A A- and B-site double-doped medium-entropy lead zirconate-based composite dielectric ceramic and its preparation method

Abstract

The present invention discloses a double-doped A and B site medium-entropy lead zirconate-based composite dielectric ceramic and a preparation method thereof. The chemical formula of the medium-entropy ceramic material of the present invention is xPbSnO 3‑ (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O3 (x = 0 to 0.03). The preparation process is to weigh SnO2, PbO, BaCO3, La2O3, Sm2O3, HfO2, ZrO2, and TiO2 respectively according to the designed stoichiometric ratio, then carry out mixing in a three-dimensional mixer, pre-sintering, wet ball milling, drying, sieving, tabletting, and finally sintering at 1235 °C in air for 3 h to obtain a dense medium-entropy ceramic. At room temperature and under a frequency test of 1 kHz, the dielectric constant of this medium-entropy ceramic can reach 825, and the dielectric loss is lower than 0.05, and it is expected to become a candidate material for a new generation of dielectric ceramics.

Description

Technical Field

[0001] The present invention relates to a lead zirconate-based complex dielectric ceramic with A and B site double-doped medium-entropy and a preparation method thereof, belonging to the technical field of medium-entropy ceramics. Background Art

[0002] Lead zirconate (PbZrO 3 ) is a typical dielectric ceramic material. After doping, its dielectric constant can be increased and the dielectric loss can be reduced.

[0003] Medium-entropy ceramic materials are multi-principal element solid solution ceramics formed by doping 3 to 4 elements in equal or approximately equal proportions. In the field of dielectric ceramics, there has been no research or report on the design and complex phase of lead zirconate with A and B site double-doped medium-entropy. This patent conducts an A and B site double-doped medium-entropy design on lead zirconate, doping three elements with similar chemical properties in equimolar ratio into the B-site lattice of lead zirconate, and simultaneously conducting a partial medium-entropy design on the A-site. This can ensure that a large amount of Pb element is contained in the A-site, and after partial medium-entropy, the degree of disorder in the A-site will increase. After A and B site double-doped medium-entropy, it can cause a lattice distortion effect in lead zirconate, increasing its degree of disorder. Adding a small amount of PbSnO 3 for complex phase ceramic design is expected to further improve the dielectric properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of a lead zirconate-based complex dielectric ceramic with A and B site double-doped medium-entropy. The chemical formula of the ceramic is: xPbSnO 3- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 - 0.03). The preparation method includes the following steps:

[0005] (1) Weigh BaCO 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 respectively according to the chemical formula of BaCO 3 、La 2 O 3 、Sm 2 O 3 、HfO 2 、ZrO2 , TiO 2 powder; Weigh SnO 3 and PbO powder respectively according to the chemical formula of PbSnO 2 .

[0006] (2) Put the above powders into a three-dimensional mixer for mixing for 30 - 50 minutes, and then carry out pre-sintering. Weigh the pre-sintered powders according to the chemical formula of xPbSnO 3- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 (x = 0 - 0.03), and then put them into a ball mill for wet ball milling and mixing respectively. After drying, carry out grinding, sieving, and tabletting; 3 and (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , and put them into a ball mill for wet ball milling and mixing respectively. After drying, carry out grinding, sieving, and tabletting;

[0007] (3) Put the pressed and unsintered ceramic sheets into a muffle furnace and sinter them in air at 1200 - 1270 °C.

[0008] Preferably, in step (2), the pre-sintering temperature of the (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 medium-entropy ceramic powder is 800 - 850 °C, and the heat preservation time is 1.8 - 2.2 h. The pre-sintering temperature of the PbSnO 3 ceramic powder is 800 - 850 °C, and the heat preservation time is 1.7 - 2.3 h.

[0009] Preferably, in step (2), the conditions for wet ball milling are: the rotation speed of the ball mill is 15 - 35 revolutions per minute, the ball milling time is 34 or 36 - 72 hours, the ball milling medium is distilled water and zirconia balls, and the mass ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9; the mass ratio of large balls, medium balls, and small balls in the zirconia balls is 1:2:3.

