Lead zirconate-based antiferroelectric ceramic as well as preparation method and application thereof

Abstract

The invention relates to the field of antiferroelectric ceramic materials, and discloses lead zirconate-based antiferroelectric ceramic, a preparation method and application thereof, the chemical composition of the ceramic is (1-x) (Pb1-y-zNayLaz) ZrO3-xABO3, A is one of La, Ca, Sr and Ba, B is one of Hf, Zr, Sn and Ti, x is more than or equal to 0.1 and less than or equal to 0.2, y is more than or equal to 0.01 and less than or equal to 0.05, and z is more than or equal to 0.01 and less than or equal to 0.05; the ceramic is obtained by doping Na, La, Ca, Sr, Ba, Hf, Zr, Sn and Ti elements in lead zirconate, and compared with pure lead zirconate antiferroelectric ceramic, the capacitance density of the ceramic is remarkably increased; when the ceramic is applied to an alternating current-direct current coupling electric field of a 0.1-1 kV / mm alternating current electric field and a 7-8 kV / mm direct current electric field, the capacitance density is remarkably increased, the amplification can reach 300%, and the energy storage performance is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of antiferroelectric ceramic materials, in particular to a lead zirconate-based antiferroelectric ceramic, a preparation method and applications thereof. BACKGROUND

[0002] Antiferroelectric ceramics are a kind of functional ceramic materials with antiferroelectric order structure and unique electric phase change characteristics, the core feature of which is that they can undergo reversible antiferroelectric-ferroelectric phase transition under the action of an electric field, and thus exhibit excellent energy storage, electrostrictive strain and other properties, and have important applications in the fields of pulse power devices, energy storage, drivers and the like. Among them, lead zirconate-based antiferroelectric ceramics are a commonly used type of material, and pure lead zirconate (PbZrO3) and its doped systems Pb 1-x La x (Zr y Sn 1-y )O3 are among the most excellent antiferroelectric materials in terms of performance.

[0003] Pure lead zirconate-based antiferroelectric ceramics have the problems of short service life, high phase transition electric field, serious phase transition hysteresis, small electrostrictive strain, slow strain response, high phase transition temperature, and low breakdown electric field, and therefore in order to solve the above problems, the prior art obtains lead zirconate-based antiferroelectric ceramics with more excellent performance by doping other elements, such as the lead zirconate-based antiferroelectric thick film with high energy storage density disclosed in CN102515755B and the preparation method thereof, and the lead zirconate-based antiferroelectric multilayer capacitor disclosed in CN106915965B and the preparation method thereof. In addition, the prior art "Research on Doping Modification of Lead Zirconate-based Antiferroelectric Ceramics" also selected low-valence monovalent alkali metal ions Li + , Na + , K + , divalent alkali metal ions Ca 2+ , Sr 2+ , Ba 2+ for A-site ion doping, and Sn 4+ , Hf 4+ , Nb 5+ , Ta 5+ and W 6+ for B-site ion doping, and the doping of elements at A and B sites can significantly improve the energy storage properties of lead zirconate-based antiferroelectric ceramics.

[0004] In addition to considering the performance of the ceramic material itself, the electric field conditions and other factors in actual application also need to be considered when lead zirconate-based antiferroelectric ceramics are applied, but the current conditions of lead zirconate-based antiferroelectric materials are usually single direct current electric field and single alternating current electric field, and there is less research on the effect of alternating current and direct current coupled electric field on lead zirconate-based antiferroelectric materials. SUMMARY

[0005] The present application provides a lead zirconate-based antiferroelectric ceramic, which has a significantly improved capacitance density compared with pure lead zirconate antiferroelectric ceramic. In addition, the capacitor element made of the ceramic has a significantly increased capacitance density under alternating direct coupling electric field (direct electric field of 7-8 kV / mm and alternating electric field of 0.1-1 kV / mm), and the capacitance density can be increased by up to 300%.

