Piezoelectric material and preparation method therefor, piezoelectric device, and electronic device

Abstract

The present application provides a piezoelectric material and a preparation method therefor, a piezoelectric device, and an electronic device. The general chemical formula of the piezoelectric material comprises: xPb(Mn1 / 2W1 / 2)O3-(1-x)[0.15Pb(Zn1 / 3Nb2 / 3)O3-0.85Pb(Zr0.5Ti0.5)O3], wherein 0.05 ≤ x ≤ 0.08. In the present application, a solid-phase synthesis method is used to improve the mechanical quality factor, electromechanical coupling coefficient, piezoelectric constant, dielectric loss, Young's modulus, etc. of the prepared piezoelectric material by doping same with lead tungstate, adjusting the range of parameter x and controlling the sintering temperature during synthesis, and preferably adding rare earth elements Yb, Er, Eu, etc.; and the preparation process is simple, and the raw materials are environmentally friendly. The piezoelectric material, when used in high-frequency piezoelectric devices and electronic devices, can meet the use requirements of high performance and low power consumption.

Description

Piezoelectric materials and their preparation methods, piezoelectric devices, electronic equipment

[0001] This application claims priority to Chinese Patent Application No. 202411586540.2, filed on November 7, 2024, entitled "Piezoelectric Materials and Preparation Methods Thereof, Piezoelectric Devices, Electronic Equipment", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of piezoelectric materials technology, specifically to a piezoelectric material and its preparation method, a piezoelectric device, and an electronic device. Background Technology

[0003] Piezoelectric materials, with their high voltage coefficient and high stability, have been widely used in electronics and communications. They can convert electrical energy into mechanical energy and are widely used in various piezoelectric devices and corresponding terminal electronic devices, such as buzzers, sensors, high-frequency resonators, ultrasonic transducers, actuators, filters, surface acoustic wave devices, and piezoelectric pumps.

[0004] Currently, piezoelectric materials are widely used in high-frequency applications (such as piezoelectric resonators, ultrasonic motors, and piezoelectric pumps) due to their advantages such as short response time and high conversion efficiency. However, under the drive of a strong ultrasonic alternating electric field, piezoelectric materials tend to generate a lot of heat, resulting in a significant temperature rise. This causes a series of problems in the devices, such as frequency drift, material cracking, silver ion migration in the electrodes, and reduced lifespan of the piezoelectric materials in humid environments, thus limiting the widespread application of piezoelectric materials.

[0005] Therefore, reducing the self-heating of piezoelectric materials is crucial for their high-frequency applications in power devices. Summary of the Invention

[0006] In view of this, the embodiments of this application provide a piezoelectric material and its preparation method, a piezoelectric device, and an electronic device, which can effectively reduce the loss of piezoelectric material, improve the power conversion efficiency, achieve wide bandwidth and high sensitivity, reduce the heat generation of piezoelectric material, and improve the performance and stability of piezoelectric material applied to piezoelectric devices and electronic devices in high-frequency applications.

[0007] In a first aspect, this application provides a piezoelectric material, the chemical formula of which includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5)O3], where 0.05≤x≤0.08.

[0008] In some embodiments, the piezoelectric material has the following general chemical formula: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3]+yQ, wherein Q comprises an oxide of at least one element selected from Yb and Eu, wherein Q is in xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y wt%, 0.2≤y≤0.6.

[0009] In some embodiments, Q is Yb2O3 and Eu2O3;

[0010] The Yb2O3 in xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y1 wt%, 0.1≤y1≤0.3;

[0011] The Eu2O3 in x Pb(Mn 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y2 wt%, 0.1≤y2≤0.3.

[0012] In some embodiments, the piezoelectric material has the following general chemical formula: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+yQ+zEr 0.1Bi 0.9 FeO3, the Er 0.1 Bi 0.9 FeO3 in x Pb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+yQ+zEr 0.1 Bi 0.9 The mass percentage of FeO3 is z wt%, z≤0.5.

[0013] In some embodiments, the piezoelectric material has the following general chemical formula: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+zEr 0.1 Bi 0.9 FeO3, the Er 0.1 Bi 0.9 FeO3 in x Pb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+zEr 0.1 Bi 0.9 The mass percentage of FeO3 is z wt%, z≤0.5. In some embodiments, the density of the piezoelectric material is 7.53 g / cm³. 3 ~7.70g / cm 3 .

[0014] In some embodiments, the piezoelectric strain constant D of the piezoelectric material 33 It ranges from 365 pC / N to 400 pC / N.

[0015] In some embodiments, the mechanical quality factor Q of the piezoelectric material m The range is 500 to 1500.

[0016] In some embodiments, the dielectric loss of the piezoelectric material is 0.2% to 0.6% at 20 kHz to 20 MHz.

[0017] Secondly, this application provides a method for preparing a piezoelectric material, the method comprising the following steps:

[0018] According to the chemical formula of the piezoelectric material described in the first aspect, powdered raw materials of ZnO, Nb2O5, Pb3O4, ZrO2 and TiO2 were weighed, mixed with the first dispersant, and then ball-milled once. The ball-milled product was dried and then pre-calcined once to obtain 0.15Pb(ZnO)2. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder;

[0019] According to the chemical formula of the piezoelectric material described in the first aspect, powder raw materials of Pb3O4, WO3, and MnCO3 were weighed, mixed with the second dispersant, and then subjected to secondary ball milling. The secondary ball milling product was dried and then subjected to secondary pre-calcination to obtain Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder;

[0020] Weigh out 92 mol% to 95 mol% of 0.15Pb(Zn) according to molar percentage. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder and 5 mol%–8 mol% Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder is mixed, the mixture is ball-milled three times, dried and then pre-calcined three times.

[0021] The product from the three pre-calcination treatments and the additives are mixed and then molded to obtain a piezoelectric material blank.

[0022] The piezoelectric material blank is heated to 1150℃~1200℃ for sintering and then cooled to obtain a piezoelectric material sheet.

[0023] A conductive layer is formed on the surface of the piezoelectric material sheet, and then polarization treatment is performed to obtain the piezoelectric material.

[0024] In some embodiments, the first dispersant includes at least one of water and ethanol.

[0025] In some embodiments, the rotation speed of the ball milling is 200 r / min to 250 r / min, and the time of the ball milling is 1 h to 5 h.

[0026] In some embodiments, the temperature of the first pre-firing treatment is 800℃~900℃, and the time of the first pre-firing treatment is 1h~10h.

[0027] In some embodiments, the second dispersant includes at least one of water and ethanol.

[0028] In some embodiments, the rotation speed of the secondary ball mill is 200 r / min to 250 r / min, and the secondary ball milling time is 1 h to 5 h.

[0029] In some embodiments, the temperature of the secondary pre-firing treatment is 750°C to 850°C, and the time of the secondary pre-firing treatment is 1 hour to 5 hours.

[0030] In some embodiments, the temperature of the three pre-firing treatments is 900℃ to 1000℃, and the time of the three pre-firing treatments is 2h to 10h.

[0031] In some embodiments, the median particle size of the product from the three pre-calcination treatments is 0.2 μm to 0.4 μm.

[0032] In some embodiments, the additives include at least one of adhesives, dispersants, solvents, and leveling agents.

[0033] In some embodiments, the amount of the additive is 14 wt% to 18 wt% of the total weight of the product from the three pre-calcination treatments.

[0034] In some embodiments, the heating rate of the sintering treatment is 1°C / min to 5°C / min, and the holding time of the sintering treatment is 30 min to 90 min.

[0035] In some embodiments, the method further includes:

[0036] Provide Q powder, said Q powder comprising an oxide of at least one element selected from Yb and Eu;

[0037] Prior to the three ball milling processes, the Q powder is added to the mixture, wherein the Q powder constitutes 0.2 wt% to 0.6 wt% of the mass percentage of the mixture and the new mixture formed by the Q powder.

