CN103957494B - Vibrating membrane and its preparation method and application - Google Patents

Abstract

The invention provides a vibrating membrane for a loudspeaker, its preparation method and application. Specifically, the present invention provides a vibrating membrane comprising a metal substrate and a metal oxide layer on at least one major surface of the substrate, wherein the metal oxide layer has one or more audio-improving and/or Or the following characteristics of sound quality: (i) the metal oxide layer has a nanotube array structure; (ii) the hardness and/or elastic modulus of the metal oxide layer are greater than the hardness and/or elasticity of the metal substrate modulus. An oxide layer is directly formed on the surface of the metal substrate through anodic oxidation treatment technology, which can effectively improve the hardness and elastic modulus of the vibrating film, and improve the audio and sound quality of the vibrating film.

Description

Vibrating film and its preparation method and application

technical field

The invention relates to the field of loudspeakers, in particular to a vibrating membrane, its preparation method and application.

Background technique

With the development of modern audio equipment technology, there are higher and higher requirements for the high-frequency diaphragm of the playback system. Traditional loudspeaker diaphragms are mostly made of organic plastic materials or their composite materials. However, the pronunciation effect of these materials is not satisfactory, especially in high-pitched and high-frequency sounds, and the sound quality is difficult to meet the application requirements.

At present, in the field of high-pitched and high-frequency pronunciation, titanium and its alloy materials are mostly used to prepare vibrating membranes. Titanium and its alloys have good corrosion resistance and mechanical properties, and are ideal metal materials for high-end vibrating membranes. However, the traditional titanium vibrating membrane has a narrow frequency response range and low sensitivity, and it is prone to split vibration at high frequencies, which seriously affects its pronunciation effect.

In summary, in the prior art, there is still a lack of satisfactory high-frequency vibrating membranes with wide frequency response range and high sensitivity. Therefore, there is an urgent need in this field to develop high-frequency vibrating membranes that can meet the requirements of treble and high frequencies. .

Contents of the invention

The object of the present invention is to provide a vibrating membrane capable of satisfying high-pitched and high-frequency requirements, its manufacturing method and application.

In a first aspect of the present invention, a vibrating membrane is provided, the vibrating membrane includes a metal substrate and a metal oxide layer on at least one main surface of the substrate, wherein the metal oxide layer has a or more of the following features to improve audio and/or sound quality:

(i) the metal oxide layer has a nanotube array structure;

(ii) The hardness and/or elastic modulus of the metal oxide layer are greater than the hardness and/or elastic modulus of the metal substrate.

In another preferred example, the hardness of the metal oxide layer is 4-6 GPa.

In another preferred example, the hardness of the substrate is 2-5 GPa.

In another preferred example, the elastic modulus of the metal oxide layer is 140-200 GPa.

In another preferred example, the elastic modulus of the base material is 70-140 GPa.

In another preferred example, the metal oxide layer makes the vibrating membrane display different colors.

In another preferred example, the base metal includes a metal selected from the group consisting of pure titanium, titanium alloy, pure aluminum, aluminum alloy, or a combination thereof.

In another preferred example, the metal oxide layer having a nanotube array structure includes titanium oxide and/or aluminum oxide.

In another preferred example, the average length of the nanotubes is 1 μm-50 μm; and/or the average diameter of the nanotubes is 20-150 nm.

In a second aspect of the present invention, a speaker is provided, the speaker comprising the diaphragm described in the first aspect of the present invention.

In a third aspect of the present invention, there is provided a method for preparing the vibrating membrane described in the first aspect of the present invention, the method comprising the following steps:

(a) provide a metal substrate;

(b) forming a first metal oxide layer having a nanotube array structure on at least one major surface of the metal substrate;

(c) peeling off the nanotubes of the first metal oxide layer to obtain a metal substrate having a nanotube array structure template on the main surface;

(d) forming a second metal oxide layer having a nanotube array structure on the main surface of the metal substrate having the nanotube array template to obtain the vibrating membrane.