[0006] The specific technical solutions of the present application are as follows: A lead zirconate-based antiferroelectric ceramic, which has a chemical composition of (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.

[0007] The present application provides a lead zirconate-based antiferroelectric ceramic, which has a chemical composition of (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.

[0008] A preparation method of the above-mentioned lead zirconate-based antiferroelectric ceramic, which comprises the following steps: (1) mixing lead zirconate-based antiferroelectric ceramic raw materials, zirconia milling balls and anhydrous ethanol and performing ball milling treatment to prepare a slurry; (2) performing pre-sintering treatment on the slurry after drying and sieving to prepare a pre-sintering material; (3) mixing the pre-sintering material with zirconia milling balls and anhydrous ethanol after grinding and performing ball milling treatment, and then drying the ball-milled slurry to prepare a powder; (4) performing cold isostatic pressing treatment on the powder to prepare a green body, and performing sintering treatment on the green body to prepare the lead zirconate-based antiferroelectric ceramic.

[0009] Preferably, the ball milling treatment in step (1) is performed at a speed of 400-600 rpm for 24-48 h.

[0010] Preferably, the mass ratio of the lead zirconate-based antiferroelectric ceramic raw materials, zirconia milling balls and anhydrous ethanol in step (1) is 1:1.8-2.2:3.8-4.2.

[0011] As preferred, the ball milling treatment in step (3) is carried out at a rotation speed of 400-600 rpm for 24-48 h.

[0012] As preferred, the mass ratio of the pre-sintered material, the zirconium oxide milling balls and the anhydrous ethanol in step (3) is 1:1.8-2.2:3.8-4.2.

[0013] As preferred, the isostatic pressing treatment in step (4) is carried out at a pressure of 200-300 MPa for 5-7 min.

[0014] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, wherein the lead zirconate-based antiferroelectric ceramic is polished and polished to form a ceramic wafer, silver layers are arranged on both sides of the ceramic wafer and sintered to form a capacitor element, and the capacitor element is placed in an alternating current field and a direct current field for use, wherein the alternating current field is 0.1-1 kV / mm, and the direct current field is 7-8 kV / mm.

[0015] As preferred, the thickness of the ceramic wafer is 0.2 mm, and the thickness of the silver layer is 0.09-0.11 mm.

[0016] As preferred, the sintering is carried out at a temperature of 400-700 ℃ for 20-30 min.

[0017] It is also found that the capacitance density of the capacitor element made of the above-mentioned lead zirconate-based antiferroelectric ceramic is significantly increased when the capacitor element is placed in an alternating-direct current coupling electric field (the alternating current field is 0-1 kV / mm, and the direct current field is 7-8 kV / mm), and the highest increase in capacitance density can reach 300 %.

[0018] Compared with the prior art, the application has the following technical effects: (1) The application provides a lead zirconate-based antiferroelectric ceramic, which has a chemical composition of (1-x)(Pb 1-y-z Na y La z )ZrO3-xABO3, and the dielectric ceramic has a significantly improved capacitance density compared with a pure lead zirconate antiferroelectric ceramic. (2) The lead zirconate-based antiferroelectric ceramic provided by the application has a significantly increased capacitance density in an alternating-direct current coupling electric field with an alternating current field of 0-1 kV / mm and a direct current field of 7-8 kV / mm, and the highest increase in capacitance density can reach 300 %. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The increase in capacitance density of the lead zirconate-based antiferroelectric ceramic of Examples 1-10 under the condition of alternating-direct current coupling electric field.

[0020] Figure 2 Capacitance density of the lead zirconate-based antiferroelectric ceramic of Example 11 under the condition of 0.1 KV / mm alternating electric field and 0~7.5 KV / mm direct current electric field.

[0021] Figure 3 Capacitance density of the lead zirconate-based antiferroelectric ceramic of Example 12 under the condition of 0.8 KV / mm alternating electric field and 0~7.5 KV / mm direct current electric field. DETAILED DESCRIPTION

[0022] The application will be further described below in conjunction with examples.

