A high dielectric constant high resistance low loss pulse power capacitor and a dielectric material and a preparation process thereof

Abstract

A dielectric material and fabrication process for a high dielectric constant, high resistance, and low loss pulse power capacitor, wherein the dielectric material is based on (Sr) 0.7 Ba x Mg 0.3‑x (Ti) 0.8 Ru y Te 0.2‑y O3 is the base material, and the following components are added: La3(Sb) z Ce 1‑z Zr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, MnCO3, MnO2, Li2SiO3, where 0 < x < 0.3, 0.1 < y < 0.2, 0.7 < z < 1.0, the pulse power type ceramic dielectric material proposed in this invention adds Ru and Te elements during the fabrication of the main substrate to form (Sr)2. 0.7 Ba x Mg 0.3‑x (Ti) 0.8 Ru y Te 0.2‑y O3, and then La3(Sb) synthesized by solid-state method was added. z Ce 1‑z Zr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, and by adjusting Mn 2+ / Mn 4+ The proportion of Li, in the presence of trace amounts of Li, results in a dielectric material with excellent electrical properties such as high dielectric constant, high resistance, and low loss. Capacitors made from this dielectric material exhibit excellent bias characteristics, stable charge and discharge performance, and large discharge current, making them suitable for use as pulse power ceramic capacitors.

Description

Technical Field

[0001] This invention belongs to the field of ceramic capacitor manufacturing, specifically relating to a dielectric material and manufacturing process for a high dielectric constant, high resistance, and low loss pulse power capacitor. Background Technology

[0002] Pulse energy storage dielectric materials can store high-density charges in a short time and release energy rapidly in the form of pulses, generating extremely high currents. Pulse power ceramic capacitors, with their excellent temperature characteristics, high withstand voltage, good insulation performance, resistance to damp heat, low dielectric loss, stable high and low temperature pulse discharge characteristics, and extremely long charge and discharge life, are widely used in new energy vehicles, laser weapons, electromagnetic catapults, and other fields. In recent years, with the rapid development of new energy vehicles, the proportion of pulse power ceramic capacitors in new energy vehicle components has gradually increased. Electric vehicles need to absorb or release large amounts of energy in a short time during overtaking, braking, and ultra-high power charging and discharging operations. Pulse power ceramic capacitors, as key components in new energy vehicles, play a crucial role in these conditions. Electric vehicles need to operate in low-temperature winter and high-temperature summer environments, which places higher demands on the temperature stability of capacitors. As electric vehicles develop towards electronification, intelligence, and information technology, the requirements for high capacitance and miniaturization have emerged. Therefore, developing pulse power dielectric materials with higher dielectric constants and more stable performance is essential to adapt to the development trends of electronification, intelligence, and information technology. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high dielectric constant, high resistance, low loss pulse power capacitor, as well as its dielectric material and manufacturing process.

[0004] The present invention adopts the following technical solution:

[0005] A dielectric material for high dielectric constant, high resistance, and low loss power capacitors, using 100 moles of (Sr) 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y Using O3 as the base material, the following components are added in molar amounts: 2-10 parts of La3(Sb) z Ce 1-z Zr3O 12 1-3 parts Ba(Zn) 1 / 6 Nb 1 / 3)(B2O4)2, 0.5~1 parts of MnCO3, 0.2~0.5 parts of MnO2, 0.1~0.2 parts of Li2SiO3, where 0 < x < 0.3, 0.1 < y < 0.2, 0.7 < z < 1.0.

[0006] Furthermore, the Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2 was synthesized from BaCO3, ZnO, Nb2O5 and B2O3 using a fixed method.

[0007] Furthermore, the (Sr) 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3 is (Sr 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 )O3.

[0008] Furthermore, the La3(Sb z Ce 1-z Zr3O 12 For La3(Sb 0.87 Ce 0.13 Zr3O 12 .