In another preference, the step (b) includes:

Configure an aqueous electrolyte solution containing fluoride ions;

In the aqueous electrolyte solution containing fluoride ions, the metal substrate is used as an anode, and the metal substrate is subjected to anodic oxidation treatment, thereby forming a nanotube array structure on at least one main surface of the metal substrate the first metal oxide layer;

And/or, said step (c) comprises:

peeling off the nanotubes in the first metal oxide layer by mechanical vibration, generating a nanotube array template on the main surface of the metal substrate, and obtaining a metal substrate with a nanotube array structure template on the main surface;

And/or, said step (d) comprises:

In the fluoride ion electrolyte aqueous solution, the metal substrate having the nanotube array template on the main surface is used as an anode, and the metal substrate is subjected to anodic oxidation treatment, and the first nanotube array template with the nanotube array structure is generated on the main surface. two metal oxide layers to obtain the vibrating membrane.

In another preferred example, after the vibrating membrane is produced, the vibrating membrane is ultrasonically cleaned in an acetone solution for 5-10 minutes.

In another preferred example, before the step of configuring the aqueous electrolyte solution containing fluoride ions, the following steps are also included:

Surface pretreatment is performed on the metal substrate.

In another preferred example, the surface pretreatment of the metal substrate includes:

Degreasing and derusting activation treatment of the metal substrate in an alkaline washing solution; and/or

degreasing and descaling activation of said metal substrate in a pickling solution; and/or

Ultrasonic cleaning is performed on the metal substrate in an acetone solution, and then the metal substrate is air-dried.

In another preferred example, the alkaline washing solution is an aqueous sodium hydroxide solution.

In another preferred example, the concentration of the sodium hydroxide alkaline washing solution is 5-20 wt.%.

In another preferred embodiment, the pickling solution includes an acid selected from the group consisting of hydrofluoric acid, nitric acid, or a combination thereof.

In another preferred example, the volume ratio of the pickling solution is: hydrofluoric acid: nitric acid: deionized water=0.1-10:0.4-40:3-300.

In another preferred example, the aqueous electrolyte solution containing fluoride ions includes a fluoride selected from the group consisting of ammonium fluoride, potassium fluoride, sodium fluoride, or a combination thereof; and/or

The aqueous electrolyte solution containing fluoride ions includes additives selected from the group consisting of deionized water, glycerol, ethylene glycol, methanol, or combinations thereof.

In another preferred example, the fluoride is ammonium fluoride, and the content of ammonium fluoride in the aqueous electrolyte solution containing fluoride ions is 0.01-2.5 wt.%.

In another preferred example, the aqueous electrolyte solution containing fluoride ions contains 0.2-20 wt.% deionized water.

In another preferred example, the aqueous electrolyte solution containing fluoride ions contains 0.01-99.9 wt.% ethylene glycol.

In another preferred embodiment, the anodizing treatment includes one or more features selected from the following group:

The anodizing voltage of the anodizing treatment is 5V～100V;

The oxidation time of the anodic oxidation treatment is 20min～150min;

The temperature of the electrolyte for the anodic oxidation treatment is 10°C to 80°C;

The counter electrode of the anodic oxidation treatment is graphite or metal.

In a fourth aspect of the present invention, there is provided a method for preparing the vibrating membrane described in the first aspect of the present invention, the method comprising the following steps:

(a1) provide a metal substrate;

(b1) In an aqueous phosphoric acid electrolyte solution, using the metal substrate as an anode, anodize the metal substrate to form a metal oxide layer on at least one main surface of the metal substrate, thereby obtaining the diaphragm.

In another preferred example, the formed metal oxide layer is a titanium oxide layer, and the thickness of the titanium oxide layer is 10 nm to 200 nm.

