CN108217628A - Three-dimensional netted carbon nanotube and its preparation method and application - Google Patents
Three-dimensional netted carbon nanotube and its preparation method and application Download PDFInfo
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- CN108217628A CN108217628A CN201810137301.7A CN201810137301A CN108217628A CN 108217628 A CN108217628 A CN 108217628A CN 201810137301 A CN201810137301 A CN 201810137301A CN 108217628 A CN108217628 A CN 108217628A
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- carbon nanotube
- dimensional
- hole
- dimensional netted
- alumina formwork
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 130
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000009415 formwork Methods 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000007743 anodising Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- 239000003990 capacitor Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000008859 change Effects 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 8
- 239000002071 nanotube Substances 0.000 description 6
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 235000014121 butter Nutrition 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000004262 dental pulp cavity Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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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
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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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of three-dimensional netted carbon nanotubes and its preparation method and application.Three dimensional carbon nanotubes of the carbon nanotube including being communicated with lateral carbon nanotube between Aligned carbon nanotubes, wherein, the Guan Zhongjun of Aligned carbon nanotubes and lateral carbon nanotube is equipped with thin carbon nanotube of the pipe diameter of one or more for 18 22nm;Method includes the use of anodizing and obtains the three-dimensional through hole alumina formwork containing impurity on hole wall, particularly first the template is placed in nickel sulfate solution after impregnating, use plasma cleaning, it places it in again in the mixed atmosphere of argon gas and acetylene, the at least 1h at 600 700 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole are equipped with the anodic oxidation aluminium formwork that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube, then, it places it in and alumina formwork is eroded in aqueous slkali, purpose product is made.Its face capacitance is big, conductivity is high, and the electrochemical energy storing device field at the same time with ultra high power density and higher capacity is with important application prospect.
Description
Technical field
The present invention relates to a kind of carbon nanotube and preparation method and purposes, especially a kind of three-dimensional netted carbon nanotube and its
Preparation method and purposes.
Background technology
Three-dimensional structure carbon material with big specific surface area is in electrochemical energy storage and environmental improvement etc. with important
Application prospect.Although the carbon nano pipe array of three-dimensional structure is good electrochemical electrode material, however, due to carbon nanotube
As other monodimension nanometer materials, because of its draw ratio height, therefore easily formed and reunited at top, carbon nano pipe array is caused to keep
Mutually isolated length is usually less than 10 μm;And relatively thin carbon nano pipe array causes its face capacitance too small, therefore, synthesis has
The certain thickness Aligned carbon nanotubes array for being mutually parallel, mutually isolating has very important in electrochemical energy storage field
Meaning.For this purpose, people have made some good tries and effort, such as entitled " A three-dimensional carbon
Nano-network for high performance lithium ion batteries ", Nano Energy, 2015,11,
500-509 (" the three-dimensional carbon managed network for being used for high performance lithium ion battery ",《The nanometer energy》O. 11th 500-509 in 2015
Page) article.The three-dimensional carbon managed network referred in this article connects upright carbon pipe by lateral carbon pipe and forms;Preparation method is first makes
Contain the method for the aluminium flake of impurity with anodic oxidation, obtain three-dimensional through hole alumina formwork, then the chemical gas using template-mediated
Phase deposition method deposits the three-dimensional carbon reticular structure mutually supported in the hole of three-dimensional through hole alumina formwork, then, dissolves
Product is obtained after alumina formwork.Though this product has preferable three-dimensional carbon web frame, there are still shortcomings, first
First, it is cavity to form the upright carbon pipe of three-dimensional carbon web frame and the tube chamber of lateral carbon pipe, and the face capacitance for resulting in product is less than normal;Its
Secondary, the conductivity of product is too low, only 159S/m.
Invention content
It is big, electric to provide a kind of face capacitance to overcome shortcoming of the prior art for the technical problem to be solved in the present invention
The high three-dimensional netted carbon nanotube of conductance.
The invention solves another technical problem be that a kind of preparation method of above-mentioned three-dimensional netted carbon nanotube is provided.
The invention solves another technical problem be that a kind of purposes of above-mentioned three-dimensional netted carbon nanotube is provided.
