Method for growing carbon nanotube array through in-situ pinning of metal foil

Abstract

The invention discloses a method for growing a carbon nanotube array by pinning a metal foil in situ, which comprises the following steps of: modifying the metal foil by adopting a dry-method treatment process or a wet-method treatment process to prepare a metal foil with a nano honeycomb structure, the metal foil with the nano honeycomb structure is characterized in that the surface of the metal foil is of a graded porous structure formed by orderly nesting and combining macropores, mesopores and micropores; a catalyst is deposited on the metal foil with the nano honeycomb structure, and metal elements in the catalyst at least comprise Fe and Co; and placing the nano honeycomb structure metal foil deposited with the catalyst in a CVD furnace, and promoting in-situ pinning growth of the carbon nanotube array on the nano honeycomb structure metal foil by adjusting the temperature, the gas flow and the time. The metal foil in-situ pinning growth carbon nanotube array prepared by the method disclosed by the invention is small in pipe diameter and long in length, so that the metal foil in-situ pinning growth carbon nanotube array has higher conductivity, the carbon nanotube array is firmly combined with the aluminum foil, and the bending resistance of the metal foil in-situ pinning growth carbon nanotube array is improved by 2-3 times compared with that of a commercial current collector aluminum foil.

Description

Technical Field

[0001] The invention relates to the technical field of carbon nanotube array preparation, and in particular to a method for growing a carbon nanotube array by in-situ pinning of a metal foil. Background Art

[0002] There are many methods for preparing carbon nanotube arrays, including chemical vapor deposition (CVD), arc discharge, laser ablation, etc. Among them, CVD has become one of the most commonly used preparation methods due to its advantages such as simple operation, easy control of growth conditions, and fast growth rate.

[0003] The existing technology usually places aluminum foil loaded with catalyst powder in a porcelain boat and sends it into a horizontal chemical vapor deposition furnace. Then, under the protection of high-purity nitrogen, the temperature is raised to the reaction temperature (such as 700-800°C), and a carbon source gas (such as acetylene) is introduced. Under the action of the catalyst, carbon atom clusters are cracked to form carbon nanotubes, which are then deposited on the surface of the aluminum foil to form carbon nanotubes. Finally, by adjusting growth conditions such as temperature, gas flow rate, pressure and other parameters, the growth rate and growth direction of the carbon nanotubes are controlled, thereby achieving the growth of carbon nanotube arrays.

[0004] However, the existing carbon nanotube preparation method often faces the problem of weak bonding between the carbon nanotubes and the aluminum foil substrate. Usually, due to the inaccurate control of growth conditions, uneven catalyst loading, and uneven size and activity of catalyst particles, the prepared carbon nanotube array cannot form an ideal orderly arrangement, but presents a disorderly distribution state, which seriously affects the overall performance of the carbon nanotube array, such as conductivity and mechanical strength. Therefore, the existing technology needs to be improved and developed. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a method for in-situ pinning growth of carbon nanotube arrays on metal foil, aiming to solve the problems of the prior art that the carbon nanotube arrays prepared on metal foil have disordered arrangement, weak bonding, excessively large tube diameters and large differences in tube diameters.

[0006] The technical solution of the present invention is as follows:

[0007] A method for growing a carbon nanotube array by in-situ pinning of a metal foil, comprising the steps of:

[0008] The metal foil is modified by a dry treatment process or a wet treatment process to obtain a nano honeycomb structure metal foil, wherein the nano honeycomb structure metal foil refers to a metal foil surface presenting a hierarchical porous structure composed of macropores, mesopores and micropores in an orderly nested combination, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm, and the metal foil is one of copper foil and aluminum foil;

[0009] A catalyst is deposited on a nano honeycomb structure metal foil by a sol-gel method, wherein the metal elements in the catalyst include at least two types of Fe and Co;

[0010] The nano honeycomb structure metal foil with the catalyst deposited thereon is placed in a CVD furnace, the vacuum pump is turned on to evacuate the CVD furnace and inert gas is introduced to remove the air in the furnace, and then the CVD furnace is heated to 400-450°C at a heating rate of 8-12°C / min, and hydrogen and inert gas are then injected;

[0011] Continue to heat the CVD furnace to 450-630°C and keep it warm for 5-40 minutes, then turn on the vacuum pump to evacuate, start injecting acetylene after evacuating the vacuum, and simultaneously introduce carbon dioxide and hydrogen to normal pressure, further introduce inert gas, carbon dioxide, and acetylene, and start exhausting after 5-40 minutes to maintain normal pressure. After the insulation is completed, introduce inert gas to naturally cool down. After the reaction is completed, a carbon nanotube array is pinned in situ on the surface of the nano-honeycomb structure metal foil to grow.

[0012] The method for in-situ pinning and growing carbon nanotube arrays by metal foil, wherein the steps of modifying the metal foil by a dry treatment process to obtain the nano honeycomb structure metal foil include:

[0013] In a vacuum environment, an inert gas is introduced, and the surface of the metal foil is bombarded for 1-30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the metal foil;

[0014] Continue to use a pulse laser to laser process the metal foil that has been micro-etched, wherein the pulse laser has a laser wavelength of 350-360 nm, a power of 1-20 W, a pulse frequency of 20-50 KHZ, a spot size controlled at 500 nm-1 μm, and a scanning speed controlled at 100-400 mm / s;

[0015] In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated metal foil for 5-15 seconds, and the oxygen flow rate is controlled to be 50-300 sccm, so as to form a dense and uniform aluminum oxide protective film layer on the surface of the metal foil;

[0016] In a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 50-400sccm, the etching gas flow rate is controlled to be 200-500sccm, the current is 1-2A, the voltage is 1000V-1500V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized metal foil for 20-40S;

[0017] In a vacuum environment, an inert gas is introduced, the gas flow rate is controlled to be 50-100sccm, the current is 0.1A-1A, and the voltage is 200V-500V. The metal foil is etched again for 2-10S using a high-energy ion beam generated by a radio frequency ion source, and finally a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores is etched on the surface of the metal foil to obtain the nano honeycomb structure metal foil.

[0018] The method for in-situ pinning and growing a carbon nanotube array by metal foil comprises the following steps: modifying the metal foil by a wet treatment process to obtain a nano honeycomb structure metal foil:

[0019] In a vacuum environment, an inert gas is introduced, and the surface of the metal foil is bombarded for 1-30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the metal foil;

[0020] In a vacuum environment, an etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to micro-etch the bombarded metal foil for 1-20 seconds, wherein the gas flow rate is controlled to be 20-500 sccm, the current is 0.05-2A, and the voltage is 500V-1500V;

[0021] The metal foil after micro-etching is placed in an electrolyte for electrochemical etching for 12-80 seconds, the temperature is 15-60°C, the frequency is 20-50Hz, and the processing voltage is 1-6V; then, it is washed in deionized water at 15-60°C for 2-20S, and then it is subjected to strong acid or strong alkali corrosion treatment at 20-60°C for 4-20S, and finally, it is washed in deionized water at 15-60°C for 2-20S to obtain the electrochemically etched metal foil;

[0022] The electrochemically etched metal foil is further subjected to a multi-stage electrochemical treatment: in the first stage, electrochemically formed in one or more mixed solutions of 0.2%-4% adipic acid, 0.5%-5% sodium chloride, 0.3%-6% oxalic acid, and 0.02%-8% hydrochloric acid, with a conductivity of 5-40 μs / cm, a pH of 4.0-7.0, a voltage of 0.1-2V, a temperature of 60-100°C, a treatment time of 40-100S, and then washed in deionized water at 20-60°C for 2-20S; in the second stage, electrochemically formed in 0.1%-5% azelaic acid, 0.5%-5 % sodium chloride, 0.3%-6% oxalic acid, 0.02%-8% hydrochloric acid, one or more mixed solutions are added for electrochemical formation, the conductivity is 10-50μs / cm, the pH is 4.0-7.0, the voltage is 0.8-2.5V, the temperature is 60-100℃, the processing time is 40-100S, and then washed in deionized water at 20-60℃ for 2-20S; the third stage, in one or more mixed solutions of 0.1%-5% azelaic acid, 0.3%-6% oxalic acid, 0.02%-8% hydrochloric acid, the conductivity is 10-50μs / cm, pH 4.0-7.0, voltage 2-4V, temperature 60-100℃, treatment time 40-100S, followed by 20-60℃ deionized water cleaning for 2-20S; the fourth stage, electrochemically formed in one or more mixed solutions of 0.1%-5% adipic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, 0.05%-6% phosphoric acid, conductivity 10-50μs / cm, pH 4.0-7.0, voltage 3-5V, temperature 60-100℃, treatment time 40-100S , then wash in deionized water at 20-60℃ for 2-20S; the fifth stage, electrochemically formed in one or more mixed solutions of 0.1%-5% azelaic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, and 0.05%-6% phosphoric acid, with a conductivity of 10-50μs / cm, a pH of 4.0-7.0, a voltage of 4-6V, a temperature of 60-100℃, and a treatment time of 40-100S, then wash in deionized water at 20-60℃ for 2-20S; finally enter the oven for treatment at 160-300℃ for 2-10 minutes;

[0023] In a vacuum environment, etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to etch the metal foil that has undergone powered multi-stage chemical treatment for 2-10S. The gas flow rate is controlled to be 50-100sccm, the current is 0.1A-1A, and the voltage is 200V-500V. Finally, a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores is etched on the surface of the metal foil to obtain a nano honeycomb structure metal foil, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

[0024] The method for in-situ pinning of a metal foil to grow a carbon nanotube array, wherein the inert gas is one or both of nitrogen and argon; and the etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride.

