A high dielectric constant pulse power type ceramic capacitor and a dielectric material therefor, and a method of manufacturing the same

Abstract

A high dielectric constant pulse power type ceramic capacitor and a dielectric material, a preparation method thereof, the dielectric material takes 100 moles of SrTiO3 as a base material, and adds the following components: Bi x Na 2‑3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 , perovskite phase (Ba 1‑1.5y Sm y )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, the dielectric material for the pulse power type ceramic capacitor provided by the application is doped with Bi x Na 2‑3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 and perovskite phase (Ba 1‑1.5y Sm y )TiO3 on the basis of the main base material SrTiO3, and the dielectric loss of the ceramic material is reduced by doping Mn / Mg elements, the sintering agent is selected as ZnCu(B2O5), the sintering temperature is reduced, the prepared dielectric material has high density, large dielectric constant, low dielectric loss, excellent bias voltage characteristics, and is suitable for being used as a pulse power type ceramic capacitor.

Description

Technical Field

[0001] The present invention belongs to the field of ceramic capacitor preparation, and in particular relates to a high dielectric constant pulse power ceramic capacitor, a dielectric material used therefor, and a preparation method thereof. Background Art

[0002] The most important application of energy storage ceramic materials is as dielectric materials for energy storage ceramic capacitors. As one of the most widely used passive electronic components, ceramic capacitors have advantages over other types of capacitors, such as large specific capacity, good moisture and heat resistance, low dielectric loss, small series equivalent resistance, and a wide range of capacitance-temperature coefficient options. In recent years, with the growth of the market for consumer products such as smartphones, tablets, and 3D TVs, the demand for ceramic capacitors has been increasing year by year. With the development of the electronics industry, exploring high-performance electronic energy storage devices has become a research hotspot in recent years. Current electronic energy storage devices include dielectric capacitors, electrochemical supercapacitors, fuel cells, and lithium batteries. Dielectric capacitors have the ability to charge and discharge rapidly, making them excellent candidates for advanced pulse power applications.

[0003] "Pulse" generally refers to an electric shock that fluctuates like a pulse within a relatively short time interval. "Power" refers to energy per unit time (J / s), and "pulse power" refers to power that appears in the form of a pulse (unit is time energy). Pulse energy storage dielectric materials store energy at a high density and then release it rapidly at short pulse intervals to produce a high-power electric shock. The core component of a pulse power device is the pulse energy storage element composed of dielectric materials. The performance of the pulse energy storage dielectric material will directly affect the output characteristics of the pulse power system. Pulse power systems are constantly evolving and are now present in various fields. For example, pulse power systems are present in new concept weapons and are an indispensable part of them. Pulse power capacitors also play an important role in large-scale laser devices.

[0004] SrTiO3-Bi 0.5 Na 0.5 As a new type of high-energy-storage relaxor ferroelectric material, TiO₃ is a leading candidate for energy storage applications. However, due to the high remnant polarization of this system, improving its energy storage properties through rational modification and doping is a key issue that needs to be addressed. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high dielectric constant pulse power ceramic capacitor and its dielectric material and preparation method.

[0006] The present invention adopts the following technical solutions:

[0007] A dielectric material for high dielectric constant pulse power ceramic capacitors, with 100 mole parts of SrTiO3 as the base material, and the following mole parts of components added: 5 to 20 parts of Bi x Na 2-3x TiO3, 1 to 3 parts of tetragonal black bronze structure phase Sr5ScTi3M7O 30 , 0.5 to 1 parts of perovskite phase (Ba 1-1.5y Sm y )TiO3, 1 to 3 parts of ZnCu(B2O5), 0.5 to 2 parts of MnCO3, 0.5 to 2 parts of MgO, 0.5 to 2 parts of Zn2SiO4; wherein, M=Ta, Nb, V, 0.4<x<0.5, 0<y<0.08.

[0008] Furthermore, the Bi x Na 2-3x TiO3 is Bi 0.5 Na 0.5 TiO3.

[0009] Furthermore, the (Ba 1-1.5y Sm y )TiO3 is (Ba 0.94 Sm 0.04 )TiO3.