[0009] A process for preparing a dielectric material for high dielectric constant, high resistance, and low loss power capacitors includes the following steps:

[0010] Step 1, Preparation of (Sr) by molten salt method 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3;

[0011] Step 2: Solid-state preparation of La3(Sb) z Ce 1-z Zr3O 12 ;

[0012] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2;

[0013] Step four, the (Sr) prepared in steps one through three... 0.7 Ba x Mg 0.3-x(Ti) 0.8 Ru y Te 0.2-y O3, La3(Sb) z Ce 1-z Zr3O 12 MnCO3, MnO2, Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, Li2SiO3, deionized water and zirconium oxide beads were added, ball milled for 4-6 hours and then dried and crushed to obtain the dielectric material for high dielectric constant, high resistance and low loss pulse power ceramic capacitors.

[0014] Further, step one specifically includes: weighing SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl respectively in a molar ratio of 0.7:x:(0.3-x):0.8:y:(0.2-y):(2~4):(2~4), adding anhydrous ethanol and zirconium oxide beads, ball milling for 6~8 hours, drying the powder, calcining at 800~900℃ for 2~3 hours, and naturally cooling to room temperature; the calcined product is ultrasonically cleaned with deionized water, and then washed and filtered multiple times until no Cl is present. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y )O3.

[0015] Furthermore, step two specifically includes: La3(Sb z Ce 1-z Zr3O 12 The specific preparation process is as follows: Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ respectively in a molar ratio of 1.5:z / 2:(1-z) / 2:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 4-6 hours. After drying, calcine the powder at 1200-1300℃ for 1-3 hours, and then naturally cool to room temperature to obtain La₃(Sb₂O₃)₂O₃. z Ce 1-z Zr3O 12 .

[0016] Furthermore, step three specifically includes: Ba(Zn) 1 / 6 Nb 1 / 3The preparation process of Ba(ZnO)2 is as follows: Weigh BaCO3, ZnO, Nb2O5, and B2O3 respectively in a molar ratio of 1:1 / 6:1 / 6:3. Add appropriate amounts of deionized water and zirconium oxide beads, mix and ball-mill for 4-6 hours. After drying, transfer the powder to a calcination temperature of 600-800℃ for 1-3 hours, and allow it to cool naturally to room temperature to obtain Ba(ZnO)2. 1 / 6Nb 1 / 3 )(B2O4)2.

[0017] A high dielectric constant, high resistance, and low loss power capacitor is fabricated using the aforementioned dielectric material.

[0018] A process for fabricating a high dielectric constant, high resistance, and low loss power 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.

[0019] As can be seen from the above description of the present invention, compared with the prior art, the beneficial effects of the present invention are:

[0020] First, the dielectric material for pulse power ceramic capacitors proposed in this invention combines the advantages of high dielectric constant and high withstand voltage of SrTiO3 and BaTiO3. By introducing Mg, Ru, and Te elements through the molten salt method, uniform dual-element co-doping of the A / B sites can be achieved, resulting in a composite structure (SrTiO3). 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y La3(Sb) was synthesized by solid-state method using O3 as the main substrate. z Ce 1-z Zr3O 12 This forms a uniform perovskite structure, and the doping with Mn is controlled to achieve this. 2+ / Mn 4+ The proportions are used to optimize the polarization intensity of ceramic materials, and a modified sintering aid Ba(Zn) is synthesized. 1 / 6 Nb 1 / 3 (B2O4)2 is used to lower the firing temperature, and trace amounts of Li2SiO3 are added to reduce energy loss, resulting in a dielectric material with high density, large dielectric constant, low dielectric loss, high resistance, and excellent bias characteristics, making it suitable for use as a pulse power ceramic capacitor.

