CN111592351A - Application of pyroelectric material - Google Patents

Application of pyroelectric material Download PDF

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CN111592351A
CN111592351A CN202010473493.6A CN202010473493A CN111592351A CN 111592351 A CN111592351 A CN 111592351A CN 202010473493 A CN202010473493 A CN 202010473493A CN 111592351 A CN111592351 A CN 111592351A
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bczt
porous
pyroelectric material
pyroelectric
ceramic powder
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CN111592351B (en
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张妍
谢文韬
吕治东
唐仲鼎
李晓茹
范凯龙
周科朝
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Central South University
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Abstract

The invention discloses an application of a pyroelectric material, wherein the pyroelectric material is used for collecting heat energy, and the heat energy is converted into electric energy by utilizing temperature change, and the pyroelectric material is a porous zirconium calcium barium titanate ceramic material; the temperature change is more than or equal to 1 ℃; the porosity of the porous zirconium calcium barium titanate ceramic material is 10-60%. The porous barium zirconate titanate ceramic material is applied to heat energy collection for the first time, and the inventor finds that the porous barium zirconate titanate can be used as a pyroelectric material, the working principle of the porous barium zirconate titanate is that when the environmental temperature changes, the upper surface and the lower surface of the material generate voltage due to the pyroelectric effect of the pyroelectric material, and heat energy is converted into electric energy.

Description

Application of pyroelectric material
Technical Field
The invention belongs to the field of heat energy collection, and particularly relates to application of a pyroelectric material.
Background
The low-temperature heat energy refers to heat energy with relatively low grade, the temperature is generally lower than 200 ℃, and the energy sources are various and comprise renewable energy sources such as solar heat energy, various industrial waste heat, geothermal energy, ocean temperature difference and the like; the total amount is huge, taking industrial waste heat as an example, statistics indicate that 50% of heat energy utilized by human beings is finally directly discharged in the form of low-grade waste heat. With the development of economy in China, the contradiction between energy production and consumption and between energy and environment is continuously increased. How to improve the utilization rate of energy and reduce the pollution to the environment draws wide attention of society. The energy utilization rate of China is only 30%, a large amount of waste heat is discharged to the environment in various forms, and the utilization of the waste heat plays an important role in improving the comprehensive energy utilization rate of China. The existing heat collector mainly utilizes the thermoelectric effect of materials, forms a temperature difference at two ends of the materials, and utilizes the Seebeck effect to enable two ends of the materials to form a potential difference so as to convert heat energy into electric energy. However, the thermoelectric conversion material requires a large temperature difference, so that the energy conversion efficiency is low under a low temperature condition, the cost is high, and the application limitation is large. Therefore, people are getting attention to collect heat energy by utilizing the pyroelectric effect of the pyroelectric material.
Pyroelectric materials are mostly used for infrared sensors, and although some researches are carried out in the field of heat energy collection, the pyroelectric materials are rarely applied. In 2018, Xufeng et al invent a novel heat energy collector by combining a magnetic phase change alloy and a pyroelectric material. The characteristic that the magnetism of the magnetic phase change alloy changes along with the temperature change is utilized, the material can obtain repeated temperature fluctuation, the peak voltage reaches 2.3V, but the material can contact a heat source when in use, and only can obtain heat energy singly, the pyroelectric material contains lead, toxicity exists, only can obtain heat energy singly, and intelligent management cannot be carried out.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an application of a pyroelectric material, wherein the pyroelectric material is used for heat energy collection.
In order to achieve the above purpose, the invention provides the following technical scheme:
the application of the pyroelectric material is that the pyroelectric material is used for collecting heat energy, the heat energy is converted into electric energy by utilizing temperature change, and the pyroelectric material is a porous zirconium calcium barium titanate (BCZT) ceramic material; the temperature change is more than or equal to 1 ℃.
