CN111170735A - Ceramic material with high electric energy storage efficiency and preparation method thereof - Google Patents
Ceramic material with high electric energy storage efficiency and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ceramic material with high electric energy storage efficiency and a preparation method thereof, belongs to the technical field of electronic ceramic materials, overcomes the problems of low electric energy storage efficiency and serious energy waste of energy storage ceramics in the prior art, and prepares a product with high electric energy storage efficiency, good chemical uniformity and good electrical stability. The electronic ceramic material of the invention has the chemical composition of (1-x) ((1-y) BaTiO3‑y(Bi0.5Na0.5)TiO3)‑xSr(Sc0.5Nb0.5)O3Wherein x is 0.05-0.15 and y is 0.35. The product of the invention has high repeatability, uniform internal crystal grain size, high chemical uniformity and electrical uniformity, and high energy storage efficiency. When the intensity of an applied electric field of the energy storage ceramic material prepared by the method is 175 kV/cm, the maximum energy storage efficiency is 91%, and the energy storage density is 1.63J/cm for carrying out thin-wall high-speed dry-mass dry. The energy storage ceramic material prepared by the invention can be applied to high powerAnd the high-stability electronic pulse component has great practical value and economic value.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a ceramic material with high electric energy storage efficiency and a preparation method thereof.
Background
The pulse power capacitor manufactured based on the energy storage ceramic material has the advantages of high power density, high charging and discharging speed, cyclic aging resistance, suitability for extreme environments such as high temperature and high pressure and the like, and plays a key role in a power electronic system. The high energy storage density ceramic capacitor can be used as an inverter of a new energy power generation system or an electric automobile; the pulse current of ultrahigh loads such as tanks, electromagnetic guns, electrified transmitting platforms and comprehensive full-electric propulsion naval vessels can be supplied in a very short time; can be used as a driving element of a particle accelerator, a microwave, a laser, a spacecraft and other high-power emitting devices. The method has large market demand and wide industrialization prospect. The development of the ceramic material with high electric energy storage efficiency can improve the utilization efficiency of energy, and the development of a novel lead-free energy storage ceramic material with high performance meets the requirement of energy utilization in a new period, and creates opportunities for the research and development of the energy storage ceramic material.
The chemistry of the material is decisive for the properties of the material. The optimization of the properties of the ceramic material is realized by changing the formula components of the ceramic material. At present, the energy storage electronic ceramic material mainly comprises a lead base (Pb-), a barium titanate base (BT-), a bismuth sodium titanate base (BNT-), a bismuth ferrite base (BF-), a potassium sodium niobate base (KNN-), a silver niobate base (AN-) and the like.
The energy storage density of the lead-based energy storage electronic ceramic is high (more than 2J/cm) in the process of carrying out high-yield. The bismuth sodium titanate-based energy storage ceramic is limited by a large coercive field and high remanent polarization, the energy storage efficiency is generally lower than 75%, and the energy storage density is generally smaller than 2J/cm for carrying out thin-wall transformation. Bismuth ferrite due to Fe3+The existing method has the defects of serious leakage conduction, difficult compact sintering, lower breakdown voltage, low energy storage density and lower efficiency. The potassium-sodium niobate-based energy storage ceramic has high requirements on preparation conditions due to a narrow sintering temperature window, and the energy storage efficiency of the potassium-sodium niobate-based energy storage ceramic is lower than 65 percent in the existing research. The silver niobate-based energy storage ceramic raw material needs silver oxide, has high price and higher cost, and the antiferroelectric material has large electrostrictive effect,is not advantageous for application in energy storage devices. In view of the above, energy storage ceramic materials with high electrical energy storage efficiency have yet to be developed in the art.
Disclosure of Invention
The invention aims to provide a ceramic material with high electric energy storage efficiency and a preparation method thereof, the formula components are novel, the prepared sample has good chemical uniformity and uniform crystal grain distribution, can bear large external voltage, can release large electric energy density and has ultrahigh electric energy storage efficiency.
The technical scheme adopted by the invention is as follows:
a ceramic material with high electric energy storage efficiency has a chemical composition of (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3And x and y represent the molar ratio in the ceramic system, wherein x is 0.05-0.15 and y is 0.35.
