CN114276133A - Piezoelectric ceramic material, application of piezoelectric ceramic material and preparation method of piezoelectric ceramic material - Google Patents

Piezoelectric ceramic material, application of piezoelectric ceramic material and preparation method of piezoelectric ceramic material Download PDF

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CN114276133A
CN114276133A CN202210089005.0A CN202210089005A CN114276133A CN 114276133 A CN114276133 A CN 114276133A CN 202210089005 A CN202210089005 A CN 202210089005A CN 114276133 A CN114276133 A CN 114276133A
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赵海燕
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Tangshan Normal University
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Abstract

The application discloses a piezoelectric ceramic material, application of the piezoelectric ceramic material and a preparation method of the piezoelectric ceramic material. The piezoceramic material is represented by formula I, namely zBiScO3‑yPb(Zn1/3Nb2/3)O3‑xPbTiO3Wherein x, y and z represent PbTiO respectively3、Pb(Zn1/3Nb2/3)O3And BiScO3X is more than or equal to 0.58 and less than or equal to 0.64, y is more than 0 and less than or equal to 0.05, and z is 1-x-y; the piezoelectric charge constant of the piezoceramic material is d at 300 DEG C33426 and 655 pC/N. The piezoelectric ceramic material can be applied to a piezoelectric energy collecting device in the high-temperature field, and through testing, the piezoelectric ceramic material in the applicationThe ceramic material can meet the requirement of a self-powered microelectronic device on electric energy in the field of 300 ℃ ultrahigh temperature.

Description

Piezoelectric ceramic material, application of piezoelectric ceramic material and preparation method of piezoelectric ceramic material
Technical Field
The invention relates to the field of high-temperature piezoelectric ceramic materials, in particular to a piezoelectric ceramic material, application of the piezoelectric ceramic material and a preparation method of the piezoelectric ceramic material.
Background
With the continuous progress of the piezoelectric energy collection technology, the piezoelectric energy collector converts vibration energy widely existing in the environment into electric energy, and can continuously supply power to small-sized low-power-consumption electronic equipment, so that the application capability of related electronic equipment in the fields of wireless sensing, data transmission, structural health monitoring and the like is improved.
Pb (Zr, Ti) O which has been commercially used at present3The Curie temperature of the (PZT) system piezoelectric material is about 180-386 ℃, and the PZT system piezoelectric material can meet the service requirement of piezoelectric energy collection application in the conventional environment below 200 ℃. In some special high-temperature environments, such as the fields of aerospace, oil exploration, nuclear industry and the like, due to the fact that the working environment temperature is high (200-300 ℃ and even higher), the depolarization temperature of the existing PZT piezoelectric material is low, and the high-temperature service requirement cannot be met. The development of a piezoelectric material for energy collection having high performance at high temperature is one of the technical keys to be solved urgently in the field.
Disclosure of Invention
In view of the problems in the background art, the present disclosure is directed to a piezoelectric ceramic material, a use of the piezoelectric ceramic material, and a method for preparing the same.
In order to achieve the above objects, the present disclosure provides a piezoelectric ceramic material, which is represented by formula I,
zBiScO3-yPb(Zn1/3Nb2/3)O3-xPbTiO3formula I
Wherein x, y and z represent PbTiO, respectively3、Pb(Zn1/3Nb2/3)O3And BiScO3X is more than or equal to 0.58 and less than or equal to 0.64, y is more than 0 and less than or equal to 0.05, and z is 1-x-y;
the piezoelectric charge constant of the piezoceramic material is d at 300 DEG C33426 and 655 pC/N.
In some embodiments, the preferred composition x is 0.60, y is 0.05, and z is 0.35.
In some embodiments, the piezoceramic material has a piezoelectric charge constant d at 300 ℃33=655pC/N。
In some embodiments, the piezoelectric ceramic material is used in a piezoelectric energy harvesting device in the high temperature field.
