CN112759390A - Has high kpPSN-PZT piezoelectric ceramic and preparation method thereof - Google Patents

Has high kpPSN-PZT piezoelectric ceramic and preparation method thereof Download PDF

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CN112759390A
CN112759390A CN201911065405.2A CN201911065405A CN112759390A CN 112759390 A CN112759390 A CN 112759390A CN 201911065405 A CN201911065405 A CN 201911065405A CN 112759390 A CN112759390 A CN 112759390A
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piezoelectric ceramic
pzt piezoelectric
ceramic
sintering
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李国荣
黄思瑜
曾江涛
郑嘹赢
时雪
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a high-k materialpPSN-PZT piezoelectric ceramic with a stoichiometric general formula of xPb (Nb) and a preparation method thereof0.5Sb0.5)O3‑(1‑x)Pb1‑ 1.5yNdy(Zr0.53Ti0.47)O3(ii) a Wherein x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1. K of the PSN-PZT piezoelectric ceramicpThe value is 0.48 to 0.82.

Description

Has high kpPSN of value-PZT piezoelectric ceramic and method for producing the same
Technical Field
The invention relates to a high-k materialpA piezoelectric ceramic and a preparation method thereof, in particular to an Nd3+A doping modified PSN-PZT piezoelectric ceramic and a preparation method thereof belong to the field of piezoelectric ceramics.
Background
Since the piezoelectric effect is discovered by the curie brother, the piezoelectric material is widely applied to life through hundreds of years of diligent research of a plurality of workers. With the continuous development of science and technology, the application of piezoelectric materials gradually permeates into high and new scientific and technological fields, such as safety monitoring systems of aerospace, flaw detection systems in engineering buildings and the like. The PSN-PZT piezoelectric ceramic is a typical ternary system and has a high electromechanical coupling coefficient. Coefficient of electromechanical coupling kpThe method is a measure of electromechanical energy conversion efficiency and is also an important parameter for evaluating excellent piezoelectric performance of the material. Having a high kpThe material can be widely applied to the fields of energy collectors, electroacoustic transducers, broadband filters, underwater acoustic transducers and the like. The progress of science and technology has prompted many researchers to continuously search for a material with a high kpNew materials of value to meet the needs of future applications.
Researchers are currently working on many different types of ternary lead-based systems, but their kpThe value is generally between 0.5 and 0.7. Such as R.Pramanik[1]K of PMN-PT prepared by controlling grain sizepThe value is only 0.7; gaoyu[2]K of PNN-PZT piezoelectric ceramics made by et alpThe value is only 0.63. And for lead-free piezoelectric ceramics, k thereofpLower value, Zhao Zhi Hao[3]K of textured BNT-BKT-BT ceramic prepared by et alpThe value is only 0.31; sridevi Swain[4]K of NBT-BT ceramic made by et alpOnly 0.21 can be reached. Currently, Nd is added to lead-containing and lead-free piezoelectric ceramics3+The piezoelectric performance can be improved, but k cannot be reducedpThe temperature is increased to more than 0.65. Ajaj Garg[5]Attempts have been made to dope Nd in the PZT system3+Is k is then addedpFrom 0.33 to 0.49. In industrial production, the better contemporary Guizhou Shenghua lucky electronic Limited company performs Sr on the PSN-PZT ceramic2+、Ba2+、Ca2+And Mg2+A complex series of dopings, but with kpThe maximum can only be improved to about 0.79. Taken together, this generally lower k is shown to bepValue and higher kpBut the complicated doping phenomenon limits the development of the fields of broadband filters, transducers and the like. Therefore, a compound having a high k was studiedpPiezoelectric materials, which are simple to dope, have a milestone significance for the development of the field of electromechanical energy conversion.
Reference documents:
[1]R.Pramanik,M.K.Sahukar,Y.Mohan,B.Praveenkumar,S.R.Sangawar,A.Arockiarajan,Effect of grain size on piezoelectric,ferroelectric and dielectric properties of PMN-PT ceramics,Ceram Int 45(5)(2019)5731-5742.
