CN111233470B - Antiferroelectric ceramic material with excellent charge and discharge performance and preparation method thereof - Google Patents

Antiferroelectric ceramic material with excellent charge and discharge performance and preparation method thereof Download PDF

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CN111233470B
CN111233470B CN202010065883.XA CN202010065883A CN111233470B CN 111233470 B CN111233470 B CN 111233470B CN 202010065883 A CN202010065883 A CN 202010065883A CN 111233470 B CN111233470 B CN 111233470B
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antiferroelectric ceramic
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翟继卫
葛广龙
黄凯威
沈波
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Tongji University
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Abstract

The invention relates to an antiferroelectric ceramic material with excellent charge and discharge performance and a preparation method thereof, wherein the antiferroelectric ceramic material has a chemical general formula of (Pb)0.97‑xBaxLa0.02)(ZrySn1‑y‑zTiz)O3(ii) a The preparation method comprises the steps of mixing a lead source, a barium source, a lanthanum source, a zirconium source, a tin source and a titanium source, performing ball milling, drying and calcining processes in sequence, performing secondary ball milling, drying, mixing with a polyvinyl alcohol solution, granulating, press-forming, binder removal and sintering processes in sequence, and obtaining the antiferroelectric ceramic material. Compared with the prior art, the effective energy storage density of the antiferroelectric ceramic material prepared by the invention can reach 12.8J/cm3The energy storage efficiency can reach 84.2 percent, and the current density reaches 1815A/cm2The discharge period reaches 51.6ns, and the power density reaches 327MW/cm3And exhibits very excellent charge and discharge properties.

Description

Antiferroelectric ceramic material with excellent charge and discharge performance and preparation method thereof
Technical Field
The invention belongs to the technical field of functional ceramics, relates to an antiferroelectric ceramic material with excellent charge and discharge performance and a preparation method thereof, and particularly relates to an antiferroelectric ceramic material with the characteristics of high energy storage density, high energy storage efficiency, large discharge current, high power density and the like and a preparation method thereof.
Background
With the progress of science and technology, pulse power technology is widely applied in various fields such as industry, architecture, biomedicine, advanced technology and the like. As an important energy storage element of a pulse power device, a capacitor accounts for a great proportion of the pulse power device, and as a direction of long-term development in the industry, research on a pulse capacitor with high energy storage density, high discharge current, high discharge speed and high power density has become a key and urgent task of research in the field of pulse power technology. The preferred dielectric materials of the pulse capacitor at present mainly comprise three types of linear ceramics, ferroelectric ceramics and antiferroelectric ceramics. The linear ceramics have dielectric linearity characteristics that the dielectric constant hardly changes with an electric field, which means that the linear ceramicsThe porcelain can only obtain considerable energy storage density under extremely high electric field. While too high an electric field is unsafe for pulsed capacitors, ferroelectric and antiferroelectric ceramics with dielectric non-linear characteristics are the preferred materials for high storage density dielectric capacitors. Wherein, the ferroelectric ceramic has spontaneous polarization and has very high dielectric constant in the absence of an external electric field, and under the action of the electric field, the dielectric constant of the ferroelectric ceramic is reduced along with the increase of the electric field, and the breakdown field intensity is usually not high, so that the energy storage density of the ceramic under high field is not large and is not more than 2J/cm3. The antiferroelectric ceramic is characterized by having a double electric hysteresis loop: the antiferroelectric ceramic is the same as the linear ceramic at lower external electric fields, which means that the antiferroelectric ceramic possesses extremely low remnant polarization; when the electric field is increased to a certain value, the phase transition from antiferroelectric to ferroelectric occurs, so that the polarization strength of the material is suddenly increased. The antiferroelectric material thus has a higher energy storage density while having a high energy storage efficiency due to a very low remanent polarization.