[0010] A method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor comprises the following steps:

[0011] Step 1: preparing SrTiO3 by molten salt method;

[0012] Step 2: Prepare Bi by solid phase method x Na 2-3x TiO3, perovskite phase (Ba 1-1.5y Sm y )TiO3, ZnCu(B2O5);

[0013] Step 3: Preparation of tetragonal black bronze structure phase Sr5ScTi3M7O by solid phase method 30 : SrCO3, Sc2O3, TiO2, and M2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 4 to 8 hours. After drying, the powder was transferred to a temperature of 1100 to 1200 ° C and calcined for 1 to 3 hours. It was naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3M7O 30 ;

[0014] Step 4: SrTiO3 and Bi prepared in steps 1 to 3 x Na 2-3xTiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 , perovskite phase (Ba 1-1.5y Sm y )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 4 to 6 hours, then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0015] Furthermore, step one specifically includes: weighing SrCO3, TiO2, NaCl, and KCl respectively in a molar ratio of 1:1:(2-4):(2-4), adding anhydrous ethanol and zirconia beads, and mixing and ball milling for 4-8 hours. After drying, the powder is calcined at a temperature of 800-900°C for 1 hour, and naturally cooled to room temperature; the calcined product is ultrasonically cleaned with deionized water, washed and filtered multiple times until no Cl- is detected; and dried after cleaning to obtain SrTiO3.

[0016] Furthermore, in step 2, Bi x Na 2-3x The preparation method of TiO3 is as follows: Bi2O3, Na2CO3, and TiO2 are weighed separately in a molar ratio of x: (2-3x): 2, deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 3 to 6 hours. After drying, the powder is calcined at a temperature of 700 to 900°C for 1 to 3 hours, and naturally cooled to room temperature to obtain Bi x Na 2-3x TiO3.

[0017] Furthermore, in step 2, the perovskite phase (Ba 1-1.5y Sm y The specific preparation method of TiO3 is as follows: BaCO3, Sm2O3, and TiO2 are weighed separately in a molar ratio of 1-1.5y:y:1, and an appropriate amount of deionized water and zirconium oxide beads are added and mixed and ball-milled for 4-8 hours. After drying, the powder is transferred to a temperature of 1100-1300°C and calcined for 1-3 hours, and naturally cooled to room temperature to obtain a perovskite phase (BaCO3). 1-1.5y Sm y )TiO3.

[0018] Furthermore, in step 2, the preparation method of ZnCu(B2O5) is as follows: ZnO, CuO, and B2O3 are weighed separately in a molar ratio of 1:1:1, an appropriate amount of deionized water and zirconium oxide beads are added, and the mixture is ball-milled for 4 to 8 hours. After drying, the powder is transferred to a temperature of 600 to 800°C and calcined for 1 to 3 hours, and naturally cooled to room temperature to obtain ZnCu(B2O5).

[0019] A high dielectric constant pulse power ceramic capacitor is prepared using the dielectric material mentioned above.

[0020] A preparation method for a high-dielectric-constant pulse power ceramic capacitor comprises the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1000-1200° C., and holding the temperature for 2-5 hours to obtain a pulse power ceramic capacitor.

[0021] It can be seen from the above description of the present invention that, compared with the prior art, the present invention has the following beneficial effects:

[0022] First, the dielectric material for pulse power ceramic capacitors proposed by the present invention is doped with Bi on the basis of the main base material SrTiO3. x Na 2-3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 and perovskite phase (Ba 1-1.5y Sm y )TiO3, and reduce the dielectric loss of ceramic materials by doping Mn / Mg elements. The sintering aid is selected as ZnCu(B2O5) to reduce the sintering temperature, so that the obtained dielectric material has high density, large dielectric constant, low dielectric loss, and excellent bias performance, which is suitable for use as pulse power ceramic capacitors;

[0023] Second, the present invention adds the perovskite structure (Ba 1-1.5y Sm y )TiO3, can be combined with perovskite structure SrTiO3, Bi 0.5 Na 0.5 TiO3 is completely dissolved to form a single perovskite structure without the influence of other impurities; the consolidation of the perovskite structure can further improve the SrTiO3-Bi 0.5 Na 0.5 Energy storage density of TiO3 system;

