CN112624757A - Sodium bismuth titanate-based relaxor ferroelectric ceramic material with wide-temperature-region high-electrocaloric effect and low-field high-electrocaloric strength and preparation method thereof - Google Patents
Sodium bismuth titanate-based relaxor ferroelectric ceramic material with wide-temperature-region high-electrocaloric effect and low-field high-electrocaloric strength and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sodium bismuth titanate based relaxor ferroelectric ceramic material with wide temperature zone high electrocaloric effect and high electrocaloric strength and a preparation method thereof, wherein the ceramic material conforms to a chemical general formula (Bi)0.5Na0.44‑xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3The preparation method comprises the following steps: according to the chemical general formula, the ceramic material is obtained by mixing the raw materials and sequentially carrying out the processes of primary ball milling, discharging, drying, presintering, secondary ball milling, granulation, press forming, binder removal and sintering. Compared with the prior art, the invention provides a novel bismuth titanateThe sodium-based relaxor ferroelectric ceramic material is used as a lead-free material, meets the requirement of environmental protection, has the advantages of low preparation cost and good stability, and has a high electric clamping effect under a low electric field and a wide temperature region high electric clamping effect, thereby having a huge application prospect in the aspect of solid refrigeration.
Description
Technical Field
The invention belongs to the technical field of electronic functional materials and devices, and relates to a novel sodium bismuth titanate-based relaxor ferroelectric ceramic material with wide-temperature-region high electrocaloric effect and high electrocaloric strength and a preparation method thereof, in particular to a (Bi) sodium titanate-based relaxor ferroelectric ceramic material0.5Na0.44- xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3The electrocaloric effect of the lead-free relaxation ferroelectric ceramic and the preparation method thereof.
Background
Conventional air conditioning refrigeration systems are designed following compressor refrigeration theory and rely on refrigerants such as freon or chlorofluorocarbons (CFCs) to drive them. When the refrigerant is volatilized into the atmospheric ozone layer, the refrigerant can catalyze the ozone to react, so that the ultraviolet radiation barrier capability in the ozone layer is greatly reduced. In order to reduce the damage to the ozone layer, people gradually adopt Hydrochlorofluorocarbons (HCFCs) which have no catalytic capacity on ozone to replace freon, but the agent accelerates the global warming process and causes serious influence on the living environment of human beings. In view of the above problems, research on new refrigeration technologies and refrigeration materials has been conducted at random. The refrigeration modes with potential development at present comprise electric card refrigeration, magnetic card refrigeration, thermoelectric coolers and the like. The efficiency of the thermoelectric cooler is low, and the magnetic card effect refrigeration needs a large superconducting magnet or a heavy permanent magnet array to provide a required large magnetic field, which is contrary to the requirement of miniaturization of devices. The electric card effect refrigeration scheme has the advantages of small equipment volume, strong working reliability and no pollution to the atmosphere, and is expected to become a substitute for the refrigeration scheme of the compressor. During 2006 + 2008, a.s.mischienko (a.s.mischienko et al, Science 311(2006)1270) and b.neese (b.neese, Science 321(2008)821) et al found a huge electrical card effect in antiferroelectric films and polymers, making electrical card solid refrigeration technology begin to be of interest to numerous researchers. During 2018 + 2019, researchers have paid more attention to electrical card refrigeration materials and devices, B.Nair (Nature 575,468 + 472(2019)), Yunda Wang (Wang et al, Science 370,129 + 133(2020)) and A.Torrell Lou (Torrell Lou et al, Science 370,125 + 129(2020)) and others utilize PbSc0.5Ta0.5O3The prepared MLCC obtains a wider temperature zoneHigh electrical card effect.
However, the practical application of the electric card material has a long way to go, the materials with high electric card effect at present generally belong to lead-based materials, are toxic to human bodies and harmful to the environment, and related regulations are issued in sequence to limit the use of the lead-containing materials in Europe. In addition, the electric card strength of the existing electric card material is low, namely the ratio between temperature change and an electric field is low, so that the ideal conversion efficiency between energy consumption and a refrigeration effect cannot be achieved, and further the wide application of the electric card material is limited. Therefore, based on the requirements of high energy conversion rate and environmental protection, it is necessary to research and develop lead-free materials with high electrocaloric effect and high electrocaloric strength.
