CN106986633B - Piezoelectric ceramic and preparation method and application thereof - Google Patents

Piezoelectric ceramic and preparation method and application thereof Download PDF

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CN106986633B
CN106986633B CN201710268809.6A CN201710268809A CN106986633B CN 106986633 B CN106986633 B CN 106986633B CN 201710268809 A CN201710268809 A CN 201710268809A CN 106986633 B CN106986633 B CN 106986633B
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piezoelectric ceramic
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戴中华
王定华
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XI'AN DINGHUA ELECTRONICS CO LTD
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Abstract

The invention discloses a piezoelectric ceramic, the main component of which is 0.36Bi (Sc)1‑XZrX)O3‑0.64PbTiO3Wherein x is 0.04-0.24. The invention also provides a preparation method and application of the piezoelectric ceramic. The piezoelectric ceramic prepared by the method has high Curie temperature (450 ℃), and piezoelectric constant d under the temperature condition of-100-300 DEG C33The piezoelectric material has the characteristics of 150-500 pc/N, low-temperature dielectric loss tan delta (less than or equal to 4%) and the like, overcomes the defect that the low-temperature piezoelectric performance of the conventional piezoelectric material cannot meet the requirements of specific indexes, is easy to sinter, has a compact structure, is simple in preparation process, and has a wide application prospect.

Description

Piezoelectric ceramic and preparation method and application thereof
Technical Field
The invention belongs to the field of electronic ceramics and piezoelectric devices, and particularly relates to high Curie temperature piezoelectric ceramics capable of being applied under a wide temperature condition, and a preparation method and application thereof.
Background
With the rapid development of modern science and technology, many electronic and electrical equipment put higher demands on performance parameters of selected piezoelectric devices. Among them, many industrial and scientific research departments such as aerospace, atomic energy, metallurgy, petrochemical industry, etc. urgently need electronic devices capable of working at wider temperature, and low-temperature piezoelectric materials are increasingly widely applied in these special fields. The curie temperature of the most commonly used piezoelectric ceramic lead zirconate titanate (PZT) is generally in the range of 320-360 ℃. PZT consisting of PbO, ZrO according to different requirements2，TiO2The piezoelectric ceramic is prepared by mixing and sintering raw material powder, and the sintering temperature of the piezoelectric ceramic taking PZT as a base is generally higher, which is about 1200-1300 ℃. However, the volatilization of lead oxide (PbO) begins around 800 ℃. Thus, lead oxide is easily volatilized during the sintering process, and the performance of the ceramic is influenced. In this regard, it has been proposed to add an excess amount to the initial charge and then place the sample in a closed crucible in order to ensure that the firing is in a lead atmosphere. Although the method ensures the performance of the ceramic, the method ignores that the lead oxide is a volatile substance, and the method considers that the temperature rise rate is increased and the volatilization of the lead oxide can be reduced. Considering the influence of the sintering temperature on the grain size, the higher the sintering temperature is, the larger the grain size is, and under the same heat preservation condition, the larger the grain size is, the piezoelectric property is reduced. If the sintering temperature and the heating time can be reducedThe method has the advantages that the process improvement is carried out, so that the volatilization of lead oxide can be reduced, the excessive growth of the grain size can be effectively controlled, and the performance is improved. Generally, PZT materials gradually depolarize with increasing ambient temperature, resulting in reduced piezoelectric performance, with an upper operating temperature limit of 1/2, typically the curie temperature, and a minimum operating temperature of about-20 ℃. However, with the rapid expansion of the human activity range and the increasing demand for intelligent materials, the demand for piezoelectric materials applicable to low-temperature environments is increasing, and the performance of the materials protected by the patent of our application can just meet the requirements.
Disclosure of Invention
The invention aims to solve the technical problem that the Curie temperature and the comprehensive piezoelectric performance of the conventional piezoelectric ceramic material cannot meet the requirements of specific indexes at the same time, and provides a piezoelectric ceramic material with high piezoelectric performance under the condition of low temperature.
