High-specific-energy high-voltage pulse power type ceramic capacitor, ceramic dielectric material for ceramic capacitor and preparation method of ceramic dielectric material

Abstract

The invention relates to a high-specific-energy high-voltage pulse power type ceramic capacitor and a ceramic dielectric material and a preparation method thereof, the ceramic dielectric material takes 100 parts by mole of SrTiO3 as a base material, and the following components are added in parts by mole: 20-30 parts of KxNa (1-x) NbO3, 3-5 parts of ReyBi (1-y) VO4, 1.0-3 parts of Na2B2O7, 1.0-3 parts of Zn3B2O6, 0.3-0.8 part of Mn3O4, 0.5-1.0 part of SiO2 and 0.03-0.1 part of LiNbO3, x is more than 0 and less than 0.7, y is more than 0 and less than 0.25, and Re is Sm, La, Gd or Nd; according to the invention, SrTiO3 is used as a base material, KxNa1-xNbO3 synthesized by a solid phase method and ReyBi1-yVO4 synthesized by a hydrothermal method are added, combined borate Na2B2O7 and Zn3B2O6 are matched with SiO2 as a sintering aid, in the presence of trace Mn and Li elements, the prepared dielectric material has relatively high energy storage density and working electric field, and a pulse power type ceramic capacitor prepared from the dielectric material has relatively high energy storage density and working electric field by adopting relatively short charging time, so that the dielectric material has relatively high energy storage density and working electric field. Therefore, the ceramic capacitor is suitable for being used as a pulse power type ceramic capacitor.

Description

Technical Field

[0001] This invention belongs to the field of ceramic capacitor preparation, specifically relating to a high-energy-density, high-voltage pulse power ceramic capacitor and its ceramic dielectric material and preparation method. Background Technology

[0002] Pulse power ceramic capacitors made of pulse energy storage dielectric materials can store high-density charge in a short time and release energy rapidly in the form of pulses to generate extremely high current. Based on their discharge characteristics, pulse power ceramic capacitors are widely used in ignition circuits, strobe lights, electronic triggers, detonation, power relay protection, lasers, electromagnetic catapults, flashlights, pulse lighting, oil field exploration, and other fields, and are indispensable electronic components.

[0003] Compared to film capacitors, ceramic capacitors offer advantages such as smaller size, miniaturization, low dielectric loss, lower cost, stable temperature characteristics, high withstand voltage, high insulation strength, resistance to damp heat, stable high and low temperature performance, and extremely long charge and discharge life. However, due to the relatively low dielectric constant of ceramic powder, the capacitance of ceramic capacitors is generally smaller. The trend towards miniaturization and lightweighting of electronic components necessitates further improvements in the dielectric constant and energy storage density of ceramic dielectric materials. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high-energy-density, high-voltage pulse power ceramic capacitor, its ceramic dielectric material, and its preparation method.

[0005] The present invention adopts the following technical solution: A ceramic dielectric material for high-energy-density, high-voltage pulse power ceramic capacitors, using 100 moles of SrTiO3 as the base material, with the following moles added: 20-30 moles of K x Na 1-x NbO3, 3-5 parts Re y Bi 1-y VO4, 1.0-3 parts Na2B2O7, 1.0-3 parts Zn3B2O6, 0.3-0.8 parts Mn3O4, 0.5-1.0 parts SiO2, 0.03-0.1 parts LiNbO3, wherein 0 < x < 0.7, 0 < y < 0.25, and Re = Sm, La, Gd or Nd.

[0006] Furthermore, the K x Na 1-x NbO3 was synthesized from K2CO3, Na2CO3, and Nb2O5 using a solid-state method.

[0007] Furthermore, the Re y Bi 1-yVO4 was synthesized from Bi(NO3)3, Re(NO3)3 and NH4VO3 by a hydrothermal method.

[0008] Furthermore, the K x Na 1-x NbO3 is K 0.5 Na 0.5 NbO3.

