CN111087238B - Sodium bismuth titanate based leadless piezoelectric ceramic and preparation method thereof - Google Patents

Sodium bismuth titanate based leadless piezoelectric ceramic and preparation method thereof Download PDF

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CN111087238B
CN111087238B CN201911401230.8A CN201911401230A CN111087238B CN 111087238 B CN111087238 B CN 111087238B CN 201911401230 A CN201911401230 A CN 201911401230A CN 111087238 B CN111087238 B CN 111087238B
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CN111087238A (en
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李凯
赵小波
俞胜平
高洪伟
丁薇薇
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Weifang Goertek Microelectronics Co Ltd
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Abstract

The invention discloses a sodium bismuth titanate-based lead-free piezoelectric ceramic and a preparation method thereof. The titaniumThe sodium bismuth sulfate-based lead-free piezoelectric ceramic has the following general formula: (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3(ii) a Wherein M is at least one of Li and K; x and y each represents BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3Occupied compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/ 3Ta2/3)O3Mole percent of (c); wherein x is more than or equal to 0.04 and less than or equal to 0.20, and y is more than or equal to 0.01 and less than or equal to 0.07. According to one embodiment of the present disclosure, the sodium bismuth titanate-based lead-free piezoelectric ceramic can exhibit excellent electrostrictive characteristics at room temperature with small changes in curie temperature.

Description

Sodium bismuth titanate based leadless piezoelectric ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of piezoelectric material preparation, in particular to sodium bismuth titanate-based lead-free piezoelectric ceramic and a preparation method thereof.
Background
Since the piezoelectric material has positive and negative piezoelectric properties and can realize interconversion between mechanical energy and electric energy, the piezoelectric material is widely applied to high and new technical fields such as piezoelectric resonators, piezoelectric buzzers, piezoelectric filters, piezoelectric transformers, piezoelectric speakers, piezoelectric igniters, piezoelectric motors and the like as an important functional material.
In recent years, piezoelectric actuators are widely used in the fields of semiconductors, automobiles, consumer electronics, medical health, and the like, and mainly include piezoelectric ceramic materials capable of generating electrostrictive strain. In the current market, lead-based piezoelectric ceramic materials, such as lead zirconate titanate (pzt) based piezoelectric ceramic materials, are widely used piezoelectric materials, and have excellent electrostrictive properties, thereby occupying a large market share. However, the lead oxide content in the lead-based piezoelectric ceramic material is generally as high as 60% or more. As is well known, lead and its compounds are extremely toxic, accumulate in human body and are not easy to be discharged, which can cause serious damage to human health. Meanwhile, the environment is very easy to be polluted in the production and use processes.
Therefore, there is a need to develop a new lead-free piezoelectric ceramic material with high electrostrictive strain to solve the problems of the prior art.
Disclosure of Invention
The invention aims to provide a novel technical scheme of sodium bismuth titanate-based lead-free piezoelectric ceramic and a preparation method thereof.
According to a first aspect of the present invention, there is provided a sodium bismuth titanate-based lead-free piezoelectric ceramic represented by the following general formula I:
(1-x-y)(Bi0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3； (I)
wherein M is at least one of Li and K;
x and y each represents BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3Occupied compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Mole percent of (c);
wherein x is more than or equal to 0.04 and less than or equal to 0.20, and y is more than or equal to 0.01 and less than or equal to 0.07.
Optionally, wherein x is more than or equal to 0.06 and less than or equal to 0.16, and y is more than or equal to 0.02 and less than or equal to 0.05.
Optionally, the lead-free piezoelectric ceramic exhibits a ferroelectric-relaxor antiferroelectric phase transition at room temperature.