[2]X.Gao,J.Wu,Y.Yu,Z.Chu,H.Shi,S.Dong,Giant Piezoelectric Coefficients in Relaxor Piezoelectric Ceramic PNN-PZT for Vibration Energy Harvesting,Adv Funct Mater 28(30)(2018)1706895.
[3]Z.-H.Zhao,M.-Y.Ye,H.-M.Ji,X.-L.Li,X.Zhang,Y.Dai,Enhanced piezoelectric properties and strain response in〈001〉textured BNT-BKT-BT ceramics,Mater Design 137(2018)184-191.
[4]S.Swain,S.Kumar Kar,P.Kumar,Dielectric,optical,piezoelectric and ferroelectric studies of NBT–BT ceramics near MPB,Ceram Int 41(9)(2015)10710-10717.
[5]A.Garg,D.C.Agrawal,Effect of rare earth(Er,Gd,Eu,Nd and La)and bismuth additives on the mechanical and piezoelectric properties of lead zirconate titanate ceramics,Materials Science and Engineering B86(2001)134-143.。
disclosure of Invention
In view of the above problems, it is a first object of the present invention to provide a dielectric ceramic having a high kpThe piezoelectric ceramic formulation for power-electricity energy conversion with different proportions of Nd3+Doping element to prepare the material with optimal kpSamples of values. The second purpose of the invention is to provide a method for preparing Nd3+The preparation method of the PSN-PZT-doped piezoelectric material is simple and stable to operate and easy to repeat, and basically meets the requirements of industrial production.
To this end, the invention provides a composition having a high kpPSN-PZT piezoelectric ceramic with a stoichiometric formula of xNb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3(ii) a Wherein x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1.
In the present disclosure, by doping with different amounts (0 < y ≦ 0.01) of Nd3+The comprehensive electrical property of the PSN-PZT is improved. In particular, Nd3+Has an ionic radius of 0.0983nm, Pb2+Has an ionic radius of 0.119nm due to Nd3+To replace Pb2+Ions occupy the A position, but the ionic valence state difference exists between the ions, so that a polarized nanometer micro area different from the matrix appears in the material, the discontinuity of polarization is generated, and further interface energy is generated, and when the material is polarized, the interface can cause the dipoles to turn to the same direction as an electric field as much as possible, so that the obtained PSN-PZT piezoelectric ceramic has high-kpThe value is obtained.
Preferably, k of the PSN-PZT piezoelectric ceramicpThe value is 0.48 to 0.82.
Further, preferably, when x is 0.02 and y is 0.01, k of the PSN-PZT piezoelectric ceramic is set to be equal topThe maximum value was 0.82.
In another aspect, the present invention provides a composition having a high kpThe preparation method of the PSN-PZT piezoelectric ceramic comprises the following steps:
(1) selecting Pb3O4、Nb2O5、Sb2O3、Nd2O3、ZrO2And TiO2Mixing the raw material powder, and pre-sintering at 900-1000 ℃ to obtain a pre-sintered material;
(2) mixing the obtained pre-sintered material and a binder, granulating and pressing into a blank;
(3) removing the glue from the obtained blank, and sintering at 1220-1300 ℃ to obtain a ceramic wafer;
(4) after silver is fired on the surface of the obtained ceramic chip, polarization treatment is carried out to obtain the ceramic chip with high kpPSN-PZT piezoelectric ceramics.
Preferably, the pre-sintering time is 2-3 hours.
Preferably, the binder is a polyvinyl alcohol aqueous solution with the mass concentration of 5 wt%.
Preferably, the mass ratio of the binder to the calcined material is 1: (0.05-0.13).
Preferably, the temperature of the rubber discharge is 400-550 ℃, and the time is 3-5 hours.
Preferably, the sintering time is 2-3 hours.
Preferably, the silver firing comprises: coating silver electrode slurry on the surface of the obtained ceramic wafer, and then burning silver for curing; wherein the temperature of the silver firing curing is 720 ℃, and the time is 0.3-0.5 hour.
