An antiferroelectric ceramic material with high saturation polarization strength and its preparation method and application

Abstract

The present invention relates to an antiferroelectric ceramic material with high saturation polarization, and a preparation method and application thereof. The chemical formula of the lead-based antiferroelectric ceramic material with high saturation polarization intensity is: Pb 1‑y‑3z / 2 La z Sr y (Zr a M b ) 1‑5x / 4 Nb x O3; wherein, 0 < x ≤ 0.1; 0 ≤ y ≤ 0.1, 0 ≤ z ≤ 0.1, and y and z are not simultaneously 0; 0 ≤ b ≤ 0.5, and a + b = 1, and M is at least one of Sn and Ti.

Description

Technical Field

[0001] The invention relates to an antiferroelectric ceramic material with high saturation polarization strength and a preparation method thereof, in particular to a lead-based antiferroelectric ceramic material with high saturation polarization strength and a preparation method thereof, belonging to the technical field of functional ceramics. Background Art

[0002] Pulse power technology can release megawatt-level electrical energy in a very short time, and is therefore widely used in lasers, accelerators, nuclear fusion, oil and gas exploration, radiation medicine, high-power microwaves, electromagnetic pulses and other fields. Pulse capacitors are key components of pulse power technology. As devices develop towards high power and miniaturization, capacitors are required to have faster discharge speeds and higher energy storage density. Compared with organic dielectric capacitors and electrolytic capacitors, ceramic capacitors have attracted much attention due to their advantages such as fast discharge speed, wide operating temperature range and low loss.

[0003] Among the dielectric materials used as pulse capacitors, antiferroelectric ceramics have higher energy storage density (up to more than ten J / cm2) than linear dielectric ceramics and ferroelectric ceramics. 3 ), faster discharge time (only a few hundred ns), more complete charge release (discharge efficiency can reach more than 85%), which is very conducive to the high power and miniaturization of devices, and has become a candidate material for the current high-performance pulse capacitor application. Many research institutions at home and abroad are actively conducting research on high-performance antiferroelectric materials based on high-power pulse capacitor applications. Summary of the invention

[0004] In view of the above problems, the object of the present invention is to provide an antiferroelectric ceramic material with high saturation polarization intensity and a preparation method thereof.

[0005] In one aspect, the present invention provides a lead-based antiferroelectric ceramic material with high saturation polarization strength, wherein the chemical formula of the lead-based antiferroelectric ceramic material is: Pb 1-y-3z / 2 La z Sr y (Zr a M b ) 1-5x / 4 Nb x O 3 ; Wherein, 0<x≤0.1; 0≤y≤0.1, 0≤z≤0.1, and y and z are not 0 at the same time; 0≤b≤0.5, and a+b=1, M=at least one of Sn and Ti.

[0006] In this field, the typical macroscopic feature of antiferroelectric materials is that they exhibit double hysteresis loops under the action of an electric field. When the external electric field rises above the forward turning field (EAF), the material changes from an antiferroelectric phase (AFE) to a ferroelectric phase (FE), the ferroelectric polarization is rearranged, and the external electrical energy is absorbed and converted into polarization energy (W re +W loss ); When the external electric field drops below the reverse transition electric field (EFA), the metastable FE returns to the AFE and releases energy instantly (W re ) and can obtain large current in the load circuit.

[0007] Moreover, the available energy storage density Wre (J / cm 3 ) can be calculated using the following formula: Among them, E is the electric field strength of the dielectric working (kV / cm), Pr and Pmax are the residual polarization strength and maximum polarization strength after the electric field is removed. It can be seen from the calculation formula that maintaining a large saturation polarization strength is the basic condition for obtaining a high energy storage density.

[0008] Based on this, the inventor creatively selected a radius smaller than Pb 2+ Ion modification by metal ions (e.g. La, Sr, etc.), based on the principle of perovskite structure tolerance factor, small radius ions replace Pb at the A position 2+ Ions can reduce the tolerance factor of the system, which is beneficial to the stability of the antiferroelectric phase and reduces hysteresis. 5+ Ion donor doping at the B site can compensate for the formation of oxygen vacancies during sintering, thereby inhibiting ionic conductivity and increasing the breakdown field strength. 5+ Doping promotes electrical uniformity and reduces polar coupling without reducing the average ionic polarizability, while maintaining the maximum saturation polarization intensity by doping small radius ions at the A site.