[0025] The method for in-situ pinning growth of carbon nanotube arrays by metal foil, wherein the catalyst is one of an iron-cobalt-nickel catalyst, an iron-cobalt-magnesium catalyst, an iron-cobalt-nickel-molybdenum catalyst, an iron-cobalt-nickel-manganese catalyst and an iron-cobalt-nickel-magnesium-manganese catalyst, the mass ratio of Fe, Co and Ni in the iron-cobalt-nickel catalyst is 15:15:1-3:3:1, the mass ratio of Fe, Co and Mg in the iron-cobalt-magnesium catalyst is 25:15:1-5:3:1, the mass ratio of Fe, Co, Ni and Mo in the iron-cobalt-nickel-molybdenum catalyst is 10:15:5:1-4:6:3:1, the mass ratio of Fe, Co, Ni and Mn in the iron-cobalt-nickel-manganese catalyst is 15:25:20:1-3:5:4:1, and the mass ratio of Fe, Co, Ni, Mg and Mn in the iron-cobalt-nickel-magnesium-manganese catalyst is 20:30:25:25:1-2:6:4:4:1.

[0026] The method for growing a carbon nanotube array by in-situ pinning of metal foil, wherein the particle size of the catalyst is 1-5 nm.

[0027] The method for in-situ pinning and growing a carbon nanotube array by metal foil, wherein the particle size of the carbon nanotubes in-situ pinned and grown on the surface of the metal part of the nano honeycomb structure is 2-30nm, and the length of the carbon nanotubes is 5-200μm.

[0028] A metal foil in-situ pinning growth carbon nanotube array material is prepared by any of the metal foil in-situ pinning growth carbon nanotube array methods of the present invention.

[0029] An application of a metal foil in-situ pinning growth carbon nanotube array material, wherein the metal foil in-situ pinning growth carbon nanotube array material of the invention is used to prepare a positive electrode sheet or a negative electrode sheet of a battery.

[0030] Beneficial effects: The nano honeycomb structure metal foil prepared by the method of the present invention provides abundant nucleation sites and a good mechanical anchoring foundation for the growth of carbon nanotubes, so that the carbon nanotubes can be tightly and firmly attached thereto, thereby realizing the in-situ pinning growth of carbon nanotube arrays on the metal foil, and effectively solving the problem of easy detachment of carbon nanotubes; the conductivity of the metal foil in-situ pinning growth carbon nanotube array material prepared by the present invention is significantly improved compared with the commercial current collector aluminum foil; the metal foil in-situ pinning growth carbon nanotube array material has high strength and good flexibility, and has a 2-3 times improvement in anti-bending performance compared with the commercial high specific surface area current collector foil; the carbon nanotube array in-situ pinning growth on the surface of the metal foil is arranged and wound regularly, the particle size of the carbon nanotubes is 2-30nm, the length is between 5-200 microns, and its specific surface area is also significantly improved compared with aluminum foil. The metal foil in-situ pinned growth carbon nanotube array material prepared by the present invention exhibits stronger interface bonding force, providing possibility for its application in high-end fields; the metal foil in-situ pinned growth carbon nanotube array material is used to prepare solid-state batteries, lithium-sulfur batteries, fluorine-lithium-manganese-based battery positive electrodes or battery negative electrodes. In battery applications, its high conductivity can reduce the ohmic resistance of the electrode and improve the battery's charge and discharge efficiency; the large specific surface area can provide more active sites for electrochemical reactions, thereby improving the battery's capacity and cycle stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The present invention is a flow chart of a method for growing carbon nanotube arrays based on in-situ pinning of metal foil.

[0032] Figure 2 This is an electron microscope image of the nano honeycomb structure aluminum foil prepared by the wet treatment process in Example 1 at a molecular scale of 100 nm.

[0033] Figure 3 This is an electron microscope image of the nano honeycomb structure aluminum foil prepared by the dry treatment process in Example 9 at a molecular scale of 100 nm.

[0034] Figure 4 This is a cross-sectional electron microscope image of the metal foil in-situ pinned growth carbon nanotube array material prepared in Example 1 at a scale of 20 μm.

[0035] Figure 5 This is a cross-sectional electron microscope image of the metal foil in-situ pinned growth carbon nanotube array material prepared in Example 9 at a scale of 4 μm.

[0036] Figure 6 a and b are plane electron microscope images of the metal foil in-situ pinned growth carbon nanotube array material in Example 1 at scales of 1 μm and 200 nm respectively; Figure 6Figures c and d are cross-sectional electron micrographs of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 1 at scales of 1 μm and 200 nm, respectively.

[0037] Figure 7 This is a plane electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 4 at a scale of 1 μm.

[0038] Figure 8 This is a cross-sectional electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 4 at a scale of 200 nm.

[0039] Fig. 9 This is a plane electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 7 at a scale of 1 μm.

[0040] Fig.10 This is a cross-sectional electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 7 at a scale of 200 nm.

[0041] Fig.11 This is a cross-sectional electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 9 at a scale of 200 nm.

[0042] Fig.12 This is a cross-sectional electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 9 at a scale of 400 nm.

[0043] Fig.13 This is a cross-sectional electron microscope image of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 11 at a scale of 200 nm.

[0044] Fig.14 This is a cross-sectional electron microscope image of the in-situ pinned growth carbon nanotube array material on aluminum foil in Example 13 at a scale of 1 μm.

[0045] Fig.15 This is a cross-sectional electron microscope image of the in-situ pinning growth carbon nanotube array material by corroding aluminum foil in Example 14 at a scale of 2 μm.

[0046] Fig.16 This is the Raman image of the metal foil in-situ pinned growth carbon nanotube array material prepared in Example 1.

[0047] Fig.17 This is a BET test diagram of the carbon nanotube array material grown by in-situ pinning of metal foil in Example 1. DETAILED DESCRIPTION

[0048] The present invention provides a method for in-situ pinning of a metal foil to grow a carbon nanotube array. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0049] See also Figure 1 , Figure 1 The present invention provides a method for in-situ pinning of a metal foil to grow a carbon nanotube array, which comprises the following steps:

[0050] S10, modifying the metal foil by a dry treatment process or a wet treatment process to obtain a nano honeycomb structure metal foil, wherein the nano honeycomb structure metal foil refers to a metal foil having a hierarchical porous structure formed by orderly nesting of macropores, mesopores and micropores on the surface, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm, and the metal foil is one of copper foil and aluminum foil;

[0051] S20, depositing a catalyst on the nano honeycomb structure metal foil by a sol-gel method, wherein the metal elements in the catalyst include at least two kinds of Fe and Co;

[0052] S30, placing the nano honeycomb structure metal foil deposited with the catalyst in a CVD furnace, first turning on the vacuum pump to evacuate the CVD furnace and introducing an inert gas to remove air from the furnace, then heating the CVD furnace to 400-450° C. at a heating rate of 8-12° C. / min, and then injecting hydrogen and inert gas;

[0053] S40, continue to heat the CVD furnace to 450-630°C and keep it warm for 5-40 minutes, then turn on the vacuum pump to evacuate, after evacuating, start injecting acetylene and simultaneously introduce carbon dioxide and hydrogen to normal pressure, further introduce inert gas, carbon dioxide and acetylene, and start exhausting after 5-40 minutes to maintain normal pressure, after the insulation is completed, introduce inert gas to naturally cool down, and after the reaction is completed, in-situ pinning and growth of carbon nanotube arrays are carried out on the surface of the nano honeycomb structure metal foil.

[0054] Specifically, the present invention firstly uses a dry treatment process or a wet treatment process to modify the metal foil, so that the surface of the metal foil presents a hierarchical porous structure composed of macropores, mesopores and micropores in an orderly nested combination, that is, a nano honeycomb structure metal foil is obtained, the macropore diameter is 100-500μm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.5-1nm. In the present invention, the metal foil is one of copper foil and aluminum foil, wherein the aluminum foil can be any one of plain aluminum foil, corroded aluminum foil and aluminum carbon foil, the plain aluminum foil refers to aluminum foil that has not been subjected to special process treatments such as embossing, coating, corrosion, and chemical formation, and has a smooth surface, maintaining the original characteristics of the metal itself; the corroded aluminum foil refers to aluminum foil that has been corroded; the aluminum carbon foil refers to aluminum foil that has carbon elements introduced into the surface of the aluminum foil by physical or chemical methods.