Preferably, the polarization treatment is carried out for 0.25 to 0.75 hour under the electric field intensity of 2 to 3kV/mm by placing the silicon oil at the temperature of 100 to 120 ℃.
Has the advantages that:
the invention adopts the traditional solid phase reaction method to prepare the high-k materialpValue of Nd3+PSN-PZT piezoelectric ceramic, xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.1, and has high kpThe piezoelectric ceramic material with simple doping has milestone significance for the development of the field of mechanical-electrical energy conversion, and can have wide prospect in the future application of the fields of energy collectors, broadband filters, underwater acoustic transducers and the like.
Drawings
FIG. 1 shows the PSN-PZT piezoelectric ceramics prepared in example 2 at a temperature range of-50 to 150 ℃ kpAnd (4) fluctuation.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In this disclosure, have a high kpPSN-PZT piezoelectric ceramic (or Nd added)2O3PSN-PZT piezoelectric ceramic or Nd3+PSN-doped PZT piezoelectric ceramic) has the stoichiometric formula: xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1. Preferably, x is more than 0.02 and less than or equal to 0.05, and y is more than 0.01 and less than or equal to 0.05.
In an alternative embodiment, kp0.48 to 0.82, piezoelectric coefficient d33240-465 pC/N, Curie temperature Tc＝254～385℃，εr＝544～1845，Qm＝75～432，tanδ＝1.5～5.1。
In one embodiment of the present invention, the Nd is added according to the conventional solid-phase reaction method for preparing ceramics2O3The PSN-PZT piezoelectric ceramic has simple and stable operation and easy repetition, and basically meets the requirement of industrial production. Generally comprising: preparing materials; (2) synthesis (presintering); (3) tabletting and forming and removing glue; (4) sintering; (5) silver burning; (6) and polarizing and the like. The following exemplary description has a high kpA preparation method of PSN-PZT piezoelectric ceramics.
Will have a high kpPSN-PZT piezoelectric ceramics of values of oxides of the elements of the stoichiometric formula (e.g. Pb)3O4、Nb2O5、Sb2O3、Nd2O3、ZrO2、TiO2Etc.) to obtain a mixed powder. Wherein the mixing mode is ball milling mixing. For example, the raw material powder and a solvent (e.g., absolute ethanol, deionized water, etc.) are mixed and ball-milled to obtain a first slurry. And drying, crushing and sieving the first slurry in a blast oven, for example, 40-120 meshes to obtain a first undersize product. Wherein, the weight ratio of the grinding balls for ball milling, the raw material powder and the solvent is preferably 4:1: 1.
And placing the mixed powder into a furnace, and performing presintering synthesis at the temperature of 900-1000 ℃ for 2-3 h to obtain a presintering material (or called presintering powder).
And (5) blank making. Mixing the pre-sintered material with a binder, granulating, and pressing into blanks (blanks or biscuit). Wherein, the binder can be a polyvinyl alcohol aqueous solution with the mass concentration of 5wt%, and the mass ratio of the pre-sintering material to the binder can be (0.05-0.13): 1.
and (6) discharging the glue. And (3) placing the blank in a furnace for removing the glue, wherein the glue removing temperature can be 400-550 ℃. The heat preservation time of the binder removal can be 3-5 hours.
And (5) sintering. And sintering the blank after the glue is removed in a furnace to obtain the ceramic chip. Wherein, the sintering temperature can be 1220-1300 ℃, and the sintering heat preservation time can be 2-3 hours. For example, when the doping amount is 0.02 and y is about 0.01, the optimum performance is obtained at a sintering temperature of 1220 ℃p＝0.82，d33＝465pC/N，Tc＝331℃，εr＝1845，Qm＝75，tanδ＝1.5。
And (4) silver burning. Coating silver electrode slurry on the surface of the ceramic chip and burning silver for curing. For example, the silver is baked and cured at 720 ℃ for 0.3 to 0.5 hours.
