CN117263677A - Lanthanide and Cr, mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof - Google Patents
Lanthanide and Cr, mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 20
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 238000011282 treatment Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 230000010287 polarization Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PMVFCJGPQOWMTE-UHFFFAOYSA-N bismuth calcium Chemical compound [Ca].[Bi] PMVFCJGPQOWMTE-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention discloses a lanthanide and Cr, mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof, aiming at CaBi 4 Ti 4 O 15 Ca at A-position of ceramic material 2+ Ions, doped substitution is carried out by adopting +3 lanthanide metal ions with 12 coordination, and Ti is aimed at B site 4+ Ion, composite high valence ion [ Cr ] 1/ 3 Mo 2/3 ] 5+ The doping substitution is carried out, the Curie temperature is not reduced, and the piezoelectric performance and the high-temperature resistivity are improved at the same time, so that the novel environment-friendly piezoelectric ceramic material with excellent comprehensive electrical performance and good high-temperature performance is providedThe temperature stability and the wide application prospect in the high temperature field. The preparation method of the invention adopts an advanced ceramic preparation process, has low firing temperature, low preparation cost, simple process, easy operation and easily controlled influencing factors, is suitable for mass industrialized production, and is beneficial to popularization and application.
Description
Technical Field
The invention relates to the technical field of piezoelectric ceramic materials, in particular to a bismuth calcium titanate high-temperature piezoelectric ceramic material with a bismuth layered structure and a preparation method thereof.
Background
At present, the most widely applied piezoelectric ceramic materials are mainly PZT-based piezoelectric ceramics with perovskite structures, but the Curie temperature of the piezoelectric ceramics is generally below 400 ℃, and the piezoelectric materials cannot work normally above the Curie temperature due to the existence of depolarization phenomena of the piezoelectric materials. With the rapid development of aerospace, geological exploration and other works and the demand of sustainable development of human society, it is necessary to find an environment-friendly piezoelectric material with high curie temperature and excellent piezoelectric performance.
The bismuth layered structure ceramic has the advantages of high Curie temperature, good fatigue resistance and the like, and is a candidate material suitable for high-temperature environment. The bismuth layer-structured ceramic material is composed of (Bi) 2 O 2 ) 2+ The layers and perovskite structure lattice layers are alternately stacked with each other, and the chemical general formula is (Bi 2 O 2 ) 2+ (A m-1 B m O 3m+1 ) 2- Wherein CaBi 4 Ti 4 O 15 (CBT) is a typical bismuth layered structure ferroelectric material, A is 12 coordinated Ca 2+ And Bi (Bi) 3+ B is 6-coordinated Ti 4+ M=4, the material having a high curie temperature (T C Low piezoelectric activity and high resonant frequency temperature coefficient, and these factors limit the application in high temperature field. Therefore, how to obtain a CBT piezoelectric ceramic material with excellent comprehensive electrical properties without reducing the Curie temperature and improving the piezoelectric activity becomes an important subject in the research of the field of high-temperature piezoelectric ceramic materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the lanthanide series and Cr, mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material for CaBi 4 Ti 4 O 15 Ca at A-position of ceramic material 2+ Ions, doped substitution is carried out by adopting +3 lanthanide metal ions with 12 coordination, and Ti is aimed at B site 4+ Ion, composite high valence ion [ Cr ] 1/3 Mo 2/3 ] 5+ The doping substitution is carried out so as to improve the piezoelectric performance and the high-temperature resistivity of the piezoelectric ceramic material without reducing the Curie temperature by the composite doping modification, thereby providing a novel environment-friendly piezoelectric ceramic material with excellent comprehensive electrical performance. Another object of the present invention is to provide the above-mentioned CaBi co-doped with Cr and Mo 4 Ti 4 O 15 A preparation method of a high-temperature piezoelectric ceramic material.
The aim of the invention is realized by the following technical scheme:
the invention provides a lanthanide and Cr, mo co-doped CaBi 4 Ti 4 O 15 High temperature piezoelectric ceramic material with +3 valence lanthanide metal ion M with 12 coordination to replace CaBi 4 Ti 4 O 15 Ca in position A of the middle 2+ Ion by compounding high valence ion [ Cr 1/3 Mo 2/3 ] 5+ Doping substituted CaBi 4 Ti 4 O 15 Ti of B-position in the middle 4+ Ions of the general chemical formula Ca 1-x M x Bi 4 Ti 4-y [Cr 1/3 Mo 2/3 ] y O 15 Wherein x is more than or equal to 0.035 and less than or equal to 0.06,0.04, y is more than or equal to 0.065, and M is La 3+ 、Nd 3+ Or Sm 3+ Ions.