The technical problem to be solved by the invention is to provide a preparation method of the piezoelectric ceramic material.
The technical problem to be solved finally by the invention is to provide the application of the piezoelectric ceramic material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a piezoelectric ceramic contains 0.36Bi (Sc) as main ingredient1-xZrx)O3-0.64PbTiO3Wherein x is 0-0.24.
Preferably, x is 0.04 to 0.24
A preparation method of piezoelectric ceramics comprises the following steps:
(1) with Bi2O3、Sc2O3、PbO、TiO2And ZrO2Weighing the raw materials according to a molar ratio of 0.18: 0.18(1-x) to 0.64: 0.36x, wherein x is 0-0.24, and carrying out primary ball milling;
(2) drying and sieving the ball-milled materials in the step (1), fully grinding and mixing the powder materials, putting the mixture into a crucible for presintering, and performing secondary ball milling on the synthetic powder materials after presintering until the ball milling reaches a micron level;
(3) drying the ball-milled materials in the step (2), adding a binder into the materials, granulating, and then pressing and molding;
(4) and (4) sealing the blank formed by pressing in the step (3) in a crucible, carrying out glue discharging treatment, and then carrying out sintering treatment to obtain the piezoelectric ceramic.
In a preferred embodiment of the present invention, after the step (4), the step (5) is further performed, and the fired piezoelectric ceramic is polished, silver-coated, and then subjected to polarization treatment. Wherein, the silver electrode is a conventional method, and the operation process is as follows: uniformly coating low-temperature silver paste on one round surface of the ceramic chip, baking for 8-20 minutes (preferably 10 minutes) in an oven at 80-100 ℃ (preferably 90 ℃), taking out, coating the silver paste on the other round surface of the ceramic, putting the ceramic into the oven for drying, then putting the ceramic into a sintering furnace for electrode burning, heating the sintering furnace to 650-720 ℃ (preferably 700 ℃) for sintering at a temperature control program of 60-120 minutes (preferably 100 minutes), keeping the temperature for 5-15 minutes (preferably 10 minutes), and naturally cooling in the furnace. Wherein the polarization treatment process comprises the step of carrying out polarization for 10-30 minutes at 100-150 ℃ and under an electric field of 3-5 kV/mm, and preferably for 20 minutes at 120 ℃ and under an electric field of 4 kV/mm.
In step (1), x is preferably 0.04 to 0.24.
In the step (1), a ball milling medium is added at the beginning of the first ball milling or in the ball milling process, wherein the ball milling medium is a composition of a solvent and milling balls. Wherein, the solvent includes but is not limited to absolute ethyl alcohol, water, acetone, glycerol or hexane, and absolute ethyl alcohol is preferred. The amount and ratio of the solvent and the grinding balls are not limited as long as they can submerge the raw material powder, and the weight ratio of the raw material powder to the ball milling medium is preferably 1: 2 to 3.5, and the weight ratio of the raw material powder to the grinding balls is preferably 1: 1 to 1.8 (more preferably 1: 1.5).
In the step (1), the first ball milling time is 12h-24h, preferably 18 h.
Through the first ball milling in the step (1), the raw material powder can be fully and uniformly mixed.
In the steps (2) and (3), the drying temperature is 80-120 ℃, preferably 90 ℃, and the higher the drying temperature is, the faster the drying process is. Generally, drying is required until the ball milling medium anhydrous ethanol is volatilized.
In the step (2), the sieving is preferably performed by a 200-mesh sieve.
In the step (2), the powder materials are ground and fully mixed, no special requirement is imposed on grinding conditions, and the main purpose is to fully mix the raw material powder.
In the step (2), the pre-sintering process comprises the following steps: heating to 700-850 ℃ from room temperature at the speed of 2-6 ℃/min, preserving heat for 2-4 h, and cooling along with the furnace; the preferable pre-sintering process is as follows: raising the temperature from room temperature to 730 ℃ and 780 ℃ (preferably 760 ℃) at the rate of 3-6 ℃/min (preferably 5 ℃/min), and cooling along with the furnace after keeping the temperature for 2-4 hours (preferably 3 hours); the most preferred pre-sintering process is: raising the temperature from room temperature to 760 ℃ at the speed of 5 ℃/min, preserving the temperature for 3 hours, and then cooling along with the furnace.