At present, many researches are focused on improving the energy storage behavior of antiferroelectric ceramics, for example, Chinese patent CN104725041A discloses a lanthanum-doped lead zirconate titanate stannate antiferroelectric ceramic with high energy storage efficiency and a preparation method thereof, the energy storage efficiency of the antiferroelectric ceramic prepared by the method reaches 90.4%, but the effective energy storage density is only 1.28J/cm3(ii) a Chinese patent CN108358630A discloses an antiferroelectric ceramic material with high energy storage density and a preparation method thereof, wherein the antiferroelectric ceramic prepared by the method has the releasable energy storage density of only 2.68J/cm under the working electric field of 23.5kV/mm3But the energy loss is large, and the energy storage efficiency is 78%; in addition, chinese patent CN107459350A discloses a dielectric energy storage antiferroelectric ceramic material and a preparation method thereof, by which energy storage efficiency of 85% (150 ℃) and stability of energy storage density can be obtained>85% (20-150 ℃) and the energy storage density is 2.77J/cm3The antiferroelectric material system of (1). According to the reported literature, the energy storage performance of the current antiferroelectric material still cannot meet the application requirements, so obtaining the antiferroelectric ceramic with high energy storage density and high energy storage efficiency still is one of the key problems to be solved urgently, and the invention is directed to solving the problemThe development of the pulse power capacitor with high energy storage density and high power density is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antiferroelectric ceramic material with excellent charge and discharge performance and a preparation method thereof, which are used for solving the problem of poor energy storage performance of the conventional antiferroelectric material.
The purpose of the invention can be realized by the following technical scheme:
an antiferroelectric ceramic material with a chemical formula of (Pb)0.97-xBaxLa0.02)(ZrySn1-y-zTiz)O3Wherein 0 is<x≤0.04，0<y<1，0≤z<1。
The invention is particularly applicable to antiferroelectric matrix ((Pb) with higher phase transition electric field0.97La0.02)(ZrySn1-y- zTiz)O3) And carrying out barium doping modification, simultaneously reducing the doping content of titanium element, and reducing the over-low breakdown electric field caused by titanium valence change, so as to obtain a balanced phase change electric field and breakdown field strength and obtain extremely high energy storage density.
Preferably, x is 0.01, 0.02, 0.03 or 0.04, y is preferably 0.6, and z is preferably 0.
The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) mixing a lead source, a barium source, a lanthanum source, a zirconium source, a tin source and a titanium source according to a chemical ratio, and sequentially performing ball milling, drying and calcining processes to obtain calcined powder;
2) sequentially carrying out secondary ball milling and drying processes on the calcined powder to obtain dried powder, mixing the dried powder with a polyvinyl alcohol solution, and then sequentially carrying out granulation and compression molding to obtain a ceramic blank;
3) and sequentially carrying out glue removal and sintering processes on the ceramic blank to obtain the antiferroelectric ceramic material.
Further, in step 1), the lead sourceIncluding Pb3O4Said barium source comprises BaCO3The lanthanum source comprises La2O3Said source of zirconium comprising ZrO2Said tin source comprises SnO2The titanium source comprises TiO2。
As a preferred embodiment, Pb is used3O4、BaCO3、La2O3、ZrO2、SnO2、TiO2The purity of (A) is more than 99%.
Further, in the step 1), the ball milling time is 14-16 h in the ball milling process.
Further, in the step 1), in the calcination process, the calcination temperature is 800-900 ℃, and the calcination time is 2-3 h.
Further, in the step 2), the secondary ball milling is high-energy ball milling, and the high-energy ball milling time is 1-2 h.
Further, in the step 2), the mass concentration of the polyvinyl alcohol solution (PVA solution) is 6-10%, and the addition amount of the polyvinyl alcohol solution is 0.1-0.5 mL/g of dry powder.
Further, in the step 2), the forming pressure in the compression forming is 4-8 MPa.
Further, in the step 3), the glue discharging temperature is 500-600 ℃ and the glue discharging time is 6-10 h in the glue discharging process.
Further, in the step 3), the sintering process is heating to 1200-1350 ℃ at a heating rate of 2-5 ℃/min, and sintering for 2-5 h under heat preservation.
