Aluminum foil base material with nano honeycomb structure and preparation method of aluminum foil base material

Abstract

The invention discloses an aluminum foil base material with a nano honeycomb structure and a preparation method thereof, the surface of the aluminum foil base material with the nano honeycomb structure is of a hierarchical porous structure formed by orderly nesting and combining macropores, mesopores and micropores, the diameter of the macropores is 100-500nm, the diameter of the mesopores is 2-6nm, and the diameter of the micropores is 0.5-1nm. Compared with a commercial current collector aluminum foil with a high specific surface area, the nano honeycomb structure aluminum foil base material provided by the invention has the advantages that the conductivity is improved by 13% or more, the tensile strength is improved by 10% or more, and the bending resistance is also improved by 70% or more; the macropores, the mesopores and the micropores are embedded into the nano honeycomb aluminum foil base material to provide abundant nucleation sites and a good mechanical anchoring foundation for the growth of the carbon nanotubes, so that the carbon nanotubes can be tightly and firmly attached to the nano honeycomb aluminum foil base material, and the in-situ pinning growth of the solid-base carbon nanotube array on the aluminum foil is realized; and the problem that the carbon nanotubes are easy to fall off is effectively solved.

Description

Technical Field

[0001] The invention relates to the technical field of aluminum foil substrate modification and preparation, and in particular to a nano honeycomb structure aluminum foil substrate and a preparation method thereof. Background Art

[0002] In the field of battery manufacturing, commercial aluminum foil is often used as a current collector material. Due to its advantages of light weight, low cost, and good conductivity, aluminum foil can effectively conduct the current generated by the positive electrode of the battery, thereby improving the overall performance of the battery. In common battery systems such as lithium-ion batteries, aluminum foil can stably carry active substances to ensure that the transmission path of electrons is unobstructed during the charging and discharging process of the battery, thereby maintaining the normal operation of the battery. Traditional commercial high-surface-rate current collector aluminum foil used in devices such as batteries and supercapacitors is usually made by immersing the metal foil in a specific corrosive solution. The corrosive solution reacts chemically with the metal foil to form micropores, nanopores or rough microstructures on the surface of the metal foil, thereby increasing the specific surface area.

[0003] However, the existing commercial high-surface-rate current collector aluminum foil also has some obvious defects in the production and application of devices such as batteries and supercapacitors. In terms of anti-bending performance, commercial high-surface-rate current collector aluminum foil may be subjected to various external forces, including vibration, extrusion, etc., during the battery assembly production or use process. The commercial high-surface-rate current collector aluminum foil has poor anti-bending performance and is prone to cracks or even breaks after repeated bending, which will destroy the current conduction path inside the battery, resulting in a decrease in battery performance, and in severe cases, the battery will fail; in terms of conductive performance, although the commercial high-surface-rate current collector aluminum foil has a certain conductivity, its conductivity is relatively low compared to metals such as silver and copper. In some application scenarios that require extremely high battery energy density and charge and discharge efficiency, the low conductivity of commercial high specific surface area current collector aluminum foil will increase the internal resistance of the battery, reduce the charge and discharge speed, and limit the application of the battery in high-power demand equipment; in terms of tensile resistance, the performance of commercial high specific surface area current collector aluminum foil is also unsatisfactory. During the battery production, assembly or use process and when subjected to external pulling force, the commercial high specific surface area current collector aluminum foil is easily stretched, deformed or even torn, which will not only affect the adhesion stability between the active material and the current collector, but may also cause serious problems such as internal short circuit, affecting the safety and service life of the battery.

[0004] These defects limit the application of existing commercial high-surface current collector aluminum foil in fields such as aerospace and high-performance electric vehicles that have extremely stringent requirements on battery performance and stability. Therefore, the existing technology still needs to be improved and developed. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a nano-honeycomb structure aluminum foil substrate and a preparation method thereof, aiming to solve the problems of poor conductivity, bending resistance and tensile strength of existing commercial high specific surface area current collector aluminum foil.

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

[0007] A nano honeycomb structure aluminum foil substrate, wherein the surface of the nano honeycomb structure aluminum foil substrate presents a hierarchical porous structure composed of orderly nested macropores, mesopores and micropores, the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm.