The porous barium zirconate titanate ceramic material is applied to heat energy collection for the first time, and the inventor finds that the porous barium zirconate titanate can be used as a pyroelectric material, the working principle of the porous barium zirconate titanate is that when the environmental temperature changes, the upper surface and the lower surface of the material generate voltage due to the pyroelectric effect of the pyroelectric material, and the heat energy is converted into electric energy, so that the porous barium zirconate titanate is not used as a pyroelectric material for heat energy collection at present, the temperature difference required by the pyroelectric material is large, the porous barium zirconate titanate is used for heat energy collection as the pyroelectric material in the invention, and the condition of converting the heat energy into the electric energy is that the temperature change is more than or equal to 1 ℃, namely, the heat energy collection and the electricity generation can be realized only by the temperature fluctuation of 1 ℃, and the efficiency of the heat energy collection.
The invention relates to an application of a pyroelectric material, wherein in the process of collecting heat energy, when the temperature change is more than or equal to 1 ℃, the peak voltage of the pyroelectric material is more than or equal to 8, and the peak current is more than or equal to 5 muA; when the temperature change is more than or equal to 5 ℃; the peak voltage of the pyroelectric material is more than or equal to 15V, and the peak current is more than or equal to 12 muA.
The invention relates to application of a pyroelectric material, wherein the porosity of a porous zirconium-calcium-barium titanate ceramic material is 10-60%. Preferably 40 to 60%, and more preferably 50 to 60%.
According to the invention, the relative dielectric constant of the prepared porous zirconium calcium barium titanate ceramic material is reduced along with the increase of porosity, and the lower the phase dielectric constant is, the higher the heat energy collection efficiency of the material is.
The invention relates to application of a pyroelectric material, wherein a porous zirconium calcium barium titanate ceramic material is a non-oriented porous structure or an oriented porous structure, and preferably is an oriented porous structure.
The inventor finds that the porous zirconium calcium barium titanate ceramic material with the oriented porous structure has better heat collecting effect and more and faster energy collection.
The invention relates to application of a pyroelectric material, wherein when a porous zirconium-calcium-barium titanate ceramic material is of a non-oriented porous structure, the preparation method comprises the following steps:
and mixing the BCZT ceramic powder with ethanol, adding corn starch and PVA, mixing again, drying to obtain mixed powder, pressing and molding the mixed powder, and calcining to obtain the porous barium zirconate titanate ceramic material.
Preferably, the addition amount of the corn starch is 0-48% of the mass of the BCZT ceramic powder. Corn starch is used as a pore-forming agent, and the porous zirconium-calcium-barium titanate ceramic material with different porosities is obtained by adding different contents of corn powder starch.
Preferably, the addition amount of the polyvinyl alcohol (PVA) is 0.5-2.5% of the mass of the BCZT ceramic powder. PVA added serves as a binder.
Preferably, the calcining procedure is to heat up to 400-700 ℃ for 3-8h, and then heat up to 1250-1550 ℃ for 3-7 h.
The invention relates to application of a pyroelectric material, wherein when a porous zirconium calcium barium titanate ceramic material is of an oriented porous structure, the preparation method comprises the following steps:
mixing BCZT ceramic powder with water, polyvinyl alcohol and ammonium polyacrylate to obtain a suspension, wherein the viscosity of the suspension is 2-45 mPa & s, placing the suspension in a mold, and then placing the mold in an oriented temperature field for oriented freezing, wherein the temperature of a cold end is changed to-198-0 ℃, the temperature of a corresponding hot end is changed to 0-20 ℃, and the freezing rate is controlled to be 1-20 ℃/min; and drying the ice blank formed by directional freezing to obtain a blank body with oriented porosity, and calcining the blank body to obtain the porous zirconium calcium barium titanate ceramic material.
In the invention, the porous zirconium calcium barium titanate ceramic material with the oriented porous structure is obtained by a freezing template method, the slurry is subjected to solvent solidification and particle rearrangement treatment in an oriented low-temperature field, the frozen ice blank is placed in a freeze dryer under a low-temperature and low-pressure environment, and the oriented porous pore channel structure with long-range order is left after the solvent is sublimated.