According to a second aspect of the present invention, there is provided a method for preparing a sodium bismuth titanate-based lead-free piezoelectric ceramic, comprising the steps of:
s1, batching:
with Bi2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Weighing and proportioning various raw materials according to the chemical composition of the sodium bismuth titanate-based lead-free piezoelectric ceramic;
s2, preparation:
s21, primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Performing primary ball milling after mixing;
s22, primary burn-in: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction;
s23, secondary ball milling: performing secondary ball milling on the powder subjected to the primary pre-sintering;
s24, secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure;
s25, carrying out ball milling for three times: carrying out ball milling on the powder subjected to the secondary pre-sintering for three times;
s26, pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
s27, sintering: heating the rough blank to obtain a compact ceramic element;
s3, polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
Optionally, in the step S21, the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5And after mixing, adding absolute ethyl alcohol into the mixture for primary ball milling, wherein the primary ball milling time is 22-26 h.
Optionally, in step S22, the primary pre-sintering temperature is 800 ℃ to 900 ℃, and the holding time is 1h to 4 h.
Optionally, in step S23, adding absolute ethanol to the powder after the primary pre-sintering for secondary ball milling, where the time for the secondary ball milling is 22h to 26 h.
Optionally, in the step S24, the secondary pre-sintering temperature is 820 ℃ to 920 ℃, and the holding time is 1h to 4 h.
Optionally, in step S25, adding absolute ethanol to the powder after the secondary pre-sintering, and performing ball milling for three times, where the time for ball milling for three times is 22h to 26 h.
Optionally, in the step S27, the sintering temperature is 1100 ℃ to 1220 ℃, and the holding time is 2h to 6 h.
Optionally, before the polarization step, silver coating is respectively carried out on two sides of the ceramic element, and then silver firing is carried out;
the silver firing temperature is 400-600 ℃, and the heat preservation time is 20-40 min.
According to one embodiment of the present disclosure, the sodium bismuth titanate-based lead-free piezoelectric ceramic can exhibit excellent electrostrictive characteristics at room temperature with less change in curie temperature. The sodium bismuth titanate-based lead-free piezoelectric ceramic also has good piezoelectric performance. In addition, the sodium bismuth titanate-based lead-free piezoelectric ceramic does not contain lead which is a highly toxic element, so that damage to human health can be avoided, and environmental burden can be reduced. The defects of the prior art are overcome. The technical task to be achieved or the technical problems to be solved by the present invention are never thought or not expected by those skilled in the art, and therefore the present invention is a new technical solution.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a flowchart of a method for preparing a sodium bismuth titanate-based lead-free piezoelectric ceramic according to an embodiment of the present disclosure.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
According to one embodiment of the present disclosure, a sodium bismuth titanate-based lead-free piezoelectric ceramic is provided. The bismuth sodium titanate-based lead-free piezoelectric ceramic can be applied to high and new technical fields such as piezoelectric resonators, piezoelectric buzzers, piezoelectric filters, piezoelectric transformers, piezoelectric speakers, piezoelectric igniters, piezoelectric motors and the like, is widely applied, and overcomes the defects of the prior art.
According to one embodiment of the present disclosure, a sodium bismuth titanate-based lead-free piezoelectric ceramic is provided. The bismuth titanate sodium-based lead-free piezoelectric ceramic is represented by the following chemical formula I:
(1-x-y)(Bi0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3； (I)
wherein M is at least one of Li and K;
x and y each represents BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3Occupied compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Mole percent of (c);
wherein x is more than or equal to 0.04 and less than or equal to 0.20, and y is more than or equal to 0.01 and less than or equal to 0.07.
For example, BaTiO when x is 0.1 and y is 0.033Comprising compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Is 10 mol%, (La)0.5M0.5)(Zn1/3Ta2/3)O3Comprising compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Is 3%. (Bi)0.5Na0.5)TiO3Comprising compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3The molar percentage of (a) is 87%. The sodium bismuth titanate-based lead-free piezoelectric ceramic comprises the following components: 0.87 (Bi)0.5Na0.5)TiO3—0.1BaTiO3—0.03(La0.5M0.5)(Zn1/3Ta2/3)O3。
Wherein (Bi)0.5Na0.5)TiO3At high temperature, ferroelectric-relaxor antiferroelectric phase transition exists by introducing BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3(M is at least one of Li and K, for example), the ferroelectric-relaxor antiferroelectric phase transition can be made to fall to room temperature, so that excellent electrostrictive properties can be obtained at room temperature. At the same time, the curie temperature changes less.