Chinese patent CN201410474671.1 discloses a method for improving the performance of dielectric electrocaloric ceramic refrigeration equipment, which uses BaTiO3And bismuth-based PbTiO3The electric card device is obtained by forming a multilayer structure, but the patent is only a design mode of the electric card refrigeration device, breakthrough research is not carried out from the single material angle, the electric card temperature change and the electric card strength are not measured by actual tests, and the related material contains lead and is harmful to human bodies.
Disclosure of Invention
The invention aims to provide a sodium bismuth titanate-based relaxor ferroelectric ceramic material with wide-temperature-range high electric clamping effect and low-field high electric clamping strength and a preparation method thereof, which are used for replacing the traditional refrigerant material and lead-based electric clamping refrigeration material, and can realize high electric clamping temperature change in a wider temperature range and high electric clamping temperature change in a lower electric field while reducing pollution or damaging the environment, thereby really promoting the application process of the electric clamping material.
The purpose of the invention can be realized by the following technical scheme:
sodium bismuth titanate based relaxor ferroelectric ceramic material with wide temperature zone high electrocaloric effect and high electrocaloric strength and chemical flux thereofHas the formula (Bi)0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3Wherein x is more than or equal to 0 and less than or equal to 0.02, and within the numerical range, the sodium bismuth titanate based relaxor ferroelectric ceramic material has a pure perovskite structure and can keep higher positive and negative electric clamping temperature change in a wider temperature zone.
Furthermore, the preferable value range of x is more than or equal to 0 and less than or equal to 0.012, and in the value range, the bismuth sodium titanate based relaxor ferroelectric ceramic material has the highest positive and negative temperature change of the positive and negative temperature change at the temperature higher than the room temperature, and in a wider temperature region, the bismuth sodium titanate based relaxor ferroelectric ceramic material shows the asymmetric temperature change effect with higher strength of the negative temperature change card under the critical electric field, and the critical electric field is lower than the saturated polarization electric field.
More preferably, x is 0.012, that is, the chemical formula of the bismuth sodium titanate-based relaxor ferroelectric ceramic material is (Bi)0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3At the moment, the ceramic material has the highest temperature change of the electric card near the room temperature, and shows an asymmetric temperature change effect with higher intensity of the negative temperature change electric card under a critical electric field, and the critical electric field is lower than a saturated polarization electric field;
specifically, the ceramic material has the positive temperature transformation clamping strength of 0.103-0.142 K.mm/kV, the negative temperature transformation clamping strength of 0.104-0.109 K.mm/kV in an electric field of 4kV/mm at the temperature of 25-60 ℃, the positive temperature transformation clamping temperature variation exceeds 0.438K and the negative temperature transformation clamping temperature variation exceeds 0.404K in an electric field of 6kV/mm at the temperature of 25-100 ℃; in addition, the asymmetric electric card effect that the negative temperature becomes higher than the positive temperature can be triggered under the low electric field of 3kV/mm at 40 ℃, and the intensity of the negative temperature transformation electric card is as high as 0.108 Kmm/kV.
A preparation method of the sodium bismuth titanate based relaxor ferroelectric ceramic material comprises the following steps: according to the chemical general formula, mixing a bismuth source, a sodium source, a potassium source, a strontium source, a titanium source and a niobium source, and sequentially carrying out primary ball milling, discharging, drying, pre-sintering, secondary ball milling, granulation, press molding, binder removal and sintering processes to obtain the bismuth titanate sodium-based relaxor ferroelectric ceramic material.
Further, the bismuth source comprises Bi2O3The sodium source comprises Na2CO3Said potassium source comprises K2CO3The strontium source comprises SrCO3The titanium source comprises TiO2Said niobium source comprising Nb2O5。
Furthermore, in the primary ball milling process and the secondary ball milling process, the ball milling time is 10-12 h.