Preferably, the grain diameter of the BCZT ceramic powder is 0.3-1 μm. The inventors have found that controlling the particle size of the ceramic particles within the above range allows the porous barium zirconate titanate ceramic material to have the optimum degree of pore orientation.
Preferably, the mass fraction of the BCZT ceramic powder in the slurry is 10-50 wt%
Preferably, the addition amount of the polyvinyl alcohol is 0.5-2.5% of the mass of the BCZT ceramic powder.
Preferably, the addition amount of the ammonium polyacrylate is 0.5-2.5% of the mass of the BCZT ceramic powder.
Preferably, the freezing medium of the directional temperature field is liquid nitrogen. In the present invention, the cold end refers to one end of the mold which is in contact with or close to the liquid level of the liquid nitrogen, and the hot end refers to the other corresponding end.
The freezing speed is controlled by controlling the contact distance between the cold end and the liquid nitrogen or the distance between the cold end and the liquid nitrogen.
Preferably, the temperature gradient of the directional temperature field is more than or equal to 0.1 ℃/mm.
Preferably, the temperature change of the cold end is-198 to-80 ℃.
Preferably, the freezing rate is 1-5 ℃/min
Preferably, the drying temperature is-100 to-10 ℃ and the pressure is 5 to 30 Pa.
Preferably, the calcination procedure is to heat up to 400-.
The invention relates to an application of a pyroelectric material, and a preparation method of BCZT ceramic powder comprises the following steps: at 0.5Ba (Ca)0.8Zr0.2)O3-0.5(Ba0.7Ca0.3)TiO3According to the stoichiometric ratio, BaCO is prepared3、CaCO3、TiO2、ZrO2And mixing to obtain mixed powder, performing ball milling on the mixed powder for more than or equal to 4 hours to obtain a ball grinding material, calcining the ball grinding material at 950-1250 ℃ for 2-6 hours, and performing ball milling and crushing on the calcined product to obtain the BCZT ceramic powder.
Advantageous effects
The porous barium zirconate titanate ceramic material is applied to heat energy collection for the first time, and the inventor finds that the porous barium zirconate titanate can be used as a pyroelectric material, the working principle of the porous barium zirconate titanate is that when the environmental temperature changes, the upper surface and the lower surface of the material generate voltage due to the pyroelectric effect of the pyroelectric material, and heat energy is converted into electric energy, so that the porous barium zirconate titanate is not used as a thermoelectric conversion material for heat energy collection at present, and the temperature difference required by the thermoelectric conversion material is large, but the porous barium zirconate titanate is used for heat energy collection as the pyroelectric material in the invention, and the condition of converting the heat energy into the electric energy is that the temperature fluctuation is more than or equal to 1 ℃, namely, the heat energy collection can be realized only by the temperature difference of 1 ℃, and the efficiency of the heat.
Drawings
Fig. 1 is a schematic diagram of a thermal energy collection intelligent system for collecting heat from a pyroelectric material.
Fig. 2 is a physical diagram of the intelligent low-grade thermal energy collection system based on the pyroelectric effect in example 1.
FIG. 3 is a graph of the relative dielectric constants of BCZT ceramic materials of example 1 with different porosities, the effect of the porosity on the relative dielectric constant at 1 kHz. It can be found that the relative dielectric constant of the prepared BCZT ceramic material is reduced along with the increase of the porosity, and the lower the phase dielectric constant is, the higher the heat energy collection efficiency of the material is.
FIG. 4 is a temperature-time curve of pyroelectric material in the intelligent system for low-grade heat energy collection based on pyroelectric effect in example 1. The peak value of the temperature change of the material is about 1 ℃ and the frequency is 0.3 Hz.
Fig. 5 is an energy-time curve of the low-grade heat energy collection intelligent system based on the pyroelectric effect in example 1.
Fig. 6 is a voltage-time curve of the intelligent system for low-grade heat energy collection based on the pyroelectric effect in example 1. As shown, the peak voltage can be measured up to 10V.