[0008] A method for preparing the nano honeycomb structure aluminum foil substrate according to the present invention comprises the following steps:

[0009] In a vacuum environment, an inert gas is introduced, and the surface of the aluminum foil substrate 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 aluminum foil substrate;

[0010] Continue to use a pulse laser to laser process the aluminum foil substrate 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;

[0011] In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated aluminum foil substrate 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 aluminum foil substrate;

[0012] 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 aluminum foil substrate for 20-40S;

[0013] 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 high-energy ion beam generated by the radio frequency ion source is used to continue to etch the aluminum foil substrate for 2-10S, and 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 the nano honeycomb aluminum foil substrate.

[0014] The method for preparing the nano honeycomb structure aluminum foil substrate, wherein in the step of bombarding the surface of the aluminum foil substrate with a high-energy ion beam generated by an anode layer ion source, the vacuum degree of the vacuum environment is 1*10 -4 Pa-4*10 2 Pa, and the inert gas is one of nitrogen and argon.

[0015] The method for preparing the nano honeycomb structure aluminum foil substrate comprises the following steps: in the step of bombarding the surface of the aluminum foil substrate with a high-energy ion beam generated by an anode layer ion source, the inert gas flow rate is controlled to be 20-500sccm, the current of the anode layer ion source is controlled to be 0.5-3A, and the voltage is controlled to be 800V-3000V.

[0016] In the method for preparing the nano honeycomb structure aluminum foil substrate, the etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride.

[0017] Beneficial effects: Compared with the existing commercial capacitors and supercapacitors with high specific surface area current collector aluminum foil (commercial high specific surface area current collector aluminum foil), the nano honeycomb aluminum foil substrate prepared by the present invention has significantly improved performance in conductivity, tensile strength, bending resistance, specific volume and other aspects. The conductivity of commercial high specific surface area current collector aluminum foil is generally 3.85*10 7 S / m, and the conductivity of the nano honeycomb aluminum foil substrate prepared by the present invention can be increased to 4.35*10 7 S / m, the improvement is as high as more than 13%, which makes it have great advantages in the fields of electronic devices, battery electrodes and other fields with strict requirements on conductive properties, and can effectively reduce resistance loss and improve energy transmission efficiency; the tensile strength of commercial high specific surface area current collector aluminum foil is 140-180MPa, while the tensile strength of the nano honeycomb aluminum foil prepared by the present invention is significantly enhanced, which can reach more than 200MPa, and the improvement is more than 10%; the commercial high specific surface area current collector aluminum foil will crack or even break due to material fatigue after repeated bending about 100 times, which limits its application in some scenes that require frequent bending, while the nano honeycomb aluminum foil prepared by the present invention has better bending resistance due to its unique surface graded porous structure. After testing, it can withstand more than 170 bendings under the same bending conditions, which greatly broadens its scope of use. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared by the dry treatment process in Example 1 at a molecular scale of 100 nm.

[0019] Figure 2 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared by the dry treatment process in Example 2 at a molecular scale of 40 nm.

[0020] Figure 3 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared by the dry treatment process in Example 3 at a molecular scale of 40 nm.

[0021] Figure 4 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared by the dry treatment process in Example 4 at a molecular scale of 100 nm.

[0022] Figure 5 This is an electron microscope image of the high specific surface area current collector aluminum foil plane of existing commercial capacitors and supercapacitors at a molecular scale of 100nm.

[0023] Figure 6 This is a cross-sectional electron microscope image of the aluminum foil in-situ pinned growth solid-based carbon nanotube array material prepared in Example 5 at a scale of 5 μm. DETAILED DESCRIPTION

[0024] The present invention provides a nano honeycomb structure aluminum foil substrate and a preparation method thereof. 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.

[0025] Example 1

[0026] A method for preparing a nano honeycomb structure aluminum foil substrate comprises the following steps:

[0027] Step 1: At a vacuum degree of 2*10 -3 In a vacuum environment of 1.5 Pa, an inert gas was introduced, and the surface of the aluminum foil substrate was 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. 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.