[0024] Third, the present invention adopts the tetragonal black bronze structure phase Sr5ScTi3M7O 30 The doping of (M=Ta, Nb, V) can refine the grains and inhibit the growth of grains. 3+ / Ta 5+ The introduction of the BNT-ST ceramics can affect the structural disorder phenomenon of the A / B site and enhance the effect of fine grains. The fine grain effect can increase the density of grain boundaries and further increase the insulation performance of the ceramics, thereby increasing the breakdown electric field strength and the energy storage density of the material. A small amount of tetragonal black bronze heterostructure doping can effectively enhance the relaxation behavior of BNT-ST ceramics and inhibit the residual polarization. PNRs can be effectively induced by the local electric field while maintaining the P under the ground electric field. max , in order to ensure the high energy storage density of the material;

[0025] Fourth, the introduction of ZnCu(B2O5) and the eutectic reaction of CuO-B2O3 sintering aid below 1000℃ can effectively reduce the sintering temperature and promote densification; and Cu 2+ The addition of is beneficial to the reduction of grain size. The smaller the size, the more uniform the microstructure and the higher the breakdown strength. DETAILED DESCRIPTION

[0026] The present invention is further described below through specific embodiments.

[0027] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1000-1200°C, and keeping the temperature for 2-5 hours to obtain a pulse power ceramic capacitor.

[0028] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 5 to 20 parts of Bi x Na 2-3x TiO3, 1 to 3 parts of tetragonal black bronze structure phase Sr5ScTi3M7O 30 , 0.5 to 1 parts of perovskite phase (Ba 1- 1.5y Sm y )TiO3, 1 to 3 parts of ZnCu(B2O5), 0.5 to 2 parts of MnCO3, 0.5 to 2 parts of MgO, 0.5 to 2 parts of Zn2SiO4; wherein M=Ta, Nb, V, 0.4<x<0.5, 0<y<0.08; Bi x Na 2-3x TiO3 is Bi 0.5 Na 0.5 TiO3; (Ba 1-1.5y Sm y )TiO3 is (Ba 0.94 Sm 0.04 )TiO3.

[0029] The preparation method thereof comprises the following steps:

[0030] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), anhydrous ethanol and zirconium oxide beads were added and mixed and ball-milled for 4-8 hours. After drying, the powder was calcined at 800-900℃ for 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0031] Step 2: Prepare Bi by solid phase method x Na 2-3x TiO3: Molar ratio x: (2-3x): 2 Weigh Bi2O3, Na2CO3, TiO2 separately, add deionized water and zirconium oxide beads, mix and ball mill for 3 to 6 hours, dry the powder and calcine it at 700 to 900℃ for 1 to 3 hours, and cool it naturally to room temperature to obtain Bi x Na 2-3x TiO3;

[0032] Step 3: Solid phase perovskite phase (Ba 1-1.5y Sm y )TiO3: BaCO3, Sm2O3, TiO2 are weighed separately in a molar ratio of 1-1.5y:y:1, and an appropriate amount of deionized water and zirconium oxide beads are added and mixed and ball-milled for 4-8 hours. After drying, the powder is transferred to a temperature of 1100-1300 ° C and calcined for 1-3 hours. It is naturally cooled to room temperature to obtain a perovskite phase (Ba 1-1.5y Sm y )TiO3;

[0033] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 4-8 hours, and after drying, transfer the powder to calcination at 600-800°C for 1-3 hours, and naturally cool to room temperature to obtain ZnCu(B2O5);

[0034] Step 5: Prepare the tetragonal black bronze structure phase Sr5ScTi3M7O by solid phase method 30 : SrCO3, Sc2O3, TiO2, and M2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 4 to 8 hours. After drying, the powder was transferred to a temperature of 1100 to 1200 ° C and calcined for 1 to 3 hours. It was naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3M7O 30 ;

[0035] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 x Na 2-3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 , perovskite phase (Ba 1-1.5y Sm y )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 4 to 6 hours, then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0036] Example 1

[0037] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1100°C and keeping the temperature for 3 hours to obtain a pulse power ceramic capacitor.