And (6) polarization treatment. And (3) placing the ceramic wafer subjected to electrode treatment in silicone oil at 100-120 ℃, and carrying out polarization treatment for 0.25-0.75 hour under the electric field intensity of 2-3 kV/mm to finally obtain the PSN-PZT piezoelectric ceramic with excellent piezoelectric property.
As a having a high kpA detailed example of a method for preparing PSN-PZT piezoelectric ceramics of values includes: weighing according to the formula of PSN-PZT piezoelectric ceramics, mixing the required raw materials with a solvent to obtain slurry after primary ball milling, drying, crushing and sieving, putting the obtained primary undersize product into a furnace, heating to 900-1000 ℃, and preserving heat for 2-3 hours to obtain a pre-sintered material; mixing the pre-sintered material with absolute ethyl alcohol, performing secondary ball milling to obtain secondary slurry, drying, crushing and sieving to obtain secondary undersize material, mixing the secondary undersize material with a polyvinyl alcohol aqueous solution, granulating, and performing compression molding to obtain a blank; keeping the prepared blank at 400-550 ℃ for 3-5 h for glue removal treatment, placing the blank in a sintering furnace, and heating to 1220 DEG CAnd (5) cooling at the temperature of 1300 ℃ for 2-3 h to obtain the ceramic wafer. And coating silver on the ceramic chip, and then carrying out polarization treatment. The silver electrode is obtained by coating the silver electrode on the surface of the blank sintered by screen printing and then sintering the silver at 720 ℃. The polarization process is that the silicon wafer is placed in silicone oil at the temperature of 100-120 ℃ and is polarized for 0.25-0.75 h under the electric field intensity of 2-3 kV/mm.
In the invention, the high-k material prepared by the traditional solid-phase reaction method has high kpValue of Nd3+PSN-PZT piezoelectric ceramic xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3The material has wide prospect in the future application of the preparation field of the electro-mechanical energy conversion devices such as a broadband filter, an energy collector, an underwater acoustic transducer and the like.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
In this embodiment, has a high kpPSN-PZT piezoelectric ceramics and a preparation method thereof, which are prepared by the following steps:
the formula stoichiometric general formula of the ternary PSN-PZT piezoelectric ceramic is as follows: xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is 0, y is 0, and raw material Pb is selected3O4、ZrO2、TiO2Mixing (analytically pure) the slurry with absolute ethyl alcohol, carrying out first ball milling to obtain first slurry, drying, placing in a furnace, and presynthesizing for 2 hours at 900-1000 ℃ to obtain presintering materials; mixing the pre-sintered material with absolute ethyl alcoholPerforming secondary ball milling to obtain second slurry; drying and crushing the second slurry to obtain a second undersize material; mixing the second undersize material with a polyvinyl alcohol aqueous solution, granulating, and performing compression molding to obtain a blank; and (3) carrying out glue discharging treatment on the blank at 400-550 ℃, then placing the blank in a sintering furnace, and carrying out sintering densification at 1220-1300 ℃ to form a piezoelectric ceramic sample. The method comprises the steps of coating silver electrodes on the surfaces of two ends of a piezoelectric ceramic sample by screen printing, after silver is burnt, polarizing the piezoelectric ceramic sample in silicone oil at the temperature of 100-120 ℃ under the condition of applying an electric field intensity of 2-3 kV/mm, and then testing electrical performance parameters of the piezoelectric ceramic sample, wherein the test results are shown in table 1.
