CN112898019B - p-n-KNbO 3 /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-KNbO 3 /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-KNbO 3 /Cu 2 S heterojunction piezoelectric ceramic, a preparation method thereof and application thereof in self-powered high-efficiency hydrogen production. The heterojunction piezoelectric ceramic comprises n-KNbO 3 Piezoelectric ceramic substrate and p-Cu forming heterojunction therewith 2 S material, said p-Cu 2 The mass fraction of S is 0.1-10wt%. KNbO provided by the invention 3 /Cu 2 The S heterojunction piezoelectric ceramic has built-in electric field, low recombination rate of charges, high piezoelectric catalytic activity, and high p-n-KNbO 3 /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 prepare hydrogen through piezoelectric catalysis. 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 a p-n-KNbO 3 /Cu 2 S heterojunction piezoelectric ceramics, in particular to p-n-KNbO 3 /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, wherein 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 oxidation-reduction reaction of substances adsorbed on the surface of the piezoelectric material. The key of the piezoelectric material is that the piezoelectric material can absorb small mechanical energy such as sound, water wave, vibration and the like to generate charge separation, so that two sides of the piezoelectric material are charged with different signs.
However, the 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-KNbO for improving piezoelectric charge separation efficiency 3 /Cu 2 S heterojunction piezoelectric ceramic material and preparation thereofThe method and the application of the vehicle-mounted self-powered high-efficiency hydrogen production to overcome the defect of low piezoelectric catalysis efficiency caused by easy recombination of charges generated by piezoelectricity in the prior hydrogen production technology.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the p-n-KNbO 3 /Cu 2 S-heterojunction piezoceramic material comprising n-KNbO 3 Piezoelectric ceramic matrix and p-Cu uniformly dispersed on surface of 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 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 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 KNbO 3 The size of the piezoelectric ceramic substrate is 20mm × 20mm × 1mm.
Alternatively, the p-Cu 2 S is dispersed in n-KNbO 3 A piezoelectric ceramic surface.
Alternatively, the p-Cu 2 S is dispersed in n-KNbO 3 One of the surfaces of the piezoelectric ceramic.
The p-n-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium salt and niobium salt with alkali to generate KNbO 3 Greenware particles;
(2) And (3) granulation: to the KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the granules into a mould 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: treating for 0.5-2 h at 1150-1350 ℃ after degumming, and cooling to obtain KNbO3 ceramic;
(6)p-n-KNbO 3 /Cu 2 s, preparation of piezoelectric ceramics: at KNbO 3 Uniformly coating copper salt solution on one side of the piezoelectric ceramic, air drying, uniformly coating sulfide solution on the other side of the piezoelectric ceramic, and coating the piezoelectric ceramic with KNbO solution 3 Surface generation of Cu 2 S film, then sintering for 2h at 600 ℃ to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) Polarization treatment: p-n-KNbO 3 /Cu 2 Polarizing the S ceramic wafer for 20-60min under the voltage of 3-5 KV/mm, and standing for 24h to obtain p-n-KNbO 3 /Cu 2 S piezoelectric ceramics.
Optionally, the potassium salt is selected from KCl, KAc, K 2 SO 4 、KNO 3 At least one of (a).
Optionally, the niobium salt is selected from at least one of niobium chloride and niobium nitrate.
Optionally, 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 (a).
Optionally, the sulfide is selected from at least one of ammonium sulfide, sodium sulfide, thioacetamide, thiourea.
Optionally, the KNbO 3 The granules are prepared from KCl 2 Niobium chloride and NaOH solution.
Optionally, the concentration of the NaOH solution is in the range of 0.1-1.0mol/L.
Optionally, the KNbO 3 The particles are made of potassium nitrate, niobium nitrate 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.
Alternatively, the sulfide is formed from CuCl 2 Reacting with ammonium sulfide.
Optionally, the sulfide is formed from CuSO 4 And ammonium sulfide.
Optionally, the sulfide is formed from CuSO 4 Reacting with sodium sulfide.
Optionally, the sulfide is formed of Cu (NO) 3 ) 2 Reacting with sodium sulfide.
Optionally, the sulfide is made of Cu (NO) 3 ) 2 Reacting with thioacetamide.
Optionally, the sulfide is formed from Cu (Ac) 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, drying, 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 the KNbO 3 Cu of surface 2 And (S) film.
Optionally, the p-n-KNbO 3 /Cu 2 The S heterojunction piezoelectric ceramic is applied to vehicle-mounted self-powered hydrogen production.
