A piezoelectric ceramic material, its preparation method and application

Abstract

This invention provides a piezoelectric ceramic material, its preparation method, and its application, belonging to the technical field of piezoelectric ceramic materials. The chemical composition of this piezoelectric ceramic material is: 0.90 (M 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 O3-0.05Bi(N) 1 / 2 Ti 1 / 2 The piezoelectric ceramic material of this invention can significantly reduce the sintering temperature while ensuring high density, excellent piezoelectric properties, and most importantly, maintaining extremely low dielectric loss and a high mechanical quality factor. The formula is: O3 + xwt%Li2CO3 + ywt%Bi3BO6 + zwt%Mn2P2O7, where M is K or Na, N is Zn, Ni, or Co, and 0.01≤x≤0.5, 0.005≤y≤0.3, 0.005≤z≤0.3.

Description

Technical Field

[0001] This invention relates to a piezoelectric ceramic material, its preparation method and application, and belongs to the technical field of piezoelectric ceramic materials. Background Technology

[0002] Piezoelectric ceramic materials are key functional materials for realizing the conversion between mechanical energy and electrical energy, playing a central role in modern technology fields such as precision actuation, sensing and detection, and ultrasonic imaging and processing. Among the many piezoelectric ceramic systems, lead zirconate titanate (Pb(Zr,Ti)O3,PZT)-based ceramic materials have long held a dominant position due to their superior comprehensive electrical properties near the quasi-isomorphic phase boundary (MPB).

[0003] To meet the specific needs of different application scenarios, PZT can be differentiated into two main types through doping: "hard" piezoelectric ceramics and "soft" piezoelectric ceramics. Soft piezoelectric ceramics typically incorporate donor doping, characterized by a high piezoelectric constant (d). 33 ) and dielectric constant (ε) r High, but mechanical quality factor (Q) m While having a relatively low mechanical quality factor (Q), it also has higher internal friction, making it ideal for applications requiring high displacement output and sensing sensitivity, such as precision positioning platforms and piezoelectric inkjet printheads. Conversely, hard piezoelectric ceramics often employ acceptor doping, characterized by a very high mechanical quality factor (Q). m ) and coercive field (E c Meanwhile, the dielectric loss (tanδ) remains at an extremely low level. These characteristics make it particularly suitable for devices that need to operate stably at high frequencies and high power, such as ultrasonic scalpels, ultrasonic welding machines, and high-frequency micro ultrasonic motors. These devices operate in a resonant state, and if the heat generated by the internal losses of the material cannot be effectively controlled, it will lead to performance degradation or even failure. Therefore, there are extremely stringent requirements for the low loss characteristics of the material (usually requiring tanδ < 1%).

[0004] Despite the excellent properties of PZT ceramics, their traditional preparation process faces severe challenges. Conventional solid-state sintering temperatures exceed 1200℃, a temperature window that severely conflicts with low-cost metallization electrode processes. Widely used silver (Ag, melting point 961℃) or copper (Cu, melting point 1083℃) pastes cannot withstand such high temperatures. Currently, to match the sintering temperature, the industry is forced to use expensive silver-palladium (Ag-Pd) alloys as internal electrodes, directly increasing the manufacturing cost of multilayer devices (such as multilayer actuators). Furthermore, the high-temperature sintering process exacerbates the volatilization of lead (Pb), affecting not only the accuracy of material stoichiometry and the reproducibility of final performance but also posing a potential threat to the environment and the health of production personnel.

