CN111763084A - Manganese-doped barium strontium titanate ceramic with high electrocaloric effect and preparation method and application thereof - Google Patents

Manganese-doped barium strontium titanate ceramic with high electrocaloric effect and preparation method and application thereof Download PDF

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CN111763084A
CN111763084A CN202010662216.XA CN202010662216A CN111763084A CN 111763084 A CN111763084 A CN 111763084A CN 202010662216 A CN202010662216 A CN 202010662216A CN 111763084 A CN111763084 A CN 111763084A
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manganese
strontium titanate
barium strontium
ceramic
temperature
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鲁圣国
牛翔
简晓东
李昊轩
梁威
姚英邦
陶涛
梁波
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Guangdong University of Technology
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Abstract

The invention belongs to the technical field of ceramics, and particularly relates to manganese-doped barium strontium titanate ceramics with a high electrocaloric effect, and a preparation method and application thereof. The Curie temperature of the manganese-doped barium strontium titanate ceramic is near room temperature, so that the use temperature suitable for the actual electric card refrigeration device in the range close to the room temperature is obtained; secondly, the dielectric property, the polarization property and the electrocaloric effect of the manganese-doped barium strontium titanate ceramic are further improved by doping manganese ions, and higher electrocaloric response can be obtained; the co-doping of strontium ions and manganese ions enables the manganese-doped barium strontium titanate ceramic to show relaxation ferroelectric characteristics, widens the working temperature range of the ceramic material, and improves the temperature stability of the material performance. The manganese-doped barium strontium titanate ceramic has wide applicable temperature range, high temperature change and high electric card effect, solves the problems of narrow electric card response temperature range and working temperature far higher than room temperature of barium titanate, and provides an environment-friendly and extremely promising electric card material for electric card refrigerating devices.

Description

Manganese-doped barium strontium titanate ceramic with high electrocaloric effect and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to manganese-doped barium strontium titanate ceramics with a high electrocaloric effect, and a preparation method and application thereof.
Background
The traditional refrigeration technology is air compression type refrigeration. On the one hand, however, the refrigerant fluoride used in the refrigeration process of air compression refrigeration can cause damage to the ozone layer, and further cause the greenhouse effect; on the other hand, the energy is lost due to heat conduction and the like in the whole refrigeration process, so that the energy utilization rate is low, and the Carnot coefficient is usually lower than a theoretical value of 50%. In addition, air compression refrigeration technology is not suitable for the refrigeration of miniaturized devices. With the rapid development of intelligent electronic devices in recent decades, and particularly the dramatic reduction of feature size in Very Large Scale Integration (VLSI) designs (7nm and below), the density of transistors on a chip has increased dramatically, resulting in extremely high heat dissipation. This not only leads to high electrical losses, but also to thermal stability problems of the electronic device. In view of the foregoing, it has become a hot spot and urgent need for current research to develop devices that are more efficient, smaller in size, and more suitable for cooling of intelligent electronic devices.
In recent years, many new refrigeration technologies have appeared, including magnetic card effect refrigeration, spring card effect refrigeration, electric card effect refrigeration, thermoelectric refrigeration, and the like. From the aspect of energy loss, the joule heat of semiconductor refrigeration cannot be eliminated, and the energy loss is high; from the aspect of miniaturization and cost, the magnetic card refrigeration needs a huge magnetic field component, and the rare earth element cost needed by the permanent magnet is high. On the contrary, the electric card refrigeration device is flexible in design, easy to miniaturize, high in energy utilization rate (higher than 60% Carnot cycle), low in cost, and friendly to environment, has become a novel refrigeration mode with huge attraction, and is regarded as a novel refrigeration mode with great potential to replace traditional vapor compression refrigeration.
