Low cost energy storage multilayer ceramic capacitor and ceramic dielectric material therefor, and method of manufacture

Abstract

A low-cost energy storage multilayer ceramic capacitor, its ceramic dielectric material, and preparation method are disclosed. The composition and percentage content of the ceramic dielectric material are as follows: [awt%(Sr 1‑x Ca x (Ti) 1‑y Zr y [)O3+bwt%(10SiO2-Al2O3-zH3BO3)], the main substrate is (Sr 1‑ x Ca x (Ti) 1‑y Zr y The sintering aid is SiO2-Al2O3-H3BO3, where 90 < a < 98, 2 < b < 10, and 0.5 < z < 1.5. During preparation, Si and B-doped mesoporous Al2O3 nanoparticles are synthesized using an ultrasonic-assisted sol-gel method as sintering aids and distributed on the surface of the main substrate by ultrasound. This effectively restricts the growth of the main substrate grains, resulting in ceramic dielectric powder with controllable grain size and uniform distribution. This ceramic powder can be matched with base metal electrodes, and at the same time, it improves the bias characteristics of capacitors while ensuring excellent electrical performance.

Description

Technical Field

[0001] This invention belongs to the field of ceramic capacitor manufacturing, specifically relating to a low-cost energy storage multilayer ceramic capacitor and its ceramic dielectric material and manufacturing method. Background Technology

[0002] With the development of the times, energy and environmental issues are becoming increasingly severe. Therefore, the application of energy storage ceramic dielectric materials in the field of energy materials is becoming increasingly important, including applications in electronic devices, automobile production, chemical engineering, and petroleum machinery. Energy storage capacitors have advantages such as high energy density, long service life, and fast charge and discharge speeds. However, commonly used energy storage capacitors employ Pd / Ag internal electrodes, which are costly. Therefore, the development of energy storage ceramic dielectric materials with lower-cost nickel electrodes is urgently needed.

[0003] Multilayer ceramic capacitors (MLCCs) offer high energy density, a wide operating temperature and frequency range, and long reliability and lifespan, meeting the quality requirements of high-power, high-voltage electronic equipment. Currently, commonly used material systems for energy storage ceramic capacitors include BaTiO3 ferroelectric materials, PLZST antiferroelectric materials, and TiO2 linear dielectric materials. However, the high-voltage nonlinearity of the BaTiO3 system limits the improvement of its energy density; PLZST has a lower withstand voltage and a smaller applicable temperature range; and the sintering performance of linear dielectric materials needs improvement. Therefore, while reducing costs, ensuring the energy storage performance of ceramic dielectric materials, such as electric field strength, bias characteristics, and reliability, is crucial. Furthermore, improving traditional solid-state methods to obtain ceramic dielectric powders with controllable particle size and distribution and good sintering performance is an urgent research challenge. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a low-cost energy storage multilayer ceramic capacitor and its preparation method. Another purpose is to provide a ceramic dielectric material for multilayer ceramic capacitors and its preparation method.

[0005] The present invention adopts the following technical solution:

[0006] A low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage, the composition and percentage content of which are: [awt%(Sr 1-x Ca x (Ti) 1-y Zr y [)O3+bwt%(10SiO2-Al2O3-zH3BO3)], the main substrate is (Sr 1-x Ca x (Ti) 1-y Zr y The sintering aid is SiO2-Al2O3-H3BO3, where 0.4≤x≤0.7, 0.4≤y≤0.7, 90<a<98, 2<b<10, and 0.5<z<1.5. During preparation, Si and B-doped mesoporous Al2O3 nanoparticles are synthesized using an ultrasonic-assisted sol-gel method as sintering aids and then distributed on the surface of the main substrate by ultrasonication.

[0007] Furthermore, the raw material composition of the sintering aid is C8H. 20 O4Si, C 12 H 27 BO3 and C9H 21 AlO3.