[0010] Preferably, in step (2), the drying conditions are as follows: the drying temperature is 80-120°C, and the drying time is 12-20 h.

[0011] Preferably, the mesh number of the sieve used in step (2) is 80-200 meshes.

[0012] Preferably, in step (2), the grinding conditions are as follows: the dried mixed powder is put into a grinding jar and ground for 20-50 minutes.

[0013] Preferably, in step (2), the diameter of the mold used for tableting is 10-13 mm, the uniaxial pressure is 160-180 MPa, and the pressure holding time is 5-15 minutes.

[0014] Preferably, in step (3), the sintering method is as follows: the same powder as the ceramic sheet is added around and on the ceramic sheet for buried sintering. The temperature of the muffle furnace is raised from room temperature to 1200-1270°C at a heating rate of 4.5°C / min, and the holding time in the muffle furnace is 2.8-3.2 hours. Then, it is cooled in the furnace to a low temperature and taken out.

[0015] The beneficial effects of the present invention are as follows:

[0016] (1) The preparation process of the present invention is simple and does not require atmosphere protection. Only an ordinary muffle furnace is needed for sintering, which has the characteristics of short sintering time, energy saving, simple process, low production cost, short production cycle, and high efficiency.

[0017] (2) The xPbSnO 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 prepared by the present invention, (x = 0-0.03) complex medium-entropy ceramics do not need to add any binder, sintering aid, and dispersant.

[0018] (3) The xPbSnO 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 prepared by the present invention, (x = 0-0.03). Under the 1 kHz frequency test, the dielectric constant of the medium-entropy ceramics measured at room temperature is 825, and the dielectric loss is lower than 0.05. Description of the Drawings

[0019] Figure 1 XRD of the xPbSnO 3- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 - 0.03) complex medium entropy ceramics.

[0020] Figure 2 SEM image of the (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 medium entropy ceramics obtained in Example 2;

[0021] Figure 3 XRD of the xPbSnO 3- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 - 0.03) complex medium entropy ceramics at room temperature dielectric constant graph.

[0022] Figure 4 XRD of the xPbSnO 3- (1 - x)(Pb 0.93 La 0.02 Ba 0.02 Sm 0.02 )(Sn 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 - 0.03) complex medium entropy ceramics at room temperature dielectric loss graph. Detailed implementation mode

[0023] The technical solution of the present invention will be further described below with reference to the accompanying drawings. However, the protection scope of the present invention is not limited to the above content.

[0024] Example 1

[0025] The chemical formula of a double-doped A and B-site medium-entropy lead zirconate-based composite dielectric ceramic is: xPbSnO 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 。

[0026] In this embodiment, x = 0, that is, (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 。

[0027] The preparation method of the above dielectric ceramic is as follows:

[0028] (1) Weigh PbO, BaCO 3 , La 2 O 3 , Sm 2 O 3 , HfO 2 , ZrO 2 , TiO 2 powders according to the stoichiometric ratio designed by the chemical formula. Put the above powders into a three-dimensional mixer for mixing for 35 minutes, and then pre-burn the mixed powders. The pre-burning temperature is 850 °C and the pre-burning time is 1.9 h. Put the pre-burned powders into a ball mill for wet ball milling and mixing. The rotation speed of the ball mill is 28 revolutions per minute, the ball milling time is 36 hours, and the ball milling medium is distilled water and zirconia balls. The mass ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9. The mass ratio of large balls, medium balls, and small balls in the zirconia balls is 1:2:3. Then dry, the drying temperature is 94 °C and the drying time is 16 h. Put the dried mixed powders into a grinding jar for grinding for 31 minutes, sieve the ground mixed powder, the mesh number of the sieve is 180 meshes, and press the sieved mixed medium-entropy powder. The diameter of the mold used for pressing is 13 mm, the uniaxial pressure is 180 MPa, and the pressure holding time is 10 minutes.

[0029] (2) Put the pressed un-sintered ceramic sheet into a muffle furnace and sinter it at 1235 °C in air. The specific method is: add the same powder as the ceramic block around and on the ceramic for buried sintering. Raise the temperature of the muffle furnace from room temperature to 1235 °C at a heating rate of 4.5 °C / min, keep the temperature in the muffle furnace for 3 hours, and then cool it with the furnace to a low temperature and take it out.

