Barium strontium titanate-based dielectric ceramic materials, preparation method and application thereof

Abstract

The present application relates to a barium strontium titanate-based dielectric ceramic material, a preparation method, and application thereof. The composition of the barium strontium titanate-based dielectric ceramic material comprises: aBaTiO3+bSrTiO3+cTiO2+dBi.sub.2O.sub.3+eMgO+fAl2O3+gCaO+hSiO2, wherein a, b, c, d, e, f, g, and h are the molar percentage of each component, 20≤a≤50 mol %, 15≤b≤30 mol %, 10≤c≤20 mol %, 0≤d≤10 mol %, 0≤e≤35 mol %, 0≤f≤6 mol %, 0≤g≤6 mol %, 0≤h≤1 mol %, and a+b+c+d+e+f+g+h=100 mol %.

Claims

1. A barium strontium titanate-based dielectric ceramic material, having a composition of aBaTiO.sub.3+bSrTiO.sub.3+cTiO.sub.2+dBi.sub.2O.sub.3+eMgO+fAl.sub.2O.sub.3+gCaO+hSiO.sub.2, wherein a, b, c, d, e, f, g, and h are the molar percentage of each component, 20≤a≤50 mol %, 15≤b≤30 mol %, 10≤c≤20 mol %, 3≤d≤10 mol %, 4≤e≤35 mol %, 0≤f≤6 mol %, 3≤g≤6 mol %, 0.1≤h≤1 mol %, and a+b+c+d+e+f+g+h=100 mol %.

2. The barium strontium titanate-based dielectric ceramic material according to claim 1, wherein the barium strontium titanate-based dielectric ceramic material has a dielectric strength of 38 to 52 kV/mm at a thickness of 0.38 mm, a dielectric constant adjustable from 800 to 2,000, a dielectric loss of less than 0.003 at 1 kHz and 25° C., and an effective energy storage density as high as 8.6 J/cm.sup.3 at 660 kV/cm.

3. The barium strontium titanate-based dielectric ceramic material according to claim 1, wherein the barium strontium titanate-based dielectric ceramic material has a permittivity variation of 7% or less between 0° C. and 40° C., and a DC resistivity of 10.sup.12 Ω.Math.cm or greater at 100° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photograph of the standard ceramic sheet prepared in Examples 1-4 of the present application for measurement of dielectric constant/dielectric loss;

(2) FIG. 2 is a photograph of the standard ceramic sheet prepared in Examples 1-4 of the present application for measurement of dielectric strength;

(3) FIG. 3 is a photograph of a long strip shape barium strontium titanate based dielectric ceramic material (length 300 mm×width 40 mm×thickness 5 mm) prepared in Example 1 of the present application;

(4) FIG. 4 shows the frequency dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 1 of the present application;

(5) FIG. 5 shows the frequency dependence of the permittivity and loss of the big round cake ceramic material prepared in Example 1 of the present application;

(6) FIG. 6 shows the temperature dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 1 of the present application;

(7) FIG. 7 shows a variation of dielectric constant with temperature of a standard ceramic sheet prepared in Example 1 of the present application;

(8) FIG. 8 shows polarization hysteresis loops under a strong electric field of a standard ceramic sheet prepared in Example 1 of the present application;

(9) FIG. 9 shows the temperature dependence of DC resistivity of a standard ceramic sheet prepared in Example 1 of the present application;

(10) FIG. 10 shows the temperature dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 2 of the present application;

(11) FIG. 11 shows the variation of dielectric constant with temperature of a standard ceramic sheet prepared in Example 2 of the present application;

(12) FIG. 12 shows the temperature dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 3 of the present application;

(13) FIG. 13 shows the variation of dielectric constant with temperature of a standard ceramic sheet prepared in Example 3 of the present application;

(14) FIG. 14 shows the temperature dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 4 of the present application;

(15) FIG. 15 shows the variation of dielectric constant with temperature of a standard ceramic sheet prepared in Example 4 of the present application;

(16) FIG. 16 shows the temperature dependence of the dielectric constant and loss of a standard ceramic sheet prepared in Example 5 of the present application;

(17) FIG. 17 shows the variation of dielectric constant with temperature of a standard ceramic sheet prepared in Example 5 of the present application; and

(18) FIG. 18 shows the comparison of the variation of dielectric constant with temperature of standard ceramic sheets prepared in Examples 1-5 of the present application.

DETAILED DESCRIPTION

(19) Selected embodiments of the present disclosure will now be described. It will be apparent to those skilled in the art from this disclosure that the following descriptions of the embodiments of the disclosure are provided for illustration only and not for the purpose of limiting the disclosure as defined by the appended claims and their equivalents.