[0038] In some embodiments, the method further includes:

[0039] According to the general chemical formula of the piezoelectric material described in the first aspect, powdered raw materials of Er₂O₃, Bi₂O₃, and Fe₂O₃ were weighed, mixed with a third dispersant, and ball-milled four times. The products from the four ball millings were dried and then pre-calcined four times to obtain Er₂O₃. 0.1 Bi 0.9 FeO3 powder;

[0040] Before the three ball milling processes, Er is added to the mixture. 0.1 Bi0.9 FeO3 powder, the Er 0.1 Bi 0.9 FeO3 powder in the mixture and the Er 0.1 Bi 0.9 The mass percentage of the new mixed product formed from FeO3 powder is less than or equal to 0.5 wt%.

[0041] In some embodiments, the third dispersant includes at least one of water and ethanol.

[0042] In some embodiments, the rotation speed of the four ball milling processes is 200 r / min to 250 r / min, and the time for the four ball milling processes is 1 h to 5 h.

[0043] In some embodiments, the temperature of the four pre-firing treatments is 800℃ to 900℃, and the time of the four pre-firing treatments is 1h to 5h.

[0044] Thirdly, this application provides a piezoelectric device, the piezoelectric device comprising the piezoelectric material described in the first aspect or the piezoelectric material prepared by the method described in the second aspect.

[0045] Fourthly, this application provides an electronic device comprising the piezoelectric device described in the third aspect.

[0046] Compared with the prior art, the piezoelectric material provided in this application is a ternary piezoelectric material consisting of lead manganese tungstate, lead zinc niobate, and lead zirconate titanate, wherein the lead zinc niobate and lead zirconate titanate are 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 O3 is used as the main material, and lead tungstate (Pb(Mn)) is used as the main material. 1 / 2 W 1 / 2 O3 is used as a dopant. Lead zinc niobate-lead zirconate titanate system exhibits high density, excellent insulation properties, good piezoelectricity, and low dielectric loss P. m The addition of lead tungsten manganate allows for hard doping of lead zinc niobate-lead zirconate titanate, reducing the polarization of piezoelectric materials and improving the mechanical quality factor Q. m This reduces internal friction loss and lowers mechanical loss P. d This also improves the temperature stability of the material at high temperatures, thereby reducing the heat generation of the piezoelectric material. Furthermore, lead manganese tungstate has an excellent electromechanical coupling constant Kp, which enables the piezoelectric material to have low dielectric loss P. mMeanwhile, lead tungsten manganese oxide has a high breakdown field strength, excellent insulation resistance, and resonant frequency temperature stability, which enables piezoelectric materials to exhibit excellent insulation resistance and temperature stability as a whole. This achieves wide bandwidth and high sensitivity of piezoelectric materials, while reducing the heating problem caused by leakage loss, improving energy conversion efficiency, and reducing heat generation. It can be widely used in piezoelectric devices and electronic equipment in the ultrasonic frequency band.

[0047] Furthermore, in ternary piezoelectric materials xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 Adding Q to [O3] results in a stoichiometric formula of xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3]+yQ. Where Q includes an oxide of at least one element selected from Yb and Eu, 0.2≤y≤0.6. By doping Q, the mechanical quality factor Q of the piezoelectric material can be improved. m It can also increase piezoelectric activity, improve the vibration velocity of piezoelectric materials and the amplitude of piezoelectric elements, thereby reducing the heat generation of piezoelectric materials.

[0048] Furthermore, in ternary piezoelectric materials xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 Add Er to O3] 0.1 Bi 0.9 FeO3, Er 0.1 Bi 0.9 FeO3 has a piezoelectric perovskite (ABO3) structure, where the A-site is occupied by the rare earth elements erbium (Er) and bismuth (Bi), and the B-site is occupied by iron (Fe). On the one hand, Er... 0.1 Bi 0.9 FeO3 can be incorporated into the host material 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5In O3, it undergoes solid solution formation with the host material to optimize the crystal structure of the host material, thereby improving the piezoelectric coefficient and electromechanical coupling coefficient of the piezoelectric material and enhancing its piezoelectric performance. On the other hand, Er 0.1 Bi 0.9 FeO3 can be embedded in the grain boundaries of the host material, inhibiting crystal growth at the grain boundaries, reducing grain size, preventing abnormal grain growth, and increasing the density of the piezoelectric material, thereby improving the mechanical strength, Young's modulus and vibration velocity of the piezoelectric material and improving its performance.

[0049] This application also provides a method for preparing piezoelectric materials. By optimizing the raw material composition formulation of the piezoelectric material and mixing the raw material composition formulation through a solid-state method, a method for preparing piezoelectric materials with 0.15Pb(Zn) can be achieved. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 Add Pb(Mn) to O3 pre-calcined powder 1 / 2 W 1 / 2 O3 pre-calcined powder, combined with sintering treatment at a specific temperature, achieves the processing of 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 Hard doping of O3, followed by further doping with specific rare earth elements Yb, Eu, and Er, improves the mechanical quality factor and piezoelectric properties of the prepared piezoelectric material. The preparation process provided in this application is easy to mass-produce, uses environmentally friendly raw materials with clear raw material composition, and can obtain piezoelectric materials with excellent comprehensive performance. Under the same configuration and driving conditions, the temperature rise is within 20°C, enabling its wide application in high-frequency piezoelectric devices and electronic equipment. Attached Figure Description

[0050] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0051] Figure 1 is a flowchart of the preparation process of the piezoelectric material provided in the embodiments of this application. Detailed Implementation

[0052] The technical solutions provided by the present invention will be further described below with reference to specific embodiments and comparative examples, but this application is not limited to the following embodiments.

[0053] To better understand the technical solution of this application, the embodiments of this application will be described in detail below with reference to the accompanying drawings.

[0054] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0055] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined with "first" or "second" may explicitly or implicitly include one or more of that feature.

[0056] The following is a brief explanation of the concepts involved in the embodiments of this application:

[0057] Piezoelectric materials are electronic materials exhibiting the piezoelectric effect, capable of converting mechanical stress into electrical signals or vice versa. The piezoelectric effect occurs when mechanical stress causes a relative displacement of the internal positive and negative charge centers, resulting in the appearance of bound charges of opposite signs on the material's surfaces. Piezoelectric materials are primarily used in the manufacture of ultrasonic transducers, underwater acoustic transducers, electroacoustic transducers, ceramic filters, ceramic transformers, ceramic frequency discriminators, high-voltage generators, infrared detectors, surface acoustic wave devices, electro-optic devices, piezoelectric pumps, piezo-hydraulic pumps, ignition and detonation devices, and piezoelectric gyroscopes, among others.

[0058] Ultrasonic frequencies typically refer to sound waves with frequencies outside the range of human hearing, generally referring to sound waves above 20kHz, which are usually called high frequencies.

[0059] Currently, the most widely used piezoelectric materials in industry include organic piezoelectric materials, polycrystalline piezoelectric ceramics, textured piezoelectric ceramics, piezoelectric thin films, and single-crystal piezoelectric materials. Single-crystal piezoelectric materials are emerging high-performance piezoelectric materials, but their cost and production capacity need further improvement.