In some embodiments, a piezoceramic material with the composition x being 0.60, y being 0.05 and z being 0.35 is preferred, and the piezoceramic material has the piezoelectric charge constant d at 300 ℃ in the application of the piezoceramic material in a piezoelectric energy collection device in the high-temperature field33655 pC/N; at 300 ℃, the peak value of the open-circuit voltage of the prepared piezoelectric energy collector is 17V; at 300 ℃, the generated power density of the prepared piezoelectric energy collector is 418 muW/cm3(ii) a The prepared piezoelectric energy harvester was charged for 40s at 300 ℃ to a 10 muF, 16V commercial electrolytic capacitor, which was charged to 7V across the capacitor when full.
In some embodiments, the method for preparing the piezoelectric ceramic material comprises the following steps: the method comprises the following steps: ZnO and Nb are used as raw materials2O5Weighing according to the chemical molar ratio, ball-milling for 4h in a horizontal ball mill by taking absolute ethyl alcohol as a medium, and then calcining for 4h at the high temperature of 1000 ℃ to synthesize ZnNb2O6A precursor; step two: with ZnNb2O6The precursor is zinc and niobium source, and the raw material Pb is3O4、TiO2、Bi2O3、Sc2O3And ZnNb2O6Weighing the piezoelectric ceramic material according to the chemical molar ratio of elements in the piezoelectric ceramic material, putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium to perform ball milling for 24 hours to obtain powder; step three: calcining the dried powder, cooling to room temperature along with the furnace, and adding absolute ethyl alcohol to perform secondary ball milling for 24 hours; step four: adding a binder into the powder obtained by secondary ball milling, pressing into a ceramic biscuit body, and heating for removing the binder; step five: sintering the biscuit body after the binder removal treatment, cooling the biscuit body to room temperature along with a furnace, and burying the ceramic biscuit body by using powder of corresponding components as protective powder during sintering; step six: and polishing the prepared ceramic wafer, sintering and infiltrating a silver electrode, and artificially polarizing to obtain the piezoelectric ceramic material.
In some embodiments, in step three, the calcination temperature is 750 ℃ to 850 ℃ and the holding time is 2 h.
In some embodiments, in the fifth step, the sintering temperature is 1050 ℃ to 1150 ℃, and the holding time is 2 hours.
In some embodiments, in step six, the artificial polarization temperature is 120 ℃, the polarization voltage is 4.5kV/mm, and the polarization time is 30 min.
The beneficial effects of this disclosure are as follows:
the piezoceramic material in the application can meet the requirement of a self-powered microelectronic device on electric energy in the field of 300 ℃ ultrahigh temperature.
Drawings
Fig. 1 is an XRD pattern of the piezoelectric ceramic material of example 1 and example 2.
Fig. 2 is an SEM image of the piezoceramic materials of example 1 and example 2.
Fig. 3 is a graph of the hysteresis loop of the piezoelectric ceramic materials of examples 1 and 2.
FIG. 4 is a graph showing the piezoelectric charge constant d at 300 ℃ measured by the in-situ quasi-static method for the piezoelectric ceramic materials of example 1, example 2 and comparative example 133
FIG. 5 is a graph of the output voltage signals of the piezoceramic materials of examples 1 and 2 assembled into a single-layer cantilever beam energy harvester under 1g acceleration excitation at 300 ℃.
FIG. 6 is a graph of the power density of a single layer of the cantilever beam energy collector fabricated from the piezoceramic materials of examples 1 and 2 under acceleration excitation of 1g at 300 ℃ as a function of the load resistance.
FIG. 7 shows the results of a single-layer energy collector fabricated from the piezoceramic materials of examples 1 and 2 charging a 10 μ F, 16V commercial electrolytic capacitor under 1g acceleration at a test temperature of 300 ℃: (a) a graph of the variation of the voltage across the capacitor with charging time; (b) graph of voltage values across the capacitor when fully charged for 40 s.
Detailed Description
[ piezoceramic materials ]
The piezoceramic material is represented by the formula I,
zBiScO3-yPb(Zn1/3Nb2/3)O3-xPbTiO3formula I
Wherein x, y and z represent PbTiO, respectively3、Pb(Zn1/3Nb2/3)O3And BiScO3X is more than or equal to 0.58 and less than or equal to 0.64, y is more than 0 and less than or equal to 0.05, and z is 1-x-y.
In some embodiments, at 300 ℃The piezoelectric charge constant of the piezoelectric ceramic material is d33426 and 655 pC/N.