Alternatively, p-n-KNbO at a temperature of 1-95 deg.C 3 /Cu 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.
Optionally, the p-n-KNbO 3 /Cu 2 S is from KNbO 3 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-KNbO into the ammonia borane aqueous solution 3 /Cu 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 generate hydrogen.
In the present invention, p-n-KNbO 3 /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-KNbO 3 /Cu 2 The S-piezoceramic material is a catalyst with piezoelectric effect. The catalyst generates piezoelectric effect in ultrasonic oscillation, and a self-established electric field is formed in the material, so that Cu is generated 2 The S has the functions 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-KNbO prepared by the invention 3 /Cu 2 The S heterojunction piezoceramic material hydrogen production system is applied to a running automobile, converts vibration energy in the running process of the automobile into electric energy, and then produces hydrogen through piezoelectric catalytic reaction to serve as automobile fuel to realize self-energy supply hydrogen production.
In one embodiment, the p-n-KNbO prepared by the invention 3 /Cu 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 p-n-KNbO provided by the invention 3 /Cu 2 The S heterojunction piezoelectric ceramic material does not use a noble metal catalyst, and has high catalytic activity, thereby reducing the production cost and maintaining high-efficiency catalytic activity.
(2) The invention provides p-n-KNbO 3 /Cu 2 The S heterojunction piezoelectric ceramic material 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-KNbO 3 /Cu 2 S heterogeneous phaseThe preparation method of the junction piezoceramic 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 by combining several embodiments.
The medicines used in the examples of the application are all commercially available.
Example 1
The p-n-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium chloride, niobium chloride and sodium hydroxide to generate KNbO 3 Greenware particles;
(2) And (3) granulation: to the KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the particles into a mold with a certain size, and pressing the particles into a greenware by a film pressing machine under the pressure of 10 MPa;
(4) Degumming: heating the greenware to 520 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) Molding: treating for 2h at 1100 deg.C after degumming, and cooling to obtain KNbO 3 A ceramic;
(6)p-n-KNbO 3 /Cu 2 s, preparation of piezoelectric ceramics: at KNbO 3 One side of the piezoelectric ceramic is uniformly coated with CuCl 2 Air drying the solution, uniformly coating an ammonium sulfide solution, washing the surface of the solution by deionized water, and carrying out constant temperature treatment at 200 ℃ for 120min to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-KNbO 3 /Cu 2 Polarizing the S ceramic wafer for 60min under the voltage of 3KV/mm, and standing for 24h to obtain p-n-KNbO 3 /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-KNbO into the solution 3 /Cu 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 ℃, 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-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium nitrate, niobium nitrate and ammonia water to generate KNbO 3 Greenware particles;
(2) And (3) granulation: to the KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the granules into a mould with a certain size, 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 keeping the temperature for 2 hours for degumming treatment;
(5) Molding: after degumming, treating for 1h at the temperature of 1200 ℃, and cooling to obtain KNbO3 ceramic;
(6)p-n-KNbO 3 /Cu 2 s, preparation of piezoelectric ceramics: at KNbO 3 One side of the piezoelectric ceramic is evenly coated with CuSO 4 The solution is dried in the air, then the ammonium sulfide solution is evenly coated,washing the surface with deionized water, and treating at 3000 deg.C for 60min to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-KNbO 3 /Cu 2 Polarizing the S ceramic chip for 50min under the voltage of 4KV/mm, and standing for 24h to obtain p-n-KNbO 3 /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-KNbO into the solution 3 /Cu 2 S heterojunction piezoelectric ceramic material, covering a 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: 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-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium chloride, niobium chloride and ammonia water to generate KNbO 3 Greenware particles;
(2) And (3) granulation: KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the granules into a mould with a certain size, 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:treating for 1h at 1150 ℃ after degumming, and cooling to obtain KNbO 3 A ceramic;
(6)p-n-KNbO 3 /Cu 2 s, preparation of piezoelectric ceramics: at KNbO 3 One side of the piezoelectric ceramic is uniformly coated with Cu (NO) 3 ) 2 Air drying, uniformly coating sodium sulfide solution, washing the surface with deionized water, and treating at 350 deg.C for 40min to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) Polarization treatment: p-n-KNbO 3 /Cu 2 Polarizing the S ceramic wafer for 20min under the voltage of 3KV/mm, and standing for 24h to obtain p-n-KNbO 3 /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-KNbO into the solution 3 /Cu 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: 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-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium nitrate, niobium chloride and potassium hydroxide to generate KNbO 3 Greenware particles;
(2) And (3) granulation: KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the particles into a mold with a certain size, and pressing the particles into a greenware by using a film pressing machine under the pressure of 30 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 1150 ℃ after degumming, and cooling to obtain KNbO 3 A ceramic;
(6)p-n-KNbO 3 /Cu 2 s, preparation of piezoelectric ceramics: at KNbO 3 One side of the piezoelectric ceramic is uniformly coated with CuCl 2 Air drying, uniformly coating with ammonium sulfide solution, washing the surface with deionized water, and treating at 320 deg.C for 30min to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) And (3) polarization treatment: p-n-KNbO 3 /Cu 2 Polarizing the S ceramic wafer for 40min under the voltage of 5KV/mm, and standing for 24h to obtain p-n-KNbO3/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-KNbO into the solution 3 /Cu 2 S heterojunction piezoelectric ceramic material, covering a 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: 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-KNbO prepared in example 1 to example 4 was used 3 /Cu 2 Drying hydrogen prepared from S heterojunction piezoelectric ceramic materialAnd (4) analyzing and detecting 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 content of the present invention and implement the 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 within the protection scope of the present invention.