In the step (2), all the parameters of the second ball milling except the ball milling time are the same as those of the first ball milling, and the ball milling time is 10-20 h, preferably 15 h.
In the step (2), the micron-sized preferred particle size range is 1-5 μm.
In the step (1) or the step (2), the ball milling mode is planetary ball milling, and other mixed ball milling modes such as mechanical vibration milling and the like can also be adopted.
In the step (1) and the step (2), the grinding balls used in the ball milling process are zirconia balls, and common grinding balls such as steel balls and the like can also be used; the ball milling tank used in the ball milling process is a zirconia ball milling tank, and common ball milling tanks such as nylon tanks can also be used.
In the step (1) and the step (2), the ball milling parameters are selected in the first ball milling process and the second ball milling process, so that the product performance is not obviously influenced, and the effect of the invention can be achieved by only adopting a ball milling process.
In the step (3), the binder includes, but is not limited to, an aqueous solution of polyvinyl alcohol, wherein the concentration of polyvinyl alcohol is 4-9 wt% (preferably 5 wt%); other binders known in the art are also possible; the addition weight of the binder is 4-10% of the weight of the dried material.
In the step (3), the pressure of the compression molding is 100-150MPa, but the invention is not limited to the pressure, as long as the compression molding process is adopted, and the effect of the invention can be achieved regardless of the pressure.
In the step (4), the glue discharging treatment comprises the following processes: raising the temperature from room temperature to 500-600 ℃ at the speed of 3-5 ℃/min, and carrying out heat preservation for 1-3h for removing the glue, wherein the preferable process is as follows: raising the temperature from room temperature to 550 ℃ at the speed of 5 ℃/min, and preserving the temperature for 2h for removing the glue.
In the step (4), the sintering treatment comprises the following processes: raising the temperature to 1000-1150 ℃ at the speed of 2-5 ℃/min, preserving the heat for 1-3h, and then cooling along with the furnace, wherein the preferable process is as follows: heating to 1090 ℃ at the speed of 5 ℃/min, preserving heat for 3h, and cooling along with the furnace.
And (3) adopting a common crucible for sealing and sintering in the pre-sintering in the step (2) and the sintering in the step (4).
The piezoelectric ceramic prepared by the preparation method is also within the protection scope of the invention.
The application of the piezoelectric ceramic in the preparation of the ultrasonic liquid detection instrument is also within the protection scope of the invention.
The ultrasonic liquid detection instrument is used for detecting parameters of liquid. The parameter is liquid level, liquid flow or liquid flow rate.
Wherein the temperature of the liquid is-100 to +300 ℃.
The application of the piezoelectric ceramic in the preparation of the ultrasonic gas detection instrument is also within the protection scope of the invention.
The ultrasonic gas detection instrument is used for detecting parameters of gas. The parameter is gas flow or gas flow rate.
Wherein the temperature of the gas is-100 to +300 ℃.
The temperature ranges of use of various liquid and gas detection meters using ultrasonic technology depend on the temperature ranges of use of their ultrasonic measuring heads, which in turn depend on the temperature ranges of use of the piezoelectric ceramic plates and measuring head structures within the measuring heads. The use temperature range of the measuring head disclosed by the prior art is-20-70 ℃. Therefore, as long as the wide-temperature piezoelectric ceramic piece is manufactured by using the method, and the structure of the measuring head is modified to work in a high-temperature or low-temperature range, a high-temperature measuring head or a low-temperature measuring head which can be used at-100-300 ℃ can be manufactured. So as to prepare various ultrasonic detection instruments which can work in the temperature range of-100 to +300 ℃ and are of high temperature type, low temperature type and wide temperature type. Including various liquid detecting instruments for detecting liquid level, liquid flow and liquid flow speed. Various gas detection instruments for detecting the gas flow and the gas flow rate are also included.