Under the action of an external electric field of 6kV/mm, the electrical strain of the sodium bismuth titanate-based lead-free piezoelectric ceramic provided by the embodiment of the invention can reach 0.24-0.31%, which is relatively close to the level of lead zirconate titanate-based ceramic. The corresponding large-signal piezoelectric coefficient can reach 400pm/V-517pm/V, and the Curie temperature is between 255 ℃ and 317 ℃. The defects of the prior art are overcome. In addition, the sodium bismuth titanate-based lead-free piezoelectric ceramic does not contain lead which is a highly toxic element, can be used for replacing the conventional lead-based piezoelectric ceramic material, and can avoid damage to human health and reduce environmental burden.
In addition, the sodium bismuth titanate-based lead-free piezoelectric ceramic provided by the embodiment of the invention has high compactness and good piezoelectric performance.
In addition, the sodium bismuth titanate-based lead-free piezoelectric ceramic provided by the embodiment of the invention has wide practicability.
Optionally, the ranges of the parameters in the chemical formula I are 0.06 ≦ x ≦ 0.16, and 0.02 ≦ y ≦ 0.05. The range is a preferable value range, and the prepared sodium bismuth titanate-based lead-free piezoelectric ceramic can show more excellent electrostrictive strain characteristics at room temperature and good piezoelectric performance, so that the level of the prepared sodium bismuth titanate-based lead titanate-based piezoelectric ceramic is closer to that of soft lead zirconate titanate-based ceramic. The comprehensive performance of the prepared sodium bismuth titanate-based lead-free piezoelectric ceramic is better.
The sodium bismuth titanate-based lead-free piezoelectric ceramic provided by the embodiment of the invention is of a perovskite structure. The ceramic material with the structure has better piezoelectric effect.
According to another embodiment of the present disclosure, there is also provided a method for preparing a sodium bismuth titanate-based lead-free piezoelectric ceramic, as shown in fig. 1, including the following steps:
s1, batching:
with Bi2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5As raw materials, and various raw materials are according to the chemical formula: (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3The materials are weighed and proportioned；
Wherein M is at least one of Li and K;
x and y each represents BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3Occupied compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Mole percent of (c);
wherein x is more than or equal to 0.04 and less than or equal to 0.20, and y is more than or equal to 0.01 and less than or equal to 0.07.
Furthermore, x is more than or equal to 0.06 and less than or equal to 0.16, and y is more than or equal to 0.02 and less than or equal to 0.05.
Specifically, the raw materials are all powder materials. And weighing and proportioning according to the proportional relation of each element in the chemical formula I. The amount of each raw material can be set by those skilled in the art according to actual needs.
S2, preparation:
s21, primary ball milling: mixing the above Bi2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5After mixing, primary ball milling is carried out.
Since the particle sizes of the respective raw materials are usually different from each other, and if the particle size is relatively large, the solid-phase reaction and the sintering step are not facilitated.
In one example of the present invention, the above-mentioned raw materials are subjected to a first ball milling treatment in advance to achieve a predetermined particle size, and the raw materials are uniformly mixed. After the raw material ingredients are completed, the above-mentioned various raw materials are charged into a ball milling jar, for example, a nylon ball milling jar, and ball milling treatment is performed on a planetary ball mill. For the ball milling, at least one of zirconia balls and agate balls can be used, for example. The grinding balls made of the two materials are not easy to damage, and after the ball milling is finished, the impurities of the powder mixture are few. Compared with a metal ball milling tank and a ceramic ball milling tank, the nylon ball milling tank adopted in the invention can not introduce other metal or oxide impurities into the powder mixture.