Further, in the pre-sintering process, the pre-sintering temperature is 800-.
Further, in the granulation process, the used binder is polyvinyl alcohol (PVA), and the addition amount of the binder is 6-10 wt%.
Furthermore, in the compression molding process, the molding pressure is 4-6 MPa.
Further, the glue discharging process specifically comprises the following steps: heating to 500-600 ℃ at the heating rate of 0.5-2 ℃/min, and calcining at constant temperature for 7-10 h.
Further, the sintering process specifically comprises: heating to 1180-1200 ℃ at the heating rate of 3-5 ℃/min, and calcining at constant temperature for 2-3 h.
The components form an R3c phase (a three-side phase) and a P4bm phase (a four-side phase) by a solid-phase sintering method, the R3c phase can form a ferroelectric phase under the action of an electric field, so that the entropy change of an electric dipole is increased, and the P4bm can be converted into an R3c ferroelectric phase, so that the entropy change of phase change entropy is increased. The single form of entropy change can not improve the entropy change to the greatest extent, and when the proportion of the two structures is proper, the comprehensive effect of the two forms of entropy change reaches the highest, namely the morphotropic phase boundary. The increase of potassium ions reduces the content of sodium ions, so that the occupation of A-site ions is more disordered, the random field effect is increased, the whole system is induced to evolve towards the relaxation direction, and the phase boundary is generated. Under the action of an electric field, the relaxation phase generated by the structure is converted into the ferroelectric phase, so that the service temperature zone of the material is widened, and the electric card strength is improved. (Bi)0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3X is more than or equal to 0<0.012 hours, the ceramic is loadedThe highest temperature change is at a temperature higher than room temperature, mainly because the range of the component is the left side of a phase boundary, more R3c phases exist, a material system is biased to a non-ergodic relaxation state, more P4bm phases appear through a high-temperature induction system, and then a quasi-homogeneous phase boundary appears, so that the high-temperature change electric card effect is obtained. x is the number of>At 0.012, more P4bm phases exist, the material system is positioned at the right side of the phase boundary, and more P4bm phases are induced at high temperature, so that the material system is far away from the phase boundary and is not beneficial to the occurrence of high-potential card effect at high temperature. When x is 0.012, the material system has a phase boundary at room temperature, and a high electrocaloric effect at room temperature can be obtained.
The invention adopts a solid-phase sintering method to prepare lead-free (Bi)0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3The ceramic material is a wide temperature range electric card material and a high electric card strength material, has a wider service temperature range, can excite higher electric card temperature change under a lower electric field, is used as a lead-free material meeting the environmental protection requirement, has the advantages of low preparation cost, good stability and the like, and has great significance for promoting the application of the electric card material.
Compared with the prior art, the invention has the following characteristics:
1) the electric card refrigeration material has electric card strength comparable to that of a lead-based material, can excite higher positive and negative electric card temperature variation in a low electric field, has the positive temperature electric card strength of 0.160 Kmm/kV in a 4kV/mm electric field, and has the negative temperature electric card strength of 0.160 Kmm/kV in a 2.5kV/mm low electric field;
2) the ceramic refrigerating material has higher electric clamping strength and positive and negative electric clamping temperature variation in a wider temperature range;
3) the ceramic material belongs to a lead-free material, does not cause environmental pollution in the processes of preparation, application and abandonment, and is an environment-friendly relaxor ferroelectric solid refrigeration material;
4) in the prior art, indirect test of the performance of the electric card is mostly adopted, namely, the electric card effect is obtained through theoretical calculation by means of parameters such as specific heat capacity, density and the like, the temperature change of the electric card is obtained through a high-sensitivity thermal resistance direct test method, and compared with an indirect test method, the method has the advantages that the obtained numerical value is closer to a real result and an actual rule, and the reference value is higher.