[0008] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0009] Step 1: Using raw materials with SrCO3, CaCO3, TiO2, and ZrO2 as the main substrates, according to (Sr... 1-x Ca x (Ti) 1-y Zr y The chemical formula (Sr) is obtained by using deionized water as the dispersion medium and zirconia balls as the grinding medium, followed by ball milling, drying, crushing, and pre-sintering. 1-x Ca x (Ti) 1-y Zr y )O3 powder;

[0010] Step 2, (Sr 1-x Ca x (Ti) 1-y Zr y After secondary ball milling, drying, and crushing, O3 powder is used to obtain (Sr) 1-x Ca x (Ti) 1-y Zr y O3 precursor powder;

[0011] Step 3, with C8H 20 O4Si, C9H 21 AlO3 and C 12 H 27 BO3 is a raw material for sintering aids. Based on the raw material ratio of SiO2-Al2O3-xH3BO3, isopropanol is used as the solvent to sinter C9H... 21 AlO3 was ultrasonically dispersed in isopropanol for 10-20 minutes.

[0012] Step 4: Using a mixed solution of anhydrous ethanol and acetic acid as a solvent, ultrasonically disperse the triblock copolymer P123 until dissolved. The volume ratio of anhydrous ethanol to acetic acid is 100:1. Then add the above-mentioned (Sr) 1-x Ca x (Ti) 1-y Zr y O3 precursor powder, adjust the pH value to the range of 0.5-1.5, and continue to sonicate to obtain a suspension. The sonication time is 10-30 min.

[0013] Step 5: Slowly add the aluminum isopropoxide solution obtained in step 3 to the above mixed suspension and ultrasonically mix evenly. The ultrasonic dispersion time is 0.5h-2h.

[0014] Step 6, C8H 20 O4Si, C 12 H 27 BO3 was dissolved in anhydrous ethanol according to the raw material ratio, and then the mixed solution described in step 5 was slowly added. The ultrasonic dispersion reaction was continued for 0.5 h to 2 h.

[0015] Step 7: Let the solution obtained in Step 6 stand at room temperature to age, then dry, pulverize and sieve to obtain the ceramic dielectric material for the low-cost energy storage multilayer ceramic capacitor.

[0016] Furthermore, in step 1, the drying temperature is 120-150℃ and the drying time is 6-15h; the pre-sintering temperature is 950-1150℃ and the holding time is 1-3h.

[0017] Furthermore, in step 2, the drying temperature is 120-150℃, and the drying time is 6-15 hours.

[0018] Furthermore, in step 7, the aging temperature is 25℃ and the aging time is 6-12h; the drying temperature is 60-80℃ and the drying time is 6-12h.

[0019] Furthermore, in steps 1 and 2, the weight ratio of deionized water to material during ball milling is 2:1, the ball milling media used is zirconia balls, the weight ratio of the ball milling media to material is 5:1, the rotation speed is 400-600 rpm / min, and the ball milling time is 3-8 hours.

[0020] A low-cost energy storage multilayer ceramic capacitor is made using the ceramic dielectric material described above.

[0021] A method for fabricating a low-cost multilayer ceramic capacitor for energy storage includes the following steps:

[0022] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 1-4 hours to obtain ceramic slurry;

[0023] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0024] Step 3: Cast the porcelain slurry obtained in Step 2 to a thickness of 6-10 μm.

[0025] Step 4: Coat a nickel electrode onto the ceramic film, then perform stacking, water equalization, slicing, degreasing, and sintering. Chamfer the rear end and attach a copper electrode to obtain the multilayer ceramic capacitor.

[0026] Furthermore, in step 4, the sintering conditions are as follows: in an H2 atmosphere, the temperature is increased to 500°C at a rate of 10°C / min, held for 4 hours to remove template agent P123 and organic matter, and then the temperature is increased to 1260°C at a rate of 5°C / min and held for 3 hours.

[0027] 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:

[0028] This invention improves upon the traditional solid-state method for preparing ceramic dielectric powders by introducing an ultrasonic-assisted sol-gel method during the synthesis of sintering aids. This successfully synthesized a mesoporous (10SiO2-Al2O3-zH3BO3) nanoscale additive and effectively incorporated it into the main substrate ((Sr) under ultrasonic irradiation. 1-x Ca x (Ti) 1-y Zr y In O3), sintering aids with mesoporous structures are ultrasonically coated onto the surface of the main substrate, so that the low melting point phase formed during high-temperature sintering has sufficient space and channels to wet the surface of solid particles through the mesoporous structure, limiting the growth of particles due to sintering, ensuring the uniformity of powder particles, and at the same time having good density.

