CN112811894B - p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramic, preparation method thereof and application of S heterojunction piezoelectric ceramic in self-powered efficient hydrogen production - Google Patents
p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramic, preparation method thereof and application of S heterojunction piezoelectric ceramic in self-powered efficient hydrogen production Download PDFInfo
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Abstract
The invention provides a p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics, a preparation method thereof and application in self-powered high-efficiency hydrogen production. The heterojunction piezoelectric ceramic comprises an n-ZnO piezoelectric ceramic matrix and p-Cu forming heterojunction with the n-ZnO piezoelectric ceramic matrix 2 S material, said p-Cu 2 The mass fraction of S is 0.1-10wt%. The invention provides ZnO/Cu 2 The S heterojunction piezoelectric ceramic has built-in electric field, low charge recombination rate, high piezoelectric catalytic activity, and the p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic can utilize water wave energy, sound wave energy and wind energy in the nature as driving forces to carry out piezoelectric catalysis to prepare hydrogen. The prepared hydrogen has high purity, does not contain carbon monoxide, hydrogen sulfide, phosphine, chloride ions and other gases which poison the fuel cell, has simple and easy preparation method, is green and environment-friendly, and does not discharge substances which are harmful to the environment.
Description
Technical Field
The invention relates to p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics, in particular to p-n-ZnO/Cu 2 An S heterojunction piezoelectric ceramic material, a preparation method thereof and application thereof in vehicle-mounted self-powered high-efficiency hydrogen production, belonging to the field of clean energy materials.
Background
The piezoelectric catalysis is a method for converting mechanical energy into chemical energy, namely, positive and negative charges are generated on the surface of a piezoelectric material under the action of external mechanical force, and the charges accelerate the redox reaction of substances adsorbed on the surface of the piezoelectric material. The piezoelectric material can absorb small mechanical energy such as sound, water waves, vibration and the like to generate charge separation, so that two sides of the piezoelectric material are charged with different signs.
However, piezoelectrically generated charges are easily recombined, resulting in poor piezoelectric catalytic efficiency. Therefore, technical means for improving the efficiency of the piezoelectric catalyst are necessary.
Disclosure of Invention
The invention aims to provide a p-n-ZnO/Cu for improving piezoelectric charge separation efficiency 2 S heterojunction piezoceramic material, preparation method thereof and application of S heterojunction piezoceramic material in vehicle-mounted self-powered high-efficiency preparation of high-purity hydrogen so as to overcome piezoelectric production in existing hydrogen production technologyThe generated charges are easy to be combined, so that the piezoelectric catalysis efficiency is not high.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic material comprises an n-ZnO piezoelectric ceramic matrix and p-Cu of heterojunction formed by the matrix 2 S material;
wherein, the p-Cu 2 The mass fraction of the S material is 0.1-10 wt%;
the p-Cu 2 The thickness of S is 0.1-10 μm.
Alternatively, the p-Cu 2 The upper limit of the mass fraction of the S material is selected from 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%; the p-Cu 2 The lower limit of the mass fraction of the S material is selected from the group consisting of 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%.
Alternatively, the p-Cu 2 The upper limit of the thickness of the S material is selected from 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm; the p-Cu 2 The lower limit of the thickness of the S material is selected from 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm.
Optionally, the ZnO piezoceramic matrix has dimensions of 20mm × 20mm × 1mm.
Alternatively, the p-Cu 2 S is dispersed on the surface of the n-ZnO piezoelectric ceramic.
Alternatively, the p-Cu 2 S is dispersed on one surface of the n-ZnO piezoelectric ceramic.
The p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particle: reacting the zinc salt with a base to form Zn (OH) 2 A particle;
(2) And (3) granulation: to the Zn (OH) prepared in step (1) 2 Adding a certain amount of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) Preparing a greenware: prepared by the step (2)Zn (OH) 2 Adding the granules into a grinding tool with a certain size, and pressing into a greenware by using a film pressing machine under the pressure of 10-30 MPa;
(4) Degumming: heating the greenware to 450-500 ℃, and carrying out degumming treatment at constant temperature for 1-2 h;
(5) Molding: after degumming, processing for 0.5h-2h at the temperature of 1150-1350 ℃, and cooling to obtain ZnO ceramics;
(6)p-n-ZnO/Cu 2 s, preparation of piezoelectric ceramics: uniformly coating a copper salt solution on one side of the ZnO piezoelectric ceramic, airing, then uniformly coating a sulfide solution to generate Cu on the surface of ZnO 2 S film, then sintering for 2h at 600 ℃ to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-ZnO/Cu 2 Polarizing the S ceramic wafer for 20-60min at the voltage of 3-5 KV/mm, and standing for 24h to obtain p-n-ZnO/Cu 2 S piezoelectric ceramics.
