CN108439975B - Strontium calcium titanate-based energy storage ceramic with stable defect structure and preparation method thereof - Google Patents

Strontium calcium titanate-based energy storage ceramic with stable defect structure and preparation method thereof Download PDF

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CN108439975B
CN108439975B CN201810476938.9A CN201810476938A CN108439975B CN 108439975 B CN108439975 B CN 108439975B CN 201810476938 A CN201810476938 A CN 201810476938A CN 108439975 B CN108439975 B CN 108439975B
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曹明贺
周亮
刘韩星
郝华
尧中华
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Wuhan University of Technology WUT
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Abstract

The invention relates to a strontium calcium titanate based energy storage ceramic with a stable defect structure and a preparation method thereof. It is substituted by Sr0.98Ca0.02TiO3Ceramic is a matrix material, and a certain amount of Nb is introduced through Ti sites; meanwhile, a trace amount of Mn is introduced into the Ti site to form an expression of Sr0.98Ca0.02Ti0.97‑xMnxNb0.03O3The ceramic system according to (1), wherein x is 0.003 to 0.009. The ceramic system has the characteristics of higher breakdown strength, larger energy storage density and the like on the basis of ensuring certain dielectric property. Preparation process with CaCO3、SrCO3、TiO2、Nb2O5And MnCO3As raw material, according to the chemical formula Sr0.98Ca0.02Ti0.97‑xMnxNb0.03O3Weighing and proportioning x ═ 0.003-0.009 in a stoichiometric ratio, mixing, ball-milling, drying, presintering at 1100-1150 ℃, performing secondary ball-milling to obtain presintering powder, sieving the presintering powder, adding an adhesive, granulating, tabletting and forming, discharging glue to obtain a ceramic blank, and performing heat preservation and sintering on the ceramic blank in the air at 1400-1460 ℃ to obtain a ceramic block.

