CN115188602A - Three-dimensional integrated carbon tube grid film, preparation method thereof and prepared capacitor device - Google Patents
Three-dimensional integrated carbon tube grid film, preparation method thereof and prepared capacitor device Download PDFInfo
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- CN115188602A CN115188602A CN202210856050.4A CN202210856050A CN115188602A CN 115188602 A CN115188602 A CN 115188602A CN 202210856050 A CN202210856050 A CN 202210856050A CN 115188602 A CN115188602 A CN 115188602A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 117
- 239000003990 capacitor Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 75
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 54
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 49
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 235000006408 oxalic acid Nutrition 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
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- 238000004806 packaging method and process Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
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- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
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- 229920002799 BoPET Polymers 0.000 claims description 2
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- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229920006255 plastic film Polymers 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims 3
- -1 tetraethylammonium Tetrafluoroborate Chemical compound 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000012528 membrane Substances 0.000 abstract description 9
- 230000004044 response Effects 0.000 abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 4
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
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- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 238000002048 anodisation reaction Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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- 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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Abstract
The invention relates to the field of carbon nano materials, in particular to a three-dimensional integrated carbon tube grid film with adjustable vertical tube diameter and tube spacing, a preparation method thereof and a prepared capacitor device. According to the invention, the regulation and control of the vertical pipe diameter and the space of the porous anodic aluminum oxide with the three-dimensional pore channel interconnection are realized by regulating and controlling the electrolyte and controlling the anodic oxidation voltage, so that the three-dimensional integrated carbon tube grid membrane with an ordered and adjustable structure is obtained, the vertical carbon tubes of the grid membrane are arranged more closely, and the grid membrane has a larger and adjustable electrochemical activity specific surface area, can improve the specific surface area of an electrode material, and further improves the energy density of a super capacitor constructed by the grid membrane. Meanwhile, a smooth ion transport channel can be provided by gaps among the upright carbon tube units, the rapid transport of electrons is ensured by the three-dimensional structure connected by the integrated chemical bond, and the carbon tube can be used as a super capacitor electrode material with high energy density, ultrahigh power density and good frequency response performance.
Description
Technical Field
The invention relates to the field of carbon nano materials, in particular to a three-dimensional integrated carbon tube grid film with adjustable vertical tube diameter and tube spacing, a preparation method thereof and a prepared capacitor device.
Background
Carbon nano materials such as carbon nano tubes, graphene and the like have the characteristics of high chemical stability, good conductivity and the like, and have wide application prospects in the fields of energy, catalysis and the like. The carbon tube array formed by the upright carbon nano tubes can be used as an electrode material for a quick response super capacitor because straight ion transport channels can be provided in parallel gaps between the carbon tubes. However, as the aspect ratio of the carbon tube increases, the top end of the carbon tube is easily agglomerated into a bundle, which results in a decrease in the specific surface area of the electrode, a decrease in the capacity of the capacitor, a slow response speed, and poor power performance. Therefore, the design and preparation of the self-supporting three-dimensional carbon tube structure can effectively prevent the agglomeration between adjacent carbon tubes, and has important significance for improving the performance of electrochemical energy storage devices such as super capacitors and the like.
The invention discloses a three-dimensional mesh carbon nano tube structure prepared by Chinese patent CN108217628A, a preparation method and application thereof.A three-dimensional mesh carbon nano tube structure is prepared by combining anodic oxidation of aluminum sheets containing trace impurities in a phosphoric acid electrolyte with subsequent selective corrosion of impurities on the pore wall of a vertical pore alumina template to obtain a three-dimensional interconnected porous anodic alumina template, and then preparing a three-dimensional interconnected carbon tube array grid film with transverse carbon nano tubes communicated between vertical carbon nano tubes by utilizing a template pore geometric morphology induced chemical vapor deposition method, so that the agglomeration of the adjacent vertical carbon tubes can be effectively prevented, and the performance of the three-dimensional mesh carbon nano tube structure as an electrochemical capacitor electrode is hopefully improved. However, the aperture (-220 nm) and the spacing (-400 nm) of the vertical holes of the three-dimensional anodic alumina template are large, so that the specific surface area of the obtained three-dimensional carbon tube grid film is small, the area specific capacitance of the three-dimensional carbon tube grid film serving as an electrode material of a super capacitor is limited, and the energy density of the capacitor is low; and the aperture size of the vertical hole in the porous alumina template is single, so that the preparation of nano structures with controllable sizes, such as vertical nanotubes or nanorods, is difficult. How to regulate and control the hole diameter of the vertical hole in the three-dimensional interconnected porous alumina template and further regulate and control the pipe diameter of the vertical carbon tube in the three-dimensional interconnected carbon tube grid so as to enable the vertical carbon tube to have larger specific surface area becomes important.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a three-dimensional integrated carbon tube grid film with adjustable tube diameter and spacing. The three-dimensional integrated carbon tube grid film with the adjustable structure is used as an electrode material of the super capacitor, so that the energy density and the frequency response performance of a device can be improved.