Example 2
In this embodiment, has a high kpPSN-PZT piezoelectric ceramics and a preparation method thereof, which are prepared by the following steps:
the formula stoichiometric general formula of the ternary PSN-PZT piezoelectric ceramic is as follows: xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is 0.02 and y is 0.01, and raw material Pb is selected3O4、ZrO2、TiO2、Nb2O5、Sb2O3、Nd2O3Mixing (analytically pure) the slurry with absolute ethyl alcohol, carrying out first ball milling to obtain first slurry, drying, placing in a furnace, and presynthesizing for 2 hours at 900-1000 ℃ to obtain presintering materials; mixing the pre-sintered material with absolute ethyl alcohol, and performing secondary ball milling to obtain second slurry; drying and crushing the second slurry to obtain a second undersize material; mixing the second undersize material with a polyvinyl alcohol aqueous solution, granulating, and performing compression molding to obtain a blank; and (3) carrying out glue discharging treatment on the blank at 400-550 ℃, then placing the blank in a sintering furnace, and carrying out sintering densification at 1220-1300 ℃ to form a piezoelectric ceramic sample. The method comprises the steps of coating silver electrodes on the surfaces of two ends of a piezoelectric ceramic sample by screen printing, after silver is burnt, polarizing the piezoelectric ceramic sample in silicone oil at the temperature of 100-120 ℃ under the condition of applying an electric field intensity of 2-3 kV/mm, and then testing electrical performance parameters of the piezoelectric ceramic sample, wherein the test results are shown in table 1.
Example 3
In this embodiment, has a high kpPSN-PZT piezoelectric ceramics and a preparation method thereof, which are prepared by the following steps:
the formula stoichiometric general formula of the ternary PSN-PZT piezoelectric ceramic is as follows: xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is 0.05 and y is 0.05, and raw material Pb is selected3O4、ZrO2、TiO2、Nb2O5、Sb2O3、Nd2O3Mixing the mixture with absolute ethyl alcohol after (analytical purification), and carrying out first ball milling to obtain first slurry; drying, placing in a furnace, and presynthesizing for 2 hours at 900-1000 ℃ to obtain a presintered material; mixing the pre-sintered material with absolute ethyl alcohol, and performing secondary ball milling to obtain second slurry; drying and crushing the second slurry to obtain a second undersize material; mixing the second undersize material with a polyvinyl alcohol aqueous solution, granulating, and performing compression molding to obtain a blank; and (3) carrying out glue discharging treatment on the blank at 400-550 ℃, then placing the blank in a sintering furnace, and carrying out sintering densification at 1220-1300 ℃ to form a piezoelectric ceramic sample. The method comprises the steps of coating silver electrodes on the surfaces of two ends of a piezoelectric ceramic sample by screen printing, after silver is burnt, polarizing the piezoelectric ceramic sample in silicone oil at the temperature of 100-120 ℃ under the condition of applying an electric field intensity of 2-3 kV/mm, and then testing electrical performance parameters of the piezoelectric ceramic sample, wherein the test results are shown in table 1.
Example 4
In this embodiment, has a high kpPSN-PZT piezoelectric ceramics and a preparation method thereof, which are prepared by the following steps:
the formula stoichiometric general formula of the ternary PSN-PZT piezoelectric ceramic is as follows: xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3X is 0.1 and y is 0.1, selecting raw material Pb3O4、ZrO2、TiO2、Nb2O5、Sb2O3、Nd2O3Mixing the mixture with absolute ethyl alcohol after (analytical purification), and carrying out first ball milling to obtain first slurry; drying, placing in a furnace, and presynthesizing for 2 hours at 900-1000 ℃ to obtain a presintered material; mixing the pre-sintered material with absolute ethyl alcoholPerforming second ball milling on the mixture to obtain second slurry; drying and crushing the second slurry to obtain a second undersize material; mixing the second undersize material with a polyvinyl alcohol aqueous solution, granulating, and performing compression molding to obtain a blank; and (3) carrying out glue discharging treatment on the blank at 400-550 ℃, then placing the blank in a sintering furnace, and carrying out sintering densification at 1220-1300 ℃ to form a piezoelectric ceramic sample. After silver electrodes are coated on the surfaces of two ends of a piezoelectric ceramic sample by screen printing, after silver is burnt, polarization is carried out in silicone oil at the temperature of 100-120 ℃ under the electric field intensity of 2-3 kV/mm, and then the electrical property parameters of the piezoelectric ceramic sample are tested, wherein the test results are shown in table 1.
