CN111138177A - Bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability and preparation method thereof - Google Patents

Abstract

The invention discloses bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability and a preparation method thereof, and the general formula of the composition is xBi_1.05FeO₃‑yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃Wherein P is Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃One or a combination of two sintering aids; x, y, t and m represent mole fractions, and x is more than or equal to 0.50 and less than or equal to 0.90 and 0<y≤0.5，0<t≤0.1，0<m is less than or equal to 0.1. The preparation method comprises the working procedures of proportioning, ball milling, forming, binder removal, sintering and the like according to the general formula of the composition, and the method for promoting sintering by adopting a low-temperature sintering aid to obtain compact piezoelectric ceramicsPolarization temperature up to T_dThe piezoelectric ceramic base with the highest piezoelectric constant of 15.7pC/N is more than 725 ℃, and the system ceramic is expected to be applied to the high-temperature fields of aerospace, nuclear power, oil exploration, automobiles and the like.

Description

Bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability and preparation method thereof

Technical Field

The invention relates to a high-temperature lead-free piezoelectric ceramic material applicable to the field of high temperature, and relates to A, B-bit composite substitution modified high-temperature lead-free piezoelectric ceramic with high-temperature stability and a preparation method thereof, in particular to bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability and a preparation method thereof.

Background

The high-temperature piezoelectric ceramic is widely applied to a plurality of special fields of aerospace, nuclear energy, metallurgy, petrochemical industry, geological exploration and the like, for example, the working temperature of a dynamic fuel injection nozzle working in an automobile is up to 300 ℃, the working temperature of a sound wave logging transducer used under an oil well is up to 200-300 ℃, and a piezoelectric vibration sensor controlled by a vector engine blade in the aerospace field and the like. As a high-temperature piezoelectric ceramic material, structural phase change does not occur at a high temperature (more than 400 ℃) so as to ensure that the temperature stability of a piezoelectric device is not deteriorated due to a high-temperature depolarization phenomenon, but due to a thermal activation aging process, the safe use temperature is limited to 1/2 of Curie temperature, a high-temperature piezoelectric system applied in the high-temperature field at present mainly comprises bismuth layer structures, tungsten bronze structures, layer perovskite structures and the like, and a single crystal material is expensive due to factors such as complex process and the like, so that the development of a lead-free piezoelectric ceramic material with excellent performance and high Curie temperature and high-temperature stability has great social significance and economic value.

BiFeO₃Has a very high Curie temperature (830 ℃), but pure BiFeO₃Has difficult sintering and is easy to generate Bi in the sintering process₂Fe₄O₉And the system can not be practically applied due to high leakage current and no polarization caused by the problems of impurity phase and the like. By synthesizing BiFeO₃In the process of (2), BaTiO with a tetragonal phase perovskite structure is introduced₃And proper amount of Mn is added, so that the resistivity of the system can be greatly improved, the generation of miscellaneous items is inhibited, and the stable ABO is obtained₃And (5) structure. Bi (Ti)_0.5Zn_0.5)O₃Is a tetragonal phase perovskite structure compound with high Curie temperature, and is mixed with BiFeO₃Can form a solid solution according to the c/a ratio and tolerance factorTheoretically, the solid solution of the two is calculated to be in monoclinic phase 0.6BiFeO₃-0.4Bi(Ti_0.5Zn_0.5)O₃T at composition_C1227 ℃ can be reached. ZHao Pan, Jun Chen et al synthesized BiFeO by high temperature and high pressure method₃-Bi(Ti_0.5Zn_0.5)O₃Ceramics, but the literature does not give piezoelectric properties. Similarly J.H.CHO, T.k.Song et al report Bi (Ti) prepared by conventional solid phase synthesis_0.5Zn_0.5)O₃-BiFeO₃Ceramics, but also fails to give piezoelectric properties.

Disclosure of Invention

The invention aims at BiFeO₃-Bi(Ti_0.5Zn_0.5)O₃The method has the advantages that the ceramic has the problem of difficult synthesis, the sintering auxiliary agent with a perovskite structure is added to promote the sintering process, the sintering temperature is reduced, the density of the ceramic is improved, the aim of obtaining the piezoelectric ceramic with high Curie temperature and high temperature stability of the system is fulfilled, the bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high temperature stability and the preparation method thereof are provided, and the depolarization temperature of the piezoelectric ceramic prepared by the method reaches T_d725 ℃ and the piezoelectric constant reaches 15.7pC/N, and the system ceramic is expected to be applied to the ultrahigh-temperature piezoelectric field.