[0021] Second, La3(Sb z Ce 1-z Zr3O 12Combining the advantages of lanthanum zirconate and cerium zirconate, such as good high-temperature stability and high radiation impedance, but with lanthanum zirconate having low thermal conductivity and poor resistance to temperature shock, it is necessary to dop with cerium zirconate, which has high thermal conductivity and low coefficient of thermal expansion, and with the fusion-promoting effect of a small amount of Sb₂O₃, La₃(Sb z Ce 1-z Zr3O 12 It exhibits good resistance to temperature shock. However, excessive cerium zirconate will cause the ceramic body to absorb too much heat and reduce its resistance. Therefore, cerium zirconate is doped into lanthanum zirconate to regulate the temperature resistance of La3(Sb). z Ce 1-z Zr3O 12 The ratio of Sb to Ce in the medium ensures that the resulting dielectric material maintains the stability of the ceramic body when faced with temperature shocks.

[0022] Third, by regulating Mn 2+ / Mn 4+ The ratio of Mn elements is precisely controlled to determine the amount of Mn elements entering the A / B sites of the main substrate. Different Mn doping amounts result in significant differences in the potential difference generated at the A / B sites, making polarization more likely to occur under an applied electric field, thus achieving higher polarization intensity. P m .

[0023] Fourth, while directly adding Nb2O5 can significantly reduce the dielectric loss of dielectric materials, it also causes a significant decrease in the dielectric constant of the dielectric material. If the sintering aid BaZnB2O4 is combined with Nb2O5 to form a ternary central ring structure of Ba-Nb-Zn, it can prevent excessive aggregation of grains during sintering, thereby preventing the disordered growth of large grains. This allows the grains to grow in an orderly manner during the sintering process, reducing the entropy of the system, thus lowering the sintering temperature, increasing the density of the ceramic body, and ultimately improving the breakdown strength of the ceramic body.

[0024] Fifth, lithium plays a crucial role in the field of energy storage materials. Adding lithium to dielectric materials can achieve the same maximum polarization intensity. P m Under the condition that the external electric field is removed, the residual polarization intensity P r The curve shifts to the right, closer to P m The curve is designed to reduce energy loss, thus preserving more energy for release during discharge. In particular, if excessive lithium is present, lithium dendrites will grow at the inner electrode boundary after a certain number of charge-discharge cycles, leading to a significant decrease in the ceramic body's breakdown strength and causing capacitor failure. Therefore, the amount of lithium added must be precisely controlled. Detailed Implementation

[0025] The present invention will be further described below through specific embodiments.

[0026] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1000~1200℃ for 2~5 hours to obtain the pulse power ceramic capacitor.

[0027] Medium material, in 100 moles of (Sr) 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y Using O3 as the base material, the following components are added in molar amounts: 2-10 parts of La3(Sb) z Ce 1-z Zr3O 12 1-3 parts Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2, 0.5~1 parts of MnCO3, 0.2~0.5 parts of MnO2, 0.1~0.2 parts of Li2SiO3, where 0 < x < 0.3, 0.1 < y < 0.2, 0.7 < z < 1.0.

[0028] Among them, Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2 was synthesized from BaCO3, ZnO, Nb2O5 and B2O3 using a fixed method.

[0029] (Sr 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3 is (Sr 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 )O3.

[0030] La3(Sb z Ce 1-z Zr3O 12 For La3(Sb 0.87 Ce 0.13 Zr3O 12 .

[0031] The preparation process of dielectric materials includes the following steps:

[0032] Step 1: Preparation of (Sr) by molten salt method 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately in a molar ratio of 0.7:x:(0.3-x):0.8:y:(0.2-y):(2~4):(2~4). Anhydrous ethanol and zirconium oxide beads were added, and the mixture was ball-milled for 6~8 hours. After drying, the powder was calcined at 800~900℃ for 2~3 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, and then washed and filtered multiple times until no Cl was found. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3;

[0033] Step 2: Solid-state preparation of La3(Sb) z Ce 1-z Zr3O 12 Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ respectively in a molar ratio of 1.5:z / 2:(1-z) / 2:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 4-6 hours. After drying, calcine the powder at 1200-1300℃ for 1-3 hours, and then cool naturally to room temperature to obtain La₃(Sb₂O₃)₂O₃. z Ce 1-z Zr3O 12 ;