[0030] Example 2

[0031] The chemical formula of an A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic is: xPbSnO 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 In this embodiment, x = 0.015, that is, 0.015PbSnO 3- 0.985(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 .

[0032] (1) According to (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 Weigh the chemical formula of BaCO 3 ,La 2 O 3 、Sm 2 O 3 , HfO 2 、ZrO 2 、TiO 2 Powder. The above powders were placed in a three-dimensional mixer for mixing for 38 minutes, and the mixed powders were pre-burned for 1.9 hours at a temperature of 845°C; the pre-burned powders were placed in a ball mill for wet ball milling mixing. The speed of the ball mill was 30 rpm, and the ball milling time was 34 hours. The ball milling media were distilled water and zirconia balls. The mass ratio of zirconia balls: material to be ground: distilled water was 3:1:0.9. The mass ratio of large balls, medium balls, and small balls in zirconia balls is 1:2:3. Then dry at a temperature of 94°C and a drying time of 16 hours. The dried mixed powder was placed in a grinding jar for grinding for 31 minutes. The ground mixed powder was sieved with a mesh size of 180 to obtain (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 Powder.

[0033] (2) According to PbSnO 3 Weigh SnO 2 , PbO powder. 2 , PbO powder is placed in a three-dimensional mixer and mixed evenly before pre-sintering. The pre-sintering time is 2 hours and the pre-sintering temperature is 840°C. The pre-sintered powder is placed in a ball mill for wet ball milling and mixing. The speed of the ball mill is 30 rpm and the ball milling time is 34 hours. The ball milling media are distilled water and zirconia balls. The mass ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9. The mass ratio of large balls, medium balls and small balls in zirconia balls is 1:2:3. Then dry at a temperature of 95°C and a drying time of 17 hours. The dried mixed powder is placed in a grinding jar and ground for 30 minutes. The ground mixed powder is sieved with a mesh size of 180 to obtain PbSnO 3 Powder.

[0034] (3) The pre-burned powder is treated as follows:

[0035] 0.015PbSnO 3- 0.985(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 Weigh the chemical formula PbSnO 3 and (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 ) 3 Powder, put the mixed powder into a ball mill for wet ball milling, the speed of the ball mill is 29 rpm, the ball milling time is 38 hours, the ball milling medium is distilled water and zirconia balls, the mass ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9. The mass ratio of large balls, medium balls and small balls in zirconia balls is 1:2:3. Then dry, the drying temperature is 92°C, and the drying time is 17h. The dried mixed powder is put into a grinding jar for grinding for 31 minutes, the ground mixed powder is sieved, the mesh number of the sieve is 150 mesh, and the sieved mixed medium entropy powder is pressed into tablets. The mold diameter used for tableting is 13mm, the uniaxial pressure is 178MPa, and the holding time is 11 minutes.

[0036] (4) Place the pressed unsintered ceramic sheet into a muffle furnace and sinter it in air at 1250 °C. Add the same powder as the ceramic sheet around and on top of the ceramic sheet for buried sintering. Raise the temperature of the muffle furnace from room temperature to 1250 °C at a heating rate of 4.5 °C / min, keep it in the muffle furnace for 3.1 hours, and then cool it to low temperature with the furnace and take it out.

[0037] Example 3

[0038] The chemical formula of a double-doped A and B site medium-entropy lead zirconate-based composite dielectric ceramic is: xPbSnO 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 . In this example, x = 0.03, that is, 0.03PbSnO 3 -0.97(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 .

