CN102864476B - Preparation method of through-hole anodic aluminum oxide template - Google Patents

Abstract

The invention discloses a preparation method directly producing a barrier-free through-hole anodic aluminum oxide template during anodizing. According to extensibility of metallic aluminum and the diffusion principle of intermetallic interface, double aluminum foil layers are laminated by pressurizing. The first aluminum foil layer is completely oxidized by single-side anodizing and reaches the second aluminum foil layer, so that a fully through-hole first porous anodic aluminum oxide film. The aluminum oxide template with 100% through holes can be obtained by the preparation method, and the need of using complex post-treatment process to remove a barrier layer is avoided. Through-hole time points can be precisely positioned according to anodizing curves. The thickness of the through-hole aluminum oxide template can be controlled by regulating thickness of the first aluminum foil layer or by double anodizing. The preparation method is applicable to the process of mild anodizing and high-field anodizing of aluminum foils in various aqueous electrolytes.

Description

A kind of preparation method of through-hole anodized aluminum template

technical field

The invention belongs to the technical field of electrochemistry, and relates to a method for preparing a through-hole porous anodized aluminum template, in particular to a method for obtaining a double-layer composite aluminum foil without a barrier layer by only anodizing on one side without special post-treatment. Facile electrochemical preparation of through-hole anodized alumina templates.

Background technique

Porous anodized aluminum (PAA) is a kind of porous material obtained by electrochemical anodization in a suitable electrolyte, with regular pore arrangement and hexagonal close-packed cells. As a nano-template material, PAA has the characteristics of simple preparation process, high pore density, large aspect ratio, regular pore arrangement, and controllable pore size. It is widely used in metals, alloys, non-metals, non-metal oxides, polymers, etc. The preparation of low-dimensional nanostructures of various materials has broad application prospects in many fields such as nonlinear optics, nanoelectronics, and electrochemistry.

As far as the application of PAA stencil is concerned, through-hole stencil is required in most cases. However, since there is a dense alumina barrier layer at the bottom of the porous layer of the PAA film, the PAA template to obtain through holes must try to remove this barrier layer. At present, the general method for preparing through-hole PAA templates is: first, use CuCl ₂ , HgCl ₂ or SnCl ₄ solution to corrode and dissolve the aluminum substrate at the bottom of the prepared PAA film to obtain a pure PAA film; then soak it in phosphoric acid solution , remove the barrier layer of the PAA film by chemical etching, and finally obtain the PAA template of the through hole. However, this method will inevitably bring some heavy metal impurities into the nanopores during the process of removing the aluminum matrix, which may limit the application of the template. In addition, the chemical corrosion process of the phosphoric acid solution to remove the barrier layer is uncontrollable, and the pores of the PAA film soaked in the phosphoric acid solution are also corroded, so the through-hole PAA template prepared by this method will have different degrees of hole expansion. Another method to remove the barrier layer of PAA film is the so-called step-down method: according to the principle that the thickness of the barrier layer is proportional to the voltage, the barrier layer is gradually thinned until the through hole is reached by gradually reducing the anodic oxidation voltage. Furneaux et al. first reported that the PAA membrane prepared in phosphoric acid solution was perforated by step-down method (Furneaux, et al. Nature, 1989, 337: 147). However, this method must strictly control process parameters such as step-down amplitude and electrolyte temperature. The entire step-down process is very complicated and time-consuming, and it is difficult to ensure 100% perforation of the barrier layer. Therefore, in most cases, it is still necessary to soak in a phosphoric acid solution to obtain a completely through-hole PAA template.

There is also a relatively simple electrochemical method for preparing PAA through-hole templates: in the perchloric acid/methanol mixture, the sample is used as the anode, and the large-area aluminum sheet is used as the cathode. Large-area through-hole PAA template (Yuan, et al. Chem. Mater., 2004, 16: 1841). However, this method has requirements on the thickness and properties of the PAA film layer, and it is difficult to control the size of the openings on one side of the barrier layer of the PAA film, the operation is very difficult, the electrolyte is not environmentally friendly, and the shape and size of the film pores may be damaged.

In summary, the current methods for preparing PAA through-hole templates have various defects, such as: heavy metal impurity contamination, complex and time-consuming process for removing barrier layers, difficulty in controlling the size of openings, and unenvironmental protection of the electrolyte. Therefore, finding a simple and efficient way to prepare PAA through-hole templates without destroying the inherent structure and size of the film, and being applicable to PAA films with different thicknesses, has become an urgent and difficult problem to be solved.

