CN116023138B - Leadless piezoelectric ceramic material applied to energy collection in wide temperature range and preparation method thereof - Google Patents
Leadless piezoelectric ceramic material applied to energy collection in wide temperature range and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000010248 power generation Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims description 14
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- 238000010361 transduction Methods 0.000 claims description 11
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- 239000011230 binding agent Substances 0.000 claims description 8
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
A leadless piezoelectric ceramic material applied to energy collection in a wide temperature range and a preparation thereof belong to the field of piezoelectric ceramic materials. The matrix chemical composition of the ceramic material is (1-x) (K 0.48 Na 0.52 )NbO 3 ‑x(Bi 0.5 Li 0.5 )ZrO 3 A material system wherein x has a value of 0.00 to 0.04, preferably wherein x has a value of 0.035. And (3) mixing according to the corresponding metering ratio, and preparing a sample by adopting the steps of wet grinding, drying, granulating, compression molding and sintering. The invention realizes that the lead-free piezoelectric energy collector has excellent power generation characteristics in a wide temperature area, and has great propulsion effect on piezoelectric energy collection technology industry.
Description
Technical Field
The invention belongs to the field of piezoelectric ceramic materials, and particularly relates to a lead-free piezoelectric ceramic material applied to energy collection in a wide temperature range and preparation thereof.
Background
Although the technology for collecting and utilizing ecological energy sources such as solar energy, wind energy and tidal energy is mature, the technology is obviously influenced by natural environment, whereas the piezoelectric energy collecting technology based on the positive piezoelectric effect is less influenced by natural environment, and has the advantages of high power density, small volume, easiness in manufacturing, integration and the like, and is widely paid attention to and rapidly developed in recent years.
The core of the piezoelectric energy collection device is a piezoelectric material, which generates electric charge under the action of external force, and the generated energy density (u) can be expressed as:
wherein d is a piezoelectric charge constant, g is a piezoelectric voltage constant, F is an acting force, and A is a material stress area. Therefore, a high energy density is mainly determined by a high value of the transduction coefficient d×g. In addition, g is closely related to d and dielectric constant (ε), which can be expressed as:
wherein ε 0 For vacuum dielectric constant, ε r Is the relative dielectric constant. Thus, in connection with equations (1) and (2), the transduction coefficient may also be expressed as:
in addition, piezoelectric energy harvesting devices often operate in harsh high temperature environments, which requires that the piezoelectric material not only have a high transduction coefficient, but also have good temperature insensitivity, for which a piezoelectric material system should be constructed in which d and ε are synergistically stable over a wide temperature region.
At present, the high-temperature piezoelectric ceramic material with a perovskite structure is mainly a lead-based piezoelectric material, and the toxicity of lead can cause serious harm to the ecological environment and human health, so that the search for a lead-free piezoelectric ceramic material capable of stably working in a wide temperature area is a research hot spot at present. Potassium sodium niobate based (KNN) lead-free piezoelectric ceramics are considered as potential candidates for wide temperature range applications due to their desirable piezoelectric properties and high curie temperatures. However, KNN-based ceramics generally exhibit excellent piezoelectric properties at the polymorphic phase boundaries, which are affected by both composition and temperature, and thus the piezoelectric properties of KNN are sensitive to temperature changes. Although the temperature stability of the KNN piezoelectric constant can be improved by a complex phase strategy, a multilayer structure design and other methods, the piezoelectric constant and the dielectric constant are required to be kept synergistically stable in a wide temperature region to realize a temperature insensitive transduction coefficient. Therefore, in order to construct the KNN-based piezoelectric ceramic material applied to energy collection in a wide temperature area, the invention constructs a dispersion orthorhombic-tetragonal (O-T) polymorphic phase boundary through fine component regulation, so that d and epsilon realize cooperative stabilization in the wide temperature area, and the piezoelectric energy collection of the lead-free ceramic material in the wide temperature area is realized by obtaining a temperature insensitive transduction coefficient.
Disclosure of Invention
The invention aims to provide a lead-free piezoelectric ceramic material which can be applied to a wide-temperature-range internal pressure electric energy collector and a preparation method thereof, and the prepared lead-free piezoelectric ceramic has high and temperature-insensitive transduction coefficients. And the power generation characteristic in a wide temperature area is characterized by the cantilever beam type energy collector. In order to realize stable energy collection performance in a wide temperature area, the invention constructs a dispersion orthogonal-tetragonal (O-T) polymorphic phase boundary through component regulation, so that d and epsilon realize cooperative stability in the wide temperature area, thereby obtaining a temperature insensitive electromechanical conversion coefficient and realizing wide temperature piezoelectric energy collection of the lead-free ceramic material.
In order to achieve the above object, the present invention adopts the following technical scheme.
The lead-free piezoelectric material with wide temperature area power generation characteristics is characterized in that the chemical composition of a matrix is as follows: (1-x) (K) 0.48 Na 0.52 )NbO 3 -x(Bi 0.5 Li 0.5 )ZrO 3 The value of x is from 0.00 to 0.04, with material systems in which the value of x is 0.035 being preferred.
