A base metal pulse energy storage capacitor doped at A and B sites, its high-entropy ceramic dielectric material, and its preparation method.

Abstract

This invention belongs to the field of capacitor fabrication, specifically relating to an A- and B-site doped base metal pulse energy storage capacitor, its high-entropy ceramic dielectric material, and its fabrication method. The raw material composition of the high-entropy ceramic dielectric material for the A- and B-site doped base metal pulse energy storage capacitor is: (Ca... 1‑x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, where 0.45 < x < 0.65, this invention uses a traditional solid-state method to prepare a ceramic dielectric material with A-site doping and B-site high entropy design through ball milling, and applies it to the preparation of base metal pulse energy storage ceramic capacitors. The prepared capacitors have low dielectric loss, high breakdown electric field, and excellent room temperature and high temperature insulation performance, and the reliability is also greatly improved.

Description

Technical Field

[0001] This invention belongs to the field of capacitor fabrication, specifically relating to a base metal pulse energy storage capacitor doped at A and B sites, its high-entropy ceramic dielectric material, and its fabrication method. Background Technology

[0002] Pulsed power systems have wide applications in resource exploration, bioelectronics, medical devices, laser weapons, and electromagnetic transmitters, permeating almost every field. Based on this, the requirements for energy storage dielectric capacitors are "high temperature, high energy density, and high reliability." Energy storage ceramic capacitors, with their high dielectric constant, low loss, and long service life, are an important component of pulsed power systems.

[0003] Electrodes have a significant impact on ceramic dielectric capacitors. Metals such as Au, Pt, Pd, and Ag, with their excellent conductivity and stability, are the preferred choice for internal electrodes in pulse ceramic dielectric capacitors. However, At and Pt are expensive, and the price of Pd has increased nearly tenfold in recent years, leading to a substantial increase in the cost of internal electrode paste. Therefore, to reduce costs, the development of pulse energy storage ceramic dielectric materials with base metal internal electrodes is imperative. Among these, base metal nickel electrodes have lower costs and higher melting points. Based on these two advantages, base metal nickel electrodes are an effective alternative to noble metal electrodes.

[0004] High-entropy ceramic materials are multi-principal-element materials doped with four or five or more elements in equal proportions, exhibiting excellent physical and chemical properties. By designing the material with high entropy, the resulting hysteresis diffusion effect can suppress ion mobility, thereby improving the ceramic material's resistance to reduction and its insulation properties. Introducing high-entropy design into pulse energy storage ceramic dielectric capacitors, especially in base metal pulse systems, is of great significance for developing a high-performance, low-cost ceramic dielectric material. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a base metal pulse energy storage capacitor doped at A and B sites, the high-entropy ceramic dielectric material used therein, and the preparation method thereof.

[0006] The present invention adopts the following technical solution: A high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at sites A and B, the raw material composition of which is: (Ca 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, where 0.45 < x < 0.65.

[0007] Furthermore, the (Ca) 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0008] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 6-12 hours. Step 2: Dry the porcelain slurry ground in Step 1 at a temperature of 100-120℃ for 18-24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a temperature of 1180-1220℃ for 1-3 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 4-8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at a temperature of 100-120℃ for 18-24 hours. After drying, the powder is sieved to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

[0009] Furthermore, in step 2, the heating rate during calcination is 3℃ / min.

[0010] A base metal pulse energy storage capacitor is prepared using the ceramic dielectric material described above.

[0011] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added and ball-milled to obtain a ceramic slurry; Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, and stir until evenly mixed to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the porcelain slurry obtained in Step 2 to obtain a porcelain film; Step 4: Print nickel electrodes on the ceramic film obtained in step 3, then stack them to the preset number of layers, and then perform water pressure equalization, slicing, degreasing, and sintering to obtain the capacitor body; Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and after sintering, obtain the base metal pulse energy storage capacitor.

[0012] Furthermore, in step four, the sintering temperature is 1260-1300℃, and the sintering time is 2-5 h.

[0013] Furthermore, in step five, the sintering temperature is 850-880℃, and the sintering time is 1-2 h.

