A pzt-based piezoelectric ceramic material with large electrostriction under low electric field and high curie temperature and a preparation method thereof

Abstract

The present application relates to a kind of PZT-based piezoelectric ceramic material with large electric strain under low electric field and high Curie temperature and its preparation method.The chemical composition of the PZT-based piezoelectric ceramic material is: Pb 1‑2n‑1.5x La x Sr n Ba n (Zr y Ti 1‑y )O3-zwt%Sn, wherein 0.004≤x≤0.007, 0.52≤y≤0.6, 0.3≤z≤0.7, 0.01≤n≤0.04.The preparation method of the PZT-based piezoelectric ceramic material includes the following steps: (1) batching; (2) calcination; (3) granulation; (4) plastic, sintering.

Description

Technical Field

[0001] This invention belongs to the field of aerospace actuators, and particularly relates to a PZT-based piezoelectric ceramic material with large electrostrain and high Curie temperature and its preparation method. Background Technology

[0002] Piezoelectric actuators, characterized by their small size, fast response, and large output torque, are widely used in modern high-tech fields such as aerospace, nuclear energy, and petrochemicals. Piezoelectric ceramic materials, as the core components of piezoelectric actuators, utilize the inverse piezoelectric effect to generate proportional strain values ​​under an electric field, achieving precise actuation. With the rapid development of electronic information technology, aerospace, and defense industries, higher demands are placed on the performance of piezoelectric ceramics in high-tech applications. These applications require piezoelectric ceramics to possess superior strain characteristics, with large strain characteristics enabling the generation of large strains even at relatively low driving electric field strengths. Actuators used in these fields, especially in aerospace, typically need to operate over a wide temperature range (room temperature to high temperatures). However, as the Curie temperature increases, the performance of piezoelectric ceramics significantly decreases, severely limiting the application of piezoelectric actuators.

[0003] For aerospace service environments, piezoelectric ceramics must not only meet the requirements of high piezoelectric coefficient and large strain characteristics under low electric field, but also have high Curie temperature. Summary of the Invention

[0004] To address the above problems, this invention aims to provide a PZT-based piezoelectric ceramic material and its preparation method that combine large electrostriction under low electric field and high Curie temperature. The ceramic material of this composition exhibits both a high Curie temperature and large electrostriction, as well as good strain performance temperature stability, and is expected to be applied in the field of aerospace actuators.

[0005] On one hand, this invention provides a PZT-based piezoelectric ceramic material that combines large electrostriction under low electric field and high Curie temperature. The chemical composition of the PZT-based piezoelectric ceramic material is: Pb 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y O3-zwt%Sn, where 0.004≤x≤0.007, 0.52≤y≤0.6, 0.3≤z≤0.7, 0.01≤n≤0.04. In Pb 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-yBased on the O3 system, an additional zwt% SnO2 is added; when x, y, z, and n exceed the above range, the piezoelectric properties and strain value of the PZT-based piezoelectric ceramic material will decrease, and the Curie temperature will drop.

[0006] This invention designs Pb 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y By using a composition of O3-zwt%Sn (PLSBZT-zwt%Sn), PZT-based piezoelectric ceramic materials with high Curie temperatures and large strains are obtained, which are expected to be applied in the field of aerospace actuators. This invention selects Pb... 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y Using O3 as the matrix material, doping with La enhances the piezoelectric properties and increases strain. This is because La is a "soft" dopant; when La enters the solid solution, it replaces Pb sites. The trivalent La ions replacing divalent Pb ions create lead vacancies, distorting the crystal lattice and facilitating domain wall movement. This movement occurs even under a relatively small electric field, thus improving the piezoelectric properties. Doping with Sn promotes the formation of a perovskite structure, further increasing its strain performance under low electric fields. Sn, upon entering the unit cell, replaces Zr or Ti sites, causing lattice distortion and reducing the grain size and domain refinement, which is more conducive to domain inversion. The combined effect of these two factors significantly improves the performance of the PZT-based piezoelectric ceramic material system of this invention.

[0007] Preferably, 0.53≤y≤0.55, 0.5≤z≤0.55. Within this range, the strain properties and Curie temperature of the material are both at a high level.