For example, the high-temperature type and low-temperature type (or collectively called wide-temperature type) piezoelectric ceramics made by the invention are made into the measuring head of the ultrasonic external liquid level meter, and the ultrasonic external liquid level meter, the ultrasonic external liquid level switch and the ultrasonic flowmeter for measuring the liquid level and the flow in the container from the outside of the container can be made. For measuring the level of cryogenic liquids at-100 c, such as liquefied natural gas, LNG, etc. The device can also be used for measuring the liquid level of high-temperature liquid at the temperature of +300 ℃, such as the monitoring and control of the superheated steam liquid level of a boiler high-pressure steam drum, the liquid level monitoring and control of a chemical high-temperature container and the like. Solves the great difficult problem which can not be solved for a long time.
Has the advantages that: aiming at the problems that the research on low-temperature and ultralow-temperature piezoelectric materials in the prior art is particularly few, and the Curie temperature and the comprehensive piezoelectric property cannot simultaneously meet the requirements of specific indexes, the invention provides the composite perovskite 0.36Bi (Sc) with high Curie temperature and excellent comprehensive piezoelectric property1-XZrX)O3-0.64PbTiO3(wherein x is 0.04 to 0.24) piezoelectric ceramics. The piezoelectric ceramic has high Curie temperature, high low temperature piezoelectric constant and low dielectric loss, and may be used in various transducers, sensors and other relevant piezoelectric devices with work temperature lower than 0 deg.c and piezoelectric constant d at high temperature33Not only does not reduce but also increases by about 15 percent, and is a piezoelectric material with good application prospect applied in low-temperature and high-temperature environments.
Drawings
FIG. 1 is a graph of piezoelectric constant d33 versus temperature. (0.36BS0.64PT-Zr is the formulation material of example 3, 0.36BS0.64PT and 0.38BS062PT of the system materials disclosed by other researchers for comparison, see the formula material d of the patent in the temperature range of-100 ℃ to 300 DEG C33Reaching 150 pc/N-500 pc/N, therefore, the formula material of the patent has higher piezoelectric performance).
Fig. 2 shows the X-ray diffraction pattern of the piezoelectric ceramic sheet obtained in example 3 (from this figure, the material has a typical three-phase structure, and no other impurity phase is found in the pattern).
FIG. 3 is a SEM photograph of the piezoelectric ceramic sheet obtained in example 3 (it is understood that the sintered ceramic is dense and has a particle size of 1 μm to 3 μm).
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1
Adding Bi2O3、Sc2O3PbO and TiO2Mixing according to the mol ratio of 18: 64, ball-milling for 18 hours, drying, sieving, grinding and fully mixing the powder, placing the powder into a crucible for presintering, raising the temperature to 760 ℃ at the speed of 5 ℃/min, keeping the temperature for presintering for 3 hours, and naturally cooling; after pre-sintering, performing secondary ball milling on the synthesized powder to micron-sized powder, drying, adding a binder (5 wt% of a polyvinyl alcohol aqueous solution), wherein the addition weight of the binder is 5% of the weight of the dried material, granulating, naturally placing for 5 hours, performing compression molding, placing the pressed columnar blank in a crucible for sealing, heating to 550 ℃ at the speed of 5 ℃/minute, performing heat preservation for 2 hours, discharging glue, heating to 1090 ℃ at the same heating speed, performing heat preservation for 3 hours, and naturally cooling along with a furnace to obtain the solid-phase sintered piezoelectric ceramic sheet.
After firing the silver electrode, the electrode was polarized for 20 minutes at 120 ℃ in silicone oil and 4kv/mm field strength, and the piezoelectric coefficient d was measured using a piezoelectric tester of the institute of acoustics of the Chinese academy of sciences33Measurement of (ZJ-6B), the piezoelectric coefficient d at room temperature (25 ℃ C.) was measured33363 pc/N. The dielectric properties were tested using a HIOKI 3532-50LCR network analyzer with a dielectric loss tan delta of 0.032 at-80 ℃ at 1k Hz.
