CN107840655B - Preparation method of bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with morphotropic phase boundary - Google Patents
Preparation method of bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with morphotropic phase boundary Download PDFInfo
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- 229910020294 Pb(Zr,Ti)O3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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Abstract
The invention relates to a preparation method of a bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with a quasi-homomorphic phase boundary, which comprises the steps of selecting raw materials, performing ball milling twice, discharging, drying, calcining to obtain ceramic powder, sintering after glue removal in a muffle furnace, and polishing the sintered ceramic chip by using abrasive paper with different particle sizes to obtain a thin ceramic chip with a bright and smooth surface. Compared with the prior art, the ceramic phase structure composition has a rhombohedral phase and a tetragonal phase, a ferroelectric domain is easy to turn under the action of an electric field, so that a large electric clamping effect can be obtained, the material is obtained by a common sintering method, the cost is low, no pollution is caused, and the prepared material has a large electric clamping effect in a relatively wide temperature region, so that the ceramic phase structure composition has a great application prospect in the aspect of solid refrigeration.
Description
Technical Field
The invention belongs to the technical field of electronic functional materials and devices, and particularly relates to a preparation method of a bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with a morphotropic phase boundary.
Background
At present, most of refrigeration devices mainly adopt freon as a refrigeration substance, and the freon consumes the ozone layer in the atmosphere and increases the greenhouse effect, thereby causing certain damage to the environment and being not beneficial to ecological civilization construction. With the increasing environmental importance of human society, new environment-friendly technology needs to be developed to replace Freon. Especially after a.s.mischienko and b.neese et al found a huge electrocaloric effect in antiferroelectric films and polymers [ a.s.mischienko et al, Science 311(2006)1270 [ b.neese, Science 321(2008)821 ], solid refrigeration technology of electrocaloric effect has received attention from numerous researchers in recent years. The electrocaloric effect refers to the reversible temperature change of a material in a polar material by applying and removing an electric field. Compared with magnetic card refrigeration, the electric card refrigeration has more practical value, so researchers in various countries are put into the electric card research. Currently, research on electrical cards is mainly focused on lead-containing systems, such as Pb (Mg)1/3Nb2/3)O3-PbTiO3，Pb(Zr,Ti)O3Etc., but the lead-containing ceramic material is not harmful to the environment and human body at the time of preparation and post-treatmentThe use of lead-containing materials is greatly limited by the successive European promulgation of relevant regulations, and therefore, the study on the electrocaloric effect of the lead-free materials is very necessary.
The bismuth potassium titanate ceramics have a tetragonal phase structure at room temperature, are not easy to sinter and have poor piezoelectric performance, so in recent years, a plurality of researchers introduce additional components and the bismuth potassium titanate to form a solid solution to improve the piezoelectric and ferroelectric performance of the bismuth potassium titanate ceramics. The electrocaloric effect of the potassium bismuth titanate system has not been studied.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of the potassium bismuth titanate-based lead-free relaxation ferroelectric ceramic with the morphotropic phase boundary, wherein the morphotropic phase boundary is formed by doping lanthanum magnesium titanate into the potassium bismuth titanate ceramic, so that the great electrocaloric effect delta T-1.2K is obtained, and the temperature stability is good.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with the morphotropic phase boundary comprises the following steps:
(1) selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is taken as a raw material;
(2) bi of the formula (1-x)0.5K0.5TiO3-xLa(Mg0.5Ti0.5)O3Weighing, performing wet ball milling, discharging, drying, and calcining twice to obtain ceramic powder;
(3) performing secondary ball milling on the calcined powder, discharging, drying, adding a binder PVA for granulation, forming under the pressure of 4-6 MPa, and pressing into a ceramic wafer;
(4) removing glue from the obtained ceramic blank in a muffle furnace, and preserving heat for 5-10 h at 500-600 ℃;
(5) and sintering the ceramic blank after removing the glue at 1000-1100 ℃, controlling the heating rate to be 3 ℃/min, keeping the temperature at the highest temperature for 2h, then cooling to room temperature along with the furnace, and polishing the sintered ceramic wafer by using abrasive paper with different particle sizes to obtain the thin ceramic wafer with a bright and smooth surface.
Preferably, in the step (2), x is 0-0.03 but is not 0.
More preferably, x in step (2) is preferably 0.01.
Preferably, the ball milling is carried out in a planetary ball mill, and absolute ethyl alcohol and zirconium dioxide balls are added into a nylon tank as ball milling media.
Preferably, the ball milling time in the step (2) is 6-8 hours, and the ball milling time in the step (3) is 8-12 hours.