[0005] To reduce sintering temperature, existing technologies primarily focus on adding sintering aids. Introducing low-melting-point oxides (such as Bi₂O₃, Li₂CO₃, etc.) or glass powders with specific compositions (such as borosilicate glass) into the formulation can significantly reduce the sintering temperature (to 850℃-950℃) while promoting ceramic densification. For example, CN110498603A provides a piezoelectric ceramic comprising glass powder, a matrix material, optional CaCO₃, and optional Li₂CO₃. The glass powder is mainly prepared from the following raw materials in parts by weight: 50-60 parts Bi₂O₃, 10-20 parts Sb₂O₃, 20-30 parts B₂O₃, 5-10 parts ZnO, and 3-5 parts SiO₂. This glass powder can act as a sintering aid for piezoelectric ceramics, reducing their sintering temperature. However, these methods generally share a common drawback: the liquid phase formed by the additives, while promoting grain growth and pore filling, often remains at grain boundaries or forms an amorphous phase. These second phases typically possess high electrical conductivity or polarization relaxation characteristics, leading to a significant increase in the material's dielectric loss (tanδ) and a reduction in the mechanical quality factor (Q). m In other words, most existing low-temperature sintering methods sacrifice the most critical properties of hard PZT ceramics: low loss and high Q. m At the cost of performance, the resulting materials cannot meet the requirements of high-frequency, high-power applications for energy conversion efficiency and long-term stability.

[0006] Therefore, there is an urgent need to develop a piezoelectric ceramic material with a low sintering temperature and excellent piezoelectric properties. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a piezoelectric ceramic material, its preparation method, and its applications. This invention develops a low-temperature sintering technology suitable for hard PZT ceramics. This technology can significantly reduce the sintering temperature to a range suitable for co-firing with pure silver electrodes (e.g., ≤900℃), while ensuring that the ceramic material achieves high density, excellent piezoelectric properties, and, most importantly, maintains extremely low dielectric loss (typically requiring tanδ <1%) and a high mechanical quality factor. This is of decisive significance for promoting the development and industrialization of next-generation low-cost, high-performance, and environmentally friendly high-frequency piezoelectric devices.

[0008] The technical solution of the present invention is as follows: A piezoelectric ceramic material with the following chemical composition: 0.90 (M 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti1 / 2 O3 + xwt% Li2CO3 + ywt% Bi3BO6 (bismuth oxyborate) + zwt% Mn2P2O7 (manganese pyrophosphate), where M is K or Na, N is Zn, Ni or Co, 0.01≤x≤0.5, 0.005≤y≤0.3, 0.005≤z≤0.3, 0.90(M 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti 1 / 2 O3 represents the matrix ceramic powder, x represents the mass percentage of Li2CO3 in the matrix ceramic powder, y represents the mass percentage of Bi3BO6 (bismuth oxyborate) in the matrix ceramic powder, and z represents the mass percentage of Mn2P2O7 (manganese pyrophosphate) in the matrix ceramic powder.

[0009] According to the preferred embodiment of the present invention, 0.01≤x≤0.2, 0.01≤y≤0.1, and 0.05≤z≤0.1.

[0010] According to the present invention, the preparation method of the above-mentioned piezoelectric ceramic material includes the following steps: (1) According to 0.90(M) 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti 1 / 2 The stoichiometric ratio of raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, Bi3BO6 (bismuth oxyborate), and Mn2P2O7 (manganese pyrophosphate) is accurately weighed, ball-milled, dried, sieved, and pre-calcined to obtain the synthesized powder. (2) The synthesized powder is dispersed by ball milling to obtain piezoelectric ceramic material.

[0011] According to a preferred embodiment of the present invention, in step (1), the M source is a K source or a Na source, wherein the K source is K2CO3 and the Na source is Na2CO3; the Pb source is PbO or Pb3O4; the Zr source is ZrO2; the Ti source is TiO2; the Mn source is MnO2; the Nb source is Nb2O5; the Bi source is Bi2O3; and the N source is a Zn source, a Ni source, or a Co source, wherein the Zn source is ZnO, the Ni source is NiO, and the Co source is Co3O4.

