CN107304046A - The direct preparation method of three-dimensional grapheme and its application on ultracapacitor - Google Patents
The direct preparation method of three-dimensional grapheme and its application on ultracapacitor Download PDFInfo
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- CN107304046A CN107304046A CN201610252741.8A CN201610252741A CN107304046A CN 107304046 A CN107304046 A CN 107304046A CN 201610252741 A CN201610252741 A CN 201610252741A CN 107304046 A CN107304046 A CN 107304046A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of method that high-quality three-dimensional grapheme is directly prepared in some dielectrics or semiconductor substrate.This method does not need extra catalyst, and have concurrently simultaneously preparation time it is short, it is with low cost the features such as.This method, such as plasma enhanced chemical vapor deposition can be realized by using different types of equipment in production（PECVD）Deng.Three-dimensional grapheme obtained by this method is had into higher quality, and because it has super large surface area, ultracapacitor or the ideal material of capacitive character molecular detector can be used as.
Description
Technical field
The invention belongs to nano material（Graphene）Manufacture and its in battery（Ultracapacitor）Using field.
Background technology
Three-dimensional grapheme is a kind of in surface area super large, the other materials with 3-D solid structure（Hereinafter referred to as base material）
On grow the material of graphene.This base material can be porous material, many down materials or nanometer powder shape material.Due to stone
Black alkene strength is in accordance with base material, thus it also possesses the features such as the 3 D stereo of base material, surface area super large.In addition graphene has
The features such as high electron mobility, chemical inertness, therefore three-dimensional grapheme is the ideal material applied to ultracapacitor.
Traditional three-dimensional grapheme preparation method includes multiple complicated step, and needs to use graphene oxide[1-6], and
Graphene oxide also needs to reduce using chemical method.And three-dimensional grapheme prepared by this method, its hole shape is irregular.
There are some to deposit method prepared by (CVD) using conventional chemical vapor in addition[3,4], these methods need to use metal catalytic
Agent, and also to fall metal etch in subsequent handling.Therefore a kind of method for directly preparing three-dimensional grapheme is invented just very
It is important.
Porous alumina（Anodic Aluminum Oxide, hereinafter referred to as AAO）It is a kind of invention in last century
The nano-porous materials in middle period, it is cheap with quite ripe easy manufacturing technology.While it is disclosed that preparation
Method can be used for other porous materials, many down materials or nanometer powder shape material, but because AAO apertures are controllable and distribution equal
It is even, with super large surface area, thus the three-dimensional grapheme grown on achievements exhibition of the present invention AAO base materials.Although in the past existing
People grows high sp on AAO3The diamond-film-like of composition[7-10], but never have high sp is successfully grown on AAO2Constituent graphite alkene
Case.
The content of the invention
The invention discloses a kind of method for directly preparing high-quality three-dimensional grapheme.This method does not need additional catalysis
Agent, is prepared with low cost.Its principle is by graphitization（graphitize）The three-dimensional manometer DLC grown on base material
Film（Diamond-Like-Carbon film, abbreviation DLC）Or amorphous carbon film（Amorphous carbon film, referred to as
a-C）And obtain three-dimensional grapheme.
If using plasma auxiliary chemical vapor deposition（Plasma Enhanced Chemical Vapor
Deposition, abbreviation PECVD）Prepared, and by the temperature control of base material in deposition process 1200 to 1450 DEG C it
Between, the graphitizing process almost can synchronously be carried out when three-dimensional DLC or three-dimensional a-C grows, so that three just be made within a few minutes
Tie up graphene.Hereinafter referred to as this method is method 1, such as shown in Fig. 1 (a).Although it should be noted that the present invention prepares three by PECVD
Graphene is tieed up, but as long as the temperature control of base material is between 1200 to 1450 DEG C in deposition process, we can also be by passing
System CVD directly prepares three-dimensional grapheme.Because graphitizing process is mainly determined by temperature[11]Although plasma can be with auxiliary
Help the process and our is more quickly made high-quality three-dimensional grapheme, but its be not graphitizing process decision because
Element.As the Raman spectrum of analysis sample as obtained by shown in Fig. 1 (d), it is concluded that it is about several receive to go out its grain size
Rice, and 2D peaks in Raman spectrum（Positioned at 2691 cm-1Place）Full width at half maximum be about 41.9cm-1（Closely planar monolayer graphite
Alkene）.The three-dimensional grapheme of high-quality thus can be made by this method.