Contents of the invention

The purpose of the present invention is to provide a method for directly preparing through-hole PAA templates in the anodic oxidation process without special post-treatment.

The technical solution for realizing the purpose of the present invention is: a method for preparing a through-hole anodized aluminum template, comprising the following steps:

Step 1. Remove the natural oxide film on the surface of high-purity aluminum foil;

Step 2. Pressurize and compound the stacked two pieces of high-purity aluminum foil, the pressurized pressure is 5-10 MPa, and the pressure holding time is 30-60 min;

Step 3, performing single-sided anodic oxidation on the composite high-purity aluminum foil;

Step 4. When the voltage on the anodizing curve changes suddenly, the current of constant-current anodizing is halved, or when the current on the anodizing curve changes suddenly, the voltage of constant-voltage anodizing remains unchanged, and then continue Oxidation ends after half an hour;

Step 5. Finally, a fully through-hole PAA template is obtained by mechanical stripping.

The removal of the natural oxide film described in step 1 is to immerse the aluminum foil in a 2wt% sodium hydroxide solution at 70°C for 2 minutes.

The pressurization described in step 2 adopts a hydraulic press.

The suitable thickness of the single-side anodized composite aluminum foil described in step 3 is 20-150 μm.

The one-sided anodizing described in step 3 can adopt mild anodizing or high field anodizing.

The single-sided anodizing described in step 3 can adopt primary anodizing or secondary anodizing.

Compared with the prior art, the present invention has significant advantages:

(1) After the first layer of aluminum foil is completely oxidized and transitioned to the second layer of aluminum foil, the barrier layer is then transferred to the second layer of aluminum foil, and the first layer of PAA film is detached by mechanical peeling, and the PAA template in the through-hole state is directly obtained. There is no need to consider the removal of the barrier layer.

(2) Since there is no need to consider the removal of the barrier layer of the PAA film, the time for preparing the through-hole PAA template is only determined by the anodic oxidation time, and the preparation efficiency is significantly improved.

(3) Since there is no need to consider the removal of the PAA film barrier layer, after the preparation is completed, the pores of the obtained PAA template are completely consistent with the state of the preparation, and there are no problems such as pore expansion and excessive corrosion, so as to realize the nanopore size of the PAA template. precise control.

(4) By adjusting the thickness of the first layer of aluminum foil, or using the secondary anodizing method, PAA through-hole templates with a thickness varying in a wide range can be prepared.

(5) By observing the change state of the anodic oxidation parameters during the PAA film preparation process, the through-hole state of the PAA film can be determined semi-quantitatively, so as to understand the degree of through-hole and control the through-hole time in time, avoiding the pure empirical removal of the barrier layer corrosion process.

(6) Since the through-hole PAA template is directly obtained in one step and is not connected to the aluminum substrate, there is no need to treat the aluminum substrate with chemical reagents, which saves resources and avoids PAA template pollution and environmental pollution, which is conducive to industrial production.

(7) The method of the present invention can be used in three types of PAA preparation systems including sulfuric acid, oxalic acid and phosphoric acid, and is suitable for both mild anodic oxidation and high-field anodic oxidation, and is also suitable for secondary anodic oxidation.

Description of drawings

Fig. 1 is a single-side constant current anodic oxidation curve diagram of a composite double-layer aluminum foil in Example 1 of the present invention.

2 is a scanning electron microscope image of the PAA through-hole template prepared in Example 1 (a is the SEM image of the bottom surface of the PAA through-hole template, and b is the SEM image of the section near the bottom of the PAA through-hole template).

FIG. 3 is a metallographic microscope image of a section of a PAA through-hole template prepared in Example 3. FIG.

Detailed ways

The present invention will be described in further detail below in conjunction with the accompanying drawings.