[0038] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 5 parts of Bi 0.5 Na 0.5 TiO3, 2.3 parts of tetragonal black bronze structure phase Sr5ScTi3Ta7O 30 , 0.5 parts of perovskite phase (Ba 0.94 Sm 0.04 )TiO3, 1 part of ZnCu(B2O5), 1 part of MnCO3, 0.5 part of MgO, and 0.5 part of Zn2SiO4.

[0039] The preparation method thereof comprises the following steps:

[0040] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), 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 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0041] Step 2: Prepare Bi by solid phase method 0.5 Na 0.5 TiO3: Bi2O3, Na2CO3, and TiO2 were weighed separately in a molar ratio of 0.5:0.5:2, deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4 hours. After drying, the powder was calcined at 850℃ for 2 hours and naturally cooled to room temperature to obtain Bi 0.5 Na 0.5 TiO3;

[0042] Step 3: Solid phase perovskite phase (Ba 0.94 Sm 0.04 )TiO3: BaCO3, Sm2O3, and TiO2 were weighed separately in a molar ratio of 0.94:0.04:1, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a temperature of 1200 ° C and calcined for 2 hours, and naturally cooled to room temperature to obtain a perovskite phase (Ba0.94 Sm 0.04 )TiO3;

[0043] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5 hours, and after drying, transfer the powder to calcination at 700°C for 3 hours and naturally cool to room temperature to obtain ZnCu(B2O5);

[0044] Step 5: Prepare the tetragonal black bronze structure phase Sr5ScTi3Ta7O by solid phase method 30 : SrCO3, Sc2O3, TiO2, Ta2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to the calcination temperature of 1120℃ for 2 hours and naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3Ta7O 30 ;

[0045] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 0.5 Na 0.5 TiO3, tetragonal black bronze structure phase Sr5ScTi3Ta7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 5 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0046] The raw material composition and preparation process of Examples 2-5 are basically the same as those of Example 1, except that the ratios of the raw materials are different. The specific parameters are shown in Table 1.

[0047] Example 6

[0048] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1100°C and keeping the temperature for 3 hours to obtain a pulse power ceramic capacitor.

[0049] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 12 parts of Bi 0.5 Na 0.5 TiO3, 2.3 parts of tetragonal black bronze structure phase Sr5ScTi3Nb7O 30 , 0.5 parts of perovskite phase (Ba0.94 Sm 0.04 )TiO3, 1 part of ZnCu(B2O5), 1 part of MnCO3, 0.5 part of MgO, and 0.5 part of Zn2SiO4.

[0050] The preparation method thereof comprises the following steps:

[0051] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), 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 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0052] Step 2: Prepare Bi by solid phase method 0.5 Na 0.5 TiO3: Bi2O3, Na2CO3, and TiO2 were weighed separately in a molar ratio of 0.5:0.5:2, deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4 hours. After drying, the powder was calcined at 850℃ for 2 hours and naturally cooled to room temperature to obtain Bi 0.5 Na 0.5 TiO3;

[0053] Step 3: Solid phase perovskite phase (Ba 0.94 Sm 0.04 )TiO3: BaCO3, Sm2O3, and TiO2 were weighed separately in a molar ratio of 0.94:0.04:1, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a temperature of 1200 ° C and calcined for 2 hours, and naturally cooled to room temperature to obtain a perovskite phase (Ba 0.94 Sm 0.04 )TiO3;

[0054] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5 hours, and after drying, transfer the powder to calcination at 700°C for 3 hours and naturally cool to room temperature to obtain ZnCu(B2O5);

[0055] Step 5: Prepare the tetragonal black bronze structure phase Sr5ScTi3Nb7O by solid phase method 30: SrCO3, Sc2O3, TiO2, Nb2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a calcination temperature of 1120 ° C for 2 hours and naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3Nb7O 30 ;

[0056] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 0.5 Na 0.5 TiO3, tetragonal black bronze structure phase Sr5ScTi3Nb7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 5 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0057] Example 7

[0058] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1100°C and keeping the temperature for 3 hours to obtain a pulse power ceramic capacitor.