Barium titanate (BaTiO)3) The base ceramic system is a lead-free ferroelectric ceramic system with good dielectric property and ferroelectric property, and as a first-order phase change ferroelectric, the polarization intensity of the base ceramic system can be changed sharply near the Curie temperature, which means that the base ceramic system can obtain larger electrocaloric response near the Curie point. However, since the curie temperature of barium titanate-based ceramics is about 120 ℃, it is much higher than the actual use temperature of electrocaloric refrigeration, room temperature. In addition, the electric card response can only occur in a narrow temperature range, and the use temperature range of the electric card refrigeration device is limited.
Therefore, the search for ceramics that achieve excellent electrocaloric response over a wide temperature range while operating at temperatures around room temperature is a problem that is currently urgently sought to be solved.
Disclosure of Invention
In view of the above, the present invention provides a manganese-doped barium strontium titanate ceramic with high electrocaloric effect, which is used to solve the problems that the electrocaloric response temperature range of barium titanate is narrow and the working temperature is much higher than room temperature.
The specific technical scheme of the invention is as follows:
the manganese-doped barium strontium titanate ceramic with high electrocaloric effect has the chemical formula of barium strontium titanate in the manganese-doped barium strontium titanate ceramic1-xSrx)(MnyTi1-y)O3；
Wherein x is 0.35-0.4, and y is 0.1-0.5%.
Preferably, x is 0.35 or 0.4 and y is 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.
The invention also provides a preparation method of the manganese-doped barium strontium titanate ceramic in the technical scheme, which comprises the following steps:
a) mixing BaCO3、SrCO3、MnO2And TiO2Mixing and calcining to obtain a calcined product;
b) mixing the calcined product with a binder and then granulating to obtain a powder dough;
c) molding the powder dough to obtain a ceramic blank;
d) and sintering the ceramic blank to obtain the manganese-doped barium strontium titanate ceramic.
Preferably, the mixing in step a) is ball milling mixing;
the BaCO3、SrCO3、MnO2And TiO2In a molar ratio of (1-x): x: y: (1-y), wherein the value ranges of x and y are consistent with the value ranges of x and y in the technical scheme;
the calcining temperature is 1180-1220 ℃, the calcining time is 2-7 h, more preferably, the calcining temperature is 1200 ℃, and the calcining time is 4 h.
In the invention, the ball milling and mixing specifically comprises the following steps: mixing BaCO3、SrCO3、MnO2And TiO2And mixing the mixture with zirconium balls and a solvent, then carrying out wet ball milling, preferably filtering out slurry after ball milling, and drying to obtain uniformly mixed ceramic powder, wherein the drying temperature is preferably 60-80 ℃, and the drying time is preferably 10-14 h.
Preferably, the rotation speed of the ball milling mixing is 200-300 rpm, and more preferably 230-270 rpm;
the ball milling and mixing time is 6-18 h, and more preferably 10-14 h;
the solvent for ball milling mixing is absolute ethyl alcohol or deionized water, and more preferably, the absolute ethyl alcohol.
In the invention, the step b) is specifically as follows: and mixing the calcined product, a binder and a solvent, and granulating to obtain the powder dough.
Preferably, the binder of step b) is selected from polyvinyl butyral and/or polyvinyl alcohol;
the solvent for granulation is selected from ethanol and/or deionized water.
Preferably, the molding treatment in the step c) comprises axial molding and cold isostatic pressing;
and the axial compression molding and the cold isostatic pressing are carried out in sequence.
Preferably, the pressure of the axial compression molding is 5-10 Mpa, and the duration time of the axial compression molding is 1-2 min;
the pressure of the cold isostatic pressing is 180-230 Mpa, the duration of the cold isostatic pressing is 3-6 min, and more preferably, the pressure of the cold isostatic pressing is 200Mpa, and the duration of the cold isostatic pressing is 5 min.
Preferably, the sintering temperature in the step d) is 1350-1450 ℃;
the sintering time is 4-6 h.
The invention also provides the application of the manganese-doped barium strontium titanate ceramic in sensors and solid refrigeration or energy storage devices.