[0009] Furthermore, the Re y Bi 1-y VO4 is Sm 0.15 Bi 0.85 VO4.

[0010] A method for preparing a ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor includes the following steps: Step 1: Preparation of K by solid-state method x Na 1-x NbO3; Step 2, Hydrothermal preparation of Re y Bi 1-y VO4; Step 3, K prepared in Steps 1 and 2 x Na 1-x NbO3, Sm y Bi 1-y VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 4-6 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0011] Further, the specific steps of step one are as follows: Weigh K2CO3, Na2CO3, and Nb2O5 respectively in molar ratios of x:1 to x:1, add anhydrous ethanol and zirconium oxide beads, mix and ball mill for 10-15 hours, dry the powder, sieve it through a 40-80 mesh sieve, calcine it at 700-900℃ for 3-5 hours, and naturally cool it to room temperature to obtain K2CO3. x Na 1-x NbO3.

[0012] Further, the specific steps of step two are as follows: Weigh Bi(NO3)3, Re(NO3)3, and NH4VO3 separately according to the molar ratio y:1-y:1. Dissolve Bi(NO3)3 and Re(NO3)3 together in deionized water by heating, and dissolve NH4VO3 in deionized water by heating. Then, add the NH4VO3 aqueous solution dropwise to the mixed solution of Bi(NO3)3 and Re(NO3)3. Mix ultrasonically for 45-60 min, stir magnetically for 30-60 min, and then adjust the pH of the mixed solution with 10 mol / L NaOH solution in a pH gradient from 1 to 13. Then, place the mixed solution in a high-temperature reactor and react at 300-500 ℃ for 4-8 h. After the reaction is completed, cool naturally to room temperature, centrifuge, and wash three times with deionized water and anhydrous ethanol. Vacuum dried at ℃; finally, the obtained precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 6-10 hours. After drying, the powder was sieved through a 40-80 mesh sieve to obtain refined Re. y Bi 1-y VO4.

[0013] A high-energy-density, high-voltage pulse power ceramic capacitor is made using any of the ceramic dielectric materials described above.

[0014] A method for preparing a high-energy-density, high-voltage pulse power ceramic capacitor includes the following steps: passing the dielectric material through an MLCC process, using 70Ag-30Pd as the internal electrode, sintering in an air atmosphere at a temperature of 1000-1200℃ for 2-5 hours to obtain the pulse power capacitor.