[0055] The present invention selects the specially treated nano honeycomb structure metal foil as the substrate for in-situ pinning growth of carbon nanotube array. This special structure provides abundant nucleation sites and good mechanical anchoring foundation for the subsequent growth of carbon nanotubes, and the carbon tubes can directly contact the metal foil, so that the carbon nanotubes can be tightly and firmly attached thereto, effectively solving the problem that the carbon nanotubes are easy to fall off. Then, the present invention directly deposits the catalyst on the aluminum foil by the sol-gel method, and then undergoes high-temperature treatment in a CVD furnace to achieve in-situ pinning growth of carbon nanotubes on the surface of the nano honeycomb structure metal foil. This process avoids cumbersome transfer steps and improves preparation efficiency and material integrity. The present invention can optimize the activity of the catalyst by adjusting the mass ratio of the catalyst constituent elements, thereby facilitating the growth of carbon nanotubes, and promoting the prepared carbon nanotubes to have uniform diameters, smooth tube walls, and less impurities; based on the selected catalyst layer material and component ratio and the selected carbon source acetylene, the present invention accurately controls the reaction temperature and reaction time through experiments, optimizes the growth process of the carbon nanotubes, and thereby obtains a carbon nanotube array with regular arrangement and winding, suitable length, and better performance.

[0056] The carbon nanotubes themselves have excellent electrical conductivity, and the thinner the diameter and the longer the length, the better the electrical conductivity. The carbon nanotube arrays grown by in-situ pinning on the surface of the nano honeycomb structure metal foil are intertwined and wound by the method of the present invention. The particle size of the carbon nanotubes is 2-30nm and the length is between 5-200 microns. Due to the regular arrangement, small particle size and moderate length, a good conductive network is formed, thereby improving the electrical conductivity of the material. Experimental data show that the electrical conductivity of the in-situ grown carbon nanotube array material of aluminum foil prepared by the method of the present invention is 3.94*10 7 s / m or more, which is 3.75*10 relative to aluminum foil 7s / m, the electrical conductivity is improved by about 6%; carbon nanotubes have extremely high elasticity and toughness, the Young's modulus is nearly 6 times that of steel, and the tensile strength is 100 times that of steel. The carbon nanotube array grown on the surface of the aluminum foil of the present invention can significantly improve the strength and flexibility of the material, especially in the bending resistance process, the interlocking high-elastic carbon nanotube array can maintain good conductivity and mechanical properties, and the bending resistance is improved by 10-40% compared with the current collector aluminum foil; the carbon nanotube array has a high specific surface area, and the specific surface area of ​​the composite foil is increased by more than 50 times compared with the pure aluminum foil. The high specific surface area can provide abundant storage space and transportation channels for lithium ions, which is beneficial to its application in lithium ion batteries and other fields.

[0057] In some embodiments, the step of modifying the metal foil by a dry treatment process to obtain a nano honeycomb structure metal foil includes: in a vacuum environment, introducing an inert gas, bombarding the surface of the metal foil with a high-energy ion beam generated by an anode layer ion source for 1-30 seconds to remove impurities on the surface of the metal foil; continuing to use a pulsed laser to laser treat the metal foil that has been micro-etched, wherein the laser wavelength of the pulsed laser is 350-360nm, the power is 1-20W, the pulse frequency is 20-50KHZ, the spot size is controlled at 500nm-1μm, and the scanning speed is controlled at 100-400mm / s; in a vacuum environment, introducing oxygen to pre-oxidize the metal foil that has been laser-treated for 5-15s, controlling the oxygen flow rate to 50-300sccm, and forming a nanostructured metal foil on the surface of the metal foil. The method comprises the following steps: introducing oxygen and etching gas in a vacuum environment, controlling the oxygen flow rate to be 50-400sccm, the etching gas flow rate to be 200-500sccm, the current to be 1-2A, the voltage to be 1000V-1500V, and using a high-energy ion beam generated by a radio frequency ion source to etch the pre-oxidized metal foil for 20-40S; introducing inert gas in a vacuum environment, controlling the gas flow rate to be 50-100sccm, the current to be 0.1A-1A, the voltage to be 200V-500V, and using a high-energy ion beam generated by a radio frequency ion source to continue etching the metal foil for another 2-10S, and finally etching a hierarchical porous structure composed of orderly nested combinations of macropores, mesopores and micropores on the surface of the metal foil to obtain the nano honeycomb structure metal foil. In this embodiment, the inert gas is one of nitrogen and argon; the etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride, but is not limited thereto.

[0058] In some embodiments, the steps of modifying the metal foil by a wet treatment process to obtain the nano honeycomb structure metal foil include: in a vacuum environment, introducing an inert gas, bombarding the surface of the metal foil with a high-energy ion beam generated by an anode layer ion source for 1-30 seconds to remove impurities on the surface of the metal foil; in a vacuum environment, introducing an etching gas, and micro-etching the bombarded metal foil with a high-energy ion beam generated by a radio frequency ion source for 1-20 seconds, wherein the gas flow rate is controlled to be 20-500sccm, the current is 0.05-2A, and the voltage is 500V-1500V; placing the micro-etched metal foil in an electrolyte for electrochemical etching for 12-80 seconds at a temperature of 15-6 0℃, frequency is 20-50Hz, and processing voltage is 1-6V; then, after washing in 15-60℃ deionized water for 2-20S, strong acid or strong alkali corrosion treatment is performed at 20-60℃ for 4-20S, and finally, it is washed in 15-60℃ deionized water for 2-20S to obtain electrochemically etched metal foil; the electrochemically etched metal foil is further subjected to multi-stage electrochemical treatment: in the first stage, electrochemically formed in one or more mixed solutions of 0.2%-4% adipic acid, 0.5%-5% sodium chloride, 0.3%-6% oxalic acid, and 0.02%-8% hydrochloric acid, the conductivity is 5-40μs / cm, the pH is 4.0-7.0, the voltage is 0.1-2V, the temperature is 60-100℃, and the treatment time is 40-100S, followed by 20-60℃ deionized water cleaning for 2-20S; the second stage, electrochemically formed in one or more mixed solutions of 0.1%-5% azelaic acid, 0.5%-5% sodium chloride, 0.3%-6% oxalic acid, and 0.02%-8% hydrochloric acid, with a conductivity of 10-50μs / cm, a pH of 4.0-7.0, a voltage of 0.8-2.5V, a temperature of 60-100℃, a processing time of 40-100S, followed by 20-60℃ deionized water cleaning for 2-20S; the third stage, electrochemically formed in one or more mixed solutions of 0.1%-5% azelaic acid, 0.3%-6% oxalic acid, and 0.02%-8% hydrochloric acid, with a conductivity of 10-50μs / cm, P H is 4.0-7.0, voltage is 2-4V, temperature is 60-100℃, treatment time is 40-100S, and then it is washed in deionized water at 20-60℃ for 2-20S; the fourth stage, it is electrochemically formed in one or more mixed solutions of 0.1%-5% adipic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, and 0.05%-6% phosphoric acid, with a conductivity of 10-50μs / cm, pH of 4.0-7.0, voltage of 3-5V, temperature of 60-100℃, treatment time is 40-100S, and then it is washed in deionized water at 20-60℃ for 2-20S; the fifth stage, it is electrochemically formed in 0.1%-5% azelaic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, 0.05%-6% phosphoric acid.0.5%-6% phosphoric acid or one or more mixed solutions are electrochemically formed, the conductivity is 10-50μs / cm, the pH is 4.0-7.0, the voltage is 4-6V, the temperature is 60-100℃, the processing time is 40-100S, and then it is washed in 20-60℃ deionized water for 2-20S; finally, it is placed in an oven at 160-300℃ for 2-10 minutes; in a vacuum environment, etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to etch the The metal foil subjected to the multi-stage electrochemical treatment is etched for 2-10S, the gas flow rate is controlled to be 50-100sccm, the current is 0.1A-1A, and the voltage is 200V-500V, and finally a hierarchical porous structure composed of macropores, mesopores and micropores is formed on the surface of the metal foil in an orderly nested combination, so as to obtain a nano honeycomb structure metal foil, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm. In this embodiment, the inert gas is one or both of nitrogen and argon; the etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride, but is not limited thereto. .

[0059] In some embodiments, the catalyst is one of an iron-cobalt-nickel catalyst, an iron-cobalt-magnesium catalyst, an iron-cobalt-nickel-molybdenum catalyst, an iron-cobalt-nickel-manganese catalyst and an iron-cobalt-nickel-magnesium-manganese catalyst, the mass ratio of Fe, Co and Ni in the iron-cobalt-nickel catalyst is 15:15:1-3:3:1, the mass ratio of Fe, Co and Mg in the iron-cobalt-magnesium catalyst is 25:15:1-5:3:1, the mass ratio of Fe, Co, Ni and Mo in the iron-cobalt-nickel-molybdenum catalyst is 10:15:5:1-4:6:3:1, the mass ratio of Fe, Co, Ni and Mn in the iron-cobalt-nickel-manganese catalyst is 15:25:20:1-3:5:4:1, and the mass ratio of Fe, Co, Ni, Mg and Mn in the iron-cobalt-nickel-magnesium-manganese catalyst is 20:30:25::25:1-2:6:4:4:1. This embodiment can optimize the activity of the catalyst by adjusting the mass ratio of the catalyst constituent elements, thereby facilitating the growth of carbon nanotubes and making the prepared carbon nanotubes uniform in diameter, smooth in wall and less in impurities.