[0060] During use, piezoelectric materials commonly experience heat generation and temperature rise, especially when driven by strong ultrasonic AC electric fields, such as in high-power devices like piezoelectric resonators, ultrasonic motors, and ultrasonic piezoelectric pumps. This heat generation and temperature rise can cause a series of problems, including: a) frequency drift, leading to decreased material performance and even preventing effective resonance; b) frequency tracking designs are often used in circuits to ensure resonance, achieving dynamic frequency tracking and avoiding temperature drift, but this introduces complex circuit design, additional power consumption, and heat generation; c) heat generation can cause material cracking, reducing reliability; simultaneously, increased temperature accelerates silver ion migration in the electrodes, significantly reducing the device's lifespan in high-temperature and humid environments, and using palladium-silver alloys or gold electrodes as alternatives leads to a sharp increase in cost; piezoelectric pumps (also known as piezoelectric fans), used as heat dissipation devices, experience significant self-heating, resulting in a substantial decrease in heat dissipation capacity, and in some scenarios, heat generation exceeds heat dissipation. In summary, the high-frequency self-heating problem of piezoelectric devices (especially piezoelectric pumps) severely limits their use in many high-precision and extremely size-constrained applications.

[0061] Heat generation in piezoelectric devices arises from an imbalance between heat generation and dissipation. Heat generation originates from the mechanical and dielectric losses of the piezoelectric material itself, while heat dissipation is primarily determined by the device's material, size, and specific surface area. Considering the limited space and material selection required for practical applications, both the device's internal and external heat dissipation capabilities are limited. Therefore, suppressing the intrinsic heating of the piezoelectric material becomes particularly important. On one hand, intrinsic heating originates from the dielectric loss P of the material. m Electrical quality factor Q can be used. e Characterized by (tanδ), namely dielectric relaxation, leakage current, and dielectric inhomogeneity; on the other hand, intrinsic heating is caused by mechanical losses P. d (i.e., internal friction) leads to the mechanical quality factor Q. m Characterization. Externally, piezoelectric materials exhibit low average vibration velocity. When a high-frequency AC signal is applied, the material's vibration velocity approaches its intrinsic limit, resulting in a significant portion of the input power being converted into heat energy. Compared to low-frequency driven piezoelectric pumps (200Hz), piezoelectric pumps operating in the ultrasonic frequency band (>20kHz) experience a substantial increase in mechanical losses.

[0062] According to the vibration velocity formula of the resonant device of the piezoelectric pump: v = Q m ·d 31 E3(Y / ρ) 1 / 2 Or v = Q m ·k 31 E3(Y / ρ) 1 / 2 Q m For mechanical quality factor, d 31 k is the piezoelectric coefficient. 31Here, is the electromechanical coupling coefficient, E is the electric field, 3 represents the polarization direction, Y is Young's modulus, and ρ is density. Increasing the vibration velocity v depends on the aforementioned parameters of the piezoelectric material. Reducing mechanical losses depends on the piezoelectric material formulation design and process optimization, and reducing internal friction P. d Improve the mechanical quality factor Q of the material m The main solutions involve formulation design and manufacturing processes. Current manufacturing processes for piezoelectric ceramics, from powder preparation and molding to sintering, are relatively advanced to a certain extent, ensuring uniform and dense microstructure and consistent grain growth in the ceramic material, leaving limited room for improvement. Therefore, formulation design becomes crucial for preparing materials with low heat generation and high power.

[0063] Lead-based piezoelectric materials possess high electromechanical coupling coefficients and high energy conversion efficiency between electrical and mechanical energy, making them suitable for use in high-frequency electronic devices. Common lead-based piezoelectric materials, such as the widely used lead zirconate titanate (PZT) series and lead-based relaxor ferroelectric materials, belong to the ABO3 perovskite structure. The piezoelectric strain constant D of common lead-based piezoelectric materials is... 33 Approximately 350p C / N, mechanical quality factor Q m Approximately 550. Research has found that when a high-frequency AC signal of 20kHz to 20MHz is applied to a lead-based piezoelectric material, a large portion of the power input to the material is converted into heat energy, causing severe heating and deterioration of the piezoelectric performance, which seriously restricts its application in high-frequency electronic devices.

[0064] In view of this, this application provides a piezoelectric material, the general chemical formula of which includes:

[0065] x Pb(Mn 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3], where 0.05≤x≤0.08.

[0066] The piezoelectric material provided in this application is a ternary piezoelectric material consisting of lead manganese tungstate, lead zinc niobate, and lead zirconate titanate, wherein the lead zinc niobate and lead zirconate titanate are 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 O3 is used as the main material, and lead tungstate (Pb(Mn)) is used as the main material. 1 / 2 W 1 / 2 O3 is used as a dopant. Lead zinc niobate-lead zirconate titanate system exhibits high density, excellent insulation properties, good piezoelectricity, and low dielectric loss P. mThe addition of lead tungsten manganate allows for hard doping of lead zinc niobate-lead zirconate titanate, reducing the polarization of piezoelectric materials and improving the mechanical quality factor Q. m This reduces internal friction loss and lowers mechanical loss P. d This also improves the temperature stability of the material at high temperatures, thereby reducing the heat generation of the piezoelectric material. Furthermore, lead manganese tungstate has an excellent electromechanical coupling constant Kp, which enables the piezoelectric material to have low dielectric loss P. m Meanwhile, lead tungsten manganese oxide has a high breakdown field strength, excellent insulation resistance, and resonant frequency temperature stability, which enables piezoelectric materials to exhibit excellent insulation resistance and temperature stability as a whole. This achieves wide bandwidth and high sensitivity of piezoelectric materials, while reducing the heating problem caused by leakage loss, improving energy conversion efficiency, and reducing heat generation. It can be widely used in piezoelectric devices and electronic equipment in the ultrasonic frequency band.

[0067] x represents lead tungsten manganate (Pb(Mn)) 1 / 2 W 1 / 2 The molar percentage of O3 in piezoelectric materials, i.e., the percentage of lead tungsten manganese oxide (Pb(Mn)) in piezoelectric materials. 1 / 2 W 1 / 2 The molar percentage of O3 can be 5 mol%, 5.5 mol%, 6 mol%, 6.5 mol%, 7 mol%, or 8 mol%, or any value within the range of 5 mol% to 8 mol%, and is not limited here. Preferably, the piezoelectric material contains lead manganese tungstate (Pb(Mn)) 1 / 2 W 1 / 2 The molar percentage of O3 is 6 mol% to 7 mol%.

[0068] As a further optional technical solution of this application, Q is also added to the piezoelectric material, that is, the general chemical formula of the piezoelectric material includes: xPb(Mn 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3]+yQ. Wherein, Q includes an oxide of at least one element selected from Yb and Eu. In some embodiments, Q is an oxide of Yb; in other embodiments, Q is an oxide of Eu; in still other embodiments, Q may be an oxide of both Yb and Eu.

[0069] In piezoelectric materials, the mass percentage of Q in the piezoelectric material is y wt%, 0.2≤y≤0.6. The mass percentage (doping amount) of Q can be 0.2wt%, 0.3wt%, 0.45wt%, 0.5wt%, 0.55wt%, or 0.6wt%, etc., or any value between 0.2wt% and 0.6wt%, which is not limited here.

[0070] It is understood that adding oxides Q, such as Yb2O3 and Eu2O3, to the piezoelectric materials in this application improves the mechanical quality factor Q of the piezoelectric materials. m This increases piezoelectric activity, improves the vibration velocity and amplitude of piezoelectric materials, and thus reduces the heat generation of piezoelectric materials.

[0071] In some implementations, Q is Yb2O3.

[0072] In some implementations, Q is Eu2O3.

[0073] Preferably, Q is a mixture of Eu₂O₃ and Yb₂O₃, meaning the general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The piezoelectric material is composed of Yb₂O₃ + y₁Yb₂O₃ + y₂Eu₂O₃. The mass percentage of Yb₂O₃ in the piezoelectric material is y₁ wt%, 0.1 ≤ y₁ ≤ 0.3, preferably 0.2 ≤ y₁ ≤ 0.3. The mass percentage of Eu₂O₃ in the piezoelectric material is y₂ wt%, 0.1 ≤ y₂ ≤ 0.3, preferably 0.25 ≤ y₂ ≤ 0.3.