The technical scheme for realizing the invention is as follows:

the bismuth ferrite-zinc bismuth titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability has the following composition general formula: xBi_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃Wherein x, y, t and m all represent mole fractions, and P is Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃One or a combination of two sintering aids, and essentially contains Li₂CO₃Wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<t≤0.1，0<m≤0.1。

The preparation method of the bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability comprises the following steps:

(1) to analyzePure Fe₂O₃、Bi₂O₃、TiO₂、ZnO、MnCO₃As a raw material, according to xBi_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+mMnCO₃Mixing materials, wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<m is less than or equal to 0.1, excessive 5.0 mol percent of Bi element compensates for volatilization of the Bi element in the sintering process, the mixed powder is ball-milled for 24 hours by taking absolute ethyl alcohol as a medium, dried and sieved in an oven at 100 ℃/12 hours, put into a high-aluminum crucible for compaction and capping, put into a closed tube furnace, introduced with pure oxygen at the heating rate of 250 ℃/h to 760 and 780 ℃ for presintering, kept for 4 hours for synthesis, cooled to below 200 ℃ and taken out for later use;

(2) to analytically pure BaCO₃、W₂O₃、CuO、Nb₂O₅As raw material, each according to Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_{1/ 3}Nb_2/3)O₃Mixing materials, ball-milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at 100 ℃/12 hours, putting the mixed powder into a high-aluminum crucible, compacting and covering the mixture, putting the mixture into a muffle furnace, pre-sintering the mixture at the temperature of 800 ℃ and 850 ℃ at the heating rate of 250 ℃/h, preserving the heat for 6 hours for synthesis, cooling the mixture to below 200 ℃, and taking the mixture out for later use;

(3) the xBi synthesized in the step (1)_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+mMnCO₃Powder with Li₂CO₃And Ba (W) synthesized in the step (2)_0.5Cu_0.5)O₃Or Ba (Cu)_1/3Nb_2/3)O₃According to xBi_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃Mixing materials, wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<m≤0.1，0<t is less than or equal to 0.1; p is Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃The combination of two sintering aids in (1), and necessarily containing Li₂CO₃Carrying out secondary ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out and drying, and sieving by a 200-mesh sieve;

(4) adding the sieved powder into a PVA solution with the mass percentage concentration of 5% for granulation, and performing compression molding in a steel die under 100MPa, wherein the inner diameter of the die is 1 cm;

(5) placing the molded plain sheet into a muffle furnace, slowly heating to 600 ℃ at the heating rate of 30 ℃/h, and keeping the temperature for 24 hours to discharge glue; then heating to 920-;

(6) polishing the sintered sample into a sheet with two smooth surfaces and a thickness of 1mm, coating a silver electrode, and burning silver at 650 ℃/30 minutes for later use;

(7) polarizing the piezoelectric ceramic plate coated with the silver electrode in silicone oil, wherein the polarizing electric field is 6000V/mm, the polarizing temperature is 150 ℃, the polarizing time is 30 minutes, and keeping the electric field to cool to the room temperature.

The invention has the positive effects that:

to solve BiFeO₃-Bi(Ti_0.5Zn_0.5)O₃The invention adopts a solid-phase ceramic sintering preparation method and adds Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃The like as a sintering aid, reduces the sintering temperature, promotes the sintering process and obtains compact BiFeO₃-Bi(Ti_0.5Zn_0.5)O₃Piezoelectric ceramics. xBi prepared by adopting the technology_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃High-temperature piezoelectric ceramic having a depolarization temperature of 725 ℃ and having a piezoelectric constant of d₃₃Piezoelectric performance of 15.7 pC/N. Therefore, the invention has significant breakthrough and innovation in technology, so that the system piezoelectric ceramic can be applied to the field of high-temperature piezoelectricity.

Detailed Description

The contents of the present invention will be further clarified by the following examples, which are not intended to limit the present invention.

