A lead zirconate-based antiferroelectric ceramic, a preparation method and applications thereof

Abstract

The application relates to the field of antiferroelectric ceramic materials and discloses a lead zirconate-based antiferroelectric ceramic, a preparation method and application thereof, the chemical composition of the ceramic is (1-x)(Pb 1‑y‑z Na y La z )ZrO3-xABO3, wherein A is one of La, Ca, Sr and Ba, B is one of Hf, Zr, Sn and Ti, 0.1<=x<=0.2, 0.01<=y<=0.05 and 0.01<=z<=0.05; the ceramic is obtained by doping Na, La, Ca, Sr, Ba, Hf, Zr, Sn and Ti elements in lead zirconate; compared with a pure lead zirconate antiferroelectric ceramic, the ceramic has a significantly increased capacitance density; the ceramic has a significantly increased capacitance density under alternating-current and direct-current coupled electric fields with an alternating-current electric field of 0.1-1 kV / mm and a direct-current electric field of 7-8 kV / mm, and the capacitance density can be increased by 300%, and the energy storage performance is further improved.

Description

Technical Field

[0001] This invention relates to the field of antiferroelectric ceramic materials, and in particular to a lead zirconate-based antiferroelectric ceramic, its preparation method, and its application. Background Technology

[0002] Antiferroelectric ceramics are a class of functional ceramic materials with an antiferroelectric ordered structure and unique electroinduced phase transition properties. Their core characteristic is the ability to undergo a reversible antiferroelectric-ferroelectric phase transition under an electric field, thus exhibiting excellent energy storage and electrostrain properties, making them important for applications in pulsed power devices, energy storage, and actuators. Lead zirconate-based antiferroelectric ceramics are currently a commonly used class of materials, with pure lead zirconate (PbZrO3) and its doped system Pb... 1-x La x (Zr y Sn 1-y O3 is one of the best-performing antiferroelectric materials currently available.

[0003] Pure lead zirconate-based antiferroelectric ceramics suffer from problems such as short lifetime, high phase transition electric field, severe phase transition hysteresis, low electrostrain performance, slow strain response, high phase transition temperature, and low breakdown electric field. Therefore, to address these issues, existing technologies involve doping with other elements to obtain lead zirconate-based antiferroelectric ceramics with superior performance. Examples include a lead zirconate-based antiferroelectric thick film with high energy density and its preparation method disclosed in CN102515755B, and a lead zirconate-based antiferroelectric multilayer capacitor and its preparation method disclosed in CN106915965B. Furthermore, the existing technology "Study on Doping Modification of Zirconate-Based Antiferroelectric Ceramics" also uses low-valence monovalent alkali metal ions, such as Li. + Na + K + Divalent alkali metal ions Ca 2+ 、Sr 2+ Ba 2+ For A-site ion doping, Sn was selected. 4+ Hf 4+ 、Nb 5+ Ta 5+ and W 6+ B-site ion doping was performed, and the energy storage characteristics of lead zirconate-based antiferroelectric ceramics can be significantly improved by elemental doping at the A and B sites.

[0004] When applying lead zirconate-based antiferroelectric ceramics, in addition to considering the performance of the ceramic material itself, various factors such as the electric field conditions in actual applications must also be considered. However, the current conditions for lead zirconate-based antiferroelectric materials are usually a single DC electric field and a single AC electric field, and there is little research on the effect of lead zirconate-based antiferroelectric materials in AC-DC coupled electric fields. Summary of the Invention

[0005] This invention provides a lead zirconate-based antiferroelectric ceramic, which significantly improves capacitance density compared to pure lead zirconate antiferroelectric ceramics. Furthermore, capacitor elements made from this ceramic exhibit significantly increased capacitance density under AC-DC coupled electric fields (DC field 7~8 kV / mm, AC field 0.1~1 kV / mm), with the increase reaching up to 300%.

[0006] The specific technical solution of this invention is as follows:

[0007] A lead zirconate-based antiferroelectric ceramic with the chemical composition (1-x)(Pb) 1-y-z Na y La z ZrO3-xABO3, where A is one of La, Ca, Sr and Ba, B is one of Hf, Zr, Sn and Ti, 0.1≤x≤0.2, 0.01≤y≤0.05, 0.01≤z≤0.05.

[0008] This invention provides a lead zirconate-based antiferroelectric ceramic with the chemical composition (1-x)(Pb). 1-y- z Na y La z In this invention, lead zirconate-based antiferroelectric ceramics are modified by AB-site doping. The alkali metal Na is used for A-site doping, and elements such as La, Ca, Sr, Ba, Hf, Zr, Sn and Ti are selected for B-site doping. The energy storage performance of the prepared lead zirconate-based antiferroelectric ceramics is significantly improved compared with that of pure lead zirconate antiferroelectric ceramics.