Description

Strontium calcium titanate-based energy storage ceramic with stable defect structure and preparation method thereof
Technical Field
The invention relates to a strontium calcium titanate based energy storage ceramic with a stable defect structure and a preparation method thereof.
Background
Due to the continuous development of the electronic industry and the large application of electronic equipment, the high-voltage ceramic capacitor is one of the electronic equipment which is widely applied, namely the high-voltage ceramic capacitor can be seen everywhere in a voltage-multiplying rectifying circuit in a display and a high-voltage power supply of a laser, a radar and an electron microscope. The high breakdown strength can improve the application range and the service life of the ceramic capacitor; the high dielectric constant can realize the miniaturization and the light weight of electronic components; low dielectric losses may reduce power consumption. In order to meet the market demands, improvements in doping, process optimization and the like are needed to ensure that the dielectric performance is ensured and the breakdown strength is improved at the same time.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a method for preparing Sr0.98Ca0.02TiO3The ceramic is co-doped with Nb and Mn to obtain Sr0.98Ca0.02Ti0.97-xMnxNb0.03O3A dielectric ceramic material. The calcium strontium titanate-based ceramic material with a stable defect structure is formed by doping calcium strontium titanate ceramic with a proper amount of aliovalent ions, and has high breakdown strength and high energy storage density.
The second technical problem to be solved by the present invention is to provide the above-mentioned Sr with stable defect structure0.98Ca0.02TiO3The preparation method of the base energy storage ceramic material has the advantages of low cost, simple process and repeatability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
sr with stable defect structure0.98Ca0.02TiO3The base energy storage ceramic material is characterized in that: expression is Sr0.98Ca0.02Ti0.97-xMnxNb0.03O3Wherein x is 0.003-0.009.
Sr with stable defect structure0.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: with CaCO3、SrCO3、TiO2、MnCO3And Nb2O5As raw material, according to the chemical formula Sr0.98Ca0.02Ti0.97-xMnxNb0.03O3Weighing and proportioning in a stoichiometric ratio of x ═ 0.003-0.009, mixing, ball-milling, drying, presintering at 1000-1150 ℃, ball-milling for the second time to obtain presintering powder, sieving the presintering powder, adding an adhesive, granulating, forming, discharging glue to obtain a ceramic blank, and sintering the ceramic blank in air at 1400-1460 ℃ in a heat preservation manner to obtain the ceramic.
According to the scheme, the ball milling is carried out for 22-24 hours in a wet method in a ball milling tank by taking absolute ethyl alcohol as a solvent and zirconia balls as a ball milling medium.
According to the scheme, the drying is to dry the powder subjected to wet ball milling for 22 to 24 hours at the temperature of between 100 and 120 ℃ until the powder is dried for later use.
According to the scheme, the adhesive for granulation is 1-2.5 wt.% of polyvinyl alcohol solution.
According to the scheme, the diameter of the formed blank is 12mm, and the thickness of the formed blank is 1 mm; the glue discharging temperature is 550-650 ℃.
According to the scheme, the heat-preservation sintering time is 2-4 h.
According to the scheme, the temperature rising rate of the discharged glue is 1-2 ℃/min.
According to the scheme, the CaCO3、TiO2、SrCO3And MnCO3Purity greater than 99%, Nb2O5The purity is more than 99.5 percent, and the grain diameter is in nanometer level.
Introducing a certain amount of donor ions Nb through Ti sites; meanwhile, a trace amount of acceptor ions Mn are introduced into the Ti site to form an expression of Sr0.98Ca0.02Ti0.97-xMnxNb0.03O3The ceramic system according to (1), wherein x is 0.003 to 0.009. Based on the co-doping of a proper amount of Nb and Mn and the effects of reducing sintering temperature and leakage conduction with trace Mn, the breakdown strength and energy storage density of the ceramic are improved.
The invention has the following beneficial effects:
(1) the invention adopts a proper amount of Nb and Mn co-doped Sr0.98Ca0.02TiO3Ceramics, Nb replacing Ti to form Ti4+E, Mn instead of Ti
Figure BDA0001664722590000021
Ti4+E and
Figure BDA0001664722590000022
formed in the ceramic
Figure BDA0001664722590000023
However, the concentration of such a defective dipole is unstable when it reaches a certain value, and a slight electric field generates a large amount of free electrons, which is not favorable for the breakdown strength of the ceramic. The invention can generate appropriate concentration by selecting appropriate amount of Nb and Mn for doping
Figure BDA0001664722590000024
The defect dipole is stably present in the ceramic, the material has a relatively stable defect structure, and the dielectric constant of the doped ceramic is increased from 290 in an undoped state to 510(x is 0.006). Mn formed by selecting a trace amount of Mn ions as acceptor ions to replace TiTiCan also be used with
Figure BDA0001664722590000025
Form a
Figure BDA0001664722590000026
Defective dipole, suppression
Figure BDA0001664722590000027
So as to reduce the ionic conductance and improve the insulating property of the ceramic, and the breakdown strength of the ceramic is improved from 23kV/mm to 30.7 kV/mm. However, when the amount of Mn is high, excessive Mn accumulates at the grain boundaries, so that a large amount of Mn appears at the grain boundaries
Figure BDA0001664722590000028
This lowers the resistivity at the grain boundary, and deteriorates the insulation of the ceramic, thereby lowering the breakdown strength. In addition, the proper amount of Mn doping reduces the current density response of the ceramic sample under the action of an electric field along with the increase of time, thereby reducing the ceramicThe energy storage efficiency can be improved by the action of leakage conduction, so that the energy storage density is from 0.630J/cm3Lifting to 0.981J/cm3
(2) The invention adopts a proper amount of Nb and Mn co-doped Sr0.98Ca0.02TiO3The ceramic can reduce the sintering temperature of the ceramic, has better compactness, obviously reduces the grain size (from 21.2 mu m to 0.38 mu m), and has simple preparation process, low cost and good repeatability.
Drawings
FIG. 1 is an XRD pattern of ceramics according to examples 1 to 3 of the present invention and comparative examples 1 and 2.
FIG. 2 is a graph showing the hysteresis loop of ceramics of examples 1 to 3 of the present invention and ceramics of comparative example 2.
FIG. 3 is an SEM image of a ceramic of comparative example 1 of the present invention.
FIG. 4 is an SEM image of a comparative example 2 ceramic of the present invention.