The preparation method also comprises the steps of sequentially polishing the prepared antiferroelectric ceramic material by using sand paper with different particle sizes to obtain a thin ceramic sheet with a bright and flat surface, spraying gold on the thin ceramic sheet to obtain a gold electrode with the diameter of 1.5-2.5 mm, and then performing heat treatment in a muffle furnace, namely roasting at the temperature of 180-220 ℃ for 0.5-1 h, wherein the obtained material can be subjected to subsequent test characterization.
Compared with the prior art, the invention has the following characteristics:
1) the barium element is selected to replace the lead element, firstly, the antiferroelectric matrix with a high antiferroelectric-ferroelectric phase transition electric field is obtained on the basis of fixing the lanthanum element content to be 2 percent, the difficulty of inducing the ferroelectric phase to appear is properly reduced by adopting a method of barium ion equivalent substitution with large ionic radius, and the doped substitution of the barium ion is beneficial to reducing the electric hysteresis width of the antiferroelectric material; meanwhile, the doping substitution of barium is beneficial to improving the resistance of the ceramic body and restricting the formation and migration of a vacancy dipole so as to improve the breakdown field strength of the material; the method comprises the steps of taking a pre-designed antiferroelectric material with a high phase-change electric field as a matrix, and balancing the phase-change electric field and a breakdown electric field by adjusting the doping content of barium ions to obtain the antiferroelectric ceramic material with high energy storage density and high energy storage efficiency;
2) preparing powder with higher activity by adopting a high-energy ball milling method;
3) the adopted solid-phase sintering method is simple in preparation method, economical and practical;
4) the antiferroelectric ceramic prepared by the optimized components has excellent charge and discharge performance.
Drawings
FIG. 1 is an XRD spectrum of 4 antiferroelectric ceramic materials in example V;
FIG. 2 is a scanning electron micrograph of 4 antiferroelectric ceramic materials of the fifth embodiment;
FIG. 3 is a hysteresis loop diagram of 4 samples to be tested in the sixth embodiment;
FIG. 4 is a graph comparing the energy storage density and the energy storage efficiency of 4 samples to be tested in the sixth embodiment;
FIG. 5 is a graph showing the charging and discharging curves of the sample to be tested prepared from the antiferroelectric ceramic material in example two under the electric field strength of 360 kV/cm;
FIG. 6 is a graph showing the discharge time, current density and power density of a sample to be tested prepared from the antiferroelectric ceramic material according to the second embodiment as a function of the electric field;
fig. 7 is hysteresis curves of 3 samples to be measured in the tenth embodiment.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
A chemical general formula of (Pb)0.97-xBaxLa0.02)(ZrySn1-y-zTiz)O3Of the antiferroelectric ceramic material of (1), wherein 0<x≤0.04，0<y<1，0≤z<1。
The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) mixing a lead source, a barium source, a lanthanum source, a zirconium source, a tin source and a titanium source, and performing ball milling, drying and calcining processes in sequence to obtain calcined powder;
2) sequentially carrying out high-energy ball milling and drying processes on the calcined powder to obtain dried powder, mixing the dried powder with a polyvinyl alcohol solution, and sequentially carrying out granulation and compression molding to obtain a ceramic blank;
3) and sequentially carrying out glue removal and sintering processes on the ceramic blank to obtain the antiferroelectric ceramic material.
Wherein, in the step 1), the lead source comprises Pb3O4The barium source comprises BaCO3The lanthanum source comprises La2O3The source of zirconium comprises ZrO2The tin source comprises SnO2The titanium source comprises TiO2And Pb used3O4、BaCO3、La2O3、ZrO2、SnO2、TiO2The purity of the compound is more than 99 percent; in the ball milling process, the ball milling time is 14-16 h (preferably 15 h); in the calcining process, the calcining temperature is 800-900 ℃ (preferably 900 ℃), and the calcining time is 2-3 h (preferably 3 h).
