CN115188602B - Three-dimensional integrated carbon tube grid film, preparation method thereof and capacitor device prepared by same - Google Patents
Three-dimensional integrated carbon tube grid film, preparation method thereof and capacitor device prepared by same Download PDFInfo
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- 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
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- 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
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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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 spacing of the porous anodic aluminum oxide interconnected by the three-dimensional pore canal are realized by regulating and controlling the electrolyte and controlling the anodic oxidation voltage, so that the three-dimensional integrated carbon pipe grid film with an orderly and adjustable structure is obtained, the vertical carbon pipes of the grid film are arranged relatively more tightly, the specific surface area of the electrochemical activity is larger and adjustable, the specific surface area of the electrode material can be increased, and the energy density of the super capacitor constructed by the electrode material is further improved. Meanwhile, gaps among the upright carbon tube units can provide smooth ion transport channels, and the three-dimensional structure of the integrated chemical bond connection ensures rapid transport of electrons, so that the electrode material can be used as an electrode material of a super capacitor 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
The carbon nano material such as carbon nano tube and graphene has the characteristics of high chemical stability, good conductivity and the like, and has wide application prospect in the fields of energy sources, catalysis and the like. The carbon tube array formed by upright carbon nano tube arrangement can be used as an electrode material for a quick response super capacitor because a straight ion transport channel can be provided in a parallel gap between the carbon tubes. However, as the length-diameter ratio of the carbon tube increases, the top ends of the carbon tube are easy to be clustered, so that the specific surface of the electrode is reduced, the capacity of the capacitor is reduced, the response speed is low, and the power performance is poor. Therefore, the self-supporting three-dimensional carbon tube structure can be designed and prepared, agglomeration between adjacent carbon tubes can be effectively prevented, and the self-supporting three-dimensional carbon tube structure has important significance for improving the performances of electrochemical energy storage devices such as super capacitors and the like.
The invention combines the anodic oxidation of aluminum sheets containing trace impurities in phosphoric acid electrolyte with the subsequent selective corrosion of impurities on the walls of a vertical hole alumina template to obtain a three-dimensional interconnected porous alumina template, and then utilizes a template hole geometry induced chemical vapor deposition method to prepare a three-dimensional interconnected carbon tube array grid film with transverse carbon nanotubes communicated between the vertical carbon nanotubes, which can effectively prevent the agglomeration between adjacent vertical carbon tubes, thereby hopefully improving the performance of the three-dimensional interconnected porous alumina template as an electrochemical capacitor electrode. However, as the aperture (-220 nm) and the spacing (-400 nm) of the vertical holes of the three-dimensional anodic aluminum oxide template are larger, the specific surface area of the obtained three-dimensional carbon tube grid film is smaller, the area specific capacitance of the three-dimensional carbon tube grid film serving as an electrode material of the super capacitor is limited, and the energy density of the capacitor is lower; and the pore size of the vertical holes in the porous alumina template is single, so that the nano-structures with controllable sizes such as vertical nano-tubes or nano-rods are difficult to prepare. How to regulate the pore diameter of the vertical pores in the three-dimensional interconnected porous alumina template, and further regulate the pipe diameter of the vertical carbon pipes in the three-dimensional interconnected carbon pipe grids, so that the three-dimensional interconnected porous alumina template has a larger specific surface area becomes important.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval. The three-dimensional integrated carbon pipe network 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 the device can be improved.
In order to achieve the above purpose, the present 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 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 oxalic acid in the mixed solution B is 0.1-0.2M, the concentration of 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 an anode and graphite as a cathode, immersing the anode into an anodic oxidation electrolyte, performing anodic oxidation for 6-24 hours at the temperature of 8-12 ℃ and under the direct current constant voltage of 55-140V, removing aluminum which is not anodized in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature of 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 tube 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 reaction gas source acetylene is 20-60sccm, and depositing a carbon layer in an interconnected pore canal of the three-dimensional porous alumina template;
and S13, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing an alumina template, and rinsing the product by deionized water to obtain the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval.
As the preparation method of the three-dimensional integrated carbon tube grid film, the preparation method is further improved:
preferably, the aluminum which is not anodized in the aluminum sheet is removed by a solution soaking method, and the specific steps are as follows: immersing the aluminum sheet in a mixed aqueous solution containing 0.1M copper chloride and 12M hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g copper chloride and 500ml hydrochloric acid solution having a mass fraction of 37% with 500ml water;
or removing the alumina template by chemical etching, wherein the etching solution is hydrofluoric acid solution with the concentration of 35-45 wt%.