[0014] Furthermore, in step one, the ball milling time is 2-5 hours; in step two, the mixing and stirring time is 8-12 hours.

[0015] Furthermore, in step three, the thickness of the ceramic film is 8-12 μm.

[0016] This invention obtains a ceramic dielectric material with A-site doping and B-site high entropy design through a traditional solid-state method, and successfully applies it to the preparation of base metal pulse energy storage ceramic capacitors.

[0017] CaTiO3 is a linear dielectric material with high breakdown strength, low electronic conductivity, and good temperature stability, making it highly advantageous for high-temperature energy storage. Therefore, this invention modifies CaTiO3. Based on the difference in ionic radius, Sr... 2+ Ionic radius and Ca 2+ Ions are similar and can enter site A, reacting with Ca. 2+ To achieve synergistic effects; in addition, Sn 4+ Zr 4+ Hf 4+ Ions and Ti 4+ With similar ionic radii, they can enter the B site, making it possible to design high-entropy B sites.

[0018] The slow diffusion effect of high-entropy perovskite oxides can slow down grain growth during sintering and improve the breakdown electric field strength. At the same time, the high-entropy design of the B site and the introduction of multiple elements can form a multiphase structure. This structure increases the disorder and random field, forming a dense microstructure, which can reduce dielectric loss and improve the breakdown electric field strength. These are all effective ways to improve the performance of pulse energy storage ceramic dielectric materials.

[0019] As can be seen from the above description of the present invention, compared with the prior art, the beneficial effects of the present invention are: (1) This invention modifies CaTiO3 material to reduce Sr 2+ Ions doping enters the A site and interacts with Ca. 2+ The synergistic effect of ions can regulate the dielectric constant of ceramic dielectric materials and improve the temperature stability of the materials; (2) Sn4+ The introduction of ions at the B site can effectively suppress Ti. 4+ Reduced to Ti 3+ It reduces the generation of oxygen vacancies, thereby reducing dielectric loss and DC conductivity; the introduction of ZrO2 can accumulate at grain boundaries, inhibit abnormal grain growth, improve the consistency and reliability of dielectric properties, and at the same time reduce the firing temperature and improve the density of ceramics; HfO2 has a similar mechanism to ZrO2 and can improve the energy storage performance and breakdown strength of ceramic materials. (3) The capacitor prepared by the high-entropy ceramic dielectric material doped at A and B sites provided by the present invention has excellent anti-reduction performance, low dielectric loss, high breakdown electric field, and good room temperature and high temperature insulation performance, and can be applied to the preparation of base metal pulse energy storage ceramic capacitors. Attached Figure Description

[0020] Figure 1 This is a scanning electron microscope (SEM) image of the ceramic capacitor of Embodiment 1 of this application; Figure 2 This is a scanning electron microscope (SEM) image of the ceramic capacitor of Comparative Example 4 of this application. Detailed Implementation

[0021] The present invention will be further described below through specific embodiments.

[0022] A base metal pulse energy storage capacitor is fabricated using a high-entropy ceramic dielectric material with A- and B-site doped base metal pulse energy storage capacitors. The raw material composition of the high-entropy ceramic dielectric material is: (Ca...) 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, and 0.45 < x < 0.65. Specifically, (Ca 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0023] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 6-12 hours. Step 2: Dry the porcelain slurry ground in Step 1 at a temperature of 100-120℃ for 18-24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1180-1220℃ for 1-3 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 4-8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at a temperature of 100-120℃ for 18-24 hours. After drying, the powder is sieved to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

[0024] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, thoroughly mix alcohol, toluene, and dispersant, add the high-entropy ceramic media material, and ball mill for 2-5 hours to obtain a ceramic slurry; Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 8-12 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 8-12 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack them to the preset number of layers, and then sinter them under a reducing atmosphere after water pressure equalization, slicing, degreasing, and sintering at a heating rate of 1℃ / min, a sintering temperature of 1260-1300℃, and a sintering time of 2-5 h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 850-880℃ for 1-2 hours to obtain the base metal pulse energy storage capacitor. Example

