CN107285767B - Non-uniform stoichiometric antiferroelectric ceramic, and preparation method and application thereof - Google Patents
Non-uniform stoichiometric antiferroelectric ceramic, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an antiferroelectric ceramic material, a preparation method and an application thereof, wherein the antiferroelectric ceramic material has a general formula shown in formula I: (Pb)0.97La0.02)(Zr0.95Ti0.05)1+yO3(ii) a In the formula I, y is more than or equal to-0.05 and less than or equal to 0.05. The antiferroelectric ceramic material has a general formula shown in formula I, and is a non-uniform nonstoichiometric antiferroelectric ceramic. Compared with the prior art, the non-stoichiometric antiferroelectric ceramic material has good energy storage characteristics. The experimental results show that: under the saturated electric field at 190-210 ℃, the energy storage efficiency is 82.1% -93.1%; the energy storage density is 0.83 to 0.98J/cm at the temperature of 190 to 210 ℃ and under a saturated electric field3(ii) a Within the temperature range of 160-220 ℃ and under the electric field with the strength of more than 30kV/cm, reversible phase transition from the antiferroelectric phase to the ferroelectric phase occurs.
Description
Technical Field
The invention relates to the technical field of antiferroelectric ceramics, in particular to an antiferroelectric ceramic with a non-uniform stoichiometric ratio, a preparation method and an application thereof.
Background
The antiferroelectric material is a material in which dipoles on adjacent ion connecting lines are arranged in an antiparallel manner within a certain temperature range, the spontaneous polarization strength is zero macroscopically, and no ferroelectric hysteresis loop exists. There are two main types of structures of antiferroelectric materials found so far: one is NaNbO3Base type, with antiparallel dipoles along the diagonal of the edges of the pseudo-cubic perovskite unit cell, and PbZrO3The basal form, whose antiparallel dipoles are along the diagonal of the pseudo-cubic perovskite surface. Wherein, PbZrO3The base-type antiferroelectric material can be converted from antiferroelectric to ferroelectric under the action of an electric field, and is accompanied with great strain and charge release, so that the base-type antiferroelectric material is an antiferroelectric material with important action value.
The antiferroelectric ceramic medium is made of antiferroelectric PbZrO3Or a solid solution based on lead zirconate titanate (PZT) piezoelectric ceramics. The antiferroelectric ceramic is a better high-voltage ceramic dielectricA material. Lead lanthanum zirconate titanate (PLZT) is a PZT lead zirconate titanate piezoelectric ceramic. The performance of PLZT material is largely studied in the prior report, such as Pb0.97La0.02[(Zr59Till)0.7Sn0.3]O3An antiferroelectric ceramic. However, PLZT ceramics prepared by non-uniform stoichiometric ratio method and their ferroelectric properties have not been reported.
Disclosure of Invention
In view of the above, the present invention provides an antiferroelectric ceramic with non-uniform stoichiometric ratio, a method for preparing the same, and applications thereof.
The invention provides an antiferroelectric ceramic material, which has a general formula shown in formula I:
(Pb0.97La0.02)(Zr0.95Ti0.05)1+yO3formula I;
in the formula I, y is more than or equal to-0.05 and less than or equal to 0.05.
Preferably, said-0.03. ltoreq. y.ltoreq.0.05.
Preferably, y is 0.05, y is 0.03, y is 0.01, y is-0.03 or y is-0.01.
Preferably, the energy storage efficiency of the antiferroelectric ceramic material is 82.1% -93.1% at 190-210 ℃ under a saturated electric field.
Preferably, the energy storage density of the antiferroelectric ceramic material is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3。
The invention provides a preparation method of the antiferroelectric ceramic material in the technical scheme, which comprises the following steps:
mixing PbO and ZrO2、TiO2And La2O3Mixing to obtain a mixed material, and ball-milling the mixed material in a ball-milling medium to obtain powder;
synthesizing the powder to obtain a synthetic material;
granulating the synthetic material, and molding to obtain a blank body;
and (3) performing plastic removal and sintering on the blank to obtain the antiferroelectric ceramic material with the general formula shown in the formula I:
(Pb0.97La0.02)(Zr0.95Ti0.05)1+yO3formula I
In the formula I, y is more than or equal to-0.05 and less than or equal to 0.05.
Preferably, the synthesis temperature is 820-880 ℃; the synthesis time is 1.5-2.5 h.