Comparative example 1:
adding Bi2O3、Sc2O3PbO and TiO2Mixing according to the mol ratio of 19: 62, ball-milling for 18 hours, drying, sieving, fully grinding and mixing the powder, placing the powder into a crucible for presintering, raising the temperature to 760 ℃ at the speed of 5 ℃/min, keeping the temperature for presintering for 3 hours, and naturally cooling; after pre-sintering, performing secondary ball milling on the synthesized powder to micron-sized powder, drying, adding a binder (5 wt% of a polyvinyl alcohol aqueous solution), wherein the addition weight of the binder is 5% of the weight of the dried material, granulating, naturally placing for 5 hours, performing compression molding, placing the pressed columnar blank in a crucible for sealing, heating to 550 ℃ at the speed of 5 ℃/minute, performing heat preservation for 2 hours, discharging glue, heating to 1090 ℃ at the same heating speed, performing heat preservation for 3 hours, and naturally cooling along with a furnace to obtain the solid-phase sintered piezoelectric ceramic sheet.
After firing the silver electrode, the electrode was polarized for 20 minutes at 120 ℃ in silicone oil and 4kv/mm field strength, and the piezoelectric coefficient d was measured using a piezoelectric tester of the institute of acoustics of the Chinese academy of sciences33Measurement of (ZJ-6B), the piezoelectric coefficient d at room temperature (25 ℃ C.) was measured33259 pc/N. The dielectric properties were tested with a HIOKI 3532-50LCR network analyzer, and the dielectric loss tan delta at-80 ℃ at 1k Hz was 0.036.
Example 2
Adding Bi2O3、Sc2O3、PbO、TiO2And ZrO2Mixing according to a mol ratio of 18: 16.92: 64: 33.84 (namely taking x as 0.06), ball-milling for 18 hours, drying, sieving, fully grinding and mixing the powder, placing the powder into a crucible for presintering, heating to 760 ℃ at a speed of 5 ℃/min, keeping the temperature for presintering for 3 hours, and naturally cooling; ball-milling the synthetic powder into micron-sized powder for the second time after pre-sintering, drying, adding a binder (5 wt% of aqueous solution of polyvinyl alcohol), granulating, naturally standing for 5 hours, and pressingAnd (3) molding, namely placing the pressed columnar blank in a crucible for sealing, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours for removing glue, heating to 1090 ℃ at the same heating speed, preserving heat for 3 hours, and naturally cooling along with a furnace to obtain the solid-phase sintered piezoelectric ceramic sheet.
After firing the silver electrode, the electrode was polarized for 20 minutes at 120 ℃ in silicone oil and 4kv/mm field strength, and the piezoelectric coefficient d was measured using a piezoelectric tester of the institute of acoustics of the Chinese academy of sciences33Measurement of (ZJ-6B), the piezoelectric coefficient d at room temperature (25 ℃ C.) was measured33405 pc/N. The dielectric properties were tested using a HIOKI 3532-50LCR network analyzer with a dielectric loss tan delta of 0.028 at-80 ℃ at 1k Hz.
The piezoelectric properties of the ceramics prepared in this example were the best, and it can be seen from fig. 1 that the piezoelectric properties measured at different temperatures were also the best.
Example 3
Adding Bi2O3、Sc2O3、PbO、TiO2And ZrO2Mixing according to a mol ratio of 18: 14.4: 64: 28.8 (namely x is 0.2), ball-milling for 18 hours, drying, sieving, fully grinding and mixing powder, placing the powder into a crucible for presintering, heating to 760 ℃ at a speed of 5 ℃/min, keeping the temperature for presintering for 3 hours, and naturally cooling; after pre-sintering, performing secondary ball milling on the synthesized powder to micron-sized powder, drying, adding a binder (5 wt% of a polyvinyl alcohol aqueous solution), wherein the addition weight of the binder is 5% of the weight of the dried material, granulating, naturally placing for 5 hours, performing compression molding, placing the pressed columnar blank in a crucible for sealing, heating to 550 ℃ at the speed of 5 ℃/minute, performing heat preservation for 2 hours, discharging glue, heating to 1090 ℃ at the same heating speed, performing heat preservation for 3 hours, and naturally cooling along with a furnace to obtain the solid-phase sintered piezoelectric ceramic sheet.