The principle of the present invention is as follows: the first layer of aluminum foil (that is, the aluminum foil that has been anodized on one side) is completely oxidized by using a pressurized composite double-layer aluminum foil through the single-sided anodic oxidation process, and transitions to the second layer of aluminum foil, thereby obtaining complete The first layer of porous anodized aluminum oxide membrane for through holes. Aluminum is a metal with excellent ductility. After laminating two pieces of aluminum foil, under the action of external force, the interface of the two layers of aluminum foil will be extruded and extended, and physical processes such as mutual anchoring and embedding will occur on the microscopic level, so that Two layers of aluminum foil are composited; as the external force continues, the atoms between the two layers of aluminum foil that have been composited begin to diffuse each other, and the interface begins to become blurred. After a period of time, a transition zone of atomic diffusion and mixing is formed. , Since the interaction between metal atoms is much higher than the purely physical interaction, the strength of the force between the two layers of aluminum foil is further increased, which also ensures that the anodizing process can transition from the first layer of aluminum foil to the second layer of aluminum foil. Since the invention adopts a single-sided anodic oxidation method, the oxidation of the aluminum foil has directionality, that is, from the first layer to the second layer. In the initial stage of oxidation, it is no different from the traditional single-piece aluminum foil anodizing process. However, when approaching the junction area of the two layers of aluminum foil, since the overall thickness of the single-layer aluminum foil is microscopically inhomogeneous, and the distribution of the electric field during the anodic oxidation process will also be different, it must lead to some positions taking the lead in the transition to the first Anodizing of two layers of aluminum foil. Since the atomic arrangement in the transition region is in a disordered state, the interatomic force is weaker than that of the main body of the aluminum foil. When the transition region at the interface of the two layers of aluminum foil is completely anodized and continues to oxidize the body of the second layer of aluminum foil, due to the aluminum anodic oxidation process Volume expansion will occur, causing the stress at the interface to increase sharply, causing the PAA film in this area to break at the interface transition zone, thereby obtaining a through-hole film. After the fracture occurs, the electrolyte quickly penetrates the fracture layer and reaches the metal aluminum layer exposed at the fracture, which has a great impact on the anodic oxidation parameters. Therefore, by observing the changes in the anodic oxidation parameters, the time point at which the fracture begins can be determined. That is, when the voltage on the anodizing curve changes suddenly, the current of constant current anodizing is halved, or when the current on the anodizing curve changes suddenly, the voltage of constant voltage anodizing remains unchanged. Complete transition to the second layer, and continue to oxidize for half an hour before ending.

The present invention is realized through the following steps: using high-purity aluminum foil, first immerse two pieces of aluminum foil in 2wt% sodium hydroxide solution at 70°C for 2 minutes to remove the natural oxide film on the surface. Then overlap two pieces of aluminum foil, fix them in the mold, and reserve a piece of separated aluminum foil outside the mold, then put the mold into the hydraulic press, the working pressure is 5-10 MPa, and the holding time is 30-60 min . Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, use the side of the first layer of aluminum foil as the anode, and then use the platinum mesh as the cathode to perform single-sided anodic oxidation. The suitable thickness range of the first layer of aluminum foil is 20-150 μm. The electrolyte can be an aqueous solution of sulfuric acid, oxalic acid or phosphoric acid, the power supply mode can be constant voltage or constant current, and the anodic oxidation type can be mild anodic oxidation or high field anodic oxidation. Measure the anodic oxidation curve in real time, and when the anodic oxidation parameters change significantly, reduce the current to half (for constant current anodic oxidation) or keep the voltage constant (for constant voltage anodic oxidation) for half an hour. Then stop the anodizing, and use a blade to cut into the unbonded area to separate the double-layer aluminum foil, and finally get the through-hole PAA template.

The present invention is further illustrated below by way of examples.

Example 1

First, two aluminum foil strips with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm were taken and soaked in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the natural oxide film on the surface of the aluminum foil. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 10 MPa, and maintained for 30 min. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, and use it as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 (high-field anodization). The oxidation time is determined by measuring the change of voltage in real time. When the voltage rises rapidly, the current is halved and stopped after 30 min. The specific test curve is shown in Figure 1. The microscopic morphology of the obtained samples is shown in Fig. 2. Figure 2(a) is the SEM image of the bottom surface of the prepared PAA through-hole template, that is, the first layer of aluminum foil after complete anodization. It can be observed that the bottom of the template that has been completely through-holed in a regular arrangement, and the average pore spacing of the PAA membrane nanopores About 120nm. Figure 2(b) is the SEM image of the cross section of the first layer of aluminum oxide film near the bottom area, it can be seen that the channel is straight and completely through the hole. Through the metallographic microscope photos of the sample cross-section, the thickness of the PAA through-hole template can be measured to be about 211.46 μm.

Example 2

First, two aluminum foil strips with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm were taken and soaked in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the natural oxide film on the surface of the aluminum foil. Two pieces of aluminum foil were overlapped and fixed in the mold, then the mold was put into the hydraulic press, pressurized at 5 MPa, and maintained for 60 min. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, and use it as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 . The oxidation time was determined by measuring the change of the voltage in real time. When the voltage rose rapidly, the current was halved and kept for 30 min before stopping. The average pore spacing of the PAA membrane nanochannels is about 117 nm, and the thickness of the PAA through-hole template is about 218.25 μm.