[0034] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 BaCO3, ZnO, Nb2O5, and B2O3 were weighed out in a molar ratio of 1:1 / 6:1 / 6:3. Appropriate amounts of deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4-8 hours. After drying, the powder was calcined at 600-800℃ for 1-3 hours and then naturally cooled to room temperature to obtain Ba(ZnO)2. 1 / 6 Nb 1 / 3 (B2O4)2;

[0035] Step four, prepare the following in steps one through three:

[0036] (Sr 0.7 Ba x Mg0.3-x (Ti) 0.8 Ru y Te 0.2-y O3, La3(Sb) z Ce 1-z Zr3O 12 MnCO3, MnO2, Ba(Zn) 1 / 6Nb 1 / 3 (B2O4)2, Li2SiO3, deionized water and zirconium oxide beads were added, ball milled for 4-6 hours and then dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0037] Example 1

[0038] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1100℃ for 3 hours to obtain the pulse power ceramic capacitor.

[0039] Medium material, in 100 moles of (Sr) 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 Using O3 as the base material, the following components are added in molar amounts: 7 parts of La3(Sb) 0.87 Ce 0.13 Zr3O 12 1 part Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2, 0.7 parts MnCO3, 0.35 parts MnO2, and 0.12 parts Li2SiO3.

[0040] Its preparation process includes the following steps:

[0041] Step 1, Preparation of (Sr) by molten salt method 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately, and anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 6 hours. After drying, the powder was calcined at 800~900℃ for 2.5 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water and washed and filtered multiple times until Cl was removed. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3;

[0042] Step 2: Solid-state preparation of La3(Sb) 0.87 Ce 0.13 Zr3O 12 Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ separately in a molar ratio of 1.5:0.435:0.065:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 5 hours. After drying, calcine the powder at 1280℃ for 2.5 hours and allow it to cool naturally to room temperature to obtain La₃(Sb₂O₃)₂O₃. 0.87 Ce 0.13 Zr3O 12 ;

[0043] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 BaCO3, ZnO, Nb2O5, and B2O3 were weighed out in a molar ratio of 1:1 / 6:1 / 6:3. A suitable amount of deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 5 hours. After drying, the powder was calcined at 720℃ for 2.5 hours and then naturally cooled to room temperature to obtain Ba(ZnO)2. 1 / 6 Nb 1 / 3 (B2O4)2;

[0044] Step four, the (Sr) prepared in steps one through three... 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3, La3(Sb) 0.87 Ce 0.13 Zr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3(B2O4)2, MnCO3, MnO2, Li2SiO3, deionized water and zirconium oxide beads were added, ball-milled for 6 hours, dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0045] Examples 2-5 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.

[0046] Comparative Examples 1-5 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.

[0047] Table 1. Composition (mol%)

[0048] <![CDATA[(Sr 0.7 Consider 0.27 Mg 0.03 )(A 0.8 Ru 0.15 Eat 0.05 )O3]]> <![CDATA[La3(Sb 0.87 What 0.13 )Zr3O 12 ]]> <![CDATA[Ba(Zn 1 / 6 Nb 1 / 3 )(B2O4)2]]> <![CDATA[MnCO3]]> <![CDATA[MnO2]]> <![CDATA[Li2SiO3]]> Example 1 100 7 1 0.7 0.35 0.12 Example 2 100 10 1 0.7 0.35 0.12 Example 3 100 7 2.5 0.7 0.35 0.12 Example 4 100 7 1 0.35 0.35 0.12 Example 5 100 7 1 0.5 0.5 0.12 Comparative Example 1 100 0 1 0.7 0.35 0.12 Comparative Example 2 100 7 0 0.7 0.35 0.12 Comparative Example 3 100 7 1 0 0.35 0.12 Comparative Example 4 100 7 1 0.7 0 0.12 Comparative Example 5 100 7 1 0.7 0.35 0

[0049] Comparative Example 6

[0050] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1100℃ for 3 hours to obtain the pulse power ceramic capacitor.