[0012] According to a preferred embodiment of the present invention, the Bi3BO6 (bismuth oxyborate) in step (1) is prepared by the following method: Bi2O3 and H3BO3 are added to a ball mill containing zirconia balls and deionized water in stoichiometric ratio and ball-milled for 4-8 hours. After drying to constant weight at 120-180°C, the mixture is calcined at 600-700°C for 3-4 hours. The calcined material is then added to a ball mill containing zirconia balls and deionized water and ball-milled for another 6-8 hours. After drying to constant weight at 120-180°C, Bi3BO6 (bismuth oxyborate) powder is obtained. During the ball milling process, the mass ratio of zirconia balls, raw materials and deionized water is 2:1:1.

[0013] According to a preferred embodiment of the present invention, the Mn2P2O7 (manganese pyrophosphate) in step (1) is prepared by the following method: MnCO3 and NH4H2PO4 are added to a ball mill containing zirconium oxide balls and anhydrous ethanol and ball-milled for 2-4 hours according to the stoichiometric ratio. After drying to constant weight at 60-80°C, the mixture is initially calcined at 300-400°C for 2-3 hours. The material obtained from the initial calcination is added to a ball mill containing zirconium oxide balls and anhydrous ethanol and ball-milled for 1-3 hours. After drying to constant weight at 60-80°C, the mixture is calcined again at 600-700°C under a nitrogen atmosphere for 3-4 hours. The material obtained from the second calcination is added to a ball mill containing zirconium oxide balls and anhydrous ethanol and ball-milled for another 3-4 hours. After drying to constant weight at 60-80°C, Mn2P2O7 (manganese pyrophosphate) powder is obtained. During the ball milling process, the mass ratio of zirconium oxide balls, raw materials and anhydrous ethanol is 2:1:1.

[0014] According to a preferred embodiment of the present invention, the ball milling step in step (1) is as follows: raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, Bi3BO6 (bismuth oxyborate), and Mn2P2O7 (manganese pyrophosphate) are mixed in stoichiometric ratio and added to a ball milling jar containing zirconia balls and deionized water for ball milling. The ball milling time is 3-6 hours, and the ball mill speed is 300-350 rpm. During the ball milling process, the mass ratio of zirconia balls, raw materials and deionized water is 2:1:1. The mass of the raw materials is the total mass of raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, Bi3BO6 (bismuth oxyborate), and Mn2P2O7 (manganese pyrophosphate).

[0015] According to a preferred embodiment of the present invention, the drying temperature in step (1) is 120-180°C, the drying time is 4-10 hours, and the moisture content is <0.3wt%; the mesh size of the sieve used for sieving is 40-60 mesh.

[0016] According to a preferred embodiment of the present invention, the pre-firing temperature in step (1) is 800-850°C and the pre-firing time is 3-5 hours.

[0017] According to a preferred embodiment of the present invention, the ball milling step (2) is as follows: the synthetic powder is added to a ball milling jar containing zirconia balls and deionized water for ball milling, the ball milling time is 5-10 hours, and the ball mill speed is 300-350 rpm; the mass ratio of zirconia balls, synthetic powder and deionized water during the ball milling process is 2:1:1.

[0018] According to the present invention, the above-mentioned piezoelectric ceramic material is used in the preparation of piezoelectric devices.

[0019] The technical features and beneficial effects of this invention are as follows: 1. The piezoelectric ceramic material of this invention uses low-valence K or Na with similar radii to replace Pb at the A sites as acceptor dopant. According to the principle of valence balance, in order to maintain charge neutrality, acceptor doping will lead to the generation of oxygen vacancies on the crystal lattice to balance the valence, forming defect dipoles. These dipoles slowly adjust their orientation in the electric field formed by spontaneous polarization, forming an internal bias field. Acceptor doping leads to an increase in coercivity, a decrease in dielectric constant, a decrease in loss, and an increase in mechanical quality factor Q. m Improvement: The material is relatively hard.