[0009] Preferably, the lead-based antiferroelectric ceramic material has an AFE-FE phase change electric field of 5 to 25 kV / mm and a FE-AFE phase change electric field of 4 to 20 kV / mm under the maximum operating electric field.

[0010] Preferably, the lead-based antiferroelectric ceramic material has a saturation polarization intensity of 45 to 55 μC / cm under the maximum operating electric field. 2 .

[0011] On the other hand, the present invention provides a method for preparing the lead-based antiferroelectric ceramic material having high saturation polarization strength, comprising:

[0012] (1) Select Pb 3 O 4 Powder,La 2 O 3 Powder, SrCO3 Powder, ZrO 2 Powder, TiO 2 Powder, SnO 2 Powder, Nb 2 O 5 Powder as raw material, according to the chemical formula: Pb 1-y-3z / 2 La z Sr y (Zr a M b ) 1-5x / 4 Nb x O 3 Weighing and mixing, and then calcining at 650° C. to 850° C. to obtain ceramic powder;

[0013] (2) mixing ceramic powder and a binder, granulating the mixture, and pressing the mixture into a ceramic blank;

[0014] (3) The ceramic green body is subjected to plasticizing and sintering to obtain a lead-based antiferroelectric ceramic material with high saturation polarization strength.

[0015] Preferably, the mixing method is wet ball milling; the parameters of the wet ball milling include: deionized water as the medium, zirconia balls or agate balls as ball milling balls; the rotation speed is 100 to 120 rpm, and the time is 12 to 36 hours; wherein the mass ratio of raw material: ball: deionized water = 1: (1.5 to 2.5): (0.8 to 1.2).

[0016] Preferably, the binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the added amount of the binder is 6-10wt.% of the weight of the ceramic powder.

[0017] Preferably, the calcination time is 1 to 4 hours.

[0018] Preferably, the temperature of the plastic discharge is 700-800°C, and the insulation time is 1-3 hours.

[0019] Preferably, the sintering temperature is 1300°C to 1400°C, and the holding time is 1 to 3 hours; preferably, the sintering heating rate is 2 to 5°C / minute; more preferably, the sintering process is carried out in a closed crucible, and ceramic powder is used for embedding.

[0020] On the other hand, the present invention provides an antiferroelectric ceramic element, comprising: the above-mentioned lead-based antiferroelectric ceramic material with high saturation polarization strength, and electrodes distributed on both sides of the lead-based antiferroelectric ceramic material with high saturation polarization strength.

[0021] Beneficial effects of the present invention:

[0022] (1) The present invention flexibly regulates small radius ions (radius smaller than Pb) at the A position. 2+ The doping amount of ions (metal ions) can be increased to obtain antiferroelectric materials with high AFE-FE phase transition electric field, low hysteresis and high energy storage efficiency;

[0023] (2) The present invention simultaneously introduces Nb at the B position to ensure that the polarization intensity does not decrease with the increase of the doping amount at the A position, thereby obtaining a greater energy storage density;

[0024] (3) The design idea of ​​antiferroelectric material components can be flexibly applied to other systems and play a guiding role in the preparation of antiferroelectric materials with high energy storage density. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The hysteresis loop of the antiferroelectric ceramic sample prepared in Example 1;

[0026] Figure 2 The hysteresis loop of the antiferroelectric ceramic sample prepared in Comparative Example 1;

[0027] Figure 3 The hysteresis loop of the antiferroelectric ceramic sample prepared in Example 2;

[0028] Figure 4 The hysteresis loop of the antiferroelectric ceramic sample prepared in Comparative Example 2;

[0029] Figure 5 The hysteresis loop of the antiferroelectric ceramic sample prepared in Example 3;

[0030] Figure 6 This is the hysteresis loop of the antiferroelectric ceramic sample prepared in Example 4. DETAILED DESCRIPTION

[0031] The present invention is further described below by the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, but not to limit the present invention.

[0032] In the present invention, the chemical composition of the high saturation polarization strength antiferroelectric ceramic material conforms to the chemical formula (Pb, Sr, La)(Zr, Ti, Sn)Nb x O 3 , wherein 0<x≤0.1. Optionally, the antiferroelectric ceramic material can be sintered at 1250℃~1400℃. The role of Nb is to maintain the maximum polarization intensity when Sr doping at the A position (to improve energy storage efficiency) reduces polarization, and at the same time can also improve the breakdown field strength. The optimal Nb doping content is 0.02.