[0008] Preferably, the Curie temperature of the PZT-based piezoelectric ceramic material is at least 250°C, and more preferably 255-270°C; the strain value of the PZT-based piezoelectric ceramic material under a 2kV / mm electric field is at least 0.16%, and more preferably 0.197%-0.203%.

[0009] On the other hand, the present invention also provides a method for preparing a PZT-based piezoelectric ceramic material that combines large electrostriction under low electric field and high Curie temperature, comprising:

[0010] (1) Weigh and mix Pb source, Zr source, Ti source, Sr source, Ba source, La source and Sn source according to the stoichiometric ratio of the chemical composition of the PZT-based piezoelectric ceramic material to obtain raw material powder;

[0011] (2) The raw material powder is calcined to obtain the synthetic powder;

[0012] (3) The synthetic powder is mixed with the binder and granulated, and then shaped to obtain a ceramic blank;

[0013] (4) The ceramic blank is subjected to plasticizing and sintering to obtain the PZT-based piezoelectric ceramic material that has both large electrostriction under low electric field and high Curie temperature.

[0014] Preferably, the Pb source is Pb3O4 powder; the Zr source is ZrO2 powder; the Ti source is TiO2 powder; the Sr source is SrCO3 powder; the Ba source is BaCO3 powder; the La source is La2O3 powder; and the Sn source is SnO2 powder.

[0015] Preferably, in step (2), the calcination temperature is 800-900°C, the time is 2-4 hours, and the heating rate is 1.5-3°C / minute.

[0016] Preferably, in step (3), the binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the amount of binder added is 5-7% of the mass of the synthetic powder.

[0017] Preferably, the temperature for extruding the plastic is 700–800°C, and the time is 2–3 hours.

[0018] Preferably, in step (4), the sintering temperature is 1280-1300°C, the time is 2-4 hours, and the heating rate is 1.5-3°C / minute.

[0019] Beneficial effects:

[0020] The PZT-based piezoelectric ceramic material obtained in this invention uses PZT as the matrix material and adds La. 3+ Simultaneously doped with Sn 4+ This improves the piezoelectric properties of the material, allowing the strain value to reach over 0.18% under a 2kV / mm electric field, and its Curie temperature to be above 250℃. Furthermore, its relatively low permittivity enables the actuator to have a faster response speed.

[0021] In this invention, a piezoelectric ceramic material with a Curie temperature higher than 250°C and large strain characteristics under low electric field is prepared by the traditional solid-state method, which is suitable as a piezoelectric multilayer actuator for aerospace applications. Attached Figure Description

[0022] Figure 1 The PZT-based piezoelectric ceramic materials prepared in Examples 1-4 and the undoped Pb prepared in Comparative Example 1 1-2n- 1.5x La x Sr n Ba n (Zr y Ti 1-y Dielectric temperature spectrum of O3 piezoelectric ceramic material; where a is undoped Pb 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y O3 piezoelectric ceramic material, b is the piezoelectric ceramic material prepared in Example 1, c is the piezoelectric ceramic material prepared in Example 2, d is the piezoelectric ceramic material prepared in Example 3, and e is the piezoelectric ceramic material prepared in Example 4;

[0023] Figure 2 The lead-free piezoelectric ceramic materials prepared in Examples 1-4 and the undoped Pb prepared in Comparative Example 1 are examples of such materials. 1-2n- 1.5x La x Sr n Ba n (Zr y Ti 1-y The monopole electroinduced strain curve of O3 piezoelectric ceramic material under an electric field of 2 kV / mm, where a is the undoped Pb. 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y O3 piezoelectric ceramic material, b is the piezoelectric ceramic material prepared in Example 1, c is the piezoelectric ceramic material prepared in Example 2, d is the piezoelectric ceramic material prepared in Example 3, and e is the piezoelectric ceramic material prepared in Example 4. Detailed Implementation

[0024] To further illustrate the invention's content, features, and practical effects, the invention will be described in detail below with reference to embodiments. It should be noted that the modification methods of the invention are not limited to these specific implementation methods. Equivalent substitutions and modifications made by those skilled in the art based on their reading of the invention's content, without departing from the spirit and essence of the invention, are also within the scope of protection claimed by this invention.