[0023] For better understanding of the content of the application, further description will be made in conjunction with specific examples. It should be understood that the following examples are only used to illustrate the application and not to limit the scope of the application.

[0024] Example 1: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3. The raw materials are three-lead tetraoxide, 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 milling treatment is performed to prepare a slurry. The ball milling treatment is at 500 rpm for 36 h. The slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh screen to obtain a powder. The powder is placed in a heat treatment furnace and heat treated at 900 ℃ for 4 h. After cooling, the powder is ground to prepare a pre-sintered material; (2) The pre-sintered material, zirconium oxide ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry. The ball milling treatment is at 500 rpm for 36 h. The slurry is dried in a 120 ℃ oven to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body. The green body is buried in a mother powder and sintered in a sintering furnace at 1330 ℃ for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0025] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, comprising the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished to a ceramic wafer of 0.3 mm in size, then silver layers of 0.1±0.01 mm are plated on the front and back surfaces of the ceramic raw material, and then the ceramic is placed in a sintering furnace at 400 ℃ for 30 min to prepare a capacitor element; (b) A capacitor element is tested for capacitance density under an alternating-current coupling electric field composed of a direct-current electric field of 7.5 KV / mm and an alternating-current electric field of 1 kV / mm.

[0026] Example 2: A method for preparing a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3. The raw materials are three-lead tetraoxide, sodium carbonate, lanthanum sesquioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide. The above-mentioned raw materials, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry. The ball milling treatment is performed at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃, and then sieved through a 200-mesh sieve to obtain a powder. The powder is placed in a heat treatment furnace and heat treated at 900 ℃ for 4 h. After cooling, the powder is ground to prepare a pre-sintered material; (2) The pre-sintered material, zirconium oxide ball mill, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry. The ball milling treatment is performed at 500 rpm for 36 h. The slurry is dried in an oven at 120 ℃ to prepare a powder; (3) The powder is subjected to isostatic pressing to form a cylindrical green body. The green body is buried in mother powder and sintered in a sintering furnace at 1330 ℃ for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0027] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in preparing a capacitor, comprising the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished to a ceramic wafer of 0.3 mm in size, then silver layers of 0.1±0.01 mm are plated on the front and back surfaces of the ceramic raw material, and then the ceramic is placed in a sintering furnace at 400 ℃ for 30 min to prepare a capacitor element; (b) A capacitor element is tested for capacitance density under an alternating-current coupling electric field composed of a direct-current electric field of 7.5 KV / mm and an alternating-current electric field of 0.9 kV / mm.

[0028] Example 3: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, and the raw materials are three lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide; the above raw materials, zirconium oxide milling balls and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is performed at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven, and then a powder is prepared by passing through a 200 mesh screen, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then cooled and ground to prepare a pre-sintered material; (2) The pre-sintered material, zirconium oxide milling balls and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is performed at 500 rpm for 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in mother powder, and sintering is performed at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0029] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in preparing a capacitor, comprising the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished according to size requirements to prepare a ceramic disc with a diameter of 0.3 mm, then a silver layer with a thickness of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material, and then the ceramic raw material is placed in a sintering furnace for heat treatment at 400 ℃ for 30 min to prepare a capacitor element; (b) A capacitor element is tested for capacitance density under an alternating-current direct-current coupled electric field composed of a direct-current electric field of 7.5 KV / mm and an alternating-current electric field of 0.8 kV / mm.