In the step 2), in the high-energy ball milling process, the high-energy ball milling time is 1-2 h; the mass concentration of the polyvinyl alcohol solution is 6-10 percent (preferably 8 percent), and the adding amount is 0.1-0.5 mL (preferably 0.3 mL) of the polyvinyl alcohol solution per gram of the dry powder; in the press molding, the molding pressure is 4 to 8 MPa (preferably 6 MPa).
In the step 3), the glue discharging temperature is 500-; the sintering process is to heat up to 1200-1350 ℃ (preferably 1300 ℃) at the heating rate of 2-5 ℃/min (preferably 3 ℃/min), and to carry out heat preservation and sintering for 2-5 h (preferably 3 h).
The preparation method also comprises the steps of sequentially grinding the prepared antiferroelectric ceramic material by using sand paper with different particle sizes to obtain a thin ceramic plate with a bright and smooth surface, then spraying gold on the thin ceramic plate to obtain a gold electrode with the diameter of 1.5-2.5 mm (preferably 2.0 mm), and then carrying out heat treatment in a muffle furnace, namely roasting for 0.5-1 h (preferably 0.5 h) at 180-220 ℃ (preferably 200 ℃), wherein the obtained material can be subjected to subsequent test characterization.
The first embodiment is as follows:
a chemical general formula of (Pb)0.96Ba0.01La0.02)(Zr0.6Sn0.4)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.3mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
Example two:
a chemical general formula of (Pb)0.95Ba0.02La0.02)(Zr0.6Sn0.4)O3ToThe preparation method of the ferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.3mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
Example three:
a chemical general formula of (Pb)0.94Ba0.03La0.02)(Zr0.6Sn0.4)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.3mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
Example four:
a chemical general formula of (Pb)0.93Ba0.04La0.02)(Zr0.6Sn0.4)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.3mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
Example five:
in this example, the antiferroelectric ceramic materials prepared in the first to fourth examples were respectively subjected to XRD and SEM characterization, and the characterization results are shown in fig. 1 and fig. 2, respectively.
As can be seen from fig. 1, the antiferroelectric ceramic materials prepared in examples one to four are all of a single perovskite structure.
As can be seen from FIG. 2, the anti-ferroelectric ceramic material prepared in the first example has more uniform grain distribution but more pores; the antiferroelectric ceramic material prepared in the second embodiment has uniform grain size distribution and fewer accumulated compact pores, and the antiferroelectric ceramic material prepared in the third embodiment has non-uniform grain size distribution, contains more pores and is not compact in structure; the antiferroelectric ceramic material prepared in the fourth embodiment contains a part of liquid phase and contains more pores.
Example six:
in this embodiment, the antiferroelectric ceramic materials prepared in the first to fourth embodiments are respectively and sequentially polished by using sand paper with different particle sizes to obtain thin ceramic sheets with bright and flat surfaces and 0.1 mm thickness, then the thin ceramic sheets are subjected to gold spraying to obtain gold electrodes with 2mm diameters, and then the gold electrodes are placed in a muffle furnace for heat treatment, i.e., the gold electrodes are roasted at 200 ℃ for 0.5 h to respectively obtain corresponding samples to be detected.
The energy storage performance characterization is performed on 4 samples to be tested, as shown in fig. 3, the hysteresis loop of the 4 samples to be tested is shown, as shown in fig. 4, the comparison graph of the effective energy storage density and the energy storage efficiency is obtained by calculation based on the hysteresis loop, and as can be seen from the comparison graph, in the first embodiment, the breakdown electric field strength of the samples to be tested is 395 kV/cm, and the maximum polarization value is 43.46 μ C/cm2The effective energy storage density is 10.7J/cm3The energy storage efficiency is 84.4%; in the second embodiment, the breakdown electric field strength of the sample to be tested is 450 kV/cm, and the maximum polarization value is 53.50 μ C/cm2The effective energy storage density is 12.8J/cm3The energy storage efficiency is 84.2%; in the third embodiment, the breakdown electric field strength of the sample to be tested is 360 kV/cm, and the maximum polarization value is 38.10 μ C/cm2The effective energy storage density is 8.43J/cm3The energy storage efficiency is 86.34%; in the fourth embodiment, the breakdown electric field strength of the sample to be tested is 320 kV/cm, and the maximum polarization value is 39.98 μ C/cm2The effective energy storage density is 7.85J/cm3The energy storage efficiency was 86.36%.