The lead-free piezoelectric ceramic material with the wide temperature area power generation characteristic is prepared by a common solid phase process and specifically comprises the following steps:
(1) According to the formula (1-x) (K) 0.48 Na 0.52 )NbO 3 -x(Bi 0.5 Li 0.5 )ZrO 3 The molar ratio of each element is measured and raw material K is weighed 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 Wherein, the value of x is 0.00-0.04;
(2) Putting the weighed raw materials into a ball milling tank, and ball milling for 24 hours in a horizontal mill by taking absolute ethyl alcohol as a medium; drying the slurry obtained after ball milling, calcining the dried powder at 850 ℃ for 6 hours, and cooling along with a furnace;
(3) Carrying out secondary ball milling and drying on the powder cooled in the step (2), and grinding and granulating the dried powder; preferably, PVA is adopted for granulation, and a polyvinyl alcohol aqueous solution with the mass concentration of 5% is adopted as a binder for granulation, wherein the binder is used in an amount of 1ml for every 10g of ceramic powder.
(4) And (3) standing the powder obtained by granulating in the step (3), performing compression molding (such as molding under the pressure of 100 MPa) to obtain a green body, performing glue discharging treatment (preferably, performing glue discharging treatment on the green body at 560 ℃), finally sintering at 1140 ℃, preserving heat for 3 hours, and cooling to room temperature along with a furnace to obtain the target material.
The prepared leadless piezoelectric material is subjected to surface polishing treatment, microstructure test, silver electrode coating and artificial polarization (such as in silicone oil at 100deg.C, at 40kV.cm) -1 Polarization for 30min at the voltage of (2) and aging for 24h at room temperature), and testing the piezoelectric performance of the sample. And finally, testing the variable-temperature power generation performance through the cantilever beam structure energy collector.
Through the fine component design and sintering process, a dense ceramic sample is obtained, wherein the preferred optimum sample composition is: 0.965 (K) 0.48 Na 0.52 )NbO 3 -0.035(Bi 0.5 Li 0.5 )ZrO 3 Having a diffuse O-T polymorphic phase boundary with a phase boundary ratio O: t=49.4: 59.6, the material performance can reach: p (P) max =19.22μC/cm 2 ,P r =14.67μC/cm 2 ,d 33 Rate of change (. DELTA.d) in the range of 25 to 80 DEG C 33 ) Less than 7%; epsilon r Rate of change (. DELTA.. Epsilon.) in the range of 25 to 80 DEG C r ) Less than 11.6%; the change rate of the transduction coefficient d.times.g in the range of 25 to 80 ℃ is [. DELTA. (d.times.g)]Less than 10%; power generation performance at room temperature 25 ℃): power P 25℃ Power generation performance at 80 ℃ =46.7 μw: power P 80℃ =35.1 μw, which can meet the usage requirements of the energy harvesting device.
Compared with the prior art, the invention has the following beneficial effects:
(1) The lead-free piezoelectric ceramic material for collecting energy in a wide temperature range has a temperature insensitive transduction coefficient d multiplied by g, has excellent power generation characteristics in a wide temperature range, and is a potential lead-free piezoelectric ceramic material applied to an energy collecting device in the wide temperature range.
(2) The leadless piezoelectric ceramic material has stable structure, simple preparation method, low cost and easy operation. The invention is applied to piezoelectric energy collection devices, can effectively recycle waste energy, is energy-saving, environment-friendly and safe, and has remarkable economic and social values.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ceramic sample of different compositions according to the present invention.
FIG. 2 shows the dielectric temperature curves of ceramic samples of different compositions according to the present invention.
FIG. 3 is a scanning electron microscope image of a ceramic sample of different composition according to the present invention.
FIG. 4 shows the hysteresis loops of ceramic samples of different compositions according to the invention.
FIG. 5 is a graph showing the relationship between piezoelectric constant and normalized piezoelectric constant of ceramic samples of different compositions according to the present invention with temperature.
FIG. 6 is a graph showing the relationship between the transduction coefficient and normalized transduction coefficient of ceramic samples of different compositions according to the present invention with temperature.
FIG. 7 is a graph comparing generated power data of ceramic samples of different compositions of the present invention at 25℃and 80 ℃.
Detailed Description
The essential features and significant advantages of the invention are further illustrated by the following examples. It should be noted that the invention is in no way limited to the embodiments presented.
Example 1:
according to chemical formula 1 (K) 0.48 Na 0.52 )NbO 3 -0(Bi 0.5 Li 0.5 )ZrO 3 Weighing raw material K 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 And ball milled in ethanol for 24 hours. Drying the mixture at 850 DEG CCalcining for 6 hours; and (3) performing secondary ball milling and granulating, performing compression molding under 100MPa to obtain a green body, and performing glue discharging treatment on the green body at 560 ℃. Finally sintering at 1140 ℃ and preserving heat for 3 hours to obtain the target material.