[0029] In the preparation of sintering aids using the sol-gel method, the introduction of Si can suppress the high-temperature phase transformation of Al2O3, while improving the sintering performance and density of the ceramic body. Boron doping, on the other hand, enhances thermal stability and inhibits nanoparticle growth. The reaction of Bo with Al-OH on the alumina surface forms BO-Al bonds, stabilizing the pore structure of the sintering aid material. The presence of ultrasound promotes the formation of the aluminum-coated template agent P123, resulting in a more effective mesoporous structure. This mesoporous structure provides sufficient channels for the formation of the low-melting-point liquid phase during sintering to wet the solid particles, further improving the density of the ceramic body.

[0030] The ceramic dielectric material for low-cost energy storage multilayer ceramic capacitors obtained by this invention has a uniform particle size distribution, a room temperature dielectric constant of approximately 150, and a loss tangent tgδ < 10 × 10⁻⁶. -4 With an electric field strength greater than 90V / μm, the capacitance change rate under different electric fields (0~50V / μm) is in the range of (0~-10.0)%, exhibiting good bias characteristics, and is suitable for producing multilayer ceramic capacitors with large capacity and high energy storage efficiency.

[0031] The low-cost energy storage multilayer ceramic capacitor obtained by this invention uses base metal nickel internal electrodes, which can replace the expensive Pd / Ag internal electrodes. Co-firing with the above-mentioned ceramic dielectric material can greatly reduce production costs. Attached Figure Description

[0032] Figure 1 Example 1 of this application ( Figure 1 (a)), Example 2 Figure 1 (b)), Comparative Example 4 Figure 1 (c) SEM image of the multilayer ceramic capacitor obtained;

[0033] Figure 2 The graph shows the capacitance change rate of the multilayer ceramic capacitors obtained in Example 2 and Comparative Example 8 of this application under different electric fields. Detailed Implementation

[0034] The present invention will be further described below through specific embodiments.

[0035] A low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage, the composition and percentage content of which are: [awt%(Sr 1-x Ca x (Ti) 1-y Zr y [)O3+bwt%(10SiO2-Al2O3-zH3BO3)], the main substrate is (Sr 1-x Ca x (Ti) 1- y Zr yThe sintering aid is SiO2-Al2O3-H3BO3, where 0.4≤x≤0.7, 0.4≤y≤0.7, 90<a<98, 2<b<10, 0.5<z<1.5. During preparation, P123 (PEO-PPO-PEO) is used as a template agent, and Si and B-doped mesoporous Al2O3 nanoparticles are synthesized using an ultrasonic-assisted sol-gel method as sintering aids, and then ultrasonically distributed onto the surface of the main substrate. Here, a and b represent the mass percentages of the main substrate and the sintering aid, respectively. The raw material composition of the main substrate is CaCO3, SrCO3, TiO2, and ZrO2; the raw material composition of the sintering aid is C8H2O. 20 O4Si, C 12 H 27 BO3 and C9H 21 AlO3.

[0036] Its preparation method includes the following steps:

[0037] Step 1: Using raw materials with SrCO3, CaCO3, TiO2, and ZrO2 as the main substrates, according to (Sr... 1-x Ca x (Ti) 1-y Zr y The chemical formula (Sr) is obtained by using deionized water as the dispersion medium and zirconia balls as the grinding medium, followed by ball milling, drying, crushing, and pre-sintering. 1-x Ca x (Ti) 1-y Zr y )O3 powder;

[0038] Step 2, (Sr 1-x Ca x (Ti) 1-y Zr y After secondary ball milling, drying, and crushing, O3 powder is used to obtain (Sr) 1-x Ca x (Ti) 1-y Zr y O3 precursor powder;

[0039] Step 3, with C8H 20 O4Si, C9H 21 AlO3 and C 12 H 27 BO3 is a raw material for sintering aids. Based on the raw material ratio of SiO2-Al2O3-xH3BO3, isopropanol is used as the solvent to sinter C9H... 21 AlO3 was ultrasonically dispersed in isopropanol for 10-20 minutes.