In summary, the present invention provides a manganese-doped barium strontium titanate ceramic with high electrical card effect, wherein the chemical formula of barium strontium titanate in the manganese-doped barium strontium titanate ceramic is (Ba)1-xSrx)(MnyTi1-y)O3(ii) a Wherein x is 0.35-0.4, and y is 0-0.5%. Experimental results show that the Curie temperature of the manganese-doped barium strontium titanate ceramic is near room temperature, and the service temperature suitable for the actual electrocaloric refrigeration device in the range close to the room temperature is obtained; secondly, the dielectric property, the polarization property and the electrocaloric effect of the manganese-doped barium strontium titanate ceramic are further improved by doping manganese ions, and higher electrocaloric response can be obtained; the co-doping of strontium ions and manganese ions enables the manganese-doped barium strontium titanate ceramic to show relaxation ferroelectric characteristics, widens the working temperature range of the ceramic material, and improves the temperature stability of the material performance. The manganese-doped barium strontium titanate ceramic can obtain high electrical card response in a wider temperature range, is an electrical card material with good dielectric property, excellent polarization property and strong electrical card response, has wide applicable temperature range, high temperature change and high electrical card effect, solves the problems of narrower electrical card response temperature range and far higher working temperature than room temperature of barium titanate, and provides an environment-friendly electrical card material for electrical card refrigeration devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an X-ray diffraction pattern of samples prepared in examples 1 to 5 of the present invention and comparative example 1;
FIG. 2 is an X-ray diffraction pattern of samples prepared in examples 6 to 10 of the present invention and comparative example 2;
FIG. 3 is a scanning electron micrograph of samples prepared in examples 1 to 5 of the present invention and comparative example 1;
FIG. 4 is a scanning electron micrograph of samples prepared in examples 6 to 10 of the present invention and comparative example 2;
FIG. 5 is a graph of dielectric constant versus temperature and frequency for samples prepared in examples 1-5 of the present invention and comparative example 1;
FIG. 6 is a graph of dielectric loss versus temperature and frequency for samples prepared in examples 1-5 of the present invention and comparative example 1;
FIG. 7 is a graph of dielectric constant versus temperature and frequency for samples prepared in examples 6-10 of the present invention and comparative example 2;
FIG. 8 is a graph of dielectric loss versus temperature and frequency for samples prepared in examples 6-10 of the present invention and comparative example 2;
FIG. 9 is a hysteresis curve plot at-30 ℃ for the samples prepared in examples 1-5 of the present invention and comparative example 1 at an applied electric field of 5 MV/m;
FIG. 10 is a hysteresis curve diagram of samples prepared in examples 1 to 5 of the present invention and comparative example 1 at room temperature under an applied electric field of 5 MV/m;
FIG. 11 is a hysteresis curve diagram at 100 ℃ under an applied electric field of 5MV/m for samples prepared in examples 1 to 5 of the present invention and comparative example 1;
FIG. 12 is a hysteresis curve plot at-30 ℃ for the samples prepared in examples 6-10 of the present invention and comparative example 2 at an applied electric field of 5 MV/m;
FIG. 13 is a hysteresis curve diagram of samples prepared in examples 6 to 10 of the present invention and comparative example 2 at room temperature under an applied electric field of 5 MV/m;
FIG. 14 is a hysteresis curve diagram at 100 ℃ under an applied electric field of 5MV/m for samples prepared in examples 6 to 10 of the present invention and comparative example 2;
FIG. 15 shows electrocaloric response values at different temperatures under an electric field of 5MV/m for samples prepared in examples 1 to 5 of the present invention and comparative example 1;
FIG. 16 is graphs showing electrocaloric response values at different temperatures under an electric field of 5MV/m for samples prepared in examples 6 to 10 according to the present invention and comparative example 2;
FIG. 17 shows the electric card response values of the samples prepared in examples 1 to 10 of the present invention and comparative examples 1 to 2 at different manganese contents under an electric field of 5 MV/m.