[0060] In some embodiments, the particle size of the iron-cobalt-nickel based catalyst is in the range of 1-5 nm. For example, the deposition times may be 1 time, 3 times, 5 times, etc., but is not limited thereto.

[0061] In some embodiments, a metal foil in-situ pinned carbon nanotube array material is also provided, wherein the material is prepared by any of the metal foil in-situ pinned carbon nanotube array methods of the present invention.

[0062] In some embodiments, an application of a metal foil in-situ pinned carbon nanotube array material is also provided, wherein the metal foil in-situ pinned carbon nanotube array material of the present invention is used to prepare a positive electrode sheet or a negative electrode sheet of a battery.

[0063] The present invention will be further explained below by means of specific embodiments:

[0064] Example 1

[0065] A method for growing a carbon nanotube array by in-situ pinning of aluminum foil comprises the following steps:

[0066] Step 1: Wet preparation of nano honeycomb structure aluminum foil, under vacuum degree of 2*10 -3 Pa vacuum environment, inert gas was introduced, and the surface of the aluminum foil substrate was bombarded for 15 seconds using the high-energy ion beam generated by the anode layer ion source to remove impurities on the surface of the aluminum foil substrate. The inert gas flow rate was controlled to be 200 sccm, the current was 1.5 A, and the voltage was 1500 V. The inert gas used was nitrogen. Under a vacuum degree of 5*10 -2Pa vacuum environment, the etching gas is introduced, and the aluminum foil substrate that has been bombarded is micro-etched for 10S by using a high-energy ion beam generated by a radio frequency ion source, wherein the gas flow rate is controlled to be 200sccm, the current is 1A, and the voltage is 1000V, and the etching gas is hydrogen; the aluminum foil substrate that has been micro-etched is placed in a 3% by mass potassium chloride solution for electrochemical etching for 40s, the temperature is 40°C, the frequency is 35Hz, and the processing voltage is 4V; then After washing in 0°C deionized water for 10S, the substrate was subjected to strong acid corrosion treatment at 40°C for 15S, wherein the strong acid was 3% by mass phosphoric acid, and finally washed in 40°C deionized water for 10S to obtain an electrochemically etched aluminum foil substrate; the electrochemically etched aluminum foil substrate was further subjected to multi-stage electrochemical formation treatment: in the first stage, the substrate was electrochemically formed in 2% adipic acid, with a conductivity of 20μs / cm, a pH of 6.0, a voltage of 1.5V, a temperature of 80°C, and a treatment time of 60S, and then the substrate was electrochemically formed in 40°C deionized water for 10S. ℃ deionized water for 10S; the second stage, electrochemically formed in a mixed solution of 3% azelaic acid and 2% sodium chloride, with a conductivity of 30μs / cm, a pH of 5.0, a voltage of 1.5V, a temperature of 80℃, and a treatment time of 80S, followed by a 40℃ deionized water wash for 10S; the third stage, electrochemically formed in a 2% azelaic acid solution, with a conductivity of 30μs / cm, a pH of 5.0, a voltage of 3V, a temperature of 80℃, and a treatment time of 80S, followed by a 40℃ deionized water wash. 10S; the fourth stage, electrochemical in 3% adipic acid solution, conductivity 30μs / cm, pH 6.0, voltage 4V, temperature 80℃, treatment time 80S, then rinse in 40℃ deionized water for 10S; the fifth stage, electrochemical in 3% sodium chloride, conductivity 30μs / cm, pH 5.0, voltage 5V, temperature 70℃, treatment time 70S, then rinse in 40℃ deionized water for 10S; finally enter the oven for 200℃ treatment for 5 minutes. -2 In a vacuum environment of 1.577 Pa, hydrogen as etching gas is introduced, and the aluminum foil substrate subjected to the electrified multi-stage chemical treatment is etched for 5 seconds using a high-energy ion beam generated by a radio frequency ion source, and the gas flow rate is controlled to be 80 sccm, the current is 0.5 A, and the voltage is 300 V. Finally, a hierarchical porous structure composed of macropores, mesopores, and micropores in an orderly nested combination is formed on the surface of the aluminum foil substrate to obtain a nano honeycomb structure aluminum foil, wherein the diameter of the macropores is 100-500 nm, the diameter of the mesopores is 2-6 nm, and the diameter of the micropores is 0.3-2 nm. The percentages in this embodiment refer to mass percentages, and the aluminum foil substrate is a bare aluminum foil;

[0067] Step 2: Depositing an iron-cobalt-nickel catalyst on a nano-honeycomb structure aluminum foil by a sol-gel method, wherein the mass ratio of Fe, Co, and Ni in the iron-cobalt-nickel catalyst is 5:5:1. The catalysts in this ratio work synergistically, and can efficiently catalyze the decomposition of the carbon source in the subsequent reaction process, promote the nucleation and growth of carbon nanotubes, and ensure that the grown carbon nanotubes have suitable key performance indicators such as tube diameter, wall thickness, and crystallinity.

[0068] Step 3: Place the nano honeycomb structure aluminum foil deposited with an iron-cobalt-nickel catalyst layer into a CVD furnace, turn on the vacuum pump to evacuate the CVD furnace, and introduce argon to remove the air in the furnace to ensure the purity of the reaction environment and prevent impurity gases from interfering with the growth of carbon nanotubes; then start heating the CVD furnace, and turn off the argon when the heating rate reaches 420°C at a rate of 10°C / min. This heating rate can not only ensure a smooth transition of the reaction system, but also gradually activate the catalyst within a suitable temperature range, thus preparing for subsequent catalytic reactions; the vacuum pump is turned on, and hydrogen and argon are injected for 10 minutes, and the vacuum pump is turned off. At this stage, hydrogen plays a role in reducing the oxide on the catalyst surface and further activating the catalyst.

[0069] Step 4: Continue to raise the temperature of the CVD furnace to 450°C and keep it warm for 10 minutes. This insulation process is a key stage in the growth of carbon nanotubes. In this temperature range, the catalyst activity reaches its peak and can continuously catalyze the decomposition of the subsequently injected carbon source acetylene; then turn on the vacuum pump to evacuate the vacuum, and after the vacuum is evacuated, start injecting acetylene and introduce carbon dioxide and hydrogen to normal pressure. Carbon dioxide, as a mild oxidant, can adjust the growth rate and structural defects of carbon nanotubes, and work together with hydrogen and acetylene to accurately control the growth process of carbon nanotubes; then introduce argon, carbon dioxide, and acetylene, and start exhausting after 10 minutes to maintain normal pressure;

[0070] Step 5: After the heat preservation is completed, argon gas is introduced to cool down. Through this series of precise temperature, gas type and time control, after the reaction is completed, a firmly pinned carbon nanotube array is grown in situ on the surface of the nano-honeycomb structure aluminum foil.

[0071] Example 2

[0072] A method for in-situ pinning growth of carbon nanotube arrays by aluminum foil, wherein the preparation steps are the same as those in Example 1, except that the mass ratio of Fe, Co, and Ni in the iron-cobalt-nickel catalyst in step 2 is changed to 15:15:1, and the steps are exactly the same as those in Example 1.

[0073] Example 3

[0074] A method for in-situ pinning of a carbon nanotube array by aluminum foil, wherein the preparation steps are the same as those in Example 1, except that the mass ratio of Fe, Co, and Ni in the iron-cobalt-nickel catalyst in step 2 is changed to 3:3:1, and the steps are exactly the same as those in Example 1.

[0075] Example 4

[0076] A method for growing a carbon nanotube array by in-situ pinning of a metal foil comprises the following steps:

[0077] Step 1: Wet preparation of nano honeycomb structure aluminum foil at a vacuum degree of 1*10 -4 Pa vacuum environment, inert gas was introduced, and the surface of the aluminum foil substrate was bombarded for 2S by the high-energy ion beam generated by the anode layer ion source to remove impurities on the surface of the aluminum foil substrate. The inert gas flow rate was controlled to be 20sccm, the current was 0.5A, and the voltage was 800V. The inert gas used was argon. Under a vacuum degree of 1*10 -4Pa vacuum environment, the etching gas is introduced, and the high-energy ion beam generated by the radio frequency ion source is used to micro-etch the bombarded aluminum foil substrate for 2S, wherein the gas flow rate is controlled to be 20sccm, the current is 0.05A, and the voltage is 500V, and the etching gas is fluorine gas; the aluminum foil substrate after micro-etching is placed in a sodium chloride electrolyte with a mass percentage of 3% for electrochemical etching for 12s, the temperature is 15°C, the frequency is 20Hz, and the processing voltage is 1V; then After washing for 2 seconds, the substrate was subjected to strong alkali corrosion treatment at 20°C for 4 seconds, wherein the strong alkali was 2% by mass sodium hydroxide, and finally washed in 15°C deionized water for 2 seconds to obtain an electrochemically etched aluminum foil substrate; the electrochemically etched aluminum foil substrate was further subjected to multi-stage electrochemical formation treatment: in the first stage, the substrate was electrochemically formed in a mixed solution of 0.2% adipic acid and 0.5% sodium chloride, with a conductivity of 5 μs / cm, a pH of 4.0, a voltage of 0.1 V, a temperature of 60°C, a treatment time of 40 seconds, and then deionized water was added at 20°C. The first stage is to be electrochemically formed in a mixed solution of 0.1% azelaic acid and 0.3% oxalic acid, with a conductivity of 10μs / cm, a pH of 4.0, a voltage of 0.8V, a temperature of 60°C, a treatment time of 40S, and then to be cleaned in deionized water at 20°C for 2S; the third stage is to be electrochemically formed in a mixed solution of 1% azelaic acid and 1% hydrochloric acid, with a conductivity of 10μs / cm, a pH of 4.0, a voltage of 2V, a temperature of 60°C, a treatment time of 40S, and then to be cleaned in deionized water at 20°C for 2S ; The fourth stage, electrochemically formed in 1% phosphoric acid solution, the conductivity is 10μs / cm, the pH is 5.0, the voltage is 3V, the temperature is 60℃, the treatment time is 40S, and then washed in deionized water at 20℃ for 2S; the fifth stage, electrochemically formed in 0.5% sodium chloride solution, the conductivity is 10μs / cm, the pH is 5.0, the voltage is 4V, the temperature is 60℃, the treatment time is 40S, and then washed in deionized water at 20℃ for 2S; finally, enter the oven for treatment at 160℃ for 2 minutes; in a vacuum degree of 1*10 -4 In a vacuum environment of 1.50 Pa, fluorine gas as etching gas is introduced, and the aluminum foil substrate subjected to the multi-stage electrochemical treatment is etched for 2 seconds using a high-energy ion beam generated by a radio frequency ion source, and the gas flow rate is controlled to be 50 sccm, the current is 0.1 A, and the voltage is 200 V. Finally, a hierarchical porous structure composed of macropores, mesopores, and micropores in an orderly nested combination is formed on the surface of the aluminum foil substrate to obtain a nano honeycomb structure aluminum foil, wherein the diameter of the macropores is 100-500 nm, the diameter of the mesopores is 2-6 nm, and the diameter of the micropores is 0.3-2 nm;

[0078] Step 2: Depositing an iron-cobalt-magnesium catalyst on a nano-honeycomb structure aluminum foil by a sol-gel method, wherein the mass ratio of Fe, Co, and Mg in the iron-cobalt-magnesium catalyst is 25:15:3: The synergistic effect of the catalysts under this ratio can efficiently catalyze the decomposition of the carbon source in the subsequent reaction process, promote the nucleation and growth of carbon nanotubes, and ensure that the grown carbon nanotubes have suitable key performance indicators such as tube diameter, wall thickness, and crystallinity; and the introduction of magnesium element further adjusts the electron cloud density of the active center of the catalyst, so that the catalyst's adsorption and activation ability for the carbon source is optimized, which is conducive to the growth of carbon nanotubes with more regular structure and better performance.

[0079] Step 3: Place the nano honeycomb structure aluminum foil deposited with iron-cobalt-magnesium catalyst into the CVD furnace, turn on the vacuum pump to evacuate the CVD furnace, introduce argon to remove the air in the furnace, and then start heating the CVD furnace. When it reaches 400°C, turn off the argon, keep the vacuum pump running, start injecting hydrogen and argon for 20 minutes, and then turn off the vacuum pump.

[0080] Step 4: Continue to heat the CVD furnace to 500°C and keep it warm for 30 minutes, then turn on the vacuum pump to evacuate the air, and after evacuating the air, start injecting acetylene and introduce carbon dioxide and hydrogen to normal pressure; then introduce argon, carbon dioxide, and acetylene, and start exhausting after 20 minutes to maintain normal pressure;

[0081] Step 5: After the heat preservation is completed, argon gas is introduced to cool down. Through this series of precise temperature, gas type and time control, after the reaction is completed, a firmly pinned carbon nanotube array is grown in situ on the surface of the nano-honeycomb structure aluminum foil.

[0082] Example 5

[0083] A method for in-situ pinning growth of carbon nanotube arrays by aluminum foil, wherein the preparation steps are the same as those of Example 4, except that the mass ratio of Fe, Co, and Mg in the iron-cobalt-magnesium catalyst in step 2 is changed to 25:15:1, and the steps are exactly the same as those of Example 4.

[0084] Example 6

[0085] A method for in-situ pinning of a carbon nanotube array by aluminum foil, wherein the preparation steps are the same as those of Example 4, except that the mass ratio of Fe, Co, and Mg in the iron-cobalt-magnesium catalyst in step 2 is changed to 5:3:1, and the steps are exactly the same as those of Example 4.

[0086] Example 7

[0087] A method for growing a carbon nanotube array by in-situ pinning of a metal foil comprises the following steps:

[0088] Step 1: Wet preparation of nano honeycomb structure aluminum foil, under vacuum degree of 4*10 2Pa, an inert gas is introduced, and the surface of the aluminum foil substrate is bombarded for 30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the aluminum foil substrate. The inert gas flow rate is controlled to be 500 sccm, the current is 3A, and the voltage is 3000V. The inert gas used is one or more of nitrogen and argon. In a vacuum environment with a vacuum degree of 5*10Pa, an etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to perform micro-etching on the bombarded aluminum foil substrate for 20 seconds, wherein the gas flow rate is controlled to be 500sccm, current is 2A, voltage is 1500V, and the etching gas is chlorine; the aluminum foil substrate after micro-etching is placed in a mixed electrolyte consisting of 5% sodium chloride and 4% hydrochloric acid for electrochemical etching for 80s, the temperature is 60°C, the frequency is 50Hz, and the processing voltage is 6V; then it is washed in 60°C deionized water for 20S and then treated with strong acid at 60°C for 20S, the strong acid is 4% nitric acid by mass, and finally it is washed in 60°C deionized water for 20S to obtain an electrochemically etched aluminum foil substrate.The electrochemically etched aluminum foil substrate was further subjected to multi-stage electrochemical treatment: the first stage was electrochemically treated in a mixed solution of 4% adipic acid and 8% hydrochloric acid, with a conductivity of 40 μs / cm, a pH of 6.0, a voltage of 2 V, a temperature of 100°C, and a treatment time of 100 s, followed by a 20 s cleaning in deionized water at 60°C; the second stage was electrochemically treated in a 5% sodium chloride solution, with a conductivity of 50 μs / cm, a pH of 7.0, a voltage of 2.5 V, a temperature of 100°C, and a treatment time of 100 s. The treatment time is 100S, followed by rinsing in deionized water at 60℃ for 20S; the third stage, electrochemical formation in 5% azelaic acid solution, conductivity is 50μs / cm, pH is 6.0, voltage is 4V, temperature is 100℃, treatment time is 100S, followed by rinsing in deionized water at 60℃ for 20S; the fourth stage, electrochemical formation in a mixed solution of 5% adipic acid and 6% phosphoric acid, conductivity is 50μs / cm, pH is 5.0, voltage is 5 ... The treatment time is 100S, followed by rinsing in 60℃ deionized water for 20S; the fifth stage, electrochemical formation in a mixed solution of 5% sodium chloride, 6% oxalic acid and 3% phosphoric acid, the conductivity is 50μs / cm, the pH is 6.0, the voltage is 6V, the temperature is 100℃, the treatment time is 100S, followed by rinsing in 60℃ deionized water for 20S; finally, it enters the oven for treatment at 300℃ for 10 minutes; in a vacuum environment with a vacuum degree of 5*10Pa, the etching gas chlorine is introduced, using The high-energy ion beam generated by the radio frequency ion source etches the aluminum foil substrate that has undergone the powered multi-stage chemical treatment for 10S, and the gas flow rate is controlled to be 100sccm, the current is 1A, and the voltage is 500V. Finally, a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain a nano honeycomb structure aluminum foil, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

[0089] Step 2: Depositing an iron-cobalt-nickel-molybdenum catalyst on a nano-honeycomb structure aluminum foil by a sol-gel method, wherein the mass ratio of Fe, Co, Ni, and Mo in the iron-cobalt-nickel-molybdenum catalyst is 10:15:5:1. The synergistic effect of the catalysts under this ratio can efficiently catalyze the decomposition of the carbon source in the subsequent reaction process, promote the nucleation and growth of carbon nanotubes, and ensure that the grown carbon nanotubes have suitable key performance indicators such as tube diameter, wall thickness, and crystallinity. The addition of molybdenum element enhances the high temperature resistance and sintering resistance of the catalyst, ensuring that the catalyst always maintains high activity during the high temperature reaction process and continuously and stably catalyzes the growth of carbon nanotubes.

[0090] Step 3: Place the nano honeycomb structure aluminum foil deposited with iron-cobalt-nickel-molybdenum catalyst into the CVD furnace, turn on the vacuum pump to evacuate the CVD furnace, introduce argon to remove the air in the furnace, and then start heating the CVD furnace. When the temperature reaches 450°C, turn off the argon, keep the vacuum pump running, start injecting hydrogen and argon for 5 minutes, and then turn off the vacuum pump.