Optionally, the zinc salt is selected from ZnCl 2 、Zn(Ac) 2 、ZnSO 4 、Zn(NO 3 ) 2 At least one of (1).
Alternatively, the base is selected from NH 3 ·H 2 At least one of O, naOH and KOH.
Optionally, the copper salt is selected from CuCl 2 、CuSO 4 、Cu(NO 3 ) 2 、Cu(Ac) 2 At least one of (1).
Optionally, the sulfide is selected from at least one of ammonium sulfide, sodium sulfide, thioacetamide, thiourea.
Optionally, the ZnO particles are made of ZnCl 2 And NaOH solution.
Alternatively, the concentration of the NaOH solution is in the range of 0.1-1.0mol/L.
Optionally, the ZnO particles are made of ZnCl 2 And NH 3 ·H 2 And O reaction.
Alternatively, the NH 3 ·H 2 The concentration range of O is 0.1-2.0mol/L.
Optionally, the ZnO particles are made of Zn (Ac) 2 And NaOH solution.
Optionally, the ZnO particles are made of Zn (Ac) 2 And NH 3 ·H 2 And O reaction.
Alternatively, the sulfide is formed from CuCl 2 And ammonium sulfide.
Optionally, the sulfide is formed from CuSO 4 And ammonium sulfide.
Optionally, the sulfide is formed from CuSO 4 Reacting with thioacetamide.
Optionally, the sulfide is made of Cu (NO) 3 ) 2 Reacting with thiourea.
Optionally, the mass concentration of the polyvinyl alcohol (PVA) solution is 4.0 to 8.0wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 5.0wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 6.0wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 7.0wt%.
Optionally, the polarization voltage is 3.0KV/mm, and the polarization time is 60min.
Optionally, the polarization voltage is 4.0KV/mm, and the polarization time is 50min.
Optionally, the polarization voltage is 5.0KV/mm, and the polarization time is 40min.
Optionally, the preparing Cu 2 The S film is also prepared by uniformly coating a sulfide solution, airing, washing the surface of the S film with deionized water, and then carrying out constant-temperature treatment at 400-450 ℃ for 20-60min to obtain Cu on the surface of ZnO 2 And (S) film.
Alternatively, the p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic is applied to vehicle-mounted self-powered hydrogen production.
Alternatively, p-n-ZnO/Cu is subjected to temperature of 1-95 deg.C 2 The hydrogen production reaction system formed by the S heterojunction piezoelectric ceramic material and the ammonia borane aqueous solution applies mechanical vibration or ultrasonic vibration to realize the preparation of the hydrogen.
Optionally, the ultrasonic vibration frequency is 10-60KHz.
Optionally, the upper frequency limit of the ultrasonic wave is 20KHz, 30KHz, 40KHz, 50KHz, 60KHz; the lower limit of the frequency of the ultrasonic wave is 10KHz, 20KHz, 30KHz, 40KHz and 50KHz.
Alternatively, the p-n-ZnO/Cu 2 S is made of ZnO and Cu 2 S is used for constructing a p-n junction.
Alternatively, a self-powered piezo-catalytic hydrogen production method, comprising the steps of:
(1) Putting ammonia borane aqueous solution into a catalytic hydrogen production reactor, and adding p-n-ZnO/Cu into the ammonia borane aqueous solution 2 S, forming a hydrogen production reaction system by using a piezoceramic material, and then sealing the reactor;
(2) Adjusting the temperature of the reactor to 1-95 ℃, then pumping the system to vacuum, and adjusting the temperature in the reactor to 20-30 ℃ after the reactor reaches a vacuum state;
(3) And applying ultrasonic waves to a hydrogen production reaction system in the reactor to enable the hydrogen production reaction system to react and produce hydrogen.