[0030] Example 4: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03)ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials are three-lead tetraoxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh sieve to obtain a powder, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then ground after cooling to prepare a pre-sintered material; (2) the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) the powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in a mother powder and sintered in a sintering furnace at 1330 ℃ for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0031] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, comprising the following steps: (a) the above-mentioned lead zirconate-based antiferroelectric ceramic is ground and polished according to size requirements to a ceramic disc of 0.3 mm, then a silver layer of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material, and then the capacitor element is prepared by sintering in a sintering furnace at 400 ℃ for 30 min; (b) the capacitor element is tested for capacitance density under an alternating-direct current coupled electric field composed of a direct current electric field of 7.5 KV / mm and an alternating current electric field of 0.7 kV / mm.

[0032] Example 5: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) the required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials are three-lead tetraoxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh sieve to obtain a powder, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then ground after cooling to prepare a pre-sintered material; (2) The pre-fired material, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120°C oven for drying to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body. The green body is buried in the mother powder and sintered at 1330°C for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0033] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished according to size requirements to prepare a ceramic disc with a diameter of 0.3 mm. Then, a silver layer with a thickness of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material. Then, the capacitor element is prepared by placing it in a sintering furnace at 400°C for 30 min of heat preservation sintering; (b) The capacitor element is subjected to an alternating-current direct-current coupled electric field composed of a direct-current electric field of 7.5 KV / mm and an alternating-current electric field of 0.6 kV / mm. The capacitance density of the capacitor element is tested.

[0034] Example 6: A preparation method of a lead zirconate-based antiferroelectric ceramic comprises the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic. The chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3. The raw materials are three-lead tetraoxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide. The above-mentioned raw materials, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120°C oven for drying, and then a powder is prepared by passing the slurry through a 200-mesh screen. The powder is placed in a heat treatment furnace and heat treated at 900°C for 4 h. After cooling, the pre-fired material is prepared by grinding; (2) The pre-fired material, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120°C oven for drying to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body. The green body is buried in the mother powder and sintered at 1330°C for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0035] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) polishing the above-mentioned lead zirconate-based antiferroelectric ceramic into a ceramic wafer with a size of 0.3 mm according to the size requirement, then plating a silver layer with a thickness of 0.1±0.01 mm on the front and back surfaces of the ceramic raw material, and then placing it in a sintering furnace at 400 ℃ for heat preservation and sintering for 30 min to prepare a capacitor element; (b) testing the capacitance density of the capacitor element under an alternating-direct current coupled electric field composed of a direct current electric field of 7.5 KV / mm and an alternating current electric field of 0.5 kV / mm.

[0036] Example 7: A preparation method of a lead zirconate-based antiferroelectric ceramic comprises the following steps: (1) weighing the required raw materials according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, the chemical formula of the lead zirconate-based antiferroelectric ceramic being 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials being three-lead tetraoxide, sodium carbonate, lanthanum sesquioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide; mixing the above-mentioned raw materials, zirconium oxide ball mill and anhydrous ethanol according to a mass ratio of 1:2:4, then performing ball milling treatment to prepare a slurry, the ball milling treatment being performed at 500 rpm for 36 h, drying the slurry in a 120 ℃ oven, and then passing the slurry through a 200-mesh screen to obtain a powder, placing the powder in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then grinding the cooled powder to prepare a pre-sintered material; (2) mixing the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol according to a mass ratio of 1:2:4, then performing ball milling treatment to prepare a slurry, the ball milling treatment being performed at 500 rpm for 36 h, and then drying the slurry to prepare a powder; (3) performing isostatic pressing forming treatment on the powder to prepare a cylindrical green body, burying the green body in a mother powder, and then placing it in a sintering furnace at 1330 ℃ for heat preservation and sintering for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0037] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) polishing the above-mentioned lead zirconate-based antiferroelectric ceramic into a ceramic wafer with a size of 0.3 mm according to the size requirement, then plating a silver layer with a thickness of 0.1±0.01 mm on the front and back surfaces of the ceramic raw material, and then placing it in a sintering furnace at 400 ℃ for heat preservation and sintering for 30 min to prepare a capacitor element; (b) The capacitor element is tested for the capacitance density under the coupling electric field of the direct current electric field of 7.5 KV / mm and the alternating current electric field of 0.4 kV / mm.