Example 1:

the preparation component is 0.90Bi_1.05FeO₃-0.10Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(W_0.5Cu_0.5)O₃+0.005MnCO₃The preparation method of the bismuth ferrite-zinc bismuth titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability comprises the following steps:

(1) to analyze pure Fe₂O₃、Bi₂O₃、TiO₂、ZnO、MnCO₃As raw material, according to 0.90Bi_1.05FeO₃-0.10Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃Preparing materials, wherein 5.0% mol of excessive Bi element compensates for volatilization of the Bi element in the sintering process, ball-milling the mixed powder for 24 hours by using absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at the speed of 100 ℃/12 hours, putting the dried powder into a high-aluminum crucible to be compacted and covered, putting the powder into a closed tube furnace, introducing pure oxygen into the closed tube furnace, pre-sintering the powder to 780 ℃ at the heating rate of 250 ℃/h, preserving heat for 4 hours for synthesis, cooling the powder to below 200 ℃, and taking the powder out for later use;

(2) to analytically pure BaCO₃、W₂O₃CuO as a raw material, in accordance with Ba (W)_0.5Cu_0.5)O₃Mixing materials, ball-milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at 100 ℃/12 hours, putting the mixed powder into a high-aluminum crucible, compacting and covering the crucible, putting the crucible into a muffle furnace, pre-sintering the mixed powder to 850 ℃ at the heating rate of 250 ℃/h, preserving heat for 6 hours, cooling the mixed powder to below 200 ℃, and taking the mixed powder out for later use;

(3) 0.90Bi synthesized in the step (1)_1.05FeO₃-0.10Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃The powder is mixed with the Ba (W) synthesized in the step (2)_0.5Cu_0.5)O₃And Li₂CO₃According to 0.9Bi_1.05FeO₃-0.10Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(W_0.5Cu_0.5)O₃+0.005MnCO₃Mixing materials, carrying out secondary ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out and drying, and sieving by a 200-mesh sieve;

(4) adding the sieved powder into a PVA solution with the mass percentage concentration of 5% for granulation, and performing compression molding in a steel die under 100MPa, wherein the inner diameter of the die is 1 cm;

(5) placing the molded plain sheet into a muffle furnace, slowly heating to 600 ℃ at the heating rate of 30 ℃/h, and keeping the temperature for 24 hours to discharge glue; then heating to 950 ℃ at the heating rate of 2 ℃/min for sintering, keeping the temperature for 240 minutes, and cooling to room temperature along with the furnace;

(6) polishing the sintered sample into a sheet with two smooth surfaces and a thickness of 1mm, coating a silver electrode, and burning silver at 650 ℃/30 minutes for later use;

(7) polarizing the piezoelectric ceramic plate coated with the silver electrode in silicone oil, wherein the polarizing electric field is 6000V/mm, the polarizing temperature is 150 ℃, the polarizing time is 30 minutes, and keeping the electric field to cool to the room temperature.

The performance measurements are as follows:

d33(pC/N)	Qm	kp(％)	εr	Td(℃)	tg δ(％)
						15.7	63.4	0.26	91.4	725	2.25

example 2:

the preparation component is 0.85Bi_1.05FeO₃-0.15Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(W_0.5Cu_0.5)O₃+0.005MnCO₃The preparation method of the bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability is the same as that of the embodiment 1, except that the sintering temperature in the step (5) is 940 ℃.

The performance measurements are as follows:

d33(pC/N)	Qm	kp(％)	εr	Td(℃)	tg δ(％)
						12.9	57	0.28	106	710	2.46

example 3:

the preparation component is 0.80Bi_1.05FeO₃-0.20Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(Cu_{1/ 3}Nb_2/3)O₃+0.005MnCO₃The preparation method of the bismuth ferrite-zinc bismuth titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability comprises the following steps:

(1) to analyze pure Fe₂O₃、Bi₂O₃、TiO₂、ZnO、MnCO₃As raw material, according to 0.80Bi_1.05FeO₃-0.20Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃Preparing materials, wherein 5.0% mol of excessive Bi element compensates for volatilization of the Bi element in the sintering process, ball-milling the mixed powder for 24 hours by using absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at the speed of 100 ℃/12 hours, putting the dried powder into a high-aluminum crucible, compacting and capping the powder, putting the powder into a closed tube furnace, introducing pure oxygen into the furnace, pre-sintering the powder to 760 ℃ at the heating rate of 250 ℃/h, preserving heat for 4 hours for synthesis, cooling the powder to below 200 ℃, and taking the powder out for later use;