In some embodiments, in formula I, it is preferable that the composition x is 0.60, y is 0.05, and z is 0.35 at 300 ℃, and the piezoelectric charge constant of the piezoceramic material is d33=655pC/N。
In some embodiments, the piezoelectric ceramic material in formula I preferably has a composition x of 0.60, y of 0.05, and z of 0.35, has high piezoelectric properties at 300 ℃ and ultra-high temperature, and has a piezoelectric charge constant of 655pC/N when tested in situ, well above which the matrix is 0.36BiScO3-0.64PbTiO3(0.36 BS-0.64PT) of d33The value of 579pC/N, high piezoelectricity provides guarantee for advanced high temperature piezoelectric device application. The invention is in BiScO3-PbTiO3Cheap PZN is introduced into (BS-PT) matrix material, so that BiScO containing expensive Sc element in original component can be reduced3The proportion of (A) is higher than the proportion of (B), so that the production cost is obviously reduced, the large-scale industrial production and application are facilitated, and the economic benefit and the social value are obvious.
[ application of piezoceramic material in piezoelectric energy collecting device in high temperature field ]
In the present application, a ceramic material of formula I, where x is 0.60, y is 0.05, and z is 0.35, is selected for application to a single-layer cantilever beam piezoelectric energy collector.
In some embodiments, the piezoceramic material has a piezoelectric charge constant d at 300 ℃33=655pC/N。
In some embodiments, the prepared piezoelectric energy harvester has an open circuit voltage peak to peak of 17V at 300 ℃.
In some embodiments, the piezoelectric energy harvester is prepared to have a generated power density of 418 μ W/cm at 300 deg.C3
In some embodiments, the piezoelectric energy harvester was prepared to charge a 10 μ F, 16V commercial electrolytic capacitor for 40s at 300 ℃, with a voltage of 7V across the capacitor when full.
The piezoelectric material with x being 0.60, y being 0.05 and z being 0.35 in formula I is selected in the application, and the best sample is obtained at 300 ℃ through in-situ testPiezoelectric charge constant d of product33655 pC/N; the single-layer cantilever beam type energy collector is assembled, the peak value of an open-circuit voltage peak is 17V at 300 ℃, and the generated power density is 418 mu W/cm3When the commercial electrolytic capacitor of 10 muF and 16V is charged for 40s, the voltage at two ends is 7V when the capacitor is fully charged, and the requirement of a self-powered microelectronic device on electric energy in the 300 ℃ ultrahigh-temperature field can be met.
[ method for producing piezoelectric ceramic Material ]
The preparation method of the piezoceramic material is used for preparing the piezoceramic material and comprises the following steps: the method comprises the following steps: ZnO and Nb are used as raw materials2O5Weighing according to the chemical molar ratio, ball-milling for 4h in a horizontal ball mill by taking absolute ethyl alcohol as a medium, and then calcining for 4h at the high temperature of 1000 ℃ to synthesize ZnNb2O6A precursor; step two: with ZnNb2O6The precursor is zinc and niobium source, and the raw material Pb is3O4、TiO2、Bi2O3、Sc2O3And ZnNb2O6Weighing the piezoelectric ceramic material according to the chemical molar ratio of elements in the piezoelectric ceramic material, putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium to perform ball milling for 24 hours to obtain powder; step three: calcining the dried powder, cooling to room temperature along with the furnace, and adding absolute ethyl alcohol to perform secondary ball milling for 24 hours; step four: adding a binder into the powder obtained by secondary ball milling, pressing into a ceramic biscuit body, and heating for removing the binder; step five: sintering the biscuit body after the binder removal treatment, cooling the biscuit body to room temperature along with a furnace, and burying the ceramic biscuit body by using powder of corresponding components as protective powder during sintering; step six: and polishing the prepared ceramic wafer, sintering and infiltrating a silver electrode, and artificially polarizing to obtain the piezoelectric ceramic material.
In the third step, the calcining temperature is 750-850 ℃, and the heat preservation time is 2 hours.
In the fifth step, the sintering temperature is 1050-1150 ℃, and the heat preservation time is 2 h.
