CN113651614A - Ceramic material with high and thermally stable piezoelectric properties for collecting piezoelectric energy and preparation thereof - Google Patents

Ceramic material with high and thermally stable piezoelectric properties for collecting piezoelectric energy and preparation thereof Download PDF

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CN113651614A
CN113651614A CN202110802608.6A CN202110802608A CN113651614A CN 113651614 A CN113651614 A CN 113651614A CN 202110802608 A CN202110802608 A CN 202110802608A CN 113651614 A CN113651614 A CN 113651614A
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侯育冬
于肖乐
郑木鹏
朱满康
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Beijing University of Technology
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Abstract

A ceramic material with high and thermally stable piezoelectric properties for collecting piezoelectric energy and a preparation method thereof belong to the field of piezoelectric ceramic materials. The material composition is xPb (Zn)1/3Nb2/3)O3‑(1‑x)Pb(HfyTi(1‑y))O3X is 0.05 to 0.20, and y is 0.45 to 0.50. The preparation method adopts a high-temperature solid-phase reaction method, and ZnO and Nb are firstly mixed2O5Calcination synthesis of ZnNb2O6Then adding other raw materials, wet grinding, drying, calcining, granulating, press forming and sintering. The piezoelectric ceramic material provided by the invention has high piezoelectric constant, excellent temperature stability and stable power generation capacity in a wide temperature range, can meet the application requirements of a piezoelectric energy collector in the wide temperature range or at high temperature, and has remarkable social significance and application value.