[0033] Optionally, the antiferroelectric ceramic material has a saturation polarization intensity greater than 40 μC / cm2 at an operating electric field of 25 to 35 kV / mm. 2, the energy storage density is 3.4 - 6.9 J / cm 3 .

[0034] Optionally, the antiferroelectric ceramic material can have a relative dielectric constant of 754 - 803, a dielectric loss of 0.001 - 0.002, an AFE-FE phase transition electric field of 4.4 - 29.7 kV / mm (for example, 28.8 kV / mm), and an FE-AFE phase transition electric field of 2.1 - 28.3 kV / mm at room temperature (20 °C).

[0035] The preparation method of the high saturation polarization intensity antiferroelectric ceramic material in the present invention is illustrated by the following examples. Preferably, (Pb,Sr,La)(Zr,Ti,Sn)Nb x O 3 powder (ceramic powder) is prepared by the traditional solid-phase reaction method.

[0036] Calculate the required masses of Pb 3 O 4 , La 2 O 3 , SrCO 3 , ZrO 2 , TiO 2 , SnO 2 , Nb 2 O 5 , and mix the materials using the wet ball milling method to obtain a mixed powder. Among them, the wet ball milling method can adopt a mass ratio of ceramic powder: ball: deionized water = 1:(1.5 - 2.5):(0.8 - 1.2). The balls can be zirconia balls or agate balls. The ball milling speed can be 100 - 120 revolutions per minute. The ball milling is divided into two stages: the rough grinding time is 8 - 14 h, and the fine grinding time is 20 - 30 h. Among them, the different times of rough grinding and fine grinding result in different particle sizes. After drying the mixed powder, it is calcined to obtain (Pb,Sr,La)(Zr,Ti,Sn)NbxO 3 powder, where 0 < x ≤ 0.1, and x is the number of moles (i.e., the ceramic powder). Among them, the drying temperature can be 90 - 110 °C, and the time can be 10 - 12 hours. The calcination temperature can be 650 °C - 850 °C, and the holding time can be 1 - 3 hours.

[0037] Add a binder to the ceramic powder for granulation, and then press it into a green body. The binder is selected as polyvinyl alcohol PVA or polyvinyl butyral PVB, and the addition amount is 6 - 10 wt.% of the weight of the ceramic powder.

[0038] The green body is degreased to remove organic substances such as the binder in the ceramic. The degreasing temperature can be 700 - 800 °C, and the holding time can be 1 - 3 h.

[0039] The antiferroelectric ceramic can be obtained by sintering the ceramic blank after plastic removal. The sintering temperature can be 1300℃~1400℃, and the holding time can be 1~3h. The sintering process is carried out in a closed small crucible, and the ceramic is buried and fired with fillers of the same component. The heating rate is 2~5℃ / min.

[0040] The high saturation polarization strength antiferroelectric ceramic is ground, cleaned, dried, screen-printed with silver paste, dried again, and silver-sintered to obtain a ceramic sample with electrodes (i.e., an antiferroelectric ceramic element). The silver-sintering conditions may be a temperature of 600-800° C. and a heat preservation time of 30-60 minutes.

[0041] The following further examples are given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0042] Embodiment 1:

[0043] (1) Press Pb 0.92 Sr 0.08 (Zr 0.98 Ti 0.02 ) 0.975 Nb 0.02 O 3 Raw material powder Pb required for chemical formula composition calculation 3 O 4 、SrCO 3 、ZrO 2 、TiO 2 , Nb 2 O 5 The materials were mixed by wet ball milling, with zirconium oxide balls as the ball milling medium, and the raw materials: balls: deionized water were mixed at a mass ratio of 1:1.5:1 for 12 hours to make the components uniform. The materials were dried at 110°C to obtain powder.