FIG. 5 is an SEM image of a ceramic of example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples for better understanding of the objects and advantages of the present invention, but the present invention is not limited to the examples below, and any modifications based on the present invention are within the scope of the present invention.
Example 1
With a purity of more than 99% CaCO3、TiO2、SrCO3、MnCO3And Nb with a purity of more than 99.5%2O5As raw material, according to the chemical formula Sr0.98Ca0.02Ti0.967Mn0.003Nb0.03O3Weighing and proportioning, and ball-milling for 24 hours in a ball-milling tank by respectively taking absolute ethyl alcohol as a solvent and zirconia balls as a ball-milling medium; then, drying the powder subjected to wet ball milling for 24 hours at 100 ℃ until the powder is dried, putting the powder into an alumina crucible for presintering for 2 hours at 1100 ℃, and sieving with a 100-mesh sieve after secondary ball milling and drying; then respectively adding 2.5 wt.% of binder for granulation, dry-pressing to form a blank body with the diameter of 12mm and the thickness of 1mm, heating to 600 ℃ at the heating rate of 1 ℃/min, preserving the heat for 2 hours, and discharging the glue to obtain the raw materialA green body; the raw material green body is subjected to heat preservation for 2 hours at 1460 ℃ in a muffle furnace to obtain Sr0.98Ca0.02Ti0.967Mn0.003Nb0.03O3A ceramic.
Sr in the above example0.98Ca0.02Ti0.967Mn0.003Nb0.03O3The XRD measured on the ceramic is shown in figure 1, wherein the prepared ceramic has no change in structure and no second phase is generated;
the energy storage density of each ceramic is obtained by integrating curves in a test result shown in fig. 2 through testing the P-E (change of polarization intensity along with the change of electric field intensity) curve of the ceramic.
And (3) testing results: sr0.98Ca0.02Ti0.967Mn0.003Nb0.03O3The ceramic dielectric constant is 408; the breakdown strength is 30.7 kV/mm; the discharge energy storage density is 0.793J/cm3
Example 2
This example provides Sr0.98Ca0.02Ti0.964Mn0.006Nb0.03O3The preparation method of the ceramic is the same as that of the example 1 except for the following different experimental steps;
in example 1, Sr is given according to the formula0.98Ca0.02Ti0.964Mn0.006Nb0.03O3Weighing and proportioning; drying the powder subjected to wet ball milling at 100 ℃ for 24 hours until the powder is dried, putting the powder into an alumina crucible to presintered at 1150 ℃ for 2 hours, and sieving the powder with a 100-mesh sieve after secondary ball milling and drying; the raw material blank is subjected to heat preservation for 2 hours at 1440 ℃ in a muffle furnace to obtain Sr0.98Ca0.02Ti0.964Mn0.006Nb0.03O3A ceramic.
Sr in the above example0.98Ca0.02Ti0.967Mn0.003Nb0.03O3The XRD measured on the ceramic is shown in figure 1, wherein the prepared ceramic has no change in structure and no second phase is generated;
sr in the above example0.98Ca0.02Ti0.964Mn0.006Nb0.03O3The dielectric constant of the ceramic sample was 514; the breakdown strength is 27.4 kV/mm; the discharge energy storage density is 0.977J/cm3
Example 3
This example provides Sr0.98Ca0.02Ti0.961Mn0.009Nb0.03O3The preparation method of the ceramic is the same as that of the example 1 except for the following different experimental steps;
in example 1, Sr is given according to the formula0.98Ca0.02Ti0.961Mn0.009Nb0.03O3Weighing and proportioning; drying the powder subjected to wet ball milling at 100 ℃ for 24 hours until the powder is dried, putting the powder into an alumina crucible to presintered at 1150 ℃ for 2 hours, and sieving the powder with a 100-mesh sieve after secondary ball milling and drying; the raw material blank is subjected to heat preservation for 2 hours at 1440 ℃ in a muffle furnace to obtain Sr0.98Ca0.02Ti0.961Mn0.009Nb0.03O3Ceramic samples.
Sr in the above example0.98Ca0.02Ti0.967Mn0.003Nb0.03O3The XRD measured on the ceramic is shown in figure 1, wherein the prepared ceramic has no change in structure and no second phase is generated;
sr in the above example0.98Ca0.02Ti0.961Mn0.009Nb0.03O3The dielectric constant of the ceramic sample is 446; the breakdown strength is 29 kV/mm; the discharge energy storage density is 0.981J/cm3
Comparative example 1
With purity of more than 99 percent of SrCO3、CaCO3And TiO2Raw materials are adopted, and the molar ratio of Sr/Ca/Ti is 0.98: 0.02: 1, weighing and proportioning, and carrying out ball milling for 24 hours in a ball milling tank by taking absolute ethyl alcohol as a solvent and zirconia balls as a ball milling medium; then, drying the powder subjected to wet ball milling for 24 hours at 100 ℃ until the powder is dried, putting the powder into an alumina crucible for presintering for 2 hours at 1100 ℃, and sieving with a 80-mesh sieve after secondary ball milling and drying; then adding 2 wt.% of binder for granulation, and dry-pressing to form granules with diameter of 12mm and thicknessRaising the temperature of a green body with the temperature of 1mm to 600 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours, and discharging the glue to obtain a green body; and (3) preserving the temperature of the green body in a muffle furnace at 1460 ℃ for 2 hours to obtain a ceramic sample. The sintering temperature, breakdown strength and energy storage density of the ceramic are shown in table 1.
Comparative example 2
With a purity of more than 99% CaCO3、TiO2、SrCO3、MnCO3Nb with purity of more than 99.5%2O5Starting material according to the formula Sr0.98Ca0.02Ti0.958Mn0.012Nb0.03O3Weighing and proportioning, and ball-milling for 22 hours in a ball-milling tank by respectively taking absolute ethyl alcohol as a solvent and zirconia balls as a ball-milling medium; then, drying the powder subjected to wet ball milling for 22 hours at 120 ℃ until the powder is dried, putting the powder into an alumina crucible for presintering for 2 hours at 1150 ℃, and sieving with a 100-mesh sieve after secondary ball milling and drying; then respectively adding 2.5 wt.% of binder for granulation, dry-pressing and molding into a green body with the diameter of about 12mm and the thickness of 1mm, heating to 600 ℃ at the heating rate of 1 ℃/min, preserving the heat for 2 hours, and discharging the glue to obtain a raw material green body; and (3) insulating the green body in a muffle furnace at 1460 ℃ for 2h to obtain a ceramic sample.
Sr in the above comparative example0.98Ca0.02Ti0.958Mn0.012Nb0.03O3The dielectric constant of the ceramic sample is 420; the breakdown strength is 23.5 kV/mm; the discharge energy storage density is 0.61J/cm3
Watch 1
Dielectric constant Breakdown strength (kV/mm) Discharge energy storage Density (J/cm)3)
Comparative example 1 290 23.7 0.630
Comparative example 2 520 23.5 0.610
Example 1 408 30.7 0.793
Example 2 514 27.4 0.977
Example 3 446 29 0.981