[0040] Step 4: Using a mixed solution of anhydrous ethanol and acetic acid as a solvent, ultrasonically disperse the triblock copolymer P123 until dissolved. The volume ratio of anhydrous ethanol to acetic acid is 100:1. Then add the above-mentioned (Sr) 1-x Ca x (Ti) 1-y Zr y O3 precursor powder, adjust the pH value to the range of 0.5-1.5, and continue to sonicate to obtain a suspension. The sonication time is 10-30 min.

[0041] Step 5: Slowly add the aluminum isopropoxide solution obtained in step 3 to the above mixed suspension and ultrasonically mix evenly. The ultrasonic dispersion time is 0.5h-2h.

[0042] Step 6, C8H 20 O4Si, C 12 H 27 BO3 was dissolved in anhydrous ethanol according to the raw material ratio, and then the mixed solution described in step 5 was slowly added. The ultrasonic dispersion reaction was continued for 0.5 h to 2 h.

[0043] Step 7: Let the solution obtained in Step 6 stand at room temperature to age, then dry, pulverize and sieve to obtain the ceramic dielectric material for the low-cost energy storage multilayer ceramic capacitor.

[0044] Specifically, in step 1, the drying temperature is 120-150℃, and the drying time is 6-15h; the pre-sintering temperature is 950-1150℃, and the holding time is 1-3h; during the ball milling process, the weight ratio of deionized water to material is 2:1, the ball milling media used is zirconia balls, the weight ratio of the ball milling media to material is 5:1, the rotation speed is 400-600rpm / min, and the ball milling time is 3-8h.

[0045] In step 2, the drying temperature is 120-150℃, and the drying time is 6-15 hours. During ball milling, the weight ratio of deionized water to material is 2:1, the ball milling media is zirconia balls, the weight ratio of the ball milling media to material is 5:1, the rotation speed is 400-600 rpm / min, and the ball milling time is 3-8 hours.

[0046] In step 7, the aging temperature is 25℃ and the aging time is 6-12 hours; the drying temperature is 60-80℃ and the drying time is 6-12 hours.

[0047] A low-cost energy storage multilayer ceramic capacitor, made of the ceramic dielectric material described above, is prepared by means of the following steps:

[0048] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 1-4 hours to obtain ceramic slurry;

[0049] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0050] Step 3: Cast the porcelain slurry obtained in Step 2 to a thickness of 6-10 μm.

[0051] Step 4: Coat a nickel electrode onto the ceramic film, then perform stacking, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0052] Example 1

[0053] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0054] Step 1, based on the ceramic dielectric material [awt%(Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The chemical formula [(10SiO2-Al2O3)] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%(10SiO2-Al2O3)] 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0055] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr0.7 O3) precursor powder;

[0056] Step 3, using C9H 21 AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0057] Step 4: Using P123 as a template agent and anhydrous ethanol and acetic acid as solvents, sonicate P123 until dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0058] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0059] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0060] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage.

[0061] A method for fabricating a ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor ceramic dielectric material includes the following steps:

[0062] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0063] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0064] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0065] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0066] Example 2

[0067] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0068] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0069] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was ball-milled a second time using zirconia balls at a weight ratio of 2:1 (deionized water to raw material) and 5:1 (zirconia balls to raw material). After ball milling, the mixture was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0070] Step 3, using C9H 21AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0071] Step 4: Using P123 as a template agent and anhydrous ethanol and acetic acid as solvents, sonicate P123 until dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0072] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0073] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0074] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3-H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0075] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0076] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0077] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0078] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0079] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0080] Comparative Example 1

[0081] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0082] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0083] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0084] Step 3, using C9H 21AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0085] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0086] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0087] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:0.5. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0088] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3-0.5H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0089] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0090] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0091] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0092] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0093] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0094] Comparative Example 2

[0095] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0096] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0097] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0098] Step 3, using C9H 21AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0099] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0100] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0101] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1.5. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0102] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3-1.5H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0103] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0104] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0105] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0106] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0107] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0108] Comparative Example 3

[0109] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0110] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-MgO-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%(10SiO2-MgO-zH3BO3)] 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0111] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was ball-milled a second time using zirconia balls at a weight ratio of 2:1 (deionized water to raw material) and 5:1 (zirconia balls to raw material). After ball milling, the mixture was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0112] Step 3: Using Mg(CH3COO)2·4H2O as the magnesium source and isopropanol as the solvent, Mg(CH3COO)2·4H2O is ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A.