In the scheme, d of the piezoelectric ceramic material 33 ≥24pC/N，T C Not less than 770 ℃; the resistivity (rho) is more than or equal to 3.0X10 at 500 DEG C 7 Omega cm, dielectric loss (tan delta) less than or equal to 0.47%; d after 600 ℃ annealing 33 ≥20pC/N。
The other object of the invention is achieved by the following technical scheme:
the invention provides the lanthanide series element and Cr, mo co-doped CaBi 4 Ti 4 O 15 A preparation method of a high-temperature piezoelectric ceramic material,the method comprises the following steps:
(1) Preparation of presynthesized precursor powders
By CaCO 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、MoO 3 As a raw material corresponding to Ca, bi, ti, cr, mo in the chemical formula, la is used 2 O 3 、Nd 2 O 3 Or Sm 2 O 3 As a raw material corresponding to M in the chemical formula; proportioning the raw materials according to the chemical quantity in the chemical formula, performing ball milling treatment for one time by taking absolute ethyl alcohol as a ball milling medium, drying, sieving, pressing and molding the obtained materials, and then placing the materials in a sealed crucible for calcination treatment; grinding and sieving the calcined material, performing secondary ball milling treatment, and drying, grinding and sieving the obtained material to obtain pre-synthesized precursor powder;
(2) Preparation of high-temperature piezoelectric ceramic material
Loading the pre-synthesized precursor powder into a graphite mold, and placing the graphite mold in a discharge plasma sintering furnace for primary calcination treatment to obtain a carbon-containing sintered product; then placing the carbon-containing sintered product in a common high-temperature furnace for secondary calcination treatment to decarburize, so as to obtain a decarburized sintered product; and finally, carrying out polarization treatment on the decarburized sintered product to obtain the high-temperature piezoelectric ceramic material.
Further, the purity of each raw material in the step (1) in the preparation method is not lower than 99.9%. The pressure of the compression molding is 4-6 Mpa; the calcination treatment is to raise the temperature to 800-850 ℃ at 5 ℃/min.
Further, in the step (2) of the preparation method, the primary calcination treatment is that the pressure of a discharge plasma sintering furnace is 25-30 MPa, the direct current pulse current is 500-550A, the temperature is increased to 800-850 ℃ at 100 ℃/min, the direct current pulse current is stopped after the heat preservation is carried out for 5-8 min, then the pressure is released, and the furnace is cooled to the room temperature. The secondary calcination treatment is that 5 ℃/min is raised to 600-650 ℃, the temperature is kept for 3-4 hours, and the mixture is cooled to room temperature along with a furnace.
Further, in the step (2) of the preparation method, the polarization treatment is that the surface of the decarburized and sintered product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then heating to 650-680 ℃ at 5 ℃/min for calcination, preserving heat for 40-60 min, and cooling to room temperature along with a furnace; finally, the polarization is carried out in high-temperature silicone oil at 180-200 ℃ by adding direct current voltage of 5-10 kV/mm, and the polarization time is 20-30 min.
The lanthanide and Cr, mo co-doped CaBi is utilized 4 Ti 4 O 15 The product is prepared by the preparation method of the high-temperature piezoelectric ceramic material.
The invention has the following beneficial effects:
(1) In the preparation of CaBi 4 Ti 4 O 15 In the process of the piezoelectric ceramic material, bismuth vacancies are necessarily formed due to volatilization of bismuth at high temperature, thereby generating vacancy defects. In order to solve the problem, the invention adopts the valence state ratio A-position Ca 2+ High ionic La 3+ 、Nd 3+ Or Sm 3+ The ion is doped and substituted, and simultaneously the valence state ratio B-bit Ti is adopted 4+ Ion-high composite ion [ Cr 1/3 Mo 2/3 ] 5+ The perovskite-like layer (A) is doped and substituted to cause A, B to be located at the defect m-1 B m O 3m+1 ) 2- Electrons are generated, thereby enhancing the bismuth oxide layer (Bi 2 O 2 ) 2+ And perovskite-like layer (A) m-1 B m O 3m+1 ) 2- The interaction between the two components changes the growth behavior of the crystal grains, and finally obtains CaBi with excellent performance 4 Ti 4 O 15 High temperature piezoelectric ceramic material.
(2) The invention adopts the advanced spark plasma sintering technology, the sintering technology has low sintering temperature and short time, thus the energy consumption is low, the density of the sintered material is high, and the CaBi with excellent performance can be obtained 4 Ti 4 O 15 High temperature piezoelectric ceramic material.
(3) The lanthanide element and Cr, mo co-doped CaBi 4 Ti 4 O 15 Piezoelectric ceramic material with Curie temperature not less than 770 ℃ and piezoelectric constant d 33 More than or equal to 24pC/N, and after annealing at 600 DEG CD of (2) 33 Not less than 20pC/N; the resistivity at 500 ℃ is more than or equal to 3.0X10 7 Omega cm, dielectric loss is less than or equal to 0.47 percent. The material has good high-temperature stability and wide application prospect in the high-temperature field.