Drawings
FIG. 1 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3X-ray powder test results of (1);
FIG. 2 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3Scanning electron microscope images of the surface topography;
FIG. 3 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3And example two prepared sodium bismuth titanate based relaxor ferroelectric ceramic material (Bi)0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3A trend graph of positive and negative electric calorie temperature changes along with temperature under a saturated electric field of 6 kV/mm;
FIG. 4 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3And example two prepared sodium bismuth titanate based relaxor ferroelectric ceramic material (Bi)0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3A trend graph of positive and negative electric calorie temperature changes along with temperature under an electric field of 4 kV/mm;
FIG. 5 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3And example two prepared sodium bismuth titanate based relaxor ferroelectric ceramic material (Bi)0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3A trend graph of positive and negative temperature transformer card strength along with temperature change under a saturated electric field of 6kV/mm and an electric field of 4 kV/mm;
FIG. 6 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3A graph of the electrical card temperature variation test result at 50 ℃ and a low electric field of 2.5 kV/mm;
FIG. 7 shows a sodium bismuth titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example one0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3A graph of the electrical card temperature variation test result at 70 ℃ and a low electric field of 2.7 kV/mm;
FIG. 8 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example two0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3X-ray powder test results of (1);
FIG. 9 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example two0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3Scanning electron microscope images of the surface topography;
FIG. 10 shows a bismuth sodium titanate-based relaxor ferroelectric ceramic material (Bi) prepared in example two0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3And (3) an electric card temperature variation test result chart under a low electric field of 3kV/mm at 40 ℃.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A sodium bismuth titanate based relaxor ferroelectric ceramic material with wide temperature range high electrocaloric effect and high electrocaloric strength, its chemical formula is (Bi)0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3Where 0. ltoreq. x.ltoreq.0.02, preferably in a range of 0. ltoreq. x.ltoreq.0.012, and still more preferably 0.005 or 0.012.
The preparation method of the sodium bismuth titanate based relaxor ferroelectric ceramic material comprises the following steps:
s1, selecting Bi with the purity of more than 99 percent2O3、Na2CO3、K2CO3、SrCO3、TiO2And Nb2O5Weighing and mixing the bismuth sodium titanate-based relaxor ferroelectric ceramic as a raw material according to the chemical general formula to obtain primary mixed powder;
s2, adding absolute ethyl alcohol and zirconium dioxide grinding balls into a nylon tank to serve as ball milling media, adding the primary mixed powder, transferring the primary mixed powder to a planetary ball mill to perform primary ball milling for 10-12 hours, discharging the material, and drying the material in a blast drying oven at 80-120 ℃ to obtain dried powder;
s3, transferring the dried powder into a muffle furnace, and pre-burning for 3-4h at 800-;
s4, performing secondary ball milling, discharging and drying on the pre-sintered powder for 10-12h by the same method as the step 2), adding 6-10 wt% of adhesive polyvinyl alcohol relative to the mass of the powder, granulating, and then performing compression molding under 4-6MPa to obtain a ceramic blank;
s5, transferring the ceramic blank into a muffle furnace, heating to 500-600 ℃ at a heating rate of 0.5-2 ℃/min (preferably 560 ℃), and removing glue at constant temperature for 7-10h to obtain a glue-removed ceramic blank;
s6, heating the binder removal ceramic blank to 1180-1200 ℃ at the heating rate of 3-5 ℃/min, sintering at the constant temperature for 2-3h, and naturally cooling to room temperature to obtain the bismuth sodium titanate-based relaxor ferroelectric ceramic material.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
The first embodiment is as follows:
sodium bismuth titanate based relaxation with wide temperature zone high electrocaloric effect and high electrocaloric strengthThe ferroelectric ceramic material has a chemical formula of (Bi)0.5Na0.435K0.065)0.92Sr0.08Ti0.99Nb0.01O3Namely x is 0.005, and the preparation method comprises the following steps:
s1, selecting Bi with the purity of more than 99 percent2O3、Na2CO3、K2CO3、SrCO3、TiO2And Nb2O5Weighing and mixing the bismuth sodium titanate-based relaxor ferroelectric ceramic serving as a raw material according to the stoichiometric ratio in the chemical general formula to obtain primary mixed powder;