Example 3

First, take a strip of aluminum foil with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm and 100 μm, and soak it in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the aluminum foil surface. natural oxide film. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 10 MPa, and maintained for 30 min. Then take out the bonded double-layer composite aluminum foil, rinse it repeatedly with deionized water, use the side of the aluminum foil with a thickness of 100 μm as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 . The oxidation time was determined by measuring the change of the voltage in real time. When the voltage rose rapidly, the current was halved and kept for 30 min before stopping. Figure 3 is a metallographic microscope photo of the cross-section of the sample. It can be seen from the figure that the thickness of the PAA through-hole template is about 111.59 μm.

Example 4

First, take a strip of aluminum foil with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm and 50 μm, and soak it in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the aluminum foil surface. natural oxide film. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 7.5 MPa, and maintained for 45 minutes. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, use the side of the aluminum foil with a thickness of 50 μm as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 . The oxidation time was determined by measuring the change of the voltage in real time. When the voltage rose rapidly, the current was halved and kept for 30 min before stopping. The thickness of the PAA through-hole template was measured to be about 60.38 μm.

Example 5

First, two aluminum foil strips with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm were taken and soaked in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the natural oxide film on the surface of the aluminum foil. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 10 MPa, and maintained for 30 min. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, and use it as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, and at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 , the first anodic oxidation was carried out on one side with constant current. After 1 h of reaction, the anodic oxidation was stopped to ensure that the first layer of aluminum foil was not completely oxidized, and the sample was soaked in a mixture of 1.8 wt% HCrO ₄ and 6 wt% H ₃ PO ₄ at 60 °C for 10 h to remove the first layer of aluminum foil. secondary oxide film. The sample is then used as an anode, and the second anodic oxidation is carried out under the conditions of the first anodic oxidation. The oxidation time was determined by measuring the change of the voltage in real time. When the voltage rose rapidly, the current was halved and kept for 30 min before stopping. The thickness of the PAA through-hole template was measured to be about 20.32 μm.

Example 6

First, take a strip of aluminum foil with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm and 50 μm, and soak it in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the aluminum foil surface. natural oxide film. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 7.5 MPa, and maintained for 45 minutes. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, use the side of the aluminum foil with a thickness of 50 μm as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, single-sided constant voltage anodization was performed at a constant temperature of 20 ^° C at a voltage of 80 V (high-field anodization). The oxidation time was determined by measuring the change of the current in real time. After the current downward trend gradually accelerated, the voltage was kept constant for 30 min and then stopped. The average pore spacing of the PAA membrane nanochannels was measured to be about 152 nm, and the thickness of the PAA through-hole template was about 54.23 μm.

Example 7

First, two aluminum foil strips with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm were taken and soaked in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the natural oxide film on the surface of the aluminum foil. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 10 MPa, and maintained for 30 min. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, and use it as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 6 M sulfuric acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 (high-field anodization). The oxidation time was determined by measuring the change of the voltage in real time. When the voltage rose rapidly, the current was halved and kept for 30 min before stopping. The average pore spacing of the PAA film nanochannels was measured to be about 47 nm, and the thickness of the PAA through-hole template was about 187 μm.

Example 8

First, take a strip of aluminum foil with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm and 50 μm, and soak it in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the aluminum foil surface. natural oxide film. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 7.5 MPa, and maintained for 45 minutes. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, use the side of the aluminum foil with a thickness of 50 μm as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.3 M oxalic acid solution as the electrolyte, single-sided constant voltage anodization was performed at a constant temperature of 10 ^° C at a voltage of 40 V (mild anodization). After 8 h of reaction, the anodic oxidation was stopped, and the sample was immersed in a mixture of 1.8 wt% HCrO ₄ and 6 wt% H ₃ PO ₄ at 60 °C for 8 h to remove the oxide film formed by the first anodization. The sample is then used as an anode, and the second anodic oxidation is carried out under the conditions of the first anodic oxidation. The oxidation time was determined by measuring the change of the current in real time. After the current downward trend gradually accelerated, the voltage was kept constant for 30 min and then stopped. The average pore spacing of the PAA membrane nanochannels was measured to be about 92 nm, and the thickness of the PAA through-hole template was about 13 μm.