[0091] Step 4: Continue to heat the CVD furnace to 600°C and keep it warm for 40 minutes, then turn on the vacuum pump to evacuate the air, and after evacuating the air, start injecting acetylene and introduce carbon dioxide and hydrogen to normal pressure; then introduce argon, carbon dioxide, and acetylene, and start exhausting after 30 minutes to maintain normal pressure;

[0092] Step 5: After the heat preservation is completed, argon gas is introduced to cool down. Through this series of precise temperature, gas type and time control, after the reaction is completed, a firmly pinned carbon nanotube array is grown in situ on the surface of the nano-honeycomb structure metal foil.

[0093] Example 8

[0094] A method for in-situ pinning of a carbon nanotube array by aluminum foil, wherein the preparation steps are the same as those of Example 7, except that the mass ratio of Fe, Co, Ni, and Mo in the iron-cobalt-nickel-molybdenum catalyst in step 2 is changed to 4:6:3:1, and the steps are exactly the same as those of Example 7.

[0095] Example 9

[0096] A method for growing a carbon nanotube array by in-situ pinning of a metal foil comprises the following steps:

[0097] Step 1: Dry preparation of nano honeycomb structure aluminum foil, under vacuum degree of 2*10 -3Pa, an inert gas is introduced, and the surface of the aluminum foil substrate is bombarded for 15 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the aluminum foil substrate, and the inert gas flow rate is controlled to be 200sccm, the current is 1.5A, and the voltage is 1500V. The inert gas used is nitrogen; the aluminum foil substrate that has been micro-etched is continued to be laser-treated using a pulsed laser, and the laser wavelength of the pulsed laser is 355nm, the power is 10W, the pulse frequency is 30KHZ, the spot size is controlled at 800nm, and the scanning speed is controlled at 200mm / s; oxygen is introduced in a vacuum environment to pre-oxidize the aluminum foil substrate that has been laser-treated for 10s, and the oxygen flow rate is controlled to be 200sccm to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate; in a vacuum environment, In an environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 200sccm, the etching gas flow rate is controlled to be 300sccm, the current is 1.5A, and the voltage is 1200V. The aluminum foil substrate that has been pre-oxidized is etched for 30S by a high-energy ion beam generated by a radio frequency ion source; in a vacuum environment, an inert gas is introduced, the gas flow rate is controlled to be 80sccm, the current is 0.5A, and the voltage is 350V. The aluminum foil substrate is further etched for 6S by a high-energy ion beam generated by a radio frequency ion source, and finally a hierarchical porous structure composed of orderly nested combinations of macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

[0098] Step 2: depositing an iron-cobalt-nickel-manganese catalyst on a nano-honeycomb structure aluminum foil by a sol-gel method, wherein the mass ratio of Fe, Co, Ni, and Mn in the iron-cobalt-nickel-manganese catalyst is 15:25:20:1. The catalysts under this ratio work synergistically, and can efficiently catalyze the decomposition of the carbon source in the subsequent reaction process, promote the nucleation and growth of carbon nanotubes, and ensure that the grown carbon nanotubes have appropriate key performance indicators such as tube diameter, wall thickness, and crystallinity. In addition, the manganese element can adjust the lattice structure of the catalyst, provide more sexual sites for the growth of carbon nanotubes, and promote their rapid and uniform growth;

[0099] Steps 3-5 are the same as in Example 1.

[0100] Example 10

[0101] A method for in-situ pinning of a carbon nanotube array by aluminum foil, wherein the preparation steps are the same as those of Example 8, except that the mass ratio of Fe, Co, Ni, and Mn in the iron-cobalt-nickel-manganese catalyst in step 2 is changed to 3:5:4:1, and the steps are exactly the same as those of Example 9.

[0102] Embodiment 11

[0103] A method for growing a carbon nanotube array by in-situ pinning of aluminum foil comprises the following steps:

[0104] Step 1: Dry preparation of nano honeycomb structure aluminum foil, under vacuum degree of 1*10 -4 Pa, an inert gas is introduced, and the surface of the aluminum foil substrate is bombarded for 2S by a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the aluminum foil substrate, and the inert gas flow rate is controlled to be 20sccm, the current is 0.5A, and the voltage is 800V. The inert gas used is argon; the aluminum foil substrate that has been micro-etched is continued to be laser-treated using a pulsed laser, and the laser wavelength of the pulsed laser is 350nm, the power is 2W, the pulse frequency is 20KHZ, the spot size is controlled at 500nm, and the scanning speed is controlled at 100mm / s; oxygen is introduced in a vacuum environment to pre-oxidize the aluminum foil substrate that has been laser-treated for 5s, and the oxygen flow rate is controlled to be 50sccm to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate; in a vacuum environment Under the condition of vacuum, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 50sccm, the etching gas flow rate is controlled to be 200sccm, the current is 1A, and the voltage is 1000V, and the aluminum foil substrate that has been pre-oxidized is etched for 20S by a high-energy ion beam generated by a radio frequency ion source; under the condition of vacuum, inert gas is introduced, the gas flow rate is controlled to be 50sccm, the current is 0.1A, and the voltage is 200V, and the aluminum foil substrate is further etched for 2S by a high-energy ion beam generated by a radio frequency ion source, and finally a hierarchical porous structure composed of orderly nested combinations of macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

[0105] Step 2: Depositing an iron-cobalt-nickel-magnesium-manganese catalyst on a nano-honeycomb structure metal foil by a sol-gel method, wherein the mass ratio of Fe, Co, Ni, Mg, and Mn in the iron-cobalt-nickel-magnesium-manganese catalyst is 20:30:25:25:1. The synergistic effect of the catalysts under this ratio can efficiently catalyze the decomposition of the carbon source in the subsequent reaction process, promote the nucleation and growth of carbon nanotubes, and ensure that the grown carbon nanotubes have suitable key performance indicators such as tube diameter, wall thickness, and crystallinity. The synergistic effect of multiple elements comprehensively improves the catalyst performance, laying a foundation for the preparation of high-quality carbon nanotube arrays.

[0106] Steps 3-5 are the same as in Example 1.

[0107] Example 12

[0108] A method for growing a carbon nanotube array by in-situ pinning of aluminum foil comprises the following steps:

[0109] Step 1: Dry preparation of nano honeycomb structure aluminum foil, under vacuum degree of 4*10 2 Pa, an inert gas is introduced, and the surface of the aluminum foil substrate is bombarded for 30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the aluminum foil substrate, and the inert gas flow rate is controlled to be 500sccm, the current is 3A, and the voltage is 3000V. The inert gas used is nitrogen; the aluminum foil substrate that has been micro-etched is continued to be laser-treated using a pulsed laser, and the laser wavelength of the pulsed laser is 360nm, the power is 20W, the pulse frequency is 50KHZ, the spot size is controlled at 1μm, and the scanning speed is controlled at 400mm / s; oxygen is introduced in a vacuum environment to pre-oxidize the aluminum foil substrate that has been laser-treated for 15s, and the oxygen flow rate is controlled to be 300sccm to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate; in a vacuum environment, In an environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 400sccm, the etching gas flow rate is controlled to be 500sccm, the current is 2A, and the voltage is 1500V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the aluminum foil substrate that has been pre-oxidized for 40S; in a vacuum environment, nitrogen is introduced, the gas flow rate is controlled to be 100sccm, the current is 1A, and the voltage is 500V, and the high-energy ion beam generated by the radio frequency ion source is used to continue to etch the aluminum foil substrate for another 10S, and finally a hierarchical porous structure composed of orderly nested combinations of macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

[0110] Step 2: depositing an iron-cobalt-nickel-magnesium-manganese catalyst on a nano-honeycomb structure aluminum foil by a sol-gel method, wherein the mass ratio of Fe, Co, Ni, Mg and Mn in the iron-cobalt-nickel-magnesium-manganese catalyst is changed to 2:6:4:4:1.

[0111] Steps 3-5 are the same as in Example 11.

[0112] Embodiment 13

[0113] A method for in-situ pinning of a carbon nanotube array by copper foil, wherein the preparation steps are the same as those of Example 1, except that the aluminum foil in step 1 is replaced by copper foil, and the steps are exactly the same as those of Example 1.

[0114] Embodiment 14

[0115] A method for in-situ pinning and growing a carbon nanotube array by corroding aluminum foil. The preparation steps are the same as those in Example 1, except that the aluminum foil in step 1 is replaced by corroded aluminum foil. The steps are exactly the same as those in Example 1.

[0116] Comparative Example 1

[0117] A method for in-situ growth of a carbon nanotube array on aluminum foil comprises the following steps:

[0118] Step 1: providing a commercial aluminum foil substrate without modifying the commercial aluminum foil substrate;

[0119] Steps 2-5 are the same as in Example 1.