Preferably, the sintering temperature is 1190-1250 ℃; the sintering time is 1.5-2.5 h.
Preferably, the ball milling media comprises ethanol and agate balls; the mass ratio of the agate balls to the mixed materials to the ethanol is 1.8-2.3: 0.8-1.2: 0.35-0.6.
The invention provides an application of the antiferroelectric ceramic material in the technical scheme or the antiferroelectric ceramic material prepared by the preparation method in the technical scheme in an energy storage capacitor.
The invention provides an antiferroelectric ceramic material, which has a general formula shown in formula I: (Pb)0.97La0.02)(Zr0.95Ti0.05)1+yO3(ii) a In the formula I, y is more than or equal to-0.05 and less than or equal to 0.05. The antiferroelectric ceramic material has a general formula shown in formula I, and is a non-uniform nonstoichiometric antiferroelectric ceramic. Compared with the prior art, the non-stoichiometric antiferroelectric ceramic material has good energy storage characteristics. The experimental results show that: under the saturated electric field at 190-210 ℃, the energy storage efficiency is 82.1% -93.1%; the energy storage density is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3(ii) a Reversible phase transition from antiferroelectric phase to ferroelectric phase occurs under the electric field with the intensity of more than 30kV/cm at the temperature of 160-220 ℃.
Drawings
FIG. 1 shows Pb prepared in example 1 of the present invention0.97La0.02(Zr0.95Ti0.05)0.97O3A dielectric and loss thermogram of the antiferroelectric ceramic material;
FIG. 2 shows Pb prepared in example 1 of the present invention0.97La0.02(Zr0.95Ti0.05)0.97O3Hysteresis curves of ceramics at different temperatures (E ═ E)60kV/cm)；
FIG. 3 shows Pb prepared in example 1 of the present invention0.97La0.02(Zr0.95Ti0.05)0.97O3Energy storage density and energy storage efficiency (E is 60kV/cm) of the ceramic at different temperatures;
FIG. 4 shows Pb prepared in example 2 of the present invention0.97La0.02(Zr0.95Ti0.05)0.99O3Hysteresis curves (E is 50kV/cm) of the ceramic at different temperatures;
FIG. 5 shows Pb prepared in example 2 of the present invention0.97La0.02(Zr0.95Ti0.05)0.99O3The energy storage density and the energy storage efficiency of the ceramic at different temperatures (E is 50 kV/cm);
FIG. 6 shows Pb prepared in example 3 of the present invention0.97La0.02(Zr0.95Ti0.05)1.01O3Electric hysteresis loops (E is 50kV/cm) of the ceramic at different temperatures;
FIG. 7 shows Pb prepared in example 3 of the present invention0.97La0.02(Zr0.95Ti0.05)1.01O3The energy storage density and the energy storage efficiency (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures;
FIG. 8 shows Pb prepared in example 4 of the present invention0.97La0.02(Zr0.95Ti0.05)1.03O3Electric hysteresis loops (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures;
FIG. 9 shows Pb prepared in example 4 of the present invention0.97La0.02(Zr0.95Ti0.05)1.03O3; the energy storage density and the energy storage efficiency (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures;
FIG. 10 shows Pb prepared in example 5 of the present invention0.97La0.02(Zr0.95Ti0.05)1.05O3Ferroelectric hysteresis loops (E is 50kV/cm) of antiferroelectric ceramic materials at different temperatures;
FIG. 11 shows Pb prepared in example 5 of the present invention0.97La0.02(Zr0.95Ti0.05)1.05O3And the energy storage density and the energy storage efficiency (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures.
Detailed Description
The invention provides an antiferroelectric ceramic material, which has a general formula shown in formula I:
(Pb0.97La0.02)(Zr0.95Ti0.05)1+yO3formula I;
in the formula I, y is more than or equal to-0.05 and less than or equal to 0.05.
In the present invention, -0.05. ltoreq. y.ltoreq.0.05, preferably, -0.03. ltoreq. y.ltoreq.0.05. In particular embodiments of the invention, y is particularly-0.03, -0.01, 0.03, or 0.05.
In the present invention, the antiferroelectric ceramic material (Pb)0.97La0.02)(Zr0.95Ti0.05)1+yO3(PLZT2/95/5) preferably has an energy storage efficiency of 82.1% -93.1% at 190-210 ℃ under a saturated electric field. The energy storage density of the antiferroelectric ceramic material is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3. The antiferroelectric ceramic material generates reversible AFE-FE ferroelectric phase transition in an electric field with the strength of more than 30kV/cm at 160-220 ℃.