Description

Ceramic material with high and thermally stable piezoelectric properties for collecting piezoelectric energy and preparation thereof
Technical Field
The invention belongs to the field of piezoelectric ceramic materials, and particularly relates to a piezoelectric ceramic material which is applied to piezoelectric energy collection and has high and thermally stable piezoelectric charge constants in a wide temperature range and a preparation method thereof.
Background
With the vigorous development of the big data era, countless wireless micro sensors are put into use for data acquisition and transmission and intelligent monitoring. However, the conventional battery used in the wireless micro sensor needs to be replaced irregularly due to limited service life, which causes a great deal of manpower and material resource consumption and resource waste. In particular, the upper limit of the working temperature of the wireless micro-sensor in special fields such as aerospace, oil and gas exploration and the like reaches 200 ℃ and even 300 ℃, which makes the work of replacing the battery for the second time extremely difficult or difficult. The piezoelectric energy collector can capture the ubiquitous mechanical vibration energy in the environment for clean power generation, and is considered as the most promising candidate for long-term power supply of the wireless micro-sensor. Piezoelectric materials with high curie temperature, high and temperature stable piezoelectric charge constants are ideal candidates for constructing piezoelectric energy collectors with high power generation capability and applicable in wide temperature regions.
At present, relaxed PbTiO3(PT for short) based piezoelectric single crystal (piezoelectric charge constant d)33>1000pC/N) and commercial soft Pb (Zr, Ti) O3(PZT for short) piezoelectric ceramics (d)33>500pC/N) has become the most widely used piezoelectric material in piezoelectric energy harvesters due to the high piezoelectric charge constant. However, the high-performance PT-based piezoelectric single crystal and soft PZT are respectively caused by inherent low ferroelectric phase transition temperature (60-120 ℃) and low Curie temperature Tc(150-260 ℃), the safe use temperature of the piezoelectric ceramic is respectively limited below 150 ℃ and 200 ℃, and the piezoelectric performance can be seriously degraded or even disappeared due to depolarization when the temperature is too high, so that the application at the temperature of more than 200 ℃ can not be met. Commercial hard PZT piezoelectric ceramics have a Curie temperature of generally more than 300 ℃ and a stable piezoelectricity of 200 ℃ or more, but have a weak piezoelectricity (d)33Less than 400pC/N) is not suitable for preparing a piezoelectric energy collector with high power generation characteristic. From a high characteristic temperature Pb (Zn)1/3Nb2/3)O3Classical 0.2PZN-0.8PZT (PZN-PZT for short)[1]Curie temperature (T) of ternary system piezoceramic materialc330 ℃ C. and a piezoelectric stability comparable to that of hard PZT, and room temperature piezoelectricity (d)33400pC/N) is superior to hard PZT, but PZN-PZT piezoelectric properties are still weaker compared to soft PZT. Therefore, the piezoelectric ceramic material with high and thermally stable piezoelectric constant at room temperature to more than 200 ℃ is developed and has important significance for promoting the development of piezoelectric materials and the application of devices.
The invention designs and utilizes a high-temperature solid-phase reaction method to prepare xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3(abbreviation of xPnN- (1-x) PHyT(1-y)) A ternary system piezoelectric ceramic material. Wherein, the optimal PZN-PHT piezoceramic material not only has high Curie temperature and room temperature piezoelectricity, but also keeps high and stable piezoelectric charge constant (d) in an ultra-wide temperature region of 10-285 DEG C33>500pC/N), the excellent comprehensive performance of which is far superior to the prior commercial PZT piezoelectric ceramics and the reported PZN-PZT ternary system piezoelectric material; meanwhile, the cantilever beam type piezoelectric energy collector manufactured by the optimal sample keeps stable output current density at 25-250 ℃. So far, the excellent piezoelectric performance and temperature stability of the system of the patent is not reported.
[1]X.Yu,Y.Hou,M.Zheng,M.Zhu,Multiscale Heterogeneity Strategy in Piezoceramics for Enhanced Energy Harvesting Performances,ACS Applied Materials&Interfaces,2021,13(15):17800-17808.
Disclosure of Invention
The invention aims to obtain a piezoelectric material xPZN- (1-x) PH with high Curie temperature and high and temperature-stable piezoelectric charge constantyT(1-y)Therefore, a solid material foundation is laid for constructing the piezoelectric energy collector with high power generation characteristic in a wide temperature area.
The material of the present invention is characterized by xpB (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Abbreviated as xPZN- (1-x) PHyT(1-y)The most preferable piezoelectric ceramic in the system of 0.05. ltoreq. x.ltoreq.0.20 and 0.45. ltoreq. y.ltoreq.0.50, preferably 0.075 and 0.49 has a high Curie temperature of 319 ℃ and a high piezoelectricity (d is 10 to 285 ℃.) (33509 to 588pC/N) at room temperature d33As a basis, in situ d33Fluctuation ratio of not more than + -10%, and in-situ d at 300 deg.C33Also 452pC/N are larger; the cantilever beam type piezoelectric energy collector assembled by the optimal sample can keep stable output current density (31-32.5 muA/cm) within 10-285 DEG C2)。
The preparation method of the ceramic material with high and thermally stable piezoelectric properties in a wide temperature zone is characterized by being prepared by a high-temperature solid-phase reaction method, and specifically comprises the following steps:
(1) synthesis of ZnNb2O6Precursor, weighing ZnO and Nb according to stoichiometric ratio2O5Putting the weighed raw materials into a ball milling tank, and putting the ball milling tank on a planetary ball mill for ball milling for 12 hours by taking absolute ethyl alcohol as a medium; drying the slurry obtained after ball milling at 100 ℃, calcining the dried slurry at 1000 ℃ for 4 hours in air atmosphere, and cooling the calcined slurry to room temperature along with the furnace;