[0025] In this invention, the chemical composition of the PZT-based piezoelectric ceramic material, which combines large electrostriction under low electric field and high Curie temperature, is: Pb 1-2n-1.5x La xSr n Ba n (Zr y Ti 1-y )O3-zwt%Sn(PLSBZT-zwt%Sn). Among them, 0.004≤x≤0.007, 0.52≤y≤0.6, 0.3≤z≤0.7, 0.01≤n≤0.04.

[0026] The PZT-based piezoelectric ceramic material of the present invention achieves a significant improvement in material strain performance and Curie temperature under low electric field. The strain value under a 2kV / mm electric field can reach more than 0.18%, and its Curie temperature is above 250℃.

[0027] The doping of Sn element in this invention causes lattice distortion in the crystal, and at the same time, it causes certain changes in the domain morphology and size of the material. The dual effect of lattice distortion and domains improves the strain performance of the system under low electric field.

[0028] The PLSBZT-0.55wt%Sn piezoelectric ceramic material has both high Curie temperature and large strain characteristics. Its Curie temperature is greater than 259.5℃, and the unipolar strain value under a 2kV / mm electric field can reach 0.203%.

[0029] Preferably, 0.53 ≤ y ≤ 0.55 and 0.5 ≤ z ≤ 0.55. Here, y is the molar content of zirconium. When 0.53 ≤ y ≤ 0.55, the material composition is near the MPB (quasi-isomorphic phase boundary) two-phase coexistence region. z is the weight ratio of Sn content to the PLSBZT basic system. When 0.5 ≤ z ≤ 0.55, the grain size of the material is relatively smaller, and the domain size is also smaller and easier to flip. If the z value is too large, the grain size will relatively increase, significantly reducing the material performance.

[0030] In this invention, PZT-based piezoelectric ceramic materials are prepared through steps including batching, mixing, calcination, molding, plasticizing, and sintering. The following exemplarily illustrates a method for preparing PZT-based piezoelectric ceramic materials that possess both large electrostriction under low electric fields and high Curie temperatures.

[0031] The synthetic powder was obtained by mixing and calcining Pb3O4, ZrO2, TiO2, SrCO3, BaCO3, La2O3 and SnO2 powders as raw materials.

[0032] In an optional embodiment, wet ball milling is used for mixing. The parameters of the wet ball milling include: the milling solvent is deionized water, the milling balls are zirconia balls, the mass ratio of raw material:zirconia balls:deionized water is (0.5-1):(1.5-3):(0.5-1), and the milling time is 4-6 hours; preferably, the mass ratio of raw material:zirconia balls:deionized water is 1:3:1, and the milling time is 4 hours.

[0033] In an optional embodiment, the ball-milled powder is dried, pressed into briquettes, and then calcined. The calcination temperature is 800–900°C, the time is 2–4 hours, and the heating rate is 1.5–3°C / minute.

[0034] In an optional embodiment, wet ball milling is used to finely grind the calcined powder. The parameters of the fine milling include: the ball milling solvent is deionized water, the grinding balls are zirconia balls, the mass ratio of raw material:zirconia balls:deionized water is (0.5-1):(1.5-3):(0.5-1), and the ball milling time is 6-8 hours; preferably, the grinding balls are zirconia balls, the mass ratio of raw material:zirconia balls:deionized water is 1:3:1, and the ball milling time is 6 hours.

[0035] The synthetic powder is mixed with a binder and granulated, then pressed and molded to obtain a ceramic blank.

[0036] In an optional embodiment, the binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the amount of binder added is 5-7% of the mass of the synthetic powder.

[0037] The pressure for compression molding is 1.4 to 3 MPa.

[0038] The temperature for plastic discharge is 700–800℃, and the time is 2–3 hours.

[0039] The PZT-based piezoelectric ceramic material is obtained by sintering the ceramic green body. To reduce Pb volatilization, a powder with the same chemical composition as the PZT-based piezoelectric ceramic material is used to cover the ceramic green body during the sintering process. The crucible is then covered and sintered to obtain the PZT-based piezoelectric ceramic material.

[0040] In an optional embodiment, the sintering temperature is 1280–1300°C, the time is 2–4 hours, and the heating rate is 1.5–3°C / minute. Excessive sintering temperature will cause severe lead loss and overheating, while insufficient temperature will result in incomplete ceramic sintering.