[0074] It is understood that adding Eu2O3 and Yb2O3 to the piezoelectric material of this application can further increase the piezoelectric activity, improve the vibration speed and amplitude of the piezoelectric material, thereby reducing the heat generation of the piezoelectric material.

[0075] As a further optional technical solution in this application, Er is also added to the piezoelectric material. 0.1 Bi 0.9 FeO3, that is, the general chemical formula of piezoelectric materials includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+z Er 0.1 Bi 0.9FeO3. Where z≤0.5.

[0076] In some embodiments, the general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+yQ+z Er 0.1 Bi 0.9 FeO3.

[0077] Preferably, the general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+y1 Yb2O3+y2 Eu2O3+z Er 0.1 Bi 0.9 FeO3.

[0078] It is understandable that Er is added to piezoelectric materials. 0.1 Bi 0.9 FeO3, Er 0.1 Bi 0.9 FeO3 has a piezoelectric perovskite (ABO3) structure, where the A-site is occupied by the rare earth elements erbium (Er) and bismuth (Bi), and the B-site is occupied by iron (Fe). On the one hand, Er... 0.1 Bi 0.9 FeO3 can be incorporated into the host material 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 In O3, it undergoes solid solution formation with the host material to optimize the crystal structure of the host material, thereby improving the piezoelectric coefficient and electromechanical coupling coefficient of the piezoelectric material and enhancing its piezoelectric performance. On the other hand, Er 0.1 Bi 0.9 FeO3 can be embedded in the grain boundaries of the host material, inhibiting crystal growth at the grain boundaries, reducing grain size, preventing abnormal grain growth, and increasing the density of the piezoelectric material, thereby improving the mechanical strength, Young's modulus and vibration velocity of the piezoelectric material and improving its piezoelectric performance.

[0079] In piezoelectric materials, Er 0.1 Bi 0.9The mass percentage of FeO3 in the piezoelectric material is z wt%, z≤0.5, Er 0.1 Bi 0.9 The mass percentage (doping amount) of FeO3 can be 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, or 0.5wt%, or any value between 0 and 0.5wt%, and is not limited here. It can be understood that when Er... 0.1 Bi 0.9 The mass percentage of FeO3 in the piezoelectric material is 0 wt%, indicating that the piezoelectric material does not contain Er. 0.1 Bi 0.9 FeO3. Preferably, Er 0.1 Bi 0.9 The mass percentage of FeO3 in the piezoelectric material is 0.1 wt%.

[0080] In some implementations, Yb2O3, Eu2O3 and Er 0.1 Bi 0.9 The total mass percentage of FeO3 in piezoelectric materials is less than or equal to 1 wt%.

[0081] In some embodiments, the density of the piezoelectric material is 7.53 g / cm³. 3 ~7.70g / cm 3 It can be 7.53 g / cm³ 3 7.55g / cm 3 7.58g / cm 3 7.60 g / cm 3 7.65g / cm 3 Or 7.70 g / cm 3 etc., without restriction.

[0082] In some embodiments, the piezoelectric strain constant D of the piezoelectric material 33 The range is 365pC / N to 400pC / N, and can be 365pC / N, 370pC / N, 375pC / N, 380pC / N, 385pC / N, 390pC / N, 395pC / N, or 400pC / N, etc., without any restrictions.

[0083] In some implementations, the mechanical quality factor Q of the piezoelectric material m The range is 500 to 1500, and can be 500, 550, 600, 680, 700, 750, 800, 900, 1000, 1050, 1120, 1200, 1300, 1400 or 1500, etc., without any restrictions.

[0084] In some embodiments, the dielectric loss of the piezoelectric material at 20 kHz to 20 MHz is 0.2% to 0.6%, which can be 0.2%, 0.3%, 0.4%, 0.5% or 0.55%, etc., and is not limited here.

[0085] The types and contents of elements in the piezoelectric material of this application can be qualitatively and quantitatively analyzed using ICP. ICP is an inductively coupled plasma spectrometer, which analyzes the analyte based on the characteristic spectral lines emitted when the atoms of the analyte in the excited state return to the ground state. ICP-OES can simultaneously determine most elements in the periodic table (metallic elements and non-metallic elements such as phosphorus, silicon, arsenic, and boron), and all have good detection limits, with detection limits at least at the PPM level.

[0086] The piezoelectric materials provided in this application can be widely used in piezoelectric devices. Piezoelectric devices can utilize the piezoelectric effect to fabricate piezoelectric power supplies, piezoelectric sensors, piezoelectric loudspeakers, ultrasonic generators, piezoelectric gyroscopes, piezoelectric resonators, piezoelectric pumps, and piezoelectric relays, etc., especially in high-frequency applications such as piezoelectric transducers, ultrasonic motors, and piezoelectric pumps, but are not limited here.

[0087] The piezoelectric device of this application can be widely used in electronic devices, such as mobile phones, tablets, e-readers, laptops, digital cameras, televisions, wearable devices, virtual reality (VR) terminal devices, augmented reality (AR) terminal devices, etc. The embodiments of this application do not limit the specific form of the electronic device.

[0088] This application also provides a method for preparing a piezoelectric material, as shown in Figure 1, comprising the following steps:

[0089] S100, according to the general chemical formula of piezoelectric materials, weigh out powder raw materials of ZnO, Nb2O5, Pb3O4, ZrO2 and TiO2, mix with the first dispersant and then ball-mill once. After drying the ball-milled product, perform a pre-calcination treatment to obtain 0.15Pb(ZnO)2. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder;

[0090] S200, according to the general chemical formula of piezoelectric materials, weigh out powder raw materials of Pb3O4, WO3 and MnCO3, mix with the second dispersant and then perform a second ball milling. After drying the product from the second ball milling, perform a second pre-calcination treatment to obtain Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder;

[0091] S300, weigh out 92 mol% to 95 mol% of 0.15Pb(Zn) according to molar percentage. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder and 5 mol%–8 mol% Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder is mixed, the mixture is ball-milled three times, dried and then pre-calcined three times.

[0092] S400 involves mixing the product from three pre-firing processes with additives and then molding it to obtain a piezoelectric material blank.

[0093] S500 involves heating the piezoelectric material blank to 1150℃~1200℃ for sintering and then cooling it to obtain the piezoelectric material sheet.

[0094] S600 involves forming a conductive layer on the surface of a piezoelectric material sheet and then performing polarization treatment to obtain the piezoelectric material.

[0095] The preparation method provided in this application achieves high-performance piezoelectric materials with 0.15Pb(Zn) by optimizing the raw material composition formulation and solid-state mixing of the raw material components. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 Pb(Mn) doped in O3 pre-calcined powder 1 / 2 W 1 / 2 O3 pre-calcined powder, combined with sintering treatment at a specific temperature, achieves the processing of 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 The hard doping of O3 reduces the polarization of piezoelectric materials, improves the mechanical quality factor, reduces internal friction loss, lowers mechanical losses, and enhances the temperature stability of the material at high temperatures, thereby reducing heat generation in the piezoelectric material. Furthermore, lead tungsten manganese tungstate possesses excellent electromechanical coupling constants, enabling the piezoelectric material to exhibit low dielectric loss. Simultaneously, the high breakdown field strength, excellent insulation resistance, and temperature stability of the resonant frequency of lead tungsten manganese tungstate contribute to the overall excellent insulation resistance and temperature stability of the piezoelectric material, reducing heat generation caused by leakage losses. This application uses environmentally friendly raw materials, employs a simple preparation process, has clearly defined raw material components, and is easy to mass-produce. The piezoelectric material prepared using this method can improve energy conversion efficiency and reduce heat generation, making it widely applicable in electronic devices operating in the ultrasonic frequency band.

[0096] The preparation method provided in this scheme is described in detail below.