The second object of the present invention is to provide a three-dimensional integrated carbon tube grid film produced by any one of the above production methods.
The invention further provides a preparation method of the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval, which 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 sheets containing trace impurities as a positive electrode and graphite as a negative electrode 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;
gradually reducing the anodic oxidation voltage to 65-140V within 1-2 hours, replacing the electrolyte with 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 performing anodic oxidation for 3-12 hours at 8-12 ℃;
then removing aluminum which is not anodized in the aluminum sheet, immersing the aluminum sheet into phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-10 minutes to prepare three-dimensional porous alumina with interconnected pore channels;
s22, placing the three-dimensional porous alumina as a template in a tube 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 reaction gas source acetylene is 20-60sccm, and depositing a carbon layer in an interconnected pore canal of the three-dimensional porous alumina template;
and S23, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing an alumina template, and rinsing the product by deionized water to obtain the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval.
As the preparation method of the three-dimensional integrated carbon tube grid film, the preparation method is further improved:
preferably, the aluminum which is not anodized in the aluminum sheet is removed by a solution soaking method, and the specific steps are as follows: immersing the aluminum sheet in a mixed aqueous solution containing 0.1M copper chloride and 12M hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g copper chloride and 500ml hydrochloric acid solution having a mass fraction of 37% with 500ml water;
or removing the alumina template by chemical etching, wherein the etching solution is hydrofluoric acid solution with the concentration of 35-45 wt%.
The invention also provides a three-dimensional integrated carbon tube grid film prepared by the preparation method.
The fifth object of the present invention is to provide an electric double layer capacitor device assembled by the three-dimensional integrated carbon pipe network grid film, which is prepared by the following steps:
and evaporating a gold film on one of the flat paved 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, taking the metal electrode plates as current collectors, and injecting aqueous electrolyte after isolating the two symmetrical electrodes by using an aqueous diaphragm for packaging, or injecting organic electrolyte after isolating the two symmetrical electrodes by using an organic electrolyte diaphragm for packaging, thus obtaining the double-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 tetraethylammonium Tetrafluoroborate (TEABF) with the concentration of 0.8-1.2mol/L 4 。
Preferably, the packaging is performed by adopting a PET film packaging shell or an aluminum plastic film packaging shell.
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 electrolyte, an aluminum sheet containing trace impurities is anodized under different voltages of 55-140V, then impurities in the walls of vertical holes are selectively corroded and reamed, an anodic aluminum oxide template of a three-dimensional interconnection pore channel is obtained, and the aperture and the pore spacing of the vertical holes of the aluminum oxide template of the three-dimensional pore can be adjusted.
2) The invention can also prepare the three-dimensional pore interconnected porous alumina template with Y-shaped or multi-branched vertical pore channels by performing anodic oxidation by taking phosphoric acid as electrolyte, then gradually reducing the voltage, and changing the electrolyte into oxalic acid or a mixed solution of oxalic acid and phosphoric acid for anodic oxidation. The porous alumina with the vertical pore diameter and the adjustable spacing and the three-dimensional interconnected pore canal is used as a template for chemical vapor deposition to grow the carbon tube, so that the three-dimensional integrated carbon tube grid membrane with the vertical carbon tube diameter and the adjustable 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 pipe network grid film with adjustable pipe diameter and spacing of the vertical carbon pipes, disclosed by the invention, the aperture and spacing of the vertical holes of the porous alumina are approximately linearly changed along with the voltage by controlling the anodic oxidation voltage of phosphoric acid, oxalic acid and mixed solution electrolyte of phosphoric acid and oxalic acid, so that the problem that transverse holes in the porous alumina are difficult to form under a lower voltage (160V) under the traditional condition is solved, and the adjustment of the vertical aperture of the three-dimensional interconnected porous anodic alumina from 100 to 200 nanometers and the vertical hole spacing from 150 to 300 nanometers is realized. Thus, the three-dimensional integrated carbon tube grid film with ordered and adjustable structure is obtained, a template is provided for the controllable preparation of the size of the vertical nano units in other nano structures with similar morphology and arrangement, and the application range of the three-dimensional interconnected porous anodic aluminum oxide template is widened. The three-dimensional integrated carbon tube grid is a stable structure with mutually connected transverse carbon tubes and vertical carbon tubes, the vertical carbon tubes can be vertical carbon tubes with uniform size, and can also be Y-shaped or multi-branch carbon tubes with hierarchical tube structures, and the carbon tube structures can be manually regulated and controlled.