[0015] 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: First, the pulsed power ceramic dielectric material proposed in this invention uses SrTiO3 as a substrate, and then adds K synthesized by a solid-state method. x Na 1-x NbO3, Re synthesized by hydrothermal method y Bi 1-y VO4, using a combination of borates: Na2B2O7 and Zn3B2O6 with SiO2 as a sintering aid, and in the presence of trace amounts of Mn and Li, produces a dielectric material with high energy storage density and operating electric field. Pulse power ceramic capacitors made from this dielectric material exhibit short charging times and no current decay during discharge, making them suitable for use as pulse power ceramic capacitors. SrTiO3, with its high bandgap, is selected as the main substrate because its Curie temperature is -250℃, making it less prone to ferroelectric phase transition. Ceramic capacitors made from this characteristic do not experience capacitance decay due to aging. K... (The sentence is incomplete and requires further context to translate accurately.) x Na 1-xNbO3, Re synthesized by hydrothermal method y Bi 1-y VO4 forms a uniform perovskite structure, and the viscosity of the ceramic slurry is controlled by Mn3O4. The optimal combination of borate and SiO2 is used to improve the density of the ceramic body and reduce the sintering temperature. The addition of trace amounts of LiNbO3 optimizes the discharge curve, so that the prepared dielectric material has a high dielectric constant and energy storage density, which is suitable for use as a pulse power ceramic capacitor. Second, K x Na 1-x NbO3 is a lead-free energy storage ceramic with an ABO3 perovskite structure and a Curie temperature as high as 420℃, enabling it to maintain good energy storage performance even at high temperatures. KNbO3-NaNbO3 can form a solid solution across the entire composition range, but the structure is not entirely the same at different composition points, thus different K / Na ion ratios result in different K... x Na 1-x NbO3 has a significant impact on the dielectric constant and energy density of SrTiO3; K x Na 1-x NbO3 and BNT(Bi) 0.5 Na 0.5 Compared to TiO3, it has a lower coercive field and can provide lower dielectric loss; Third, Sm is partially doped into BiVO4 to form Sm y Bi 1-y VO4 and Bi can effectively improve the dielectric constant of SrTiO3 ceramic dielectrics, but Bi 3+ Ag is formed after being captured by the Ag-Pd electrode. + Migration channels reduce the voltage withstand strength of the ceramic body, leading to breakdown and short circuits, and causing Sm ions with larger ionic radii to migrate. 3+ Partial replacement of Bi 3+ It can effectively reduce Ag + Formation of migration channels. Sm 3+ Introducing BiVO4 into BiVO4 via the hydrothermal method of vanadate can effectively avoid Bi loss due to the low melting point of Bi2O3 in the solid-state method; Fourth, K x Na 1-xDue to the high process sensitivity of NbO3 and the difficulty in achieving densification through traditional ceramic processes, research progress on it has been slow for a long time. However, the combined sintering aid of Na2B2O7 and Zn3B2O6 with SiO2 can effectively reduce the number of pores in ceramic sintering. Compared with traditional sintering aids, the borate ions in borates have a lower molecular weight, and at the same weight, the more numerous borate anions can play a better role in sintering. The sintering aid effect of borates with different cations varies greatly. During sintering, it prevents excessive aggregation of grains, thereby preventing the disordered growth of large grains and ensuring that the grains grow in an orderly manner during the sintering process. The combination of Na2B2O7 and Zn3B2O6 with SiO2 lowers the sintering temperature, improves the density of the ceramic body, and thus improves the puncture resistance of the ceramic body. Fifth, Li has a stable discharge cycle and a smooth discharge curve with no "bumps" on the discharge sine curve. Combined with the characteristic of Nb to improve the insulation strength of ceramics, Li can be successfully introduced into the ceramic body without the risk of lithium dendrites causing Li loss. Detailed Implementation

[0016] The present invention will be further described below through specific embodiments.

[0017] A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The preparation method includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at a temperature of 1000-1200℃ for 2-5 hours to obtain the pulse power capacitor.

[0018] Ceramic dielectric material, based on 100 moles of SrTiO3, with the following moles added: 20-30 moles of K x Na 1-x NbO3, 3-5 parts Re y Bi 1-y VO4, 1.0-3 parts Na2B2O7, 1.0-3 parts Zn3B2O6, 0.3-0.8 parts Mn3O4, 0.5-1.0 parts SiO2, 0.03-0.1 parts LiNbO3, where 0 < x < 0.7, 0 < y < 0.25, Re = Sm, La, Gd or Nd; specifically, K x Na 1-x NbO3 was synthesized from K2CO3, Na2CO3, and Nb2O5 using a solid-state method; Re y Bi 1-y VO4 was synthesized from Bi(NO3)3, Re(NO3)3, and NH4VO3 via a hydrothermal method; furthermore, K x Na 1-x NbO3 is K0.5 Na 0.5 NbO3; Re y Bi 1-y VO4 is Sm 0.15 Bi 0.85 VO4.