(20) In the present disclosure, a composition of a barium strontium titanate based dielectric ceramic material system with high dielectric strength, a high dielectric constant and high dielectric stability comprises: aBaTiO.sub.3+bSrTiO.sub.3+cTiO.sub.2+d Bi.sub.2O.sub.3+eMgO+fAl.sub.2O.sub.3+gCaO+hSiO.sub.2, wherein a, b, c, d, e, f, g, and h are the mole percentage of each component, 20≤a≤50 mol %, 15≤b≤30 mol %, 10≤c≤20 mol %, 0≤d≤10 mol %, 0≤e≤35 mol %, 0≤f≤6 mol %, 0≤g≤6 mol %, 0≤h≤1 mol %, and a+b+c+d+e+f+g+h=100 mol %. In the composition, if the content of TiO.sub.2 is too high, the dielectric constant of the material will be greatly reduced, the dielectric loss will be increased, and both the energy storage density and energy storage efficiency will be reduced; if the content of TiO.sub.2 is too low, the dielectric stability of the material will be greatly reduced under an external field, and the energy storage efficiency will be reduced.

(21) In an optional embodiment, 20≤a≤50 mol %, 15≤b≤30 mol %, 10≤c≤20 mol %, 3≤d≤10 mol %, 4≤e≤35 mol %, 0≤f≤6 mol %, 3≤g≤6 mol %, 0.1≤h≤1 mol %, and a+b+c+d+e+f+g+h=100 mol %.

(22) In the disclosure, the barium strontium titanate based dielectric ceramic material has the advantages of being lead free and environmentally friendly, a simple preparation process, being able to be used for large size sample preparation, etc. It is very suitable for the manufacture of various high-pressure energy storage and transmission media, and has great application value in the field of high power and pulse power. A preparation method of the barium strontium titanate based dielectric ceramic material is exemplarily illustrated as follows.

(23) According to the chemical composition (aBaTiO.sub.3+bSrTiO.sub.3+cTiO.sub.2+dBi.sub.2O.sub.3+eMgO+fAl.sub.2O.sub.3+gCaO+hSiO.sub.2), a Ti source, a Ba source, a Sr source, a Bi source, a Mg source, a Ca source, an Al source and a Si source are weighed, mixed, and pre-sintered to obtain a mixed powder. Wherein, the Ti source is selected from TiO.sub.2, C.sub.16H.sub.36O.sub.4Ti, C.sub.12H.sub.28O.sub.4Ti, SrTiO.sub.3, BaTiO.sub.3 and TiCl.sub.4 etc. The Ba source is selected from BaO, BaCO.sub.3, C.sub.4H.sub.6BaO.sub.4, Ba(NO.sub.3).sub.2 and BaTiO.sub.3, etc. The Sr source is selected from SrO, SrCO.sub.3, C.sub.4H.sub.6SrO.sub.4, Sr(NO.sub.3).sub.2 and SrTiO.sub.3, etc. The Bi source is selected from Bi.sub.2O.sub.3, BiCl.sub.3, Bi(OH).sub.3, Bi.sub.5(OH).sub.9(NO.sub.3).sub.4, etc. The MgO source is selected from MgO, MgCO.sub.3, C.sub.4H.sub.6MgO.sub.4, MgTiO.sub.3, etc. The CaO source is selected from CaO, CaCO.sub.3, C.sub.4CaH.sub.6O.sub.4.H.sub.2O, CaTiO.sub.3, etc. The Al source is selected from Al.sub.2O.sub.3, Al(NO.sub.3).sub.3, Al(OH)C.sub.4H.sub.6O.sub.4, etc. The Si source is selected from SiO.sub.2, (C.sub.2H.sub.5O).sub.4Si, C.sub.16H.sub.36O.sub.4Si, etc. The mixed powder can be further subjected to grinding or ball milling, so that the particle size of the mixed powder is between 0.2 μm and 2.5 μm, which can facilitate subsequent pressing.

(24) In an optional embodiment, the pre-sintering time is lengthened with the increase of the mole number of the prepared powder. The temperature of pre-sintering can be 1,000° C. to 1,150° C. The pre-sintering time can be 2 to 12 hours.

(25) The mixed powder is mixed with a binder, then subjected to spray granulated and press molding to form a green body. The binder can be selected from polyvinyl alcohol, polyvinyl butyral, methylcellulose, etc. The amount of binder can be 0.2 to 3 wt %, preferably 0.5 to 1 wt % of the total mass of the mixed powder. The press molding method can be isostatic pressing, dry pressing, etc. The pressure of isostatic pressing can be 180 to 300 MPa.