[0025] A base metal pulse energy storage capacitor is fabricated using a high-entropy ceramic dielectric material with A- and B-site doped base metal pulse energy storage capacitors. The raw material composition of the high-entropy ceramic dielectric material is: (Ca...) 0.45 Sr 0.55 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, specifically, (Ca 0.45 Sr 0.55 (Sn) 0.2 Zr 0.2Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0026] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

[0027] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0028] Comparative Example 1 A base metal pulse energy storage capacitor is made of ceramic dielectric material, wherein the raw material composition of the ceramic dielectric material is: (Ca 0.6 Sr 0.4 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, specifically, (Ca 0.6 Sr 0.4 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0029] The preparation method of ceramic dielectric materials includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the ceramic medium material.

[0030] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0031] Comparative Example 2 A base metal pulse energy storage capacitor is made of ceramic dielectric material, wherein the raw material composition of the ceramic dielectric material is: (Ca 0.3 Sr 0.7 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, specifically, (Ca 0.3 Sr 0.7 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0032] A method for preparing a ceramic dielectric material includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the ceramic medium material.

[0033] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0034] Comparative Example 3 A base metal pulse energy storage capacitor is made of ceramic dielectric material, wherein the raw material composition of the dielectric material is: Ca(Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, specifically, Ca(Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SnO2, ZrO2, HfO2 and TiO2.

[0035] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the ceramic medium material.

[0036] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0037] Comparative Example 4 A base metal pulse energy storage capacitor is made of ceramic dielectric material, wherein the raw material composition of the ceramic dielectric material is: Ca 0.45 Sr 0.55 TiO3, specifically, Ca 0.45 Sr 0.55 The raw materials for TiO3 are CaCO3, SrCO3 and TiO2.

[0038] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SrCO3 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: The porcelain slurry ground in Step 1 is dried at 120℃ for 24 hours. The dried powder is then sieved and calcined in a muffle furnace at a heating rate of 3℃ / min to 1200℃ for 2 hours to obtain Ca. 0.45 Sr 0.55 TiO3 powder; Step 3: Mix the above powder with SnO2, ZrO2 and HfO2 evenly, and ball mill it with deionized water and zirconia balls as the dispersion medium for 8 hours and 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the ceramic medium material.

[0039] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0040] Comparative Example 5 A base metal pulse energy storage capacitor is made of ceramic dielectric material, wherein the raw material composition of the ceramic dielectric material is: (Ca 0.45 Sr 0.55 (Sn) 0.25 Zr 0.25 Hf 0.25 Ti 0.25 O3, specifically, (Ca 0.45 Sr 0.55 (Sn) 0.25 Zr 0.25 Hf 0.25 Ti 0.25 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0041] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

[0042] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0043] Comparative Example 6 A base metal pulse energy storage capacitor is fabricated using a high-entropy ceramic dielectric material with A- and B-site doped base metal pulse energy storage capacitors. The raw material composition of the high-entropy ceramic dielectric material is: (Ba... 0.45 Sr 0.55 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, specifically, (Ba 0.45 Sr 0.55 (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are BaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

[0044] A method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites includes the following steps: Step 1: Using BaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 10 hours. Step 2: Dry the porcelain slurry ground in Step 1 at 120℃ for 24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a heating rate of 3℃ / min and a calcination temperature of 1200℃ for 2 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at 120°C for 24 hours. After drying, sieve the powder to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

[0045] A method for preparing a base metal pulse energy storage capacitor specifically includes the following steps: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added. The mixture is then ball-milled for 4 hours to obtain a ceramic slurry. Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, stir and mix evenly for 10 hours to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the ceramic slurry obtained in Step 2 to obtain a ceramic film with a thickness of 11 μm. Step 4: Print nickel electrodes on the ceramic film obtained in Step 3, then stack 40 layers, and after water equalization, slicing, and degreasing, sinter in a reducing atmosphere with a heating rate of 1℃ / min, a sintering temperature of 1280℃, and a sintering time of 3h to obtain the capacitor body. Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and sinter at 860°C for 1.5 h to obtain the base metal pulse energy storage capacitor.