Claims (8)

1. Sr with stable defect structure0.98Ca0.02TiO3The base energy storage ceramic material is characterized in that: expression is Sr0.98Ca0.02Ti0.97-xMnxNb0.03O3Wherein x is 0.003-0.009.
2. Sr in claim 1 having a stable defect structure0.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: with CaCO3、SrCO3、TiO2、Nb2O5And MnCO3As raw material, according to the chemical formula Sr0.98Ca0.02Ti0.97- xMnxNb0.03O3Weighing and proportioning in a stoichiometric ratio of x ═ 0.003-0.009, mixing, ball-milling, drying, presintering at 1000-1150 ℃, ball-milling for the second time to obtain presintering powder, sieving the presintering powder, adding an adhesive, granulating, forming, discharging glue to obtain a ceramic blank, and sintering the ceramic blank in air at 1400-1460 ℃ in a heat preservation manner to obtain the ceramic.
3. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: the ball milling condition is that absolute ethyl alcohol is used as a solvent, zirconia balls are used as a ball milling medium, and the wet ball milling is carried out in a ball milling tank for 22-24 hours.
4. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: and the drying is to dry the powder subjected to wet ball milling for 22 to 24 hours at the temperature of between 100 and 120 ℃ until the powder is dried for later use.
5. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: the adhesive for granulation is 1-2.5 wt.% of polyvinyl alcohol solution.
6. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: the formed blank body has the diameter of 12mm and the thickness of 1 mm.
7. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: the heat preservation sintering time is 2-4 h.
8. Sr having a stable defect structure according to claim 20.98Ca0.02TiO3The preparation method of the base energy storage ceramic material is characterized by comprising the following steps: the glue discharging temperature is 550-650 ℃; the temperature rise rate of the discharged glue is 1-2 ℃/min.
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