(26) The green body is sintered at 1220 to 1300° C. to obtain barium strontium titanate based dielectric ceramic material. The temperature and holding time of sintering can be determined according to the molar number of the prepared powder. The holding time of sintering can be 2 to 24 hours. When one or more of MgO, Al.sub.2O.sub.3 or CaO increases in large quantities, the temperature and/or holding time of sintering increases; when one or more of Bi.sub.2O.sub.3 or SiO.sub.2 increases in large quantities, the temperature and/or holding time of sintering decreases.

(27) Standard ceramic sheets are prepared from strontium barium titanate based dielectric ceramic material, and then painted with a silver electrode and fired for measurement of the dielectric properties and electrical strength.

(28) In addition, the barium strontium titanate based dielectric ceramic material with the high dielectric constant, high dielectric strength and high dielectric stability obtained in the present application can achieve a size of greater than or equal to 300 mm in at least one dimension.

(29) Hereinafter, the present invention will be better described with the following representative examples. It is understood that the following examples are only used to explain this invention and do not limit the scope of this invention, and any non-essential improvements and modifications made by a person skilled in the art based on this invention all fall into the protection scope of this invention. The specific parameters below are only exemplary, and a person skilled in the art can choose proper values within an appropriate range according to the description of this article, and are not restricted to the specific values cited below.

Example 1

(30) BaTiO.sub.3, SrTiO.sub.3, TiO.sub.2, Bi.sub.2O.sub.3, MgO, Al.sub.2O.sub.3, CaCO.sub.3 and SiO.sub.2 were weighed according to the formula of 0.27BaTiO.sub.3+0.22SrTiO.sub.3+0.13TiO.sub.2+0.036Bi.sub.2O.sub.3+0.29MgO+0.012Al.sub.2O.sub.3+0.04CaO+0.002SiO.sub.2, mixed by wet ball milling using water as the medium and agate balls as the grinding balls for 24 hours, discharged, and dried to give powders. The powders were pre-sintered at 1,050° C. for 6 hours, and then subjected to wet ball milling followed by drying, to give mixed powders having a particle size of 0.5 to 1.0 μm. The mixed powders were mixed with polyvinyl alcohol (PVA) at a ratio of 0.008 g PVA to 1 g mixed powders, and subjected to spray granulation, followed by isostatic pressing at a pressure of 200 MPa, to give green bodies with various sizes. The green bodies were sintered at 1,270° C. for 10 hours, and then naturally cooled to room temperature to give ceramic blocks. The obtained ceramic blocks were subjected to cutting and fine grinding to give a cuboid ceramic sheet having a length of 300 mm, a width of 40 mm, and a thickness of 5 mm (as shown in FIG. 3, ceramic material after processing and silver electrode firing) and cylindrical ceramic sheets having a diameter of 30 mm and a thickness of 1 mm, 0.38 mm and 0.14 mm, respectively.

(31) The obtained ceramic sheets were coated with a silver electrode and fired for measurements of dielectric properties and dielectric strength. FIG. 4 shows the frequency dependence of dielectric constant and dielectric loss of the ceramic standard sheets (diameter 30 mm, thickness 1 mm) in this example. The dielectric constant of the ceramic sheet is about 1,080 in the frequency range of 100 Hz to 1 MHz, basically unchanged with the frequency, and the dielectric loss is about 0.0015 at 1 kHz. FIG. 5 shows the frequency dependence of the capacitance and dielectric loss of a large round cake ceramic material prepared in this example. It can be seen from FIG. 5 that although the ceramic size is greatly increased, the capacitance value is basically unchanged in the frequency range of 100 Hz to 1 MHz, and the dielectric loss is about 0.0015 at 1 kHz. FIG. 6 shows the temperature dependence of dielectric constant and dielectric loss of a ceramic standard sheet prepared in this example, and FIG. 7 shows a variation of dielectric constant with temperature of this sheet. As can be seen in FIG. 6 and FIG. 7, the dielectric constant gradually decreases as the temperature increases from −50° C., and the variation in permittivity are from +4.8 to −4.7 (at −0° C. to 40° C.) and +10.87 to −15.6 (at −30° C. to 85° C.). FIG. 8 shows the polarization hysteresis loops of a ceramic material prepared in this example under different electric fields. It can be seen from FIG. 8 that as the electric field increases until reaching a strong field, the polarization strength increases, and the electric polarization of the ceramic material tends to gradually become unstable, but the ceramic is highly efficient at energy storage, and the effective energy storage density and efficiency are: w: 8.6 J/cm.sup.3 η: 71% at 660 kV/cm; w: 2.1 J/cm.sup.3, η: 80% at 223 kV/cm. The dielectric strengths of the ceramic material at room temperature are 40.5 kV/mm, 51.6 kV/mm, 66 kV/mm (at 1 mm, 0.38 mm, 0.14 mm), respectively. FIG. 9 shows the curve of the DC resistivity of the ceramic material prepared by this example, as a function of temperature. It can be seen that, as the temperature increases from 40° C. to 150° C. the resistivity of the ceramic material decreases from 6.5×10.sup.13 Ω.Math.cm to 1.4×10.sup.11 Ω.Math.cm, but is still above 10.sup.12 Ω.Math.cm at 100° C., which shows that this material has good insulating properties. The relationship between the electric field and the electric polarization of the ceramic material was measured by a TF-2000 ferroelectric analyzer, and the energy storage density and energy storage efficiency of the ceramic material were calculated by Origin software.