[0038] Example 8 A preparation method of a lead zirconate-based antiferroelectric ceramic includes the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3. The raw materials are three-lead tetraoxide, sodium carbonate, lanthanum sesquioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide. The above raw materials, zirconium oxide milling balls, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry. The ball milling treatment is performed at 500 rpm for 36 h. The slurry is dried in a 120 ℃ oven and then sieved through a 200-mesh screen to obtain a powder. The powder is placed in a heat treatment furnace and heat treated at 900 ℃ for 4 h. After cooling, the powder is ground to prepare a pre-sintered material. (2) The pre-sintered material, zirconium oxide milling balls, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry. The ball milling treatment is performed at 500 rpm for 36 h. The slurry is dried in a 120 ℃ oven to prepare a powder. (3) The powder is subjected to isostatic pressing to form a cylindrical green body. The green body is embedded in a mother powder and sintered at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0039] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor includes the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished to a ceramic disc of 0.3 mm in size, and then a silver layer of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic disc. The ceramic disc is then placed in a sintering furnace and sintered at 400 ℃ for 30 min to prepare a capacitor element. (b) The capacitor element is tested for the capacitance density under the coupling electric field of the direct current electric field of 7.5 KV / mm and the alternating current electric field of 0.3 kV / mm.

[0040] Example 9 A preparation method of a lead zirconate-based antiferroelectric ceramic includes the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, raw materials are three-lead tetraoxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is 500 rpm, the time is 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh screen to obtain a powder, the powder is placed in a heat treatment furnace and heat treated at 900 ℃ for 4 h, and then ground after cooling to prepare a pre-sintered material; (2) the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4 to perform ball milling treatment to prepare a slurry, the ball milling treatment is 500 rpm, the time is 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) the powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in a mother powder and sintered at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0041] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, comprising the following steps: (a) the above-mentioned lead zirconate-based antiferroelectric ceramic is ground and polished according to size requirements to form a 0.3 mm ceramic wafer, then a 0.1±0.01 mm silver layer is plated on the front and back surfaces of the ceramic raw material, and then the capacitor element is prepared by sintering at 400 ℃ for 30 min in a sintering furnace; (b) a capacitor element is tested for capacitance density under an alternating-current and direct-current coupled electric field composed of a 7.5 KV / mm direct-current electric field and a 0.2 kV / mm alternating-current electric field.

[0042] Example 10: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) the required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03)ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials are three-lead tetraoxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh sieve to obtain a powder, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then ground after cooling to prepare a pre-sintered material; (2) the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) the powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in a mother powder and sintered in a sintering furnace at 1330 ℃ for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0043] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, comprising the following steps: (a) the above-mentioned lead zirconate-based antiferroelectric ceramic is ground and polished according to size requirements to a ceramic disc of 0.3 mm, then a silver layer of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material, and then the capacitor element is prepared by sintering in a sintering furnace at 400 ℃ for 30 min; (b) the capacitor element is tested for capacitance density under an alternating-direct current coupled electric field composed of a direct current electric field of 7.5 KV / mm and an alternating current electric field of 0.1 kV / mm.

[0044] Example 11: A preparation method of a lead zirconate-based antiferroelectric ceramic, comprising the following steps: (1) the required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, and the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials are three-lead tetraoxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh sieve to obtain a powder, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then ground after cooling to prepare a pre-sintered material; (2) The pre-fired material, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120 ℃ oven for drying to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body. The green body is buried in the mother powder and sintered at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0045] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished according to the size requirement to prepare a ceramic disc with a diameter of 0.3 mm. Then, a silver layer with a thickness of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material. Then, the capacitor element is prepared by placing it in a sintering furnace at 400 ℃ for 30 min of heat preservation sintering; (b) The capacitor element is subjected to an alternating-current coupling electric field composed of a direct-current electric field of 0~7.5 KV / mm and an alternating-current electric field of 0.1 kV / mm. The capacitance density of the capacitor element is tested.