4) The grid film prepared by the invention has relatively tighter vertical carbon tube arrangement, larger and adjustable electrochemical activity specific surface area, and can improve the specific surface area of electrode materials, thereby improving the energy density of super capacitors constructed by the grid film. Meanwhile, gaps among the upright carbon tube units can provide smooth ion transport channels, and the three-dimensional structure of the integrated chemical bond connection ensures rapid transport of electrons, so that the electrode material can be used as an electrode material of a super capacitor with high energy density, ultrahigh power density and good frequency response performance.
The carbon tube grid film is used as an electrode, and after the double-layer capacitor is assembled, the surface capacitance is realized at 120HzRespectively reach 2.7, 2.4 and 2.5mF/cm 2 The phase angles are about-71.7 degrees, -72.5 degrees, -77.6 degrees, respectively, showing good electrochemical performance and potential as a fast response supercapacitor.
Drawings
Fig. 1 is a schematic diagram of a preparation flow of 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 having vertical pore diameters of about 100 nm, 150 nm, and 200 nm, respectively, prepared in examples 1-3; fig. 2 (d-f) is a cross-sectional SEM photograph of the prepared three-dimensional integrated carbon tube grid film having vertical tube diameters of about 100 nm, 150 nm and 200 nm, respectively.
FIG. 3 (a) is a cross-sectional SEM photograph and an enlarged view (b) of a three-dimensional interconnected porous alumina template having "Y-shaped" vertical cells prepared in example 4; fig. 3 (c) is a cross-sectional SEM picture of the three-dimensional integrated carbon tube grid film in which the vertical carbon tube is prepared in a "Y-shape" and an enlarged view (d).
FIG. 4 (a, b) is a Cyclic Voltammetry (CV) curve at a sweep rate of 100mV/s to 500V/s for a three-dimensional integrated carbon tube grid film assembled supercapacitor of example 1 having a vertical tube diameter of about 100 nanometers; fig. 4 (c, d) is a constant current charge-discharge (GCD) curve.
Fig. 5 (a-c) are electrochemical properties of three-dimensional integrated carbon tube grid film assembled supercapacitor with vertical tube diameter of about 100 nm prepared in example 1: a bode plot (a), a nyquist plot (b), and an area specific capacitance versus frequency plot (c) obtained from an Electrochemical Impedance Spectrum (EIS); FIG. 5 (d) is a graph of pore size and spacing of vertical pores in a three-dimensionally interconnected porous anodized aluminum template at an anodic oxidation voltage of 55-140V, with a mixed acid solution of oxalic acid and phosphoric acid as an electrolyte.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
Aluminum sheet containing trace impurities (wherein the content distribution is that aluminum is more than or equal to 98%, copper is less than or equal to 0.15%, iron is less than or equal to 0.41%, and silicon is less than or equal to 0.05%)
The vertical pipe diameter refers to the outer diameter of a vertical carbon pipe in a three-dimensional integrated carbon pipe grid, and the pipe spacing refers to the distance between the centers of adjacent vertical carbon pipes.