[0113] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-MgO-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0114] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0115] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Mg, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0116] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-MgO-H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage;

[0117] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost ceramic dielectric material for energy storage multilayer capacitors includes the following steps:

[0118] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0119] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0120] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0121] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0122] Comparative Example 4

[0123] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0124] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [(Al2O3-zH3BO3)] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%(Al2O3-zH3BO3)] 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0125] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was ball-milled a second time using zirconia balls at a weight ratio of 2:1 (deionized water to raw material) and 5:1 (zirconia balls to raw material). After ball milling, the mixture was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0126] Step 3, using C9H 21 AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0127] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 to sintering aid Al2O3-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0128] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0129] Step 6, place C 12 H 27 BO3 is prepared with C in a 1:1 weight ratio of Al to B. 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0130] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(Al2O3-H3BO3)] Low-cost energy storage multilayer ceramic capacitor ceramic dielectric material.

[0131] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0132] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0133] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0134] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0135] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0136] Comparative Example 5

[0137] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0138] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0139] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0140] Step 3, using C9H 21 AlO3 was used as the aluminum source, isopropanol as the solvent, and C9H was stirred magnetically. 21 AlO3 is dissolved in isopropanol solution to obtain solution A;

[0141] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, stir P123 until dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 97:3, and 97wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was stirred to obtain a suspension;

[0142] Step 5: Add solution A to the above suspension to obtain solution B;

[0143] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and stirred for 10 min. Then, solution B was added and the reaction was continued with stirring.

[0144] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3-1H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0145] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0146] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0147] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0148] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0149] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0150] Comparative Example 6

[0151] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0152] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0153] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was ball-milled a second time using zirconia balls at a weight ratio of 2:1 (deionized water to raw material) and 5:1 (zirconia balls to raw material). After ball milling, the mixture was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0154] Step 3, using C9H 21 AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0155] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 98:2, and 98wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0156] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0157] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0158] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [98wt% (Sr)] is obtained. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+2wt%(10SiO2-Al2O3-H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage;

[0159] A method for fabricating a multilayer ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor dielectric material includes the following steps:

[0160] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0161] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0162] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0163] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0164] Comparative Example 7

[0165] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0166] Step 1, based on the ceramic dielectric material [awt%(Sr 1-x Ca x (Ti) 1-y Zr y The chemical formula [10SiO2-Al2O3-zH3BO3] was used, with SrCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3. The weight ratio of deionized water to raw materials was 2:1, and the weight ratio of zirconia balls to raw materials was 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((SrO3+bwt%)[10SiO2-Al2O3-zH3BO3] ... 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0167] Step 2, for the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0168] Step 3, using C9H 21 AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0169] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Sr 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 90:10, and 90wt% of (Sr) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0170] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0171] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0172] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and pulverized to obtain [90wt% (Sr)]. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+10wt%(10SiO2-Al2O3-H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0173] A method for fabricating a ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor ceramic dielectric material includes the following steps:

[0174] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0175] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0176] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0177] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0178] Comparative Example 8

[0179] A method for preparing a low-cost ceramic dielectric material for multilayer ceramic capacitors for energy storage includes the following steps:

[0180] Step 1, based on the ceramic dielectric material [97wt% (Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The chemical formula [(10SiO2-Al2O3-zH3BO3)] was prepared by mixing BaCO3 and CaCO3 in a molar ratio of 7:3 and ZrO2 and TiO2 in a molar ratio of 7:3, with deionized water and raw materials in a weight ratio of 2:1 and zirconia balls and raw materials in a weight ratio of 5:1. After ball milling, the mixture was dried and pulverized, and then pre-sintered at 1100℃ to obtain ((Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 )O3) powder;