The preparation method of the ceramic material with high electric energy storage efficiency comprises the following steps:
1) for (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3The chemical proportion of the components of the formula is calculated, and then high-purity Bi is weighed2O3、、Na2CO3、BaCO3、SrCO3、Sc2O3、TiO2And Nb2O5Adding absolute ethyl alcohol into the raw material powder, fully ball-milling to obtain a uniform mixture, and drying in a drying oven;
2) sieving the powder prepared in the step 1), pre-sintering at 880-920 ℃, naturally cooling to room temperature, discharging, ball-milling again, and drying to obtain powder;
3) adding polyvinyl alcohol into the powder obtained in the step 2), uniformly mixing, and pressing into round blank sheets under the pressure of 150MPa by using a powder tablet press;
4) and (3) insulating the round blank sheet prepared in the step 3) at 600 ℃ to discharge internal organic matters, and then heating to 1140-1180 ℃ at a certain rate to perform high-temperature sintering to prepare the ceramic material with high electric energy storage efficiency.
Further, in the step 4), the heat preservation time at 600 ℃ is 4 h, the heat preservation time during sintering at 1140-1180 ℃ is 4 h, and the heating rate is 3 ℃/min.
Further, in the step 1), the rotating speed of the ball mill is 340 r/min, the ball milling time is 24 hours, and the temperature of the drying oven is set to be 80 ℃; in the step 2), the powder is placed in a high-purity alumina crucible during pre-sintering, and the heat preservation time is 2 hours.
Further, in the step 3), the concentration of the polyvinyl alcohol solution is 5%, and the adding amount is 6% -7%.
The invention has the following advantages:
the energy storage ceramic prepared by the solid-phase sintering method is greatly improved in electric energy storage efficiency compared with the existing energy storage ceramic capacitor. The sample prepared by the process flow can synthesize high-performance ceramic material at high temperature without vacuum and high-pressure synthesis conditions, and the ceramic material has uniform grain size, high chemical uniformity and high electrical uniformity. When the intensity of an external electric field of the ceramic material prepared by the method is 175 kV/cm, the maximum energy storage efficiency is 91%, and the energy storage density is 1.63J/cm for carrying out thin-wall high-speed dry-mass dry-. The energy storage ceramic material prepared by the invention has technical innovation and breakthrough in performance in terms of components and performance, can be completely applied to high-power and high-stability electronic pulse components, and has great practical value and economic value.
Drawings
FIG. 1 shows the energy storage ceramic of 0.90(BT-35BNT) -0.10SSN in example 1X-A ray diffraction pattern;
FIG. 2 is a microstructure of the 0.90(BT-35BNT) -0.10SSN energy storage ceramic of example 1;
FIG. 3 is a hysteresis loop of the BT-35BNT energy storage ceramic in example 2;
FIG. 4 is a graph of the hysteresis loop of the 0.85(BT-35BNT) -0.15 SSN energy storage ceramic obtained in example 3 at 1180 ℃;
FIG. 5 is a dielectric thermogram of the 0.90(BT-35BNT) -0.10SSN energy storage ceramic of example 4 at a sintering temperature of 1170 ℃;
FIG. 6 is a hysteresis curve diagram of the 0.90(BT-35BNT) -0.10SSN energy storage ceramic in example 4 at a sintering temperature of 1170 ℃.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific embodiments.
The invention relates to a ceramic material with high electric energy storage efficiency and a preparation method thereof, and the chemical composition of the formula is (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3The material is prepared by a solid-phase sintering method.
The method comprises the following steps:
1. weighing raw materials
According to (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3The chemical composition of (A) is calculated according to the stoichiometric proportion, and high-purity Bi is weighed2O3、Na2CO3、BaCO3、SrCO3、Sc2O3、TiO2And Nb2O5Raw material powder.
2. Ball milling and drying:
placing the raw material mixed powder into a ball milling tank, adding absolute ethyl alcohol, ball milling for 24 h on a planetary ball mill, taking out, and placing in a drying oven 80 DEGoAnd C, drying.
3. Pre-sintering:
placing the powder after ball milling and drying in a high-purity alumina crucible, and putting the crucible in a high-temperature sintering furnace 880-920oAnd C, pre-sintering. The heat preservation time of the pre-sintering is 2 hours.
4. Granulating and tabletting:
and ball-milling the pre-sintered powder for 24 hours again, drying, adding 7 wt% of PVA for granulation, then applying 150MPa of pressure on a tablet press, and carrying out compression molding to obtain a wafer with the diameter of 12 mm and the thickness of 1.2-1.5 mm.
5. And (3) high-temperature sintering:
pressing the wafer at 600oC, preserving heat for 4 h, discharging glue, and putting in a high-temperature sintering furnace 1140-1180oAnd C, sintering. The heat preservation time of the high-temperature sintering is 4 hours. And after sintering, cooling the sample to room temperature along with the furnace to obtain the ceramic material with high electric energy storage efficiency.