[0046] Example 12: A preparation method of a lead zirconate-based antiferroelectric ceramic comprises the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic. The chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3. The raw materials are three-lead tetraoxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide. The above-mentioned raw materials, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120 ℃ oven for drying, and then a powder is prepared by passing the slurry through a 200-mesh screen. The powder is placed in a heat treatment furnace and heat treated at 900 ℃ for 4 h of heat preservation. After cooling, the pre-fired material is prepared by grinding; (2) The pre-fired material, zirconia ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is 500 rpm, and the time is 36 h. The slurry is placed in a 120 ℃ oven for drying to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body. The green body is buried in the mother powder and sintered at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0047] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) polishing the above-mentioned lead zirconate-based antiferroelectric ceramic into a ceramic wafer with a size of 0.3 mm according to the size requirement, then plating a silver layer with a thickness of 0.1±0.01 mm on the front and back surfaces of the ceramic raw material, and then placing it in a sintering furnace at 400 ℃ for heat preservation and sintering for 30 min to prepare a capacitor element; (b) testing the capacitance density of the capacitor element under an alternating-current direct-current coupled electric field composed of a direct-current electric field of 0~7.5 KV / mm and an alternating-current electric field of 0.8 kV / mm.

[0048] Embodiment 13: A preparation method of a lead zirconate-based antiferroelectric ceramic comprises the following steps: (1) weighing the required raw materials according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, the chemical formula of the lead zirconate-based antiferroelectric ceramic being 0.90(Pb 0.96 Na 0.01 La 0.03 )ZrO3-0.04BaSnO3-0.05SrSnO3-0.01SrTiO3, the raw materials being three-lead tetraoxide, sodium carbonate, lanthanum sesquioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide and tin dioxide; mixing the above-mentioned raw materials, zirconium oxide ball mill and anhydrous ethanol according to a mass ratio of 1:2:4, and then performing ball milling treatment to prepare a slurry, the ball milling treatment being performed at 500 rpm for 36 h, and then placing the slurry in a 120 ℃ oven for drying, and then passing the slurry through a 200-mesh screen to prepare a powder, and then placing the powder in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then grinding the cooled powder to prepare a pre-sintered material; (2) mixing the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol according to a mass ratio of 1:2:4, and then performing ball milling treatment to prepare a slurry, the ball milling treatment being performed at 500 rpm for 36 h, and then placing the slurry in a 120 ℃ oven for drying to prepare a powder; (3) performing isostatic pressing forming treatment on the powder to prepare a cylindrical green body, and then burying the green body in a mother powder, and then placing it in a sintering furnace at 1330 ℃ for heat preservation and sintering for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0049] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor comprises the following steps: (a) polishing the above-mentioned lead zirconate-based antiferroelectric ceramic into a ceramic wafer with a size of 0.3 mm according to the size requirement, then plating a silver layer with a thickness of 0.1±0.01 mm on the front and back surfaces of the ceramic raw material, and then placing it in a sintering furnace at 400 ℃ for heat preservation and sintering for 30 min to prepare a capacitor element; (b) A DC electric field of 0~7.5 KV / mm and an AC electric field of 0.8 kV / mm are applied to the capacitor element to test the capacitance density of the capacitor element.

[0050] Embodiment 14 A preparation method of a lead zirconate-based antiferroelectric ceramic includes the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb0.94Na0.03La0.03)ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3, and the raw materials are three-lead tetraoxide, sodium carbonate, lanthanum sesquioxide, zirconium dioxide, barium carbonate, strontium carbonate, titanium dioxide, and tin dioxide; the above-mentioned raw materials, zirconium oxide milling balls, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is performed at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven, and then a powder is prepared by passing the dried slurry through a 200-mesh screen; the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then the pre-sintered material is prepared by grinding after cooling; (2) The pre-sintered material, zirconium oxide milling balls, and anhydrous ethanol are mixed in a mass ratio of 1:2:4, and then ball milling treatment is performed to prepare a slurry, the ball milling treatment is performed at 500 rpm for 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) The powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in mother powder, and the sintering furnace is heated and sintered at 1330 ℃ for 2 h to prepare a lead zirconate-based antiferroelectric ceramic.