And step five, sintering the biscuit body after the binder removal treatment, cooling the biscuit body to room temperature along with a furnace, and burying the ceramic biscuit body by taking powder of corresponding components as protective powder during sintering so as to avoid the loss of lead and bismuth elements in the biscuit body due to high-temperature volatilization.
In some embodiments, in step six, the artificial polarization temperature is 120 ℃, the polarization voltage is 4.5kV/mm, and the polarization time is 30 min.
[ test ]
The disclosure is further illustrated with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Example 1
According to the formula zBiScO3-yPb(Zn1/3Nb2/3)O3-xPbTiO3Wherein x is 0.60, y is 0.05, and z is 0.35.
The method comprises the following steps: ZnO and Nb are used as raw materials2O5Weighing according to the chemical molar ratio, ball-milling for 4h in a horizontal ball mill by taking absolute ethyl alcohol as a medium, and then calcining for 4h at the high temperature of 1000 ℃ to synthesize ZnNb2O6A precursor;
step two: with ZnNb2O6The precursor is zinc and niobium source, and the raw material Pb is3O4、TiO2、Bi2O3、Sc2O3And ZnNb2O6Weighing the piezoelectric ceramic material according to the chemical molar ratio of elements in the piezoelectric ceramic material, putting the weighed raw materials into a ball milling tank, putting the ball milling tank into a horizontal ball mill by taking absolute ethyl alcohol as a medium, carrying out ball milling for 24 hours to obtain powder, and drying the powder at the temperature of 100 ℃;
step three: calcining at 850 ℃ for 2h, cooling to room temperature along with the furnace, and adding absolute ethyl alcohol to perform secondary ball milling for 24 h;
step four: adding a binder into the powder obtained by secondary ball milling, pressing into a ceramic biscuit body, and heating for removing the binder;
step five: calcining the biscuit body subjected to the binder removal treatment at 1150 ℃ for 2h for sintering, cooling to room temperature along with a furnace, and burying the ceramic biscuit body by taking powder of corresponding components as protective powder during sintering;
step six: and (3) polishing the prepared ceramic wafer, sintering and infiltrating a silver electrode, and polarizing in silicone oil at 120 ℃ for 30min under the voltage of 4.5kV/mm to obtain the piezoelectric ceramic material.
And assembling the obtained piezoelectric ceramic material into a single-layer cantilever beam type energy collector, and carrying out high-temperature energy collection performance test. The test results are shown in Table 1.
Example 2
According to the formula zBiScO3-xPbTiO3-yPb(Zn1/3Nb2/3)O3Wherein x is 0.61, y is 0.05, and z is 0.34, the same as in example 1.
And assembling the obtained piezoelectric ceramic material into a single-layer cantilever beam type energy collector, and carrying out high-temperature energy collection performance test. The test results are shown in Table 1.
Comparative example 1
Using a matrix of 0.36BiScO3-0.64PbTiO3Assembling to obtain a single-layer cantilever beam type energy collector, and testing the high-temperature energy collection performance. The test results are shown in Table 1.
The XRD patterns of the piezoceramic materials of example 1 and example 2 are shown in fig. 1;
SEM images of the piezoceramic materials of example 1 and example 2 are shown in fig. 2;
the hysteresis loop diagrams of the piezoceramic materials of example 1 and example 2 are shown in FIG. 3;
piezoelectric charge constant d at 300 ℃ of the piezoelectric ceramic materials of example 1, example 2 and comparative example 1 measured by in-situ quasi-static method33See FIG. 4;
the piezoceramic materials of example 1 and example 2 are assembled into a single-layer cantilever beam type energy collector, and the output voltage signal under the acceleration excitation of 1g at 300 ℃ is shown in figure 5;
the piezoceramic materials of example 1 and example 2 are assembled into a single-layer cantilever beam type energy collector, and the power density under the acceleration excitation of 1g at 300 ℃ is shown in a graph 6 along with the change of a load resistance value;
the piezoceramic materials of examples 1 and 2 assembled into a single layer energy harvester when charging a 10 muf, 16V commercial electrolytic capacitor under 1g acceleration excitation at a test temperature of 300 ℃: (a) the voltage variation of the capacitor across the capacitor with charging time is shown in fig. 7; (b) the voltage across the capacitor when charged for 40s is full is shown in figure 7.