[0059] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 12 parts of Bi 0.5 Na 0.5 TiO3, 2.3 parts of tetragonal black bronze structure phase Sr5ScTi3V7O 30 , 0.5 parts of perovskite phase (Ba 0.94 Sm 0.04 )TiO3, 1 part of ZnCu(B2O5), 1 part of MnCO3, 0.5 part of MgO, and 0.5 part of Zn2SiO4.

[0060] The preparation method thereof comprises the following steps:

[0061] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), 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 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0062] Step 2: Prepare Bi by solid phase method 0.5 Na 0.5 TiO3: Bi2O3, Na2CO3, and TiO2 were weighed separately in a molar ratio of 0.5:0.5:2, deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4 hours. After drying, the powder was calcined at 850℃ for 2 hours and naturally cooled to room temperature to obtain Bi 0.5 Na 0.5 TiO3;

[0063] Step 3: Solid phase perovskite phase (Ba 0.94 Sm 0.04 )TiO3: BaCO3, Sm2O3, and TiO2 were weighed separately in a molar ratio of 0.94:0.04:1, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a temperature of 1200 ° C and calcined for 2 hours, and naturally cooled to room temperature to obtain a perovskite phase (Ba 0.94 Sm 0.04 )TiO3;

[0064] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5 hours, and after drying, transfer the powder to calcination at 700°C for 3 hours and naturally cool to room temperature to obtain ZnCu(B2O5);

[0065] Step 5: Prepare the tetragonal black bronze structure phase Sr5ScTi3V7O by solid phase method 30 : SrCO3, Sc2O3, TiO2, and V2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a calcination temperature of 1120°C for 2 hours and naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3V7O 30 ;

[0066] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 0.5 Na 0.5 TiO3, tetragonal black bronze structure phase Sr5ScTi3V7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 5 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0067] The raw material composition and preparation method of Comparative Examples 1-7 are basically the same as those of Example 3, except that the raw material ratios are different. The specific parameters are shown in Table 1.

[0068] Comparative Example 8

[0069] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1100°C and keeping the temperature for 3 hours to obtain a pulse power ceramic capacitor.

[0070] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 12 parts of Bi 0.5 Na 0.5 TiO3, 2.3 parts of tetragonal black bronze structure phase Sr5LaTi3Ta7O 30 , 0.5 parts of perovskite phase (Ba 0.94 Sm 0.04 )TiO3, 1 part of ZnCu(B2O5), 1 part of MnCO3, 0.5 part of MgO, and 0.5 part of Zn2SiO4.

[0071] The preparation method thereof comprises the following steps:

[0072] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), 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 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0073] Step 2: Prepare Bi by solid phase method 0.5 Na 0.5 TiO3: Bi2O3, Na2CO3, and TiO2 were weighed separately in a molar ratio of 0.5:0.5:2, deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4 hours. After drying, the powder was calcined at 850℃ for 2 hours and naturally cooled to room temperature to obtain Bi 0.5 Na 0.5 TiO3;

[0074] Step 3: Solid phase perovskite phase (Ba 0.94 Sm 0.04)TiO3: BaCO3, Sm2O3, and TiO2 were weighed separately in a molar ratio of 0.94:0.04:1, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a temperature of 1200 ° C and calcined for 2 hours, and naturally cooled to room temperature to obtain a perovskite phase (Ba 0.94 Sm 0.04 )TiO3;

[0075] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5 hours, and after drying, transfer the powder to calcination at 700°C for 3 hours and naturally cool to room temperature to obtain ZnCu(B2O5);

[0076] Step 5: Prepare the tetragonal black bronze structure phase Sr5LaTi3Ta7O by solid phase method 30 : SrCO3, La2O3, TiO2, Ta2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a calcination temperature of 1120℃ for 2 hours and naturally cooled to room temperature to obtain the tetragonal black bronze structure Sr5LaTi3Ta7O 30 ;

[0077] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 0.5 Na 0.5 TiO3, tetragonal black bronze structure phase Sr5LaTi3Ta7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 5 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0078] Comparative Example 9

[0079] A high dielectric constant pulse power ceramic capacitor is made of dielectric material. The preparation method includes the following steps: subjecting the dielectric material to an MLCC process, using 70Ag-30Pd as an inner electrode, sintering in an air atmosphere at a temperature of 1100°C and keeping the temperature for 3 hours to obtain a pulse power ceramic capacitor.