Example 5
The procedure for preparing PSN-PZT piezoelectric ceramic in this example 5 is as shown in example 2 except that: x is 0.07 and y is 0.07.
Example 6
The procedure for preparing PSN-PZT piezoelectric ceramic in this example 6 is as described in example 2 except that: x is 0.02 and y is 0.
Example 7
The procedure for preparing PSN-PZT piezoelectric ceramic in this example 7 is as described in example 2 except that: x is 0 and y is 0.01.
TABLE 1 addition of Nd in the present invention2O3PSN-PZT piezoelectric ceramic performance parameter comparison:
Figure BDA0002259166810000061
Figure BDA0002259166810000071
。
by carrying out performance test on the sample, the test data shows that the Nd-added material provided by the invention2O3The PSN-PZT piezoelectric ceramic has good comprehensive performance and high kpWhile maintaining a high TcAnd the low tan delta is suitable for preparing a broadband filter, an underwater acoustic transducer and other power-electricity conversion electronic components. Especially when x is 0.02 and y is 0.01 in the formulaWhen nearby, the ternary piezoelectric ceramic PSN-PNZT has higher kpThe temperature stability was investigated, and the results are shown in FIG. 1, where k is in the temperature range of-50 ℃ to 120 ℃pValue and k at room temperaturepThe values are compared, the fluctuation range is within 10 percent, and good temperature stability is shown.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. Has high kpPSN-PZT piezoelectric ceramic having a value, characterized in that the stoichiometric formula of the PSN-PZT piezoelectric ceramic is xPb (Nb)0.5Sb0.5)O3-(1-x)Pb1-1.5yNdy(Zr0.53Ti0.47)O3(ii) a Wherein x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1.
2. The PSN-PZT piezoelectric ceramic of claim 1, wherein k of the PSN-PZT piezoelectric ceramicpThe value is 0.48 to 0.82.
3. PSN-PZT piezoelectric ceramic according to claim 1 or 2, characterized in that x =0.02, y = 0.01; preferably, k of the PSN-PZT piezoelectric ceramicpThe value was 0.82.
4. A polymer of any one of claims 1-3 having a high kpThe preparation method of the PSN-PZT piezoelectric ceramic is characterized by comprising the following steps:
(1) selecting Pb3O4、Nb2O5、Sb2O3、Nd2O3、ZrO2And TiO2As raw material powder and mixedPre-sintering at 900-1000 ℃ to obtain a pre-sintered material;
(2) mixing the obtained pre-sintered material and a binder, granulating and pressing into a blank;
(3) removing the glue from the obtained blank, and sintering at 1220-1300 ℃ to obtain a ceramic wafer;
(4) after silver is fired on the surface of the obtained ceramic chip, polarization treatment is carried out to obtain the ceramic chip with high kpPSN-PZT piezoelectric ceramics.
5. The method according to claim 4, wherein the pre-sintering time is 2 to 3 hours.
6. The preparation method according to claim 4 or 5, wherein the binder is a 5wt% polyvinyl alcohol aqueous solution or deionized water; preferably, the mass ratio of the binder to the pre-sintering material is 1 (0.05-0.13).
7. The preparation method according to any one of claims 4 to 6, wherein the temperature of the binder removal is 400 to 550 ℃ and the time is 3 to 5 hours.
8. The method according to any one of claims 4 to 7, wherein the sintering time is 2 to 3 hours.
9. The production method according to any one of claims 4 to 8, wherein the firing of silver includes: coating silver electrode slurry on the surface of the obtained ceramic wafer, and then burning silver for curing; wherein the temperature of the silver firing curing is 720 ℃, and the time is 0.3-0.5 hour.
10. The method according to any one of claims 4 to 9, wherein the polarization treatment is carried out by placing the silicon oil at 100 to 120 ℃ and polarizing the silicon oil at an electric field strength of 2 to 3kV/mm for 0.25 to 0.75 hour.
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