[0120] Test Case

[0121] The nano honeycomb structure aluminum foils prepared in Example 1 and Example 9 were observed by electron microscope. The results are as follows: Figure 2-Figure 3 As shown, Figure 2 This is an electron microscope image of the nano honeycomb structure metal foil prepared by the wet processing process in Example 1. Figure 3 This is an electron microscope image of the nano honeycomb structure metal foil prepared by dry processing in Example 9. Figure 2-Figure 3 It can be seen that the surface of the aluminum foil presents a porous structure, with pores of different sizes nested with each other, and macropores, mesopores and micropores distributed in an orderly manner, which shows that the wet process in Example 1 and the dry process in Example 9 both produced nano-honeycomb structure metal foils with graded porous microstructure characteristics on the surface.

[0122] The cross-sectional images of the aluminum foil in-situ pinned growth carbon nanotube array materials prepared in Example 1 and Example 9 were observed by electron microscope, and the results are shown in the following figure:

[0123] in, Figure 4 This is a cross-sectional electron microscope image of the aluminum foil in-situ pinned growth carbon nanotube array material prepared in Example 1 at a scale of 20 μm. Figure 5 This is a cross-sectional electron microscopy image of the aluminum foil in-situ pinned growth carbon nanotube array material prepared in Example 9 at a scale of 4 μm. Figure 4 and Figure 5 It can be seen that carbon nanotubes grow vertically on the upper and lower surfaces of the aluminum foil. The carbon nanotubes are pinned in situ and grow on the surface of the aluminum foil, forming a relatively regular array morphology.

[0124] in, Figure 6 a and b in the figure are plane electron microscope images of the in-situ pinned growth carbon nanotube array material of aluminum foil in Example 1 at scales of 1 μm and 200 nm, respectively. Figure 6 It can be seen from a (scale bar is 1 μm) that the carbon nanotubes are evenly distributed on the surface of the aluminum foil, without obvious large-area agglomeration or sparse areas, and the overall coverage is good, which indicates that the growth of carbon nanotubes has a certain uniformity and consistency, which is conducive to the stable performance in subsequent applications; Figure 6Figure b (scale is 200nm) shows the microstructure of carbon nanotubes more clearly. It can be seen that carbon nanotubes are intertwined and entangled to form a three-dimensional through-network structure. The existence of this network structure may help to enhance the conductivity and mechanical properties of the material, because the interconnection between carbon nanotubes can provide more conductive pathways and stress transfer paths; in the high-magnification plane electron microscope image b, the diameter of the carbon nanotubes is relatively uniform, the tube wall is relatively smooth, and there are no obvious defects, which shows that the growth quality of carbon nanotubes is high and their structural integrity is good, which is conducive to maintaining the excellent physical and chemical properties of carbon nanotubes themselves, such as high conductivity and high mechanical strength.

[0125] Figure 6 Figures c and d are cross-sectional electron micrographs of the in-situ pinned growth carbon nanotube array material of aluminum foil in Example 1 at scales of 1 μm and 200 nm, respectively, where: Figure 6 Middle c (scale is 1 μm) shows that the carbon nanotube array has obvious interweaving regularity in the direction perpendicular to the aluminum foil surface. This vertically oriented growth mode is beneficial in some specific applications (such as elastic current collectors, etc.) because it can provide more efficient charge transport and better flexibility. Figure 6 The middle d (scale is 200nm) further confirms the vertical growth characteristics of carbon nanotubes, and it can be seen that the spacing between carbon nanotubes is relatively uniform, which helps to ensure the consistency and stability of material performance. From the cross-sectional electron microscope image, it can be judged that the density of the carbon nanotube array is moderate, neither too sparse to cause insufficient performance, nor too dense to cause squeezing, affecting its growth quality and performance. This moderate density is conducive to ensuring good interaction between carbon nanotubes while giving full play to the performance advantages of each carbon nanotube.

[0126] in, Figure 7 This is a plane electron microscope image of the in-situ pinning growth of carbon nanotube array material with aluminum foil in Example 4 at a scale of 1 μm. Figure 8 This is a cross-sectional electron microscope image of the in-situ pinning growth of carbon nanotube array material with aluminum foil in Example 4 at a scale of 200 nm. Figure 7 and Figure 8 It can be seen that many slender tubular structures grow on the aluminum foil, which is a typical feature of carbon nanotubes. These carbon nanotubes are intertwined and entangled with each other to form a relatively dense elastic array.

[0127] in, Fig. 9 This is a plane electron microscope image of the in-situ pinned growth carbon nanotube array material of aluminum foil in Example 7 at a scale of 1 μm. Fig.10 This is a cross-sectional electron microscope image of the in-situ pinning growth of carbon nanotube array material with aluminum foil in Example 7 at a scale of 200 nm. Fig. 9 and Fig.10It can also be seen that many slender tubular structures grow on the aluminum foil, which is a typical feature of carbon nanotubes. These carbon nanotubes are intertwined and entangled with each other to form a relatively dense elastic array.

[0128] in, Fig.11 This is a cross-sectional electron microscope image of the in-situ pinning growth of carbon nanotube array material with aluminum foil in Example 9 at a scale of 200 nm. Fig.12 This is a cross-sectional electron microscope image of the metal foil in-situ pinned growth carbon nanotube array material at a scale of 400 nm in Example 9. Figure 11-12 A large number of slender carbon nanotube structures can be clearly seen. These carbon nanotubes are intertwined to form a complex network structure. The distribution of carbon nanotubes is relatively uniform, and most of the carbon nanotubes are entangled and bent. This is because the catalytic growth rates of iron, cobalt, nickel, manganese, etc. are not completely consistent during the growth process and are affected by van der Waals interactions and spatial constraints.

[0129] in, Fig.13 This is a cross-sectional electron microscope image of the in-situ pinned growth carbon nanotube array material on the aluminum foil in Example 11 at a scale of 200 nm. It can be seen from the image that many slender tubular structures grow on the aluminum foil, which is a typical feature of carbon nanotubes. These carbon nanotubes are intertwined and entangled to form a relatively dense elastic array.

[0130] in, Fig.14 This is a cross-sectional electron microscope image of the carbon nanotube array material in situ pinned growth on copper foil in Example 13 at a scale of 1 μm. It can be seen from the image that many slender tubular structures are grown on the copper foil, which is a typical feature of carbon nanotubes. These carbon nanotubes are intertwined and entangled with each other to form a relatively dense elastic array, indicating that the method of the present invention can also in situ grow elastic and intertwined carbon nanotube array materials on copper foil.

[0131] in, Fig.15 This is a cross-sectional electron microscope image of the in-situ pinning growth of carbon nanotube array material on corroded aluminum foil in Example 14 at a scale of 2 μm. It can be seen from the image that many clustered and entangled tubular structures grow on the corroded aluminum foil, which is a typical feature of carbon nanotubes, indicating that the method of the present invention can also in-situ grow mutually entangled carbon nanotube array materials on corroded aluminum foil.

[0132] Fig.16 This is the Raman graph of the metal foil in-situ pinned growth carbon nanotube array material prepared in Example 1. From the graph, we can see two obvious carbon nanotube characteristic peaks, one at 1300 cm -1 The D peak is at 1580 cm -1 The G peaks on the left and right, and I D / I G =1.03,ID / I G The ratio is an important parameter for evaluating the quality and structural integrity of carbon nanotubes; generally speaking, the lower the I D / I G The ratio indicates that the carbon nanotubes contain certain disordered structures and defects. In this embodiment, ID / IG=1.03, indicating that there are certain defects in the carbon nanotube array grown in situ on the aluminum foil, which indicates that the carbon nanotube array can act as a three-dimensional conductive network and increase active sites for energy storage, and has good application potential.

[0133] Fig.17 This is the BET test diagram of the carbon nanotube array material in situ pinned growth on the metal foil in Example 1. It can be seen from the figure that the carbon nanotube array in situ pinned growth on the aluminum foil in Example 1 has a rich pore structure and a high specific surface area, which is significantly different from the aluminum foil itself. These characteristics make the carbon nanotube array have potential application prospects and advantages in many fields.

[0134] Ultrasonic vibration tests were performed on the metal foil in-situ pinned growth carbon nanotube array material prepared in Example 1 and the aluminum foil in-situ grown carbon nanotube array material prepared in Comparative Example 1. Specifically, the material samples prepared in Example 1 and Comparative Example 1 were placed in an ultrasonic cleaning machine, respectively, and vibrated for 1-5 hours under specific frequency (such as 20-50kHz) and power (such as 100-500W). After taking out, the adhesion of the carbon nanotubes on the surface of the aluminum foil was observed by scanning electron microscopy. The results showed that only a small amount of carbon nanotubes fell off the sample in Example 1, and the overall array structure was not affected, while a large amount of carbon nanotubes fell off the sample in Comparative Example 1, which shows that the carbon nanotube array in Example 1 is pinned to the surface of the aluminum foil, and its pinning firmness to the aluminum foil surface is better, while the carbon nanotube array in Comparative Example 1 has poor bonding firmness to the aluminum foil surface.