In the invention, p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic material can convert mechanical energy into electric energy, and the action principle is that the original electrically neutral material generates non-coincident positive and negative charge centers under the action of external force by utilizing the asymmetry of the structure of the material, so that two ends or two surfaces of the material have different charges. The mechanical vibration or the ultrasonic vibration realizes the conversion of mechanical energy and electric energy.
The reaction mechanism of the piezoelectric catalytic hydrogen production provided by the invention is that NH is carried out in the presence of a proper catalyst 3 BH 3 Hydrogen may be released by solvolysis or thermal decomposition, as shown in formula (I) below:
NH 3 BH 3 (aq)+2H 2 O(l)＝NH 4 + (aq)+BO 2 - (aq)+3H 2 (g) Formula (I)
In the present invention, p-n-ZnO/Cu 2 The S-piezoceramic material is a catalyst with piezoelectric effect. The catalyst generates piezoelectric effect in ultrasonic oscillation, self-established electric field is formed in the material, and Cu is contained in the material 2 Of SThe hydrogen production method has the effects of reducing the recombination rate of positive and negative charges and improving the separation efficiency of the positive and negative charges, thereby further improving the hydrogen production efficiency.
The hydrogen prepared by the method is high-purity hydrogen, and does not contain carbon monoxide, hydrogen sulfide and other pollutants which poison fuel cell electrode materials.
In one embodiment, the p-n-ZnO/Cu prepared by the invention 2 The S-heterojunction piezoceramic material hydrogen production system is applied to running automobiles, converts vibration energy in the running process of the automobiles into electric energy, and then produces hydrogen through piezoelectric catalytic reaction to serve as automobile fuel to realize self-powered hydrogen production.
In one embodiment, the p-n-ZnO/Cu prepared by the invention 2 The S heterojunction piezoceramic material hydrogen production system is applied to a production workshop with high noise, and converts sound waves generated in the workshop production into electric energy to realize self-powered hydrogen production.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic material does not use a noble metal catalyst, and has high catalytic activity, so that the production cost is reduced, and high-efficiency catalytic activity is maintained.
(2) The p-n-ZnO/Cu2S heterojunction piezoelectric ceramic material provided by the invention can efficiently prepare high-purity hydrogen by utilizing mechanical energy such as water wave energy, wind energy, sound wave energy and the like in the nature, and realizes the collection and utilization of natural energy.
(3) The invention provides p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material is simple and easy to implement, green and environment-friendly, and does not discharge harmful substances to the environment.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The technical solution of the present invention is further explained below with reference to several examples.
The medicines used in the examples of the application are all commercially available.
Example 1
The p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particles: reacting zinc chloride with sodium hydroxide to generate Zn (OH) 2 Particles;
(2) And (3) granulation: to the Zn (OH) prepared in step (1) 2 Adding 5.0wt% of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) Preparing a greenware: zn (OH) prepared in the step (2) 2 Adding the granules into a grinding tool with the diameter of 20mm multiplied by 20mm, and pressing the granules into a greenware by a film pressing machine under the pressure of 10 MPa;
(4) Degumming: heating the greenware to 520 ℃, and keeping the temperature for 2 hours for degumming;
(5) Molding: after degumming, treating for 2h at 1100 ℃, and cooling to obtain ZnO ceramics;
(6)p-n-ZnO/Cu 2 s, preparation of piezoelectric ceramics: one side of ZnO piezoelectric ceramic is evenly coated with CuCl 2 Air drying the solution, uniformly coating an ammonium sulfide solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 200 ℃ for 120min to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) Polarization treatment: mixing p-n-ZnO/Cu 2 Polarizing the S ceramic wafer for 60min at the voltage of 3KV/mm, and standing for 24h to obtain p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L 3 BH 3 Adding the solution into a reactor, and adding the p-n-ZnO/Cu into the solution 2 S, covering a quartz glass plate on the heterojunction piezoelectric ceramic material and sealing the reactor;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 2
The p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particle: reacting zinc acetate with ammonia water to generate Zn (OH) 2 Particles;
(2) And (3) granulation: adding Zn (OH) prepared in the step (1) 2 Adding 6.0wt% of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) Preparing a greenware: zn (OH) prepared in the step (2) 2 Adding the granules into a grinding tool with the diameter of 20mm multiplied by 20mm, and pressing the granules into a greenware by a film pressing machine under the pressure of 15 MPa;
(4) Degumming: heating the greenware to 450 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) Molding: treating for 1h at the temperature of 1200 ℃ after degumming, and cooling to obtain ZnO ceramics;