[0051] Medium material, in 100 moles of (Sr) 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 Using O3 as the base material, the following components are added in molar amounts: 7 parts of La3CeZr3O 12 1 part Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2, 0.7 parts MnCO3, 0.35 parts MnO2, and 0.12 parts Li2SiO3.

[0052] Its preparation process includes the following steps:

[0053] Step 1, Preparation of (Sr) by molten salt method 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately, and anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 6 hours. After drying, the powder was calcined at 800~900℃ for 2.5 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water and washed and filtered multiple times until Cl was removed. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3;

[0054] Step 2: Preparation of La3CeZr3O by solid-state method 12 Weigh La₂O₃, Ce₂O₃, and ZrO₂ separately in a molar ratio of 1.5:0.5:3, add deionized water and zirconium oxide beads, mix and ball mill for 5 hours, dry, and then calcine the powder at 1280℃ for 2.5 hours. After natural cooling to room temperature, La₃CeZr₃O₃ is obtained. 12 ;

[0055] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 BaCO3, ZnO, Nb2O5, and B2O3 were weighed out in a molar ratio of 1:1 / 6:1 / 6:3. A suitable amount of deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 5 hours. After drying, the powder was calcined at 720℃ for 2.5 hours and then naturally cooled to room temperature to obtain Ba(ZnO)2. 1 / 6 Nb 1 / 3 (B2O4)2;

[0056] Step four, the (Sr) prepared in steps one through three... 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3、La3CeZr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, MnCO3, MnO2, Li2SiO3, deionized water and zirconium oxide beads were added, ball-milled for 6 hours, dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0057] Comparative Example 7

[0058] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1100℃ for 3 hours to obtain the pulse power ceramic capacitor.

[0059] Medium material, in 100 moles of (Sr) 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 Using O3 as the base material, the following components are added in molar amounts: 7 parts of La3(Sb) 0.7 Ce 0.3 Zr3O 12 1 part Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2, 0.7 parts MnCO3, 0.35 parts MnO2, and 0.12 parts Li2SiO3.

[0060] Step 1: Preparation of (Sr) by molten salt method 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately, and anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 6 hours. After drying, the powder was calcined at 800~900℃ for 2.5 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water and washed and filtered multiple times until Cl was removed. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3;

[0061] Step 2: Solid-state preparation of La3(Sb) 0.7 Ce 0.3 Zr3O 12Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ separately in a molar ratio of 1.5:0.35:0.15:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 5 hours. After drying, calcine the powder at 1280℃ for 2.5 hours and allow it to cool naturally to room temperature to obtain La₃(Sb₂O₃)₂O₃. 0.7 Ce 0.3 Zr3O 12 ;

[0062] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 BaCO3, ZnO, Nb2O5, and B2O3 were weighed out in a molar ratio of 1:1 / 6:1 / 6:3. A suitable amount of deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 5 hours. After drying, the powder was calcined at 720℃ for 2.5 hours and then naturally cooled to room temperature to obtain Ba(ZnO)2. 1 / 6 Nb 1 / 3 (B2O4)2;

[0063] Step four, the (Sr) prepared in steps one through three... 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3, La3(Sb) 0.7 Ce 0.3 Zr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, MnCO3, MnO2, Li2SiO3, deionized water and zirconium oxide beads were added, ball-milled for 6 hours, dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0064] Comparative Example 8

[0065] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1100℃ for 3 hours to obtain the pulse power ceramic capacitor.

[0066] Medium material, in 100 moles of (Sr) 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 Using O3 as the base material, the following components are added in molar amounts: 7 parts of La3(Sb)0.3 Ce 0.7 Zr3O 12 1 part Ba(Zn) 1 / 6 Nb 1 / 3 )(B2O4)2, 0.7 parts MnCO3, 0.35 parts MnO2, and 0.12 parts Li2SiO3.