[0051] An application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor includes the following steps: (a) The above-mentioned lead zirconate-based antiferroelectric ceramic is polished according to size requirements to form a 0.3 mm ceramic wafer, then a 0.1±0.01 mm silver layer is plated on the front and back surfaces of the ceramic raw material, and then the ceramic wafer is placed in a sintering furnace at 400 ℃ for heat treatment and sintering for 30 min to prepare a capacitor element; (b) A DC electric field of 9 KV / mm and an AC electric field of 0.6 kV / mm are applied to the capacitor element to test the capacitance density of the capacitor element.

[0052] Embodiment 15 A preparation method of a lead zirconate-based antiferroelectric ceramic includes the following steps: (1) The required raw materials are weighed according to the stoichiometric ratio of the lead zirconate-based antiferroelectric ceramic, the chemical formula of the lead zirconate-based antiferroelectric ceramic is 0.90(Pb 0.92 Na 0.03 La 0.05ZrO3-0.091CaTiO3-0.009SrSnO3, raw materials are three-lead tetroxide, sodium carbonate, lanthanum trioxide, zirconium dioxide, 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 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, the slurry is dried in a 120 ℃ oven and then sieved through a 200 mesh screen to prepare a powder, the powder is placed in a heat treatment furnace for heat treatment at 900 ℃ for 4 h, and then ground to prepare a pre-sintered material after cooling; (2) the pre-sintered material, zirconium oxide ball mill and anhydrous ethanol are mixed in a mass ratio of 1:2:4 to perform ball milling treatment to prepare a slurry, the ball milling treatment is at 500 rpm for 36 h, and the slurry is dried in a 120 ℃ oven to prepare a powder; (3) the powder is subjected to isostatic pressing forming treatment to prepare a cylindrical green body, the green body is buried in a mother powder and sintered at 1330 ℃ for 2 h in a sintering furnace to prepare a lead zirconate-based antiferroelectric ceramic.

[0053] The application of the above-mentioned lead zirconate-based antiferroelectric ceramic in the preparation of a capacitor, comprising the following steps: (a) the above-mentioned lead zirconate-based antiferroelectric ceramic is ground and polished to a ceramic disc of 0.3 mm according to size requirements, then a silver layer of 0.1±0.01 mm is plated on the front and back surfaces of the ceramic raw material, and then the capacitor element is prepared by sintering at 400 ℃ for 30 min in a sintering furnace; (b) a capacitor element is tested for capacitance density under an alternating-current direct-current coupled electric field composed of a direct-current electric field of 12 KV / mm and an alternating-current electric field of 0.3 kV / mm.

[0054] As shown in Figure 1 , Figure 2 and Figure 3 , the lead zirconate-based antiferroelectric ceramic (0.90(Pb 0.96 Na 0.01 La 0.03When the AC-DC coupling electric field is added to the lead zirconate-based antiferroelectric ceramic, the AC-DC coupling electric field can significantly improve the capacitance density of the ceramic, and the capacitance density can be increased by 300% at most; in addition, through exploration of the influence of different AC electric fields and different DC electric fields on the capacitance density of the ceramic, it is found that the AC electric field and the DC electric field have no significant effect on the capacitance density of the ceramic when reaching a certain value (the DC electric field is 7.5 KV / mm, and the AC electric field is 0.8 kV / mm). In addition, further analysis shows that the DC electric field has a very significant effect on the capacitance density of the ceramic when the DC electric field is 6-7.5 kV / mm, and the capacitance density of the ceramic is further increased with the increase of the AC electric field strength in the range of 0.1-0.8 kV / mm. The above results show that the AC-DC coupling electric field has a positive effect on improving the capacitance density of the lead zirconate-based antiferroelectric ceramic, and the effect is significant.