[0097] S100, according to the general chemical formula of piezoelectric materials, weigh out powder raw materials of ZnO, Nb2O5, Pb3O4, ZrO2 and TiO2, mix with the first dispersant and then ball-mill once. After drying the ball-milled product, perform a pre-calcination treatment to obtain 0.15Pb(ZnO)2. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder.

[0098] Specifically, the first dispersant is ethanol, which can be anhydrous ethanol. In other cases, the first dispersant can also be deionized water, etc.

[0099] After mixing the powder raw material and the first dispersant, the mixture is subjected to ball milling once. Zirconia balls are used for the first ball milling. The amount of dispersant is 1 to 2 times the total weight of the powder raw material and the zirconia balls. It can be 1, 1.5, 1.7, 1.8 or 2 times, or any value between 1 and 2 times. No limit is imposed here.

[0100] In some implementations, the ball milling speed is 200 r / min to 250 r / min per cycle, and the ball milling time is 1 h to 5 h per cycle.

[0101] In some embodiments, the drying temperature of the product from a single ball milling operation is 80°C to 150°C, and can be 80°C, 90°C, 100°C, 120°C, 140°C, or 150°C, etc. The drying time is 1 hour to 6 hours, and can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, etc., or other values ​​within the above range, which are not limited here.

[0102] In some embodiments, the temperature of the first pre-firing treatment is 800℃ to 900℃, and can be 800℃, 810℃, 820℃, 830℃, 840℃, 850℃, 860℃, 870℃, 880℃, 890℃, or 900℃, etc., and is not limited here. The time of the first pre-firing treatment is 1 hour to 10 hours, and can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, etc., and is not limited here.

[0103] In some embodiments, the process includes ball milling the product obtained from the pre-firing process after the initial pre-firing process to reduce the grain size and improve the strength and toughness of the material.

[0104] In some implementations, after ball milling, 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5The particle size D90 of the O3 pre-calcined powder is controlled between 0.5 μm and 0.7 μm, preferably 0.6 μm. The D50 is controlled between 0.3 μm and 0.5 μm, preferably 0.4 μm.

[0105] S200, according to the general chemical formula of piezoelectric materials, weigh out powder raw materials of Pb3O4, WO3 and MnCO3, mix with the second dispersant and then perform a second ball milling. After drying the product from the second ball milling, perform a second pre-calcination treatment to obtain Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder.

[0106] Specifically, the second dispersant is ethanol, specifically anhydrous ethanol. In other cases, the second dispersant can also be deionized water, etc.

[0107] The powder raw material and the second dispersant are mixed and then subjected to secondary ball milling. Zirconia balls are used for the secondary ball milling. The amount of dispersant is 1 to 2 times the total weight of the powder raw material and the zirconia balls; it can be 1, 1.5, 1.7, 1.8 or 2 times, or any value between 1 and 2 times, which is not limited here.

[0108] In some embodiments, the rotational speed of the secondary ball mill is 200 r / min to 250 r / min, and can be 200 r / min, 210 r / min, 220 r / min, 230 r / min, 240 r / min, or 250 r / min, etc. The secondary ball milling time is 1 hour to 5 hours, and can be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, etc.

[0109] In some embodiments, the drying temperature of the product from the secondary ball milling is 80℃ to 150℃, which can be 80℃, 90℃, 100℃, 120℃, 140℃ or 150℃, etc., and the drying time is 1h to 6h, which can be 1h, 2h, 3h, 4h, 5h or 6h, etc., or other values ​​within the above range, which are not limited here.

[0110] In some embodiments, the temperature of the secondary pre-firing treatment is 750℃ to 850℃, and can be 750℃, 760℃, 770℃, 780℃, 790℃, 800℃, 810℃, 820℃, 830℃, 840℃, or 850℃, etc., and is not limited here. The time of the secondary pre-firing treatment is 1 hour to 5 hours, and can be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, etc., and is not limited here.

[0111] In some embodiments, the secondary pre-firing process is followed by a ball milling step on the product obtained from the secondary pre-firing process to reduce the grain size and improve the strength and toughness of the material.

[0112] In some implementations, after ball milling, Pb(Mn) 1 / 2 W 1 / 2 The particle size D90 of the O3 pre-calcined powder is controlled between 0.6 μm and 0.7 μm, preferably 0.65 μm.

[0113] S300, weigh out 92 mol% to 95 mol% of 0.15Pb(Zn) according to molar percentage. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder and 5 mol%–8 mol% Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder was mixed, and the mixture was ball-milled three times, dried, and then pre-calcined three times.

[0114] In some embodiments, Q powder is added to the mixture prior to the three ball milling processes, which allows 0.15Pb(Zn) to be added. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder and Q powder can be directly mixed, or 0.15Pb(Zn) can be added first. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder is mixed, and then Q powder is added and mixed evenly.

[0115] The Q powder comprises an oxide of at least one element selected from Yb and Eu. In specific examples, the Q powder may be, for example, at least one of Yb₂O₃ and Eu₂O₃. Preferably, in some embodiments, the Q powder may be, for example, Yb₂O₃, and in other embodiments, the Q powder may be, for example, Eu₂O₃. More preferably, the Q powder comprises Eu₂O₃ and Yb₂O₃.

[0116] The mass percentage of Q powder in the mixed product is 0.2wt% to 0.6wt%, and can be 0.2wt%, 0.3wt%, 0.45wt%, 0.50wt%, 0.53wt%, 0.56wt%, 0.58wt%, or 0.6wt%, etc.

[0117] By adding Q, this application can increase piezoelectric activity, improve the vibration velocity and amplitude of piezoelectric materials, and thus reduce the heat generation of piezoelectric materials.

[0118] In some implementations, Er is added to the mixture prior to the third ball milling. 0.1 Bi 0.9 FeO3 powder, which can contain 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder and Er 0.1 Bi 0.9 FeO3 powder can be directly mixed, or 0.15Pb(Zn) can be added first. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder is mixed, and then Er is added. 0.1 Bi 0.9 The FeO3 powder was mixed evenly.

[0119] In another embodiment, 0.15Pb(Zn) can be added before the three ball milling processes. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder, Q powder and Er 0.1 Bi 0.9 FeO3 powder was mixed to obtain a mixed product.

[0120] Er 0.1 Bi 0.9 The mass percentage of FeO3 powder in the mixed product is less than or equal to 0.5 wt%, and can be 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, or 0.5 wt%, etc.

[0121] Specifically, Er 0.1 Bi 0.9 FeO3 powder was prepared using the following steps:

[0122] According to Er 0.1 Bi 0.9 The general chemical formula of FeO3 powder is as follows: weigh Er2O3, Bi2O3 and Fe2O3 powder raw materials, mix them with the third dispersant and ball mill them four times. After drying the products from the four ball millings, they are pre-calcined four times.

[0123] The third dispersant is ethanol, specifically anhydrous ethanol. In other cases, the third dispersant can also be deionized water, etc.

[0124] The powder raw material and the third dispersant are mixed and then ball-milled four times. Zirconia balls are used for the four ball millings. The amount of the third dispersant is 1 to 2 times the total weight of the powder raw material and the zirconia balls. It can be 1, 1.5, 1.7, 1.8 or 2 times, or any value between 1 and 2 times. No limit is imposed here.

[0125] In some embodiments, the rotational speed of the four ball milling cycles is 200 r / min to 250 r / min, and can be 200 r / min, 210 r / min, 220 r / min, 230 r / min, 240 r / min, or 250 r / min, etc. The time for the four ball milling cycles is 1 hour to 5 hours, and can be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, etc.

[0126] In some embodiments, the drying temperature of the product after four ball millings is 80℃ to 150℃, specifically 80℃, 90℃, 100℃, 120℃, 140℃ or 150℃, etc., and the drying time is 1h to 6h, specifically 1h, 2h, 3h, 4h, 5h or 6h, etc., and of course, other values ​​within the above range are also possible, which are not limited here.