[0009] A method for preparing the above-mentioned lead zirconate-based antiferroelectric ceramic includes the following steps:

[0010] (1) The lead zirconate-based antiferroelectric ceramic raw material, zirconium oxide ball mill and anhydrous ethanol are mixed and ball milled to form a slurry;

[0011] (2) The slurry is dried and sieved, and then pre-fired to produce pre-fired material;

[0012] (3) After grinding the pre-burned material, it is mixed with zirconia ball milling machine and anhydrous ethanol and then ball milled. The slurry after ball milling is dried and made into powder:

[0013] (4) The powder is cold isostatically pressed to form a blank, and the blank is sintered to form lead zirconate-based antiferroelectric ceramic.

[0014] As a preferred option, the conditions for ball milling in step (1) are: rotation speed of 400~600 rpm and time of 24~48 h.

[0015] Preferably, in step (1), the mass ratio of lead zirconate-based antiferroelectric ceramic raw material, zirconium oxide ball mill, and anhydrous ethanol is 1:1.8~2.2:3.8~4.2.

[0016] As a preferred option, the conditions for ball milling in step (3) are: rotation speed of 400~600 rpm and time of 24~48 h.

[0017] Preferably, the mass ratio of pre-burned material, zirconia ball mill, and anhydrous ethanol in step (3) is 1:1.8~2.2:3.8~4.2.

[0018] As a preferred option, the conditions for the isostatic pressing process in step (4) are: pressure 200~300 MPa, time 5~7 min.

[0019] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of capacitors involves grinding and polishing the lead zirconate-based antiferroelectric ceramic to form a ceramic disc, depositing a silver layer on both sides of the ceramic disc and sintering it to form a capacitor element, and then placing the capacitor element in an AC electric field and a DC electric field, wherein the AC electric field is 0.1~1 kV / mm and the DC electric field is 7~8 kV / mm.

[0020] Preferably, the ceramic disc has a thickness of 0.2 mm and the silver layer has a thickness of 0.09~0.11 mm.

[0021] Preferably, the sintering conditions are: temperature of 400~700 ℃ and time of 20~30 min.

[0022] The present invention also found that when the capacitor element made of the above-mentioned lead zirconate-based antiferroelectric ceramic is placed in an AC-DC coupled electric field (AC field of 0~1 kV / mm, DC field of 7~8 kV / mm), the capacitance density of the capacitor element increases significantly, with the highest increase reaching 300%.

[0023] Compared with the prior art, this application has the following technical effects:

[0024] (1) This invention provides a lead zirconate-based antiferroelectric ceramic with the chemical composition (1-x)(Pb 1-y-z Na y La z ZrO3-xABO3, this dielectric ceramic has a significantly higher capacitance density compared to pure lead zirconate antiferroelectric ceramics;

[0025] (2) The lead zirconate-based antiferroelectric ceramics provided by the present invention have significantly increased capacitance density under AC-DC coupling electric fields of 0~1 kV / mm AC electric field and 7~8 kV / mm DC electric field, with the highest increase in capacitance density reaching 300%. Attached Figure Description

[0026] Figure 1 The increase in capacitance density of lead zirconate-based antiferroelectric ceramics in Examples 1 to 10 under AC / DC coupled electric field conditions is shown.

[0027] Figure 2 The capacitance density of the lead zirconate-based antiferroelectric ceramic of Example 11 under AC electric field conditions of 0.1 KV / mm and DC electric field conditions of 0~7.5 KV / mm.

[0028] Figure 3 The capacitance density of the lead zirconate-based antiferroelectric ceramic of Example 12 under AC electric field conditions of 0.8 KV / mm and DC electric field conditions of 0~7.5 KV / mm. Detailed Implementation

[0029] The present invention will be further described below with reference to embodiments.

[0030] To better understand the content of this invention, further explanation is provided below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of this invention.

[0031] Example 1:

[0032] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0033] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0034] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0035] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0036] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0037] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0038] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 1 kV / mm AC electric field.

[0039] Example 2:

[0040] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0041] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0042] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0043] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0044] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0045] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0046] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.9 kV / mm AC electric field.

[0047] Example 3:

[0048] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0049] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0050] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0051] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0052] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0053] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0054] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.8 kV / mm AC electric field.

[0055] Example 4:

[0056] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0057] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0058] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0059] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0060] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0061] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0062] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.7 kV / mm AC electric field.

[0063] Example 5:

[0064] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0065] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0066] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0067] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0068] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0069] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0070] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.6 kV / mm AC electric field.

[0071] Example 6:

[0072] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0073] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La0.03 ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0074] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0075] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0076] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0077] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0078] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.5 kV / mm AC electric field.

[0079] Example 7:

[0080] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0081] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0082] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0083] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0084] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0085] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0086] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.4 kV / mm AC electric field.