[0019] Its preparation method includes the following steps: Step 1: Preparation of K by solid-state method x Na 1-x NbO3: Weigh K2CO3, Na2CO3, and Nb2O5 separately in molar ratios x:1-x:1, add anhydrous ethanol and zirconium oxide beads, mix and ball mill for 10-15 hours, dry, sieve through a 40-80 mesh sieve, calcine at 700-900℃ for 3-5 hours, and naturally cool to room temperature to obtain K2CO3. x Na 1-x NbO3; Step 2, Hydrothermal preparation of Re y Bi 1-y VO4: Weigh Bi(NO3)3, Re(NO3)3, and NH4VO3 separately in molar ratios y:1-y:1. Dissolve Bi(NO3)3 and Re(NO3)3 together in deionized water by heating, and dissolve NH4VO3 in deionized water by heating. Then, add the NH4VO3 aqueous solution dropwise to the mixed solution of Bi(NO3)3 and Re(NO3)3. Mix ultrasonically for 45-60 min, stir magnetically for 30-60 min, and then adjust the pH of the mixed solution with 10 mol / L NaOH solution in a 2-gradient manner from 1 to 13. Then, place the mixed solution in a high-temperature reactor and react at 300-500 ℃ for 4-8 h. After the reaction, cool naturally to room temperature, centrifuge, wash three times with deionized water and anhydrous ethanol, and vacuum dry at 80 ℃. Finally, add anhydrous ethanol and zirconium oxide beads to the precipitate and ball mill for 6-10 h. After drying, the powder is sieved through a 40-80 mesh sieve to obtain refined Re. y Bi 1-y VO4; Step 3, K prepared in Steps 1 and 2 x Na 1-x NbO3, Sm y Bi 1-y VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 4-6 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0020] Example 1 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0021] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Sm 0.15 Bi 0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0022] Its preparation method includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.5 Na 0.5 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85 Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Sm0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0023] Examples 2-6 have the same raw material composition and preparation process as Example 1, except that the proportions of each raw material are different. For details, please refer to Table 1.

[0024] Comparative Examples 1-6 have the same raw material composition and preparation process as Example 1, except that the raw material ratios are different. Specific parameters are detailed in Table 1.

[0025] Table 1. Composition (mol%) Group <![CDATA[SrTiO3]]> <![CDATA[K 0.5 Na 0.5 NbO3]]> <![CDATA[Sm 0.15 With a 0.85 VO4]]> <![CDATA[Na2B2O7]]> <![CDATA[Zn3B2O6]]> <![CDATA[Mn3O4]]> <![CDATA[SiO2]]> <![CDATA[LiNbO3]]> Example 1 100 23 3.7 1.3 1.2 0.56 0.8 0.072 Example 2 100 30 3.7 1.3 1.2 0.56 0.8 0.072 Example 3 100 23 4.5 1.3 1.2 0.56 0.8 0.072 Example 4 100 23 3.7 2.3 1.2 0.56 0.8 0.072 Example 5 100 23 3.7 1.3 2.5 0.56 0.8 0.072 Example 6 100 23 3.7 1.3 1.2 0.56 0.5 0.072 Comparative Example 1 100 0 3.7 1.3 1.2 0.56 0.8 0.072 Comparative Example 2 100 23 0 1.3 1.2 0.56 0.8 0.072 Comparative Example 3 100 23 3.7 0 1.2 0.56 0.8 0.072 Comparative Example 4 100 23 3.7 1.3 0 0.56 0.8 0.072 Comparative Example 5 100 23 3.7 1.3 1.2 0 0.8 0.072 Comparative Example 6 100 23 3.7 1.3 1.2 0.56 0 0.072 Example 7 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0026] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts La 0.15 Bi 0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0027] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.5 Na 0.5 NbO3; Step 2, Preparation of La by hydrothermal method 0.15 Bi 0.85Bi(NO3)3, La(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and La(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and La(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined La4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, La 0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0028] Example 8 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0029] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Gd 0.15 Bi 0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0030] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. x Na 1-x NbO3; Step 2, hydrothermal preparation of Gd 0.15 Bi 0.85 VO4: Bi(NO3)3, Gd(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Gd(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Gd(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 70 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Gd4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Gd 0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0031] Example 9 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0032] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Nd 0.15 Bi0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0033] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. x Na 1-x NbO3; Step 2, Hydrothermal preparation of Nd 0.15 Bi 0.85 Bi(NO3)3, Nd(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Nd(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Nd(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 70 h. After drying, the powder was sieved through a 40-80 mesh sieve to obtain refined Nd2O3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Nd 0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0034] Comparative Example 7 A high-energy-density, high-voltage pulse power ceramic capacitor is prepared using ceramic dielectric material. The preparation method includes the following steps: the dielectric material is subjected to an MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in an air atmosphere at a temperature of 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0035] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.7 Na 0.3 NbO3, 3.7 parts Sm 0.15 Bi 0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0036] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.7 Na 0.3 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.7:0.3:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.7 Na 0.3 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85 Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.7 Na 0.3 NbO3, Sm0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0037] Comparative Example 8 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0038] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.3 Na 0.7 NbO3, 3.7 parts Sm 0.15 Bi 0.85 VO4, 1.3 parts Na2B2O7, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0039] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.3 Na 0.7 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.3:0.7:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.3 Na 0.7 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.3 Na 0.7 NbO3, Sm 0.15 Bi 0.85 VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0040] Comparative Example 9 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0041] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Sm 0.15 Bi 0.85 VO4, 1.3 parts BaB2O4, 1.2 parts Zn3B2O6, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0042] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.5 Na 0.5 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85 VO4: Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Sm 0.15 Bi 0.85 VO4 is mixed with SrTiO3, BaB2O4, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0043] Comparative Example 10 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0044] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Sm 0.15 Bi0.85 VO4, 1.3 parts CaB2O4, 1.2 parts BiBO3, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0045] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 780℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.5 Na 0.5 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85 Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 4.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4.