For example, in this step, Bi may be added in the case of performing primary ball milling2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5And adding absolute ethyl alcohol into the formed mixture, and performing first mixing grinding, wherein solid raw materials in the various raw materials are added in the form of powder. And the addition of the absolute ethyl alcohol can increase the viscosity of the raw materials, so that the first mixing and grinding is more sufficient, and the obtained powder is finer and more uniform. In the present example, the first mixing and milling is performed by ball milling. Secondly, the time of one-time ball milling is preferably controlled to be 22h-26h, so that Bi can be ensured2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5The mixing is more uniform. Further, the time for one ball milling was controlled to 24 hours. The powder can become finer and more uniform. The addition of auxiliary agents (such as deionized water, absolute ethyl alcohol and the like), ball milling time and the like can be selected according to actual needs by a person skilled in the art. And then, drying the mixture after the first mixing and grinding to remove the absolute ethyl alcohol.
Bi is added to the above-mentioned raw materials2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5The mixing and grinding mode is not limited to the ball milling mode, and the mixing and grinding mode can be set by a person skilled in the art according to actual needs.
Through one-time ball milling, various raw materials can be uniformly mixed and reach a preset granularity, the specific surface area of the raw materials is large, the activity is high, and the perovskite structure is easy to react and form.
S22, primary burn-in: and heating the powder subjected to primary ball milling and drying to perform solid-phase reaction.
The above-mentioned various raw materials are chemically reacted as reactants at a predetermined temperature. For example, in the first pre-burning, various raw materials are subjected to solid phase reaction at the high temperature of 800-900 ℃ for 1-4 h. The purpose of the pre-burning is: the solid phase chemical reaction of various raw materials is sufficient and uniform, solid solution with fixed composition is generated, and a main crystal phase is formed; and carbon dioxide and moisture in the raw materials are removed, and the sintering shrinkage and deformation of the rough blank are reduced, so that the appearance size of the ceramic product is controlled. Further, the primary sintering temperature is 850 ℃, and the heat preservation time is 2 hours.
S23, secondary ball milling: and performing secondary ball milling on the powder subjected to the primary pre-sintering.
After the secondary ball milling, the materials which are subjected to the primary pre-sintering and the solid-phase reaction can be mixed more uniformly, so that the conversion rate of the perovskite structure formed by the reaction is higher, and the purity is also improved.
In one example of the present invention, the powder after the primary pre-sintering is loaded into a nylon ball mill tank together with zirconia balls and absolute ethyl alcohol, and secondary ball milling is performed on a planetary ball mill, wherein the ball milling time can be controlled to be 22h-26h, for example. Further, the time of the secondary ball milling may be 24 hours.
The ball milling is the same as the primary ball milling. Specifically, the addition of the absolute ethyl alcohol can increase the viscosity of the first pre-sintering powder, so that the second mixing and grinding is more sufficient, and the obtained first pre-sintering powder is more fine and uniform.
And drying the powder subjected to the secondary mixing and grinding to obtain mixed powder. And the anhydrous ethanol can be removed through the drying step, so that the adverse effect of the anhydrous ethanol on the subsequent sintering is avoided.
The method of mixing and grinding the powder after the primary calcination in the present invention is not limited to the ball milling method described above, and those skilled in the art can set the method according to actual needs. Likewise, the skilled person can select the added auxiliary agents (such as deionized water, absolute ethyl alcohol, etc.), ball milling time, etc. according to the actual needs.
S24, secondary pre-burning: and heating the powder subjected to secondary ball milling and drying to obtain the powder with the pure perovskite structure.
And (4) heating the powder subjected to secondary ball milling and drying to obtain a pure perovskite structure.
In the second pre-sintering, the raw materials in the powder state react at 820-920 ℃ for 1-4 h to form a perovskite structure. The perovskite structure formed under the reaction condition has high purity and high conversion rate.