[0080] The dielectric material is based on 100 mole parts of SrTiO3 and is added with the following mole parts: 12 parts of Bi 0.5 Na 0.5 TiO3, 2.3 parts of tetragonal black bronze structure phase Sr5GdTi3Ta7O30 , 0.5 parts of perovskite phase (Ba 0.94 Sm 0.04 )TiO3, 1 part of ZnCu(B2O5), 1 part of MnCO3, 0.5 part of MgO, and 0.5 part of Zn2SiO4.

[0081] The preparation method thereof comprises the following steps:

[0082] Step 1: Preparation of SrTiO3 by molten salt method: SrCO3, TiO2, NaCl, and KCl were weighed separately in a molar ratio of 1:1:(2-4):(2-4), 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 1 hour and naturally cooled to room temperature. The calcined product was ultrasonically cleaned with deionized water, washed and filtered several times until there was no Cl - After being detected and washed and dried, SrTiO3 is obtained;

[0083] Step 2: Prepare Bi by solid phase method 0.5 Na 0.5 TiO3: Bi2O3, Na2CO3, and TiO2 were weighed separately in a molar ratio of 0.5:0.5:2, deionized water and zirconium oxide beads were added, and the mixture was ball-milled for 4 hours. After drying, the powder was calcined at 850℃ for 2 hours and naturally cooled to room temperature to obtain Bi 0.5 Na 0.5 TiO3;

[0084] Step 3: Solid phase perovskite phase (Ba 0.94 Sm 0.04 )TiO3: BaCO3, Sm2O3, and TiO2 were weighed separately in a molar ratio of 0.94:0.04:1, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to a temperature of 1200 ° C and calcined for 2 hours, and naturally cooled to room temperature to obtain a perovskite phase (Ba 0.94 Sm 0.04 )TiO3;

[0085] Step 4: Prepare ZnCu(B2O5) by solid-phase method: weigh ZnO, CuO, and B2O3 in a molar ratio of 1:1:1, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 5 hours, and after drying, transfer the powder to calcination at 700°C for 3 hours and naturally cool to room temperature to obtain ZnCu(B2O5);

[0086] Step 5: Prepare the tetragonal black bronze structure phase Sr5GdTi3Ta7O by solid phase method 30: SrCO3, Gd2O3, TiO2, Ta2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 5 hours. After drying, the powder was transferred to the calcination temperature of 1120℃ for 2 hours and naturally cooled to room temperature to obtain the tetragonal black bronze structure Sr5GdTi3Ta7O 30 ;

[0087] Step 6: SrTiO3 and Bi prepared in steps 1 to 5 0.5 Na 0.5 TiO3, tetragonal black bronze structure phase Sr5GdTi3Ta7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 5 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

[0088] Table 1 Composition (mol%)

[0089] <![CDATA[SrTiO3]]> <![CDATA[Bi 0.5 On 0.5 TiO3]]> <![CDATA[Sr5ScTi3Ta7O 30 ]]> <![CDATA[(Ba 0.94 Sm 0.04 )TiO3]]> <![CDATA[ZnCu(B2O5)]]> <![CDATA[MnCO3]]> MgO <![CDATA[Zn2SiO4]]> Example 1 100 5 2.3 0.5 1 1 0.5 0.5 Example 2 100 9.5 2.3 0.5 1 1 0.5 0.5 Example 3 100 12 2.3 0.5 1 1 0.5 0.5 Example 4 100 15 2.3 0.5 1 1 0.5 0.5 Example 5 100 20 2.3 0.5 1 1 0.5 0.5 Comparative Example 1 100 0 2.3 0.5 1 1 0.5 0.5 Comparative Example 2 100 12 0 0.5 1 1 0.5 0.5 Comparative Example 3 100 12 2.3 0 1 1 0.5 0.5 Comparative Example 4 100 12 2.3 0.5 0 1 0.5 0.5 Comparative Example 5 100 12 2.3 0.5 0.5 1 0.5 0.5 Comparative Example 6 100 12 2.3 0.5 2 1 0.5 0.5 Comparative Example 7 100 12 2.3 0.5 5 1 0.5 0.5