If base material temperature during PECVD is not higher than 900 DEG C, this process only produces DLC or a-C.Need to incite somebody to action
The DLC or a-C arrived is in vacuum or gaseous mixture containing hydrogen（Such as hydrogen/argon gas gaseous mixture, mixed proportion：The argon of 5% hydrogen+95%
Gas）In, using after annealing between being further heated to 1200 ~ 1450 DEG C in electric furnace, heating wire or tube furnace, so as to obtain three-dimensional
Graphene.Hereinafter referred to as this method is method 2, such as shown in Fig. 1 (b).It is noted that similar to method 1, although the step in method 2
Rapid 1 is made DLC or a-C by PECVD, but can be also made up of conventional CVD method[7-10].Fig. 1 (f) is three-dimensional made from method 2
Graphite Raman spectrum.
Method 1 is identical with the pecvd process parameter of the step 1 of method 2.PECVD technological parameter is：Hydrogen（H2）: 0-
2000 sccm（It is adjustable, it is general to use 750 sccm）；Alkane（Such as methane）, alkene（Such as ethene）Or alkynes（Such as acetylene）Deng：
0-500 sccm（It is adjustable, it is general to use 10 sccm）；Microwave plasma power：50-5000 watts（It is adjustable, it is general to use
1800 watts or so）；Air pressure：Not higher than 300 Torr（It is adjustable, it is general using 80 Torr or so）.
The step 1 of method 1 and method 2, which can also be used, realizes ion beam depositing（IBD）Realize, its technological parameter is：Hydrogen
（H2）: 0-2000 sccm（It is adjustable, generally 0 sccm）；Alkane（Such as methane）, alkene（Such as ethene）Or alkynes（Such as acetylene）
Deng：0-500 sccm（It is adjustable, it is general to use 75 sccm）；Microwave plasma power：50-2000 watts（It is adjustable, typically
Using 400 watts or so）；Air pressure：Not higher than 300 Torr.
Comparison diagram 1 (a) can be seen that with (b), although the technological parameter of two methods is identical, but base material temperature is differed
It is larger.The key of high-quality three-dimensional grapheme is made by method 1 and is to maintain base material temperature between 1200 ~ 1450 DEG C.Control base
The temperature of material has a variety of methods.Active control including the use of external heat means during PECVD or IBD to base
Material is heated.Passive control methods are including the use of support（Shelf）Base material is hanging, itself and PECVD or IBD walls are reduced as far as possible
Or the contact area of cooling system, it is effectively increased base material temperature.In addition, for powdered base material, can also place it in low
To increase its temperature on pallet, platform or the conveyer belt of thermal conductivity.As shown in Figure 3.
Pass through some other means analyzing to the three-dimensional grapheme that is prepared on AAO, such as SEM
（Scanning Electron Microscope, abbreviation SEM）, transmission electron microscope（Transmission Electron
Microscope, abbreviation TEM）And electron energy loss spectroscopy (EELS)（Electron Energy Loss Spectroscopy, referred to as
EELS）Deng.From Fig. 2 (a) as can be seen that the three-dimensional grapheme prepared by this method still possesses preferable loose structure, thus can
To ensure that three-dimensional grapheme inherits the feature of AAO super large surface area.And it is that 40%, pH is 3.5 that the sample is placed in into concentration
Also it is not corroded after 22 hours in hydrofluoric acid, reflects that AAO is completely covered in three-dimensional grapheme.From Fig. 2 (b) as can be seen that as it
It is preceding to be analyzed by Raman spectrum, the three-dimensional grapheme of gained closely planar monolayer graphene；And by Fig. 2's (c)
EELS data are calculated it has also been discovered that obtained three-dimensional grapheme is containing the sp for having more than 77%2Composition, with very high product
Matter.