s2, adding absolute ethyl alcohol and zirconium dioxide grinding balls into a nylon tank to serve as ball milling media, adding the primary mixed powder, transferring the primary mixed powder into a planetary ball mill to perform primary ball milling for 12 hours, discharging the material, and drying the material in a blast drying oven at 100 ℃ to obtain dried powder;
s3, filling the dried powder into a corundum crucible, compacting, transferring into a muffle furnace, heating to 850 ℃ at a heating rate of 3 ℃/min, and presintering for 4 hours at constant temperature to obtain presintered powder;
s4, performing secondary ball milling, discharging and drying on the pre-sintered powder for 12 hours in sequence by the same method as the step 2), adding adhesive polyvinyl alcohol accounting for 8 wt% of the powder, granulating, and then performing compression molding under the pressure of 5MPa to obtain a ceramic blank with the diameter of 10mm and the thickness of 1 mm;
s5, transferring the ceramic blank into a muffle furnace, heating to 560 ℃ at a heating rate of 1 ℃/min, and discharging glue at constant temperature for 10h to obtain a discharged ceramic blank;
s6, heating the binder removal ceramic blank to 1200 ℃ at the heating rate of 3 ℃/min, sintering at constant temperature for 3h, and naturally cooling to room temperature to obtain the bismuth sodium titanate based relaxor ferroelectric ceramic material.
The embodiment also comprises the step of carrying out material structure characterization and electric card performance test on the obtained bismuth titanate sodium-based relaxor ferroelectric ceramic material, which specifically comprises the following steps:
1) the obtained ceramic material is ground into powder by a mortar and then is subjected to XRD test, and the obtained ceramic material is polished and then is subjected to SEM test after being thermally corroded for 0.5h at 1080 ℃, and the test results are as follows:
the XRD diffraction pattern of the resulting ceramic material is shown in FIG. 1, from which it can be seen that the phase structure of the ceramic material is a single ABO3A perovskite structure;
as shown in fig. 2, the SEM image of the ceramic material obtained shows that the ceramic material has perfect grain growth and no obvious second phase, and the ceramic sheet has a compact structure and no obvious pores;
2) after the obtained ceramic material is subjected to grinding, polishing and double-sided silver electrode coating in sequence, an electric card temperature change test is carried out, and the test result is as follows:
as shown in fig. 3, which is a graph of the change trend of positive and negative electrical blocking temperature changes of the obtained ceramic material with temperature under a saturated electric field of 6kV/mm, it can be seen from the graph that under a saturated electric field of 50-125 ℃ and 6kV/mm, the positive electrical blocking temperature changes of the ceramic material exceed 0.539K, and the negative electrical blocking temperature changes exceed 0.505K;
as shown in FIG. 4, which is a graph of the variation trend of positive and negative electric blocking temperature of the obtained ceramic material with temperature under an electric field of 4kV/mm, it can be seen from the graph that under an electric field of 50-90 ℃ and 4kV/mm, the positive electric blocking temperature of the ceramic material is higher than 0.518K, and the negative electric blocking temperature is higher than 0.474K;
FIG. 5 shows the trend of the positive and negative temperature change of the ceramic material with temperature under different electric fields, and it can be seen from the graph that under the electric field of 4kV/mm, the positive temperature transformation clamping strength of the ceramic material reaches 0.130-0.160 K.mm/kV, and the negative temperature transformation clamping strength reaches 0.119-0.148 K.mm/kV;
FIG. 6 shows the result of the temperature variation test of the ceramic material under a low electric field of 2.5kV/mm at 50 deg.C, wherein the temperature variation of the positive and negative electric cards shows asymmetric phenomena, the negative temperature becomes high up to 0.400K, the strength of the negative temperature variation card reaches up to 0.160 K.mm/kV, and the higher temperature variation of the electric card is triggered under the low electric field;
as shown in FIG. 7, the test result of the temperature change of the positive and negative electric cards of the obtained ceramic material at 70 ℃ and a low electric field of 2.7kV/mm shows that the temperature change of the positive and negative electric cards shows asymmetric phenomena, the negative temperature becomes high to 0.437K, the strength of the negative temperature change card reaches 0.162 K.mm/kV, and the higher negative temperature change of the electric cards is triggered under the low electric field.