Example 2

(32) BaTiO.sub.3, SrTiO.sub.3, TiO.sub.2 Bi.sub.2O.sub.3, MgO, Al.sub.2O.sub.3, CaCO.sub.3 and SiO.sub.2 were weighed according to the formula of 0.25BaTiO.sub.3+0.20SrTiO.sub.3+0.13TiO.sub.2+0.036Bi.sub.2O.sub.3+0.33MgO+0.012Al.sub.2O.sub.3+0.04CaO+0.002SiO.sub.2, and then subjected to the same process as in Example 1 except that the holding time of sintering was 4 hours, to obtain the ceramic material. FIG. 10 shows the temperature dependence of dielectric constant and dielectric loss of the ceramic material in the example. It can be seen that the dielectric constant of the ceramic material is about 1,020, and the dielectric loss is about 0.0024 at room temperature and 1 kHz. As the temperature increases from −50° C., the dielectric constant decreases gradually. FIG. 11 shows a variation in permittivity with temperature of the ceramic material prepared in the example. It can be seen that the variation in permittivity of the ceramic material ranges are from +4.6 to −4.7 (at −0° C. to 40° C.) and +10.58 to −15.4 (at −30° C. to 85° C.). The dielectric strength at room temperature is 43.7 kV/mm at 1 mm, and 52.3 kV/mm at 0.38 mm, respectively.

Example 3

(33) BaTiO.sub.3, SrTiO.sub.3, TiO.sub.2 Bi.sub.2O.sub.3, MgO, Al.sub.2O.sub.3, CaCO.sub.3 and SiO.sub.2 were weighed according to the formula of 0.28BaTiO.sub.3+0.23 SrTiO.sub.3+0.15TiO.sub.2+0.04Bi.sub.2O.sub.3+0.245MgO+0.013Al.sub.2O.sub.3+0.04CaO+0.002SiO.sub.2, and then subjected to the same process as in Example 1 except that the holding time of sintering was 4 hours, to obtain the ceramic material. FIG. 12 shows the temperature dependence of dielectric constant and dielectric loss of the ceramic material in the example. It can be seen that the dielectric constant of the ceramic material is about 1,228, and the dielectric loss is about 0.0004 at room temperature and 1 kHz. As the temperature increases from −50° C., the dielectric constant decreases gradually. FIG. 13 shows a variation in permittivity with temperature of the ceramic material prepared in the example. It can be seen that the variation in permittivity of the ceramic material are from +5.0 to −4.9 (at −0° C. to 40° C.) and +11.67 to −15.7 (at −30° C. to 85° C.). The dielectric strength at room temperature is 38.4 kV/mm at 1 mm, and 48.7 kV/mm at 0.38 mm, respectively.

Example 4

(34) BaTiO.sub.3, SrTiO.sub.3, TiO.sub.2 Bi.sub.2O.sub.3, MgO, Al.sub.2O.sub.3, CaCO.sub.3 and SiO.sub.2 were weighed according to the formula of 0.412BaTiO.sub.3+0.275SrTiO.sub.3+0.16TiO.sub.2+0.055Bi.sub.2O.sub.3+0.04MgO+0.055CaO+0.003SiO.sub.2, and then subjected to the same process as in Example 1 except that the temperature and holding time of sintering were 1,260° C. and 4 hours, to obtain the ceramic material. FIG. 14 shows the temperature dependence of dielectric constant and dielectric loss of the ceramic material in the example. It can be seen that the dielectric constant of the ceramic material is about 1,385, and the dielectric loss is about 0.0021 at room temperature and 1 kHz. As the temperature increases from −50° C., the dielectric constant decreases gradually. FIG. 15 shows a variation in permittivity with temperature of the ceramic material prepared in the example. It can be seen that the variation in permittivity of the ceramic material is from +4.2 to −6.4 (at −0° C. to 40° C.) and +6.90 to −22.36 (at −30° C. to 85° C.). The dielectric strength at room temperature is 35.8 kV/mm at 1 mm, and 44.4 kV/mm at 0.38 mm, respectively.