Preferably, in the step (2), the mixture is calcined twice in a muffle furnace, the temperature is controlled to be 850-950 ℃, the mixture is kept for 1-3 hours, and then the mixture is cooled to room temperature along with the furnace.
Preferably, the drying in the step (2) and the step (3) is carried out by adopting an air-blast drying oven, and the drying temperature is 100-120 ℃.
Preferably, the PVA mentioned in step (3) is added in an amount of 5% by weight of the powder.
Preferably, the ceramic wafer polished in the step (5) is coated with high-temperature silver paste on the front surface and the back surface, and is subjected to silver firing treatment in a muffle furnace, wherein the muffle furnace is controlled to be constant in temperature of 500-600 ℃ for 0.5-1 hour during the treatment.
Compared with the prior art, the ceramic phase structure prepared by the invention has rhombohedral phase and tetragonal phase, and the ferroelectric domain is easy to turn over under the action of an electric field, so that a large electrocaloric effect can be obtained. The ceramic can be obtained by a common sintering method, the cost is low, no pollution is caused, and the prepared material has a large electric clamping effect in a quite wide temperature zone, so that the ceramic has a great application prospect in the aspect of solid refrigeration and has the following advantages:
(1) the novel potassium bismuth titanate based lead-free relaxation ferroelectric ceramic provided by the invention has a great electric card effect, and when the adjusting component is positioned in the morphotropic phase boundary, the component is 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The optimal electrocaloric effect delta T-1.2K is obtained, and the temperature is betterAnd (4) degree stability.
(2) Incorporating an additional component La (Mg)0.5Ti0.5)O3The method overcomes the defects that pure potassium bismuth titanate ceramics are not easy to sinter and the like, and when the pure potassium bismuth titanate ceramics are positioned in the morphotropic phase boundary, the piezoelectric property of the material also achieves the optimal d33～103pC/N。
(3) The ceramic does not contain lead, does not cause harm to the environment in the processes of production, use and abandonment, and is an environment-friendly ferroelectric refrigeration material.
Drawings
FIG. 1 shows a novel potassium bismuth titanate-based lead-free relaxor ferroelectric ceramic 0.99Bi obtained in example 10.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3XRD spectrum (SEM spectrum enclosed inside);
FIG. 2 shows the novel potassium bismuth titanate-based lead-free relaxor ferroelectric ceramic 0.99Bi obtained in example 20.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3High temperature medium temperature maps at different frequencies;
FIG. 3 shows the novel potassium bismuth titanate-based lead-free relaxor ferroelectric ceramic 0.99Bi obtained in example 30.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The electric hysteresis loop of (1);
FIG. 4 shows the novel potassium bismuth titanate-based lead-free relaxor ferroelectric ceramic 0.99Bi obtained in example 40.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Under different temperatures (25-120 ℃), the constant field intensity E is 4kV/mm electric card effect.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
(1) Selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is used as a raw material of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic. According to the chemical formula 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Weighing, adding absolute ethyl alcohol into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, tamping, covering a crucible cover, putting the corundum crucible into a muffle furnace for calcining, heating to 920 ℃ at the temperature of 5 ℃/min, and keeping the temperature for 2 hours, wherein the calcining times are two.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5 wt% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank subjected to glue removal obtained in the step (3) at the temperature of 1080 ℃, wherein the heating rate is 2 ℃/min, and the temperature is kept at the highest temperature for 2 hours. And then naturally cooling to room temperature to obtain the potassium bismuth titanate based lead-free relaxation ferroelectric ceramic.
(5) The fired ceramic plate was pulverized into powder with a mortar and subjected to XRD and SEM tests.
FIG. 1 shows the obtained lead-free relaxor ferroelectric ceramic 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The XRD diffraction pattern of the compound is shown in figure 1, and the phase structures are all shown to be single ABO3And (5) structure. The SEM chart shows that the crystal grain of the bismuth potassium titanate-based ceramic is flaky, and the prepared ceramic chip has a compact structure and no obvious air holes.
Example 2
(1) Selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is used as a raw material of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic. According to the chemical formula 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Weighing, adding absolute ethyl alcohol into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, tamping, covering a crucible cover, putting the corundum crucible into a muffle furnace for calcining, heating to 920 ℃ at the temperature of 5 ℃/min, and keeping the temperature for 2 hours, wherein the calcining times are two.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5 wt% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank subjected to glue removal obtained in the step (3) at the temperature of 1080 ℃, wherein the heating rate is 2 ℃/min, and the temperature is kept at the highest temperature for 2 hours. And then naturally cooling to room temperature to obtain the potassium bismuth titanate based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. High-temperature silver paste is uniformly coated on two sides of the ceramic, then the ceramic is placed into a muffle furnace for glue discharging, and the temperature is raised to 600 ℃ at the speed of 5 ℃/min and then the ceramic is kept for half an hour.