[0041] The obtained PZT-based piezoelectric ceramic material is used to prepare piezoelectric elements. This can be achieved by silvering, silver calcination, and polarization treatments on the PZT-based piezoelectric ceramic material.

[0042] In an optional embodiment, the obtained PZT-based piezoelectric ceramic material is processed into thin sheets of the required size, cleaned, dried, screen-printed with silver paste, dried again, and finally subjected to a silver-firing treatment. The silver-firing treatment is performed at a temperature of 650–750°C for 30–60 minutes, with a heating rate of 2–5°C / min. The polarization conditions can be 120±5°C, a voltage of 2–4 kV, and polarization for 15–20 minutes.

[0043] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0044] Example 1

[0045] The chemical composition of the PZT-based piezoelectric ceramic material in Example 1, which exhibits both large electrostriction under low electric field and high Curie temperature, is (Pb) 0.931 La 0.006 Sr 0.03 Ba 0.03 (Zr 0.535 Ti 0.465 )O3-zwt%Sn, where z=0.4.

[0046] The preparation method of the PZT-based piezoelectric ceramic material with both large electrostriction under low electric field and high Curie temperature in Example 1 includes:

[0047] (1) Pb3O4, ZrO2, TiO2, SrCO3, BaCO3, La2O3, and SnO2 were weighed according to the stoichiometric ratio and mixed using wet ball milling at a mass ratio of raw materials:zirconia balls: deionized water = 1:3:1. The mixture was ball-milled for 4 hours to ensure uniform mixing of all components. After drying, the mixture was passed through a 40-mesh sieve and then pressed into blocks. The blocks were then calcined at a heating rate of 2℃ / min to 850℃ and held at that temperature for 2 hours to obtain the synthesized powder.

[0048] (2) The obtained synthetic powder was crushed, ground, and sieved. It was then further finely ground using a wet ball mill at a mass ratio of raw material:zirconia balls: deionized water = 1:3:1 for 6 hours. The finely ground ceramic powder was then dried. PVA binder was then added for granulation. The amount of binder added was 6% of the mass of the synthetic powder. The powder was pressed into sheet-like ceramic blanks under a pressure of 1.5 MPa. The ceramic blanks were heated to 700℃ and held for 2 hours for desizing.

[0049] (3) Place the ceramic blank after plastic removal in a crucible. In order to reduce the volatilization of Pb, cover the blank with ceramic powder with the same composition as in step (1), cover the crucible, heat the blank to 1280°C at a heating rate of 2°C / min, sinter the blank, keep it at the temperature for 2 hours, and cool it with the furnace to obtain the sheet-like PZT-based piezoelectric ceramic material.

[0050] The sintered ceramic sheet is ground to a thickness of 0.5-1mm, cleaned, dried, screen-printed with silver paste, dried again, heated to 750℃ at a heating rate of 2℃ / min for silver firing, and held at that temperature for 30 minutes to obtain the piezoelectric ceramic element.

[0051] The piezoelectric ceramic element prepared in Example 1 was polarized under the following conditions: 120±5℃, 2-4kV voltage, and polarization time of 15 min. The piezoelectric and dielectric properties of the polarized piezoelectric ceramic element were then tested, and the results are shown in Table 1. Figure 1 and Figure 2 .

[0052] Example 2

[0053] The chemical composition of the PZT-based piezoelectric ceramic material in Example 2, which exhibits both large electrostriction under low electric fields and high Curie temperatures, is Pb. 0.931 La 0.006 Sr 0.03 Ba 0.03 (Zr 0.535 Ti 0.465 O3-zwt%Sn, where z=0.5. The preparation method of the piezoelectric ceramic material is as described in Example 1.

[0054] The piezoelectric ceramic element prepared in Example 2 was polarized under the following conditions: 120±5℃, 2-4kV voltage, and polarization time of 15 min. The piezoelectric and dielectric properties of the polarized piezoelectric ceramic element were then tested, and the results are shown in Table 1. Figure 1 and Figure 2 The dielectric temperature spectrum and unipolar electrostriction curve of the piezoelectric ceramic material prepared in Example 2 are shown below. Figure 1 and 2 As shown.