Example 1
A preparation method of a three-dimensional integrated carbon tube frame with a vertical tube diameter of about 100 nanometers and a 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 oxalic acid in the mixed solution B is 0.1M, the concentration of 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 an anode and graphite as a cathode, carrying out anodic oxidation for 12 hours at 15 ℃ under a direct-current constant pressure of 55V, 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 placing the aluminum sheet in a 5wt% phosphoric acid solution at 40 ℃ to soak the aluminum sheet for 5 minutes to obtain a three-dimensional pore-channel interconnected porous anodic aluminum oxide template with the thickness of about 17 micrometers, the vertical pore diameter of about 100 nanometers and the interval of about 150 nanometers;
(2) Placing the three-dimensional pore passage interconnection porous anodic aluminum oxide template with the vertical pore diameter of about 100 nanometers obtained in the step (1) in a high-temperature tubular furnace, and reacting air source acetylene (C) at 1000 ℃ and under the vacuum degree of minus 0.1Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 20min, and the three-dimensional carbon pipe network grid film with the alumina template is obtained by carrying out surface plasma cleaning after cooling;
(3) And (3) placing the three-dimensional carbon pipe network grid film with the alumina template obtained in the step (2) in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template, and rinsing and drying the aluminum template to obtain the three-dimensional integrated carbon pipe frame with the vertical pipe diameter of about 100 nanometers and the interval 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 oxalic acid in the mixed solution B is 0.1M, the concentration of 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 an anode and graphite as a cathode, carrying out anodic oxidation for 15 hours at 10 ℃ under direct current constant pressure of 105V, placing the aluminum sheet into 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 placing the aluminum sheet into a 5wt% phosphoric acid solution at 40 ℃ to soak the aluminum sheet for 15 minutes to obtain a three-dimensional pore passage interconnection porous anodic aluminum oxide 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 passage interconnection porous anodic aluminum oxide template with the vertical pore diameter of about 150 nanometers obtained in the step (1) in a high-temperature tubular furnace, and reacting air source acetylene (C) at 1000 ℃ and under the vacuum degree of minus 0.1Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 30min, and the three-dimensional carbon pipe network grid film with the alumina template is obtained by carrying out surface plasma cleaning after cooling;
(3) And (3) placing the three-dimensional carbon pipe network grid film with the alumina template obtained in the step (2) in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template, and rinsing and drying the alumina template to obtain the three-dimensional integrated carbon pipe frame with the vertical pipe 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 oxalic acid in the mixed solution B is 0.1M, the concentration of 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 an anode and graphite as a cathode, carrying out anodic oxidation for 6 hours at 10 ℃ under 140V direct current constant pressure, placing the aluminum sheet 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 placing the aluminum sheet in a 5wt% phosphoric acid solution at 40 ℃ to soak the aluminum sheet for 20 minutes to obtain a three-dimensional interconnected pore porous anodic aluminum oxide template with the thickness of about 26 microns, the vertical pore diameter of about 200 nanometers and the interval of about 300 nanometers;
(2) Placing the three-dimensional pore passage interconnection porous anodic aluminum oxide template with the vertical pore diameter of about 200 nanometers obtained in the step (1) in a high-temperature tubular furnace, and reacting air source acetylene (C) at 1000 ℃ and under the vacuum degree of minus 0.1Mpa 2 H 4 ) The flow is 60sccm, the reaction time is 40min, and the three-dimensional carbon pipe network grid film with the alumina template is obtained by carrying out surface plasma cleaning after cooling;
(3) And (3) placing the three-dimensional carbon pipe network grid film with the alumina template obtained in the step (2) in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template, and rinsing and drying the aluminum template to obtain the three-dimensional integrated carbon pipe frame with the vertical pipe diameter of about 200 nanometers and the interval of about 300 nanometers.
Example 4
The preparation method of the three-dimensional integrated carbon tube frame with the Y-shaped vertical carbon tube comprises the following steps:
(1) Taking 0.3M phosphoric acid solution as electrolyte, taking aluminum sheets containing trace impurities as anode and graphite as cathode, and carrying out anodic oxidation for 2.5 hours under direct current constant pressure of 195V at 0 ℃;
(2) After the anodic oxidation voltage was gradually reduced 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 into a mixed solution of 0.1M copper chloride and 12M hydrochloric acid solution to corrode aluminum which is not anodized, and immersing the aluminum oxide into a phosphoric acid solution with the mass fraction of 5% for 10min at 40 ℃ to obtain three-dimensional pore-channel interconnected porous aluminum oxide with the thickness of about 10 microns and Y-shaped vertical pore channels;
(3) Placing the three-dimensional pore passage interconnection porous alumina with the Y-shaped vertical pore passage obtained in the step (2) in a high-temperature tubular furnace, and performing surface plasma cleaning after cooling at 1000 ℃ and under the vacuum degree of minus 0.1Mpa, wherein the flow of a reaction gas source acetylene (C2H 4) is 60sccm, the reaction time is 40min, so as to obtain the three-dimensional carbon pipe network grid membrane with the alumina template;
(4) And (3) placing the three-dimensional carbon pipe network grid film with the alumina template obtained in the step (3) in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template, and rinsing and drying to obtain the three-dimensional integrated carbon pipe frame with the Y-shaped vertical carbon pipe.