FIG. 2 shows the preparation of lead-free relaxor ferroelectric ceramic 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The dielectric temperature spectrum of (1). T can be obviously observed from a dielectric thermogrammThe ferroelectric material gradually moves to a high temperature direction along with the increase of the frequency, has dielectric dispersion characteristics, and is a typical relaxor ferroelectric.
Example 3
(1) Selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is used as a raw material of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic. According to the chemical formula 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Weighing, adding absolute ethyl alcohol into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, tamping, covering a crucible cover, putting the corundum crucible into a muffle furnace for calcining, heating to 920 ℃ at the temperature of 5 ℃/min, and keeping the temperature for 2 hours, wherein the calcining times are two.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5 wt% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank subjected to glue removal obtained in the step (3) at the temperature of 1080 ℃, wherein the heating rate is 2 ℃/min, and the temperature is kept at the highest temperature for 2 hours. And then naturally cooling to room temperature to obtain the potassium bismuth titanate based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. High-temperature silver paste is uniformly coated on two sides of the ceramic, then the ceramic is placed into a muffle furnace for glue discharging, and the temperature is raised to 600 ℃ at the speed of 5 ℃/min and then the ceramic is kept for half an hour.
FIG. 3 shows the obtained lead-free relaxor ferroelectric ceramic 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The hysteresis loop (P-E). From the hysteresis loop we can see that the P-E is very saturated and the material is very stressedThe electrical performance of the ferroelectric is improved.
Example 4
(1) Selecting raw material BBi with purity of more than 99%2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is used as a raw material of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic. According to the chemical formula 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Weighing, adding absolute ethyl alcohol into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, tamping, covering a crucible cover, putting the corundum crucible into a muffle furnace for calcining, heating to 850 ℃ at the temperature of 5 ℃/min, and keeping the temperature for 2 hours, wherein the calcining times are two.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5 wt% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank subjected to glue removal obtained in the step (3) at the temperature of 1080 ℃, wherein the heating rate is 2 ℃/min, and the temperature is kept at the highest temperature for 2 hours. And then naturally cooling to room temperature to obtain the potassium bismuth titanate based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. High-temperature silver paste is uniformly coated on two sides of the ceramic, then the ceramic is placed into a muffle furnace for glue discharging, and the temperature is raised to 600 ℃ at the speed of 5 ℃/min and then the ceramic is kept for half an hour.
(6) And (4) polarizing the ceramic chip obtained in the step (5), then putting the ceramic chip into a temperature-controlled heat insulation device, and detecting the temperature change caused by applying/removing the electric field by using a heat insulation calorimeter.
FIG. 4 shows the obtained lead-free relaxor ferroelectric ceramic 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Under different temperatures (25-120 ℃), constant field intensity E is equal to the temperature change value induced by 4kV/mm electric field. From this we can see that 0.99Bi at room temperature0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3The temperature change reaches delta T-1.2K, and the relative change value in the whole temperature interval is less than or equal to 10 percent, so the large electrocaloric ceramic material with good temperature stability is beneficial to the practical application of solid refrigeration.
Example 5
The preparation method of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with the morphotropic phase boundary comprises the following steps:
(1) selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is taken as a raw material;
(2) according to the chemical formula 0.99Bi0.5K0.5TiO3-0.01La(Mg0.5Ti0.5)O3Weighing materials, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank as ball milling media, performing wet ball milling for 6 hours, discharging, drying by adopting a blast drying oven at the drying temperature of 100 ℃, performing twice calcination to obtain ceramic powder, controlling the temperature during calcination to 920 ℃, preserving the temperature for 2 hours, and then cooling to room temperature along with the furnace;
(3) performing secondary ball milling on the calcined powder for 8 hours, discharging, drying by adopting an air-blast drying oven at the drying temperature of 100 ℃, adding a binder PVA (polyvinyl alcohol) with the powder amount of 5 wt% for granulation, molding under the pressure of 4MPa, and pressing into a ceramic wafer;
(4) carrying out glue discharging on the obtained ceramic blank in a muffle furnace, and preserving heat for 10h at 550 ℃;
(5) sintering the ceramic blank after glue discharging at 1080 ℃, controlling the heating rate to be 3 ℃/min, preserving heat for 2h at the highest temperature, then cooling to the room temperature along with a furnace, polishing the sintered ceramic piece by using abrasive paper with different granularities to obtain a thin ceramic piece with a bright and flat surface, coating high-temperature silver paste on the front side and the back side, carrying out silver firing treatment in a muffle furnace, and controlling the muffle furnace to keep the constant temperature at 600 ℃ for 0.5h during the treatment. The purpose of plating silver paste on both sides is for subsequent electrical performance testing.