Although processing procedure laid out above is using AAO as base material.But confirm in an experiment, the PECVD can be used for three oxidations
Any high temperature resistant base material such as two aluminium powders, Si powder, planar silicon, and CVD can also prepare three on alundum (Al2O3) powder
Tie up graphene.It is to control base material temperature between 1200 to 1450 DEG C that one of committed step of three-dimensional grapheme, which is made,.
Due to polyaniline（Polyaniline）Can be by introducing fake capacitance（pseudocapacitance）Increase electrode electricity
Hold, thus polyaniline is attached to after the material, because three-dimensional grapheme has a superhigh specific surface area in itself, the ratio between material electricity
Appearance is significantly greatly increased.Therefore, polyaniline attachment, the high-quality three-dimensional grapheme that is prepared by this method can be as ultracapacitor
Ideal material.
Brief description of the drawings
Fig. 1：(a), PECVD directly prepares three-dimensional grapheme method schematic diagram（Method 1）；(b), PECVD substeps prepare three-dimensional
Graphene method schematic diagram（Method 2）, wherein step 2 is the structural representation of three-dimensional grapheme sample.；(c), prepared on AAO
Comparison diagram before and after three-dimensional grapheme；(d), the Raman spectrum of the three-dimensional grapheme as made from method 1；(e), by the step 1 of method 2
Obtained three-dimensional DLC or a-C Raman spectrum；(f), the Raman spectrum of the three-dimensional grapheme as made from the step 2 of method 2.
Fig. 2：(a) the SEM top views of the three-dimensional grapheme, prepared on AAO；(b) three-dimensional graphite, prepared on AAO
The TEM sectional views of alkene；(c) three-dimensional grapheme and a-C EELS comparison diagrams, prepared on AAO.
Fig. 3：It is various by making sample be not directly contacted with PECVD walls and cooling system, so as to realize passive control sample
The schematic diagram of product temperature methods：(a), sample is placed in individual plasma region using shelf,；(b), using shelf by sample
Product are placed between two heating regions；(c), sample and PECVD walls and cooling system are separated using support, and subtracted as far as possible
The contact area of limited bracket and sample；(d), made using low thermal conductivity material and place powder sample（It can also be used for non-powder-like
Product）Platform, pallet or conveyer belt.
Bibliography
1. Salunkhe, R. R., Hsu, S. H., Wu, K. C. W. & Yamauchi, Y. Large-Scale
Synthesis of Reduced Graphene Oxides with Uniformly Coated Polyaniline for
Supercapacitor Applications. Chemsuschem.7, 1551–1556, (2014).
2. Gao, H. & Duan, H. 2D and 3D graphene materials: Preparation and
bioelectrochemical applications. Biosens. Bioelectron. 65C, 404–419, (2014).
3. Han, S., Wu, D., Li, S., Zhang, F. & Feng, X. Porous graphene
materials for advanced electrochemical energy storage and conversion devices.Adv. Mater. 26, 849–864, (2014).
4. Cao, X. et al. Preparation of novel 3D graphene networks for
supercapacitor applications. Small 7, 3163–3168, (2011).
5. Zhang, L. et al. Porous 3D graphene-based bulk materials with
exceptional high surface area and excellent conductivity for supercapacitors.Sci. Rep. 3, 1408, (2013).
6. Xiao, X. et al. Lithographically defined three-dimensional grapheme
structures. ACS Nano 6, 3573–3579, (2012).
7. Bae, E. J. et al. Selective Growth of Carbon Nanotubes on Pre-
patterned Porous Anodic Aluminum Oxide. Adv. Mater. 14, 277–279, (2002).