[0055] Example 3

[0056] The chemical composition of the PZT-based piezoelectric ceramic material in Example 3, which exhibits both large electrostriction under low electric fields and high Curie temperatures, is Pb. 0.931 La 0.006 Sr 0.03 Ba 0.03 (Zr 0.535 Ti 0.465O3-zwt%Sn, where z = 0.55. The preparation method of the piezoelectric ceramic material is as described in Example 1.

[0057] The piezoelectric ceramic element prepared in Example 3 was polarized under the following conditions: 120±5℃, 2-4kV voltage, and polarization time of 15 min. The piezoelectric and dielectric properties of the polarized piezoelectric ceramic element were then tested, and the results are shown in Table 1. Figure 1 and Figure 2 .

[0058] Example 4

[0059] The chemical composition of the PZT-based piezoelectric ceramic material in Example 4, which exhibits both large electrostriction under low electric fields and high Curie temperatures, is Pb. 0.931 La 0.006 Sr 0.03 Ba 0.03 (Zr 0.535 Ti 0.465 O3-zwt%Sn, where z = 0.6. The preparation method of the piezoelectric ceramic material is as described in Example 1.

[0060] The piezoelectric ceramic element prepared in Example 4 was polarized under the following conditions: 120±5℃, 2-4kV voltage, and polarization time of 15 min. The piezoelectric and dielectric properties of the polarized piezoelectric ceramic element were then tested, and the results are shown in Table 1. Figure 1 and Figure 2 .

[0061] Comparative Example 1

[0062] The chemical composition of the piezoelectric ceramic material in Comparative Example 1 is Pb. 0.931 La 0.006 Sr 0.03 Ba 0.03 (Zr 0.535 Ti 0.465 O3 where z = 0. The preparation method of the piezoelectric ceramic material is as described in Example 1.

[0063] The piezoelectric ceramic element prepared in Comparative Example 1 was polarized under the following conditions: 120±5℃, 2–4kV voltage, and polarization time of 15 min. The piezoelectric and dielectric properties of the polarized piezoelectric ceramic element were tested, and the results are shown in Table 1. Figure 1 and Figure 2 .

[0064] Table 1 lists the piezoelectric and dielectric properties (d) of the polarized PZT-based piezoelectric ceramic materials prepared in Examples 1-4 and Comparative Example 1, respectively. 33 T c Furthermore, electrostriction can be directly measured by experimental instruments, ε rk can be calculated from the capacitance at room temperature and the sample thickness and area. p and Q m It can be calculated from the resonant and anti-resonant frequencies.

[0065] Table 1:

[0066]

[0067] Table 1 shows that the piezoelectric coefficient, strain, and dielectric constant ε of the material are... r and electromechanical coupling coefficient k p The Sn doping concentration initially increases and then decreases with increasing concentration. When the Sn doping concentration reaches 0.6 wt%, the overall performance decreases compared to the optimal state (0.55 wt% Sn doping), but it is still higher than that of the undoped piezoelectric ceramic material (Comparative Example 1). With increasing Sn doping concentration, the Curie temperature of the system fluctuates slightly, but remains above 250℃.

[0068] Figure 1 The PZT-based piezoelectric ceramic materials prepared in Examples 1-4 and the undoped Pb prepared in Comparative Example 1 1-2n- 1.5x La x Sr n Ba n (Zr y Ti 1-y Dielectric temperature spectrum of O3 piezoelectric ceramic material. As can be seen from the figure, although the Curie temperature of the system decreases slightly after Sn doping, it is still above 250℃.

[0069] Figure 2 The lead-free piezoelectric ceramic materials prepared in Examples 1-4 and the undoped Pb prepared in Comparative Example 1 are examples of such materials. 1-2n- 1.5x La x Sr n Ba n (Zr y Ti 1-y The figure shows the monopole electrostriction curve of O3 piezoelectric ceramic material under an electric field of 2 kV / mm. As can be seen from the figure, after Sn doping, the monopole strain of the material under an electric field of 2 kV / mm is significantly improved. The monopole strain of Example 3 is nearly 20% higher than that of Comparative Example 1.