In the present invention, the antiferroelectric ceramic material is specifically Pb0.97La0.02(Zr0.95Ti0.05)0.97O3、Pb0.97La0.02(Zr0.95Ti0.05)0.99O3、Pb0.97La0.02(Zr0.95Ti0.05)1.01O3、Pb0.97La0.02(Zr0.95Ti0.05)1.03O3Or Pb0.97La0.02(Zr0.95Ti0.05)1.05O3。
The invention provides a preparation method of the antiferroelectric ceramic material in the technical scheme, which comprises the following steps:
mixing PbO and ZrO2、TiO2And La2O3Mixing to obtain a mixturePerforming ball milling on the mixed material in a ball milling medium to obtain powder;
synthesizing the powder to obtain a synthetic material;
granulating the synthetic material, and molding to obtain a blank body;
and (3) performing plastic removal and sintering on the blank to obtain the antiferroelectric ceramic material with the general formula shown in the formula I:
(Pb0.97La0.02)(Zr0.95Ti0.05)1+yO3formula I;
in the formula I, y is more than or equal to-0.05 and less than or equal to 0.05.
The invention uses PbO and ZrO2、TiO2And La2O3Mixing to obtain a mixed material, and ball-milling the mixed material in a ball-milling medium to obtain powder. In the present invention, the PbO and ZrO are2、TiO2And La2O3The amount of (A) is weighed according to the composition of the chemical formula shown in formula I.
In the invention, the ball-milling medium comprises ethanol and agate balls; the mass ratio of the agate balls to the mixed materials to the ethanol is preferably 1.8-2.3: 0.8-1.2: 0.35-0.6; more preferably 2:1: 0.5. The rotation speed of the ball mill is 700-800 rpm, more preferably 730-770 rpm, and most preferably 750 rpm; the time for ball milling is preferably 22-26 h, more preferably 23-25 h, and most preferably 24 h. The invention dries the ball-milled mixed material at 100 ℃ preferably to obtain powder.
The invention synthesizes the powder to obtain the synthetic material. The present invention preferably places the powder in an alumina crucible, well known to those skilled in the art, and the synthesis is carried out with a lid seal. The synthesis temperature is preferably 820-880 ℃, more preferably 840-870 ℃ and most preferably 850 ℃; the synthesis time is preferably 1.5-2.5 h, more preferably 1.8-2.2 h, and most preferably 2 h.
The invention carries out granulation and molding on the synthetic material to obtain a green body. The invention preferably ball-mills the composite material again and then dries. And (4) granulating the dried synthetic material. The invention preferably adopts polyvinyl alcohol solution for granulation; the mass fraction of the polyvinyl alcohol solution is preferably 4-6%, and more preferably 5%. Granulating, sieving and molding. The invention is preferably pressed and molded under 300MPa to obtain a blank. The shape of the blank body is preferably a circular sheet shape; the diameter of the disk-shaped blank is 12mm, and the thickness of the disk-shaped blank is 1.2-1.4 mm.
The invention carries out plastic removal and sintering on the green body to obtain the antiferroelectric ceramic material with the general formula shown in the formula I. The plastic removal is preferably carried out for 1-3 h at 650-700 ℃. The purpose of plastic removal is to allow the organic matter in the green body to be discharged.
In the invention, the sintering temperature is preferably 1190-1250 ℃; the sintering time is preferably 1.5-2.5 h. The invention preferably adopts lead zirconate powder for burning. The invention preferably heats up to the needed sintering temperature at a heating rate of not less than 2 ℃/min. Naturally cooling to obtain the antiferroelectric ceramic material with the general formula shown in the formula I.
The invention also provides an application of the antiferroelectric ceramic material in the technical scheme or the antiferroelectric ceramic material prepared by the preparation method in the technical scheme in an energy storage capacitor.
The invention preferably performs a ferroelectric property test on the antiferroelectric ceramic material, and the test method comprises the following steps:
polishing the antiferroelectric ceramic material to the thickness of 0.5-0.7 mm, coating silver paste on the upper surface and the lower surface of the antiferroelectric ceramic material, placing the antiferroelectric ceramic material in a heating furnace, heating to 650 ℃, preserving the temperature for 120min, naturally cooling to room temperature to obtain a ceramic element, and testing the ferroelectric property of the ceramic element.