[0028] Step 2, continue to use a pulse laser to laser process the aluminum foil substrate that has been micro-etched, wherein the laser wavelength of the pulse laser is 355 nm, the power is 10 W, the pulse frequency is 30 KHZ, the spot size is controlled at 800 nm, and the scanning speed is controlled at 200 mm / s;

[0029] Step 3: In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated aluminum foil substrate for 10 seconds, and the oxygen flow rate is controlled to be 200 sccm to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate;

[0030] Step 4, in a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 200 sccm, the etching gas flow rate is controlled to be 300 sccm, the current is 1.5 A, the voltage is 1200 V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized aluminum foil substrate for 30 seconds;

[0031] Step 5. In a vacuum environment, nitrogen is introduced, the gas flow rate is controlled to be 80 sccm, the current is 0.5 A, and the voltage is 350 V. The high-energy ion beam generated by the radio frequency ion source is used to continue etching the aluminum foil substrate for 6S again, and 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 the nano honeycomb aluminum foil substrate, 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.

[0032] Example 2

[0033] A method for preparing a nano honeycomb structure aluminum foil substrate comprises the following steps:

[0034] Step 1: At a vacuum degree of 1*10 -4 In a vacuum environment of 1.5 Pa, an inert gas was introduced, and the surface of the aluminum foil substrate was bombarded for 2 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 was controlled to be 20 sccm, the current was 0.5 A, and the voltage was 800 V. The inert gas used was argon.

[0035] Step 2, continue to use a pulse laser to laser process the aluminum foil substrate that has been micro-etched, wherein the pulse laser has a laser wavelength of 350 nm, a power of 2 W, a pulse frequency of 20 KHZ, a spot size controlled at 500 nm, and a scanning speed controlled at 100 mm / s;

[0036] Step 3: In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated aluminum foil substrate for 5 seconds, and the oxygen flow rate is controlled to be 50 sccm, so as to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate;

[0037] Step 4, in a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 50 sccm, the etching gas flow rate is controlled to be 200 sccm, the current is 1A, the voltage is 1000V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized aluminum foil substrate for 20S;

[0038] Step 5. In a vacuum environment, introduce argon gas, control the gas flow rate to 50sccm, the current to 0.1A, the voltage to 200V, and use the high-energy ion beam generated by the radio frequency ion source to continue etching the aluminum foil substrate for 2S, and finally etch a hierarchical porous structure composed of orderly nested macropores, mesopores and micropores on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm.

[0039] Example 3

[0040] A method for preparing a nano honeycomb structure aluminum foil substrate comprises the following steps:

[0041] Step 1: At a vacuum degree of 4*10 2 In a vacuum environment of 1.5 Pa, an inert gas was introduced, and the surface of the aluminum foil substrate was 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 was controlled to be 500 sccm, the current was 3A, and the voltage was 3000 V. The inert gas used was nitrogen.

[0042] Step 2, continue to use a pulse laser to laser process the aluminum foil substrate that has been micro-etched, wherein the pulse laser has a laser wavelength of 360 nm, a power of 20 W, a pulse frequency of 50 KHZ, a spot size controlled at 1 μm, and a scanning speed controlled at 400 mm / s;

[0043] Step 3: In a vacuum environment, oxygen is introduced to pre-oxidize the laser-treated aluminum foil substrate for 15 seconds, and the oxygen flow rate is controlled to be 300 sccm to form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate;

[0044] Step 4, in a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 400 sccm, the etching gas flow rate is controlled to be 500 sccm, the current is 2A, the voltage is 1500V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized aluminum foil substrate for 40S;

[0045] Step 5. In a vacuum environment, nitrogen is introduced, the gas flow rate is controlled to be 100 sccm, the current is 1A, and the voltage is 500V. The high-energy ion beam generated by the radio frequency ion source is used to continue to etch the aluminum foil substrate for 10S again, and finally a hierarchical porous structure composed of orderly nested macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm.

[0046] Example 4

[0047] A method for preparing a nano honeycomb structure aluminum foil substrate comprises the following steps:

[0048] Step 1: At a vacuum degree of 1*10 -4 In a vacuum environment of 1.5 Pa, an inert gas was introduced, and the surface of the aluminum foil substrate was 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 was controlled to be 20 sccm, the current was 3A, and the voltage was 2500V. The inert gas used was nitrogen.