[0039] (1) Weigh BaCO 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 separately according to the chemical formula of 3 、La 2 O 3 、Sm 2 O 3 、HfO 2 、ZrO 2 、TiO 2Powder. The above-mentioned powders were respectively put into a three-dimensional mixer for mixing for 43 minutes. The mixed powder was pre-sintered. The pre-sintering time was 1.9 h and the pre-sintering temperature was 843 °C. The pre-sintered powder was put into a ball mill for wet ball milling and mixing. The rotation speed of the ball mill was 30 revolutions per minute, the ball milling time was 34 hours, and the ball milling medium was distilled water and zirconia balls. The mass ratio of zirconia balls: material to be ground: distilled water was 3:1:0.9. The mass ratio of large balls, medium balls, and small balls in the zirconia balls was 1:2:3. Then it was dried. The drying temperature was 95 °C and the drying time was 17 h. The dried mixed powder was put into a grinding tank for grinding for 30 minutes. The ground mixed powder was sieved. The mesh number of the sieve was 180 meshes, and (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 powder was obtained.

[0040] (2) According to the chemical formula of PbSnO 3 , SnO 2 and PbO powders were weighed respectively. After the SnO 2 and PbO powders were put into a three-dimensional mixer and mixed evenly, they were pre-sintered. The pre-sintering time was 2 h and the pre-sintering temperature was 840 °C. The pre-sintered powder was put into a ball mill for wet ball milling and mixing. The rotation speed of the ball mill was 28 revolutions per minute, the ball milling time was 38 hours, and the ball milling medium was distilled water and zirconia balls. The mass ratio of zirconia balls: material to be ground: distilled water was 3:1:0.9. The mass ratio of large balls, medium balls, and small balls in the zirconia balls was 1:2:3. Then it was dried. The drying temperature was 95 °C and the drying time was 18 h. The dried mixed powder was put into a grinding tank for grinding for 30 minutes. The ground mixed powder was sieved. The mesh number of the sieve was 180 meshes, and PbSnO 3 powder was obtained.

[0041] (3) The pre-sintered powder was weighed according to the chemical formula of 0.03PbSnO 3- 0.97(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 respectively to weigh PbSnO 3 and (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 Powder, put the mixed powder into a ball mill for wet ball milling. The rotation speed of the ball mill is 33 revolutions per minute, the ball milling time is 38 hours, the ball milling medium is distilled water and zirconia balls, and the mass ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9. The mass ratio of large balls, medium balls and small balls in the zirconia balls is 1:2:3. Then dry, the drying temperature is 98 °C, and the drying time is 15 h. Put the dried mixed powder into a grinding jar for grinding for 31 minutes, sieve the ground mixed powder, the mesh number of the sieve is 200 mesh, and press the sieved mixed medium-entropy powder. The diameter of the mold used for pressing is 13 mm, the uniaxial pressure is 175 MPa, and the pressure holding time is 11.5 minutes.

[0042] (4) Put the pressed unsintered ceramic sheet into a muffle furnace and sinter it at 1255 °C in air. Add the same powder as the ceramic sheet around and on the ceramic sheet for buried firing. Raise the temperature of the muffle furnace from room temperature to 1255 °C at a heating rate of 4.5 °C / min, keep the temperature in the muffle furnace for 2.9 hours, and then cool it in the furnace to low temperature and take it out.

[0043] Figure 1 For the xPbSnO prepared in Examples 1 to 3 3- (1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 to 0.03) XRD patterns of the complex medium-entropy ceramics; It can be seen from Figure 1 that all three medium-entropy ceramics are single-phase perovskite structures, and almost no impurity phases can be seen.

[0044] Figure 2 For the (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 SEM micrographs of the medium-entropy ceramics. It can be seen from Figure 2 that the relative density is relatively high, and the grains are irregular polygons.

[0045] Figure 3 For the xPbSnO prepared in Examples 1 to 33- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 to 0.03) Dielectric constant graph of the complex medium entropy ceramic at room temperature; It can be seen from the figure that at room temperature, under the test of 1 kHz frequency, (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 The dielectric constant is 825, much higher than 100 of the matrix material. 0.015PbSnO 3- 0.985(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 The dielectric constant of the complex medium entropy ceramic is 630, 0.03PbSnO 3- 0.97(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 The dielectric constant of the complex medium entropy ceramic is 574. Compared with the PbZrO 3 matrix material, after double doping of A and B sites to medium entropy and adding PbSnO 3 the dielectric constant increases.