In order to realize the purpose, the invention adopts the following technical scheme: a preparation method of a three-dimensional integrated carbon tube grid film comprises the following steps:
s11, adding oxalic acid and ethanol into water to obtain a mixed solution A, and taking the mixed solution A as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution A is 0.1-0.2M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution A; or adding oxalic acid, phosphoric acid and ethanol into water to obtain a mixed solution B, and taking the mixed solution B as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution B is 0.1-0.2M, the concentration of the phosphoric acid is 0.05-0.25M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution B;
taking an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode, immersing the aluminum sheet into an anodic oxidation electrolyte, anodizing for 6-24h at the temperature of 8-12 ℃ and under the direct-current constant voltage of 55-140V, removing aluminum which is not subjected to anodic oxidation in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-20 minutes to prepare the three-dimensional porous alumina with interconnected pore channels;
s12, placing the three-dimensional porous alumina as a template in a tubular furnace for chemical vapor deposition, wherein the chemical vapor deposition pressure is (0.1-0.08) Mpa, the temperature is 900-1100 ℃, the time is 20-50 minutes, the flow of a reaction gas source acetylene is 20-60sccm, and a carbon layer is deposited in an interconnected pore channel of the three-dimensional porous alumina template;
and S13, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing the alumina template, rinsing the product by deionized water, and thus obtaining the three-dimensional integrated carbon tube grid film with adjustable tube diameter and spacing.
The preparation method of the three-dimensional integrated carbon tube grid film is further improved as follows:
preferably, the method for removing aluminum which is not subjected to anodic oxidation in the aluminum sheet by a solution soaking method comprises the following specific steps: immersing an aluminum sheet in a mixed aqueous solution containing 0.1M of copper chloride and 12M of hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g of copper chloride and 500ml of a hydrochloric acid solution having a mass fraction of 37% with 500ml of water;
or removing the alumina template by chemical corrosion, wherein the corrosive liquid is hydrofluoric acid solution with the concentration of 35-45 wt%.
Another object of the present invention is to provide a three-dimensional integrated carbon tube mesh membrane prepared by any one of the above-mentioned preparation methods.
The invention also aims to provide a preparation method of the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and space, which specifically comprises the following steps:
s21, preparing a phosphoric acid aqueous solution with the concentration of 0.25-0.35M as an anodic oxidation electrolyte;
immersing aluminum sheet containing trace impurities as an anode and graphite as a cathode into an anodic oxidation electrolyte, and carrying out anodic oxidation for 2-8 hours at the temperature of 0-5 ℃ and under the direct-current constant voltage of 185-195V;
after the anodic oxidation voltage is gradually reduced to 65-140V within 1-2 hours, the electrolyte is replaced by an aqueous solution containing 0.15M oxalic acid or an aqueous solution containing 0.05-0.25M oxalic acid and 0.03-0.07M phosphoric acid, and the anodic oxidation is carried out for 3-12 hours at the temperature of 8-12 ℃;
removing aluminum which is not subjected to anodic oxidation in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-10 minutes to prepare the three-dimensional porous alumina with interconnected pore channels;
s22, placing the three-dimensional porous alumina as a template in a tubular furnace for chemical vapor deposition, wherein the chemical vapor deposition pressure is (0.1-0.08) Mpa, the temperature is 900-1100 ℃, the time is 20-50 minutes, the flow of a reaction gas source acetylene is 20-60sccm, and a carbon layer is deposited in an interconnected pore channel of the three-dimensional porous alumina template;
and S23, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing the alumina template, rinsing the product by deionized water, and thus obtaining the three-dimensional integrated carbon tube grid film with adjustable tube diameter and spacing.