(2) to analytically pure BaCO₃、CuO、Nb₂O₅As a raw material, according to Ba (Cu)_1/3Nb_2/3)O₃Mixing materials, ball-milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at 100 ℃/12 hours, putting the mixed powder into a high-aluminum crucible, compacting and covering the crucible, putting the crucible into a muffle furnace, pre-sintering the mixed powder to 850 ℃ at the heating rate of 250 ℃/h, preserving heat for 6 hours, cooling the mixed powder to below 200 ℃, and taking the mixed powder out for later use;

(3) 0.80Bi synthesized in the step (1)_1.05FeO₃-0.20Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃The powder is mixed with Ba (Cu) synthesized in the step (2)_1/3Nb_2/3)O₃And Li₂CO₃According to 0.80Bi_1.05FeO₃-0.20Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(Cu_1/3Nb_2/3)O₃+0.005MnCO₃Mixing materials, carrying out secondary ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out and drying, and sieving by a 200-mesh sieve;

(4) adding the sieved powder into a PVA solution with the mass percentage concentration of 5% for granulation, and performing compression molding in a steel die under 100MPa, wherein the inner diameter of the die is 1 cm;

(5) placing the molded plain sheet into a muffle furnace, slowly heating to 600 ℃ at the heating rate of 30 ℃/h, and keeping the temperature for 24 hours to discharge glue; then heating to 960 ℃ at the heating rate of 2 ℃/min for sintering, keeping the temperature for 240 minutes, and cooling to room temperature along with the furnace;

(6) polishing the sintered sample into a sheet with two smooth surfaces and a thickness of 1mm, coating a silver electrode, and burning silver at 650 ℃/30 minutes for later use;

(7) polarizing the piezoelectric ceramic plate coated with the silver electrode in silicone oil, wherein the polarizing electric field is 6000V/mm, the polarizing temperature is 150 ℃, the polarizing time is 30 minutes, and keeping the electric field to cool to the room temperature.

The performance measurements are as follows:

d33(pC/N)	Qm	kp(％)	εr	Td(℃)	tg δ(％)
						11.6	67.4	0.29	119	705	2.17

example 4:

the preparation component is 0.88Bi_1.05FeO₃-0.12Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.025Ba(Cu_{1/ 3}Nb_2/3)O₃+0.005MnCO₃The preparation method of the bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability is the same as that of the embodiment 3, except that the sintering temperature in the step (5) is 940 ℃.

The performance measurements are as follows:

d33(pC/N)	Qm	kp(％)	εr	Td(℃)	tg δ(％)
						13.5	59.4	0.22	126	715	1.98

example 5:

the preparation component is 0.88Bi_1.05FeO₃-0.12Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.005MnCO₃The preparation method of the bismuth ferrite-zinc bismuth titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability comprises the following steps:

(1) to analyze pure Fe₂O₃、Bi₂O₃、TiO₂、ZnO、MnCO₃As raw material, according to 0.88Bi_1.05FeO₃-0.12Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃Preparing materials, wherein 5.0% mol of excessive Bi element compensates for volatilization of the Bi element in the sintering process, ball-milling the mixed powder for 24 hours by using absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at the speed of 100 ℃/12 hours, putting the dried powder into a high-aluminum crucible, compacting and capping the powder, putting the powder into a closed tube furnace, introducing pure oxygen into the furnace, pre-sintering the powder to 760 ℃ at the heating rate of 250 ℃/h, preserving heat for 4 hours for synthesis, cooling the powder to below 200 ℃, and taking the powder out for later use;

(2) 0.88Bi synthesized in the step (1)_1.05FeO₃-0.12Bi(Ti_0.5Zn_0.5)O₃+0.005MnCO₃Powder with Li₂CO₃According to 0.88Bi_1.05FeO₃-0.12Bi(Ti_0.5Zn_0.5)O₃+0.003Li₂CO₃+0.005MnCO₃Mixing materials, carrying out secondary ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out and drying, and sieving by a 200-mesh sieve;

(3) adding the sieved powder into a PVA solution with the mass percentage concentration of 5% for granulation, and performing compression molding in a steel die under 100MPa, wherein the inner diameter of the die is 1 cm;

(4) placing the molded plain sheet into a muffle furnace, slowly heating to 600 ℃ at the heating rate of 30 ℃/h, and keeping the temperature for 24 hours to discharge glue; then heating to 960 ℃ at the heating rate of 2 ℃/min for sintering, keeping the temperature for 240 minutes, and cooling to room temperature along with the furnace;

(5) polishing the sintered sample into a sheet with two smooth surfaces and a thickness of 1mm, coating a silver electrode, and burning silver at 650 ℃/30 minutes for later use;

(6) polarizing the piezoelectric ceramic plate coated with the silver electrode in silicone oil, wherein the polarizing electric field is 6000V/mm, the polarizing temperature is 150 ℃, the polarizing time is 30 minutes, and keeping the electric field to cool to the room temperature.