[0046] Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Sm 0.15 Bi 0.85 VO4 is mixed with SrTiO3, CaB2O4, BiBO3, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 5 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0047] Comparative Example 11 A high-energy-density, high-voltage pulse power ceramic capacitor is made of ceramic dielectric material. The manufacturing process includes the following steps: the dielectric material is subjected to MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air atmosphere at 1080℃ for 2 hours to obtain the pulse power ceramic capacitor.

[0048] A ceramic dielectric material, based on 100 moles of SrTiO3, contains the following moles of components: 23 parts of K. 0.5 Na 0.5 NbO3, 3.7 parts Sm 0.15 Bi 0.85 VO4, 2.5 parts Na2B2O7, 0.56 parts Mn3O4, 0.8 parts SiO2, and 0.072 parts LiNbO3.

[0049] Its preparation process includes the following steps: Step 1: Preparation of K by solid-state method 0.5 Na 0.5 Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately in a molar ratio of 0.5:0.5:1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 13 hours. After drying, the powder is sieved through an 80-mesh sieve and calcined at 860℃ for 4.5 hours. After naturally cooling to room temperature, K₂CO₃ is obtained. 0.5 Na 0.5 NbO3; Step 2, hydrothermal preparation of Sm 0.15 Bi 0.85 Bi(NO3)3, Sm(NO3)3, and NH4VO3 were weighed separately at a molar ratio of 0.15:0.85:1. Bi(NO3)3 and Sm(NO3)3 were dissolved together in deionized water by heating, and NH4VO3 was dissolved in deionized water by heating. The NH4VO3 aqueous solution was then added dropwise to the mixed solution of Bi(NO3)3 and Sm(NO3)3. The mixture was ultrasonically mixed for 50 min and magnetically stirred for 45 min. The pH of the mixed solution was then adjusted from 1 to 13 using a 10 mol / L NaOH solution in a 2-gradient manner. The mixed solution was then placed in a high-temperature reactor and reacted at 380 ℃ for 5 h. After the reaction, the mixture was naturally cooled to room temperature, centrifuged, washed three times with deionized water and anhydrous ethanol, and vacuum dried at 80 ℃. Finally, the precipitate was mixed with anhydrous ethanol and zirconium oxide beads and ball-milled for 7 h. After drying, the powder was sieved through an 80-mesh sieve to obtain refined Sm4VO3. 0.15 Bi 0.85 VO4; Step 3, K prepared in Steps 1 and 2 0.5 Na 0.5 NbO3, Sm 0.15Bi 0.85 VO4, SrTiO3, Na2B2O7, SiO2, Mn3O4, and LiNbO3 were mixed, and deionized water and zirconium oxide beads were added. After ball milling for 5 hours, the mixture was dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

[0050] The pulse power ceramic capacitors prepared in Examples 1-9 and Comparative Examples 1-11 were tested and the following data were obtained, as shown in Table 2 below.