The technical issues of to solve the present invention, used technical solution are that three-dimensional netted carbon nanotube includes upright carbon
The three dimensional carbon nanotubes of lateral carbon nanotube are communicated between nanotube, particularly:
The Aligned carbon nanotubes and the Guan Zhongjun of lateral carbon nanotube are equipped with the thin carbon nanotube of one or more, described thin
The pipe diameter of carbon nanotube is 18-22nm.
As being further improved for three-dimensional netted carbon nanotube:
Preferably, the thin carbon nanotube being equipped in Aligned carbon nanotubes and the pipe of lateral carbon nanotube is 1-5 roots.
Preferably, the pipe diameter of Aligned carbon nanotubes be 200-300nm, tube spacing 180-220nm, lateral carbon nanotube
Pipe diameter be 50-90nm, tube spacing 40-60nm.
To solve another technical problem of the present invention, another used technical solution is above-mentioned three-dimensional netted carbon
The preparation method of nanotube includes the use of anodizing and obtains the three-dimensional through hole alumina formwork containing impurity on hole wall, especially
It is that key step is as follows:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the sulfuric acid of 0.06-0.10mol/L
Nickel (NiSO4) impregnate in solution to take out after at least 10h and dry, then be used for plasma cleaning at least 15min, it obtains on hole wall
Three-dimensional through hole alumina formwork containing sulfuric acid nickel particle;
Step 2, the flow for the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall being placed in argon gas (Ar) is
60-100ml/min, acetylene flow be (C2H4) 4-8ml/min mixed atmosphere in, at least 1h, obtains at 600-700 DEG C
The Kong Zhongjun of three-dimensional through hole is equipped with the anodic oxidation aluminium formwork that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube;
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork, and three-dimensional netted carbon nanotube is made.
Preparation method as three-dimensional netted carbon nanotube is further improved:
Preferably, it is using the process of the three-dimensional through hole alumina formwork containing impurity on anodizing acquisition hole wall,
It is first 38-42 according to the volume ratio of the phosphoric acid of 80-90wt%, second alcohol and water:190-210:1760 ratio mixes three, obtains
It is placed in -2-2 DEG C of electrolyte to electrolyte, then by the aluminium flake containing impurity, in the DC constant voltage anodic oxygen of 170-190V
Change 13-17h, then, place it in saturation butter of tin (SnCl4) in solution after the removal unoxidized aluminium in the back side, it is placed in 38-42
DEG C 3-7wt% phosphoric acid (H3PO4) at least 15min is impregnated in solution, upright bore dia is obtained as 200-300nm, pitch of holes
For 180-220nm, lateral bore dia is 50-90nm, pitch of holes is the three-dimensional through hole oxygen containing impurity on the hole wall of 40-60nm
Change aluminum alloy pattern plate.
Preferably, the impurity in the aluminium flake containing impurity for iron and silicon≤0.55wt%, copper≤0.05wt%, manganese≤
0.05wt%, magnesium≤0.05wt%, zinc≤0.05wt%, the content of balance aluminum is 99-99.5wt%.
Preferably, aqueous slkali is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
Preferably, a concentration of 2-4mol/L during aqueous slkali corrosion oxidation aluminum alloy pattern plate, temperature are 35-45 DEG C.
To solve another technical problem of the present invention, another used technical solution is above-mentioned three-dimensional netted carbon
The purposes of nanotube is:
Three-dimensional netted carbon nanotube is used to make electrochemical capacitor.
Purposes as three-dimensional netted carbon nanotube is further improved:
Preferably, the process for making electrochemical capacitor is that first by two panels, its one side has sputtered golden film and has been fixed with successively
Completely cut off between the three-dimensional netted carbon nanotube of metal foil electrodes piece with water system capacitor diaphragm, then place it in 0.8-1.2mol/L
Sulfuric acid (H2SO4) solution in.