(2) according to xPN- (1-x) PHyT(1-y)(x is more than or equal to 0.05 and less than or equal to 0.20 and y is more than or equal to 0.45 and less than or equal to 0.50) respectively weighing Pb in corresponding stoichiometric ratio of the piezoelectric ceramic material3O4、ZnNb2O6、HfO2、TiO2Putting the weighed raw materials into a ball milling tank, placing the ball milling tank on a horizontal ball mill for ball milling for 24 hours by taking absolute ethyl alcohol as a ball milling medium, and drying the obtained mixture at 100 ℃;
(3) putting the dried powder into a sealed alumina crucible, calcining the powder in an air atmosphere at 800-900 ℃, preferably 850 ℃, keeping the temperature for 2h, and cooling the powder to room temperature along with the furnace;
(4) putting the calcined product into a ball milling tank, placing the ball milling tank on a horizontal ball mill for ball milling for 24 hours by taking absolute ethyl alcohol as a ball milling medium, and drying the obtained slurry at 100 ℃;
(5) adding a polyvinyl alcohol (PVA) solution binder into the dried powder, pressing the powder under 100MPa of uniaxial pressure to prepare a ceramic biscuit, and carrying out glue removal treatment on the biscuit body at 560 ℃ for 3 h;
(5) and sintering the biscuit subjected to the binder removal treatment at 950-1100 ℃, preferably 1050 ℃, preserving the heat for 2 hours, and cooling to room temperature along with the furnace.
And (3) polishing the surface of the sintered piezoelectric ceramic piece, sintering and infiltrating a silver electrode, and polarizing for 30min in silicone oil at 120 ℃ under the voltage of 4 kV/mm. And (5) after aging for 24 hours at room temperature, testing the electrical property of the sample.
Wherein, the optimal sample composition for obtaining the pure perovskite structure is that x/y is 0.075/0.49. The dielectric temperature spectrum test shows that the Curie temperature of the ceramic material is 319 ℃ when x/y is 0.075/0.49; through in-situ temperature change and quasi-static d33Test, piezoelectric charge constant d at 25 ℃33540 pC/N; at room temperature d33On the basis of d within 10-285 DEG C33The fluctuation rate is less than +/-10% and is kept at the amplitude of 509-588 pC/N.
Compared with the prior art, the invention has the following advantages:
(1) the optimal PZN-PHT piezoelectric material has high Curie temperature and room temperature piezoelectricity, and is superior to the current commercial PZT piezoelectric ceramic and the reported PZN-PZT piezoelectric ceramic.
(2) The optimal PZN-PHT piezoelectric material in the invention keeps a high and stable piezoelectric charge constant in a wide temperature range, which is superior to the reported commercial PZT and PZN-PZT materials.
Drawings
Fig. 1 shows the dielectric temperature spectrum of a ceramic material in which x/y is 0.05/0.49(PHT-1), x/y is 0.075/0.49(PHT-2), x/y is 0.10/0.49(PHT-3), x/y is 0.125/0.48(PHT-4), and x/y is 0.20/0.48(PHT-5) in an embodiment of the present invention.
FIG. 2 shows the room temperature d of ceramic materials with x/y of 0.05/0.49(PHT-1), x/y of 0.075/0.49(PHT-2), x/y of 0.10/0.49(PHT-3), x/y of 0.125/0.48(PHT-4), and x/y of 0.20/0.48(PHT-5) in the practice of the present invention33And Curie temperature TcComparison with commercial PZT piezoceramic materials and reported PZN-PZT[1-2]。
FIG. 3 shows the (a) in-situ d of ceramic material (PHT-5) with x/y being 0.05/0.49(PHT-1), x/y being 0.075/0.49(PHT-2), x/y being 0.10/0.49(PHT-3), x/y being 0.125/0.48(PHT-4), and x/y being 0.20/0.48(PHT-5) in the present invention33Temperature dependence, (b) temperature stability; (c) in situ temperature change d of optimum x/y ═ 0.075/0.49(PHT-2) piezoceramics with reported commercial PZT and PZN-PZT33Comparison[1-2]。
FIG. 4(a) is a schematic diagram of an in-situ temperature-varying cantilever beam type piezoelectric energy collection and test system[1](ii) a (b) The izod energy collector assembled from the optimal PZN-PHT sample outputs current density peak to peak values at different temperatures.
[1]X.Yu,Y.Hou,M.Zheng,M.Zhu,Multiscale Heterogeneity Strategy in Piezoceramics for Enhanced Energy Harvesting Performances,ACS Applied Materials&Interfaces,2021,13(15):17800-17808.
[2]F.Li,Z.Xu,X.Wei,X.Yao,Temperature-and dc bias field-dependent piezoelectric effect of soft and hard lead zirconate titanate ceramics,Journal of Electroceramics,2009,24(4):294-299.
Detailed Description
The essential features and the significant advantages of the invention are further clarified by the following examples. It should be noted that the invention is in no way limited to the embodiments presented.
Example 1:
chemical formula of material xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein x is 0.05 and y is 0.49. Firstly, ZnO and Nb are added2O5Weighing according to stoichiometric ratio, ball-milling for 12h, drying the slurry obtained after ball-milling at 100 ℃, calcining for 4h at 1000 ℃ in air atmosphere to obtain ZnNb2O6. Then weighing Pb according to stoichiometric ratio3O4、ZnNb2O6、HfO2、TiO2And ball milling is carried out in an absolute ethyl alcohol medium for 24 hours. The obtained slurry is calcined for 2 hours at 850 ℃ after being dried. Ball-milling the calcined product in an absolute ethyl alcohol medium for 24 hours, drying the slurry, adding 5 wt.% of PVA binder, pressing into a ceramic biscuit, carrying out degumming treatment at 560 ℃, and sintering at 1050 ℃ for 2 hours. And printing and sintering the sintered ceramic wafer, infiltrating a silver electrode, and polarizing for 30min in silicone oil at 120 ℃ under the voltage of 4kV/mm to obtain the corresponding piezoelectric ceramic material.
Example 2:
chemical formula of material xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein x is 0.075 and y is 0.49. The ceramic material was prepared as in example 1.
Example 3:
chemical formula of material xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein x is 0.10 and y is 0.49. The ceramic material was prepared as in example 1.
Example 4:
chemical formula of material xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein x is 0.125 and y is 0.48. The ceramic material was prepared as in example 1.
Example 5:
chemical formula of material xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein x is 0.20 and y is 0.48. The ceramic material was prepared as in example 1.
TABLE 1 Properties of the above examples
Figure BDA0003165255740000061