[0181] Step 2, for the main substrate ((Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The material was subjected to secondary ball milling with deionized water at a weight ratio of 2:1 and zirconia balls at a weight ratio of 5:1. After ball milling, the material was dried and pulverized to obtain (Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3) precursor powder;

[0182] Step 3, using C9H 21 AlO3 was used as the aluminum source, and isopropanol as the solvent to prepare C9H 21 AlO3 was ultrasonically dispersed in isopropanol solution for 20 min to obtain solution A;

[0183] Step 4: Using PEO-PPO-PEO triblock copolymer (P123) as a template agent and anhydrous ethanol and acetic acid as solvents, P123 is ultrasonically dissolved; according to the main substrate (Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The weight ratio of O3 and sintering aid 10SiO2-Al2O3-zH3BO3 is 97:3, and 97wt% of (Ba) is added. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 O3 precursor powder was further ultrasonically dispersed for 30 minutes to obtain a suspension;

[0184] Step 5: Add solution A to the above suspension and continue the ultrasonic reaction to obtain solution B;

[0185] Step 6, C8H 20 O4Si and C 12 H 27 BO3 is prepared by mixing C8H with Al, Si, and B in a weight ratio of 10:1:1. 20 O4Si and C 12 H 27 BO3 was dissolved in anhydrous ethanol and sonicated for another 10 minutes. Then, solution B was added and the sonication reaction was continued.

[0186] Step 7: The solution obtained in Step 6 is allowed to stand at room temperature for 12 hours, then dried at 80°C, and after pulverization, [97wt% (Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 [O3+3wt%(10SiO2-Al2O3-H3BO3)] Low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage.

[0187] A method for fabricating a ceramic capacitor based on the aforementioned low-cost energy storage multilayer ceramic capacitor ceramic dielectric material includes the following steps:

[0188] Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the above-mentioned low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 2 hours to obtain ceramic slurry;

[0189] Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors.

[0190] Step 3: Cast the ceramic slurry obtained in Step 2 to a thickness of 8 μm.

[0191] Step 4: Coat a nickel electrode onto the ceramic film, then perform lamination, water equalization, slicing, degreasing, and sintering. Attach a copper electrode to the chamfered rear end to obtain the low-cost energy storage multilayer ceramic capacitor. The sintering conditions are as follows: heat to 500°C at a rate of 10°C / min in an H2 atmosphere, hold for 4 hours to remove template agent P123 and organic matter, then heat to 1260°C at a rate of 5°C / min and hold for 3 hours.

[0192] The dielectric properties of the multilayer ceramic capacitors prepared above were tested, and the specific results are shown in Table 1.

[0193] Table 1 shows the dielectric performance parameters of multilayer ceramic dielectric capacitors made from the above-mentioned low-cost energy storage ceramic dielectric materials.

[0194]

[0195]

[0196] The basic electrical properties of the multilayer ceramic dielectric capacitors prepared in Examples 1 and 2, and Comparative Examples 1 and 2 were compared, as shown in Table 1. The molar ratio of SrCO3 to CaCO3 was 7:3, the molar ratio of ZrO2 to TiO2 was 7:3, and the main substrate ((Sr) 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 When the ratio of Al₂O₃ to sintering aid (10SiO₂-Al₂O₃-H₃BO₃) is 97:3, and the ratio of Al, Si, and B in the sintering aid is 10:1:1, its dielectric constant is approximately 145, its loss is low, and its resistivity at room temperature (25℃) is 2.5 × 10⁻⁶. 5 With an impedance of MΩ and an electric field strength of approximately 70V / μm, and a capacitance temperature coefficient ranging from -1650 to -1250ppm / K, it exhibits superior electrical performance. Compared to Comparative Examples 3 and 4, Example 2 shows that the modification and sintering aid effect of the (10SiO2-MgO-H3BO3) sintering aid obtained by replacing Al2O3 with MgO is not significant, resulting in varying degrees of attenuation in dielectric loss, insulation resistance, and electric field strength. This may be because the MgO system cannot effectively form a mesoporous structure using the ultrasonic-assisted sol-gel method of this patent; while the removal of Si significantly reduces the sintering aid effect, leading to a deterioration in capacitor performance.