[0087] Example 8:

[0088] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0089] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0090] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0091] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0092] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0093] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0094] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.3 kV / mm AC electric field.

[0095] Example 9:

[0096] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0097] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0098] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0099] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0100] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0101] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0102] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.2 kV / mm AC electric field.

[0103] Example 10:

[0104] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0105] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0106] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0107] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0108] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0109] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0110] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 7.5 kV / mm DC electric field and a 0.1 kV / mm AC electric field.

[0111] Example 11:

[0112] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0113] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0114] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0115] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0116] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0117] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0118] (b) Apply an AC-DC coupled electric field consisting of a DC electric field of 0~7.5 kV / mm and an AC electric field of 0.1 kV / mm to the capacitor element and test the capacitance density of the capacitor element.

[0119] Example 12:

[0120] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0121] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0122] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0123] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0124] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0125] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0126] (b) Apply an AC-DC coupled electric field consisting of a DC electric field of 0~7.5 kV / mm and an AC electric field of 0.8 kV / mm to the capacitor element and test the capacitance density of the capacitor element.

[0127] Example 13:

[0128] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0129] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.96 Na 0.01 La 0.03ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4 and then ball-milled to form a slurry. The ball milling process is carried out at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder is then heat-treated in a heat treatment furnace at 900 ℃ for 4 h. After cooling, it is ground to form a pre-calcined material.

[0130] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0131] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0132] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0133] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0134] (b) Apply an AC-DC coupled electric field consisting of a DC electric field of 0~7.5 kV / mm and an AC electric field of 0.8 kV / mm to the capacitor element and test the capacitance density of the capacitor element.

[0135] Example 14:

[0136] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0137] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb0.94Na0.03La0.03)ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3. The raw materials are lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide. Mix the above raw materials, zirconium oxide ball mill and anhydrous ethanol in a mass ratio of 1:2:4 and then ball mill them to make a slurry. The ball milling process is 500 rpm for 36 h. After drying the slurry in an oven at 120 ℃, it is passed through a 200-mesh sieve to obtain powder. The powder is placed in a heat treatment furnace and heat-treated at 900 ℃ for 4 h. After cooling, it is ground to make a pre-fired material.

[0138] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0139] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0140] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0141] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0142] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 9 kV / mm DC electric field and a 0.6 kV / mm AC electric field.

[0143] Example 15:

[0144] A method for preparing lead zirconate-based antiferroelectric ceramics includes the following steps:

[0145] (1) Weigh the required raw materials according to the stoichiometric ratio of lead zirconate-based antiferroelectric ceramics. The chemical formula of lead zirconate-based antiferroelectric ceramics is 0.90(Pb). 0.92 Na 0.03 La 0.05ZrO3-0.091CaTiO3-0.009SrSnO3, with raw materials including lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, strontium carbonate, titanium dioxide, and tin dioxide, was prepared by mixing the above raw materials, zirconium oxide ball mill, and anhydrous ethanol in a mass ratio of 1:2:4 and then ball milling them to form a slurry. The ball milling process was carried out at 500 rpm for 36 h. The slurry was dried in an oven at 120 ℃ and then passed through a 200-mesh sieve to obtain powder. The powder was then heat-treated in a heat treatment furnace at 900 ℃ for 4 h, cooled, and ground to form a pre-calcined material.

[0146] (2) The pre-burned material, zirconium oxide ball mill and anhydrous ethanol were mixed in a mass ratio of 1:2:4 and then ball milled to make a slurry. The ball milling was performed at 500 rpm for 36 h. The slurry was then dried in an oven at 120 ℃ to make powder.

[0147] (3) The powder is subjected to isostatic pressing to form a cylindrical blank, and the blank is embedded in the master powder and sintered in a sintering furnace at 1330 °C for 2 h to produce lead zirconate-based antiferroelectric ceramic.

[0148] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the fabrication of capacitors includes the following steps:

[0149] (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished into a ceramic disc of 0.3 mm according to the size requirements. Then, a silver layer of 0.1 ± 0.01 mm is plated on both sides of the ceramic raw material. Then, it is placed in a sintering furnace at 400 °C and sintered for 30 min to make a capacitor element.

[0150] (b) The capacitance density of the capacitor element is tested by applying an AC-DC coupled electric field consisting of a 12 kV / mm DC electric field and a 0.3 kV / mm AC electric field.

[0151] like Figure 1 , Figure 2 and Figure 3 As shown, the lead zirconate-based antiferroelectric ceramic (0.90(Pb)) prepared in this invention... 0.96 Na 0.01 La 0.03When an AC / DC coupled electric field is applied to a ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3 composite ceramic, the capacitance density can be significantly increased, with the increase reaching up to 300%. Furthermore, after investigating the effects of different AC and DC electric fields on the ceramic capacitance density, it was found that after reaching certain values ​​(7.5 kV / mm for DC and 0.8 kV / mm for AC), the increase in ceramic capacitance density became insignificant. Further analysis revealed that the DC electric field had a highly significant effect on increasing the ceramic capacitance density in the range of 6–7.5 kV / mm, while the AC electric field showed a further increase in capacitance density with increasing AC field strength in the range of 0.1–0.8 kV / mm. These results indicate that the applied AC / DC coupled electric field has a positive and significant effect on increasing the capacitance density of lead zirconate-based antiferroelectric ceramics.