[0055] The application further provides 0.90(Pb 0.94 Na 0.03 La 0.03 )ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3 and 0.90(Pb 0.92 Na 0.03 La 0.05 )ZrO3-0.091CaTiO3-0.009SrSnO3 two kinds of lead zirconate-based antiferroelectric ceramics, and it is found that the AC-DC coupling electric field has a significant effect on improving the capacitance density of the two kinds of lead zirconate-based antiferroelectric ceramics when the AC-DC coupling electric field is added to the two kinds of lead zirconate-based antiferroelectric ceramics. The capacitance density of the 0.90(Pb 0.94 Na 0.03 La 0.03 )ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3 ceramic can be increased by 270% at most, and the capacitance density of the 0.90(Pb 0.92 Na 0.03 La 0.05 )ZrO3-0.091CaTiO3-0.009SrSnO3 ceramic can be increased by 260% at most. In addition, through exploration of the AC electric field and the DC electric field, it is found that the optimal AC-DC coupling electric field conditions of the lead zirconate-based antiferroelectric ceramics of different materials also have differences. The optimal AC-DC coupling electric field conditions of the 0.90(Pb 0.94 Na 0.03 La 0.03)ZrO3-0.09BaTiO3-0.03CaTiO3-0.007SrSnO3 in a 9 KV / mm DC electric field and 0.6 kV / mm AC electric field, the capacitance density increment reaches the threshold value; 0.90(Pb 0.92 Na 0.03 La 0.05 )ZrO3-0.091CaTiO3-0.009SrSnO3 in a 12 KV / mm DC electric field and 0.3 kV / mm AC electric field, the capacitance density increment reaches the threshold value.

[0056] The above is only the preferred embodiment of the present application, not any limitation of the present application, any simple modification, change and equivalent transformation according to the technical essence of the present application to the above embodiment, still belongs to the protection scope of the technical scheme of the present application.

Claims

1. A lead zirconate-based antiferroelectric ceramic, characterized in that, The chemical composition is (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.

2. A method for preparing lead zirconate-based antiferroelectric ceramics according to claim 1, characterized in that, Includes the following steps: (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; (2) The slurry is dried and sieved, and then pre-fired to produce pre-fired material; (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: (4) The powder is cold isostatically pressed to form a blank, and the blank is sintered to form lead zirconate-based antiferroelectric ceramic.

3. The preparation method according to claim 2, characterized in that, The conditions for ball milling in step (1) are: rotation speed 400~600 rpm, time 24~48 h.

4. The preparation method according to claim 2 or 3, characterized in that, 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.

5. The preparation method according to claim 2, characterized in that, The conditions for ball milling in step (3) are: rotation speed 400~600 rpm, time 24~48 h.

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

2.

7. The preparation method according to claim 2, characterized in that, The conditions for the medium static pressure molding process in step (4) are: pressure 200~300 MPa, time 5~7 min.

8. The application of the lead zirconate-based antiferroelectric ceramic according to claim 1 in the preparation of capacitors, characterized in that, Lead zirconate-based antiferroelectric ceramics are ground and polished to form ceramic discs. Silver layers are applied to both sides of the ceramic discs and sintered to form capacitor elements. The capacitor elements are then used in AC and DC electric fields, with AC electric fields of 0.1~1 kV / mm and DC electric fields of 7~8 kV / mm.

9. The application according to claim 8, characterized in that, The ceramic disc is 0.2 mm thick, and the silver layer is 0.09~0.11 mm thick.

10. The application according to claim 8, characterized in that, The sintering conditions are: temperature 400~700 ℃, time 20~30 min.

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