[0067] Its preparation process includes the following steps:

[0068] Step 1, Preparation of (Sr) by molten salt method 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately, and anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 6 hours. After drying, the powder was calcined at 800~900℃ for 2.5 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water and washed and filtered multiple times until Cl was removed. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3;

[0069] Step 2: Solid-state preparation of La3(Sb) 0.3 Ce 0.7 Zr3O 12 Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ separately in a molar ratio of 1.5:0.15:0.35:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 5 hours. After drying, calcine the powder at 1280℃ for 2.5 hours and allow it to cool naturally to room temperature to obtain La₃(Sb₂O₃)₂O₃. 0.3 Ce 0.7 Zr3O 12 ;

[0070] Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3BaCO3, ZnO, Nb2O5, and B2O3 were weighed out in a molar ratio of 1:1 / 6:1 / 6:3. A suitable amount of deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 5 hours. After drying, the powder was calcined at 720℃ for 2.5 hours and then naturally cooled to room temperature to obtain Ba(ZnO)2. 1 / 6 Nb 1 / 3 (B2O4)2;

[0071] Step four, the (Sr) prepared in steps one through three... 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3, La3(Sb) 0.3 Ce 0.7 Zr3O 12 Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, MnCO3, MnO2, Li2SiO3, deionized water and zirconium oxide beads were added, ball-milled for 6 hours, dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0072] Comparative Example 9

[0073] A high dielectric constant, high resistance, and low loss pulse power ceramic capacitor is fabricated using dielectric material. The fabrication process 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 1100℃ for 3 hours to obtain the pulse power ceramic capacitor.

[0074] Medium material, in 100 moles of (Sr) 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 Using O3 as the base material, the following components are added in molar amounts: 7 parts of La3(Sb) 0.87 Ce 0.13 Zr3O 12 1 part BaZnB2O4, 0.33 parts Nb2O5, 0.7 parts MnCO3, 0.35 parts MnO2, and 0.12 parts Li2SiO3.

[0075] Its preparation process includes the following steps:

[0076] Step 1: Preparation of (Sr) by molten salt method 0.7 Ba 0.27 Mg 0.03(Ti) 0.8 Ru 0.15 Te 0.05 SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl were weighed separately, and anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 6 hours. After drying, the powder was calcined at 800~900℃ for 2.5 hours and then naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water and washed and filtered multiple times until Cl was removed. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3;

[0077] Step 2: Solid-state preparation of La3(Sb) 0.87 Ce 0.13 Zr3O 12 Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ separately in a molar ratio of 1.5:0.435:0.065:3. Add deionized water and zirconium oxide beads, mix and ball-mill for 5 hours. After drying, calcine the powder at 1280℃ for 2.5 hours and allow it to cool naturally to room temperature to obtain La₃(Sb₂O₃)₂O₃. 0.87 Ce 0.13 Zr3O 12 ;

[0078] Step 3, solid-state method for preparing BaZnB2O4: Weigh BaCO3, ZnO and B2O3 respectively in a molar ratio of 1:1:2, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5h, dry and transfer the powder to calcine at 720℃ for 2.5h, and cool naturally to room temperature to obtain BaZnB2O4.

[0079] Step four, the (Sr) prepared in steps one through three... 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3, La3(Sb) 0.87 Ce 0.13 Zr3O 12 BaZnB2O4, Nb2O5, MnCO3, MnO2, and Li2SiO3 were added to deionized water and zirconium oxide beads, ball-milled for 6 hours, and then dried and crushed to obtain the dielectric material for high dielectric constant pulse power ceramic capacitors.

[0080] The pulse power ceramic capacitors prepared in Examples 1-5 and Comparative Examples 1-7 were tested and the following data were obtained, as shown in Table 2 below.