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 of which are shown in fig. 2 (a-c); cross-sectional Scanning Electron Microscope (SEM) pictures of the three-dimensional integrated carbon tube 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 anodic oxidation voltage, three-dimensional porous alumina templates having vertical pore diameters of about 100, 150 and 200 nm and pore pitches of about 150, 225 and 300 nm can be obtained, and after growing carbon tubes by chemical vapor deposition induced by template pores, three-dimensional integrated carbon tube frames having vertical pore diameters of about 100, 150 and 200 nm and pitches of about 150, 225 and 300 nm can be obtained.
The results of scanning SEM pictures of a three-dimensional interconnected porous alumina template with "Y-shaped" vertical channels and a three-dimensional integrated carbon tube frame with "Y-shaped" vertical carbon tubes of example 4 are shown in FIGS. 3 (a-d). From fig. 3, it can be seen that the three-dimensional porous alumina with the vertical pore canal of the hierarchical pore structure in the shape of Y and the three-dimensional integrated carbon tube frame with the vertical carbon tube in the shape of Y are successfully prepared.
Further, the three-dimensional integrated carbon pipe network grid film prepared in example 1 was assembled into an electric double layer capacitor: one of the surfaces of the grid film is evaporated with a layer of gold film, two samples with the same area and thickness are used as symmetrical electrodes, the samples are isolated by a diaphragm, and the capacitor is packaged in 0.1M sulfuric acid electrolyte, and the test results are as follows:
the electrochemical performance test of the three-dimensional integrated carbon tube frame prepared in example 1, which had a thickness of about 17 μm and a vertical tube diameter of about 100 nm and a pitch of about 150 nm, as an electrode material for an electric double layer capacitor, showed that, as shown in fig. 4, it was seen that: at a sweep rate of 100mV/s to 2000mV/s, the CV curves are all nearly rectangular in shape, exhibiting nearly ideal double layer capacitor characteristics; and at a high scanning speed of 500V/s, the constant-current charge-discharge test result can still maintain a nearly rectangular shape, and the constant-current charge-discharge test result is an ideal isosceles triangle and shows typical double-electric-layer characteristics. This demonstrates that the prepared three-dimensional integrated carbon tube frame with the vertical tube diameter of about 100 nanometers has better power performance when applied to an electrode of an electric double layer capacitor.
Meanwhile, in order to further prove the superiority of the three-dimensional integrated carbon tube frame with the thickness of about 17 micrometers, the vertical tube diameter of about 100 nanometers and the interval of about 150 nanometers, which is prepared by the method, the electrochemical impedance spectrum test is carried out by taking the sample obtained in the example 1 as the electrode material of the double-layer super capacitor, and the result is shown in figure 5. The sample obtained in example 1 has an imaginary resistance in the Nyquist plot close to perpendicular to the real axis, shows ideal capacitive characteristics, and has a small equivalent series resistance (1.2 Ω); in the Bode graph reflecting the relationship between the phase angle and the frequency, the phase angle of the low frequency region is close to-90 degrees, which also shows the characteristics of an ideal capacitor, and the phase angle is-71.7 degrees at the frequency of 100-120Hz, which shows good rapid frequency response capability, and shows effective ion transport and electron conduction in the electrode. The area specific capacitance at 120Hz frequency can reach very high 2.7mF/cm 2 . It can be seen that the three-dimensional integrated carbon tube frame prepared in example 1 has a vertical tube diameter of about 100 nm and a spacing of about 150 nm, and has a high area specific capacitance and good frequency response performance. This is because the three-dimensional integrated carbon tube frame having a vertical tube diameter of about 100 nm and a pitch of about 150 nm has a higher active material load, thereby increasing the electrochemical activity specific surface area. The carbon tube structure of the interconnection of the transverse carbon tube and the vertical carbon tube also improves the conductivity of the electrode material, and the vertical carbon tube with the vertical opening provides a smooth channel for rapid ion transport, so that the three-dimensional integrated carbon tube frame with the vertical tube diameter of about 100 nanometers and the interval of about 150 nanometers has good frequency response performance when the three-dimensional integrated carbon tube frame is used as the electrode material of the supercapacitor.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (10)
1. The preparation method of the three-dimensional integrated carbon tube grid film is characterized by comprising the following steps of:
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 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 oxalic acid in the mixed solution B is 0.1-0.2M, the concentration of 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 an anode and graphite as a cathode, immersing the anode into an anodic oxidation electrolyte, performing anodic oxidation for 6-24 hours at the temperature of 8-12 ℃ and under the direct current constant voltage of 55-140V, removing aluminum which is not anodized in the aluminum sheet, immersing the aluminum sheet into a phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature of 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 tube 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 reaction gas source acetylene is 20-60sccm, and depositing a carbon layer in an interconnected pore canal of the three-dimensional porous alumina template;
and S13, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing an alumina template, and rinsing the product by deionized water to obtain the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval.