(4) The preparation method of the invention adopts an advanced ceramic preparation process, has low firing temperature, low preparation cost, simple process, easy operation and easily controlled influencing factors, is suitable for mass industrialized production, and is beneficial to popularization and application.
Drawings
The invention will be described in further detail with reference to examples and figures:
FIG. 1 is a schematic illustration of a CaBi co-doped with lanthanoid elements and Cr, mo prepared in accordance with an embodiment of the present invention 4 Ti 4 O 15 XRD patterns of high temperature piezoceramic, and comparative piezoceramic materials;
FIG. 2 is a schematic illustration of a CaBi co-doped with lanthanoid elements and Cr, mo prepared in accordance with an embodiment of the present invention 4 Ti 4 O 15 The dielectric constant of the high temperature piezoelectric ceramic changes with temperature.
Detailed Description
Embodiment one:
this example is a CaBi co-doped with lanthanoid with Cr and Mo 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material comprises the following steps:
(1) Preparation of presynthesized precursor powders
With CaCO of 99.9% purity 3 、La 2 O 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、MoO 3 As and of the chemical formula Ca 0.95 La 0.05 Bi 4 Ti 3.945 [Cr 1/3 Mo 2/3 ] 0.055 O 15 Corresponding to Ca, la, bi, ti, cr, mo, proportioning the raw materials according to the stoichiometric amount in the chemical formula, then taking absolute ethyl alcohol as a ball milling medium, performing ball milling treatment on a planetary ball mill for 24 hours according to ball, material and absolute ethyl alcohol=4:1:3 at a rotating speed of 400r/min, drying the obtained material, sieving with a 80-mesh sieve, and pressing under 4Mpa to obtain the productPlacing the mixture in a sealed crucible, heating to 800 ℃ at a speed of 5 ℃/min, and calcining in an oxidizing atmosphere for 2 hours; grinding the calcined material, sieving with an 80-mesh sieve, performing secondary ball milling treatment by adopting the same process as the primary ball milling treatment, and drying, grinding and sieving with an 80-mesh sieve the obtained material to obtain pre-synthesized precursor powder;
(2) Preparation of high-temperature piezoelectric ceramic material
(2-1) loading 0.8g of the pre-synthesized precursor powder into a cylindrical graphite mold with the diameter of 20mm, placing the cylindrical graphite mold into a discharge plasma sintering furnace, setting the pressure to be 25MPa and the direct current pulse current to be 500A, heating to 800 ℃ at 100 ℃/min for primary calcination treatment, keeping the temperature for 5min, stopping the direct current pulse current, releasing the pressure, and cooling to room temperature along with the furnace to obtain a carbon-containing sintered product;
(2-2) placing the carbon-containing sintered product in a common high-temperature furnace, carrying out secondary calcination treatment at a speed of 5 ℃/min to 600 ℃ to carry out decarburization, preserving heat for 3 hours, and cooling to room temperature along with the furnace to obtain a decarburized sintered product;
(2-3) subjecting the decarburized fired product to a polarization treatment, wherein the surface of the decarburized fired product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then, heating to 650 ℃ at 5 ℃ per minute for calcination, preserving heat for 40 minutes, and cooling to room temperature along with a furnace; finally, the high-temperature piezoelectric ceramic material is prepared by polarizing the high-temperature silicon oil at 180 ℃ with direct current voltage of 5-10 kV/mm for 20 min.
Embodiment two:
this example is a CaBi co-doped with lanthanoid with Cr and Mo 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is different from the embodiment in that:
1. the chemical formula of this example is Ca 0.952 Nd 0.048 Bi 4 Ti 3.945 [Cr 1/3 Mo 2/3 ] 0.055 O 15 The raw material corresponding to Nd is Nd 2 O 3 。
2. The calcination temperature in step (1) is 820 ℃; the calcination temperature in step (2-1) was 820 ℃.
Embodiment III:
this example is a CaBi co-doped with lanthanoid with Cr and Mo 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is different from the embodiment in that:
1. the chemical formula of this example is Ca 0.955 Sm 0.045 Bi 4 Ti 3.945 [Cr 1/3 Mo 2/3 ] 0.055 O 15 The raw material corresponding to Sm is Sm 2 O 3 。
2. The calcination temperature in step (1) is 820 ℃; the calcination temperature in step (2-1) was 820 ℃.
Comparative example:
undoped CaBi of the chemical formula 4 Ti 4 O 15 As a comparative example, the preparation process was the same as in example one.
As can be seen from FIG. 1, each diffraction peak of the piezoelectric ceramic materials prepared in each example and comparative example is completely matched with the standard spectrum PDF 00-052-1640, which shows that the obtained material is CaBi with single crystal phase 4 Ti 4 O 15 A material.