In another preferred embodiment, the anodic oxidation treatment has one or more characteristics selected from the following group:

The voltage of the anodizing treatment is 5V～100V;

The oxidation time of the anodic oxidation treatment is 5min～60min;

The temperature of the electrolyte for the anodic oxidation treatment is 10°C to 80°C;

The counter electrode of the anodic oxidation treatment is graphite or metal.

In another preferred example, the proportion of the phosphoric acid electrolyte solution is 0.1-20 wt.% H ₃ PO ₄ aqueous solution, and the solvent is deionized water.

In another preferred example, before the step of configuring the aqueous phosphoric acid electrolyte solution, the following steps are also included:

Surface pretreatment is performed on the metal substrate.

In another preferred example, the surface pretreatment of the metal substrate includes:

Degreasing and derusting activation treatment of the metal substrate in an alkaline washing solution; and/or

degreasing and descaling activation of said metal substrate in a pickling solution; and/or

Ultrasonic cleaning is performed on the metal substrate in an acetone solution, and then the metal substrate is air-dried.

In another preferred example, the alkaline washing solution is an aqueous sodium hydroxide solution.

In another preferred example, the concentration of the sodium hydroxide alkaline washing solution is 5-20 wt.%.

In another preferred embodiment, the pickling solution includes an acid selected from the group consisting of hydrofluoric acid, nitric acid, or a combination thereof.

In another preferred example, the volume ratio of the pickling solution is: hydrofluoric acid: nitric acid: deionized water=0.1-10:0.4-40:3-300.

It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.

Description of drawings

Fig. 1 shows the vibrating membrane with pure titanium layer-dense titanium oxide layer structure generated under different anodizing voltages in the present invention, and the anodizing voltages are respectively:

(a) 10V, (b) 30V, (c) 50V;

Fig. 2 shows among the present invention (a) the nanotube array template of the class bowl shape that generates on the pure titanium layer and (b) the nanotube array that generates on the pure titanium layer;

Fig. 3 shows the change curve of the hardness and elastic modulus of a vibrating membrane with the pressing depth in the embodiment of the present invention.

detailed description

After extensive and in-depth research, the inventor found that a layer of oxide of the metal substrate is formed on the surface of the metal substrate as the high-frequency vibrating film through repeated tests, which can effectively improve the hardness and elastic modulus of the high-frequency vibrating film. . With the help of this idea, the inventors found that a highly ordered array of metal oxide nanotubes can be constructed on the surface of the metal substrate through an advanced multi-step anodizing treatment technology. The adjustment of diameter and length can effectively improve the audio frequency and sound quality of the vibrating membrane. At the same time, through the anodic oxidation treatment technology, a multi-color dense metal oxide layer can also be formed on the surface of the metal substrate. The oxide layer has a hardness and elastic modulus superior to that of the original metal substrate, and can be used as a high-quality vibration film. The present invention has been accomplished on this basis.

diaphragm

The vibrating membrane of the present invention includes a metal substrate and a metal oxide layer formed by anodic oxidation on the surface of the metal substrate. The generated metal oxide layer can increase the hardness and elastic modulus of the bulk metal substrate, significantly improving the use of the metal substrate. Diaphragm speakers for audio and sound quality.

metal oxide layer

The metal oxide layer of the present invention is directly prepared on the surface of the metal substrate through anodic oxidation treatment, wherein the metal oxide layer has one or more of the following features for improving audio and/or sound quality:

(i) the metal oxide layer has a nanotube array structure;

(ii) The hardness and/or elastic modulus of the metal oxide layer are greater than the hardness and/or elastic modulus of the metal substrate.

nanotube array structure

The nanotube array structure of the present invention refers to a layer of metal oxide nanotubes arranged in a highly orderly manner on the surface of the metal substrate, and the included angle between the radial direction of these nanotubes and the surface of the metal substrate is 70-90° .