(6)p-n-ZnO/Cu 2 s, preparation of piezoelectric ceramics: one side of ZnO piezoelectric ceramic is evenly coated with CuSO 4 Drying the solution, uniformly coating an ammonium sulfide solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 250 ℃ for 100min to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-ZnO/Cu 2 Polarizing the S ceramic wafer for 50min at the voltage of 4KV/mm, and standing for 24h to obtain p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L 3 BH 3 Adding the solution into a reactor, and adding the p-n-ZnO/Cu into the solution 2 S, covering a quartz glass plate on the heterojunction piezoelectric ceramic material and sealing the reactor;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 3
The p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particle: reacting zinc sulfate with potassium hydroxide to produce Zn (OH) 2 Particles;
(2) And (3) granulation: adding Zn (OH) prepared in the step (1) 2 Adding 7.0wt% of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) Preparing a greenware: zn (OH) prepared in the step (2) 2 Adding the granules into a grinding tool with the diameter of 20mm multiplied by 20mm, and pressing the granules into a greenware by a film pressing machine under the pressure of 20 MPa;
(4) Degumming: heating the greenware to 500 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) Molding: after degumming, treating for 1h at the temperature of 1150 ℃, and cooling to obtain ZnO ceramics;
(6)p-n-ZnO/Cu 2 s, preparation of piezoelectric ceramics: one side of ZnO piezoelectric ceramic is uniformly coated with Cu (NO) 3 ) 2 Drying the solution, uniformly coating a sodium sulfide solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 300 ℃ for 80min to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) And (3) polarization treatment: polarizing the p-n-ZnO/Cu2S ceramic wafer for 20min at the voltage of 3KV/mm, and standing for 24h to obtain the p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L 3 BH 3 Adding the solution into a reactor, and adding the p-n-ZnO/Cu into the solution 2 S heterojunction piezoelectricA ceramic material covering the quartz glass plate and sealing the reactor;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: the reactor is placed in a 28KHz ultrasonic cleaner, the ultrasonic is turned on, the hydrogen production system is adjusted to a system circulation state, then the experiment is carried out, and the hydrogen yield of each hour is detected by a gas chromatograph every other hour.
Example 4
The p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particle: reacting zinc nitrate with ammonia water to generate Zn (OH) 2 Particles;
(2) And (3) granulation: adding Zn (OH) prepared in the step (1) 2 Adding 8.0wt% of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) Preparing a greenware: zn (OH) prepared in the step (2) 2 Adding the granules into a grinding tool with the diameter of 20mm multiplied by 20mm, and pressing the granules into a greenware by a film pressing machine under the pressure of 20 MPa;
(4) Degumming: heating the greenware to 480 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) Molding: treating for 1h at the temperature of 1150 ℃ after degumming, and cooling to obtain ZnO ceramics;
(6) preparing p-n-ZnO/Cu2S piezoelectric ceramics: one side of ZnO piezoelectric ceramic is uniformly coated with CuCl 2 Drying the solution, uniformly coating an ammonium sulfide solution, washing the surface of the solution by deionized water, and then carrying out constant-temperature treatment at 350 ℃ for 30min to generate Cu on the surface of ZnO 2 S film, sintering for 2h at 620 ℃ to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-ZnO/Cu 2 Polarizing the S ceramic wafer for 40min at the voltage of 5KV/mm, and standing for 24h to obtain p-n-ZnO/Cu 2 S heterojunction piezoelectric ceramics.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L 3 BH 3 Adding the solution into a reactor, and adding the p-n-ZnO/Cu into the solution 2 S, covering a quartz glass plate on the heterojunction piezoelectric ceramic material and sealing the reactor;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 5
The p-n-ZnO/Cu obtained in examples 1 to 4 were mixed 2 And (3) drying the hydrogen prepared from the S heterojunction piezoelectric ceramic material, and then carrying out analysis and detection in a gas chromatograph, wherein impurity gases such as carbon monoxide, hydrogen sulfide, phosphine, chloride ions and the like are not detected.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. P-n-ZnO/Cu 2 The application of the S heterojunction piezoelectric ceramic material is characterized in that the p-n-ZnO/Cu 2 The S heterojunction piezoelectric ceramic material comprises an n-ZnO piezoelectric ceramic matrix and p-Cu which forms a heterojunction with the n-ZnO piezoelectric ceramic matrix 2 S material; wherein, the p-Cu 2 The mass fraction of the S material is 0.1-10 wt%; the p-Cu 2 The thickness of S material is 0.1-10 μm, and the p-n-ZnO/Cu 2 S heterojunction piezoceramic material in self-powered hydrogen productionThe application is to p-n-ZnO/Cu at the temperature of 1-95 DEG C 2 The hydrogen production reaction system formed by the S heterojunction piezoelectric ceramic material and the ammonia borane aqueous solution applies mechanical vibration or ultrasonic vibration to realize the preparation of the hydrogen.