[0044] (2) The dried powder was passed through a 40-mesh sieve, pressed into blocks in an air atmosphere, heated to 850°C at a rate of 2°C / min, and calcined for 2 hours to obtain a composite composition of Pb 0.92 Sr 0.08 (Zr 0.98 Ti 0.02 ) 0.975 Nb 0.02 O 3 Powder;

[0045] (3) The calcined powder was further finely ground for 24 hours, and after drying, 6% PVA was added to the powder for granulation. After aging for 24 hours, a ceramic blank with a diameter of 13 mm was pressed out;

[0046] (4) keeping the obtained green billet at 750° C. for 2 hours to discharge organic matter in the green billet;

[0047] (5) placing the sample after plasticizing in an alumina crucible and covering it with a filler of the same component to prevent the volatilization of the lead component, covering the crucible with a lid and heating the temperature to 1320° C. at a rate of 2° C. / min, and keeping the temperature for 2 hours to obtain an antiferroelectric ceramic material;

[0048] (6) The fired ceramic sample was ground on both sides to 0.1 mm and then cleaned. Then, a 1.5 mm diameter electrode was prepared on one side of the ceramic and a full electrode was prepared on the other side by magnetron sputtering.

[0049] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes in Example 1 was measured at room temperature (25°C). The maximum test electric field was 34.5 kV / mm, the AFE-FE phase transition electric field was 28.83 kV / mm, and the FE-AFE phase transition electric field was 23.65 kV / mm. Under the working electric field of 34.5 kV / mm, the saturated polarization intensity was 55 μC / cm 2 ; Compared with the undoped Sr group Pb(Zr 0.98 Ti 0.02 ) 0.975 Nb 0.02 O 3 Compared with the hysteresis loop of 2 The maximum releasable energy storage density is 9.44 J / cm 3 . See Figure 1 .

[0050] Embodiment 2:

[0051] (1) Press Pb 0.89 La 0.02 Sr 0.08 (Zr 0.5 Sn 0.37 Ti 0.13 ) 0.975 Nb 0.02 O 3 Raw material powder Pb required for chemical formula composition calculation 3 O 4 ,La 2 O 3 、SrCO 3 、ZrO 2 、TiO 2 SnO 2 , Nb2 O 5 The materials were mixed by wet ball milling, with zirconium oxide balls as the ball milling medium, and the raw materials: balls: deionized water were mixed at a mass ratio of 1:1.5:1 for 12 hours to make the components uniform. The materials were dried at 110°C to obtain powder.

[0052] (2) The dried powder was passed through a 40-mesh sieve, pressed into blocks in an air atmosphere, heated to 850°C at a rate of 2°C / min, and calcined for 2 hours to obtain a composite composition of Pb 0.89 La 0.02 Sr 0.08 (Z r0.5 Sn 0.37 Ti 0.13 ) 0.975 Nb 0.02 O 3 Powder (ceramic powder);

[0053] (3) The calcined powder was further finely ground for 24 hours, and after drying, 6% PVA was added to the powder for granulation. After aging for 24 hours, a ceramic blank with a diameter of 13 mm was pressed out;

[0054] (4) keeping the obtained green billet at 750° C. for 2 hours to discharge organic matter in the green billet;

[0055] (5) placing the sample after plasticizing in an alumina crucible and covering it with a filler of the same component to prevent the volatilization of the lead component, covering the crucible with a lid and heating the temperature to 1320° C. at a rate of 2° C. / min, and keeping the temperature for 2 hours to obtain an antiferroelectric ceramic material;

[0056] (6) The fired ceramic sample was ground on both sides to 0.1 mm and then cleaned. Then, a 1.5 mm diameter electrode was prepared on one side of the ceramic and a full electrode was prepared on the other side by magnetron sputtering.

[0057] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes was measured at room temperature (25°C). The maximum test electric field was 40kV / mm, the AFE-FE phase transition electric field was 4.4kV / mm, and the FE-AFE phase transition electric field was 3.3kV / mm. Under the working electric field of 40kV / mm, the saturation polarization intensity was 55μC / cm 2 The maximum releasable energy storage density is 4.86 J / cm 3 . See Figure 2 .

[0058] Embodiment 3:

[0059] The preparation process of the lead-based antiferroelectric ceramic material with high saturation polarization strength in this embodiment 3 is similar to that in embodiment 1, the only difference is that the chemical composition is Pb 0.94 La 0.04(Zr 0.65 Sn 0.35 ) 0.925 Nb 0.06 O 3 .

[0060] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes was measured at room temperature (25°C). The maximum test electric field was 32kV / mm, the AFE-FE phase transition electric field was 18.5kV / mm, and the FE-AFE phase transition electric field was 17.4kV / mm. Under the working electric field of 32kV / mm, the saturated polarization intensity was 41.1μC / cm 2 The maximum releasable energy storage density is 6.25 J / cm 3 . See Figure 5 .