FIG. 7 is a porous morphology diagram of the porous zirconium calcium barium titanate ceramic material prepared in example 1.
FIG. 8 is a porous morphology diagram of the porous zirconium calcium barium titanate ceramic material prepared in example 2.
Fig. 9 is an energy-time curve of the low-grade heat energy collection intelligent system based on the pyroelectric effect in example 2.
FIG. 10 is a porous morphology diagram of the porous barium zirconate titanate ceramic material prepared in comparative example 1
Detailed Description
Example 1
The preparation and application of non-oriented porous zirconium calcium barium titanate ceramic material,
use ofAnalytical grade (Sigma Aldrich) BaCO3(99％)、CaCO3(99％)、TiO2(99.9%) and ZrO2 (99%) as starting materials, weighed in stoichiometric proportions; ball-milling the weighed materials for 4 hours, and then uniformly mixing; calcining the mixture at 1200 ℃ for 3h, and then performing additional ball milling for 24 hours;
mixing the ground mixture powder with ethanol for 12 hours, dividing into 5 parts, respectively adding pore-forming agent corn starch with different contents, and then mixing with 1 wt.% of PVA binder; after drying, carrying out single-shaft cold pressing on the powder to form pellets with the diameter of 13mm and the thickness of 1.5 mm; the cold-pressed pellets are firstly heated to 600 ℃ for 3h, the organic additives are removed, and then the cold-pressed pellets are sintered for 4h at 1400 ℃ to obtain 5 porous zirconium calcium barium titanate ceramic material samples;
wherein, when the corn starch is added to be 0 wt.%, the porosity of the compact zirconium calcium barium titanate ceramic material is 4%;
when the corn starch is added to the ceramic material to reach 23 wt.%, the porosity of the obtained porous barium zirconate calcium titanate ceramic material is 24 percent, when the corn starch is added to reach 31 wt.%, the porosity of the obtained porous barium zirconate calcium titanate ceramic material is 36 percent, when the corn starch is added to reach 42 wt.%, the porosity of the obtained porous barium zirconate calcium titanate ceramic material is 43 percent
When the corn starch is added to reach 50 wt.%, the porosity of the obtained porous zirconium calcium barium titanate ceramic material is 52%
Cutting the sample of the porous zirconium-calcium-barium titanate ceramic material by threads to adjust the size, and plating a layer of electrode (gold) on the material; polarizing the material; and then used in a thermal energy collection intelligence system (as shown in figure 2). The prepared heat energy collection intelligent system can realize heat energy collection with the ambient temperature fluctuation larger than 1 ℃, and carries out energy management through the cloud.
In fig. 2, the hardware system includes three parts, namely a main control module STM32F103(ARM, 5.20 × 4.42cm), a charging PC board (3.09 × 2.18cm), and an 18620 lithium battery charging box (9.15 × 4.28 cm). The system has small volume and low cost, and is greatly convenient for installation and later maintenance.
Wherein FIG. 3 shows the relative dielectric constants of the samples of the porous barium zirconate titanate ceramic material with different porosities in example 1, and the influence of the porosity on the relative dielectric constant is shown under the condition of 1 kHz. It can be found that the relative dielectric constant of the prepared BCZT ceramic material decreases with the increase of the voidage, and the lower the phase dielectric constant, the higher the heat energy collection efficiency of the material.
Wherein, fig. 4 is a temperature-time curve of the pyroelectric material in the low-grade heat energy collection intelligent system based on the pyroelectric effect of the porous zirconium calcium barium titanate ceramic material with the porosity of 52% prepared in the example 1. The peak value of the temperature change of the material is about 1 ℃ and the frequency is 0.3 Hz. The heat energy can be converted into the electric energy as long as the temperature difference is more than or equal to 1 ℃.
Fig. 5 shows an energy-time curve of the low-grade thermal energy collection intelligent system based on the pyroelectric effect in example 1.