The method of the present invention is a conventional method unless otherwise specified. The raw material powder and the purity of BaCO used in the invention3(99%)、Na2CO3(99.99%)、SrCO3(99%)、Bi2O3(99%)、Sc2O3(99.99%)、TiO2(99%) and Nb2O5(99.99%) were purchased from the national pharmaceutical group chemical reagents, Inc. The energy density and energy efficiency data related to the invention are from polarization-electric field intensity (measured by Agilent ferroelectric comprehensive analyzer)P-E) And calculating a curve.
Example 1
The chemical composition is 0.90(0.65 BaTiO)3-0.35(Bi0.5Na0.5)TiO3) -0.10Sr(Sc0.5Nb0.5)O3The formula of the energy storage ceramic comprises the steps of weighing high-purity raw materials according to a stoichiometric proportion, adding absolute ethyl alcohol, carrying out ball milling in a planetary ball mill for 24 hours, and drying to obtain a mixed material. Then the mixed material is placed in a sintering furnace for sintering at 900 DEGoPre-sintering for 2 h under C, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, adding 7 wt% of polyvinyl alcohol solution, uniformly mixing in a mortar, and pressing by compression molding to obtain a wafer with the diameter of 12 mm and the thickness of 1.5 mm. The pressed wafer was sintered in a sintering furnace at 600 foC, keeping the temperature for 4 hours, and removing glue by 3oThe temperature is raised to 1170 at the temperature rise rate of C/minoC, sintering and keeping the temperature for 4 hours. After sintering, the ceramic material is naturally cooled to room temperature along with the furnace to obtain the 0.90(BT-35BNT) -0.10SSN ceramic material with high electric energy storage efficiency.
The crystal phase structure of the sintered sample was measured by an X-ray diffractometer (D2 Phaser, Bruker), and as shown in FIG. 1, the crystal structure of the sample exhibited a typical perovskite pseudo-cubic structure, and no diffraction peaks of other hetero-phases. The surface topography scanning electron microscope image of the obtained energy storage ceramic is shown in figure 2, and the ceramic crystal grain structure is arranged compactly and has good crystallinity.
Example 2
The chemical composition is 0.65BaTiO3-0.35(Bi0.5Na0.5)TiO3The formula of the method comprises the steps of weighing high-purity raw materials according to a stoichiometric proportion, adding absolute ethyl alcohol, carrying out ball milling in a planetary ball mill for 24 hours, and drying to obtain a mixed material. Then the mixed material is placed in a sintering furnace for sintering at 900 DEGoPre-sintering for 2 h under C, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, adding 7 wt% of polyvinyl alcohol solution, uniformly mixing in a mortar, and pressing by compression molding to obtain a wafer with the diameter of 12 mm and the thickness of 1.5 mm. The pressed wafer was sintered in a sintering furnace at 600 foC, keeping the temperature for 4 hours, and removing glue by 3oIncreasing the temperature to 1160 degree C/minoC, sintering and keeping the temperature for 4 hours. And after sintering, naturally cooling to room temperature along with the furnace to obtain the energy storage ceramic.
Measuring the polarization curve by Agilent ferroelectric analyzer according to the formulas (1), (2), (3)ηThe energy storage characteristics of the BT-35BNT sample in example 2 were calculated. As shown in FIG. 3, when the electric field strength is 105 kV/cm, the maximum polarization of the sample is 39.71 pC/N, the residual polarization is 29.82 pC/N, the maximum energy storage efficiency is 13.5%, and the energy storage density is 0.37J/cm.
Example 3
The chemical composition is 0.85(0.65 BaTiO)3-0.35(Bi0.5Na0.5)TiO3) -0.15Sr(Sc0.5Nb0.5)O3The formula of the method comprises the steps of weighing high-purity raw materials according to a stoichiometric proportion, adding absolute ethyl alcohol, carrying out ball milling in a planetary ball mill for 24 hours, and drying to obtain a mixed material. The mixture is then placed in a sintering furnace for sintering at 920oPre-sintering for 2 h under C, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, adding 7 wt% of polyvinyl alcohol solution, uniformly mixing in a mortar, and pressing by compression molding to obtain a wafer with the diameter of 12 mm and the thickness of 1.5 mm. The pressed wafer was sintered in a sintering furnace at 600 foC, keeping the temperature for 4 hours, and removing glue by 3oThe temperature is increased to 1180 at the temperature rising rate of C/minoC, sintering and keeping the temperature for 4 hours. After sinteringAnd naturally cooling the furnace to room temperature to obtain the 0.85(BT-35BNT) -0.15 SSN energy storage ceramic.
And measuring a polarization curve graph by using an Agilent ferroelectric analyzer, and calculating to obtain the energy storage characteristics of the sample in the embodiment 3. As shown in FIG. 4, the applied electric field strength was 190 kV/cm, the maximum polarization of the sample was 16.06 pC/N, the residual polarization was 0.56 pC/N, and the electric energy storage efficiency was 92.70%.