The preparation method of the three-dimensional integrated carbon tube grid film is further improved as follows:
preferably, the method for removing aluminum which is not subjected to anodic oxidation in the aluminum sheet by a solution soaking method comprises the following specific steps: immersing an aluminum sheet in a mixed aqueous solution containing 0.1M of copper chloride and 12M of hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g of copper chloride and 500ml of a hydrochloric acid solution having a mass fraction of 37% with 500ml of water;
or removing the alumina template by chemical corrosion, wherein the corrosive liquid is hydrofluoric acid solution with the concentration of 35-45 wt%.
The fourth purpose of the invention is to provide a three-dimensional integrated carbon tube grid film prepared by any one of the preparation methods.
The fifth object of the present invention is to provide an electric double layer capacitor device assembled by the three-dimensional integrated carbon tube grid film, which is prepared by the following steps:
and (2) evaporating a layer of gold film on one of the flat surfaces of the three-dimensional integrated carbon tube grid film, cutting the three-dimensional integrated carbon tube grid film into two symmetrical electrodes with the same area, using the metal electrode plate as a current collector, isolating the two symmetrical electrodes by using an aqueous diaphragm, injecting aqueous electrolyte, and then packaging, or isolating by using an organic electrolyte diaphragm, injecting organic electrolyte, and then packaging to obtain the double-electric-layer capacitor device.
As a further improvement of the electric double layer capacitor device:
preferably, the aqueous electrolyte is a sulfuric acid solution of 0.8 to 1.2 mol/L.
Preferably, the organic electrolyte is 0.8 to 1.2mol/L tetraethylammonium tetrafluoroborateTEABF 4 。
Preferably, a PET film packaging shell or an aluminum plastic film packaging shell is adopted for packaging.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, oxalic acid or a mixed solution of oxalic acid and phosphoric acid is used as an electrolyte, an aluminum sheet containing trace impurities is subjected to anodic oxidation under different voltages of 55-140V, then the impurities in the wall of the vertical hole are selectively corroded and reamed, an anodic alumina template with three-dimensional interconnected pore channels is obtained, and the adjustment of the pore diameter and the pore space of the vertical hole of the alumina template with three-dimensional pores can be realized.
2) The invention can also prepare the three-dimensional pore interconnecting porous alumina template with Y-shaped or multi-branch vertical pore channels by using phosphoric acid as the electrolyte for anodic oxidation, gradually reducing the voltage, and replacing the electrolyte with oxalic acid or a mixed solution of oxalic acid and phosphoric acid for anodic oxidation. The porous alumina with three-dimensional interconnected pore channels and adjustable vertical aperture and spacing is used as a template to carry out chemical vapor deposition to grow the carbon tubes, so that the three-dimensional integrated carbon tube grid film with adjustable vertical carbon tube diameter and spacing can be obtained. The preparation method is simple and convenient to operate and high in repeatability.
3) According to the preparation method of the three-dimensional integrated carbon tube grid membrane with the adjustable vertical carbon tube diameter and the adjustable vertical carbon tube spacing, the problem that transverse holes in porous alumina are difficult to form under lower voltage (< 160V) under the traditional condition is solved by controlling the anodic oxidation voltage of phosphoric acid, oxalic acid and mixed solution electrolyte thereof, and the vertical hole diameter and the vertical hole spacing of the three-dimensional interconnected porous anodic alumina are adjustable from 100 to 200 nanometers and from 150 to 300 nanometers. Thereby obtaining the three-dimensional integrated carbon tube grid film with ordered and adjustable structure, providing a template for the size controllable preparation of vertical nanometer units in other similar morphologies and arranged nanometer structures, and widening the application range of the three-dimensional interconnected porous anodic alumina template. The three-dimensional integrated carbon tube grid is a stable structure with the interconnection of horizontal carbon tubes and vertical carbon tubes, and the vertical carbon tubes can be vertical carbon tubes with uniform size, or Y-shaped or multi-branch carbon tubes with a hierarchical structure, and the structure of the carbon tubes can be artificially regulated and controlled.