[0127] Specifically, the four pre-firing processes are carried out in an alumina crucible.

[0128] In some embodiments, the temperature of the four pre-firing treatments is 800℃ to 900℃, specifically 800℃, 810℃, 820℃, 830℃, 840℃, 850℃, 860℃, 870℃, 880℃, 890℃, or 900℃, etc., and is not limited here. The time for the four pre-firing treatments is 1 hour to 5 hours, specifically 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, etc., and is not limited here.

[0129] In some embodiments, the process of ball milling the product obtained from the four pre-firing processes is included after the four pre-firing processes to reduce the grain size and improve the strength and toughness of the material.

[0130] In some implementations, after ball milling, Er 0.1 Bi 0.9 The particle size D90 of FeO3 powder is controlled between 0.4 μm and 0.6 μm, preferably 0.5 μm.

[0131] This application can control the particle size distribution of the ball milling product by controlling the rotation speed of the grinding balls, the amount of material added, and the ball milling time, thereby obtaining materials of the required size. It can also improve the uniformity of each component in the piezoelectric material and improve the reliability of the piezoelectric material.

[0132] In some embodiments, the mass ratio of the mixture, grinding balls, and solvent in the three-stage ball milling is (1-3):1:(0.5-2), preferably 2:1:1. In some embodiments, the grinding balls used in the three-stage ball milling are zirconium balls, and the solvent in the three-stage ball milling can be, for example, water.

[0133] In some embodiments, the rotational speed of the three ball milling processes is 200 r / min to 250 r / min, and can be 200 r / min, 210 r / min, 220 r / min, 230 r / min, 240 r / min, or 250 r / min, etc. The time for the three ball milling processes is 6 h to 8 h, and can be 6 h, 6.5 h, 7 h, 7.5 h, or 8 h, etc.

[0134] In some embodiments, the drying temperature of the product after three ball millings is 80℃ to 150℃, which can be 80℃, 90℃, 100℃, 120℃, 140℃ or 150℃, etc., and the drying time is 1h to 6h, which can be 1h, 2h, 3h, 4h, 5h or 6h, etc., or other values ​​within the above range, which are not limited here.

[0135] The temperature for the three pre-firing treatments is 900℃~1000℃, but can be 900℃, 910℃, 920℃, 930℃, 940℃, 950℃, 960℃, 970℃, 980℃, 990℃, or 1000℃, etc., and is not limited here. The time for the three pre-firing treatments is 2h~10h, but can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, etc., and is not limited here.

[0136] The three pre-firing processes were carried out under sealed conditions.

[0137] In some embodiments, the median particle size of the product from the three pre-calcination treatments is 0.2 μm to 0.4 μm, and can be 0.2 μm, 0.25 μm, 0.28 μm, 0.32 μm, 0.35 μm, or 0.4 μm, etc., without limitation. For example, ball milling, drying, and further fine grinding can be used to control the particle size of the product from the three pre-calcination treatments within the above range, which is beneficial to the uniformity and consistency of the material.

[0138] S400 involves mixing the products from three pre-firing processes with additives and then molding them to obtain piezoelectric material blanks.

[0139] In this step, the product from the three pre-calcination treatments and the additives are mixed and ball-milled to obtain a slurry of the desired viscosity, which is then cast and molded. The resulting product is then cut to obtain a piezoelectric material blank of the desired shape.

[0140] In some embodiments, the additives include at least one of adhesives, dispersants, solvents, and leveling agents.

[0141] The adhesive can be, for example, polyvinyl butyral, or of other types, without limitation.

[0142] Dispersants can be, for example, polyacrylic acid, polyacrylamide, etc., and of course, other types of dispersants are not limited here.

[0143] Solvents can be, for example, water, ethanol, propanol, acetone and acetate, and of course, other types of solvents are not limited here.

[0144] The leveling agent can be, for example, polydimethylsiloxane, or of course, other types of leveling agents, which are not limited here.

[0145] The amount of additive used is 14wt% to 18wt% of the total weight of the product from the three pre-calcination treatments. It can be 14wt%, 15wt%, 16wt%, 17wt%, or 18wt%, or any value between 14wt% and 18wt%, and there is no limitation here.

[0146] In some embodiments, after the three pre-firing treatments, the process further includes: removing the adhesive from the product after the three pre-firing treatments. Specifically, the product after the three pre-firing treatments is heated to 250°C to 280°C at a rate of 0.5°C / min to 2°C / min, held at that temperature for 120 min to 200 min, then heated from 250°C to 280°C to 350°C to 380°C at a rate of 0.5°C / min to 2°C / min, held at 350°C to 380°C for 120 min to 200 min, and then heated to 500°C to 550°C at a rate of 1°C / min to 2°C / min and held for 120 min to 200 min, in order to remove adhesives, leveling agents, and other impurities and organic matter.

[0147] S500 involves heating the piezoelectric material blank to 1150℃~1200℃ for sintering and then cooling it to obtain the piezoelectric material sheet.

[0148] The sintering process specifically includes the following steps: sintering ceramic blanks and lead zirconate titanate powder using a buried firing method, followed by cooling to obtain piezoelectric material sheets. Using the buried firing method reduces lead volatilization, maintains the lead's chemical formula, increases sintering density, improves material properties, and prevents oxidation.

[0149] The sintering temperature is 1150℃~1200℃, but can be 1150℃, 1160℃, 1170℃, 1180℃, 1190℃, or 1200℃, etc., without limitation. The heating rate of the sintering process is 1℃ / min~5℃ / min, but can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, or 5℃ / min, etc., without limitation. The holding time of the sintering process is 30min~90min, but can be 30min, 40min, 50min, 60min, 70min, 80min, or 90min, etc., without limitation.

[0150] S60: A conductive layer is formed on the surface of a piezoelectric material sheet, and then polarization treatment is performed to obtain a piezoelectric material.

[0151] In some embodiments, a conductive paste can be coated onto the sintered piezoelectric material sheet, and then sintered at 600°C to 800°C to form a conductive layer. The conductive paste can be conductive silver paste, conductive copper paste, etc., and is not limited thereto.

[0152] Specifically, a silver conductive layer is formed on a piezoelectric material sheet; then, it is polarized for 30 minutes in silicone oil at 100℃~140℃ under a DC electric field with an electric field strength of 2KV / mm~3.5KV / mm.

[0153] The embodiments of the present invention will be further described below with reference to several examples. However, the embodiments of the present invention are not limited to the specific embodiments described below. Appropriate modifications can be made within the scope of the original claims.

[0154] Example 1

[0155] (1) Weigh 61.249g of ZnO powder, 200.034g of Nb2O5 powder, 3439.63g of Pb3O4 powder, 788.213g of ZrO2 powder, and 510.873g of TiO2 powder and mix them. Add 10000g of zirconia grinding beads and 10000ml of anhydrous ethanol, place the mixture in a ball mill jar, and ball mill the mixture using a planetary ball mill at a speed of 200r / min for 5h. After ball milling, filter out the grinding beads and dry the remaining slurry for 4h to obtain a mixed powder. Place the mixed powder in an alumina crucible and calcine at 850℃ for 2h. After the powder cools to room temperature, ball mill it for 4h to obtain 0.15Pb(ZnO)2 powder. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder.

[0156] (2) Weigh 1137.185g of Pb3O4 powder, 576.817g of WO3 powder, and 285.997g of MnCO3 powder and mix them. Add 4000g of zirconia grinding beads and 4000ml of anhydrous ethanol, place the mixture in a ball mill jar, and ball mill the mixture using a planetary ball mill at a speed of 200r / min for 5h. After ball milling, filter out the grinding beads and dry the remaining slurry for 4h to obtain a mixed powder. Place the mixed powder in an alumina crucible and calcine at 800℃ for 1.5h. After the powder cools to room temperature, ball mill it for 4h to obtain Pb(MnCO3)2O4 powder. 1 / 2 W 1 / 2 O3 pre-calcined powder.