The invention provides an antiferroelectric ceramic material, which has a general formula shown in formula I: (Pb)0.97La0.02)(Zr0.95Ti0.05)1+yO3(ii) a In the formula I, y is more than or equal to-0.05 and less than or equal to 0.05. The antiferroelectric ceramic material has a general formula shown in formula I, and is a non-uniform nonstoichiometric antiferroelectric ceramic. Compared with the prior art, the non-stoichiometric antiferroelectric ceramic material has good energy storage characteristics. The experimental results show that: under the saturated electric field at 190-210 ℃, the energy storage efficiency is 82.1% -93.1%; the energy storage density is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3(ii) a The reversible antiferroelectric phase occurs under the electric field with the strength of more than 30kV/cm at the temperature of 160-220 DEG CAnd (4) phase transition to a ferroelectric phase.
In order to further illustrate the present invention, the following examples are provided to describe in detail a non-uniform stoichiometric antiferroelectric ceramic, its preparation method and its application, but they should not be construed as limiting the scope of the present invention.
Example 1
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.95Ti0.05)0.97O3
(1) Weighing PbO and ZrO according to the chemical formula of the antiferroelectric ceramic2、TiO2、La2O3Mixing materials in a ball mill, ball: material preparation: the weight ratio of the absolute ethyl alcohol is 2:1:0.5, the ball milling medium is absolute ethyl alcohol and agate balls, the rotating speed of the ball mill is 750r/min, and the ball milling time is 24 hours; then drying the raw materials at 100 ℃;
(2) putting the powder dried in the step (1) into an alumina crucible, covering and sealing the alumina crucible, and synthesizing the powder for 2 hours at 850 ℃;
(3) performing ball milling on the synthetic material obtained in the step (2) again, drying at 100 ℃, adding 5 wt% of PVA solution for granulation, sieving, and then pressing and forming into a blank under the pressure of 300MPa, wherein the blank has the diameter of 12mm, the thickness of 1.2-1.4 mm and is in a shape of a circular sheet; then, the plastic removal comprises heat preservation for 1-3 hours at 650-700 ℃;
(4) and (4) burying and burning the blank body of the organic matter discharged in the step (3) by adopting lead zirconate powder, wherein the heating rate is not lower than 2 ℃/min, keeping the temperature for 2h at 1190-1250 ℃, and cooling along with the furnace to obtain the lanthanum-doped lead zirconate titanate antiferroelectric ceramic material.
The method comprises the steps of grinding a sintered antiferroelectric ceramic material sample into a wafer with the diameter of 12mm and the thickness of 0.5-0.7 mm, cleaning, drying, coating silver paste on the front side and the back side, drying again, heating to 650 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2h to burn the silver to obtain the ceramic element.
The ceramic component prepared in example 1 was measured for dielectric temperature spectrum and hysteresis loop at different temperatures, and the results are shown in FIG. 1, and FIG. 1 is Pb prepared in example 10.97La0.02(Zr0.95Ti0.05)0.97O3A dielectric and loss thermogram of the antiferroelectric ceramic material; measuring the dielectric constant as a function of dielectric loss is an important matter and means of studying the dielectricity and structure of antiferroelectric materials, and from FIG. 1 it can be observed that there are two distinct phase transitions, where the first peak represents the antiferroelectric to ferroelectric phase transition (T)0) The second peak represents the transition from the ferroelectric phase to the paraelectric phase (T)C)。
FIG. 2 shows Pb prepared in example 1 of the present invention0.97La0.02(Zr0.95Ti0.05)0.97O3Hysteresis curves (E is 60kV/cm) of the ceramic at different temperatures, wherein the abscissa E represents the electric field strength and the ordinate P represents the polarization strength. As can be seen from fig. 2: the antiferroelectric ceramic material is a stable AFE phase within the temperature range of 160-210 ℃, the ferroelectric hysteresis loop is of a narrow oblique type, and the paraelectric Phase (PE) is adopted when the temperature is higher than 215 ℃.