4) The vertical carbon tubes of the grid film prepared by the invention are arranged more closely, have larger and adjustable electrochemical activity specific surface area, and can improve the specific surface area of an electrode material, thereby improving the energy density of a super capacitor constructed by the grid film. Meanwhile, a smooth ion transport channel can be provided by gaps among the upright carbon tube units, and the three-dimensional structure connected by the integrated chemical bonds ensures the rapid transport of electrons, so that the carbon tube can be used as a supercapacitor electrode material with high energy density, ultrahigh power density and good frequency response performance.
The invention uses the carbon tube grid film as an electrode to assemble an electric double layer capacitor, and the surface capacitance reaches 2.7, 2.4 and 2.5mF/cm respectively at 120Hz 2 The phase angle is about-71.7 degrees, -72.5 degrees, -77.6 degrees respectively, and the electrochemical performance is good and the potential of the super capacitor is quick response.
Drawings
Fig. 1 is a schematic view of a process for preparing a three-dimensional integrated carbon tube grid film.
FIGS. 2 (a-c) are cross-sectional Scanning Electron Microscope (SEM) pictures of three-dimensional interconnected porous anodized aluminum templates with vertical pore sizes of about 100 nm, 150 nm, and 200 nm, respectively, prepared in examples 1-3; FIG. 2 (d-f) is SEM image of the cross-section of the three-dimensional integrated carbon tube lattice membrane with vertical tube diameter of about 100 nm, 150 nm and 200 nm.
FIG. 3 (a) is a sectional SEM picture of a three-dimensional interconnected porous alumina template with Y-shaped vertical channels prepared in example 4 and an enlarged view thereof (b); fig. 3 (c) is a sectional SEM picture of the three-dimensional integrated carbon tube mesh membrane in which the vertical carbon tubes prepared are "Y-shaped" and an enlarged view thereof (d).
FIG. 4 (a, b) is the Cyclic Voltammetry (CV) curves at the sweep rate of 100mV/s to 500V/s for the three-dimensional integrated carbon nanotube mesh film assembled supercapacitor prepared in example 1 and having a vertical tube diameter of about 100 nm; fig. 4 (c, d) shows a constant current charge/discharge (GCD) curve.
FIG. 5 (a-c) shows electrochemical performance of the three-dimensional integrated carbon tube lattice membrane assembled supercapacitor made in example 1 and having a vertical tube diameter of about 100 nm: a bode plot (a), an nyquist curve (b) and an area-specific capacitance-frequency relationship curve (c) obtained from an Electrochemical Impedance Spectroscopy (EIS); FIG. 5 (d) is a graph showing the relationship between the anodic oxidation voltage and the pore diameter and the distance between the vertical pores in the three-dimensionally interconnected porous anodic alumina template at an anodic oxidation voltage of 55-140V when the mixed acid solution of oxalic acid and phosphoric acid is used as the electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Aluminum sheet containing trace impurities (wherein the content distribution is that aluminum is more than or equal to 98 percent, copper is less than or equal to 0.15 percent, iron is less than or equal to 0.41 percent, and silicon is less than or equal to 0.05 percent)
The vertical pipe diameter refers to the outer diameter of the vertical carbon tubes in the three-dimensional integrated carbon tube grid, and the pipe spacing refers to the distance between the centers of the adjacent vertical carbon tubes.