Example 5

(35) BaTiO.sub.3, SrTiO.sub.3, TiO.sub.2 Bi.sub.2O.sub.3, MgO, Al.sub.2O.sub.3, CaCO.sub.3 and SiO.sub.2 were weighed according to the formula of 0.466BaTiO.sub.3+0.25SrTiO.sub.3+0.12TiO.sub.2+0.06Bi.sub.2O.sub.3+0.04MgO+0.06CaO+0.004SiO.sub.2, and then subjected to the same process as in Example 1 except that the temperature and holding time of sintering were 1,250° C. and 4 hours, to obtain the ceramic material. FIG. 16 shows the temperature dependence of dielectric constant and dielectric loss of the ceramic material in the example. It can be seen that the dielectric constant of the ceramic material is about 1,611, and the dielectric loss is about 0.0016 at room temperature and 1 kHz. As the temperature increases from −50° C., the dielectric constant decreases gradually. FIG. 17 shows a variation in permittivity with temperature of the ceramic material prepared in the example. It can be seen that the variation in permittivity of the ceramic material is from +6.4 to −5.8 (at −0° C. to 40° C.) and +12.85 to −19.35 (at −30° C. to 85° C.). The dielectric strength at room temperature is 30.5 kV/mm at 1 mm, 38.2 kV/mm at 0.38 mm, respectively.

(36) TABLE-US-00001 TABLE 1 Dielectric Properties of the Barium Strontium Titanate Based Dielectric Ceramic Sheets (Diameter 30 mm) Prepared in Examples 1-5 Dielectric Dielectric Variation of Variation of Dielectric Dielectric Strength (kV/ Strength (kV/ Permittivity Permittivity Constant Loss mm at 1 mm) mm at 0.38 mm) with Temperature with Temperature (25° C., (25° C., Electrode Electrode (0° C. to (−30° C. to Example 1 kHz) 1 kHz) Φ = 8 mm Φ = 1.5 mm 40° C.) 85° C.) 1 1080 0.0015 40.5 51.6 +4.8 to −4.7 +10.87 to −15.6 2 1020 0.0024 43.7 52.3 +4.6 to −4.7 +10.58 to −15.4 3 1228 0.0004 38.4 48.7 +5.0 to −4.9 +11.67 to −15.7 4 1385 0.0021 35.8 44.4 +4.2 to −6.4  +6.90 to −22.36 5 1611 0.0016 30.5 38.2 +6.4 to −5.8  +12.85 to −19.35

(37) In the material system of the present application, the contents of BaTiO.sub.3, SrTiO.sub.3, MgO and Al.sub.2O.sub.3 largely regulate the dielectric constant of the ceramic material. Especially, the dielectric constant of the ceramic material increases with the increase in BaTiO.sub.3 content. The dielectric constant of the ceramic material decreases with the increase in MgO and Al.sub.2O.sub.3. The content of TiO.sub.2, Bi.sub.2O.sub.3 and CaO determines the broadening degree of dielectric Curie peak, that is, the temperature stability of dielectric properties of the ceramic material. From the examples, it can be seen that the comprehensive influence of the contents of BaTiO.sub.3, SrTiO.sub.3, MgO and Al.sub.2O.sub.3 largely regulates the dielectric constant of the ceramic material.

(38) The above examples show that the material system of the present application can be used to prepare ceramic materials with high dielectric constant, high dielectric strength and high dielectric stability. The dielectric strength of the prepared ceramic materials is as high as 52 kV/mm, the dielectric constant can be adjusted between 800 and 2,000, the dielectric loss is less than 0.003 (at 1 kHz), the variation in permittivity with temperature is 7% or less (0° C. to 40° C.), and the frequency stability is good. The material also has the advantages of being lead free and environmentally friendly, having a simple preparation process, etc. It is very suitable for high frequency capacitors, UHV capacitors, solid-state pulse forming lines and other components, and has great application value in the field of high power and pulse power.

(39) It should be understood that the embodiments herein are illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description preceding them, and all changes that fall within metes and bounds of the claims, or equivalence of such metes and bounds thereof are therefore intended to be embraced by the claims.