FIG. 3 shows Pb prepared in example 1 of the present invention0.97La0.02(Zr0.95Ti0.05)0.97O3Energy storage density and energy storage efficiency (E60 kV/cm) of the ceramic at different temperatures. As can be seen from fig. 3: the energy storage efficiency of the antiferroelectric ceramic material is not greatly changed along with the temperature and is higher than 80 percent. Wherein the storage energy density is 1.20J/cm at 195 deg.C3The available energy density can reach 0.98J/cm at most3The energy storage efficiency is 81.7%;
example 2
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.95Ti0.05)0.99O3
The preparation process of example 1 was repeated according to the above formulation;
the results of the measurement of the hysteresis loops at different temperatures of the ceramic element prepared in example 2 according to the present invention are shown in FIG. 4, and FIG. 4 is Pb prepared in example 2 according to the present invention0.97La0.02(Zr0.95Ti0.05)0.99O3Hysteresis curves (E is 50kV/cm) of the ceramic at different temperatures, wherein the abscissa E represents the electric field intensity and the ordinate P represents the polarization intensity. As can be seen from FIG. 4, the antiferroelectric ceramic material is stable AFE phase in the temperature range of 180-210 ℃, the hysteresis loop is "narrow-slope type", and the paraelectric Phase (PE) is obtained when the temperature is higher than 215 ℃.
FIG. 5 shows Pb prepared in example 2 of the present invention0.97La0.02(Zr0.95Ti0.05)0.99O3The energy storage density and the energy storage efficiency (E is 50kV/cm) of the ceramic at different temperatures. As can be seen from fig. 5: the energy storage efficiency of the antiferroelectric ceramic material is not changed greatly with the temperature and is higher than 85.7 percent. Wherein the storage energy density is 1.0J/cm at 195 deg.C3The available energy density can reach 0.87J/cm at most3The energy storage efficiency was 87%.
Example 3
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.95Ti0.05)1.01O3
The preparation process of example 1 was repeated according to the above formulation;
the ceramic element of this example was measured for hysteresis loops at different temperatures according to the present invention, and the results are shown in FIG. 6, in which FIG. 6 shows Pb prepared in example 3 of the present invention0.97La0.02(Zr0.95Ti0.05)1.01O3The hysteresis loop (E is 50kV/cm) of the ceramic at different temperatures, the abscissa E represents the electric field strength, and the ordinate P represents the polarization strength. As can be seen from fig. 6: the ceramic is stable AFE phase in the temperature range of 180-210 ℃, the electric hysteresis loop is in a narrow oblique type, and the paraelectric Phase (PE) is formed when the temperature is higher than 215 ℃.
FIG. 7 shows Pb prepared in example 3 of the present invention0.97La0.02(Zr0.95Ti0.05)1.01O3The energy storage density and energy storage efficiency (E ═ 50kV/cm) of the antiferroelectric ceramic material at different temperatures can be seen from fig. 7: the energy storage efficiency of the antiferroelectric ceramic material is not greatly changed along with the temperature and is higher than 84.1 percent. Wherein the storage energy density is 1.06J/cm at 195 deg.C3The available energy density can reach 0.91J/cm at most3The energy storage efficiency was 85.8%.
Example 4
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.95Ti0.05)1.03O3
The preparation process of example 1 was repeated according to the above formulation;
the invention performs the measurement of the hysteresis loop at different temperatures and the calculation of the energy storage density and the energy storage efficiency on the ceramic element of the embodiment, and the result is shown in fig. 8, and fig. 8 is Pb prepared in the embodiment 4 of the invention0.97La0.02(Zr0.95Ti0.05)1.03O3The ferroelectric hysteresis loop (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures, the abscissa E is the electric field intensity, and the ordinate P is the polarization intensity. As can be seen from fig. 8: the antiferroelectric ceramic material is a stable AFE phase within the temperature range of 185-215 ℃, the ferroelectric hysteresis loop is of a narrow oblique type, and the paraelectric Phase (PE) is adopted when the temperature is higher than 220 ℃.