In the preparation method provided by the invention, the purity of the formed perovskite structure can be higher through repeated powdering treatment and pre-sintering steps, so that the finally formed bismuth sodium titanate-based lead-free piezoelectric ceramic can show excellent electrostrictive strain characteristics at room temperature. Particularly, under the action of an external electric field of 6kV/mm, the strain can reach 0.24-0.31 percent, the strain is close to the level of lead zirconate titanate-based ceramic, the corresponding large-signal piezoelectric coefficient can reach 400pm/V-517pm/V, and the Curie temperature is between 255-317 ℃. Meanwhile, the piezoelectric performance of the finally formed sodium bismuth titanate-based lead-free piezoelectric ceramic is better.
S25, carrying out ball milling for three times: and carrying out ball milling on the powder subjected to the secondary pre-sintering for three times.
And mixing the powder subjected to the secondary pre-sintering with zirconia balls and absolute ethyl alcohol, putting the mixture into a nylon ball milling tank, and carrying out third ball milling on a planetary ball mill. Wherein, the time of the third ball milling can be controlled to be 22h-26 h. Further, the time for the three times of mixed grinding can be 24 hours. After three times of ball milling, the materials after the secondary pre-sintering can be mixed more uniformly.
The same principle of ball milling in the first two times is that the viscosity of the second pre-sintered powder can be increased by adding the absolute ethyl alcohol, so that the third mixing and milling is more sufficient, and the obtained second pre-sintered powder is finer and more uniform.
And drying the powder after the third mixed grinding to obtain mixed powder. The anhydrous ethanol can be effectively removed through the drying step, and the adverse effect of the anhydrous ethanol on the subsequent sintering is avoided.
The method of performing the mixing and grinding of the powder after the secondary pre-firing in this step is not limited to the ball milling method, and those skilled in the art can set the method according to actual needs. Likewise, the skilled person can select the added auxiliary agents (such as deionized water, absolute ethyl alcohol, etc.), ball milling time, etc. according to the actual needs.
S26, pressing: pressing the powder subjected to the three ball milling processes into a rough blank with a preset shape.
In one example of the present invention, the powder obtained after three ball-milling operations is charged into a mold and pressed into a preform of a predetermined shape.
In step S26, a mold may be previously prepared according to the shape of the piezoelectric ceramic product. The material is formed into a predetermined shape in a mold by filling, compacting, etc.
S27, sintering: and heating the rough blank to obtain the compact ceramic element.
The rough blank obtained in step S26 is placed in a heating device to be sintered to obtain a dense ceramic element. The heating device used for sintering may be, for example, an atmospheric sintering furnace, a vacuum sintering furnace, etc., and those skilled in the art may select the heating device according to actual needs.
Wherein sintering refers to converting a powder material into a dense body. The rough blank can form a ceramic element with a compact structure through a sintering process. The ceramic element is represented by formula I. Spontaneous polarization exists in all directions in the crystal of the ceramic element, and no polarity is presented to the outside from the macroscopic view. The regions where the spontaneous polarizations are in the same direction are called electric domains.
In one example of the invention, the rough blank is placed into a vacuum sintering furnace for high-temperature sintering, wherein the sintering temperature is controlled to be 1100-1220 ℃, and the holding time is 2-6 h. Under the condition, the lead-free piezoelectric ceramic product formed by sintering the materials has uniform quality and good density.
S3, polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
The electric domains of the ceramic element can be turned by polarization, namely the spontaneous polarization of the electric domains is forced to be aligned by the polarization, so that the ceramic element presents polarity.
Preferably, the step of poling comprises plating electrodes on the ceramic element to facilitate poling. By polarization, the ceramic element becomes a piezoelectric ceramic device having piezoelectric properties.
In other examples, the ceramic element is directly polarized in an atmospheric environment, which also enables the ceramic element to have piezoelectric properties.
For example, before the polarization step, silver is coated on two surfaces of the ceramic element respectively, and then silver is fired to form a silver layer, wherein the silver firing temperature is controlled to be 400-600 ℃, the heat preservation time is controlled to be 20-40 min, and the silver layer is used as an electrode layer.