The lanthanide series element and Cr, mo co-doped CaBi prepared by the embodiment of the invention 4 Ti 4 O 15 The dielectric constant of the high temperature piezoelectric ceramic is plotted as a function of temperature as shown in fig. 2. The results of the performance test of the piezoelectric ceramic materials of the examples and comparative examples of the present invention are shown in table 1.
TABLE 1 Properties of the ceramic materials of examples and comparative examples according to the invention
Claims (9)
1. Lanthanide and Cr, mo co-doped CaBi 4 Ti 4 O 15 A high-temperature piezoelectric ceramic material, which is made of high-temperature piezoelectric ceramic,the method is characterized in that: substitution of CaBi by M doping with 12 coordinated +3 valent lanthanide metal ions 4 Ti 4 O 15 Ca in position A of the middle 2+ Ion by compounding high valence ion [ Cr 1/ 3 Mo 2/3 ] 5+ Doping substituted CaBi 4 Ti 4 O 15 Ti of B-position in the middle 4+ Ions of the general chemical formula Ca 1-x M x Bi 4 Ti 4-y [Cr 1/ 3 Mo 2/3 ] y O 15 Wherein x is more than or equal to 0.035 and less than or equal to 0.06,0.04, y is more than or equal to 0.065, and M is La 3+ 、Nd 3+ Or Sm 3+ Ions.
2. The lanthanide-Cr-Mo co-doped CaBi according to claim 1 4 Ti 4 O 15 The high-temperature piezoelectric ceramic material is characterized in that: d of the piezoelectric ceramic material 33 ≥24pC/N，T C Not less than 770 ℃; the resistivity (rho) is more than or equal to 3.0X10 at 500 DEG C 7 Omega cm, dielectric loss (tan delta) less than or equal to 0.47%; d after 600 ℃ annealing 33 ≥20pC/N。
3. Co-doped CaBi with Cr and Mo according to claim 1 or 2 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of:
(1) Preparation of presynthesized precursor powders
By CaCO 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、MoO 3 As a raw material corresponding to Ca, bi, ti, cr, mo in the chemical formula, la is used 2 O 3 、Nd 2 O 3 Or Sm 2 O 3 As a raw material corresponding to M in the chemical formula; proportioning the raw materials according to the chemical quantity in the chemical formula, performing ball milling treatment for one time by taking absolute ethyl alcohol as a ball milling medium, drying, sieving, pressing and molding the obtained materials, and then placing the materials in a sealed crucible for calcination treatment; grinding and sieving the calcined material, and performing secondary ball milling treatment to obtainDrying, grinding and sieving the materials to obtain pre-synthesized precursor powder;
(2) Preparation of high-temperature piezoelectric ceramic material
Loading the pre-synthesized precursor powder into a graphite mold, and placing the graphite mold in a discharge plasma sintering furnace for primary calcination treatment to obtain a carbon-containing sintered product; then placing the carbon-containing sintered product in a common high-temperature furnace for secondary calcination treatment to decarburize, so as to obtain a decarburized sintered product; and finally, carrying out polarization treatment on the decarburized sintered product to obtain the high-temperature piezoelectric ceramic material.
4. The lanthanide-Cr-Mo co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the purity of each raw material in the step (1) is not lower than 99.9 percent.
5. The lanthanide-Cr-Mo co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the pressure of the compression molding in the step (1) is 4-6 Mpa; the calcination treatment is to raise the temperature to 800-850 ℃ at 5 ℃/min.
6. The lanthanide-Cr-Mo co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the primary calcination treatment in the step (2) is that the pressure of a discharge plasma sintering furnace is 25-30 MPa, the direct current pulse current is 500-550A, the temperature is raised to 800-850 ℃ at 100 ℃/min, the direct current pulse current is stopped after the heat preservation is carried out for 5-8 min, then the pressure is released, and the furnace is cooled to the room temperature.
7. The lanthanide-Cr-Mo co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: and (3) in the step (2), the secondary calcination treatment is that the temperature is raised to 600-650 ℃ at 5 ℃/min, the temperature is kept for 3-4 hours, and the mixture is cooled to the room temperature along with a furnace.
8. The lanthanide-Cr-Mo co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the polarization treatment in the step (2) is that the surface of the decarburized and burnt product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then heating to 650-680 ℃ at 5 ℃/min for calcination, preserving heat for 40-60 min, and cooling to room temperature along with a furnace; finally, the polarization is carried out in high-temperature silicone oil at 180-200 ℃ by adding direct current voltage of 5-10 kV/mm, and the polarization time is 20-30 min.
9. Co-doping CaBi with Cr, mo using a lanthanide according to one of claims 3-8 4 Ti 4 O 15 The product is prepared by the preparation method of the high-temperature piezoelectric ceramic material.
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