Example 2:
according to the chemical formula 0.975 (K) 0.48 Na 0.52 )NbO 3 -0.025(Bi 0.5 Li 0.5 )ZrO 3 Weighing raw material K 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 Otherwise, the same as in example 1 was conducted.
Example 3:
according to chemical formula 0.965 (K) 0.48 Na 0.52 )NbO 3 -0.035(Bi 0.5 Li 0.5 )ZrO 3 Weighing raw material K 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 Otherwise, the same as in example 1 was conducted.
Example 4:
according to the chemical formula 0.96 (K) 0.48 Na 0.52 )NbO 3 -0.04(Bi 0.5 Li 0.5 )ZrO 3 Weighing raw material K 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 Otherwise, the same as in example 1 was conducted.
Table 1 comparison of the performance of the above examples
Note that: the temperature range is 25-80 ℃.
Claims (1)
1. The application of the leadless piezoelectric ceramic material is applied to energy collection in a wide temperature range of 25-80 ℃, and the matrix chemical composition of the leadless piezoelectric ceramic material is as follows: (1-x) (K) 0.48 Na 0.52 )NbO 3 -x(Bi 0.5 Li 0.5 )ZrO 3 A material system wherein x has a value of 0.035; the material system has a dispersion orthorhombic-tetragonal (O-T) polymorphic phase boundary, and the phase structure proportion is O: t=49.4: 50.6;
the material performance reaches: p (P) max =19.22μC/cm 2 ,P r =14.67μC/cm 2 ,d 33 Rate of change Δd in the range of 25 to 80 DEG C 33 Less than 7%; epsilon r The rate of change delta epsilon in the range of 25 to 80 DEG C r Less than 11.6%; the change rate delta (d multiplied by g) of the transduction coefficient d multiplied by g in the range of 25-80 ℃ is less than 10%; power generation performance at room temperature 25 ℃): power P 25℃ Power generation performance at 80 ℃ =46.7 μw: power P 80℃ =35.1 μw, meeting the usage requirements of the energy harvesting device;
the preparation method specifically comprises the following steps:
(1) According to the formula (1-x) (K) 0.48 Na 0.52 )NbO 3 -x(Bi 0.5 Li 0.5 )ZrO 3 The molar ratio of each element is measured and raw material K is weighed 2 CO 3 、Na 2 CO 3 、Nb 2 O 5 、Li 2 CO 3 、Bi 2 O 3 ZrO (ZrO) 2 Wherein, the value of x is 0.035;
(2) Placing the weighed powder into a ball milling tank, placing the powder into a horizontal ball mill for ball milling for at least 24 hours by taking absolute ethyl alcohol as a medium, and then drying to obtain corresponding ceramic powder;
(3) Granulating with binder, press molding, removing binder, sintering at 1140 deg.C, and maintaining for 3 hr to obtain ceramic material;
granulating with 5% polyvinyl alcohol aqueous solution as binder, molding under 100MPa, and removing binder at 560 deg.C;
the amount of the binder is 1ml binder for every 10g ceramic powder.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007022854A (en) * | 2005-07-15 | 2007-02-01 | Toyota Motor Corp | Potassium-sodium niobate based lead-free piezoelectric ceramic, and method for producing the same |
JP2011195359A (en) * | 2010-03-18 | 2011-10-06 | Tdk Corp | Dielectric ceramic composition |
CN108275999A (en) * | 2018-04-02 | 2018-07-13 | 齐鲁工业大学 | A kind of preparation method of potassium niobate sodium-based leadless piezoelectric ceramic |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007022854A (en) * | 2005-07-15 | 2007-02-01 | Toyota Motor Corp | Potassium-sodium niobate based lead-free piezoelectric ceramic, and method for producing the same |
JP2011195359A (en) * | 2010-03-18 | 2011-10-06 | Tdk Corp | Dielectric ceramic composition |
CN108275999A (en) * | 2018-04-02 | 2018-07-13 | 齐鲁工业大学 | A kind of preparation method of potassium niobate sodium-based leadless piezoelectric ceramic |
Non-Patent Citations (3)
Title |
---|
Enhanced electrical properties, phase structure, and temperature-stable dielectric of (K0.48Na0.52)NbO3-Bi0.5Li0.5ZrO3 ceramics;Wu Bo等;Ceramics International;第44卷(第1期);第1172-1175页 * |
New potassium–sodium niobate material system:a giant-d33 and high-TC lead-free piezoelectric;Zheng Ting等;Dalton Transactions;第43卷(第30期);第11759-11766页 * |
Wu Bo等.Enhanced electrical properties, phase structure, and temperature-stable dielectric of (K0.48Na0.52)NbO3-Bi0.5Li0.5ZrO3 ceramics.Ceramics International.2017,第44卷(第1期),第1172-1175页. * |
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