[0090] The pulse power ceramic capacitors prepared in Examples 1-7 and Comparative Examples 1-9 were tested to obtain the following data, as shown in Table 2:

[0091] Table 2 Basic electrical properties

[0092]

[0093] Where: K: dielectric constant; DF: loss tangent; TCC: temperature coefficient of capacitance.

[0094] As can be seen from the above table, the present application provides Examples 1 to 7, which can obtain pulse power ceramic dielectric materials with better performance by regulating the content of each component; among them, the pulse power ceramic capacitor prepared in Example 3 can provide a higher dielectric constant (K=590), a more stable capacitance temperature coefficient (-3000±500ppm / K), the highest breakdown electric field (>48.85V / μm), and excellent discharge current (>1700A).

[0095] By comparing Example 3 with Comparative Example 1, it can be seen that the linear structure of SrTiO3 and the non-ferroelectric structure of Bi 0.5 Na 0.5 Although the TiO3 composite also has energy storage characteristics and good breakdown strength, its dielectric constant is relatively low (K < 300), so the trial production of multilayer ceramic capacitors will be restricted in this application.

[0096] By comparing Example 3 with Comparative Examples 2 to 4, it can be seen that the relaxor ferroelectric structure of SrTiO3-Bi 0.5 Na 0.5 TiO3 ceramics, through the composite tetragonal black bronze structure phase Sr5ScTi3Ta7O 30 , perovskite phase (Ba 0.94 Sm 0.04 )TiO3, and ZnCu(B2O5) can both increase the breakdown electric field strength of the ceramic system, thereby increasing the energy storage density of the material and giving ceramic capacitors excellent discharge characteristics.

[0097] By comparing Example 3 with Comparative Examples 5-7, it can be seen that the introduction of the ternary sintering aid ZnCu (B2O5) can effectively reduce the sintering temperature, promote densification, and improve the breakdown strength; however, the doping amount of ZnCu (B2O5) is limited to 1 mol% of Example 3. Too little or too much doping amount will affect the grain size and reduce the breakdown strength to a certain extent.

[0098] By comparing Example 3 with Comparative Examples 8-9, it can be seen that the tetragonal black bronze structure phase Sr5ScTi3Ta7O is limited to the rare earth element Ta and the rare earth element Sc. 30 By doping a small amount of heterostructure phase, the relaxation behavior of ST-BNT ceramics can be effectively enhanced, thereby obtaining a stable capacitance temperature coefficient and a higher breakdown electric field.

[0099] In summary, the dielectric material for pulse power ceramic capacitors proposed in the present invention is doped with Bi on the basis of the main base material SrTiO3. x Na 2-3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 and perovskite phase (Ba 1-1.5y Sm y )TiO3, and reduce the dielectric loss of the ceramic material by doping Mn / Mg elements. ZnCu(B2O5) is selected as the sintering aid to reduce the sintering temperature, so that the obtained dielectric material has high density, large dielectric constant, low dielectric loss, and excellent bias characteristics, making it suitable for use as a pulse power ceramic capacitor.

[0100] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made according to 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 dielectric material for a high dielectric constant pulse power ceramic capacitor, characterized in that: 100 mole parts of SrTiO3 as the base material, the following mole parts are added: 5~20 parts of Bi x Na 2-3x TiO3, 1~3 parts of tetragonal black bronze structure phase Sr5ScTi3M7O 30 , 0.5~1 parts of perovskite phase (Ba 1-1.5y Sm y )TiO3, 1-3 parts of ZnCu(B2O5), 0.5-2 parts of MnCO3, 0.5-2 parts of MgO, 0.5-2 parts of Zn2SiO4; wherein M=Ta, Nb, V, 0.4<x<0.5, 0<y<0.08; The Bi x Na 2-3x TiO3 is Bi 0.5 Na 0.5 TiO3; Said (Ba 1-1.5y Sm y )TiO3 is (Ba 0.94 Sm 0.04 )TiO3.