Table 1 comparative table of properties of the above examples
Figure BDA0003487422510000071
As can be seen from Table 1, the piezoceramic material of example 1 has a d at 300 ℃33The dielectric ceramic material can reach 655pC/N which is far larger than the base material in the comparative example 1, and in addition, when the piezoelectric ceramic materials in the examples 1 and 2 are applied to a high-temperature piezoelectric energy collector, the energy collection performances of open-circuit voltage peak-to-peak value, power density, electrolytic capacitor charging and the like are far better than the base material. The piezoelectric ceramic material can meet the requirement of a self-powered microelectronic device on electric energy in the 300 ℃ ultrahigh temperature field.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.

Claims (8)

1. A piezoelectric ceramic material is represented by formula I,
zBiScO3-yPb(Zn1/3Nb2/3)O3-xPbTiO3formula I
Wherein x, y and z represent PbTiO, respectively3、Pb(Zn1/3Nb2/3)O3And BiScO3X is more than or equal to 0.58 and less than or equal to 0.64, y is more than 0 and less than or equal to 0.05, and z is 1-x-y;
the piezoelectric charge constant of the piezoceramic material is d at 300 DEG C33426 and 655 pC/N.
2. Piezoceramic material according to claim 1, characterized in that,
the preferred composition x is 0.60, y is 0.05 and z is 0.35
At 300 ℃, the piezoelectric ceramic materialThe piezoelectric charge constant of the material is d33=655pC/N。
3. Use of a piezoceramic material according to any one of claims 1-2 in a piezoelectric energy harvesting device in the field of high temperatures.
4. The piezoceramic material according to claim 3, for use in a piezoelectric energy harvesting device in the high temperature field, characterized in that,
preferably, the composition x is 0.60, y is 0.05, and z is 0.35;
the piezoelectric charge constant of the piezoceramic material is d at 300 DEG C33=655pC/N;
At 300 ℃, the peak value of the open-circuit voltage of the prepared piezoelectric energy collector is 17V;
at 300 ℃, the generated power density of the prepared piezoelectric energy collector is 418 muW/cm3
The prepared piezoelectric energy harvester was charged for 40s at 300 ℃ to a 10 muF, 16V commercial electrolytic capacitor, which was charged to 7V across the capacitor when full.
5. A method for producing a piezoelectric ceramic material, for producing the piezoelectric ceramic material according to claim 1, comprising the steps of:
the method comprises the following steps: ZnO and Nb are used as raw materials2O5Weighing according to the chemical molar ratio, ball-milling for 4h in a horizontal ball mill by taking absolute ethyl alcohol as a medium, and then calcining for 4h at the high temperature of 1000 ℃ to synthesize ZnNb2O6A precursor;
step two: with ZnNb2O6The precursor is zinc and niobium source, and the raw material Pb is3O4、TiO2、Bi2O3、Sc2O3And ZnNb2O6Weighing the piezoelectric ceramic material according to the chemical molar ratio of elements in the piezoelectric ceramic material, putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium to perform ball milling for 24 hours to obtain powder;
step three: calcining the dried powder, cooling to room temperature along with the furnace, and adding absolute ethyl alcohol to perform secondary ball milling for 24 hours;
step four: adding a binder into the powder obtained by secondary ball milling, pressing into a ceramic biscuit body, and heating for removing the binder;
step five: sintering the biscuit body after the binder removal treatment, cooling the biscuit body to room temperature along with a furnace, and burying the ceramic biscuit body by using powder of corresponding components as protective powder during sintering;
step six: and polishing the prepared ceramic wafer, sintering and infiltrating a silver electrode, and artificially polarizing to obtain the piezoelectric ceramic material.
6. The method for producing a piezoelectric ceramic material according to claim 5,
in the third step, the calcining temperature is 750-850 ℃, and the heat preservation time is 2 hours.
7. The method for producing a piezoelectric ceramic material according to claim 5,
in the fifth step, the sintering temperature is 1050-1150 ℃, and the heat preservation time is 2 h.
8. The method for producing a piezoelectric ceramic material according to claim 5,
in the sixth step, the artificial polarization temperature is 120 ℃, the polarization voltage is 4.5kV/mm, and the polarization time is 30 min.
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Application publication date: 20220405