FIG. 6 shows a porous barium zirconate titanate ceramic material having a porosity of 52% prepared in example 1.
The voltage-time curve of the low-grade heat energy collection intelligent system based on the pyroelectric effect. As shown, the peak voltage can be measured up to 10V.
FIG. 7 is a graph showing the porous morphology of the porous zirconium calcium barium titanate ceramic material with the porosity of 36% in example 1.
Example 2
Adding BCZT ceramic powder (average particle size of 0.6 micrometer) into 5 parts of water with different contents, mixing polyvinyl alcohol and ammonium polyacrylate to obtain 5 parts of suspension, respectively placing the suspension in a mold, and then placing the mold in a liquid nitrogen environment for directional freezing, wherein the temperature of a cold end is-100 ℃, the temperature of a hot end is 6 ℃, and the freezing rate is controlled to be 3 ℃/min; drying the ice blank formed by directional freezing at-60 ℃ under the pressure of 3Pa
And (3) obtaining a blank with oriented porosity, heating the blank to 600 ℃, preserving heat for 3h, then heating to 1400 ℃, preserving heat for 4h, and calcining to obtain 5 parts of porous zirconium calcium barium titanate ceramic material.
Wherein, the BCZT ceramic powder is subjected to unidirectional pressing and sintering to obtain the compact zirconium-calcium-barium titanate ceramic material, and the porosity is 4%.
Wherein the mass fraction of the BCZT ceramic powder in the suspension is 45 wt%, the viscosity of the suspension is 45mP & s, the added amount of the polyvinyl alcohol is 0.8% of the mass of the BCZT ceramic powder, and the added amount of the ammonium polyacrylate is 0.8% of the mass of the BCZT ceramic powder; the porosity of the finally obtained porous zirconium calcium barium titanate ceramic material is 24 percent
Wherein the mass fraction of the BCZT ceramic powder in the suspension is 35 wt%, the viscosity of the suspension is 29mP & s, the amount of the added polyvinyl alcohol is 0.8% of the mass of the BCZT ceramic powder, and the amount of the added ammonium polyacrylate is 0.8% of the mass of the BCZT ceramic powder; the porosity of the finally obtained porous zirconium calcium barium titanate ceramic material is 36%, as shown in fig. 8.
Wherein the mass fraction of the BCZT ceramic powder in the suspension is 25 wt%, the viscosity of the suspension is, the amount of polyvinyl alcohol added into 13mP & s is 0.8% of the mass of the BCZT ceramic powder, and the amount of ammonium polyacrylate added is 0.8% of the mass of the BCZT ceramic powder; the porosity of the finally obtained porous zirconium calcium barium titanate ceramic material is 43 percent
Wherein the mass fraction of the BCZT ceramic powder in the suspension is 15 wt%, the viscosity of the suspension is 6mP & s, the added amount of the polyvinyl alcohol is 0.8% of the mass of the BCZT ceramic powder, and the added amount of the ammonium polyacrylate is 0.8% of the mass of the BCZT ceramic powder; the porosity of the finally obtained porous zirconium calcium barium titanate ceramic material is 52 percent.
Fig. 9 is an energy-time curve of the low-grade thermal energy collection intelligent system based on the pyroelectric effect in example 2, and it can be seen from the graph that the oriented porous barium zirconate titanate ceramic material has more and faster energy collection compared with the non-oriented porous barium zirconate titanate ceramic material.
Comparative example 1
The other conditions were identical to those for preparing the porous zirconium calcium barium titanate ceramic material having a porosity of 36% in example 2, except that the viscosity of the suspension was 76 mP.s.
When the viscosity of the suspension is not well controlled in the preparation process, the formed porous channel has poor long-range order degree, so that the mechanical property is greatly reduced, subsequent tests and applications cannot be carried out, and the specific morphology is as shown in fig. 10.

Claims (10)

1. The application of the pyroelectric material is characterized in that: the method comprises the following steps of (1) using a pyroelectric material for heat energy collection, and converting heat energy into electric energy by utilizing temperature change, wherein the pyroelectric material is a porous zirconium calcium barium titanate ceramic material; the temperature change is more than or equal to 1 ℃.