Example 9

First, take a strip of aluminum foil with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm and 20 μm, and soak it in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the surface of the aluminum foil. natural oxide film. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 10 MPa, and maintained for 30 min. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, use the side of the aluminum foil with a thickness of 20 μm as the anode for anodic oxidation, and use the platinum mesh as the cathode. With 0.3 M sulfuric acid solution as the electrolyte, single-sided constant voltage anodization was performed at a constant temperature of 0 ^° C at a voltage of 25 V (mild anodization). After 5 h of reaction, the anodization was stopped, and the sample was soaked in a mixture of 1.8 wt% HCrO ₄ and 6 wt% H ₃ PO ₄ at 60 °C for 4 h to remove the oxide film formed by the first anodization. Then, the sample was used as the anode, and the 0.3 M sulfuric acid solution was used as the electrolyte, and the second anodic oxidation was carried out under the conditions of the first anodic oxidation. The oxidation time was determined by measuring the change of the current in real time. After the current downward trend gradually accelerated, the voltage was kept constant for 30 min and then stopped. The thickness of the PAA through-hole template was measured to be about 7.57 μm.

Example 10

First, two aluminum foil strips with a purity of 99.99%, a length of 70 mm, a width of 20 mm, and a thickness of 150 μm were taken and soaked in 2 wt% NaOH solution at 70 ^° C for 2 min to remove the natural oxide film on the surface of the aluminum foil. Two pieces of aluminum foil were overlapped and fixed in the mold, and then the mold was put into a hydraulic press, pressurized at 7.5 MPa, and maintained for 45 minutes. Then take out the double-layer composite aluminum foil that has been bonded, rinse it repeatedly with deionized water, and use it as the anode for anodic oxidation, and then use the platinum mesh as the cathode. Using 0.75 M oxalic acid solution as the electrolyte, the single-sided constant current anodization was carried out at a constant temperature of 20 ^° C at a current density of 50 mA·cm ^-2 . Stop the anodic oxidation after 1 h of reaction to ensure that the first layer of aluminum foil is not completely oxidized, and soak the sample in a mixture of 1.8 wt% HCrO ₄ and 6 wt% H ₃ PO ₄ at 60 °C for 10 h to remove the primary oxidation membrane. Then, the sample was used as the anode, 0.5 M phosphoric acid solution was used as the electrolyte, and a voltage of 60 V was used at a constant temperature of 20 ^° C to carry out the second anodic oxidation on one side at constant voltage. The oxidation time was determined by measuring the change of the current in real time. After the current downward trend gradually accelerated, the voltage was kept constant for 30 min and then stopped. Since the voltage used in the experiment is much lower than the self-organization voltage 195 V of the PAA film in phosphoric acid solution, a PAA template with a zigzag nanopore structure was obtained. The thickness of the PAA through-hole template was measured to be about 10.58 μm.

Claims (8)

1. a preparation method for through-hole anodic aluminum oxide template, is characterized in that said method comprising the steps of:

The Natural Oxide Film on step 1, removal high-purity aluminum foil surface;

Step 2, carry out pressurization compound to the two panels high-purity aluminum foil be stacked, moulding pressure is 5-10 MPa, and the dwell time is 30-60 min;

Step 3, one side anodic oxidation is carried out to the high-purity aluminum foil of compound;

Step 4, after sudden change appears in the voltage on anodic oxidation curve, then anodised for constant current electric current to be reduced by half, or after sudden change appears in the electric current on anodic oxidation curve, then maintain constant voltage anodised voltage constant, then terminate after continuing to be oxidized half an hour;

Step 5, last, the PAA template of complete through hole is namely obtained by mechanically peel.

2. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the removal Natural Oxide Film described in step 1 is in the sodium hydroxide solution of 2wt % aluminium foil being immersed 70 DEG C 2 minutes.

3. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the pressurization described in step 2 adopts oil press.

4. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the thickness of the clad aluminum foil of the coverlet surface anode oxidation described in step 3 is 20-150 μm.

5. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the anode oxidation process described in step 3 adopts constant current oxidation pattern or constant voltage oxidation model.

6. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that using clad aluminum foil as anode in the one side anodic oxidation described in step 3, using platinum guaze as negative electrode; Electrolytic solution used comprises sulfuric acid, oxalic acid or phosphorus aqueous acid.

7. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the one side anodic oxidation described in step 3 adopts gentle anodic oxidation or High-Field anodic oxidation.

8. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the one side anodic oxidation described in step 3 adopts an anodic oxidation or two-step anodization.