[0081] Table 2 Performance Test Table

[0082]

[0083] Where K is the dielectric constant; TCC is the temperature coefficient of capacitance; IR is the insulation resistance; and DF is the loss tangent.

[0084] As can be seen from the table above, Examples 1-5 of this application show that by adjusting the content of each component, pulse power ceramic dielectric materials with good performance can be obtained; among them, the pulse power ceramic capacitor prepared in Example 1 can provide a higher dielectric constant ( K = 632), relatively stable capacitor temperature coefficient (-2100±200) ppm / K The highest breakdown electric field (>49.43) V / μm Highest insulation resistance: 14980 MΩ ; and excellent discharge current (>1800 Ω) A ).

[0085] A comparison between Example 1 and Comparative Example 1 shows that La3(Sb) 0.87 Ce 0.13 Zr3O 12 Not only maintain (Sr 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 O3 high K The addition of important doping materials, and the fusion of the two materials, can significantly improve the breakdown electric field and discharge current of the material.

[0086] A comparison of Example 1 and Comparative Example 2 shows that without the sintering aid Ba(Zn) 1 / 6 Nb 1 / 3 The presence of (B₂O₄)₂ causes a rapid deterioration in the electrical properties of the ceramic body after firing. The K value decreases to 376, the TCC increases significantly, the breakdown electric field decreases to 33.24 V / μm, and the loss increases to 32.9 × 10⁻⁶. -4 The discharge current decreased to 1223 A; comparing Example 1 and Comparative Example 9, it was found that adding Nb2O5 alone to the material resulted in a lower dielectric loss: 2.2 × 10⁻⁶. -4 However, the remaining electrical properties are significantly reduced, so the appropriate amount of sintering aid plays an important role in the sintering process of ceramic materials.

[0087] A comparison between Example 1 and Comparative Examples 3-4 shows that Mn 2+ / Mn 4+ The ratio needs to be limited to Mn 2+ / Mn 4+ A ratio of 2:1 is needed to effectively increase the discharge current of the material, Mn 2+ / Mn 4+ An excessively high or low ratio is detrimental to improving the polarization intensity of the material. P m .

[0088] By comparing Example 1 and Comparative Example 5, it can be seen that adding trace amounts of Li can further improve the energy storage density of the material, which is reflected in the increase of discharge current.

[0089] A comparison of Example 1 and Comparative Examples 6-8 shows that if La3(Sb) is changed... 0.87 Ce 0.13 Zr3O 12 The Sb / Ce ratio is crucial; excessively high or low Ce doping levels cannot fully leverage the high stability of La and Ce. The Sb / Ce ratio needs to be limited to 0.87 / 0.13 as in Example 1 to achieve optimal electrical performance in the resulting dielectric material.

[0090] In summary, the pulsed power ceramic dielectric material proposed in this invention incorporates Ru and Te elements during the fabrication of the main substrate to produce (Sr) 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3, and then La3(Sb) synthesized by solid-state method was added. z Ce 1-z Zr3O 12 Synthetic modified sintering aid Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, and by adjusting Mn 2+ / Mn 4+ A higher polarization intensity is achieved by increasing the ratio. P m The presence of trace amounts of Li gives the dielectric material excellent electrical properties such as high dielectric constant, high resistance, and low loss. Capacitors made from this dielectric material have excellent bias characteristics, stable charge and discharge performance, and large discharge current, making them suitable for use as pulse power ceramic capacitors.

Claims

1. A dielectric material for high dielectric constant, high resistance, and low loss power capacitors, characterized in that: At 100 moles of (Sr 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y Using O3 as the base material, the following components are added in molar amounts: 2-10 parts of La3(Sb) z Ce 1-z Zr3O 12 1-3 parts Ba(Zn) 1 / 6 Nb 1 / 3 (B₂O₄)₂, 0.5~1 parts of MnCO₃, 0.2~0.5 parts of MnO₂, 0.1~0.2 parts of Li₂SiO₃, wherein, 0<x<0.3, 0.1<y<0.2, 0.7<z<1.0; The Ba(Zn 1 / 6 Nb 1 / 3 )(B2O4)2 was synthesized from BaCO3, ZnO, Nb2O5 and B2O3 using a solid-state method.