[0046] Figure 4 For xPbSnO prepared in Examples 1 to 3 3- (1 - x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 , (x = 0 to 0.03) Dielectric loss graph of the complex medium entropy ceramic at room temperature; From Figure 4It can be seen that at room temperature and under a 1 kHz frequency test, (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 has a dielectric loss of 0.043, and 0.015PbSnO 3- 0.985(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 the dielectric loss of the complex medium entropy ceramic is 0.027, and 0.03PbSnO 3- 0.97(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 the dielectric loss of the complex medium entropy ceramic is 0.006, and 0.03PbSnO 3- 0.97(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O 3 has the minimum dielectric loss at 1 kHz.

Claims

1. A medium entropy lead zirconate based composite dielectric ceramic with dual doping at A and B sites, characterized in that: The medium entropy dielectric ceramic is designed for medium entropy at the B position and partially designed for medium entropy at the A position, and forms a composite ceramic with PbSnO3. The chemical formula of the medium entropy dielectric ceramic is: xPbSnO3-(1-x)(Pb 0.96 The 0.01 They 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 You 1 / 3 )O3,(x=0.0.03)。 2. The method for preparing the A and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 1, characterized in that: The following steps are involved: (1) According to (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O3, weigh BaCO3, La2O3, Sm2O3, HfO2, ZrO2, TiO2 powders respectively, and weigh SnO2 and PbO powders respectively according to the chemical formula of PbSnO3; (2) The above powders were placed in a three-dimensional mixer for mixing for 30 to 50 minutes, and then pre-calcined. The pre-calcined powders were mixed according to the formula xPbSnO3-(1-x)(Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O3 (x = 0 ~ 0.03) chemical formula weigh PbSnO3 and (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )O3, respectively put them into a ball mill for wet ball milling, and then grind, sieve and tablet press after drying; (3) The pressed unsintered ceramic pieces are placed in an alumina crucible, and the alumina crucible containing the ceramic pieces is placed in a muffle furnace for burial firing.

3. The method for preparing the A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 2, characterized in that: The conditions for wet ball milling in step (2) are as follows: the rotation speed of the ball mill is 15 to 35 rpm, the ball milling time is 34 or 36 to 72 hours, the ball milling medium is distilled water and zirconia balls, the weight ratio of zirconia balls: material to be ground: distilled water is 3:1:0.9, and the mass ratio of large balls, medium balls, and small balls in the zirconia balls is 1:2:

3.

4. The method for preparing the A- and B-position dual-doped mid-entropy lead zirconate-based ceramic according to claim 2, characterized in that: The drying temperature in step (2) is 80 to 120° C. and the drying time is 12 to 20 hours.

5. The method for preparing the A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 2, characterized in that: The grinding conditions in step (2) are as follows: the dried mixed powder is placed in a grinding jar for grinding for 20 to 50 minutes, and the ground mixed powder is sieved with a sieve having a mesh size of 80 to 200 meshes.

6. The method for preparing the A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 2, characterized in that: The diameter of the mold used for tableting in step (2) is 10-13 mm, the uniaxial pressure is 160-180 MPa, and the holding time is 5-15 minutes.

7. The method for preparing the A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 2, characterized in that: In step (2), (Pb 0.96 La 0.01 Ba 0.01 Sm 0.01 )(Hf 1 / 3 Zr 1 / 3 Ti 1 / 3 )The pre-sintering temperature of the O3 medium entropy ceramic powder is 800-850°C, and the holding time is 1.8-2.2h; the pre-sintering temperature of the PbSnO3 ceramic powder is 800-850°C, and the holding time is 1.7-2.3h.

8. The method for preparing the A- and B-site dual-doped mid-entropy lead zirconate-based composite dielectric ceramic according to claim 2, characterized in that: In step (3), the burying method is to add the same powder as the ceramic sheet around and on the top of the ceramic sheet for burying, and raise the temperature of the muffle furnace from room temperature to 1200-1270°C at a heating rate of 4.5°C / min. The insulation time in the muffle furnace is 2.8-3.2 hours, and then the furnace is cooled to a low temperature and taken out.

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