According to one embodiment of the disclosure, the sodium bismuth titanate-based lead-free piezoelectric ceramic can show good electrostrictive strain characteristics at room temperature, and the electrostrictive strain can reach 0.24-0.31% under the action of an external electric field of 6kV/mm, which is close to the level of lead zirconate titanate-based ceramic. The corresponding large-signal piezoelectric coefficient can reach 400pm/V-517pm/V, and the Curie temperature is between 255 ℃ and 317 ℃. The defects of the prior art are overcome. The sodium bismuth titanate-based lead-free piezoelectric ceramic also has good piezoelectric performance. Meanwhile, the preparation method also has lower sintering temperature so as to achieve energy conservation and emission reduction, and is beneficial to reducing the preparation cost and promoting the practical process.
In addition, the lead-free piezoelectric ceramic obtained by the preparation method belongs to a lead-free system and has the characteristic of environmental friendliness. Can be completely used for replacing the prior lead-based piezoceramic material, can avoid the damage to the human health and reduce the environmental burden.
In addition, the preparation method belongs to a solid-phase reaction method, and is easy to realize large-scale production.
Example 1
The sodium bismuth titanate-based lead-free piezoelectric ceramic is prepared according to the preparation method, wherein:
the bismuth sodium titanate based lead-free piezoelectric ceramic is prepared according to the formula that x is 0.04 and y is 0.07: 0.89 (Bi)0.5Na0.5)TiO3—0.04BaTiO3—0.07(La0.5M0.5)(Zn1/3Ta2/3)O3；
Primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Mixing, adding zirconia balls and absolute ethyl alcohol, then putting into a nylon ball milling tank together, and carrying out primary ball milling on a planetary ball mill for 22 hours;
pre-burning for one time: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction, wherein the temperature of primary presintering is 800 ℃, and the heat preservation time is 4 hours;
secondary ball milling: adding zirconia balls and absolute ethyl alcohol into the powder subjected to the primary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out secondary ball milling on a planetary ball mill for 24 hours;
and (3) secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure, wherein the temperature of secondary presintering is 900 ℃, and the heat preservation time is 2.5 hours;
and (3) ball milling for the third time: adding zirconia balls and absolute ethyl alcohol into the powder subjected to secondary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out three-time ball milling on a planetary ball mill for 26 hours;
pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
and (3) sintering: heating the rough blank to obtain a compact ceramic element, wherein the heating sintering temperature is 1100 ℃, and the heat preservation time is 6 hours;
polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
Example 2
The sodium bismuth titanate-based lead-free piezoelectric ceramic is prepared according to the preparation method, wherein:
the bismuth sodium titanate based lead-free piezoelectric ceramic is prepared according to the formula that x is 0.06 and y is 0.05: 0.89 (Bi)0.5Na0.5)TiO3—0.06BaTiO3—0.05(La0.5M0.5)(Zn1/3Ta2/3)O3；
Primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Mixing, adding zirconia balls and absolute ethyl alcohol, then putting into a nylon ball milling tank together, and carrying out primary ball milling on a planetary ball mill for 23 hours;
pre-burning for one time: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction, wherein the temperature of primary presintering is 900 ℃, and the heat preservation time is 1 h;
secondary ball milling: adding zirconia balls and absolute ethyl alcohol into the powder subjected to the primary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out secondary ball milling on a planetary ball mill for 25 hours;
and (3) secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure, wherein the temperature of secondary presintering is 820 ℃, and the heat preservation time is 4 hours;
and (3) ball milling for the third time: adding zirconia balls and absolute ethyl alcohol into the powder subjected to secondary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out three-time ball milling on a planetary ball mill for 26 hours;
pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
and (3) sintering: heating the rough blank to obtain a compact ceramic element, wherein the heating sintering temperature is 1220 ℃, and the heat preservation time is 2 hours;
polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
Example 3
The sodium bismuth titanate-based lead-free piezoelectric ceramic is prepared according to the preparation method, wherein:
the bismuth sodium titanate based lead-free piezoelectric ceramic is prepared according to the formula that x is 0.16 and y is 0.02: 0.82 (Bi)0.5Na0.5)TiO3—0.16BaTiO3—0.02(La0.5M0.5)(Zn1/3Ta2/3)O3；
Primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Mixing, adding zirconia balls and absolute ethyl alcohol, then putting into a nylon ball milling tank together, and carrying out primary ball milling on a planetary ball mill for 26 hours;
pre-burning for one time: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction, wherein the temperature of primary presintering is 850 ℃, and the heat preservation time is 3 hours;