Anodizing

The oxide layer formed by the natural oxidation of the metal surface is soft, thin and easy to corrode. Therefore, anodic oxidation treatment is often used to form an anodic oxide film with high corrosion resistance and hardness on the metal surface. The anodic oxidation treatment of the present invention refers to placing the metal substrate as the anode in the corresponding electrolyte, and under the action of specific conditions and an applied current, electrolysis is carried out, and a layer of oxide of the metal is formed on the surface of the metal substrate as the anode. TLC.

Preparation method of vibrating membrane

The invention also provides a preparation method of the vibrating film of the invention. Typically, this method includes:

Provide metal substrate;

Generating a metal oxide layer on at least one main surface of the metal substrate to obtain the vibrating film, specifically, a preferred method for preparing the vibrating film, comprising the following steps:

Carry out surface pretreatment on the metal substrate, successively carry out degreasing and derusting activation treatment in alkaline washing solution and pickling solution, then use ultrasonic cleaning in acetone solution, take it out and air dry;

An aqueous electrolyte solution containing fluoride ions is configured for anodic oxidation treatment;

In the aqueous electrolyte solution containing fluoride ions, the metal substrate is used as an anode, and the metal substrate is subjected to anodic oxidation treatment, thereby generating a first metal having a nanotube array structure on at least one main surface of the metal substrate. Oxide layer, the counter electrode used in anodizing treatment is a metal or graphite plate;

peeling the nanotubes in the first metal oxide layer from the surface of the metal substrate to obtain a metal substrate with a nanotube array template on the main surface;

In the aqueous electrolyte solution, the metal substrate having a nanotube array template on the main surface is used as an anode, and the metal substrate is anodized to generate a second metal having a nanotube array structure on the main surface. an oxide layer to obtain the vibrating membrane, and the counter electrode used for anodic oxidation treatment is a metal or graphite plate;

The resulting vibrating membrane having a metal substrate-second metal oxide layer structure with a nanotube array structure is subjected to subsequent ultrasonic cleaning treatment in an acetone solution.

Preferably, the anodizing voltage of the above-mentioned anodizing treatment is 5V-100V, the oxidation time is 20min-150min, and the electrolyte temperature is 10°C-100°C.

In addition, in the present invention, another preferred method for preparing the vibrating membrane includes the following steps:

Carry out surface pretreatment on the metal substrate, successively carry out degreasing and derusting activation treatment in alkaline washing solution and pickling solution, then use ultrasonic cleaning in acetone solution, take it out and air dry;

Configure phosphoric acid electrolyte solution;

Using the metal substrate as an anode in the aqueous electrolyte solution, the metal substrate is subjected to anodic oxidation treatment, thereby generating a metal oxide layer on the surface of the metal substrate to obtain the vibrating film, wherein the generated metal is oxidized Layers are rendered in different colors.

Subsequent ultrasonic cleaning treatment is performed on the generated above-mentioned vibrating membrane in an acetone solution.

application

The vibrating membrane of the present invention can be used in various commonly used electroacoustic transducers, such as loudspeakers, and can be used in various sound-generating electronic and electrical equipment. Even better, in treble and high-frequency sound-generating devices, the sound effect is better.

The main advantages of the present invention include:

(a) An oxide layer is directly formed on the surface of the metal substrate through anodic oxidation treatment technology, which can effectively increase the hardness and elastic modulus of the vibrating film, and improve the audio frequency and sound quality of the vibrating film.

(b) The metal oxide layer with a nanotube array structure of the present invention is prepared by a multi-step anodic oxidation treatment technique, and the nanotubes generated for the first time are peeled off from the surface of the metal substrate as a template for secondary or multiple generation, The generated metal oxide nanotubes are not easy to fall under mechanical vibration, have higher strength and corrosion resistance, and can be used as the surface of the vibrating membrane to have better acoustic performance.