[0051] Table 2 Performance Test Table Where K is the dielectric constant; TCC is the temperature coefficient of capacitance; IR is the insulation resistance; and DF is the loss tangent.

[0052] As shown in the table above, Examples 1-9 of this application investigate the effect of component content on the electrical properties of pulse power ceramic dielectric materials by fine-tuning the content of each component; among them, the pulse power ceramic capacitor prepared in Example 1 has the best overall electrical performance: a higher dielectric constant ( K = 525), lower loss tangent (Df=3.4), and more stable capacitor temperature coefficient (-2500±200). ppm / K The highest breakdown electric field (>53.18) V / μm High insulation resistance: 15320 MΩ And excellent discharge current (>3000) A ).

[0053] By comparing Example 2 with Comparative Examples 7 and 8, it can be seen that K x Na 1-x NbO3 is an important component for improving the dielectric constant of SrTiO3 materials, K x Na 1-x The amount of NbO3 added needs to be limited to 23% mol and K + / Na + The ratio needs to be kept at 1:1 to obtain optimal dielectric properties and high voltage withstand while maintaining the dielectric constant.

[0054] A comparison of Examples 1 and 3 with Comparative Example 2 shows that Sm 3+ Partial replacement of Bi 3+ Subsequently, grain growth was suppressed, effectively reducing the formation of oxygen vacancies caused by bismuth volatilization at high temperatures, and effectively improving the electrical breakdown strength. However, Sm 3+ Excessive Sm content leads to a decrease in the dielectric constant of the dielectric material. That is, there is a peak value in the amount of Sm added. After exceeding this peak value, the balance between polarization response and charge storage is broken, resulting in a deteriorating effect.

[0055] Examples 4-6 and Comparative Examples 9-11 illustrate the effects of different borate combinations, contents, and SiO2 additions on the sintering of dielectric materials. Suitable sintering aids can significantly reduce sintering temperature and optimize electrical performance parameters. Example 1 provides the optimal borate combination: Na2B2O7 and Zn3B2O6 with a trace amount of SiO2, achieving the lowest dielectric loss: Df = 3.4. However, combinations of Zn3B2O6 with BaB2O4 and BiBO3 with CaB2O4 negatively impact the dielectric loss of the ceramic. Single borates, such as Na2B2O7 in Comparative Example 11, exhibit poor sintering aid effects and generally decrease dielectric properties. Based on these examples, the sintering aid effect of combined borates is superior to increasing the content of a single borate.

[0056] In summary, the dielectric material for the pulse power ceramic capacitor proposed in this invention uses SrTiO3, which has a high bandgap and is not prone to ferroelectric phase transition, as the main substrate. Based on this characteristic, the capacitance of the ceramic capacitor made from it does not exhibit aging-related degradation. The K-type capacitor synthesized by SrTiO3 doping solid-state method... x Na 1-x NbO3, Sm synthesized by hydrothermal method y Bi 1-y VO4 forms a uniform perovskite structure. The preferred combination of borate Na2B2O7 and Zn3B2O6 with SiO2 improves the density of the ceramic body and lowers the sintering temperature. The addition of trace amounts of LiNbO3 optimizes the discharge curve, resulting in a dielectric material with high dielectric constant and energy storage density, suitable for use as a pulse power ceramic capacitor.