2. The method for preparing the three-dimensional integrated carbon tube grid film according to claim 1, wherein the method for removing aluminum in the aluminum sheet which is not anodized by a solution soaking method comprises the following specific steps: immersing the aluminum sheet in a mixed aqueous solution containing 0.1M copper chloride and 12M hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g copper chloride and 500ml hydrochloric acid solution having a mass fraction of 37% with 500ml water;
or removing the alumina template by chemical etching, wherein the etching solution is hydrofluoric acid solution with the concentration of 35-45 wt%.
3. A three-dimensional integrated carbon tube grid film produced by the production method of claim 1 or 2.
4. The preparation method of the three-dimensional integrated carbon tube grid film is characterized by comprising the following steps of:
s21, preparing a phosphoric acid aqueous solution with the concentration of 0.25-0.35M as an anodic oxidation electrolyte;
immersing aluminum sheets containing trace impurities as a positive electrode and graphite as a negative electrode 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;
gradually reducing the anodic oxidation voltage to 65-140V within 1-2 hours, replacing the electrolyte with 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 performing anodic oxidation for 3-12 hours at 8-12 ℃;
then removing aluminum which is not anodized in the aluminum sheet, immersing the aluminum sheet into phosphoric acid solution with the concentration of 5-10wt%, and keeping the temperature at 35-45 ℃ for 5-10 minutes to prepare three-dimensional porous alumina with interconnected pore channels;
s22, placing the three-dimensional porous alumina as a template in a tube 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 reaction gas source acetylene is 20-60sccm, and depositing a carbon layer in an interconnected pore canal of the three-dimensional porous alumina template;
and S23, cooling the deposited sample to room temperature, cleaning a carbon layer on the surface, removing an alumina template, and rinsing the product by deionized water to obtain the three-dimensional integrated carbon tube grid film with adjustable pipe diameter and interval.
5. The method for preparing the three-dimensional integrated carbon tube grid film according to claim 4, wherein the method for removing aluminum in the aluminum sheet which is not anodized by a solution soaking method comprises the following specific steps: immersing the aluminum sheet in a mixed aqueous solution containing 0.1M copper chloride and 12M hydrochloric acid, the mixed aqueous solution being obtained by mixing 17g copper chloride and 500ml hydrochloric acid solution having a mass fraction of 37% with 500ml water;
or removing the alumina template by chemical etching, wherein the etching solution is hydrofluoric acid solution with the concentration of 35-45 wt%.
6. A three-dimensional integrated carbon tube grid film produced by the production method of claim 4 or 5.
7. An electric double layer capacitor device assembled from the three-dimensional integrated carbon network grid film of claim 3 or 6, characterized by being prepared by the steps of:
and evaporating a gold film on one of the flat paved 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, taking the metal electrode plates as current collectors, and injecting aqueous electrolyte after isolating the two symmetrical electrodes by using an aqueous diaphragm for packaging, or injecting organic electrolyte after isolating the two symmetrical electrodes by using an organic electrolyte diaphragm for packaging, thus obtaining the double-layer capacitor device.
8. The electric double layer capacitor device according to claim 7, wherein the aqueous electrolyte is a sulfuric acid solution of 0.8 to 1.2 mol/L.
9. The electric double layer capacitor device of claim 7, wherein the organic electrolyte is 0.8-1.2mol/L tetraethylammonium tetrafluoroborate, TEABF 4 。
10. The electric double layer capacitor device according to claim 7, wherein the encapsulation is performed using a PET film encapsulation case or an aluminum plastic film encapsulation case.
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