2. The use of a pyroelectric material as claimed in claim 1, characterized in that: in the process of collecting heat energy, when the temperature change is more than or equal to 1 ℃, the peak voltage of the pyroelectric material is more than or equal to 8, and the peak current is more than or equal to 5 muA; when the temperature change is more than or equal to 5 ℃; the peak voltage of the pyroelectric material is more than or equal to 15V, and the peak current is more than or equal to 12 muA.
3. Use of a pyroelectric material according to claim 1 or 2, characterized in that: the porosity of the porous zirconium calcium barium titanate ceramic material is 10-60%; preferably 40 to 60%.
4. Use of a pyroelectric material according to claim 1 or 2, characterized in that: the porous zirconium calcium barium titanate ceramic material is a non-oriented porous structure or an oriented porous structure, and preferably is an oriented porous structure.
5. Use of a pyroelectric material according to claim 1 or 2, characterized in that: when the porous zirconium calcium barium titanate ceramic material is in a non-oriented porous structure, the preparation method comprises the following steps: and mixing the BCZT ceramic powder with ethanol, adding corn starch and PVA, mixing again, drying to obtain mixed powder, pressing and molding the mixed powder, and calcining to obtain the porous barium zirconate titanate ceramic material.
6. Use of a pyroelectric material according to claim 5, characterized in that:
the addition amount of the corn starch is 0-48% of the mass of the BCZT ceramic powder; the addition amount of the polyvinyl alcohol is 0.5-2.5% of the mass of the BCZT ceramic powder; the calcining procedure is that the temperature is firstly increased to 400-700 ℃ and is preserved for 3-8h, and then the temperature is increased to 1250-1550 ℃ and is preserved for 3-7 h.
7. Use of a pyroelectric material according to claim 1 or 2, characterized in that: when the porous zirconium calcium barium titanate ceramic material is an oriented porous structure, the preparation method comprises the following steps: mixing BCZT ceramic powder with water, polyvinyl alcohol and ammonium polyacrylate to obtain a suspension, wherein the viscosity of the suspension is 2-30 mPa & s, placing the suspension in a mold, and then placing the mold in an oriented temperature field for oriented freezing, wherein the temperature of a cold end is changed to-198-0 ℃, the temperature of a corresponding hot end is changed to 0-20 ℃, and the freezing rate is controlled to be 1-20 ℃/min; and drying the ice blank formed by directional freezing to obtain a blank body with oriented porosity, and calcining the blank body to obtain the porous zirconium calcium barium titanate ceramic material.
8. Use of a pyroelectric material according to claim 7, characterized in that: the grain diameter of the BCZT ceramic powder is 0.3-1 μm; in the slurry, the mass fraction of the BCZT ceramic powder is 10-50 wt.%;
the addition amount of the polyvinyl alcohol is 0.5-2.5% of the mass of the BCZT ceramic powder; the addition amount of the ammonium polyacrylate is 0.5-2.5% of the mass of the BCZT ceramic powder.
9. Use of a pyroelectric material according to claim 7, characterized in that: the drying temperature is-100 to-10 ℃, and the pressure is 5-30 Pa; the calcination procedure comprises the steps of firstly heating to 400-.
10. Use of a pyroelectric material according to claim 7, characterized in that: the preparation method of the BCZT ceramic powder comprises the following steps: at 0.5Ba (Ca)0.8Zr0.2)O3-0.5(Ba0.7Ca0.3)TiO3According to the stoichiometric ratio, BaCO is prepared3、CaCO3、TiO2、ZrO2And mixing to obtain mixed powder, performing ball milling on the mixed powder for more than or equal to 4 hours to obtain a ball grinding material, calcining the ball grinding material at 950-1250 ℃ for 2-6 hours, and performing ball milling and crushing on the calcined product to obtain the BCZT ceramic powder.
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