[0020] 2. The piezoelectric ceramic material of this invention uses Mn as an acceptor dopant, which enters the PZT-PZN perovskite lattice with +2 and +3 valences, promoting the densification sintering and grain growth of the ceramic. At the same time, based on the Jam-Taylor effect, the lattice structure is distorted, and the system transforms from a tetragonal phase to a trigonal phase, which reduces the Curie temperature Tc and dielectric loss, and improves the mechanical quality factor Q. m promote.

[0021] 3. The piezoelectric ceramic material of the present invention has a significantly lower sintering temperature but little change in performance due to the addition of the third phase Bi-N-Ti.

[0022] 4. The piezoelectric ceramic material of this invention contains Li₂CO₃. Li₂CO₃ itself has a low melting point of approximately 723°C. At the sintering temperature, it completely transforms into a liquid phase, encapsulating the ceramic particles. The liquid phase significantly reduces the ion diffusion barrier, making it easier for Pb, Zr, and Ti to migrate and rapidly densify. Simultaneously, Li can replace Pb at the A-site as an acceptor dopant, reducing the dielectric constant, decreasing losses, and improving the mechanical quality factor Q. m promote.

[0023] 5. The piezoelectric ceramic material of the present invention contains bismuth oxyborate (Bi3BO6). Bi3BO6 has a melting point of about 726°C and can quickly form a liquid phase, significantly reducing the sintering temperature of PZT (by 100-200°C). The liquid phase wets the PZT particles, accelerating ion diffusion and promoting grain rearrangement and densification. 3+ Partially replaces Pb 2+ By regulating lattice distortion and optimizing phase boundary ratios, the piezoelectric response is improved. Glass phase pinning of domain walls enhances the mechanical quality factor Q. m This reduces dielectric loss (tanδ) and improves insulation and withstand voltage performance.

[0024] 6. The piezoelectric ceramic material of this invention contains manganese pyrophosphate (Mn2P2O7). Mn2P2O7 decomposes at high temperature into MnO + P2O5, with P2O5 forming a low-melting-point glassy phase, promoting liquid-phase sintering and increasing density. Mn ions enter the B-site of PZT as acceptor dopant, compensating for oxygen vacancies and inhibiting grain growth. This reduces leakage current and dielectric loss, and improves insulation resistance and time stability. It also modulates the domain structure, increasing non-180° domains and improving the piezoelectric constant d. 33 With electromechanical coupling coefficient k t It inhibits oxygen vacancy migration, improves aging performance, and extends device lifespan. Attached Figure Description

[0025] Figure 1 The image shows a SEM image of the piezoelectric ceramic material prepared in Example 1. Detailed Implementation

[0026] The present invention will be further described below through specific embodiments, but is not limited thereto.

[0027] The Bi3BO6 used in the examples was prepared according to the following method: Bi2O3 and H3BO3 were added to a ball mill containing zirconia balls and deionized water in a stoichiometric ratio and ball-milled for 6 hours. After drying to constant weight at 150°C, the mixture was placed in a box furnace and calcined at 650°C for 4 hours. The calcined material was then added to a ball mill containing zirconia balls and deionized water and ground for another 6 hours. After drying to constant weight at 150°C, Bi3BO6 powder was obtained. During the ball milling process, the mass ratio of zirconia balls, raw materials, and deionized water was 2:1:1. The mass of the raw materials was the total mass of Bi2O3 and H3BO3, or the mass of the calcined material.

[0028] Mn2P2O7 was prepared by the following method: MnCO3 and NH4H2PO4 were added to a ball mill containing zirconia balls and anhydrous ethanol in a stoichiometric ratio and ball-milled for 3 hours. After drying to constant weight at 70°C, the mixture was initially calcined in a box furnace at 350°C for 3 hours. The material obtained from the initial calcination was then added to a ball mill containing zirconia balls and anhydrous ethanol and ball-milled for 2 hours. After drying to constant weight at 70°C, the mixture was calcined a second time at 650°C under a nitrogen atmosphere for 4 hours. The material obtained from the second calcination was then added to a ball mill containing zirconia balls and anhydrous ethanol and ground for another 4 hours. After drying to constant weight at 70°C, Mn2P2O7 powder was obtained. During the ball milling process, the mass ratio of zirconia balls, raw materials, and anhydrous ethanol was 2:1:1. The mass of the raw materials was the total mass of MnCO3 and NH4H2PO4, the mass of the material obtained from the initial calcination, or the mass of the material obtained from the second calcination.