[0057] 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 ceramic dielectric material for high-energy-density, high-voltage pulse power ceramic capacitors, characterized in that: Using 100 moles of SrTiO3 as the base material, the following components were added in moles: 20-30 moles of K. x Na 1-x NbO3, 3-5 parts Re y Bi 1-y VO4, 1.0-3 parts Na2B2O7, 1.0-3 parts Zn3B2O6, 0.3-0.8 parts Mn3O4, 0.5-1.0 parts SiO2, 0.03-0.1 parts LiNbO3, wherein 0 < x < 0.7, 0 < y < 0.25, and Re = Sm, La, Gd or Nd.

2. The ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 1, characterized in that: The K x Na 1-x NbO3 was synthesized from K2CO3, Na2CO3, and Nb2O5 using a solid-state method.

3. The ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 1, characterized in that: The Re y Bi 1-y VO4 was synthesized from Bi(NO3)3, Re(NO3)3 and NH4VO3 by a hydrothermal method.

4. The ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 1, characterized in that: The K x Na 1-x NbO3 is K 0.5 Na 0.5 NbO3.

5. The ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 1, characterized in that: The Re y Bi 1-y VO4 is Sm 0.15 Bi 0.85 VO4.

6. The method for preparing a ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 1, characterized in that: Includes the following steps: Step 1: Preparation of K by solid-state method x Na 1-x NbO3; Step 2, Hydrothermal preparation of Re y Bi 1-y VO4; Step 3, K prepared in Steps 1 and 2 x Na 1-x NbO3, Sm y Bi 1-y VO4 is mixed with SrTiO3, Na2B2O7, Zn3B2O6, SiO2, Mn3O4, and LiNbO3. Deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 4-6 hours, then dried and crushed to obtain the ceramic dielectric material for high-energy-density high-voltage pulse power ceramic capacitors.

7. The method for preparing a ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 6, characterized in that: Step 1: Weigh K₂CO₃, Na₂CO₃, and Nb₂O₅ separately at molar ratios x:1-x:

1. Add anhydrous ethanol and zirconium oxide beads, mix and ball-mill for 10-15 hours. After drying, sieve the powder through a 40-80 mesh sieve and calcine at 700-900℃ for 3-5 hours. Allow to cool naturally to room temperature to obtain K₂CO₃. x Na 1-x NbO3.

8. The method for preparing a ceramic dielectric material for a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 6, characterized in that: Step two is as follows: Weigh Bi(NO3)3, Re(NO3)3, and NH4VO3 separately according to the molar ratio y:1-y:

1. Dissolve Bi(NO3)3 and Re(NO3)3 together in deionized water by heating, and dissolve NH4VO3 in deionized water by heating. Then, add the NH4VO3 aqueous solution dropwise to the mixed solution of Bi(NO3)3 and Re(NO3)3. Mix ultrasonically for 45-60 min, stir magnetically for 30-60 min, and then adjust the pH of the mixed solution with 10 mol / L NaOH solution in a 2-gradient manner from 1 to 13. Then, place the mixed solution in a high-temperature reactor and react at 300-500 ℃ for 4-8 h. After the reaction, cool naturally to room temperature, centrifuge, wash three times with deionized water and anhydrous ethanol, and vacuum dry at 80 ℃. Finally, add anhydrous ethanol and zirconium oxide beads to the precipitate and ball mill for 6-10 h. After drying, the powder is sieved through a 40-80 mesh sieve to obtain refined Re. y Bi 1-y VO4.

9. A high-energy-density, high-voltage pulse power ceramic capacitor, characterized in that: It is prepared using the ceramic dielectric material described in any one of claims 1 to 5.

10. The method for preparing a high-energy-density, high-voltage pulse power ceramic capacitor according to claim 9, characterized in that: Includes the following steps: The dielectric material is subjected to an MLCC process, with 70Ag-30Pd as the internal electrode, and sintered in air at a temperature of 1000-1200℃ for 2-5 hours to obtain the pulse power capacitor.

Images