Detailed Description
The invention provides manganese-doped barium strontium titanate ceramic with high electrocaloric effect, which is used for solving the problems that the electrocaloric response temperature range of barium titanate is narrow and the working temperature is far higher than the room temperature.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.65Sr0.35Mn0.001Ti0.999O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1400 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.65Sr0.35Mn0.001Ti0.999O3。
Example 2
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.65Sr0.35Mn0.002Ti0.998O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1350 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.65Sr0.35Mn0.002Ti0.998O3。
Example 3
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.65Sr0.35Mn0.003Ti0.997O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃ and sieving the dried slurry with a 80-mesh sieve to obtain the productTo ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1450 ℃, and obtaining a sample after natural cooling in the furnace, wherein the chemical formula is Ba0.65Sr0.35Mn0.003Ti0.997O3。
Example 4
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.65Sr0.35Mn0.004Ti0.996O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, keeping the temperature at 1350 ℃ for 4 hours, and waiting for the furnaceNaturally cooling to obtain sample with chemical formula of Ba0.65Sr0.35Mn0.004Ti0.996O3。
Example 5
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.65Sr0.35Mn0.005Ti0.995O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1400 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.65Sr0.35Mn0.005Ti0.995O3。
Example 6
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.6Sr0.4Mn0.001Ti0.999O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4Mn0.001Ti0.999O3。
Example 7
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.6Sr0.4Mn0.002Ti0.998O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4Mn0.002Ti0.998O3。
Example 8
Will have a purity of99% of BaCO3、SrCO3、MnO2And TiO2Push Ba0.6Sr0.4Mn0.003Ti0.997O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4Mn0.003Ti0.997O3。
Example 9
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.6Sr0.4Mn0.004Ti0.996O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4Mn0.004Ti0.996O3。
Example 10
BaCO with the purity of 99 percent3、SrCO3、MnO2And TiO2Push Ba0.6Sr0.4Mn0.005Ti0.995O3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4Mn0.005Ti0.995O3。
Comparative example 1
BaCO with the purity of 99 percent3、SrCO3And TiO2Push Ba0.65Sr0.35TiO3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for mixing for 12 hours to obtain the mixtureAnd drying the slurry at 65 ℃ after filtering, and sieving the dried slurry with a 80-mesh sieve to obtain ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1400 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.65Sr0.35TiO3。
Comparative example 2
BaCO with the purity of 99 percent3、SrCO3And TiO2Push Ba0.6Sr0.4TiO3Weighing the mixed materials according to the stoichiometric ratio, adding absolute ethyl alcohol and zirconium balls, putting the mixture into a planetary ball mill for 12 hours for mixing, filtering the obtained slurry, drying the slurry at 65 ℃, and sieving the dried slurry with a 80-mesh sieve to obtain the ceramic powder. Wherein the volume ratio of the absolute ethyl alcohol to the total volume of the zirconium balls to the total volume of all the powder materials is 1: 2: 1.
calcining the obtained ceramic powder in a muffle furnace, keeping the temperature at 1200 ℃ for 4 hours to obtain a calcined product, sieving the calcined product, mixing the calcined product with 7 wt% of a binding agent polyvinyl butyral ethanol solution, uniformly grinding, and drying at 65 ℃ to obtain a powder dough.
And (3) putting the obtained powder dough into a mold, carrying out axial compression molding, maintaining the pressure at 6MPa for 1 minute to obtain a wafer block with the diameter of 12mm and the thickness of 1mm, putting the wafer block into a vacuum bag, vacuumizing, and maintaining the pressure of 200MPa for 5 minutes by using a cold isostatic press to obtain a ceramic blank.
Sintering the ceramic blank in air atmosphere, preserving heat for 4 hours at 1360 ℃, and naturally cooling in a furnace to obtain a sample with a chemical formula of Ba0.6Sr0.4TiO3。
Example 11
In this example, the samples obtained in examples 1 to 10 and comparative examples 1 to 2 were tested to obtain X-ray diffraction patterns, and the results are shown in FIGS. 1 and 2.