It is relative to the advantageous effect of the prior art:
First, purpose product obtained is characterized respectively using scanning electron microscope, transmission electron microscope and electrochemical workstation,
As a result, it can be seen that purpose product is communicated with the three dimensional carbon nanotubes of lateral carbon nanotube between Aligned carbon nanotubes, and upright
The Guan Zhongjun of carbon nanotube and lateral carbon nanotube is equipped with the thin carbon nanotube that 1-5 diameter of root canal is 18-22nm;Wherein, uprightly
The pipe diameter of carbon nanotube is 200-300nm, tube spacing 180-220nm, the pipe diameter of lateral carbon nanotube is 50-90nm,
Tube spacing is 40-60nm.This three dimensional carbon nanotubes formed by being communicated with lateral carbon nanotube between Aligned carbon nanotubes it is every
Root Guan Zhongjun is equipped with the purpose product that more thin carbon nanotube is assembled into, both since the carbon reticular structure of three dimensional carbon nanotubes has
Speciality;Again because of the more thin carbon nanotubes that every Guan Zhongjun is equipped with, and except the face capacitance for substantially increasing purpose product, make
It remains to maintain parallel four under the cyclic voltammetry scan rate of superelevation sweep speed 500V/s as electrochemical capacitor electrode
Side shape, in 1mA/cm2Constant current charge-discharge in show 6.8mF/cm2Except high face capacitance density, and also produce purpose simultaneously
The conductivity of object is greatly improved, it is made to be up to 578S/m.So as to be applied to the electrification of ultra high power density
It learns in capacitor and filter circuit.
Second, preparation method science, effectively.The purpose product that face capacitance is big, conductivity is high has not only been made --- it is three-dimensional
Mesh carbon nanotube also reduces its resistance as electrode for capacitors, and then purpose product is made to have ultra high power at the same time
The electrochemical energy storing device field of density and higher capacity has important application prospect.
Description of the drawings
Fig. 1 is that purpose product made from preparation method is characterized using scanning electron microscope (SEM) and transmission electron microscope (TEM)
One of result.A figures in Fig. 1 are the SEM image of purpose product, and b figures are the local high magnification SEM of purpose product shown in a figures
Image, c figures are the SEM image in the section of purpose product, and d figures are the TEM image of purpose product;As seen from Figure 1, purpose product
Be interconnected the three dimensional carbon nanotubes of (a figures) for Aligned carbon nanotubes and lateral carbon nanotube, and Aligned carbon nanotubes and transverse direction
More thin carbon nanotube (b figures, c figures and d figures) is equipped in carbon nanotube.
Fig. 2 is the cyclic voltammetric obtained after being characterized to purpose product obtained using the electrochemical workstation of Germany's production
One of curve graph.A figures in Fig. 2 be purpose product under the cyclic voltammetry scan rate of 100-1000mV/s, show one
Close to the volt-ampere curve shape of rectangle, show that it has the capacitive property close to preferable double layer capacitor;B figures are purpose product
Under the superelevation sweep speed of 500V/s, remain to show an approximate parallelogram, illustrate the power of its superelevation
Characteristic.
Fig. 3 is the electrochemistry obtained after being characterized to purpose product obtained using the electrochemical workstation of Germany's production
One of can scheme.A figures in Fig. 3 are the constant current charge-discharge test result figure of purpose product, in 1mA/cm2And 20mA/cm2's
Under current density, specific capacitance is respectively 6.8mF/cm2And 5.7mF/cm2, high face specific capacitance is shown, is also showed that simultaneously
Almost without voltage drop, illustration purpose product has relatively low resistance;B figures are the ion of purpose product and the fast transport of electronics
Mechanism schematic diagram explains the reason of ion quickly diffuses to form high power density;C figures are using purpose product as during electrode
Nyquist (Nyquis) figure, the imaginary part resistance in figure are approximately perpendicular to X-axis, illustrate its performance with ideal capacitor, it
Equivalent series resistance for 0.19 Ω, smaller resistance illustrates that it has higher power density;D figures are the phase of purpose product
To the response diagram of frequency, the low frequency region phase angle in the figure equally also illustrates the property of its ideal capacitor close to -90 ° at angle
Energy.