[0046] The dielectric properties of the capacitors prepared in Example 1 and Comparative Examples 1-6 were tested, and the specific results are shown in Table 1. The capacitors prepared in Example 1, Comparative Examples 4 and 5 were subjected to high voltage capacitance tests, and the specific results are shown in Table 2.

[0047] Table 1. Dielectric Performance Parameters of Capacitors

[0048] Table 2 Capacitor High Voltage Test Parameters

[0049] As shown in the table above, the base metal pulse energy storage capacitor prepared in Example 1 has a dielectric constant of 140, a dielectric loss of 1.8, and a room temperature insulation resistance of 3.0 × 10⁻⁶. 6 Ω, insulation resistance at high temperature (125℃) is 1.0 × 10⁻⁶. 4 The breakdown electric field strength is 90 V / μm. Compared with the undoped Sr comparative example 3, the performance is significantly improved. This is because Sr is equivalently substituted at the A-site, forming a continuous solid solution, which can suppress Ti... 4+ Sr is reduced, which decreases the generation of oxygen vacancies and increases the breakdown electric field strength. In addition, Sr doping can refine the grains and promote the densification of the ceramic body, thereby reducing grain boundary defects, lowering the resistance between grain boundaries, and thus improving the insulation performance.

[0050] By comparing Example 1 and Comparative Example 1, reducing the Sr content resulted in a decrease in dielectric constant, a decrease in high-temperature insulation resistance, and a reduction in breakdown electric field strength. Compared with Comparative Example 2, increasing the Sr content resulted in an increase in dielectric constant, a significant increase in dielectric loss, and an impact on both insulation resistance and breakdown electric field strength. This is because excessive Sr doping causes the system to no longer be a single perovskite phase, but rather to easily generate multiphase structures and impurity phases. At the same time, high doping levels lead to the introduction of defects, which in turn increases dielectric loss, decreases insulation resistance, and further reduces the breakdown electric field.

[0051] Comparative Example 4: Ca synthesized using the traditional ball milling method 0.45 Sr 0.55 TiO3 powder, a pre-calcined intermediate, was mixed and ground with SnO2, ZrO2, and HfO2 to obtain a non-high-entropy ceramic dielectric powder. Compared with Example 1, Comparative Example 4 showed a higher dielectric loss, and both insulation strength and breakdown electric field strength were reduced. Furthermore, Example 1 and Comparative Example 4 underwent a long-term high-temperature and high-pressure test at 85°C and 3 times the rated voltage to preliminarily assess the reliability of the capacitors. Table 2 shows that after the high-temperature and high-pressure test, the dielectric loss of the capacitor in Example 1 increased, and the insulation resistance decreased from 3.0 × 10⁻⁶. 6 Ω decreased to 4.5 × 10 5 In Comparative Example 4, the capacitor failed after high-temperature and high-pressure testing. This is because the high-entropy design at the B site in Example 1 can alleviate the growth of ceramic grains during sintering. At the same time, the aggregation of ZrO2 and HfO2 at the grain boundaries also inhibits abnormal grain growth. The synergistic effect of the two can improve the breakdown electric field strength and insulation performance of the capacitor, thereby greatly improving its reliability.

[0052] On the other hand, comparing the scanning electron microscope images of Example 1 and Comparative Example 4, such as Figure 1 , Figure 2As shown, Example 1, with its high-entropy design at site B, introduces multiple elements such as Zr, Sn, and Hf, forming a multiphase structure. This structure increases the system's disorder and random field, making the ceramic body more compact. Therefore, Example 1 exhibits a more compact dielectric layer structure. Furthermore, Sn... 4+ The introduction of Ti can suppress 4+ Reduced to Ti 3+ This reduces oxygen vacancies; therefore, the high entropy design of the B site and the synergistic effect of multiple elements can reduce dielectric loss, improve breakdown electric field strength and insulation performance.

[0053] T 4+ The presence of [a specific substance] can refine the grains, increase grain boundaries, reduce the electric field stress of the nickel electrode, and increase the breakdown electric field strength. As can be seen from Comparative Example 5 in Table 1, reducing the Ti [specific element] [is beneficial]. 4+ The content of Ti significantly reduces its breakdown electric field strength; in addition, Ti 4+ Nickel can diffuse into the dielectric lattice, improving insulation resistance. Under long-term high-voltage pulse conditions, it optimizes reliability and service life. In Comparative Example 5, after high-voltage testing, dielectric loss increased and insulation resistance also decreased significantly.