[0061] Embodiment 4:

[0062] The preparation process of the lead-based antiferroelectric ceramic material with high saturation polarization strength in this embodiment 4 is similar to that in embodiment 1, the only difference is that the chemical composition is Pb 0.94 La 0.04 (Zr 0.65 Sn 0.35 ) 0.995 Nb 0.004 O 3 .

[0063] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes was measured at room temperature (25°C). The maximum test electric field was 32kV / mm, the AFE-FE phase transition electric field was 29.7kV / mm, and the FE-AFE phase transition electric field was 28.3kV / mm. Under the working electric field of 32kV / mm, the saturated polarization intensity was 34.5μC / cm 2 The maximum releasable energy storage density is 6.92 J / cm 3 . See Figure 6 .

[0064] Comparative Example 1

[0065] (1) According to Pb(Zr 0.98 Ti 0.02 ) 0.975 Nb 0.02 O 3 Pb required for chemical formula calculation 3 O 4 、ZrO 2 、TiO 2 , Nb 2 O 5The materials were mixed by wet ball milling, with zirconium oxide balls as the ball milling medium, and the raw materials: balls: deionized water were mixed at a mass ratio of 1:1.5:1 for 12 hours to make the components uniform. Dry at 110°C;

[0066] (2) The dried powder was passed through a 40-mesh sieve, pressed into blocks in an air atmosphere, heated to 850°C at a rate of 2°C / min, and calcined for 2 hours to obtain a composite composition of Pb(Zr 0.98 Ti 0.02 ) 0.975 Nb 0.02 O 3 Powder (ceramic powder);

[0067] (3) The calcined powder was further finely ground for 24 hours, and after drying, 6% PVA was added to the powder for granulation. After aging for 24 hours, a ceramic blank with a diameter of 13 mm was pressed out;

[0068] (4) keeping the obtained green billet at 750° C. for 2 hours to discharge organic matter in the green billet;

[0069] (5) placing the sample after plasticizing in an alumina crucible and covering it with a filler of the same component to prevent the volatilization of the lead component, covering the crucible with a lid and heating the temperature to 1320° C. at a rate of 2° C. / min, and keeping the temperature for 2 hours to obtain an antiferroelectric ceramic material;

[0070] (6) The fired ceramic sample was ground on both sides to 0.1 mm and then cleaned. Then, a 1.5 mm diameter electrode was prepared on one side of the ceramic and a full electrode was prepared on the other side by magnetron sputtering.

[0071] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes in Comparative Example 1 was measured at room temperature (25°C). The maximum test electric field was 16.2 kV / mm, the AFE-FE phase transition electric field was 10.4 kV / mm, and the FE-AFE phase transition electric field was 2.16 kV / mm. Under the working electric field of 16.2 kV / mm, the saturated polarization intensity was 56 μC / cm 2 The maximum releasable energy storage density is 1.61 J / cm 3 . See Figure 3 .

[0072] Comparative Example 2

[0073] (1) Press Pb 0.895 La 0.02 Sr 0.08 (Zr 0.5 Sn 0.37 Ti 0.13 ) 0.9975 O 3Chemical formula (a small amount of Pb in the composition of Comparative Example 2 enters the B position, while all Nb in Example 2 enters the B position and replaces it, and the difference is only the Nb in the B position) The raw material powder Pb required for composition calculation 3 O 4 ,La 2 O 3 、SrCO 3 、ZrO 2 、TiO 2 SnO 2 The materials were mixed by wet ball milling, with zirconium oxide balls as the ball milling medium, and the raw materials: balls: deionized water were mixed at a mass ratio of 1:1.5:1 for 12 hours to make the components uniform. Dry at 110°C;

[0074] (2) The dried powder was passed through a 40-mesh sieve, pressed into blocks in an air atmosphere, heated to 850°C at a rate of 2°C / min, and calcined for 2 hours to obtain a composite composition of Pb 0.895 La 0.02 Sr 0.08 (Zr 0.5 Sn 0.37 Ti 0.13 ) 0.9975 O 3 Powder (ceramic powder);

[0075] (3) The calcined powder was further finely ground for 24 hours, and after drying, 6% PVA was added to the powder for granulation. After aging for 24 hours, a ceramic blank with a diameter of 13 mm was pressed out;

[0076] (4) keeping the obtained green billet at 750° C. for 2 hours to discharge organic matter in the green billet;

[0077] (5) placing the sample after plasticizing in an alumina crucible and covering it with a filler of the same component to prevent the volatilization of the lead component, covering the crucible with a lid and heating the temperature to 1320° C. at a rate of 2° C. / min, and keeping the temperature for 2 hours to obtain an antiferroelectric ceramic material;

[0078] (6) The fired ceramic sample was ground on both sides to 0.1 mm and then cleaned. Then, a 1.5 mm diameter electrode was prepared on one side of the ceramic and a full electrode was prepared on the other side by magnetron sputtering.