[0049] Step 2, continue to use a pulse laser to laser process the aluminum foil substrate that has been micro-etched, wherein the laser wavelength of the pulse laser is 355 nm, the power is 18 W, the pulse frequency is 40 KHZ, the spot size is controlled at 900 nm, and the scanning speed is controlled at 300 mm / s;

[0050] Step 3: Introduce oxygen into the laser-treated aluminum foil substrate for pre-oxidation treatment for 5 seconds under a vacuum environment, control the oxygen flow rate to 300 sccm, and form a dense and uniform aluminum oxide protective film layer on the surface of the aluminum foil substrate;

[0051] Step 4: In a vacuum environment, oxygen and etching gas are introduced, the oxygen flow rate is controlled to be 50 sccm, the etching gas flow rate is 500 sccm, the current is 1A, the voltage is 1500V, and the high-energy ion beam generated by the radio frequency ion source is used to etch the pre-oxidized aluminum foil substrate for 20-40 seconds.

[0052] Step 5. In a vacuum environment, an inert gas is introduced, the gas flow rate is controlled to be 50 sccm, the current is 1A, and the voltage is 200V. The high-energy ion beam generated by the radio frequency ion source is used to continue to etch the aluminum foil substrate for 10S again, and finally a hierarchical porous structure composed of orderly nested macropores, mesopores and micropores is etched on the surface of the aluminum foil substrate to obtain the nano honeycomb aluminum foil substrate, wherein the macropore diameter is 100-500nm, the mesopore diameter is 2-6nm, and the micropore diameter is 0.3-2nm.

[0053] The nano honeycomb aluminum foil substrates prepared in Examples 1 to 4 were observed by electron microscope. The results are as follows: Figure 1-Figure 4 As shown, Figure 1 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared in Example 1 at a molecular scale of 100 nm. Figure 2 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared in Example 2 at a molecular scale of 40 nm. Figure 3 This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared in Example 3 at a molecular scale of 40 nm. Figure 4This is an electron microscope image of the nano honeycomb aluminum foil substrate prepared in Example 4 at a molecular scale of 100 nm. Figure 1-Figure 4 It can be seen that the surfaces of the nano honeycomb aluminum foil substrates prepared in Examples 1-4 of the present invention all present a hierarchical porous structure composed of an orderly nested combination of macropores, mesopores and micropores, 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, indicating that the method of the present invention has produced an aluminum foil with a nano honeycomb structure.

[0054] Figure 5 This is a plane SEM image of the existing commercial high specific surface area current collector aluminum foil. Figure 5 It can be seen that the surface of the commercial current collector aluminum foil presents a relatively complex microscopic morphology, with numerous irregular holes and protrusions, but the sizes and shapes of these holes vary, and the distribution is relatively random, without obvious regularity and order. The pore structure of the commercial capacitor current collector foil is randomly distributed, lacking the ordered macropore-mesopore-micropore ordered nested composite structure (such as the nano honeycomb aluminum foil prepared in Examples 1-4) Figure 1-4 As shown in the figure, the ordered hierarchical porous structure of nano honeycomb aluminum foil can better store and transport ions and optimize the electrochemical performance of the electrode; although the commercial current collector aluminum foil has a certain specific surface area, the nano honeycomb aluminum foil can provide a larger and more effective specific surface area through a carefully designed hierarchical porous structure, and has more active sites to interact with the electrode active materials, thereby showing better performance in the electrochemical reaction. The commercial current collector foil has a disadvantage in this regard; at the same time, the special structure of the nano honeycomb aluminum foil also gives it better mechanical properties and structural stability.

[0055] The conductivity, bending resistance and tensile strength of the nano honeycomb aluminum foil substrate prepared in Examples 1-4 and the commercial high specific surface area current collector aluminum foil were tested. The results are shown in Table 1:

[0056] Table 1 Performance test results

[0057]

[0058] From the data in Table 1, we can see that the conductivity of commercial high specific surface area current collector aluminum foil is generally around 3.85*10 7 S / m, and the conductivity of the nano honeycomb aluminum foil substrate prepared by the present invention can be increased to 4.35*10 7S / m, the improvement is as high as more than 13%, which makes it have great advantages in the fields of electronic devices, battery electrodes and other fields with strict requirements on conductive properties, and can effectively reduce resistance loss and improve energy transmission efficiency; the tensile strength of commercial high specific surface area current collector aluminum foil is 140-180MPa, while the tensile strength of the nano honeycomb aluminum foil prepared by the present invention is significantly enhanced, which can reach more than 200MPa, and the improvement is more than 10%; the commercial high specific surface area current collector aluminum foil will crack or even break due to material fatigue after repeated bending about 100 times, which limits its application in some scenes that require frequent bending, while the nano honeycomb aluminum foil prepared by the present invention has better bending resistance due to its unique surface graded porous structure. After testing, it can withstand more than 170 bendings under the same bending conditions, which greatly broadens its scope of use.