[0157] (3) Weigh 30.983g of Er₂O₃ powder, 339.672g of Bi₂O₃ powder, and 129.344g of Fe₂O₃ powder and mix them. Add 1000g of zirconia grinding beads and 1000ml of anhydrous ethanol, place the mixture in a ball mill jar, and ball mill it using a planetary ball mill at a speed of 200r / min for 6h. After ball milling, filter out the grinding beads and dry the remaining slurry for 4h to obtain a mixed powder. Place the mixed powder in an alumina crucible and calcine it at 850℃ for 1.5h. After the powder cools to room temperature, ball mill it for 4h to obtain Er₂O₃ powder. 0.1 Bi 0.9 FeO3 powder.

[0158] (4) Weigh 931.842g of 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder, 68.158g of Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder, 1g Er 0.1 Bi 0.9 FeO3 powder (0.1 wt%), 2.5 g Yb2O3 (0.25 wt%), and 2.5 g Eu2O3 (0.25 wt%) were mixed, and 2000 g of zirconia grinding beads and 1000 ml of deionized water were added. The mixture was placed in a ball mill jar and ball-milled using a planetary ball mill at a speed of 200 r / min for 5 h. After ball milling, the grinding beads were filtered out, and the remaining slurry was dried for 4 h to obtain a mixed powder. The mixed powder was placed in an alumina crucible, vibrated and compacted, sealed, and calcined at 950 °C for 2 h to obtain material 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3. The obtained material was ball-milled for 6 hours, dried, and then finely ground again for 20 minutes. The D50 of the obtained powder was 0.3 μm.

[0159] (5) Add the material obtained in step (4) to polyvinyl butyral ester (18 wt%), polyacrylic acid (2.2 wt%), 250 ml of deionized water and polydimethylsiloxane (10 wt%) and tumble it. After tumbling, cast it into a disc and cut it into a disc with a diameter of 13.5 mm.

[0160] (6) Heat the material obtained in step (5) to 250°C at a rate of 1°C / min, hold for 120 min, then heat from 250°C to 350°C at a rate of 0.5°C / min, hold at 350°C for 120 min, then heat to 550°C at a rate of 1°C / min and hold for 120 min.

[0161] (7) Place the material obtained in step (5) into a lead-containing pad and place it in a crucible. Then, bury it in a muffle furnace: raise the temperature to 1160℃ at 3℃ / min and hold for 1h. Coat the sintered product with medium-temperature silver paste and sinter it. Then, polarize it in silicone oil at 120℃ with an electric field of 3kv / mm to obtain a piezoelectric material sheet.

[0162] The piezoelectric material prepared in this embodiment has the general chemical formula 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3.

[0163] The piezoelectric material of Example 1 was subjected to ICP-OES testing to test the content of each metal element in the piezoelectric material. The results are shown in Table 1. As can be seen from Table 1, the tested content of each metal element is basically consistent with the formula calculation.

[0164] Table 1. Mass content of each metal element obtained by ICP-OES test of the piezoelectric material of Example 1.

[0165] Example 2

[0166] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with the following composition: 0.05Pb(Mn) 1 / 2 W 1 / 2 )O3-0.95[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3.

[0167] Example 3

[0168] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with the following composition: 0.08Pb(Mn) 1 / 2 W 1 / 2 )O3-0.92[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3.

[0169] Example 4

[0170] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with the following composition: 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.1wt%Yb2O3+0.1wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3.

[0171] Example 5

[0172] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with the following composition: 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5Ti 0.5 )O3]+0.3wt%Yb2O3+0.3wt%Eu2O3+0.1wt%Er 0.1 Bi 0.9 FeO3.

[0173] Example 6

[0174] Unlike Example 1, the amount of raw materials added is different. In step (4), Eu2O3 is not added, and the mass fraction of Yb2O3 added is 0.3wt%, so that the prepared piezoelectric material is 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3] + 0.3wt% Yb2O3 + 0.1wt% Er 0.1 Bi 0.9 FeO3.

[0175] Example 7

[0176] Unlike Example 1, the amount of raw materials added is different. In step (4), Yb2O3 is not added, and the mass fraction of Eu2O3 added is 0.3wt%, so that the prepared piezoelectric material is 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3] + 0.3wt%Eu2O3 + 0.1wt%Er 0.1 Bi 0.9 FeO3.

[0177] Example 8

[0178] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with a composition of 0.06Pb(Mn). 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.3wt%Er 0.1 Bi 0.9 FeO3.

[0179] Example 9

[0180] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with a composition of 0.06Pb(Mn). 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3+0.5wt%Er 0.1 Bi 0.9 FeO3.

[0181] Example 10

[0182] Unlike Example 1, the amount of raw materials added is different; Er is not added in step (4). 0.1 Bi 0.9 FeO3 makes the prepared piezoelectric material 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+0.25wt%Yb2O3+0.25wt%Eu2O3.

[0183] The piezoelectric material of Example 10 was subjected to ICP-OES testing to test the content of each metal element in the piezoelectric material. The results are shown in Table 2. As can be seen from Table 2, the tested content of each metal element is basically consistent with the formula calculation.

[0184] Table 2. Mass content of each metal element obtained by ICP-OES test of the piezoelectric material of Example 10.

[0185] Example 11

[0186] Unlike Example 1, the amount of raw materials added is different. In step (4), Yb2O3 and Eu2O3 are not added, so that the prepared piezoelectric material is 0.06Pb(Mn) 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3] + 0.1wt% Er 0.1 Bi 0.9 FeO3.

[0187] Example 12

[0188] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with a composition of 0.06Pb(Mn). 1 / 2 W 1 / 2 )O3-0.94[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3].

[0189] The piezoelectric material of Example 12 was subjected to ICP-OES testing to test the content of each metal element in the piezoelectric material. The results are shown in Table 3. As can be seen from Table 3, the tested content of each metal element is basically consistent with the formula calculation.

[0190] Table 3. Mass content of each metal element obtained by ICP-OES testing of the piezoelectric material prepared in Example 12.

[0191] Example 13

[0192] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with a composition of 0.05Pb(Mn). 1 / 2 W 1 / 2 )O3-0.95[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3].

[0193] Example 14

[0194] Unlike Example 1, the amount of raw materials added was different, resulting in a piezoelectric material with a composition of 0.08Pb(Mn). 1 / 2 W 1 / 2 )O3-0.95[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.92Pb(Zr) 0.5 Ti 0.5 )O3].

[0195] Comparative Example 1

[0196] Directly using commercially available 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 O3 powder is used as a piezoelectric material.

[0197] Comparative Example 2

[0198] Unlike Example 1, the amount of raw materials added was different, resulting in a final piezoelectric material with a composition of 0.1Pb(Mn). 1 / 2 W 1 / 2 )O3-0.9[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3].

[0199] Performance testing:

[0200] Performance tests were conducted on the above embodiments and comparative examples, and the test results are shown in Table 4. In the table, Embodiments 1 to 14 are referred to as S1 to S14, and Comparative Examples 1 to 2 are referred to as D1 to D2.

[0201] Table 4. Performance tests of piezoelectric materials prepared in each example and comparative example

[0202] As can be seen from Examples 1-14, at 0.15Pb(Zn) 1 / 3 Nb 2 / 3 O3-0.92Pb(Zr) 0.5 Ti 0.5 Adding Pb(Mn) to O3 piezoelectric materials 1 / 2 W 1 / 2 O3, Q (Yb oxides and / or Eu oxides), Er 0.1 Bi 0.9 The inclusion of FeO3 and other substances into the piezoelectric material enables hard doping, reduces the polarization of the piezoelectric material, lowers dielectric loss, improves the mechanical quality factor and piezoelectric properties of the piezoelectric material, achieves a wide bandwidth and high sensitivity of the piezoelectric material, reduces the heating problem caused by leakage loss of the piezoelectric material, increases the vibration speed of the piezoelectric material, and reduces the heating of the piezoelectric material, making the piezoelectric material widely used in electronic devices in the ultrasonic frequency band.