(c) Titanium or aluminum and its alloy materials have high strength, excellent corrosion resistance and mechanical properties. Through advanced multi-step anodic oxidation treatment technology, highly ordered nanotube arrays can be constructed on the surface of titanium or aluminum alloy diaphragms. The nanotube array will also have a significant impact on the audio and sound quality of the speaker. By adjusting the diameter and length of the nanotubes in the nanotube array, the audio and sound quality of the vibrating membrane can also be improved. It is a vibrating membrane that can meet the needs of high-pitched and high-frequency applications. .

(d) The surface of titanium alloy is treated by electrochemical anodizing, which not only can form a richly colored oxide layer on the surface, but also has a hardness and elastic modulus higher than that of the bulk material, which can significantly improve the audio frequency of the speaker and sound quality.

Implementation Example 1

Diaphragm No.1

Next, the vibrating membrane is prepared with pure titanium as the metal substrate, including the following steps:

(1) Perform surface pretreatment on the pure titanium metal base material, successively wash in 5-20wt.% sodium hydroxide aqueous solution for 2-10 minutes, and the temperature of the sodium hydroxide washing solution is 40-150°C. After cleaning the metal substrate with clean water, put it into the pickling solution for cleaning for 2-10 minutes. The proportion of the pickling solution is hydrofluoric acid (10ml) + nitric acid (40ml) + deionized water (300ml). The acid-washed vibrating membrane was then ultrasonically cleaned in acetone solution, removed and air-dried.

(2) Prepare a 3wt.% phosphoric acid electrolyte aqueous solution for electrochemical anodic oxidation.

(3) Perform anodic oxidation treatment on the pure titanium metal substrate in an aqueous electrolyte solution, and the counter electrode used in the anodic oxidation treatment is a graphite electrode. The anodic oxidation voltages were 20V, 30V and 50V respectively, the oxidation time was 10min, and the electrolyte temperature during the oxidation process was 20°C.

(4) The surface of the vibrating membrane is subjected to subsequent ultrasonic cleaning treatment in an acetone solution after anodic oxidation. As diaphragm No.1.

The vibrating film prepared in Example 1 is shown in Figure 1. By changing the voltage, oxide layers of different colors can be formed on the surface of the vibrating film. The thickness of the oxide layer is about 10-200 nm. The hardness and elastic modulus are significantly higher than those of the substrate, which can improve the frequency response characteristics of the speaker and effectively improve its sound quality.

Implementation Example 2

Diaphragm No.2

Next, the vibrating membrane is prepared with pure titanium as the metal substrate, including the following steps:

(1) Perform surface pretreatment on the pure titanium metal base material, first wash in 5-20wt.% sodium hydroxide aqueous solution for 2-10 minutes, and the temperature of the alkaline washing solution is 40-150°C. After washing with water, put it into the pickling solution for 2-10 minutes. The proportion of the pickling solution is hydrofluoric acid (10ml) + nitric acid (40ml) + deionized water (300ml). The pure titanium metal substrate after pickling is then ultrasonically cleaned in acetone solution, taken out and air-dried.

(2) Prepare a fluoride electrolyte solution for electrochemical anodic oxidation, the content of NH ₄ F in the electrolyte is 0.25wt.%, the content of deionized water is 2wt.%, and the rest is ethylene glycol.

(3) Perform anodic oxidation treatment on the pure titanium vibrating diaphragm in an aqueous electrolyte solution, the counter electrode used in the anodic oxidation treatment is a graphite electrode, and the electrolyte temperature during the oxidation process is 20°C. Anodizing is carried out in two steps. The first step is anodizing voltage of 60V and oxidation time of 60 minutes. Then, the formed nanotube oxide can be peeled off by mechanical vibration, and a bowl-like nanotube array template is formed on the substrate, as shown in the attached figure. 2a shown. The second step of anodizing is to continue anodizing on the bowl-like nanotube array template. The oxidation time is 60 minutes, and a highly ordered titanium oxide nanotube array with a length of 20 μm can be prepared, as shown in Figure 2b. Show.

(4) The surface of the vibrating membrane is subjected to subsequent ultrasonic cleaning treatment in an acetone solution after anodic oxidation. As diaphragm No.2.