secondary ball milling: adding zirconia balls and absolute ethyl alcohol into the powder subjected to primary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out secondary ball milling on a planetary ball mill for 23 hours;
and (3) secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure, wherein the temperature of secondary presintering is 920 ℃, and the heat preservation time is 1 h;
and (3) ball milling for the third time: adding zirconia balls and absolute ethyl alcohol into the powder subjected to secondary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out three-time ball milling on a planetary ball mill for 25 hours;
pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
and (3) sintering: heating the rough blank to obtain a compact ceramic element, wherein the heating sintering temperature is 1200 ℃, and the heat preservation time is 3 hours;
polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
Example 4
The sodium bismuth titanate-based lead-free piezoelectric ceramic is prepared according to the preparation method, wherein:
the bismuth sodium titanate based lead-free piezoelectric ceramic is prepared according to the formula that x is 0.11 and y is 0.04: 0.85 (Bi)0.5Na0.5)TiO3—0.11BaTiO3—0.04(La0.5M0.5)(Zn1/3Ta2/3)O3；
Primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Mixing, adding zirconia balls and absolute ethyl alcohol, then putting into a nylon ball milling tank together, and carrying out primary ball milling on a planetary ball mill for 24 hours;
pre-burning for one time: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction, wherein the temperature of primary presintering is 880 ℃, and the heat preservation time is 1.5 h;
secondary ball milling: adding zirconia balls and absolute ethyl alcohol into the powder subjected to the primary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out secondary ball milling on a planetary ball mill for 26 hours;
and (3) secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure, wherein the temperature of secondary presintering is 850 ℃, and the heat preservation time is 3 hours;
and (3) ball milling for the third time: adding zirconia balls and absolute ethyl alcohol into the powder subjected to secondary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out three-time ball milling on a planetary ball mill for 24 hours;
pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
and (3) sintering: heating the rough blank to obtain a compact ceramic element, wherein the heating sintering temperature is 1175 ℃, and the heat preservation time is 3 hours;
polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
Example 5
The sodium bismuth titanate-based lead-free piezoelectric ceramic is prepared according to the preparation method, wherein:
the components are mixed according to the conditions that x is 0.2 and y is 0.01, and then the composition of the bismuth sodium titanate-based lead-free piezoelectric ceramic is obtainedComprises the following steps: 0.79 (Bi)0.5Na0.5)TiO3—0.2BaTiO3—0.01(La0.5M0.5)(Zn1/3Ta2/3)O3；
Primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Mixing, adding zirconia balls and absolute ethyl alcohol, then putting into a nylon ball milling tank together, and carrying out primary ball milling on a planetary ball mill for 25 hours;
pre-burning for one time: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction, wherein the temperature of primary presintering is 830 ℃, and the heat preservation time is 3.5 hours;
secondary ball milling: adding zirconia balls and absolute ethyl alcohol into the powder subjected to the primary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out secondary ball milling on a planetary ball mill for 26 hours;
and (3) secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure, wherein the temperature of secondary presintering is 860 ℃, and the heat preservation time is 3 hours;
and (3) ball milling for the third time: adding zirconia balls and absolute ethyl alcohol into the powder subjected to secondary pre-sintering, then putting the powder into a nylon ball milling tank together, and carrying out three-time ball milling on a planetary ball mill for 26 hours;
pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
and (3) sintering: heating the rough blank to obtain a compact ceramic element, wherein the heating sintering temperature is 1150 ℃, and the heat preservation time is 5 hours;
polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
The sodium bismuth titanate-based lead-free piezoelectric ceramics prepared in the above examples 1 to 5 exhibit excellent electrostrictive characteristics at room temperature. Under the action of an external electric field of 6kV/mm, the strain can reach 0.24-0.31%, the corresponding large-signal piezoelectric coefficient can reach 400-517pm/V, and the Curie temperature is between 255-317 ℃.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims (11)

1. A sodium bismuth titanate-based lead-free piezoelectric ceramic is characterized by being represented by the following general formula I:
(1-x-y)(Bi0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3；(I)
wherein M is at least one of Li and K;
x and y each represents BaTiO3And (La)0.5M0.5)(Zn1/3Ta2/3)O3Occupied compound (1-x-y) (Bi)0.5Na0.5)TiO3—xBaTiO3—y(La0.5M0.5)(Zn1/3Ta2/3)O3Mole percent of (c);
wherein x is more than or equal to 0.04 and less than or equal to 0.20, and y is more than or equal to 0.01 and less than or equal to 0.07.