Comparing the XRD pattern of the sample prepared in the embodiment 1-10 in the figure 1 and the sample prepared in the embodiment 2 with a standard JCPDS card, the sample prepared by the preparation method provided by the invention has a pure perovskite structure, and the co-doping of manganese ions and strontium ions does not introduce a hetero-phase. Meanwhile, as the doping concentration of the manganese ions is gradually increased, the diffraction peak of the sample slightly shifts to a low angle, and the Bragg equation 2dsin theta is equal to n lambda, which shows that the manganese ions with larger radius replace the perovskite structure ABO3Relatively small radius of Ti at the B site4+Ions. In addition, the diffraction peak of the (200) crystal plane in the vicinity of the angle of 45 ℃ was a single peak and was not a split peak, indicating that the samples obtained in examples 1 to 10 were pseudocubic phases belonging to the 3m3 point group or phases in which weak cubic phases and tetragonal phases coexist. The strontium ion doping causes lattice distortion and fluctuation of structural components, so that the samples prepared in examples 1-10 exhibit relaxation-type ferroelectric properties in structure and electrical properties.
Example 12
In this example, the samples prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to electron microscope scanning, and the results are shown in fig. 3 and 4.
The result shows that the sample obtained by the preparation method provided by the invention has clear, compact and uniform crystal grains, and the size of the crystal grains is 1-6 microns, so that the sintering condition provided by the invention can meet the dynamic window of crystal boundary diffusion and crystal boundary migration of the sample in the sintering process.
Example 13
In this example, the dielectric temperature spectra were measured on the samples prepared in examples 1 to 10 and comparative examples 1 to 2.
The Agilent 4284A impedance analyzer is adopted to measure the dielectric constant and dielectric loss of the samples prepared in the examples 1-10 and the comparative examples 1-2 according to the temperature and frequency, and the measured results are shown in the figures 5-8. Due to the large amount of doping of strontium ionsThe structural composition of the sample fluctuates, the Curie temperature of the manganese-doped barium strontium titanate ceramic sample shifts to low temperature along with the increase of the concentration of strontium ions, for example, when the doping amount of strontium ions is increased from 35% to 40% without doping manganese ions, the Curie point of the sample is reduced from 23.9 ℃ to 14.3 ℃. Meanwhile, the action effect of the manganese ions on the Curie point of the sample is the same as that of the strontium ions. In addition, as can be seen from a dielectric thermogram, the doping of the manganese ions enhances the characteristics of the sample relaxation type ferroelectric, and widens the phase transition temperature range of the material. More importantly, in a sample with a certain amount of strontium ions, the doping of the manganese ions is increased, so that the dielectric constant of the sample is increased and then decreased. In particular, at a frequency of 1kHz and at a temperature of 8.7 ℃ of its Curie point, in the sample of example 6 (Ba)0.6Sr0.4)(Mn0.001Ti0.999)O3The maximum dielectric constant of 18,100 is obtained, and the dielectric loss is only 0.9%. It is noted that, with the increase of the doping amount of the manganese ions, the dielectric loss of the sample is firstly reduced and then increased, and the change rule of the dielectric constant can be shown by integrating the change rule of the dielectric constant when doping Mn2+When the concentration is lower, the dielectric property of the sample can be obviously improved, on one hand, the dielectric constant of the sample is improved, and on the other hand, the dielectric loss of the sample is reduced. The reason for this is Mn2+Acceptor-type doping of the ions. Mn in the raw material during high-temperature sintering4+(MnO2) Two electrons can be released to compensate the oxygen vacancy defect of the ceramic sample, so that the oxygen deficiency concentration and free or weakly bound carriers are reduced, the dielectric property is improved to a certain extent, and the dielectric loss is reduced. Meanwhile, manganese ions with different valence states replace Ti at the b position in a crystal structure4+The ions act as acceptors and also generate undesirably increased free carriers (holes). Second, as an acceptor defect charge center, Mn2+Not only can capture free electrons, but also can be used as a defect energy level to reduce the band gap of a dielectric material, so that the dielectric property of a sample is reduced. When Mn is present2+When the doping amount is low, the compensation effect of manganese ions on oxygen vacancies is dominant, and the dielectric property is improved. On the contrary, when the content of the doped manganese ions is slightly higher, the doped manganese ions are rather highThe dielectric properties of the sample are reduced.