Claims (8)
1. P-n-KNbO 3 /Cu 2 Use of an S-heterojunction piezoceramic material, characterized in that the p-n-KNbO 3 /Cu 2 The S heterojunction piezoelectric ceramic material comprises n-KNbO 3 Piezoelectric ceramic substrate and the n-KNbO 3 p-Cu of surface of 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 the S material is 0.1-10 μm; the p-n-KNbO 3 /Cu 2 The S heterojunction piezoelectric ceramic material is applied to self-powered hydrogen production, and is used for p-n-KNbO at the temperature of 1-95 DEG C 3 /Cu 2 And 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. The p-n-KNbO of claim 1 3 /Cu 2 The application of S heterojunction piezoelectric ceramic material is characterized in that the p-Cu is 2 S material is dispersed in n-KNbO 3 A surface of the piezoelectric ceramic substrate;
the p-Cu 2 S material is dispersed in n-KNbO 3 One surface of the piezoelectric ceramic substrate.
3. The p-n-KNbO of any one of claims 1-2 3 /Cu 2 Use of an S-heterojunction piezoceramic material, characterized in that the p-n-KNbO 3 /Cu 2 The preparation method of the S heterojunction piezoelectric ceramic material comprisesThe method comprises the following steps:
(1) Preparation of KNbO 3 Greenware particles: reacting potassium salt and niobium salt with alkali to generate KNbO 3 Greenware particles;
(2) And (3) granulation: to the KNbO prepared in the step (1) 3 Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) Preparing a greenware: KNbO prepared in the step (2) 3 Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into 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 1150-1350 ℃, cooling and obtaining KNbO 3 A ceramic;
（6）p-n-KNbO 3 /Cu 2 s ceramic preparation: at KNbO 3 Uniformly coating copper salt solution on one side of the ceramic, air drying, uniformly coating sulfide solution on the other side of the ceramic, and coating the copper salt solution on KNbO 3 Formation of Cu on ceramic surface 2 S film, then sintering for 2h at 600 ℃ to obtain compact and uniform p-n-KNbO 3 /Cu 2 S ceramic;
(7) And (3) polarization treatment: mixing p-n-KNbO 3 /Cu 2 Polarizing the S ceramic for 20-60min under the voltage of 3-5 KV/mm, and standing for 24h to obtain p-n-KNbO 3 /Cu 2 S heterojunction piezoceramic material.
4. The p-n-KNbO of claim 3 3 /Cu 2 The application of S heterojunction piezoelectric ceramic material is characterized in that the potassium salt is selected from KCl, KAc and K 2 SO 4 、KNO 3 At least one of;
the niobium salt is selected from at least one of niobium chloride and niobium nitrate;
the base is selected from NH 3 ·H 2 At least one of O, naOH and KOH.
5. The p-n-KNbO of claim 3 3 /Cu 2 S heterojunction piezoelectric ceramic materialThe application of the material is characterized in that the mass concentration of the polyvinyl alcohol solution is 4.0 wt% -8.0 wt%.
6. The p-n-KNbO of claim 3 3 /Cu 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-KNbO of claim 3 3 /Cu 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, drying, 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 the KNbO 3 Cu of ceramic surface 2 And (5) forming an S film.
8. The p-n-KNbO of claim 1 3 /Cu 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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