[0079] The hysteresis loop of the antiferroelectric ceramic sample plated with electrodes in Comparative Example 2 was measured at room temperature (25°C). The maximum test electric field was 25 kV / mm, the AFE-FE phase transition electric field was 9.43 kV / mm, and the FE-AFE phase transition electric field was 9.32 kV / mm. Under the working electric field of 25 kV / mm, the saturated polarization intensity was 39 μC / cm 2 The maximum releasable energy storage density is 3.58 J / cm 3. See Figure 4 .

[0080] Table 1 shows the saturation polarization strength of the antiferroelectric ceramic materials prepared in Examples 1-2 and Comparative Examples 1-2 at room temperature:

[0081]

Claims

1. A lead-based antiferroelectric ceramic material with high saturation polarization strength, It is characterized in that The chemical formula of the lead-based antiferroelectric ceramic material is: Pb 1-y-3z / 2 La z Sr y (Zr a M b ) 1-5x / 4 Nb x O 3 ; Wherein, 0.02≤x≤0.1; 0.08≤y≤0.1, 0.02≤z≤0.1; 0≤b≤0.5, and a+b=1, M=at least one of Sn and Ti; The lead-based antiferroelectric ceramic material has a saturation polarization intensity of 45 to 55 μC / cm under the maximum working electric field. 2 .

2. The lead-based antiferroelectric ceramic material with high saturation polarization strength according to claim 1, It is characterized in that The lead-based antiferroelectric ceramic material has an AFE-FE phase change electric field of 5 to 25 kV / mm and a FE-AFE phase change electric field of 4 to 20 kV / mm under the maximum working electric field.

3. A method for preparing a lead-based antiferroelectric ceramic material having a high saturation polarization strength as claimed in any one of claims 1 to 2, It is characterized in that include: (1) Select Pb 3 O 4 Powder, La 2 O 3 Powder, SrCO 3 Powder, ZrO 2 Powder, TiO 2 Powder, SnO 2 Powder, Nb 2 O 5 Powder as raw material, according to the chemical formula Pb 1-y-3z / 2 La z Sr y (Zr a M b ) 1-5x / 4 Nb x O 3 Weighing and mixing, and then calcining at 650° C. to 850° C. to obtain ceramic powder; (2) mixing ceramic powder and binder, granulating, and pressing to obtain ceramic green body; (3) The ceramic green body is subjected to plasticizing and sintering to obtain a lead-based antiferroelectric ceramic material with high saturation polarization strength.

4. The preparation method according to claim 3, It is characterized in that The mixing method is wet ball milling; the parameters of the wet ball milling include: deionized water as the medium, zirconium oxide balls or agate balls as ball milling balls; the rotation speed is 100 to 120 revolutions per minute, and the time is 12 to 36 hours; wherein the mass ratio of raw material: ball: deionized water = 1: (1.5 to 2.5): (0.8 to 1.2).

5. The preparation method according to claim 3, It is characterized in that The binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB). The added amount of the binder is 6-10 wt.% of the weight of the ceramic powder.

6. The preparation method according to claim 3, It is characterized in that The calcination time is 1 to 4 hours.

7. The preparation method according to claim 3, It is characterized in that The temperature of the plastic discharge is 700-800° C., and the heat preservation time is 1-3 hours.

8. The preparation method according to claim 3, It is characterized in that The sintering temperature is 1300° C. to 1400° C., and the heat preservation time is 1 to 3 hours.

9. The preparation method according to claim 8, It is characterized in that The heating rate of the sintering is 2-5°C / min.

10. The preparation method according to claim 8, It is characterized in that The sintering process is carried out in a closed crucible, and ceramic powder is used for embedding.

11. An antiferroelectric ceramic element, It is characterized in that include: The lead-based antiferroelectric ceramic material with high saturation polarization strength as described in any one of claims 1-2, and electrodes distributed on both sides of the lead-based antiferroelectric ceramic material with high saturation polarization strength.

Images