[0197] By comparing the compactness of Examples 1 and 2, such as Figure 1 As shown, compared with Example 1 ( Figure 1(a) Compared to the addition of element B, the density of the ceramic dielectric capacitor body is improved. Figure 1 (b)); Through the example of Example 2 ( Figure 1 (b) and Comparative Example 6 Figure 1 Compared with (c), when the amount of sintering aid added is reduced, the density of the capacitor ceramic body decreases. This is because the addition of an appropriate amount of sintering aid can enable the capacitor to form a low-melting-point liquid phase during high-temperature sintering, thereby improving sintering performance; and the addition of element B can enable the system to form a molten liquid phase when it reaches the melting point or softening point during the heating process. Under the action of capillary effect, the particle surface is wetted, and the particles tend to be densely packed, thereby improving the density of the ceramic; in addition, the doping of element B can inhibit the growth of nanoparticles while improving thermal stability. B reacts with Al-OH on the surface of alumina to form BO-Al bonds, which can stabilize the pore structure of the sintering aid material.

[0198] By comparing Example 2 with Comparative Example 5, the acoustic cavitation effect of ultrasound accelerates the self-assembly process of the sol-gel method, making it easier to form aluminum-coated P123 micelles, which can form mesoporous structures after high-temperature calcination; the presence of ultrasound can also cause the sintering aid to collide with the precursor powder of the main substrate, promoting the sintering aid to be more uniformly dispersed on the surface of the main substrate, which can suppress the growth of particles during sintering.

[0199] By comparing Example 2 and Comparative Example 8, it can be seen from the figure that when the ceramic magnetic dielectric material [97wt% (Ba 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 After replacing Ba with Sr in the system [10SiO2-Al2O3-zH3BO3], the concentration of Ba was [97wt% (Sr)]. 0.7 Ca 0.3 (Ti) 0.3 Zr 0.7 The multilayer ceramic dielectric capacitor prepared by the ceramic dielectric material of the [10SiO2-Al2O3-H3BO3] system exhibits good stability under an electric field of 0-30V / μm, with capacitance variation within the range of (0 to -10%). The capacitance variation is relatively stable under different voltages. Therefore, the low-cost energy storage ceramic dielectric capacitor prepared by this system has good bias characteristics.

[0200] 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 low-cost ceramic dielectric material for multilayer ceramic capacitors used in energy storage, characterized in that: Its composition and percentage content are: [a wt%(Sr 1-x Ca x (Ti) 1-y Zr y [O3+b wt% (10SiO2-Al2O3-zH3BO3)], with Sr as the main substrate. 1-x Ca x (Ti) 1-y Zr y The sintering aid is SiO2-Al2O3-H3BO3, where 0.4≤x≤0.7, 0.4≤y≤0.7, 90<a<98, 2<b<10, 0.5<z<1.

5. During preparation, Si and B doped mesoporous Al2O3 nanoparticles are synthesized by ultrasonic-assisted sol-gel method as sintering aids and distributed on the surface of the main substrate by ultrasonication. The raw material composition of the sintering aid is C8H. 20 O4Si, C 12 H 27 BO3 and C9H 21 AlO3.

2. The method for preparing a low-cost ceramic dielectric material for a multilayer ceramic capacitor for energy storage according to claim 1, characterized in that: Includes the following steps: Step 1: Using raw materials with SrCO3, CaCO3, TiO2, and ZrO2 as the main substrates, according to (Sr... 1-x Ca x (Ti) 1-y Zr y The chemical formula (Sr) is obtained by using deionized water as the dispersion medium and zirconia balls as the grinding medium, followed by ball milling, drying, crushing, and pre-sintering. 1-x Ca x (Ti) 1-y Zr y )O3 powder; Step 2, (Sr 1-x Ca x (Ti) 1-y Zr y After secondary ball milling, drying, and crushing, O3 powder is used to obtain (Sr) 1-x Ca x (Ti) 1- y Zr y O3 precursor powder; Step 3, with C8H 20 O4Si, C9H 21 AlO3 and C 12 H 27 BO3 is a raw material for sintering aids. Based on the raw material ratio of SiO2-Al2O3-xH3BO3, isopropanol is used as the solvent to sinter C9H... 21 AlO3 was ultrasonically dispersed in isopropanol for 10-20 minutes. Step 4: Using a mixed solution of anhydrous ethanol and acetic acid as a solvent, ultrasonically disperse the triblock copolymer P123 until dissolved. The volume ratio of anhydrous ethanol to acetic acid is 100:

1. Then add the above-mentioned (Sr... 1-x Ca x (Ti) 1-y Zr y O3 precursor powder, adjust the pH value to the range of 0.5-1.5, and continue to sonicate to obtain a suspension. The sonication time is 10-30 min. Step 5: Slowly add the aluminum isopropoxide solution obtained in step 3 to the above suspension and mix it evenly by ultrasonication. The ultrasonic dispersion time is 0.5h-2h. Step 6, C8H 20 O4Si, C 12 H 27 BO3 was dissolved in anhydrous ethanol according to the raw material ratio, and then the mixed solution described in step 5 was slowly added. The ultrasonic dispersion reaction was continued for 0.5 h to 2 h. Step 7: Let the solution obtained in Step 6 stand at room temperature to age, then dry, pulverize and sieve to obtain the ceramic dielectric material for the low-cost energy storage multilayer ceramic capacitor.

3. The method for preparing a low-cost ceramic dielectric material for a multilayer ceramic capacitor for energy storage according to claim 2, characterized in that: In step 1, the drying temperature is 120-150℃ and the drying time is 6-15h; the pre-sintering temperature is 950-1150℃ and the holding time is 1-3h.

4. The method for preparing a low-cost ceramic dielectric material for a multilayer ceramic capacitor for energy storage according to claim 2, characterized in that: In step 2, the drying temperature is 120-150℃ and the drying time is 6-15 hours.

5. The method for preparing a low-cost ceramic dielectric material for a multilayer ceramic capacitor for energy storage according to claim 2, characterized in that: In step 7, the aging temperature is 25℃ and the aging time is 6-12 hours; the drying temperature is 60-80℃ and the drying time is 6-12 hours.

6. The method for preparing a low-cost ceramic dielectric material for a multilayer ceramic capacitor for energy storage according to claim 2, characterized in that: In steps 1 and 2, the weight ratio of deionized water to material during ball milling is 2:1, the ball milling media used is zirconia balls, the weight ratio of ball milling media to material is 5:1, the rotation speed is 400-600 rpm / min, and the ball milling time is 3-8 hours.

7. A low-cost energy storage multilayer ceramic capacitor, characterized in that: It is made using the ceramic dielectric material described in claim 1.

8. The method for preparing a low-cost energy storage multilayer ceramic capacitor according to claim 7, characterized in that: Includes the following steps: Step 1: Using a small vertical sand mill, add alcohol, toluene and dispersant to grind the low-cost energy storage multilayer ceramic capacitor with ceramic dielectric material for 1-4 hours to obtain ceramic slurry; Step 2: Add polyvinyl butyral (PVB) and dioctyl phthalate (DOP) to the ceramic slurry described in Step 1, continue grinding, and mix evenly to obtain a low-cost ceramic dielectric material slurry for energy storage multilayer ceramic capacitors. Step 3: Cast the porcelain slurry obtained in Step 2 to a thickness of 6-10 μm. Step 4: Coat a nickel electrode onto the ceramic film, then perform stacking, water pressure equalization, slicing, degreasing, and sintering. Chamfer the rear end and attach a copper electrode to obtain the multilayer ceramic capacitor.

9. The method for preparing a low-cost energy storage multilayer ceramic capacitor according to claim 8, characterized in that: In step 4, the sintering conditions are as follows: in an H2 atmosphere, the temperature is increased to 500℃ at a rate of 10℃ / min and held for 4 h to remove the template agent P123 and organic matter, and then the temperature is increased to 1260℃ at a rate of 5℃ / min and held for 3 h.

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