The oxide on the surface of the vibrating film prepared in Example 2 has a unique structure of highly ordered oxide nanotube arrays, which obviously can significantly affect the audio frequency and sound quality of the speaker.

Test Example

1. The test data of hardness and elastic modulus of diaphragm No.1.

The thickness of the titanium oxide layer of vibrating membrane No.1 is 100nm. As shown in Figure 3, when the indentation depth is between 0 and 100nm, the vibrating membrane maintains a high hardness. After the indentation depth is higher than 100nm, especially at 150nm Afterwards, the hardness of the vibrating membrane began to decrease rapidly, indicating that the hardness of the titanium oxide layer of the vibrating membrane was significantly higher than that of the substrate. At the same time, the elastic modulus of the vibrating membrane also drops sharply after the indentation depth is higher than 100nm (as shown in Figure 3b). It shows that the oxide layer produced by phosphoric acid electrolyte solution has a hardness and elastic modulus significantly higher than that of the matrix.

2. The pure titanium layer, the vibrating film No.1 and the vibrating film No.2 are the sound quality evaluation of the speaker No.1, the speaker No.2 and the speaker No.3 made of the vibrating film.

Loudspeaker No. 1, loudspeaker No. 2, and loudspeaker No. 3 were manufactured using the above-mentioned pure titanium layer, vibrating membrane No. 1, and vibrating membrane No. 2 as vibrating membranes, respectively. The sound quality of speaker No.1, speaker No.2 and speaker No.3 will be tested below.

Sound quality evaluation items and scale setting: set 5 items, namely three-dimensional sense, positioning sense, space sense, layering sense and thickness sense. Among them, the three-dimensional sense is mainly composed of the sense of space (surrounding sense), positioning (direction), and layering (thickness) of the sound. The sound with these senses of hearing is called stereo; The source is recorded in different directions of left and right, up and down, and front and back, and then the receiver receives the replayed sound and reproduces the direction of the sound source in the original sound field; the sense of space refers to the one-time reflection of the delayed direct sound and the multiple times The reflected reverberation sound reaches the two ears from all directions, which has an important impact on the auditory judgment of the size of the surrounding space, and makes the human ear feel surrounded; the sense of layering refers to the balanced frequency response of the high, middle and low frequencies of the sound, rich high-pitched harmonics, clear, slender and Not harsh, the midrange is bright and prominent, full and full but not harsh, the bass is thick but not nasal; the sense of thickness refers to the bass is calm and powerful, thick but not muddy, the treble is not lacking, the volume is moderate, there is a certain brightness, the reverberation is appropriate, and the distortion is small .

The maximum scale of each of the above items is 9, and each item is scored as a unit of 1 point. The meaning of each scale value corresponding to each item is shown in Table 1.

Inspection procedures: provide samples and inspection forms to the evaluation experts, and require the evaluation experts to evaluate various indicators according to the requirements of the form. The evaluation results conducted are only for the lateral comparison of the above three diaphragms.

Result statistics: The evaluation results of all commentators are valid. Calculate the arithmetic mean of the individual evaluation results of each commentator, and keep the result to one decimal place, and add the arithmetic mean of each individual item to get the total score. The result Rounded to one decimal place.

Table 1 corresponds to the significance of each scale value of each item

Score Stereoscopic positioning sense Sense of space Layering Thickness 9 very good very good very strong very clear very good 8 it is good it is good powerful clear it is good 7 better better stronger clearer better 6 slightly better slightly better slightly stronger slightly clearer slightly better 5 middle middle middle middle middle 4 slightly worse slightly worse slightly weaker slightly blurred slightly worse 3 poor poor weaker more vague poor 2 Difference Difference weak blurry Difference 1 very poor very poor very weak very vague very poor

Table 2 Sensory evaluation results

sample Stereoscopic positioning sense Sense of space Layering Thickness total Speaker No.1 5 5 5 5 5 5 Speaker No.2 6 5 5 6 7 5 Speaker No.3 6 7 6 6 5 5

It can be seen from Table 2 that the three-dimensionality, thickness and layering of the vibrating membrane after phosphoric acid oxidation are better than that of the untreated vibrating membrane, and the three-dimensionality, positioning, space and layering of the vibrating membrane prepared with highly ordered nanotube arrays The feel is significantly better than the untreated diaphragm.