2. The sodium bismuth titanate-based lead-free piezoelectric ceramic according to claim 1, characterized in that: wherein x is more than or equal to 0.06 and less than or equal to 0.16, and y is more than or equal to 0.02 and less than or equal to 0.05.
3. The sodium bismuth titanate-based lead-free piezoelectric ceramic according to claim 1, characterized in that: the lead-free piezoelectric ceramic has ferroelectric-relaxor antiferroelectric phase transition at room temperature.
4. A method for preparing a sodium bismuth titanate-based lead-free piezoelectric ceramic according to claim 1, comprising the steps of:
s1, batching:
with Bi2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Weighing and proportioning various raw materials according to the chemical composition of the sodium bismuth titanate-based lead-free piezoelectric ceramic;
s2, preparation:
s21, primary ball milling: the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5Performing primary ball milling after mixing;
s22, primary burn-in: heating the powder subjected to primary ball milling and drying to perform solid-phase reaction;
s23, secondary ball milling: performing secondary ball milling on the powder subjected to the primary pre-sintering;
s24, secondary pre-burning: heating the powder subjected to secondary ball milling and drying to obtain powder with a pure perovskite structure;
s25, carrying out ball milling for three times: carrying out ball milling on the powder subjected to the secondary pre-sintering for three times;
s26, pressing: pressing the powder subjected to the three ball milling into a rough blank with a preset shape;
s27, sintering: heating the rough blank to obtain a compact ceramic element;
s3, polarization: and polarizing the ceramic element to obtain the sodium bismuth titanate-based lead-free piezoelectric ceramic.
5. The method of claim 4, wherein: in the step S21, the Bi is added2O3、Na2CO3、TiO2、BaCO3、La2O3、M2CO3ZnO and Ta2O5And after mixing, adding absolute ethyl alcohol into the mixture for primary ball milling, wherein the primary ball milling time is 22-26 h.
6. The method of claim 4, wherein: in the step S22, the primary presintering temperature is 800-900 ℃, and the heat preservation time is 1-4 h.
7. The method of claim 4, wherein: in the step S23, adding absolute ethanol to the powder after the primary pre-sintering for secondary ball milling, wherein the time of the secondary ball milling is 22h-26 h.
8. The method of claim 4, wherein: in the step S24, the secondary pre-sintering temperature is 820-920 ℃, and the heat preservation time is 1-4 h.
9. The method of claim 4, wherein: in the step S25, the anhydrous ethanol is added to the powder after the secondary pre-sintering for three ball milling, and the time of the three ball milling is 22h to 26 h.
10. The method of claim 4, wherein: in the step S27, the sintering temperature is 1100-1220 ℃, and the heat preservation time is 2-6 h.
11. The method of claim 4, wherein: before the polarization step, silver coating is respectively carried out on two sides of the ceramic element, and then silver firing is carried out;
the silver firing temperature is 400-600 ℃, and the heat preservation time is 20-40 min.
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