In addition, as shown in fig. 5, the underdamping curve of the sample to be tested prepared from the antiferroelectric ceramic material in the second embodiment is shown, and it can be seen from the figure that when the electric field strength is 360 kV/cm, and the electrode diameter is 2mm, the maximum discharge current of the sample to be tested can reach 57A; as shown in FIG. 6, the discharge of the sample to be measuredThe time, the current density and the power density are plotted with the change of the electric field intensity, and as can be seen from the graph, the current density of the sample to be measured is 1815A/cm2Discharge period of 51.6ns and power density of 327MW/cm3The material shows that the material has very excellent charge and discharge performance. Compared with Chinese patent CN107459350B (2.77J/cm)3Effective energy storage density of), CN104725041A (1.28J/cm)3Effective energy storage density of) and CN108358630A (2.68J/cm)3Effective energy storage density) of the ferroelectric ceramic material prepared by the invention has higher energy storage density. Meanwhile, the method is similar to Chinese patent CN110342925A (202.3 MW/cm)3Power density of (1) and 1498.6A/cm2) In contrast, the extremely high power density (327 MW/cm) of the antiferroelectric ceramic material prepared by the present invention3) With an extremely large current density (1815A/cm)2) Exhibit great advantages.
Example seven:
a chemical general formula of (Pb)0.96Ba0.01La0.02)(Zr0.35Sn0.6Ti0.05)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2、TiO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.1mL of the polyvinyl alcohol solution/g of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
And sequentially polishing the prepared antiferroelectric ceramic material by using sand paper with different particle sizes to obtain a thin ceramic sheet with a bright and flat surface, spraying gold on the thin ceramic sheet to obtain a gold electrode with the diameter of 1.5 mm, and performing heat treatment in a muffle furnace, namely roasting at 220 ℃ for 0.5 h to obtain the material, wherein the obtained material can be subjected to subsequent test characterization.
Example eight:
a chemical general formula of (Pb)0.96Ba0.01La0.02)(Zr0.65Sn0.3Ti0.5)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2、TiO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.3mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
And sequentially polishing the prepared antiferroelectric ceramic material by using sand paper with different particle sizes to obtain a thin ceramic sheet with a bright and flat surface, spraying gold on the thin ceramic sheet to obtain a gold electrode with the diameter of 2mm, and performing heat treatment in a muffle furnace, namely roasting at 200 ℃ for 0.5 h to obtain the material, wherein the obtained material can be subjected to subsequent test characterization.
Example nine:
a chemical general formula of (Pb)0.96Ba0.01La0.02)(Zr0.5Sn0.45Ti0.05)O3The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) selecting Pb with the purity of more than 99 percent3O4、BaCO3、La2O3、ZrO2、SnO2、TiO2As raw materials of the antiferroelectric ceramic material, respectively weighing and mixing according to chemical compositions to obtain a mixture;
2) sequentially carrying out ball milling on the mixture for 15 h, discharging, drying and calcining at 900 ℃ for 3 h to obtain calcined powder;
3) sequentially carrying out high-energy ball milling, discharging and drying on the calcined powder for 2 hours to obtain dry powder;
4) mixing the dried powder with 8wt% of polyvinyl alcohol solution (the addition amount of the polyvinyl alcohol solution is 0.5mL of the polyvinyl alcohol solution per gram of the dried powder), and then sequentially granulating and pressing under 6 MPa to form a ceramic blank;
5) and (3) placing the ceramic blank in a muffle furnace, carrying out glue discharging treatment for 10 h at 600 ℃, then heating to 1300 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 3 h to obtain the antiferroelectric ceramic material.