All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (10)

1. a kind of vibrating membrane, it is characterised in that the vibrating membrane includes metal base and positioned at least one master of the base material Metal oxide layer on surface, wherein, the metal oxide layer has one or more improvement acoustic characteristics and/or tonequality Following characteristics：

(i) metal oxide layer has orderly nano-tube array structure；

(ii) hardness of the metal oxide layer and/or modulus of elasticity are more than the hardness and/or springform of the metal base Amount；

And the metal oxide layer is generated by anodized.

2. vibrating membrane according to claim 1, it is characterised in that the substrate metal includes the metal being selected from the group：It is pure Titanium, titanium alloy, fine aluminium, aluminium alloy, or its combination.

3. vibrating membrane according to claim 1, it is characterised in that the metal oxide with nano-tube array structure Layer includes titanium oxide and/or aluminum oxide.

4. vibrating membrane according to claim 3, it is characterised in that the average length of the nanotube is 1 μm~50 μm； And/or the average diameter of the nanotube is 20~150nm.

5. a kind of loudspeaker, it is characterised in that the loudspeaker includes the vibrating membrane described in any one of Claims 1-4.

6. a kind of preparation method of vibrating membrane as claimed in claim 1, it is characterised in that comprise the following steps：

(a) metal base is provided；

(b) first metal oxide of the generation with nano-tube array structure at least one main surface of the metal base Layer；

(c) nanotube of first metal oxide layer is peeled off, obtaining main surface has nano-tube array structure template Metal base；

(d) second with nano-tube array structure is generated on main surface of the metal base with the nano-tube array template Metal oxide layer, obtain the vibrating membrane.

7. the preparation method of vibrating membrane according to claim 6, it is characterised in that the step (b) includes：

Configure the electrolyte aqueous solution containing fluorine ion；

In the electrolyte aqueous solution containing fluorine ion, using the metal base as anode, the metal base is carried out Anodized, so as to which generation has the first of nano-tube array structure at least one main surface of the metal base Metal oxide layer；

And/or the step (c) includes：

The nanotube in first metal oxide layer is peeled off by mechanical oscillation, in the main table of the metal base Nano-tube array template is generated on face, obtaining main surface has the metal base of nano-tube array structure template；

And/or the step (d) includes：

In described fluorine ion electrolyte aqueous solution, there is the metal base of the nano-tube array template as sun using main surface Pole, anodized is carried out to the metal base, there is the second metal of nano-tube array structure in the main Surface Creation Oxide skin(coating), obtain the vibrating membrane.

8. preparation method according to claim 7, it is characterised in that the electrolyte aqueous solution containing fluorine ion includes The fluoride being selected from the group：Ammonium fluoride, potassium fluoride, sodium fluoride or its combination；And/or

The electrolyte aqueous solution containing fluorine ion includes the additive being selected from the group：Deionized water, glycerine, ethylene glycol, Methanol or its combination.

9. preparation method according to claim 8, it is characterised in that the fluoride is ammonium fluoride, it is described containing fluorine from The content of ammonium fluoride is 0.01~2.5wt.% in the electrolyte aqueous solution of son.

10. a kind of preparation method of vibrating membrane as claimed in claim 1, it is characterised in that comprise the following steps：

(a1) metal base is provided；

(b1) in the phosphoric acid electrolyte aqueous solution, using the metal base as anode, anodic oxidation is carried out to the metal base Processing, generates metal oxide layer at least one main surface of the metal base, obtains the vibrating membrane.