[0135] Furthermore, the conductivity, bending resistance, carbon nanotube particle size and length of the metal part in-situ grown carbon nanotube array materials prepared in Examples 1 to 12 and the commercial high surface area current collector aluminum foil were tested, and the results are shown in Table 1:

[0136] Table 1 Performance test results

[0137]

[0138] It can be seen from Table 1 that the aluminum foil in-situ grown carbon nanotube array material prepared by the method of the present invention has a smaller tube diameter and a longer length, and therefore has a higher electrical conductivity, and its bending resistance is improved by 2-3 times compared with commercial high surface area ratio current collector aluminum foil.

[0139] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for growing a carbon nanotube array by in-situ pinning of a metal foil, characterized in that: Includes steps: The metal foil is modified by a dry treatment process or a wet treatment process to obtain a nano honeycomb structure metal foil, wherein the nano honeycomb structure metal foil refers to a metal foil surface presenting a hierarchical porous structure composed of macropores, mesopores and micropores in an orderly nested combination, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm, and the metal foil is one of copper foil and aluminum foil; A catalyst is deposited on a nano honeycomb structure metal foil by a sol-gel method, wherein the metal elements in the catalyst include at least two types of Fe and Co; The nano honeycomb structure metal foil with the catalyst deposited thereon is placed in a CVD furnace, the vacuum pump is turned on to evacuate the CVD furnace and inert gas is introduced to remove the air in the furnace, and then the CVD furnace is heated to 400-450°C at a heating rate of 8-12°C / min, and hydrogen and inert gas are then injected; Continue to heat the CVD furnace to 450-630°C and keep it warm for 5-40 minutes, then turn on the vacuum pump to evacuate, start injecting acetylene after evacuating the vacuum, and simultaneously introduce carbon dioxide and hydrogen to normal pressure, further introduce inert gas, carbon dioxide, and acetylene, and start exhausting after 5-40 minutes to maintain normal pressure. After the insulation is completed, introduce inert gas to naturally cool down. After the reaction is completed, a carbon nanotube array is pinned in situ on the surface of the nano-honeycomb structure metal foil to grow.

2. The method for growing carbon nanotube arrays by in-situ pinning of metal foil according to claim 1, characterized in that: The steps of modifying the metal foil by a dry process to obtain the nano honeycomb structure metal foil include: In a vacuum environment, an inert gas is introduced, and the surface of the metal foil is bombarded for 1-30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the metal foil; Continue to use a pulse laser to laser process the metal foil that has been micro-etched, wherein the pulse laser has a laser wavelength of 350-360 nm, a power of 1-20 W, a pulse frequency of 20-50 KHZ, a spot size controlled at 500 nm-1 μm, and a scanning speed controlled at 100-400 mm / s; In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated metal foil for 5-15 seconds, and the oxygen flow rate is controlled to be 50-300 sccm, so as to form a dense and uniform aluminum oxide protective film layer on the surface of the metal foil; In a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 50-400sccm, the etching gas flow rate is controlled to be 200-500sccm, the current is 1-2A, the voltage is 1000V-1500V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized metal foil for 20-40S; In a vacuum environment, an inert gas is introduced, the gas flow rate is controlled to be 50-100sccm, the current is 0.1A-1A, and the voltage is 200V-500V. The metal foil is etched again for 2-10S using a high-energy ion beam generated by a radio frequency ion source, and finally a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores is etched on the surface of the metal foil to obtain the nano honeycomb structure metal foil.

3. The method for growing carbon nanotube arrays by in-situ pinning of metal foil according to claim 1, characterized in that: The steps of modifying the metal foil by a wet processing process to obtain the nano honeycomb structure metal foil include: In a vacuum environment, an inert gas is introduced, and the surface of the metal foil is bombarded for 1-30 seconds using a high-energy ion beam generated by an anode layer ion source to remove impurities on the surface of the metal foil; In a vacuum environment, an etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to micro-etch the bombarded metal foil for 1-20 seconds, wherein the gas flow rate is controlled to be 20-500 sccm, the current is 0.05-2A, and the voltage is 500V-1500V; The metal foil after micro-etching is placed in an electrolyte for electrochemical etching for 12-80 seconds, the temperature is 15-60°C, the frequency is 20-50Hz, and the processing voltage is 1-6V; then, it is washed in deionized water at 15-60°C for 2-20S, and then it is subjected to strong acid or strong alkali corrosion treatment at 20-60°C for 4-20S, and finally, it is washed in deionized water at 15-60°C for 2-20S to obtain the electrochemically etched metal foil; The electrochemically etched metal foil is further subjected to a multi-stage electrochemical treatment: in the first stage, electrochemically formed in one or more mixed solutions of 0.2%-4% adipic acid, 0.5%-5% sodium chloride, 0.3%-6% oxalic acid, and 0.02%-8% hydrochloric acid, with a conductivity of 5-40 μs / cm, a pH of 4.0-7.0, a voltage of 0.1-2V, a temperature of 60-100°C, a treatment time of 40-100S, and then washed in deionized water at 20-60°C for 2-20S; in the second stage, electrochemically formed in 0.1%-5% azelaic acid, 0.5%-5 % sodium chloride, 0.3%-6% oxalic acid, 0.02%-8% hydrochloric acid, one or more mixed solutions are added for electrochemical formation, the conductivity is 10-50μs / cm, the pH is 4.0-7.0, the voltage is 0.8-2.5V, the temperature is 60-100℃, the processing time is 40-100S, and then washed in deionized water at 20-60℃ for 2-20S; the third stage, in one or more mixed solutions of 0.1%-5% azelaic acid, 0.3%-6% oxalic acid, 0.02%-8% hydrochloric acid, the conductivity is 10-50μs / cm, pH 4.0-7.0, voltage 2-4V, temperature 60-100℃, treatment time 40-100S, followed by 20-60℃ deionized water cleaning for 2-20S; the fourth stage, electrochemically formed in one or more mixed solutions of 0.1%-5% adipic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, 0.05%-6% phosphoric acid, conductivity 10-50μs / cm, pH 4.0-7.0, voltage 3-5V, temperature 60-100℃, treatment time 40-100S , then wash in deionized water at 20-60℃ for 2-20S; the fifth stage, electrochemically formed in one or more mixed solutions of 0.1%-5% azelaic acid, 0.5%-5% sodium chloride, 0.5%-6% oxalic acid, and 0.05%-6% phosphoric acid, with a conductivity of 10-50μs / cm, a pH of 4.0-7.0, a voltage of 4-6V, a temperature of 60-100℃, and a treatment time of 40-100S, then wash in deionized water at 20-60℃ for 2-20S; finally enter the oven for treatment at 160-300℃ for 2-10 minutes; In a vacuum environment, etching gas is introduced, and a high-energy ion beam generated by a radio frequency ion source is used to etch the metal foil that has undergone powered multi-stage chemical treatment for 2-10S. The gas flow rate is controlled to be 50-100sccm, the current is 0.1A-1A, and the voltage is 200V-500V. Finally, a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores is etched on the surface of the metal foil to obtain a nano honeycomb structure metal foil, wherein the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.3-2nm.

4. The method for in-situ growth of carbon nanotube arrays by metal foil pinning according to claim 2 or 3, characterized in that: The inert gas is one or two of nitrogen and argon; the etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride.

5. The method for growing carbon nanotube arrays by in-situ pinning of metal foil according to claim 1, characterized in that: The catalyst is one of an iron-cobalt-nickel catalyst, an iron-cobalt-magnesium catalyst, an iron-cobalt-nickel-molybdenum catalyst, an iron-cobalt-nickel-manganese catalyst and an iron-cobalt-nickel-magnesium-manganese catalyst. The mass ratio of Fe, Co and Ni in the iron-cobalt-nickel catalyst is 15:15:1-3:3:1, the mass ratio of Fe, Co and Mg in the iron-cobalt-magnesium catalyst is 25:15:1-5:3:1, the mass ratio of Fe, Co, Ni and Mo in the iron-cobalt-nickel-molybdenum catalyst is 10:15:5:1-4:6:3:1, the mass ratio of Fe, Co, Ni and Mn in the iron-cobalt-nickel-manganese catalyst is 15:25:20:1-3:5:4:1, and the mass ratio of Fe, Co, Ni, Mg and Mn in the iron-cobalt-nickel-magnesium-manganese catalyst is 20:30:25:25:1-2:6:4:4:

1.

6. The method for growing carbon nanotube arrays by in-situ pinning of metal foil according to claim 1, characterized in that: The particle size of the catalyst is 1-5 nm.

7. The method for growing carbon nanotube arrays by in-situ pinning of metal foil according to claim 1, characterized in that: The particle size of the carbon nanotubes grown by in-situ pinning on the surface of the metal part of the nano honeycomb structure is 2-30 nm, and the length of the carbon nanotubes is 5-200 μm.

8. A metal foil in-situ pinning growth carbon nanotube array material, characterized in that: The carbon nanotube array is prepared by the method for in-situ pinning growth of a carbon nanotube array by metal foil as described in any one of claims 1-7.

9. An application of a metal foil in-situ pinning growth carbon nanotube array material, characterized in that: The metal foil in-situ pinned growth carbon nanotube array material as claimed in claim 8 is used to prepare a positive electrode sheet or a negative electrode sheet of a battery.

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