FIG. 9 shows Pb prepared in example 4 of the present invention0.97La0.02(Zr0.95Ti0.05)1.03O3；And the energy storage density and the energy storage efficiency (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures. As can be seen from fig. 9: the energy storage efficiency of the antiferroelectric ceramic material is not changed greatly with the temperature and is higher than 85.9 percent. Wherein the storage energy density is 0.95J/cm at 205 deg.C3The available energy density can reach 0.83J/cm at most3The energy storage efficiency is 87.4 percent
Example 5
The material composition is as follows: pb0.97La0.02(Zr0.95Ti0.05)1.05O3
The preparation process of example 1 was repeated according to the above formulation;
the present inventors measured the hysteresis loop at different temperatures and calculated the energy storage density and the energy storage efficiency of the ceramic element of this example, and the results are shown in fig. 10, and fig. 10 shows Pb prepared in example 5 of the present invention0.97La0.02(Zr0.95Ti0.05)1.05O3Electric hysteresis of antiferroelectric ceramic material at different temperaturesLine (E ═ 50kV/cm), abscissa E is electric field strength, and ordinate P is polarization strength. As can be seen from FIG. 10, the ceramic material is stable AFE phase in the temperature range of 180-215 ℃, the hysteresis loop is "narrow inclined", and the paraelectric Phase (PE) is obtained when the temperature is higher than 220 ℃.
FIG. 11 shows Pb prepared in example 5 of the present invention0.97La0.02(Zr0.95Ti0.05)1.05O3And the energy storage density and the energy storage efficiency (E is 50kV/cm) of the antiferroelectric ceramic material at different temperatures. As can be seen from fig. 11: the energy storage efficiency of the ceramic is not changed greatly with the temperature and is higher than 82 percent. Wherein the storage energy density is 1.01J/cm at 200 deg.C3The available energy density can reach 0.86J/cm at most3The energy storage efficiency was 85.1%.
From the above examples, the present invention provides an antiferroelectric ceramic material having a general formula shown in formula I: (Pb)0.97La0.02)(Zr0.95Ti0.05)1+yO3(ii) a In the formula I, y is more than or equal to-0.05 and less than or equal to 0.05. The antiferroelectric ceramic material has a general formula shown in formula I, and is a non-uniform nonstoichiometric antiferroelectric ceramic. Compared with the prior art, the non-stoichiometric antiferroelectric ceramic material has good energy storage characteristics. The experimental results show that: under the saturated electric field at 190-210 ℃, the energy storage efficiency is 82.1% -93.1%; the energy storage density is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3(ii) a Reversible phase transition from antiferroelectric phase to ferroelectric phase occurs under the electric field with the intensity of more than 30kV/cm at the temperature of 160-220 ℃.
The antiferroelectric ceramic material provided by the invention shows good energy storage characteristics of PLZT2/95/5 antiferroelectric ceramic, and due to the unique preparation method of the heterogeneous stoichiometric ratio, the application of PLZT2/95/5 antiferroelectric ceramic to a high-density energy storage device has important significance.
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 (6)
1. An antiferroelectric ceramic material having the general formula shown in formula I:
(Pb0.97La0.02) (Zr0.95Ti0.05)1+yO3 formula I;
formula I wherein y =0.05, y =0.03, y =0.01, y = -0.03 or y = -0.01;
the antiferroelectric ceramic material is non-uniform nonstoichiometric antiferroelectric ceramic;
the energy storage efficiency of the antiferroelectric ceramic material is 82.1% -93.1% at 190-210 ℃ in a saturated electric field;
the energy storage density of the antiferroelectric ceramic material is 0.83-0.98J/cm at 190-210 ℃ under a saturated electric field3。
2. A method of preparing the antiferroelectric ceramic material of claim 1, comprising the steps of:
mixing PbO and ZrO2、TiO2And La2O3Mixing to obtain a mixed material, and ball-milling the mixed material in a ball-milling medium to obtain powder;
synthesizing the powder to obtain a synthetic material;
granulating the synthetic material, and molding to obtain a blank body;
and (3) performing plastic removal and sintering on the blank to obtain the antiferroelectric ceramic material with the general formula shown in the formula I:
(Pb0.97La0.02) (Zr0.95Ti0.05)1+yO3 formula I
Formula I wherein y =0.05, y =0.03, y =0.01, y = -0.03 or y = -0.01.
3. The preparation method according to claim 2, wherein the synthesis temperature is 820-880 ℃; the synthesis time is 1.5-2.5 h.
4. The preparation method according to claim 2, wherein the sintering temperature is 1190-1250 ℃; the sintering time is 1.5-2.5 h.
5. The method of claim 2, wherein the ball milling media comprises ethanol and agate balls; the mass ratio of the agate balls to the mixed materials to the ethanol is 1.8-2.3: 0.8-1.2: 0.35-0.6.
6. Use of the antiferroelectric ceramic material according to claim 1 or the antiferroelectric ceramic material prepared by the preparation method according to any one of claims 2 to 5 in an energy storage capacitor.
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