[0029] Example 1 A piezoelectric ceramic material with the following chemical composition: 0.90 (K 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3Nb 2 / 3 O3-0.05Bi(Ni) 1 / 2 Ti 1 / 2 )O3+0.1wt% Li2CO3+0.03wt% Bi3BO6+0.03wt% Mn2P2O7.

[0030] The preparation method of the above-mentioned piezoelectric ceramic material includes the following steps: (1) The raw materials K2CO3, Pb3O4, ZrO2, TiO2, MnO2, Nb2O5, Bi2O3, NiO, Li2CO3, Bi3BO6, and Mn2P2O7 were mixed according to the stoichiometric ratio and added to a ball mill jar containing zirconia balls and deionized water for ball milling. The ball milling time was 4 hours and the ball mill speed was 320 rpm. During the ball milling process, the mass ratio of zirconia balls, raw materials and deionized water was 2:1:1 (the mass of the raw materials was the total mass of K2CO3, Pb3O4, ZrO2, TiO2, MnO2, Nb2O5, Bi2O3, NiO, Li2CO3, Bi3BO6 and Mn2P2O7). After ball milling, the powder was dried in an oven at 150°C for 6 hours and the moisture content was tested to be 0.25%. After sieving through a 40-mesh sieve, the powder was pre-calcined in a box furnace at 850°C for 4 hours to obtain the synthetic powder. (2) The synthetic powder obtained in step (1) is added to a ball mill jar containing zirconia balls and deionized water for ball milling. The ball milling time is 6 hours and the ball mill speed is 320 rpm. During the ball milling process, the mass ratio of zirconia balls, synthetic powder and deionized water is 2:1:1. After ball milling, the powder is dried and sieved through an 80-mesh sieve to obtain piezoelectric ceramic material powder.

[0031] Figure 1 The image shows a SEM image of the piezoelectric ceramic material obtained in Example 1. Figure 1 It can be seen that the prepared powder has good size uniformity, with a particle size of about 500nm, which is a nano-sized powder.

[0032] Example 2 A piezoelectric ceramic material as described in Example 1, except that x = 0.05; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0033] Example 3 A piezoelectric ceramic material as described in Example 1, except that x = 0.15; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0034] Example 4 A piezoelectric ceramic material as described in Example 1, except that: y = 0.01; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0035] Example 5 A piezoelectric ceramic material as described in Example 1, except that: y = 0.05; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0036] Example 6 A piezoelectric ceramic material as described in Example 1, except that z = 0.01; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0037] Example 7 A piezoelectric ceramic material as described in Example 1, except that z = 0.05; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0038] Example 8 A piezoelectric ceramic material is described in Example 1, except that K is replaced with Na; The preparation method of the above piezoelectric ceramic material is as described in Example 1, except that Na2CO3 is used instead of K2CO3 in step (1).

[0039] Example 9 A piezoelectric ceramic material as described in Example 1, except that Ni is replaced with Zn; The preparation method of the above piezoelectric ceramic material is as described in Example 1, except that ZnO is used instead of NiO in step (1).

[0040] Comparative Example 1 A piezoelectric ceramic material with the following chemical composition: 0.90 (K 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3Nb 2 / 3 O3-0.05Bi(Ni) 1 / 2 Ti 1 / 2 O3; The preparation method of the above-mentioned piezoelectric ceramic material is as described in Example 1.

[0041] Comparative Example 2 A piezoelectric ceramic material is described in Example 1, except that Li2CO3 is not added in step (1).

