is amplified, and the conversion of base material, still be in the row of protection scope of the present invention.
Claims (7)
1. quick preparation device of vertical orientated Graphene on a large scale is characterized in that comprising process furnace (1), bores electrode (2) more, high pressure negative electricity power supply (3), silica tube (4), substrate (5), ceramics insulator (6) and motorized precision translation stage (7); Many cone electrodes (2), substrate (5) and insulating ceramic body (6) are arranged in the silica tube (4), and silica tube (4) is placed in the process furnace (1); Substrate (5) is in the face of many cone electrodes (2) cone point; Substrate (5) links to each other with motorized precision translation stage (7); Substrate (5) ground connection is bored electrode (2) more and is linked to each other with high pressure negative electricity power supply (3);
Described many cone electrodes (2) are two to be embedded with upper conical electrod-array, and the adjacent conical electrode is parallel, between adopt ceramics insulator (6) to be separated by, spacing is 1～10 millimeter;
The tapering of the single tapered electrode in described many cone electrodes (2) is 1:3～1:20;
Described substrate (5) is 1～20 millimeter with the spacing of many cone electrodes (2) cone point.
2. a kind of quick preparation according to claim 1 device of vertical orientated Graphene on a large scale, it is characterized in that: each tapered electrode in described many cone electrodes (2) all adopt independently high pressure negative electricity power supply (3) power supply.
3. a kind of quick preparation according to claim 1 device of vertical orientated Graphene on a large scale is characterized in that: described base material be in gold and silver, copper, aluminium, iron, stainless steel, silicon and the carbon one or more.
4. a use quick preparation of installing the as claimed in claim 1 method of vertical orientated Graphene on a large scale is characterized in that its step is as follows:
1) opens process furnace (1), in normal pressure hydrogen and rare gas element mixed atmosphere, substrate (5) is heated to 600～900
oC;
2) keep process furnace (1) furnace temperature constant, opening high pressure negative electricity power supply (3), adjusting service voltage is 1～6 kilovolt, take substrate (5) as anode, take many cones electrode (2) as negative electrode, 600～900
oProduce plasma body and continuous discharge in C normal pressure rare gas element, hydrocarbon polymer and the steam mixed atmosphere, discharging current is 0.1～2 milliampere;
3) in discharge process, keep process furnace (1) furnace temperature constant, substrate (5) under the driving of motorized precision translation stage (7) with the speed translation of 0.01～1 mm/second, in the translation process, keep substrate (5) and many cone electrode (2) spacings constant, be 30 seconds～1 hour discharge time;
4) after discharge finishes, keep process furnace (1) furnace temperature constant, substrate (5) is reduced in hydrogen atmosphere;
5) after reduction finishes, close process furnace (1), substrate (5) is cooled to room temperature in hydrogen and inert gas atmosphere, and obtains vertical orientated Graphene on substrate (5) surface.
5. according to claim
4Described a kind of quick preparation is the method for vertical orientated Graphene on a large scale, it is characterized in that: in described rare gas element, hydrocarbon polymer and the steam mixed atmosphere, the volume percent of rare gas element and hydrocarbon polymer is 0.01～100:1, and steam relative humidity is 5～100%.
6. according to claim
4Described a kind of quick preparation is the method for vertical orientated Graphene on a large scale, it is characterized in that: described rare gas element is argon gas or helium.
7. according to claim
4Described a kind of quick preparation is the method for vertical orientated Graphene on a large scale, it is characterized in that: described hydrocarbon polymer is one or more in methane, ethane, ethene and the acetylene.
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| CN102936010A (en) * | 2012-10-12 | 2013-02-20 | 南昌绿扬光电科技有限公司 | Method for growing upright graphene on substrate through vapor deposition |
| CN103813608A (en) * | 2013-04-16 | 2014-05-21 | 杜志刚 | Plasma high pressure gas heating method |
| CN103813609A (en) * | 2013-04-16 | 2014-05-21 | 杜志刚 | Plasma carbon dioxide high pressure gas heating device method |
| CN103813606A (en) * | 2013-04-16 | 2014-05-21 | 杜志刚 | Plasma high pressure gas heating device |
| CN103219166A (en) * | 2013-04-25 | 2013-07-24 | 浙江大学 | Current collector with surface being decorated with vertical orientated grapheme and preparation method thereof |
| CN103808161B (en) * | 2014-01-28 | 2016-04-20 | 浙江大学 | A kind of automatic entrance-exit the grey sintering atmosphere stove of on-line monitoring and method of work thereof |
| CN104451828B (en) * | 2014-11-14 | 2017-01-11 | 东南大学 | Method for preparing vertically aligned graphene oxide film |
| CN110106492A (en) * | 2019-05-05 | 2019-08-09 | 苏州大学 | Quickly prepare the method for vertical graphene |
| CN110101882B (en) * | 2019-05-06 | 2024-02-20 | 浙江大学 | High-temperature steam sterilization device |
| CN112794316A (en) * | 2020-12-30 | 2021-05-14 | 浙江大学杭州国际科创中心 | Device and method for continuously preparing vertically-oriented graphene on large scale by using plasma |
| CN113061871B (en) * | 2021-03-23 | 2022-10-04 | 江西师范大学 | Method for preparing vertical graphene film in high-quality, rapid and large-area mode |
| CN113044835A (en) * | 2021-04-09 | 2021-06-29 | 浙江大学 | Preparation method of two-dimensional sheet material vertical orientation assembly |
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| CN102148368B (en) * | 2011-02-24 | 2012-07-25 | 宁波工程学院 | Preparation method of lithium ion battery anode composite material and special device thereof |
| CN102157315B (en) * | 2011-03-21 | 2013-04-03 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
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