2. p-n-ZnO/Cu according to claim 1 2 The application of S heterojunction piezoelectric ceramic material is characterized in that the p-Cu is 2 The S material is dispersed on the surface of the n-ZnO piezoelectric ceramic matrix;
the p-Cu 2 The S material is dispersed on one surface of the n-ZnO piezoelectric ceramic matrix.
3. p-n-ZnO/Cu according to any of claims 1-2 2 The application of the S heterojunction piezoelectric ceramic material is characterized in that the p-n-ZnO/Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of Zn (OH) 2 And (3) particle: reacting the zinc salt with a base to form Zn (OH) 2 A particle;
(2) And (3) granulation: adding Zn (OH) prepared in the step (1) 2 Adding a certain amount of polyvinyl alcohol solution into the granules, and then carrying out ball milling granulation;
(3) Preparing a greenware: zn (OH) prepared in the step (2) 2 Adding the granules into a grinding tool with a certain size, and pressing into a greenware by a film pressing machine under the pressure of 10-30 MPa;
(4) Degumming: heating the greenware to 450-500 ℃, and carrying out degumming treatment at constant temperature for 1-2 h;
(5) Molding: after degumming, processing for 0.5h-2h at the temperature of 1150-1350 ℃, and cooling to obtain ZnO ceramics;
（6）p-n-ZnO/Cu 2 s ceramic preparation: uniformly coating a copper salt solution on one side of the ZnO ceramic, airing, then uniformly coating a sulfide solution to generate Cu on the surface of the ZnO ceramic 2 S film, then sintering for 2h at 200-350 ℃ to obtain compact and uniform p-n-ZnO/Cu 2 S ceramic;
(7) And (3) polarization treatment: p-n-ZnO/Cu 2 The S ceramic is polarized by 20-60 ℃ under the voltage of 3-5 KV/mmmin, standing for 24h to obtain p-n-ZnO/Cu 2 S heterojunction piezoceramic material.
4. p-n-ZnO/Cu according to claim 3 2 The application of S heterojunction piezoelectric ceramic material is characterized in that the zinc salt is selected from ZnCl 2 、Zn(Ac) 2 、ZnSO 4 、Zn(NO 3 ) 2 At least one of;
the base is selected from NH 3 ·H 2 At least one of O, naOH and KOH.
5. p-n-ZnO/Cu according to claim 3 2 The application of the S heterojunction piezoceramic material is characterized in that the mass concentration of the polyvinyl alcohol solution is 4.0 wt% -8.0 wt%.
6. p-n-ZnO/Cu according to claim 3 2 The application of the S heterojunction piezoelectric ceramic material is characterized in that the copper salt is selected from CuCl 2 、CuSO 4 、Cu(NO 3 ) 2 、Cu (Ac) 2 At least one of;
the sulfide is selected from at least one of ammonium sulfide, sodium sulfide, thioacetamide and thiourea.
7. The p-n-ZnO/Cu of claim 3 2 Use of an S heterojunction piezoceramic material, characterized in that the generated Cu 2 The S film is also prepared by uniformly coating a sulfide solution, airing, washing the surface of the S film with deionized water, and then carrying out constant-temperature treatment at 200-350 ℃ for 20-60min to obtain Cu on the surface of the ZnO ceramic 2 And (5) forming an S film.
8. p-n-ZnO/Cu according to claim 1 2 The application of the S heterojunction piezoelectric ceramic material is characterized in that: the frequency of the ultrasonic wave is 10-60KHz.
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