2. The dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 1, characterized in that: The (Sr) 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3 is (Sr 0.7 Ba 0.27 Mg 0.03 (Ti) 0.8 Ru 0.15 Te 0.05 )O3.

3. The dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 1, characterized in that: The La3(Sb) z Ce 1-z Zr3O 12 For La3(Sb 0.87 Ce 0.13 Zr3O 12 .

4. The method for preparing a dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 1, characterized in that: Includes the following steps: Step 1, Preparation of (Sr) by molten salt method 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3; Step 2: Solid-state preparation of La3(Sb) z Ce 1-z Zr3O 12 ; Step 3: Solid-state preparation of Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2; Step four, the (Sr) prepared in steps one through three... 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y O3, La3(Sb) z Ce 1-z Zr3O 12 MnCO3, MnO2, Ba(Zn) 1 / 6 Nb 1 / 3 (B2O4)2, Li2SiO3, deionized water and zirconium oxide beads were added, ball milled for 4-6 hours and then dried and crushed to obtain the dielectric material for high dielectric constant, high resistance and low loss pulse power ceramic capacitors.

5. The method for preparing a dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 4, characterized in that: Step one specifically includes: weighing SrCO3, BaCO3, MgO, TiO2, RuO2, TeO2, NaCl, and KCl respectively in a molar ratio of 0.7:x:(0.3-x):0.8:y:(0.2-y):(2~4):(2~4), adding anhydrous ethanol and zirconium oxide beads, and ball milling for 6~8 hours. After drying, the powder is calcined at 800~900℃ for 2~3 hours and then naturally cooled to room temperature. The calcined product is ultrasonically cleaned with deionized water, and then washed and filtered multiple times until no Cl is present. - It was detected; after cleaning and drying, (Sr) was obtained. 0.7 Ba x Mg 0.3-x (Ti) 0.8 Ru y Te 0.2-y )O3.

6. The method for preparing a dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 4, characterized in that: Step two specifically includes: La3(Sb z Ce 1-z Zr3O 12 The specific preparation method is as follows: Weigh La₂O₃, Sb₂O₃, Ce₂O₃, and ZrO₂ respectively in a molar ratio of 1.5:z / 2:(1-z) / 2:

3. Add deionized water and zirconium oxide beads, mix and ball-mill for 4-6 hours. After drying, calcine the powder at 1200-1300℃ for 1-3 hours, and then naturally cool to room temperature to obtain La₃(Sb₂O₃)₂O₃. z Ce 1-z Zr3O 12 .

7. The method for preparing a dielectric material for a high dielectric constant, high resistance, and low loss power capacitor according to claim 4, characterized in that: Step three specifically includes: Ba(Zn) 1 / 6 Nb 1 / 3 The preparation method of (B2O4)2 is as follows: Weigh BaCO3, ZnO, Nb2O5, and B2O3 respectively in a molar ratio of 1:1 / 6:1 / 6:

3. Add appropriate amounts of deionized water and zirconium oxide beads, mix and ball-mill for 4-6 hours. After drying, transfer the powder to a calcination temperature of 600-800℃ for 1-3 hours, and allow it to cool naturally to room temperature to obtain Ba(ZnO)2. 1 / 6Nb 1 / 3 )(B2O4)2.

8. A high dielectric constant, high resistance, and low loss power capacitor, characterized in that: It is prepared using the dielectric material described in claim 1.

9. The method for preparing a high dielectric constant, high resistance, and low loss power capacitor according to claim 8, 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 high dielectric constant, high resistance, and low loss power capacitor.

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