Example 1
A preparation method of a three-dimensional integrated carbon tube frame with the vertical tube diameter of about 100 nanometers and the spacing of about 150 nanometers comprises the following steps:
(1) Adding oxalic acid, phosphoric acid and ethanol into water to obtain a mixed solution B, and taking the mixed solution B as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution B is 0.1M, the concentration of the phosphoric acid is 0.05M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution B; taking an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode, carrying out anodic oxidation for 12h at 15 ℃ and 55V direct current constant pressure, placing the aluminum sheet in a mixed solution of 0.1M copper chloride and 12M hydrochloric acid solution to corrode back aluminum which is not subjected to anodic oxidation, and then soaking the aluminum sheet in 5wt% phosphoric acid solution at 40 ℃ for 5min to obtain a three-dimensional pore interconnected porous anodic alumina template with the thickness of about 17 micrometers, the vertical pore diameter of about 100 nanometers and the spacing of about 150 nanometers;
(2) Placing the three-dimensional pore canal interconnecting porous anodic alumina template with the vertical pore diameter of about 100 nanometers obtained in the step (1) in a high-temperature tube furnace, and reacting with a gas source acetylene (C) at the temperature of 1000 ℃ and the vacuum degree of-0.1 Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 20min, and surface plasma cleaning is carried out after cooling to obtain a three-dimensional carbon tube grid film with an aluminum oxide template;
(3) And (3) placing the three-dimensional carbon tube grid film with the alumina template obtained in the step (2) in 20wt% hydrofluoric acid solution to chemically corrode the alumina template, rinsing and drying to obtain the three-dimensional integrated carbon tube frame with the vertical tube diameter of about 100 nanometers and the spacing of about 150 nanometers.
Example 2
A preparation method of a three-dimensional integrated carbon tube frame with a vertical tube diameter of about 150 nanometers and a spacing of about 225 nanometers comprises the following steps:
(1) Adding oxalic acid, phosphoric acid and ethanol into water to obtain a mixed solution B, and taking the mixed solution B as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution B is 0.1M, the concentration of the phosphoric acid is 0.05M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution B; taking an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode, carrying out anodic oxidation for 15h at 10 ℃ and 105V of direct current constant pressure, placing the anode in a mixed solution of 0.1M copper chloride and 12M hydrochloric acid solution to corrode aluminum which is not subjected to anodic oxidation, and then soaking the aluminum in 5wt% phosphoric acid solution at 40 ℃ for 15min to obtain a three-dimensional pore interconnected porous anodic alumina template with the thickness of about 25 micrometers, the vertical pore diameter of about 150 nanometers and the spacing of about 225 nanometers;
(2) Placing the three-dimensional pore canal interconnecting porous anodic alumina template with the vertical pore diameter of about 150 nanometers obtained in the step (1) in a high-temperature tube furnace, and reacting with a gas source acetylene (C) at the temperature of 1000 ℃ and the vacuum degree of-0.1 Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 30min, and surface plasma cleaning is carried out after cooling to obtain a three-dimensional carbon tube grid film with an aluminum oxide template;
(3) And (3) placing the three-dimensional carbon tube grid film with the alumina template obtained in the step (2) in 20wt% hydrofluoric acid solution to chemically corrode the alumina template, rinsing and drying to obtain the three-dimensional integrated carbon tube frame with the vertical tube diameter of about 150 nanometers and the spacing of about 225 nanometers.
Example 3
A preparation method of a three-dimensional integrated carbon tube frame with a vertical tube diameter of about 200 nanometers and a spacing of about 300 nanometers comprises the following steps:
(1) Adding oxalic acid, phosphoric acid and ethanol into water to obtain a mixed solution B, and taking the mixed solution B as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution B is 0.1M, the concentration of the phosphoric acid is 0.05M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution B; taking an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode, carrying out anodic oxidation for 6h at 10 ℃ and 140V of direct current constant pressure, placing the anode in a mixed solution of 0.1M copper chloride and 12M hydrochloric acid solution to corrode aluminum which is not subjected to anodic oxidation, and then soaking the aluminum in 5wt% phosphoric acid solution at 40 ℃ for 20min to obtain a three-dimensional interconnected pore passage porous anodic alumina template with the thickness of about 26 micrometers, the vertical pore diameter of about 200 nanometers and the spacing of about 300 nanometers;
(2) Placing the three-dimensional pore canal interconnecting porous anodic alumina template with the vertical pore diameter of about 200 nanometers obtained in the step (1) in a high-temperature tube furnace, and reacting with a gas source acetylene (C) at the temperature of 1000 ℃ and the vacuum degree of-0.1 Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 40min, and surface plasma cleaning is carried out after cooling to obtain a three-dimensional carbon tube grid film with an aluminum oxide template;
(3) And (3) placing the three-dimensional carbon tube grid film with the alumina template obtained in the step (2) in 20wt% hydrofluoric acid solution to chemically corrode the alumina template, rinsing and drying to obtain the three-dimensional integrated carbon tube frame with the vertical tube diameter of about 200 nanometers and the spacing of about 300 nanometers.