2. The method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor according to claim 1, characterized in that: The following steps are involved: Step 1: preparing SrTiO3 by molten salt method; Step 2: Prepare Bi by solid phase method x Na 2-3x TiO3, perovskite phase (Ba 1-1.5y Sm y )TiO3, ZnCu(B2O5); Step 3: Preparation of tetragonal black bronze structure phase Sr5ScTi3M7O by solid phase method 30 : SrCO3, Sc2O3, TiO2, and M2O5 were weighed in a molar ratio of 5:0.5:3:3.5, and an appropriate amount of deionized water and zirconium oxide beads were added and mixed and ball-milled for 4-8 hours. After drying, the powder was transferred to a temperature of 1100-1200 ° C and calcined for 1-3 hours. It was naturally cooled to room temperature to obtain the tetragonal black bronze structure phase Sr5ScTi3M7O 30 ; Step 4: SrTiO3 and Bi prepared in steps 1 to 3 x Na 2-3x TiO3, tetragonal black bronze structure phase Sr5ScTi3M7O 30 , perovskite phase (Ba 1-1.5y Sm y )TiO3, ZnCu(B2O5), MnCO3, MgO, Zn2SiO4, add deionized water and zirconia beads, ball mill for 4-6 hours and then dry and crush to obtain the dielectric material for the high dielectric constant pulse power ceramic capacitor.

3. The method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor according to claim 2, characterized in that: The first step specifically comprises: weighing SrCO3, TiO2, NaCl, and KCl in a molar ratio of 1:1:(2~4):(2~4), adding anhydrous ethanol and zirconia beads, mixing and ball milling for 4~8h, drying the powder and calcining it at a temperature of 800~900℃ for 1h, and naturally cooling it to room temperature; the calcined product is ultrasonically cleaned with deionized water, washed and filtered several times until there is no Cl - After cleaning and drying, SrTiO3 is obtained.

4. The method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor according to claim 2, characterized in that: In step 2, Bi x Na 2-3x The preparation method of TiO3 is as follows: weigh Bi2O3, Na2CO3, and TiO2 in a molar ratio of x: (2-3x): 2, add deionized water and zirconium oxide beads, mix and ball mill for 3-6 hours, dry the powder and calcine it at 700-900℃ for 1-3 hours, and cool it naturally to room temperature to obtain Bi x Na 2-3x TiO3.

5. The method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor according to claim 2, characterized in that: In step 2, the perovskite phase (Ba 1-1.5y Sm y )TiO3 preparation method is as follows: weigh BaCO3, Sm2O3, TiO2 in a molar ratio of 1-1.5y:y:1 respectively, add appropriate amount of deionized water and zirconium oxide beads, mix and ball mill for 4-8 hours, after drying, transfer the powder to calcination at 1100-1300℃ for 1-3 hours, and cool naturally to room temperature to obtain the perovskite phase (Ba 1- 1.5y Sm y )TiO3.

6. The method for preparing a dielectric material for a high dielectric constant pulse power ceramic capacitor according to claim 2, characterized in that: In step 2, the preparation method of ZnCu(B2O5) is as follows: ZnO, CuO, and B2O3 are weighed separately in a molar ratio of 1:1:1, an appropriate amount of deionized water and zirconia beads are added, and the mixture is ball-milled for 4 to 8 hours. After drying, the powder is transferred to a temperature of 600 to 800°C and calcined for 1 to 3 hours, and naturally cooled to room temperature to obtain ZnCu(B2O5).

7. A high dielectric constant pulse power ceramic capacitor, characterized in that: The dielectric material according to claim 1 is used for preparation.

8. The method for preparing a high dielectric constant pulse power ceramic capacitor according to claim 7, wherein: The following steps are involved: The dielectric material is subjected to an MLCC process, with 70Ag-30Pd as an inner electrode, and sintered in an air atmosphere at a temperature of 1000-1200° C. for 2-5 hours to obtain a pulse power ceramic capacitor.

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