Example two:
a sodium bismuth titanate based relaxor ferroelectric ceramic material with wide temperature range high electrocaloric effect and high electrocaloric strength, its chemical formula is (Bi)0.5Na0.428K0.072)0.92Sr0.08Ti0.99Nb0.01O3Namely x is 0.012, and the preparation method comprises the following steps:
s1, selecting Bi with the purity of more than 99 percent2O3、Na2CO3、K2CO3、SrCO3、TiO2And Nb2O5Weighing and mixing the bismuth sodium titanate-based relaxor ferroelectric ceramic serving as a raw material according to the stoichiometric ratio in the chemical general formula to obtain primary mixed powder;
s2, adding absolute ethyl alcohol and zirconium dioxide grinding balls into a nylon tank to serve as ball milling media, adding the primary mixed powder, transferring the primary mixed powder into a planetary ball mill to perform primary ball milling for 12 hours, discharging the material, and drying the material in a blast drying oven at 100 ℃ to obtain dried powder;
s3, filling the dried powder into a corundum crucible, compacting, transferring into a muffle furnace, heating to 850 ℃ at a heating rate of 3 ℃/min, and presintering for 4 hours at constant temperature to obtain presintered powder;
s4, performing secondary ball milling, discharging and drying on the pre-sintered powder for 12 hours in sequence by the same method as the step 2), adding adhesive polyvinyl alcohol accounting for 8 wt% of the powder, granulating, and then performing compression molding under the pressure of 5MPa to obtain a ceramic blank with the diameter of 10mm and the thickness of 1 mm;
s5, transferring the ceramic blank into a muffle furnace, heating to 560 ℃ at a heating rate of 1 ℃/min, and discharging glue at constant temperature for 10h to obtain a discharged ceramic blank;
s6, heating the binder removal ceramic blank to 1200 ℃ at the heating rate of 3 ℃/min, sintering at constant temperature for 3h, and naturally cooling to room temperature to obtain the bismuth sodium titanate based relaxor ferroelectric ceramic material.
The embodiment also comprises the step of carrying out material structure characterization and electric card performance test on the obtained bismuth titanate sodium-based relaxor ferroelectric ceramic material, which specifically comprises the following steps:
1) the obtained ceramic material is ground into powder by a mortar and then is subjected to XRD test, and the obtained ceramic material is polished and then is subjected to SEM test after being thermally corroded for 0.5h at 1080 ℃, and the test results are as follows:
the XRD diffraction pattern of the resulting ceramic material is shown in FIG. 8, from which it can be seen that the phase structure of the ceramic material is a single ABO3A perovskite structure;
as shown in fig. 9, which is an SEM image of the obtained ceramic material, it can be seen that the ceramic material has perfect grain growth and no obvious second phase, and the ceramic sheet has a compact structure and no obvious pores;
2) after the obtained ceramic material is subjected to grinding, polishing and double-sided silver electrode coating in sequence, an electric card temperature change test is carried out, and the test result is as follows:
as shown in fig. 3, which is a graph of the variation trend of positive and negative electrical blocking temperature changes of the obtained ceramic material with temperature under a saturated electric field of 6kV/mm, it can be seen from the graph that under a saturated electric field of 25-100 ℃ and 6kV/mm, the positive electrical blocking temperature changes of the ceramic material exceed 0.438K, and the negative electrical blocking temperature changes exceed 0.404K;
as shown in FIG. 4, which is a graph of the variation trend of positive and negative electric blocking temperature of the obtained ceramic material with temperature under an electric field of 4kV/mm, it can be seen that under an electric field of 25-60 ℃ and 4kV/mm, the positive electric blocking temperature of the ceramic material is higher than 0.412K, and the negative electric blocking temperature is higher than 0.414K;
FIG. 5 shows the trend of the positive and negative temperature change of the ceramic material with temperature under different electric fields, and it can be seen from the graph that the positive temperature transformation clamping strength of the ceramic material reaches 0.103-0.142 Kmm/kV, and the negative temperature transformation clamping strength reaches 0.104-0.109 Kmm/kV;
as shown in FIG. 10, which is a graph of the electrical clamping temperature variation test result of the obtained ceramic material at a low electric field of 3kV/mm at 40 ℃, the positive and negative electrical clamping temperature variations show an asymmetric phenomenon, the negative temperature variation reaches 0.325K, the negative temperature variation clamping strength reaches 0.108 K.mm/kV, and the higher electrical clamping temperature variation is triggered under the low electric field.