[0054] Comparative Example 6 uses Ca 2+ Replace with Ba 2+ It can be seen that the dielectric constant of the capacitor is increased, and it has good insulation performance at both room temperature and high temperature. However, the breakdown electric field is significantly attenuated, which may be due to the presence of Ba. 2+ Such a system may promote grain growth, and the reduction of grain boundaries leads to increased local electric field stress, which is not conducive to the application of pulse energy storage capacitors.

[0055] The above description is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites, characterized in that: Its raw material composition is: (Ca 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 O3, where 0.45 < x < 0.

65.

2. The high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at sites A and B, as described in claim 1, is characterized in that: The (Ca) 1-x Sr x (Sn) 0.2 Zr 0.2 Hf 0.2 Ti 0.4 The raw materials for O3 are CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2.

3. The method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites according to claim 1, characterized in that: Includes the following steps: Step 1: Using CaCO3, SrCO3, SnO2, ZrO2, HfO2 and TiO2 as raw materials, and deionized water and zirconia balls as dispersion media, mix and grind them at a speed of 600 rpm for 6-12 hours. Step 2: Dry the porcelain slurry ground in Step 1 at a temperature of 100-120℃ for 18-24 hours. After drying, sieve the powder and calcine it in a muffle furnace at a temperature of 1180-1220℃ for 1-3 hours. Step 3: The powder mixed at the first time is subjected to secondary grinding. Deionized water and zirconia balls are used as the dispersion medium for ball milling. The ball milling time is 4-8 hours and the ball milling speed is 600 rpm. Step 4: Dry the ceramic slurry from Step 3 at a temperature of 100-120℃ for 18-24 hours. After drying, the powder is sieved to obtain the high-entropy ceramic dielectric material for base metal pulse energy storage capacitors doped at sites A and B.

4. The method for preparing a high-entropy ceramic dielectric material for a base metal pulse energy storage capacitor doped at A and B sites according to claim 3, characterized in that: In step 2, the heating rate during calcination is 3℃ / min.

5. A base metal pulse energy storage capacitor, characterized in that: It is prepared using the ceramic dielectric material described in claim 1 or 2.

6. The method for preparing a base metal pulse energy storage capacitor according to claim 5, characterized in that: Specifically, the following steps are included: Step 1: Using a vertical sand mill, alcohol, toluene, and dispersant are thoroughly mixed, and the high-entropy ceramic media material is added and ball-milled to obtain a ceramic slurry; Step 2: Mix polyvinyl butyral, dioctyl phthalate, alcohol, and toluene evenly, add the mixture to the ceramic slurry described in Step 1, and stir until evenly mixed to obtain a high-entropy ceramic dielectric material slurry for base metal pulse energy storage capacitors. Step 3: Cast the porcelain slurry obtained in Step 2 to obtain a porcelain film; Step 4: Print nickel electrodes on the ceramic film obtained in step 3, then stack them to the preset number of layers, and then perform water pressure equalization, slicing, degreasing, and sintering to obtain the capacitor body; Step 5: Attach copper electrodes to the capacitor body obtained in Step 4, and after sintering, obtain the base metal pulse energy storage capacitor.

7. The method for preparing a base metal pulse energy storage capacitor according to claim 6, characterized in that: In step four, the sintering temperature is 1260-1300℃ and the sintering time is 2-5 h.

8. The method for preparing a base metal pulse energy storage capacitor according to claim 6, characterized in that: In step five, the sintering temperature is 850-880℃ and the sintering time is 1-2 hours.

9. The method for preparing a base metal pulse energy storage capacitor according to claim 6, characterized in that: In step one, the ball milling time is 2-5 hours; in step two, the mixing and stirring time is 8-12 hours.

10. The method for preparing a base metal pulse energy storage capacitor according to claim 6, characterized in that: In step three, the thickness of the ceramic film is 8-12 μm.

Images