Specific embodiment
The preferred embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
It buys from market or is voluntarily made first:
As the aluminium flake containing impurity, impurity in aluminium flake for iron and silicon≤0.55wt%, copper≤0.05wt%, manganese≤
0.05wt%, magnesium≤0.05wt%, zinc≤0.05wt%, the content of balance aluminum is 99-99.5wt%;
Phosphoric acid;
Ethyl alcohol;
Butter of tin solution;
Nickel sulfate solution;
Plasma cleaner;
Argon gas;
Acetylene gas;
Sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as aqueous slkali.
Wherein,
Obtaining the process of the three-dimensional through hole alumina formwork containing impurity on hole wall using anodizing is, first according to
The phosphoric acid of 80-90wt%, the volume ratio of second alcohol and water are 38-42:190-210:1760 ratio mixes three, is electrolysed
Liquid, then the aluminium flake containing impurity is placed in -2-2 DEG C of electrolyte, in the DC constant voltage anodic oxygen 13- of 170-190V
17h then, places it in saturation butter of tin solution after removing the unoxidized aluminium in the back side, is placed in 38-42 DEG C of 3-7wt%
Phosphoric acid solution in impregnate at least 15min, obtain upright bore dia be 200-300nm, pitch of holes 180-220nm, laterally
Bore dia be 50-90nm, pitch of holes is the three-dimensional through hole alumina formwork containing impurity on the hole wall of 40-60nm.
Then:
Embodiment 1
Prepare the specific steps are:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the nickel sulfate solution of 0.06mol/L
It takes out and dries after middle immersion 14h.It is used for plasma cleaning 15min again, obtains the three-dimensional containing sulfuric acid nickel particle on hole wall
Nanohole alumine template.
Step 2, the flow that the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall is placed in argon gas is 60ml/
Min, acetylene flow be in the mixed atmosphere of 8ml/min, the 2h at 600 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole is equipped with carbon and receives
The anodic oxidation aluminium formwork of thin carbon nanotube is equipped in mitron, carbon nanotube.
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork;Wherein, aqueous slkali is sodium hydroxide solution, corrosion oxidation aluminum dipping form
A concentration of 2mol/L, temperature during plate are 45 DEG C.It is made and is similar to shown in Fig. 1 and as shown in the curve in Fig. 2 and Fig. 3
Three-dimensional netted carbon nanotube.
Embodiment 2
Prepare the specific steps are:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the nickel sulfate solution of 0.07mol/L
It takes out and dries after middle immersion 13h.It is used for plasma cleaning 18min again, obtains the three-dimensional containing sulfuric acid nickel particle on hole wall
Nanohole alumine template.
Step 2, the flow that the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall is placed in argon gas is 70ml/
Min, acetylene flow be 7ml/min mixed atmosphere in, the 1.8h at 625 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole is equipped with carbon
The anodic oxidation aluminium formwork of thin carbon nanotube is equipped in nanotube, carbon nanotube.
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork;Wherein, aqueous slkali is sodium hydroxide solution, corrosion oxidation aluminum dipping form
A concentration of 2.5mol/L, temperature during plate are 43 DEG C.It is made and is similar to shown in Fig. 1 and as shown in the curve in Fig. 2 and Fig. 3
Three-dimensional netted carbon nanotube.
Embodiment 3
Prepare the specific steps are:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the nickel sulfate solution of 0.08mol/L
It takes out and dries after middle immersion 12h.It is used for plasma cleaning 20min again, obtains the three-dimensional containing sulfuric acid nickel particle on hole wall
Nanohole alumine template.
Step 2, the flow that the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall is placed in argon gas is 80ml/
Min, acetylene flow be 6ml/min mixed atmosphere in, the 1.5h at 650 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole is equipped with carbon
The anodic oxidation aluminium formwork of thin carbon nanotube is equipped in nanotube, carbon nanotube.
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork;Wherein, aqueous slkali is sodium hydroxide solution, corrosion oxidation aluminum dipping form
A concentration of 3mol/L, temperature during plate are 40 DEG C.It is made as shown in Figure 1, and the three-dimensional as shown in the curve in Fig. 2 and Fig. 3
Mesh carbon nanotube.