[0059] Furthermore, the macroporous, mesoporous, and microporous nano-honeycomb aluminum foil substrate prepared by the method of the present invention can also provide 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 the solid-base carbon nanotube array on the aluminum foil, effectively solving the problem of easy detachment of the carbon nanotubes. The following is an explanation through specific embodiments:

[0060] Example 5

[0061] A method for in-situ pinning of aluminum foil to grow a solid-base carbon nanotube array comprises the following steps:

[0062] Step 1: The preparation of the nano honeycomb aluminum foil substrate is the same as that in Example 1;

[0063] Step 2: plasma clean the nano honeycomb aluminum foil substrate, and deposit an iron-cobalt-nickel-manganese catalyst on the nano honeycomb aluminum foil substrate by a sol-gel method, wherein the mass ratio of Fe, Co, Ni, and Mn in the iron-cobalt-nickel-manganese catalyst is 3:5:4:1. 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. 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.

[0064] Step 3: Place the aluminum foil with the iron-cobalt-nickel catalyst layer deposited into the CVD furnace, start 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 temperature rises to 420°C at a heating 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.

[0065] 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;

[0066] 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 fixed carbon nanotube array is grown in situ on the surface of the nano honeycomb aluminum foil substrate.

[0067] Comparative Example 1

[0068] A method for in-situ growth of a carbon nanotube array on aluminum foil comprises the following steps:

[0069] Step 1: Providing a commercial high specific surface area current collector aluminum foil;

[0070] Steps 2-5 are the same as in Example 5.

[0071] The aluminum foil in-situ pinning growth solid-based carbon nanotube array prepared in Example 5 was observed by electron microscope. The results are as follows: Figure 6 As shown, from Figure 6 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.

[0072] Ultrasonic vibration tests were performed on the aluminum foil in-situ pinned growth solid-base carbon nanotube array material prepared in Example 5 and the aluminum foil in-situ grown carbon nanotube array material prepared in Comparative Example 1. Specifically, the material samples prepared in Example 5 and Comparative Example 1 were respectively placed in an ultrasonic cleaning machine, and vibrated for 1-5 hours under specific frequency (such as 20-50kHz) and power (such as 100-500W). After being taken 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 from the sample in Example 5, and the overall array structure was not affected, while a large amount of carbon nanotubes fell off from the sample in Comparative Example 1, which shows that the carbon nanotube array in Example 5 is pinned to the surface of the aluminum foil with a nano-honeycomb structure, 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.

[0073] 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 nano honeycomb structure aluminum foil substrate, characterized in that: The surface of the nano honeycomb structure aluminum foil substrate presents a hierarchical porous structure composed of macropores, mesopores and micropores in an orderly nested combination, 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.

2. A method for preparing the nano honeycomb structure aluminum foil substrate as claimed in claim 1, characterized in that: Includes steps: In a vacuum environment, an inert gas is introduced, and the surface of the aluminum foil substrate 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 aluminum foil substrate; Continue to use a pulse laser to laser process the aluminum foil substrate 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 aluminum foil substrate 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 aluminum foil substrate; 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 aluminum foil substrate 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 high-energy ion beam generated by the radio frequency ion source is used to continue to etch the aluminum foil substrate for 2-10S, and 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 the nano honeycomb aluminum foil substrate.

3. The method for preparing the nano honeycomb structure aluminum foil substrate according to claim 2, characterized in that: In the step of bombarding the surface of the aluminum foil substrate with a high-energy ion beam generated by the anode layer ion source, the vacuum degree of the vacuum environment is 1*10 -4 Pa-4*10 2 Pa, and the inert gas is one of nitrogen and argon.

4. The method for preparing the nano honeycomb structure aluminum foil substrate according to claim 2, characterized in that: In the step of bombarding the surface of the aluminum foil substrate with a high-energy ion beam generated by an anode layer ion source, the inert gas flow rate is controlled to be 20-500sccm, the current of the anode layer ion source is controlled to be 0.5-3A, and the voltage is controlled to be 800V-3000V.

5. The method for preparing the nano honeycomb structure aluminum foil substrate according to claim 2, characterized in that: The etching gas is one or more of hydrogen, fluorine, nitrogen trifluoride, chlorine and carbon tetrafluoride.

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