And sequentially polishing the prepared antiferroelectric ceramic material by using sand paper with different particle sizes to obtain a thin ceramic sheet with a bright and flat surface, spraying gold on the thin ceramic sheet to obtain a gold electrode with the diameter of 2mm, and performing heat treatment in a muffle furnace, namely roasting at 200 ℃ for 0.5 h to obtain the material, wherein the obtained material can be subjected to subsequent test characterization.
Example ten:
in this embodiment, the antiferroelectric ceramic materials prepared in the seventh to ninth embodiments are respectively and sequentially polished by using sand paper with different particle sizes to obtain thin ceramic sheets with bright and flat surfaces and 0.1 mm thickness, then the thin ceramic sheets are subjected to gold spraying to obtain gold electrodes with 2mm diameters, and then the gold electrodes are placed in a muffle furnace for heat treatment, i.e., the gold electrodes are roasted at 200 ℃ for 0.5 h to respectively obtain corresponding samples to be detected.
And (3) performing energy storage performance characterization on the 3 samples to be tested, wherein the energy storage performance characterization is shown in fig. 7 as an electric hysteresis loop of the 3 samples to be tested. In general, the samples seven to nine to be tested all show lower breakdown electric fields, so that complete double hysteresis loops are not observed. Comparing example one with example eight and example nine, in the case that the Zr/Sn ratio is not much different, since a small amount of Ti is introduced4+Resulting in a large difference in the antiferroelectric bihysteresis loop. At the same time, Ti4+The introduction of (2) greatly reduces the breakdown field strength of the ceramic body, which is unfavorable for ceramic energy storage. Thus, Ti can be determined4+It is disadvantageous in terms of energy storage, and the smaller the doping content, the better. The antiferroelectric component selected in the present invention is reasonable and correct.
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 (5)

1. An antiferroelectric ceramic material, characterized in that the antiferroelectric ceramic material has a chemical formula of (Pb)0.97- xBaxLa0.02)(ZrySn1-y-zTiz)O3Wherein 0 is<x≤0.04，0<y<1，0≤z<1；
The preparation method of the antiferroelectric ceramic material comprises the following steps:
1) mixing a lead source, a barium source, a lanthanum source, a zirconium source, a tin source and a titanium source according to a chemical ratio, and sequentially performing ball milling, drying and calcining processes to obtain calcined powder; wherein in the ball milling process, the ball milling time is 14-16 h; in the calcining process, the calcining temperature is 800-900 ℃, and the calcining time is 2-3 h;
2) sequentially carrying out secondary ball milling and drying processes on the calcined powder to obtain dried powder, mixing the dried powder with a polyvinyl alcohol solution, and then sequentially carrying out granulation and compression molding to obtain a ceramic blank; wherein the secondary ball milling is high-energy ball milling, and the high-energy ball milling time is 1-2 h;
3) sequentially carrying out glue removal and sintering processes on the ceramic blank to obtain the antiferroelectric ceramic material; wherein the sintering process is heating to 1200-1350 ℃ at the heating rate of 2-5 ℃/min, and sintering for 2-5 h.
2. An antiferroelectric ceramic material as claimed in claim 1, wherein in step 1) said source of lead comprises Pb3O4Said barium source comprises BaCO3The lanthanum source comprises La2O3Said source of zirconium comprising ZrO2Said tin source comprises SnO2The titanium source comprises TiO2。
3. The antiferroelectric ceramic material according to claim 1, wherein the mass concentration of the polyvinyl alcohol solution in step 2) is 6-10%.
4. The antiferroelectric ceramic material according to claim 1, wherein in step 2), said press forming is performed under a forming pressure of 4-8 MPa.
5. The antiferroelectric ceramic material as claimed in claim 1, wherein in the step 3), the glue discharging temperature is 500-600 ℃ and the glue discharging time is 6-10 h.
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