Embodiment 4
Prepare the specific steps are:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the nickel sulfate solution of 0.09mol/L
It takes out and dries after middle immersion 11h.It is used for plasma cleaning 23min again, obtains the three-dimensional containing sulfuric acid nickel particle on hole wall
Nanohole alumine template.
Step 2, the flow that the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall is placed in argon gas is 90ml/
Min, acetylene flow be 5ml/min mixed atmosphere in, the 1.3h at 675 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole is equipped with carbon
The anodic oxidation aluminium formwork of thin carbon nanotube is equipped in nanotube, carbon nanotube.
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork;Wherein, aqueous slkali is sodium hydroxide solution, corrosion oxidation aluminum dipping form
A concentration of 3.5mol/L, temperature during plate are 38 DEG C.It is made and is similar to shown in Fig. 1 and as shown in the curve in Fig. 2 and Fig. 3
Three-dimensional netted carbon nanotube.
Embodiment 5
Prepare the specific steps are:
Step 1, the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in the nickel sulfate solution of 0.10mol/L
It takes out and dries after middle immersion 10h.It is used for plasma cleaning 25min again, obtains the three-dimensional containing sulfuric acid nickel particle on hole wall
Nanohole alumine template.
Step 2, the flow for the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall being placed in argon gas is
100ml/min, acetylene flow be 4ml/min mixed atmosphere in, the 1h at 700 DEG C, the Kong Zhongjun for obtaining three-dimensional through hole is put
There is the anodic oxidation aluminium formwork that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube.
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodic oxygen that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Change aluminum alloy pattern plate, which is placed in aqueous slkali, erodes alumina formwork;Wherein, aqueous slkali is sodium hydroxide solution, corrosion oxidation aluminum dipping form
A concentration of 4mol/L, temperature during plate are 35 DEG C.It is made and is similar to shown in Fig. 1 and as shown in the curve in Fig. 2 and Fig. 3
Three-dimensional netted carbon nanotube.
Select respectively again and be used as the aluminium flake containing impurity, the impurity in aluminium flake be iron and silicon≤0.55wt%, copper≤
0.05wt%, manganese≤0.05wt%, magnesium≤0.05wt%, zinc≤0.05wt%, the content of balance aluminum is 99-99.5wt%, is made
For the sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution of aqueous slkali, above-described embodiment 1-5 is repeated, it is similary to be made
As or be similar to three-dimensional netted carbon nanotube shown in Fig. 1 and as shown in the curve in Fig. 2 and Fig. 3.
The purposes of three-dimensional netted carbon nanotube is:
By three-dimensional netted carbon nanotube for making electrochemical capacitor, the knot as shown in the curve in Fig. 2 and Fig. 3 is obtained
Fruit;Wherein, the process for making electrochemical capacitor is, two panels its one side has first been sputtered golden film successively and has been fixed with metal platinum electricity
Between the three-dimensional netted carbon nanotube of pole piece with water system capacitor diaphragm completely cut off, then place it in 0.8-1.2mol/L sulfuric acid it is molten
In liquid.
Obviously, those skilled in the art can be to three-dimensional netted carbon nanotube of the present invention and its preparation method and application
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and change to the present invention
Type belongs within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these modification and variations
It is interior.
Claims (10)
1. a kind of three-dimensional netted carbon nanotube, the three-dimensional carbon nanometer including being communicated with lateral carbon nanotube between Aligned carbon nanotubes
Pipe, is characterized in that:
The Aligned carbon nanotubes and the Guan Zhongjun of lateral carbon nanotube are equipped with the thin carbon nanotube of one or more, and the thin carbon is received
The pipe diameter of mitron is 18-22nm.
2. three-dimensional netted carbon nanotube according to claim 1, it is characterized in that Aligned carbon nanotubes and lateral carbon nanotube
Pipe in the thin carbon nanotube that is equipped be 1-5 roots.
3. three-dimensional netted carbon nanotube according to claim 1, it is characterized in that the pipe diameter of Aligned carbon nanotubes is 200-
300nm, tube spacing 180-220nm, the pipe diameter of lateral carbon nanotube is 50-90nm, tube spacing 40-60nm.