Claims (4)

1. A ceramic material having both high and thermally stable piezoelectric properties for piezoelectric energy harvesting, characterized in that the ceramic material has a chemical composition formula represented by: xPb (Zn)1/3Nb2/3)O3-(1-x)Pb(HfyTi(1-y))O3Wherein the value of x is 0.05-0.20, the value of y is 0.45-0.50, and preferably the value of x is 0.075 and the value of y is 0.49.
2. A piezoelectric energy harvesting ceramic material having both high and thermally stable piezoelectric properties according to claim 1, wherein the optimum piezoelectric ceramic in the system of x-0.075 and y-0.49 has a high Curie temperature of 319 ℃ and a high piezoelectricity d in the range of 10 to 285 ℃33509 to 588pC/N at room temperature d33As a basis, in situ d33The fluctuation rate is not more than +/-10%, and the cantilever beam type piezoelectric energy collector assembled by the optimal sample can keep stable output current density of 31-32.5 mu A/cm at the temperature of 25-250 DEG C2。
3. A method for preparing the ceramic material of claim 1, wherein the ceramic material is prepared by the steps of:
(1) synthesis of ZnNb2O6Precursor, weighing ZnO and Nb according to stoichiometric ratio2O5Putting the weighed raw materials into a ball milling tank, and putting the ball milling tank on a planetary ball mill for ball milling for 12 hours by taking absolute ethyl alcohol as a medium; drying the slurry obtained after ball milling at 100 ℃, calcining the dried slurry at 1000 ℃ for 4 hours in air atmosphere, and cooling the calcined slurry to room temperature along with the furnace;
(2) weighing Pb according to stoichiometric ratio3O4、ZnNb2O6、HfO2、TiO2Putting the weighed raw materials into a ball milling tank, placing the ball milling tank on a horizontal ball mill for ball milling for 24 hours by taking absolute ethyl alcohol as a ball milling medium, and drying the obtained mixture at 100 ℃;
(3) putting the dried material into a closed alumina crucible, calcining for 2h at 850 ℃, and then adding absolute ethyl alcohol to perform secondary ball milling for 24 h;
(3) adding a polyvinyl alcohol solution binder into the powder obtained by secondary ball milling, pressing into a ceramic biscuit, and heating at 560 ℃ for binder removal for 3 hours;
(4) and placing the biscuit body after the binder removal in a closed alumina crucible, sintering for 2h at 1050 ℃, and cooling to room temperature along with the furnace.
4. Use of the ceramic material according to claim 1 for a piezoelectric energy harvester.
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Citations (11)

* Cited by examiner, † Cited by third party
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