Example 14
In this example, the P-E hysteresis loop diagrams were obtained by measuring the samples prepared in examples 1 to 10 and comparative examples 1 to 2 at-30 ℃, room temperature and 100 ℃ with an applied electric field of 5MV/m, and the results are shown in FIGS. 9 to 14, using a radial multiferroic comprehensive test system as the test equipment.
Fig. 9-14 show characteristic P-E hysteresis loops for typical relaxed ferroelectrics. With Mn2+The content is increased and the residual polarization intensity of the sample is increased from the sample (Ba)0.65Sr0.35)TiO36.10. mu.C/cm2Decrease to sample (Ba)0.65Sr0.35)(Mn0.005Ti0.995)O32.21. mu.C/cm2At the same time, from sample (Ba)0.6Sr0.4)TiO35.64. mu.C/cm2Decrease to sample (Ba)0.6Sr0.4)(Mn0.005Ti0.995)O30.26. mu.C/cm2This means that the P-E loop becomes thinner. In addition, the saturation polarization of the sample increases and then decreases with the increase of the content of manganese ions, which coincides with the trend of the dielectric constant. And, sample (Ba)0.65Sr0.35)(Mn0.002Ti0.998)O3The maximum saturation polarization intensity is obtained under the conditions of-30 ℃ and the applied electric field of 5MV/m, and is 21.68 mu C/cm2. In general, for a certain amount of strontium ion doped BSMT ceramic samples, a small amount of manganese ion doping can improve the polarization performance of the samples, not only improves the saturation polarization strength, reduces the residual polarization strength and coercive field, but also enhances the relaxation type ferroelectric properties of the samples.
Example 15
In this example, the samples prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to a 5MV/m applied electric field to obtain a graph of the relationship between the adiabatic temperature change value and the temperature, and the test method adopted was a thermocouple direct measurement method, and the measurement results are shown in FIGS. 15 to 17.
The strength of the electrocaloric effect in electrocaloric materials can be isothermal caused by the application and removal of an applied electric fieldEntropy change (Δ S) and adiabatic temperature change (Δ T) were evaluated. This is because, under adiabatic conditions, since the total entropy of the material system is unchanged and the electronic entropy is negligible, when the applied electric field is removed from the sample, the dipole polarization entropy of the material increases, and in order to maintain the total entropy of the material unchanged, the lattice vibration entropy decreases, the lattice vibration decreases, and the temperature of the material decreases. When the applied electric field disappears, the dipole entropy of the material under adiabatic conditions increases. Meanwhile, the lattice entropy decreases, resulting in a decrease in the temperature of the material since the total entropy of the material is constant. Curie temperature (T)c) Is the transition point of the ferroelectric from the ferroelectric phase to the paraelectric phase at the Curie temperature TcWhere the change in polarization is greatest. Thus, in general, the maximum electrocaloric effect is obtained around the curie temperature. At 21 deg.C, under the test condition of external electric field of 5MV/m, in Ba0.6Sr0.4Mn0.001Ti0.999O3The maximum adiabatic temperature change Δ T was obtained in the samplemax2.75K, and has an objective electrocaloric strength value of 0.55K (MV/m)-1. In addition, we obtained adiabatic temperature changes consistently greater than 2.2K over a wide temperature range (-20 ℃ to 100 ℃) in the same sample, which again illustrates the relaxor ferroelectric properties of the manganese-doped barium strontium titanate ceramic sample, which is due to fluctuations in the ceramic microstructure and composition caused by co-doping of strontium ions and manganese ions. As the manganese ion content increases, the maximum electrocaloric response of the different components in the measured temperature range increases and then decreases, which is the same as its dielectric and polarization properties. Essentially, the increase of the electrocaloric response of the sample is due to the combined effect of the increase of