8. Yao, B. D. & Wang, N. Carbon Nanotube Arrays Prepared by MWCVD. J. Phys. Chem. B 105, 11395–11398, (2001).
9. Chen, P.-L., Chang, J.-K., Kuo, C.-T. & Pan, F.-M. Anodic aluminum
oxide template assisted growth of vertically aligned carbon nanotube arrays
by ECR-CVD. Diam. Relat. Mater. 13, 1949–1953, (2004).
10. Schneider, J. J. et al. Catalyst free growth of a carbon nanotube–
alumina composite structure. Inorg. Chimica Acta 361, 1770–1778, (2008).
11. Prasad, B. L. V. et al. Heat-treatment effect on the nanosized
graphite π-electron system during diamond to graphite conversion. Phys. Rev. B 62, 11209–11218, (2000)。
Claims (5)
1. a kind of method for preparing three-dimensional grapheme, its principle includes（1）Use the dielectric material with nanostructured（It is such as porous
Alundum (Al2O3) etc.）Or semi-conducting material（Such as nano-silicon powder or Nano diamond powder）As base material,（2）On base material
Growing three-dimensional diamond-film-like or three-dimensional, amorphous carbon film（Including nanotube）,（3）By the three-dimensional diamond-like grown on base material
Stone film or three-dimensional, amorphous carbon film（Including nanotube）Deng in same growth process（Or in next process）It is heated to
After annealing between 1000 to 2000 DEG C, principle（3）For the feature of this preparation method.
2. the principle described in claim 1（2）And principle（3）Plasma enhanced chemical vapor deposition can be used（PECVD）Or
Ion beam depositing（IBD）Realized in same process, PECVD and IBD technique is respectively such as specification [0009] and the
[0010] described in section, it is characterized in that active control base material temperature is between 1000 to 2000 DEG C.
3. the method for the active control base material temperature described in claim 2, can pass through（4）Control substrate location makes it not connect directly
Touch PECVD or IBD walls and increase its temperature,（5）Other materials are placed between base material and PECVD or IBD walls and increase base
Material temperature,（6）Use auxiliary heater meanses（Such as electric-heating-wire-heating）Increase base material temperature.
4. the principle described in claim 1（3）Can with realization principle（2）Carried out in different processes, it is characterized in that in vacuum
Or will pass through principle in the gaseous mixture environment containing hydrogen（2）Obtained material is retreated between being heated to 1000 to 2000 DEG C
Fire.
5. by polyaniline（Polyaniline）Be attached to three-dimensional grapheme prepared by method as described in claim 1, and by this
Material as ultracapacitor electrode.
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Citations (2)
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| CN103956275A (en) * | 2014-05-19 | 2014-07-30 | 常州立方能源技术有限公司 | Method for preparing three-dimensional graphene network enhanced activated carbon supercapacitor electrode piece |
| CN105063571A (en) * | 2015-08-26 | 2015-11-18 | 吉林大学 | Preparation method for three-dimensional graphene on stainless steel substrate |
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2016
- 2016-04-22 CN CN201610252741.8A patent/CN107304046A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956275A (en) * | 2014-05-19 | 2014-07-30 | 常州立方能源技术有限公司 | Method for preparing three-dimensional graphene network enhanced activated carbon supercapacitor electrode piece |
| CN105063571A (en) * | 2015-08-26 | 2015-11-18 | 吉林大学 | Preparation method for three-dimensional graphene on stainless steel substrate |
Non-Patent Citations (2)
| Title |
|---|
| HUALIN ZHAN,ET AL.: "Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition", 《SCIENTIFIC REPORTS》 * |
| MI ZHOU ,ET AL.: "Highly Conductive Porous Graphene/Ceramic Composites for Heat Transfer and Thermal Energy Storage", 《ADV. FUNCT. MATER.》 * |
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Application publication date: 20171031 |