The test results of the first and second examples are combined to show that (Bi) in the present invention0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3The ceramic material has higher electric card strength and electric card temperature change in a wider temperature zone range, has practical significance for reducing the applicable voltage of the electric card material and triggering the higher electric card temperature change at the same time, is favorable for the practical application of solid refrigeration, and has great significance for promoting the practical application process of the electric card material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A sodium bismuth titanate based relaxor ferroelectric ceramic material with wide temperature zone high electrocaloric effect and high electrocaloric strength is characterized in that the general chemical formula of the sodium bismuth titanate based relaxor ferroelectric ceramic material is (Bi)0.5Na0.44-xK0.06+x)0.92Sr0.08Ti0.99Nb0.01O3Wherein x is more than or equal to 0 and less than or equal to 0.02.
2. The sodium bismuth titanate-based relaxor ferroelectric ceramic material having a wide temperature range high electrocaloric effect and high electrocaloric strength as claimed in claim 1, wherein the ceramic has a maximum electrocaloric positive temperature change at room temperature when x is 0.012.
3. A method for preparing a sodium bismuth titanate-based relaxor ferroelectric ceramic material as claimed in claim 1, characterized in that the method comprises: according to the chemical general formula, mixing a bismuth source, a sodium source, a potassium source, a strontium source, a titanium source and a niobium source, and sequentially carrying out primary ball milling, discharging, drying, pre-sintering, secondary ball milling, granulation, press molding, binder removal and sintering processes to obtain the bismuth titanate sodium-based relaxor ferroelectric ceramic material.
4. The method of claim 3, wherein the bismuth source comprises Bi2O3The sodium source comprises Na2CO3Said potassium source comprises K2CO3The strontium source comprises SrCO3The titanium source comprises TiO2Said niobium source comprising Nb2O5。
5. The method for preparing the bismuth sodium titanate-based relaxor ferroelectric ceramic material according to claim 3, wherein the ball milling time is 10-12h in both the primary ball milling and the secondary ball milling.
6. The method for preparing the bismuth sodium titanate-based relaxor ferroelectric ceramic material as claimed in claim 3, wherein the pre-sintering temperature is 800-900 ℃ and the pre-sintering time is 3-4 h.
7. The method for preparing a bismuth sodium titanate-based relaxor ferroelectric ceramic material as claimed in claim 3, wherein the binder used in the granulation process is polyvinyl alcohol and the binder is added in an amount of 6-10 wt%.
8. The method for preparing a bismuth sodium titanate based relaxor ferroelectric ceramic material according to claim 3, wherein the forming pressure is 4-6MPa during the press forming process.
9. The method for preparing the sodium bismuth titanate-based relaxor ferroelectric ceramic material according to claim 3, wherein the glue removing process specifically comprises: heating to 500-600 ℃ at the heating rate of 0.5-2 ℃/min, and calcining at constant temperature for 7-10 h.
10. The method for preparing a bismuth sodium titanate based relaxor ferroelectric ceramic material according to claim 3, wherein the sintering process is specifically: heating to 1180-1200 ℃ at the heating rate of 3-5 ℃/min, and calcining at constant temperature for 2-3 h.
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