Example 4
A method for preparing a three-dimensional integrated carbon tube frame with a Y-shaped vertical carbon tube comprises the following steps:
(1) Taking 0.3M phosphoric acid solution as electrolyte, aluminum sheet containing trace impurities as anode and graphite as cathode, and carrying out anodic oxidation for 2.5 hours at the constant direct current of 195V at 0 ℃;
(2) After gradually decreasing the anodization voltage to 65V over 1.5 hours, the electrolyte was replaced with a 0.15M oxalic acid solution and anodized at 10 ℃ for 8 hours. Then immersing the aluminum oxide powder into a mixed solution of 0.1M copper chloride and 12M hydrochloric acid solution to corrode the aluminum without anodic oxidation, and then immersing the aluminum oxide powder into a phosphoric acid solution with the mass fraction of 5% to keep the temperature at 40 ℃ for 10min to obtain three-dimensional pore interconnecting porous alumina with the thickness of about 10 microns and a Y-shaped vertical pore;
(3) Placing the three-dimensional pore channel interconnected porous alumina with the Y-shaped vertical pore channel obtained in the step (2) into a high-temperature tubular furnace, controlling the flow of a reaction gas source acetylene (C2H 4) to be 60sccm and the reaction time to be 40min at the temperature of 1000 ℃ and the vacuum degree of-0.1 Mpa, cooling, and then performing surface plasma cleaning to obtain a three-dimensional carbon tube grid film with an alumina template;
(4) And (4) placing the three-dimensional carbon tube grid film with the alumina template obtained in the step (3) in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template, rinsing and drying to obtain a Y-shaped three-dimensional integrated carbon tube frame with the vertical carbon tubes.
Assembly and testing of electrochemical capacitors
Cross-sectional Scanning Electron Microscope (SEM) pictures of the three-dimensional interconnected porous anodized aluminum templates prepared in examples 1 to 3, the results are shown in fig. 2 (a-c); the results of Scanning Electron Microscope (SEM) pictures of the cross-section of the three-dimensional integrated carbon nanotube mesh films prepared in examples 1 to 3 are shown in fig. 2 (d-f). As can be seen from fig. 2, by adjusting the anodization voltage, three-dimensional porous alumina templates with vertical pore diameters of about 100, 150 and 200 nm and pore distances of about 150, 225 and 300 nm can be obtained, and after carbon tubes are grown by template pore-induced chemical vapor deposition, three-dimensional integrated carbon tube frames with vertical tube diameters of about 100, 150 and 200 nm and distances of about 150, 225 and 300 nm are obtained.
Scanning SEM pictures of three-dimensional interconnected porous alumina template with "Y-shaped" vertical channels and three-dimensional integrated carbon tube frame with "Y-shaped" vertical carbon tubes for example 4 are shown in fig. 3 (a-d). As can be seen from FIG. 3, the three-dimensional pore channel interconnected porous alumina with a hierarchical pore structure and a vertical carbon tube in a Y shape and the three-dimensional integrated carbon tube frame with the vertical carbon tube in a Y shape are successfully prepared.
Further, the three-dimensional integrated carbon nanotube mesh film fabricated electric double layer capacitor prepared in example 1: one surface of the grid film is evaporated with a layer of gold film, two samples with the same area and thickness are taken as symmetrical electrodes and isolated by a diaphragm, and the capacitor is packaged in 0.1M sulfuric acid electrolyte, and the test results are as follows:
electrochemical performance tests were performed on three-dimensional integrated carbon tube frames prepared in example 1, having a thickness of about 17 μm, a vertical tube diameter of about 100 nm, and a pitch of about 150 nm, as an electric double layer capacitor electrode material, and the results are shown in fig. 4, where it can be seen that: under the sweep rate of 100mV/s to 2000mV/s, the shapes of CV curves are all close to rectangles, and the characteristics of the double-layer capacitor are nearly ideal; under the high scanning speed of 500V/s, the shape of the electrode still can be kept to be nearly rectangular, and the constant current charging and discharging test result shows an ideal isosceles triangle and shows typical double-electric-layer characteristics. This shows that the three-dimensional integrated carbon tube frame with vertical tube diameter of about 100 nm has better power performance when applied to the double electric layer capacitor electrode.