4. the preparation method of three-dimensional netted carbon nanotube described in a kind of claim 1 includes the use of anodizing and obtains hole wall
On the three-dimensional through hole alumina formwork containing impurity, it is characterised in that key step is as follows:
Step 1, the nickel sulfate that the three-dimensional through hole alumina formwork containing impurity on hole wall is first placed in 0.06-0.10mol/L is molten
It impregnates to take out after at least 10h in liquid and dry, then be used for plasma cleaning at least 15min, obtain containing nickel sulfate on hole wall
The three-dimensional through hole alumina formwork of particle;
Step 2, the flow that the three-dimensional through hole alumina formwork containing sulfuric acid nickel particle on hole wall is placed in argon gas is 60-100ml/
Min, acetylene flow be 4-8ml/min mixed atmosphere in, at least 1h at 600-700 DEG C is obtained in the hole of three-dimensional through hole
It is equipped with the anodic oxidation aluminium formwork that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube;
Step 3, the Kong Zhongjun of three-dimensional through hole is equipped with to the anodised aluminium that thin carbon nanotube is equipped in carbon nanotube, carbon nanotube
Template, which is placed in aqueous slkali, erodes alumina formwork, and three-dimensional netted carbon nanotube is made.
5. the preparation method of three-dimensional netted carbon nanotube according to claim 4, it is characterized in that being obtained using anodizing
On hole wall the process of the three-dimensional through hole alumina formwork containing impurity be, first according to the phosphoric acid of 80-90wt%, second alcohol and water
Volume ratio is 38-42:190-210:1760 ratio mixes three, obtains electrolyte, then the aluminium flake containing impurity is placed in-
In 2-2 DEG C of electrolyte, in the DC constant voltage anodic oxygen 13-17h of 170-190V, then, four chlorination of saturation is placed it in
After removing the unoxidized aluminium in the back side in solution of tin, at least 15min is impregnated in the phosphoric acid solution for the 3-7wt% for being placed in 38-42 DEG C, is obtained
To upright bore dia be 200-300nm, pitch of holes 180-220nm, lateral bore dia is 50-90nm, pitch of holes 40-
Three-dimensional through hole alumina formwork containing impurity on the hole wall of 60nm.
6. the preparation method of three-dimensional netted carbon nanotube according to claim 5, it is characterized in that in the aluminium flake containing impurity
Impurity for iron and silicon≤0.55wt%, copper≤0.05wt%, manganese≤0.05wt%, magnesium≤0.05wt%, zinc≤0.05wt%,
The content of balance aluminum is 99-99.5wt%.
7. the preparation method of three-dimensional netted carbon nanotube according to claim 4, it is characterized in that aqueous slkali is sodium hydroxide
Solution or potassium hydroxide solution or lithium hydroxide solution.
8. the preparation method of three-dimensional netted carbon nanotube according to claim 4, it is characterized in that aqueous slkali corrosion oxidation aluminium
A concentration of 2-4mol/L, temperature during template are 35-45 DEG C.
9. a kind of purposes of three-dimensional netted carbon nanotube described in claim 1, it is characterised in that:
Three-dimensional netted carbon nanotube is used to make electrochemical capacitor.
10. the purposes of three-dimensional netted carbon nanotube according to claim 9, it is characterized in that making the mistake of electrochemical capacitor
Cheng Wei, two panels its one side first sputtered into golden film successively and be fixed between the three-dimensional netted carbon nanotube of metal foil electrodes piece with
Water system capacitor diaphragm completely cuts off, then places it in the sulfuric acid solution of 0.8-1.2mol/L.
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CN115188602A (en) * | 2022-07-11 | 2022-10-14 | 中国科学院合肥物质科学研究院 | Three-dimensional integrated carbon tube grid film, preparation method thereof and prepared capacitor device |
CN115188602B (en) * | 2022-07-11 | 2023-06-27 | 中国科学院合肥物质科学研究院 | Three-dimensional integrated carbon tube grid film, preparation method thereof and capacitor device prepared by same |
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