Example 6
The preparation method of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with the morphotropic phase boundary comprises the following steps:
(1) selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is taken as a raw material;
(2) according to the chemical formula 0.97Bi0.5K0.5TiO3-0.03La(Mg0.5Ti0.5)O3Weighing materials, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank as ball milling media, performing wet ball milling for 8 hours, discharging, drying by adopting a blast drying oven at the drying temperature of 120 ℃, performing twice calcination to obtain ceramic powder, controlling the temperature during calcination to 920 ℃, preserving the temperature for 2 hours, and then cooling to room temperature along with the furnace;
(3) performing secondary ball milling on the calcined powder for 12 hours, discharging, drying by adopting an air-blast drying oven at the drying temperature of 120 ℃, adding a binder PVA (polyvinyl alcohol) with the powder amount of 5 wt% for granulation, molding under the pressure of 4MPa, and pressing into a ceramic wafer;
(4) carrying out glue discharging on the obtained ceramic blank in a muffle furnace, and preserving heat for 0.5h at 600 ℃;
(5) sintering the ceramic blank after glue discharging at 1080 ℃, controlling the heating rate to be 3 ℃/min, preserving heat for 2h at the highest temperature, then cooling to the room temperature along with a furnace, polishing the sintered ceramic piece by using abrasive paper with different granularities to obtain a thin ceramic piece with a bright and flat surface, coating high-temperature silver paste on the front side and the back side, carrying out silver firing treatment in a muffle furnace, and controlling the muffle furnace to keep the constant temperature at 600 ℃ for 0.5h during the treatment.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. The preparation method of the bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with the morphotropic phase boundary is characterized by comprising the following steps:
(1) selecting raw material Bi with the purity of more than 99 percent2O3，K2CO3，TiO2，La2O3，TiO2，4(MgCO3)·Mg(OH)2·5H2O is taken as a raw material;
(2) bi of the formula (1-x)0.5K0.5TiO3-xLa(Mg0.5Ti0.5)O3Weighing, carrying out wet ball milling, discharging, drying, and carrying out twice calcination to obtain ceramic powder, wherein x is 0-0.03 but not 0;
(3) performing secondary ball milling on the calcined powder, discharging, drying, adding a binder PVA for granulation, forming under the pressure of 4-6 MPa, and pressing into a ceramic wafer;
(4) removing glue from the obtained ceramic blank in a muffle furnace, and preserving heat for 5-10 h at 500-600 ℃;
(5) and sintering the ceramic blank after removing the glue at 1000-1100 ℃, controlling the heating rate to be 3 ℃/min, keeping the temperature at the highest temperature for 2h, then cooling to room temperature along with the furnace, and polishing the sintered ceramic wafer by using abrasive paper with different particle sizes to obtain the thin ceramic wafer with a bright and smooth surface.
2. The method for preparing a potassium bismuth titanate-based lead-free relaxor ferroelectric ceramic of a morphotropic phase boundary according to claim 1, wherein x in the step (2) is 0.01.
3. The method for preparing bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic of morphotropic phase boundary according to claim 1, characterized in that, two ball-milling are carried out in a planetary ball mill, and absolute ethyl alcohol and zirconium dioxide balls are added in a nylon pot as ball-milling media.
4. The method for preparing the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic of the morphotropic phase boundary according to claim 1, wherein the ball milling time in the step (2) is 6 to 8 hours, and the ball milling time in the step (3) is 8 to 12 hours.
5. The method for preparing the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic with the morphotropic phase boundary according to claim 1, characterized in that in the step (2), the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic is calcined twice in a muffle furnace, the temperature is controlled to be 850-950 ℃, the temperature is kept for 1-3 h, and then the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic is cooled to room temperature along with the furnace.
6. The method for preparing the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic with the morphotropic phase boundary according to claim 1, wherein the drying in the steps (2) and (3) is performed by using an air-blowing drying oven, and the drying temperature is 100-120 ℃.
7. The method for preparing bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic of morphotropic phase boundary according to claim 1, characterized in that the amount of PVA added in step (3) is 5 wt% of the powder.
8. The method for preparing the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic with the morphotropic phase boundary according to claim 1, wherein the ceramic sheet polished in the step (5) is further coated with high temperature silver paste on both front and back surfaces and subjected to silver firing treatment in a muffle furnace.
9. The method for preparing the bismuth potassium titanate-based lead-free relaxor ferroelectric ceramic of the morphotropic phase boundary according to claim 8, wherein the muffle furnace is controlled to be constant at 500-600 ℃ for 0.5-1 hour during the silver firing treatment.
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