Meanwhile, in order to further prove the superiority of the high-area-ratio capacitive performance of the three-dimensional integrated carbon tube frame prepared by the method of the present invention, which has the thickness of about 17 micrometers, the vertical tube diameter of about 100 nanometers and the pitch of about 150 nanometers, the sample obtained in example 1 is used as an electric double layer supercapacitor electrode material to perform an electrochemical impedance spectroscopy test, and the result is shown in fig. 5. The imaginary part resistance of the sample obtained in example 1 is close to being vertical to the real axis in the Nyquist diagram, shows ideal capacitance characteristics, and has a small equivalent series resistance (1.2 Ω); in the Bode diagram reflecting the relationship between the phase angle and the frequency, the phase angle of a low-frequency region is close to-90 degrees, which also shows the characteristics of an ideal capacitor of the capacitor, and the phase angle is-71.7 degrees under the frequency of 100-120Hz, which shows good rapid frequency response capability and indicates effective ion transport and electron conduction in the electrode. The area specific capacitance can reach very high 2.7mF/cm under the frequency of 120Hz 2 . It can be seen that example 1 produces a verticalThe three-dimensional integrated carbon tube frame with the tube diameter of about 100 nanometers and the spacing of about 150 nanometers has higher area specific capacitance and good frequency response performance. This is because the three-dimensional integrated carbon tube frame with the vertical tube diameter of about 100 nm and the pitch of about 150 nm has higher active material load, thereby increasing the electrochemical activity specific surface area. The carbon tube structure with the cross carbon tube and the vertical carbon tube connected with each other also improves the conductivity of the electrode material, and the vertical carbon tube with the vertical opening provides a smooth channel for the rapid transportation of ions, so that the three-dimensional integrated carbon tube frame with the vertical diameter of about 100 nanometers and the spacing of about 150 nanometers has good frequency response performance when being used as the electrode material of the super capacitor.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the scope of the invention as set forth in the claims should be deemed to be a part of the present invention.
Claims (10)
1. A preparation method of a three-dimensional integrated carbon tube grid film is characterized by comprising the following steps:
s11, adding oxalic acid and ethanol into water to obtain a mixed solution A, and taking the mixed solution A as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution A is 0.1-0.2M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution A; or adding oxalic acid, phosphoric acid and ethanol into water to obtain a mixed solution B, and taking the mixed solution B as an anodic oxidation electrolyte, wherein the concentration of the oxalic acid in the mixed solution B is 0.1-0.2M, the concentration of the phosphoric acid is 0.05-0.25M, and the absolute ethanol accounts for 1/10 of the total volume of the mixed solution B;
immersing an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode into an anodic oxidation electrolyte, carrying out anodic oxidation for 6-24h at the temperature of 8-12 ℃ under the constant direct current voltage of 55-140V, removing aluminum which is not subjected to anodic oxidation in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-20 min to prepare the three-dimensional porous alumina with interconnected pore channels;
s12, placing the three-dimensional porous alumina as a template in a tubular furnace for chemical vapor deposition, wherein the chemical vapor deposition pressure is (0.1-0.08) Mpa, the temperature is 900-1100 ℃, the time is 20-50 minutes, the flow of a reaction gas source acetylene is 20-60sccm, and a carbon layer is deposited in an interconnected pore channel of the three-dimensional porous alumina template;
and S13, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing the alumina template, and rinsing the product by using deionized water to obtain the three-dimensional integrated carbon tube grid film with adjustable tube diameter and spacing.
2. The method for preparing the three-dimensional integrated carbon tube grid film according to claim 1, wherein aluminum which is not subjected to anodic oxidation in the aluminum sheet is removed by a solution soaking method, and the method comprises the following specific steps: immersing an aluminum sheet in a mixed aqueous solution containing 0.1M of copper chloride and 12M of hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g of copper chloride and 500ml of a hydrochloric acid solution having a mass fraction of 37% with 500ml of water;
or removing the alumina template by chemical corrosion, wherein the corrosive liquid is hydrofluoric acid solution with the concentration of 35-45 wt%.