[0203] According to the test data of Example 10, the piezoelectric material provided in this application, even without the addition of Er, shows that... 0.1 Bi 0.9 FeO3 can also achieve a high mechanical quality factor, low dielectric loss, and improved vibration velocity, while its heat generation is far lower than that of commercially available 0.15Pb(Zn)3. 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 O3 material.

[0204] According to the test data of Example 11, the piezoelectric material provided in this application can achieve a high mechanical quality factor, low dielectric loss, and improved vibration velocity even without the addition of Yb oxide and Eu oxide. Its heat generation is far lower than that of commercially available 0.15Pb(Zn) piezoelectric material. 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 O3 material.

[0205] The above description is merely a specific embodiment of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this invention should be included within the protection scope of this invention. The protection scope of this invention should be determined by the scope of the claims.

Claims

1. A piezoelectric material, characterized in that, The general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3], where 0.05≤x≤0.

08.

2. The piezoelectric material according to claim 1, characterized in that, The general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 [O3]+yQ, wherein Q comprises an oxide of at least one element selected from Yb and Eu, wherein Q is in xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y wt%, 0.2≤y≤0.

6.

3. The piezoelectric material according to claim 2, characterized in that, Q is Yb2O3 and Eu2O3; The Yb2O3 in xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y1 wt%, 0.1≤y1≤0.3; The Eu2O3 in x Pb(Mn 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 The mass percentage of O3]+yQ is y2 wt%, 0.1≤y2≤0.

3.

4. The piezoelectric material according to claim 2 or 3, characterized in that, The general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+yQ+zEr 0.1 Bi 0.9 FeO3, the Er 0.1 Bi 0.9 FeO3 in x Pb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+yQ+zEr 0.1 Bi 0.9 The mass percentage of FeO3 is z wt%, z≤0.

5.

5. The piezoelectric material according to claim 1, characterized in that, The general chemical formula of the piezoelectric material includes: xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+zEr 0.1 Bi 0.9 FeO3, the Er 0.1 Bi 0.9 FeO3 in xPb(Mn) 1 / 2 W 1 / 2 )O3-(1-x)[0.15Pb(Zn 1 / 3 Nb 2 / 3 O3-0.85Pb(Zr) 0.5 Ti 0.5 )O3]+zEr 0.1 Bi 0.9 The mass percentage of FeO3 is z wt%, z≤0.

5.

6. The piezoelectric material according to any one of claims 1 to 5, characterized in that, It satisfies at least one of the following characteristics: a) The density of the piezoelectric material is 7.53 g / cm³. 3 ~7.70g / cm 3 ; b) The piezoelectric strain constant D of the piezoelectric material 33 The value is 365 pC / N to 400 pC / N; c) The mechanical quality factor Q of the piezoelectric material m The range is 500 to 1500; d) The dielectric loss of the piezoelectric material is 0.2% to 0.6% at 20 kHz to 20 MHz.

7. A method for preparing a piezoelectric material, characterized in that, The method includes the following steps: According to the chemical formula of the piezoelectric material according to any one of claims 1 to 5, powder raw materials of ZnO, Nb2O5, Pb3O4, ZrO2 and TiO2 are weighed, mixed with a first dispersant, and then ball-milled once. The ball-milled product is dried and then pre-calcined once to obtain 0.15Pb(ZnO)2. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder; According to the chemical formula of the piezoelectric material according to any one of claims 1 to 5, powdered raw materials of Pb3O4, WO3 and MnCO3 are weighed, mixed with a second dispersant, and then subjected to secondary ball milling. The secondary ball milling product is dried and then subjected to secondary pre-calcination treatment to obtain Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder; Weigh out 92 mol% to 95 mol% of 0.15Pb(Zn) according to molar percentage. 1 / 3 Nb 2 / 3 O3-0.85(Zr) 0.5 Ti 0.5 O3 pre-calcined powder and 5 mol%–8 mol% Pb(Mn) 1 / 2 W 1 / 2 O3 pre-calcined powder is mixed, the mixture is ball-milled three times, dried and then pre-calcined three times. The product from the three pre-calcination treatments and the additives are mixed and then molded to obtain a piezoelectric material blank. The piezoelectric material blank is heated to 1150℃~1200℃ for sintering and then cooled to obtain a piezoelectric material sheet. A conductive layer is formed on the surface of the piezoelectric material sheet, and then polarization treatment is performed to obtain the piezoelectric material.

8. The method for preparing the piezoelectric material according to claim 7, characterized in that, The method satisfies at least one of the following characteristics: a) The first dispersant comprises at least one of water and ethanol; b) The rotation speed of the ball milling is 200 r / min to 250 r / min, and the time of the ball milling is 1 h to 5 h; c) The temperature of the first pre-firing treatment is 800℃~900℃, and the time of the first pre-firing treatment is 1h~10h; d) The second dispersant comprises at least one of water and ethanol; e) The rotation speed of the secondary ball mill is 200 r / min to 250 r / min, and the time of the secondary ball mill is 1 h to 5 h; f) The temperature of the secondary pre-firing treatment is 750℃~850℃, and the time of the secondary pre-firing treatment is 1h~5h; g) The temperature of the three pre-firing treatments is 900℃~1000℃, and the time of the three pre-firing treatments is 2h~10h; h) The median particle size of the product from the three pre-calcination treatments is 0.2 μm to 0.4 μm; i) The additives include at least one of adhesives, dispersants, solvents, and leveling agents; j) The amount of the auxiliary agent is 14wt% to 18wt% of the total weight of the product from the three pre-calcination treatments; k) The heating rate of the sintering treatment is 1℃ / min to 5℃ / min, and the holding time of the sintering treatment is 30min to 90min.

9. The method for preparing the piezoelectric material according to claim 7, characterized in that, The method further includes: Provide Q powder, said Q powder comprising an oxide of at least one element selected from Yb and Eu; Prior to the three ball milling processes, Q powder is added to the mixture, wherein the mass percentage of Q powder in the mixture and the new mixture formed by the Q powder is 0.2 wt% to 0.6 wt%.

10. The method for preparing the piezoelectric material according to claim 7 or 9, characterized in that, The method further includes: According to the chemical formula of the piezoelectric material described in claim 4 or 5, powdered raw materials of Er2O3, Bi2O3, and Fe2O3 are weighed, mixed with a third dispersant, and ball-milled four times. The ball-milled products are dried and then pre-calcined four times to obtain Er2O3. 0.1 Bi 0.9 FeO3 powder; Before the three ball milling processes, Er is added to the mixture. 0.1 Bi 0.9 FeO3 powder, the Er 0.1 Bi 0.9 FeO3 powder in the mixture and the Er 0.1 Bi 0.9 The mass percentage of the new mixed product formed from FeO3 powder is less than or equal to 0.5 wt%.

11. The method for preparing the piezoelectric material according to claim 10, characterized in that, The method satisfies at least one of the following characteristics: a) The third dispersant includes at least one of water and ethanol; b) The rotation speed of the four ball milling processes is 200 r / min to 250 r / min, and the time of the four ball milling processes is 1 h to 5 h; c) The temperature of the four pre-firing treatments is 800℃~900℃, and the time of the four pre-firing treatments is 1h~5h.

12. A piezoelectric device, characterized in that, The piezoelectric device comprises the piezoelectric material according to any one of claims 1 to 6 or the piezoelectric material prepared by the method according to any one of claims 7 to 11.

13. An electronic device, characterized in that, The electronic device includes the piezoelectric device of claim 12.

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