[0042] Comparative Example 3 A piezoelectric ceramic material as described in Example 1, except that Bi3BO6 is not added.

[0043] Comparative Example 4 A piezoelectric ceramic material as described in Example 1, except that Mn2P2O7 is not added.

[0044] Experimental Example 1 The piezoelectric ceramic material powders obtained in the examples and comparative examples were subjected to granulation, pressing, sintering, and silver polarization, and then their performance was tested. The specific steps are as follows: The piezoelectric ceramic material powder was added to a 15wt% polyvinyl alcohol aqueous solution for granulation, and the mass of the polyvinyl alcohol aqueous solution was 10% of the mass of the piezoelectric ceramic material powder. After granulation, the ceramic green body was dry-pressed at 4MPa using a pressing machine to obtain a ceramic green body. The obtained ceramic green body was heated to the sintering temperature in an air atmosphere at a heating rate of 5℃ / min, and sintered at the sintering temperature for 2 hours. After cooling to room temperature in the furnace, it was removed to obtain a piezoelectric ceramic sheet. The piezoelectric ceramic sheet was silver-coated on both sides with a wire mesh, heated to 800℃ at a heating rate of 5℃ / min and held for 30 minutes for silver firing. Then, polarization treatment was performed, and the piezoelectric ceramic sheet was polarized in silicone oil at 120℃ with a polarization field strength of 2kV / mm for 30 minutes. After polarization, the performance was tested, and the sintering temperature and test results are shown in Table 1.

[0045] Table 1. Performance test results of the piezoelectric ceramic material powders obtained in the examples and comparative examples.

[0046] In Table 1, the piezoelectric ceramic material of Comparative Example 1 was not sintered into ceramic at 900℃, and its sintering performance at 1150℃ is shown in Table 1; the piezoelectric ceramic material of Comparative Example 2 was not sintered into ceramic at 900℃.

[0047] The piezoelectric ceramics prepared by adding Li2CO3, Bi3BO6, and Mn2P2O7 composite additives in this invention exhibit significant performance advantages: Li2CO3, as a key additive, enables ceramic formation in Examples 1-9 at 900℃, which is 250℃ lower than the sintering temperature of Comparative Example 1 without additives; without Li2CO3, ceramic formation is impossible. The synergistic doping of Li2CO3 and Mn2P2O7 significantly improves the piezoelectric properties, with the piezoelectric coefficient d in Example 1 being significantly higher. 33 With a maximum value of 365 pC / N, far exceeding that of the comparative ratios, the electromechanical coupling coefficient is also superior. The Curie temperature of the system is maintained at 330-345℃, exhibiting good high-temperature stability. Meanwhile, the mechanical quality factor exceeds 1000, and the dielectric loss is only 0.4%-0.5%, far lower than that of the comparative ratios, resulting in a significant improvement in energy efficiency. Even after fine-tuning the composition, it can still maintain low-temperature sintering and excellent performance, with an optimal ratio. Moreover, all three additives are indispensable, working synergistically to achieve a comprehensive effect of low-temperature sintering, high voltage, low loss, and high stability.

Claims

1. A piezoelectric ceramic material, characterized in that, Its chemical composition is: 0.90 (M 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti 1 / 2 O3+xwt% Li2CO3+ywt% BiB3O6+zwt% Mn2P2O7, where M is K or Na, N is Zn, Ni or Co, 0.01≤x≤0.2, 0.01≤y≤0.1, 0.05≤z≤0.1, 0.90(M 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti 1 / 2 O3 represents the matrix ceramic powder, x represents the mass percentage of Li2CO3 in the matrix ceramic powder, y represents the mass percentage of BiB3O6 in the matrix ceramic powder, and z represents the mass percentage of Mn2P2O7 in the matrix ceramic powder.