3. A three-dimensional integrated carbon tube mesh film prepared by the preparation method of claim 1 or 2.
4. A preparation method of a three-dimensional integrated carbon tube grid film is characterized by comprising the following steps:
s21, preparing a phosphoric acid aqueous solution with the concentration of 0.25-0.35M as an anodic oxidation electrolyte;
immersing an aluminum sheet containing trace impurities as a positive electrode and graphite as a negative electrode into an anodic oxidation electrolyte, and anodizing for 2-8 hours at the temperature of 0-5 ℃ and under the direct-current constant voltage of 185-195V;
after the anodic oxidation voltage is gradually reduced to 65-140V within 1-2 hours, the electrolyte is replaced by an aqueous solution containing 0.15M oxalic acid or an aqueous solution containing 0.05-0.25M oxalic acid and 0.03-0.07M phosphoric acid, and the anodic oxidation is carried out for 3-12 hours at the temperature of 8-12 ℃;
removing aluminum which is not subjected to anodic oxidation in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-10 minutes to prepare the three-dimensional porous alumina with interconnected pore channels;
s22, placing the three-dimensional porous alumina as a template in a tubular furnace for chemical vapor deposition, wherein the chemical vapor deposition pressure is (0.1-0.08) Mpa, the temperature is 900-1100 ℃, the time is 20-50 minutes, the flow of a reaction gas source acetylene is 20-60sccm, and a carbon layer is deposited in an interconnected pore channel of the three-dimensional porous alumina template;
and S23, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing the alumina template, rinsing the product by deionized water, and thus obtaining the three-dimensional integrated carbon tube grid film with adjustable tube diameter and spacing.
5. The method for preparing the three-dimensional integrated carbon tube grid film according to claim 4, wherein aluminum which is not subjected to anodic oxidation in the aluminum sheet is removed by a solution soaking method, and the method comprises the following specific steps: immersing an aluminum sheet in a mixed aqueous solution containing 0.1M of copper chloride and 12M of hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g of copper chloride and 500ml of a hydrochloric acid solution having a mass fraction of 37% with 500ml of water;
or removing the alumina template by chemical corrosion, wherein the corrosive liquid is hydrofluoric acid solution with the concentration of 35-45 wt%.
6. A three-dimensional integrated carbon tube mesh film prepared by the preparation method of claim 4 or 5.
7. An electric double layer capacitor device assembled from the three-dimensional integrated carbon tube mesh film of claim 3 or 6, characterized by being produced by the steps of:
and evaporating a gold film on one of the plain surfaces of the three-dimensional integrated carbon tube grid film, cutting the three-dimensional integrated carbon tube grid film into two symmetrical electrodes with the same area as a current collector, and injecting aqueous electrolyte into the two symmetrical electrodes after the two symmetrical electrodes are isolated by an aqueous diaphragm for packaging, or injecting organic electrolyte into the two symmetrical electrodes after the two symmetrical electrodes are isolated by an organic electrolyte diaphragm for packaging, thus obtaining the double-electric-layer capacitor device.
8. The electric double layer capacitor device of claim 7, wherein the aqueous electrolyte is a 0.8-1.2mol/L sulfuric acid solution.
9. The edlc device of claim 7, wherein the organic electrolyte is 0.8-1.2mol/L tetraethylammonium Tetrafluoroborate (TEABF) 4 。
10. The edlc device of claim 7, wherein the encapsulation is performed using a PET film encapsulation case or an aluminum plastic film encapsulation case.
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| US20100298135A1 (en) * | 2009-05-22 | 2010-11-25 | Mcgill University | Porous aluminum oxide templates |
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| US20100298135A1 (en) * | 2009-05-22 | 2010-11-25 | Mcgill University | Porous aluminum oxide templates |
| US20150371788A1 (en) * | 2013-01-22 | 2015-12-24 | Asahi Kasei Kabushiki Kaisha | Lithium Ion Capacitor |
| CN108217628A (en) * | 2018-02-10 | 2018-06-29 | 中国科学院合肥物质科学研究院 | Three-dimensional netted carbon nanotube and its preparation method and application |
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