The performance measurements are as follows:

d33(pC/N)	Qm	kp(％)	εr	Td(℃)	tg δ(％)
						9.5	69.4	0.253	110	720	2.68

the upper and lower limits and interval values of the ingredients listed in the invention and the upper and lower limits and interval values of the process parameters can all realize the invention, and the implementation is not always carried out here.

Claims (2)

1. The bismuth ferrite-zinc bismuth titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability is characterized in that: the general formula of the composition is xBi_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃Wherein x, y, t and m represent mole fractions, and P is Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃One or a combination of two sintering aids, and essentially contains Li₂CO₃Wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<t≤0.1，0<m≤0.1。

2. The method for preparing the bismuth ferrite-zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability of claim 1, which is characterized in that: the preparation method comprises the following steps:

(1) to analyze pure Fe₂O₃、Bi₂O₃、TiO₂、ZnO、MnCO₃As a raw material, according to xBi_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+mMnCO₃Mixing materials, wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<m is less than or equal to 0.1, ball milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at the speed of 100 ℃/12 hours, putting the mixed powder into a high-aluminum crucible, compacting and covering the crucible, putting the crucible into a closed tube furnace, introducing pure oxygen into the furnace, pre-sintering the mixture at the temperature of 760 and 780 ℃ at the heating rate of 250 ℃/h, preserving the heat for 4 hours, synthesizing the mixture, cooling the mixture to below 200 ℃, and taking the mixture out for later use;

(2) to analytically pure BaCO₃、W₂O₃、CuO、Nb₂O₅As raw material, each according to Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃Mixing materials, ball-milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, drying and sieving the mixed powder in an oven at 100 ℃/12 hours, putting the mixed powder into a high-aluminum crucible, compacting and covering the mixture, putting the mixture into a muffle furnace, pre-sintering the mixture at the temperature of 800 ℃ and 850 ℃ at the temperature rise rate of 250 ℃/h, preserving heat for 6 hours for synthesis, cooling the mixture to below 200 ℃, and taking the mixture out for later use;

(3) the xBi synthesized in the step (1)_1.05FeO₃-yBi(Ti_0.5Zn_0.5)O₃+mMnCO₃Powder with Li₂CO₃And Ba (W) synthesized in the step (2)_0.5Cu_0.5)O₃Or Ba (Cu)_1/3Nb_2/3)O₃According to xBiFeO₃-yBi(Ti_0.5Zn_0.5)O₃+tP+mMnCO₃Proportioning, P is Ba (W)_0.5Cu_0.5)O₃、Ba(Cu_1/3Nb_2/3)O₃、Li₂CO₃One or a combination of two sintering aids, and essentially contains Li₂CO₃Wherein x is more than or equal to 0.5 and less than or equal to 0.9 and 0<y≤0.50，0<m≤0.1，0<t is less than or equal to 0.1, and the mixture is subjected to secondary ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taken out, dried and sieved by a 200-mesh sieve;

(4) adding the sieved powder into a PVA solution with the mass percentage concentration of 5% for granulation, and performing compression molding in a steel die under 100MPa, wherein the inner diameter of the die is 1 cm;

(5) placing the molded plain sheet into a muffle furnace, slowly heating to 600 ℃ at the heating rate of 30 ℃/h, and keeping the temperature for 24 hours to discharge glue; then heating to 920-;

(6) polishing the sintered sample into a sheet with two smooth surfaces and a thickness of 1mm, coating a silver electrode, and burning silver at 650 ℃/30 minutes for later use;

(7) polarizing the piezoelectric ceramic plate coated with the silver electrode in silicone oil, wherein the polarizing electric field is 6000V/mm, the polarizing temperature is 150 ℃, the polarizing time is 30 minutes, and keeping the electric field to cool to the room temperature.