After firing the silver electrode, the electrode was polarized for 20 minutes at 120 ℃ in silicone oil and 4kv/mm field strength, and the piezoelectric coefficient d was measured using a piezoelectric tester of the institute of acoustics of the Chinese academy of sciences33Measurement of (ZJ-6B), the piezoelectric coefficient d at room temperature (25 ℃ C.) was measured33231 pc/N. Dielectric properties were tested using a HIOKI 3532-50LCR network analyzer at-80 deg.C at 1k HzThe dielectric loss tan δ was 0.037.
Example 4
Adding Bi2O3、Sc2O3PbO and TiO2According to the molar ratio of 18: 64, 0.4% by weight of ZrO was added2Then mixing (taking x as 0.06), ball-milling for 18 hours, drying, sieving, grinding and fully mixing the powder, placing the powder into a crucible for presintering, heating to 790 ℃ at the speed of 5 ℃/min, keeping the temperature for presintering for 3 hours, and naturally cooling; after pre-sintering, performing secondary ball milling on the synthesized powder to obtain micron-sized powder, drying, adding a binder (5 wt% of a polyvinyl alcohol aqueous solution), wherein the addition weight of the binder is 5% of the weight of the dried material, granulating, naturally placing for 5 hours, performing compression molding, placing the pressed columnar blank in a crucible for sealing, heating to 600 ℃ at the rate of 3 ℃/min, performing heat preservation for 2 hours to remove glue, heating to 1120 ℃ at the same heating rate, performing heat preservation for 3 hours, and naturally cooling along with a furnace to obtain the solid-phase sintered piezoelectric ceramic sheet.
After firing the silver electrode, the electrode was polarized for 20 minutes at 120 ℃ in silicone oil and 4kv/mm field strength, and the piezoelectric coefficient d was measured using a piezoelectric tester of the institute of acoustics of the Chinese academy of sciences33Measurement of (ZJ-6B), the piezoelectric coefficient d at room temperature (25 ℃ C.) was measured33360 pc/N. The dielectric properties were tested with a HIOKI 3532-50LCR network analyzer, and the dielectric loss tan delta at-80 ℃ at 1k Hz was 0.039.
Example 5
A certain petroleum and petrochemical company, 11 Yue Shandong, 2016, uses a vertical tank with a heat-insulating layer, normal pressure and 150 ℃ temperature, and an explosion-proof environment on site, and uses a high-temperature external liquid level meter made of the high-temperature ceramic chip to measure liquid level, so that the signal amplitude is stable, the measurement is accurate, and normal and stable measurement can be realized.
Example 6
A certain company, Shaanxi, 5 months in 2016, uses asphalt as a high-temperature liquid medium, a reaction kettle as a container, a stirrer and a heat-insulating layer under normal pressure, the temperature is 170 ℃, and an explosion-proof environment is arranged on site.
Example 7
In a 10-month Ningxia chemical plant in 2016, a high-temperature liquid medium is o-nitroaniline, a container is a reaction kettle and is provided with a heat-insulating layer, the temperature is 200 ℃, an explosion-proof environment is arranged on the spot, a high-temperature external-measurement liquid level switch made of the high-temperature ceramic wafer of the patent monitors the liquid level, the signal amplitude is stable, the measurement is accurate, and the normal and stable measurement can be realized.
Example 8
In a certain chemical plant of Anhui 10 months in 2016, a high-temperature liquid medium is a mixed liquid of coal gas and water, a container is a gas-liquid separator, a heat-insulating layer is arranged, the temperature is 250 ℃, an explosion-proof environment is arranged on the spot, a high-temperature external liquid level meter made of the high-temperature ceramic wafer is used for measuring the liquid level, the signal amplitude is stable, the measurement is accurate, and the normal stable measurement can be realized.