[0070] The Curie temperature T of the piezoelectric ceramic material prepared in Example 1 of this invention c =261.2℃, electrostrain 0.181%, compared with undoped Pb prepared in Comparative Example 1 1-2n-1.5x La x Sr n Ba n (Zr yTi 1-y The O3 piezoelectric ceramic material exhibits a strain increase of over 6% compared to unipolar electrostriction. The Curie temperature T of the piezoelectric ceramic prepared in Example 2 is [not specified]. c =261.4℃, electrostrain 0.197%, compared with undoped Pb prepared in Comparative Example 1 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y Compared to unipolar electrostriction, O3 piezoelectric ceramic materials exhibit a 16% increase in strain, resulting in a significant improvement in overall performance. The piezoelectric ceramic material prepared in Example 3 demonstrates optimal piezoelectric properties. The piezoelectric coefficient d... 33 The ratio is 527 pC / N, and the unipolar strain can reach 0.203%, compared with the undoped Pb prepared in Comparative Example 1. 1-2n-1.5x La x Sr n Ba n The (ZryTi1-y)O3 piezoelectric ceramic material exhibits nearly 20% higher electrostriction compared to unipolar materials, while maintaining a Curie temperature above 250°C. The piezoelectric ceramic material prepared in Example 4 has an electrostriction of 0.18%, a Curie temperature of 269.4°C, and a piezoelectric coefficient d0. 33 The value is 495 pC / N. Although properties such as strain and piezoelectric coefficient are lower than those of Example 3, they are still better than those of Comparative Example 1.

Claims

1. A PZT-based piezoelectric ceramic material exhibiting both large electrostriction under low electric field and high Curie temperature, characterized in that, The chemical composition of the PZT-based piezoelectric ceramic material is: Pb 1-2n-1.5x La x Sr n Ba n (Zr y Ti 1-y O3-zwt%Sn, where 0.004≤x≤0.007, 0.52≤y≤0.6, 0.3≤z≤0.7, 0.01≤n≤0.04; The preparation method of the PZT-based piezoelectric ceramic material includes: (1) Weigh and mix Pb source, Zr source, Ti source, Sr source, Ba source, La source and Sn source according to the stoichiometric ratio of the chemical composition of the PZT-based piezoelectric ceramic material to obtain raw material powder; (2) The raw material powder is calcined to obtain the synthetic powder; (3) The synthetic powder is mixed with the binder and granulated, and then shaped to obtain a ceramic blank; (4) The ceramic blank is subjected to plastic removal and sintering to obtain the PZT-based piezoelectric ceramic material with both large electrostriction under low electric field and high Curie temperature; the sintering temperature is 1280~1300℃, the time is 2~4 hours, and the heating rate is 1.5~3℃ / minute.

2. The PZT-based piezoelectric ceramic material according to claim 1, characterized in that, 0.53≤y≤0.55, 0.5≤z≤0.

55.

3. The PZT-based piezoelectric ceramic material according to claim 1 or 2, characterized in that, The Curie temperature of the PZT-based piezoelectric ceramic material is at least 250°C; the strain value of the PZT-based piezoelectric ceramic material under an electric field of 2 kV / mm is at least 0.16%.

4. The PZT-based piezoelectric ceramic material according to claim 3, characterized in that, The Curie temperature of the PZT-based piezoelectric ceramic material is 255–270℃; the strain value of the PZT-based piezoelectric ceramic material under a 2kV / mm electric field is 0.197%–0.203%.

5. The PZT-based piezoelectric ceramic material according to claim 1, characterized in that, The Pb source is Pb3O4 powder; the Zr source is ZrO2 powder; the Ti source is TiO2 powder; the Sr source is SrCO3 powder; the Ba source is BaCO3 powder; the La source is La2O3 powder; and the Sn source is SnO2 powder.

6. The PZT-based piezoelectric ceramic material according to claim 1, characterized in that, In step (2), the calcination temperature is 800-900℃, the time is 2-4 hours, and the heating rate is 1.5-3℃ / minute.

7. The PZT-based piezoelectric ceramic material according to claim 1, characterized in that, In step (3), the binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the amount of binder added is 5-7% of the mass of the synthetic powder.

8. The PZT-based piezoelectric ceramic material according to claim 1, characterized in that, The temperature for plastic discharge is 700–800℃, and the time is 2–3 hours.

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