2. The method for preparing the piezoelectric ceramic material according to claim 1, characterized in that, The steps include the following: (1) According to 0.90(M) 0.01 Pb 0.99 (Zr) 0.5 Ti 0.5 O3-0.05Pb(Mn) 1 / 3 Nb 2 / 3 )O3-0.05Bi(N 1 / 2 Ti 1 / 2 The stoichiometric ratio of raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, BiB3O6, and Mn2P2O7 is accurately weighed, ball-milled, dried, sieved, and pre-calcined to obtain the synthesized powder. (2) The synthesized powder is dispersed by ball milling to obtain piezoelectric ceramic material.

3. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, In step (1), the M source is a K source or a Na source, where the K source is K2CO3 and the Na source is Na2CO3; the Pb source is PbO or Pb3O4; the Zr source is ZrO2; the Ti source is TiO2; the Mn source is MnO2; the Nb source is Nb2O5; the Bi source is Bi2O3; and the N source is a Zn source, a Ni source, or a Co source, where the Zn source is ZnO, the Ni source is NiO, and the Co source is Co3O4.

4. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, The BiB3O6 in step (1) is prepared by the following method: Bi2O3 and H3BO3 are added to a ball mill containing zirconia balls and deionized water in stoichiometric ratio and ball milled for 4-8 hours. After drying to constant weight at 120-180℃, the mixture is calcined at 600-700℃ for 3-4 hours. The calcined material is then added to a ball mill containing zirconia balls and deionized water and ball milled for another 6-8 hours. After drying to constant weight at 120-180℃, BiB3O6 powder is obtained. During the ball milling process, the mass ratio of zirconia balls, raw materials and deionized water is 2:1:

1.

5. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, The Mn2P2O7 described in step (1) is prepared by the following method: MnCO3 and NH4H2PO4 are added to a ball mill containing zirconia balls and anhydrous ethanol and ball-milled for 2-4 hours according to the stoichiometric ratio. After drying to constant weight at 60-80℃, the mixture is initially calcined at 300-400℃ for 2-3 hours. The material obtained from the initial calcination is added to a ball mill containing zirconia balls and anhydrous ethanol and ball-milled for 1-3 hours. After drying to constant weight at 60-80℃, the mixture is calcined again at 600-700℃ for 3-4 hours under a nitrogen atmosphere. The material obtained from the second calcination is added to a ball mill containing zirconia balls and anhydrous ethanol and ball-milled for another 3-4 hours. After drying to constant weight at 60-80℃, Mn2P2O7 powder is obtained. During the ball milling process, the mass ratio of zirconia balls, raw materials and deionized water is 2:1:

1.

6. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, The ball milling step in step (1) is as follows: the raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, BiB3O6, and Mn2P2O7 are mixed according to the stoichiometric ratio and then added to a ball milling jar containing zirconium oxide and deionized water for ball milling. The ball milling time is 3-6 hours and the ball mill speed is 300-350 rpm. During the ball milling process, the mass ratio of zirconium oxide, raw materials and deionized water is 2:1:

1. The mass of the raw materials is the total mass of raw materials M source, Pb source, Zr source, Ti source, Mn source, Nb source, Bi source, N source, Li2CO3, BiB3O6 and Mn2P2O7.

7. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, The drying temperature in step (1) is 120-180℃, the drying time is 4-10 hours, and the moisture content is <0.3wt%; the mesh size of the sieve used for sieving is 40-60 mesh. The pre-firing temperature is 800-850℃, and the pre-firing time is 3-5 hours.

8. The method for preparing the piezoelectric ceramic material according to claim 2, characterized in that, The ball milling step (2) is as follows: the synthetic powder is added to a ball milling jar containing zirconia balls and deionized water for ball milling. The ball milling time is 5-10 hours and the ball mill speed is 300-350 rpm. The mass ratio of zirconia, synthetic powder and deionized water during the ball milling process is 2:1:

1.

9. The application of the piezoelectric ceramic material according to claim 1 in the preparation of piezoelectric devices.

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