Example 9
In a certain petrochemical plant in Chongqing of 11 months in 2016, a high-temperature liquid medium is a methanol paraffin solution, a container is a reaction tower, the temperature is 150 ℃, an explosion-proof environment is arranged on the spot, and a high-temperature external liquid level meter made of the high-temperature ceramic wafer of the utility model is used for measuring the liquid level, so that the signal amplitude is stable, the measurement is accurate, and the normal and stable measurement can be realized.

Claims (17)

1. A piezoelectric ceramic comprising 0.36Bi (Sc) as a main component1-XZrX)O3-0.64PbTiO3Wherein x is 0.04-0.24.
2. A preparation method of piezoelectric ceramics is characterized by comprising the following steps:
(1) with Bi2O3、Sc2O3、PbO、TiO2And ZrO2Raw materials are mixed according to a molar ratio of 0.18: 0.18 (1-x): 0.64: 0.64: weighing 0.36x, wherein x is 0.04-0.24, and carrying out primary ball milling;
(2) drying and sieving the ball-milled materials in the step (1), fully grinding and mixing the powder materials, putting the mixture into a crucible for presintering, and performing secondary ball milling on the synthetic powder materials after presintering until the ball milling reaches a micron level;
(3) drying the ball-milled materials in the step (2), adding a binder into the materials, granulating, and then pressing and molding;
(4) and (4) sealing the blank formed by pressing in the step (3) in a crucible, carrying out glue discharging treatment, and then carrying out sintering treatment to obtain the piezoelectric ceramic.
3. The method for producing a piezoelectric ceramic according to claim 2, wherein step (5) is performed after step (4), and the fired piezoelectric ceramic is ground, polished, silver-plated, and then subjected to polarization treatment.
4. The method for preparing a piezoelectric ceramic according to claim 2, wherein in the step (1), the weight ratio of the raw material to the grinding balls is 1: 1-1.8.
5. The method for preparing a piezoelectric ceramic according to claim 2, wherein in the step (2), the pre-sintering process comprises: heating to 700-850 ℃ from room temperature at the speed of 2-5 ℃/min, preserving heat for 2-4 h, and cooling along with the furnace.
6. The method for preparing a piezoelectric ceramic according to claim 2, wherein in the step (3), the binder is an aqueous solution of polyvinyl alcohol, wherein the concentration of the polyvinyl alcohol is 4-9 wt%; the addition weight of the binder is 4-10% of the weight of the dried material.
7. The method for preparing a piezoelectric ceramic according to claim 2, wherein in the step (4), the gel removal treatment comprises the following steps: heating to 500-600 ℃ from room temperature at the speed of 3-5 ℃/min, and carrying out heat preservation for 1-3h for removing the glue.
8. The method for preparing a piezoelectric ceramic according to claim 2, wherein in the step (4), the sintering treatment comprises the following steps: raising the temperature to 1000-1150 ℃ at the speed of 2-5 ℃/min, preserving the heat for 1-3h, and cooling along with the furnace.
9. A piezoelectric ceramic produced by the production method according to any one of claims 2 to 8.
10. Use of a piezoelectric ceramic according to claim 1 or 9 in the manufacture of an ultrasonic liquid meter.
11. The use of claim 10, wherein the ultrasonic liquid level meter is used to measure a parameter of a liquid.
12. Use according to claim 11, wherein the parameter is liquid level, liquid flow or liquid flow rate.
13. Use according to claim 11, wherein the liquid is at a temperature of-100 to +300 ℃.
14. Use of the piezoelectric ceramic according to claim 1 or 9 for the production of an ultrasonic gas meter.
15. The use according to claim 14, wherein the ultrasonic gas meter is used to measure a parameter of a gas.
16. The use according to claim 15, wherein said parameter is gas flow or gas flow rate.
17. Use according to claim 14, wherein the gas has a temperature of-100 to +300 ℃.
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