the dielectric property and the polarization property caused by the manganese ion doping. When the content of manganese ions is less doped, the dielectric loss caused by oxygen vacancies in the manganese ion valence-change compensation material is reduced, so that on one hand, the saturation polarization strength of the manganese-doped barium strontium titanate ceramic sample is increased, and larger polarization strength change can be obtained at the Curie temperature, and further higher electric card response is obtained. On the other hand, the reduction of oxygen vacancy defects means that the defect electric dipoles which are difficult to steer are reduced, the overturning barrier of the electric dipoles is reduced, mainly reflected in the reduction of coercive field and the reduction of residual planned intensity, and the sample can obtain fasterResponse speed, thereby leading to higher electric card response. Therefore, according to the formula provided by the invention, the doping content of strontium ions and manganese ions can be adjusted, the dielectric property, the polarization property and the electrocaloric effect of the barium titanate material are improved, the Curie point of a sample is moved to be close to room temperature, the temperature range of ferroelectric phase-to-paraelectric phase transition is widened, and a promising ferroelectric ceramic material system which can be used in the actual refrigeration field based on the electrocaloric effect is provided.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The manganese-doped barium strontium titanate ceramic with high electrocaloric effect is characterized in that the chemical formula of barium strontium titanate in the manganese-doped barium strontium titanate ceramic is (Ba)1-xSrx)(MnyTi1-y)O3；
Wherein x is 0.35-0.4, and y is 0.1-0.5%.
2. The manganese-doped barium strontium titanate ceramic of claim 1, wherein x is 0.35 or 0.4 and y is 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.
3. The preparation method of the manganese-doped barium strontium titanate ceramic of claim 1 or 2, which is characterized by comprising the following steps:
a) mixing BaCO3、SrCO3、MnO2And TiO2Mixing and calcining to obtain a calcined product;
b) mixing the calcined product with a binder and then granulating to obtain a powder dough;
c) molding the powder dough to obtain a ceramic blank;
d) and sintering the ceramic blank to obtain the manganese-doped barium strontium titanate ceramic.
4. The method of claim 3, wherein the mixing of step a) is ball milling;
the BaCO3、SrCO3、MnO2And TiO2In a molar ratio of (1-x): x: y: (1-y);
the calcining temperature is 1180-1220 ℃, and the calcining time is 2-7 h.
5. The preparation method according to claim 4, wherein the rotation speed of the ball milling and mixing is 200-300 rpm;
the ball milling and mixing time is 6-18 h;
the ball-milling mixed solvent is absolute ethyl alcohol and/or deionized water.
6. The method of claim 3, wherein the binder of step b) is selected from polyvinyl butyral and/or polyvinyl alcohol;
the solvent for granulation is selected from ethanol and/or deionized water.
7. The method as claimed in claim 3, wherein the molding process of step c) comprises axial press molding and cold isostatic press molding;
and the axial compression molding and the cold isostatic pressing are carried out in sequence.
8. The preparation method according to claim 7, wherein the pressure of the axial compression molding is 5-10 MPa, and the duration of the axial compression molding is 1-2 min;
the pressure of the cold isostatic pressing is 180-230 Mpa, and the duration time of the cold isostatic pressing is 3-6 min.
9. The preparation method according to claim 3, wherein the sintering temperature in the step d) is 1350-1450 ℃;
the sintering time is 4-6 h.
10. The use of the manganese-doped barium strontium titanate ceramic of claim 1 or 2 in sensors, solid state refrigeration or energy storage devices.
CN202010662216.XA 2020-07-10 2020-07-10 Manganese-doped barium strontium titanate ceramic with high electrocaloric effect and preparation method and application thereof Pending CN111763084A (en)

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