Example 4
The chemical composition is 0.90(0.65 BaTiO)3-0.35(Bi0.5Na0.5)TiO3) -0.10Sr(Sc0.5Nb0.5)O3The formula of the energy storage ceramic comprises the steps of weighing high-purity raw materials according to a stoichiometric proportion, adding absolute ethyl alcohol, carrying out ball milling in a planetary ball mill for 24 hours, and drying to obtain a mixed material. The mixture is then placed in a sintering furnace for sintering at 920oPre-sintering for 2 h under C, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, adding 7 wt% of polyvinyl alcohol solution, uniformly mixing in a mortar, and pressing by compression molding to obtain a wafer with the diameter of 12 mm and the thickness of 1.5 mm. The pressed wafer was sintered in a sintering furnace at 600 foC, keeping the temperature for 4 hours, and removing glue by 3oThe temperature is raised to 1170 at the temperature rise rate of C/minoC, sintering and keeping the temperature for 4 hours. And after sintering, naturally cooling to room temperature along with the furnace to obtain the 0.90(BT-35BNT) -0.10SSN energy storage ceramic.
The dielectric properties were measured using an HP4980A analyzer at 10kHz, 100kHz, 1000kHz, and a test temperature range of-160 kHzoCTo 200oCAs can be seen from fig. 5, the dielectric constant of the sample has dispersion, the relaxation characteristic is obvious, and the dielectric loss is small at different test frequencies.
The ferroelectric property of the sample was measured by an Agilent ferroelectric analyzer at a frequency of 10 Hz, as shown in FIG. 6, when the applied electric field strength was 175 kV/cm, the maximum polarization of the sample was 24.54 pC/N, the remanent polarization was 1.51 pC/N, the energy storage density was 1.63J/cm, and the maximum energy storage efficiency was 91%.
In consideration of the above, the embodiment 4 is the best embodiment, and the energy storage ceramic material prepared by the method has large energy storage density and storage efficiency.
The above embodiments are merely illustrative of the principles and effects of the present invention, and it will be apparent to those skilled in the art that the present invention can be implemented by making several values and modifications within the upper and lower limits of the ceramic formulation and sintering temperature range of the present invention without departing from the inventive concept of the present invention, and these values and modifications are included in the scope of the present invention.
Claims (5)
1. A ceramic material with high electric energy storage efficiency is characterized in that the chemical composition of the ceramic material is (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3And x and y represent the molar ratio in the ceramic system, wherein x is 0.05-0.15 and y is 0.35.
2. The method of preparing a high electrical energy storage efficiency ceramic material of claim 1, comprising the steps of:
1) for (1-x) ((1-y) BaTiO3-y(Bi0.5Na0.5)TiO3)-xSr(Sc0.5Nb0.5)O3The chemical proportion of the components of the formula is calculated, and then high-purity Bi is weighed2O3、、Na2CO3、BaCO3、SrCO3、Sc2O3、TiO2And Nb2O5Adding absolute ethyl alcohol into the raw material powder, fully ball-milling to obtain a uniform mixture, and drying in a drying oven;
2) sieving the powder prepared in the step 1), pre-sintering at 880-920 ℃, naturally cooling to room temperature, discharging, ball-milling again, and drying to obtain powder;
3) adding polyvinyl alcohol into the powder obtained in the step 2), uniformly mixing, and pressing into round blank sheets under the pressure of 150MPa by using a powder tablet press;
4) and (3) insulating the round blank sheet prepared in the step 3) at 600 ℃ to discharge internal organic matters, and then heating to 1140-1180 ℃ at a certain rate to perform high-temperature sintering to prepare the ceramic material with high electric energy storage efficiency.
3. The method for preparing a ceramic material with high electric energy storage efficiency according to claim 2, wherein in the step 4), the holding time at 600 ℃ is 4 h, the holding time at 1140-1180 ℃ for sintering is 4 h, and the heating rate is 3 ℃/min.
4. The preparation method of the ceramic material with high electric energy storage efficiency according to claim 1 or 2, characterized in that in the step 1), the rotation speed of the ball mill is 340 r/min, the ball milling time is 24 h, and the temperature of the drying oven is set to 80 ℃; in the step 2), the powder is placed in a high-purity alumina crucible during pre-sintering, and the heat preservation time is 2 hours.
5. The method for preparing a ceramic material with high electric energy storage efficiency according to claim 4, wherein in the step 3), the polyvinyl alcohol solution has a concentration of 5% and is added in an amount of 6% -7%.
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