[0152] The present invention also provides 0.90 (Pb) 0.94 Na 0.03 La 0.03 )ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO and 0.90(Pb 0.92 Na 0.03 La 0.05 Two types of lead zirconate-based antiferroelectric ceramics, ZrO3-0.091CaTiO3-0.009SrSnO3, were tested. Applying an AC / DC coupled electric field to these ceramics revealed that the applied field significantly increased the capacitance density of the two types of lead zirconate-based antiferroelectric ceramics, reaching 0.90 (Pb). 0.94 Na 0.03 La 0.03 The capacitance density increase of ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3 ceramics can reach up to 270%, and 0.90 (Pb) 0.92 Na 0.03 La 0.05 The capacitance density increase of ZrO3-0.091CaTiO3-0.009SrSnO3 ceramics can reach up to 260%. Furthermore, investigations into the AC and DC electric field strengths revealed that the optimal AC / DC coupling electric field conditions for lead zirconate-based antiferroelectric ceramics differed among different materials. (0.90(Pb)) 0.94 Na 0.03 La 0.03The capacitance density increase of ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3 reached the threshold under the conditions of 9 kV / mm DC electric field and 0.6 kV / mm AC electric field; 0.90 (Pb 0.92 Na 0.03 La 0.05 The capacitance density increase of ZrO3-0.091CaTiO3-0.009SrSnO3 reached the threshold under the conditions of 12 kV / mm DC electric field and 0.3 kV / mm AC electric field.

[0153] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A lead zirconate-based antiferroelectric ceramic, characterized by, The chemical composition comprises: 0.90 (Pb 0.96 Na 0.01 La 0.03 )Zr03- 0.04 BaSn03- 0.05 SrSn03- 0.01 SrTi03or 0.90 (Pb 0.94 Na 0.03 La 0.03 )Zr03- 0.09 BaTi03- 0.03 CaTi03- 0.007 SrSnO or 0.90 (Pb 0.92 Na 0.03 La 0.05 )ZrO3-0.091CaTiO3-0.009SrSnO3.

2. A method of producing a lead zirconate-based antiferroelectric ceramic according to claim 1, characterized by, The method comprises the following steps: (1) Lead zirconate-based antiferroelectric ceramic raw materials, zirconia ball mill and anhydrous ethanol are mixed and ball milled to prepare a slurry; (2) The slurry is dried and sieved, and then pre-sintered to prepare a pre-sintered material; (3) The pre-sintered material is ground and mixed with zirconia ball mill and anhydrous ethanol, and then ball milled, and the ball-milled slurry is dried to prepare a powder; (4) The powder is cold isostatic pressed to form a green body, and the green body is sintered to prepare a lead zirconate-based antiferroelectric ceramic.

3. The production method according to claim 2, characterized by, The ball milling condition in step (1) is: rotation speed 400-600 rpm, time 24-48 h.

4. The production method according to claim 2 or 3, characterized by, The mass ratio of lead zirconate-based antiferroelectric ceramic raw materials, zirconia ball mill and anhydrous ethanol in step (1) is 1:1.8-2.2:3.8-4.

2.

5. The production method according to claim 2, characterized by, The ball milling condition in step (3) is: rotation speed 400-600 rpm, time 24-48 h.

6. The production method according to claim 2 or 5, characterized by, The mass ratio of pre-sintered material, zirconia ball mill and anhydrous ethanol in step (3) is 1:1.8-2.2:3.8-4.

2.

7. The production method according to claim 2, characterized by, The cold isostatic pressing condition in step (4) is: pressure 200-300 MPa, time 5-7 min.

8. Use of a lead zirconate-based antiferroelectric ceramic according to claim 1 for the production of a capacitor, characterized in that, The lead zirconate-based antiferroelectric ceramic is polished to prepare a ceramic wafer, silver layers are arranged on both sides of the ceramic wafer and sintered to prepare a capacitor element, and the capacitor element is used in an alternating electric field and a direct electric field, the alternating electric field is 0.1-1 kV / mm, and the direct electric field is 7-8 kV / mm.

9. Use according to claim 8, characterized in that, The thickness of the ceramic wafer is 0.2 mm, and the thickness of the silver layer is 0.09-0.11 mm.

10. Use according to claim 8, characterized in that, The sintering condition is: temperature 400-700 ℃, time 20-30 min.

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