CN111018516A - Barium titanate-based high-energy-density electronic ceramic and preparation method thereof - Google Patents
Barium titanate-based high-energy-density electronic ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to barium titanate-based high-energy storage density electronic ceramic and a preparation method thereof, and the barium titanate-based high-energy storage density electronic ceramic comprises the following steps: sr is2+,Bi3+,Mg2+,Nb5+Ion doping into barium titanate ceramic to form (1-x) Ba(1‑y)SryTiO3‑xBi(Mg2/3Nb1/3)03So that it is within the crossover region; calculating the chemical proportion of the formula components obtained in the step one, and weighing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5And performing ball milling, drying, pre-sintering, tabletting and sintering on the powder to obtain the barium titanate-based high-energy-storage-density electronic ceramic. The invention introduces electric domain engineering, Landau free energy calculation and the like in the component design process, skillfully finds out the cross region, greatly improves the energy storage performance of the ceramic prepared by the solid phase method compared with the prior product,the process flow is simple, the prepared sample has uniform grain size, high chemical uniformity and high electrical uniformity, and high energy storage density and efficiency are shown.
Description
Technical Field
The invention relates to the field of electronic components, in particular to barium titanate-based high-energy-storage-density electronic ceramic and a preparation method thereof.
Background
The pulse power capacitor 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, meets the requirement of energy utilization in a new period, 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 a hybrid electric vehicle; can supply working current with ultra-high load of 100kA for tanks, electromagnetic guns, electrified transmitting platforms, comprehensive full-electric propulsion naval vessels and the like, and the duration time of the formed high-energy pulse is not less than 10-1s; the composite material can be used as a driving element of a particle accelerator, a high-power transmitting device of microwaves, lasers, spacecrafts and the like, and has large market demand and wide industrialization prospect. The element manufacturing enterprises of all countries in the world invest huge investments in research and development of new products, new technologies, new processes, new materials and new equipment of electronic ceramics and elements thereof. The accelerated development of modern science and technology presents a serious challenge to electronic ceramic materials and creates an opportunity for research and development in the field.
At present, starting from the chemical composition of the material, the optimization of the performance of the material is realized by changing the conditions of the preparation and synthesis process. 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 lead-based energy storage electronic ceramic has high energy storage density (more than 2J/cm)3) But the energy storage efficiency is lower (less than 70 percent) and the lead element which is a toxic heavy metal is contained, thus being harmful to the health of human bodies. The bismuth sodium titanate-based energy storage ceramic is limited by large coercive field and high remanent polarization, the energy storage efficiency is generally lower than 75%, and the energy storage density is generally less than 2J/cm3. The bismuth ferrite has low breakdown voltage due to serious leakage conduction, so the energy storage density is less than 1.5J/cm3. The potassium-sodium niobate-based energy storage ceramic has a narrow sintering window, so that the requirement on preparation conditions is high, and the energy storage efficiency is lower than 65%. The silver niobate-based energy storage ceramic raw material needs silver oxide, has high price and high cost, and the prepared productFerroelectric materials have large electrostrictive effect, which is not favorable for application in energy storage devices. The barium titanate-based energy storage ceramic has low raw material price and low preparation condition requirement, is easy to sinter a compact ceramic structure at high temperature, and is easy to obtain higher breakdown voltage, so the barium titanate-based energy storage ceramic is suitable for being applied to a pulse power element with high energy storage density and has higher engineering practical value.
Disclosure of Invention
The invention aims to provide barium titanate-based high-energy-storage-density electronic ceramic and a preparation method thereof. The prepared sample has high energy storage density and efficiency and good temperature stability.
The technical scheme adopted by the invention is as follows:
the preparation method of the barium titanate-based high energy storage density electronic ceramic is characterized by comprising the following steps:
the method comprises the following steps:
the method comprises the following steps: sr is2+,Bi3+,Mg2+,Nb5+Ion doping into barium titanate ceramic to form (1-x) Ba(1-y)SryTiO3-xBi(Mg2/3Nb1/3)03So that it is within the crossover region;
step two: calculating the chemical proportion of the formula components obtained in the step one, and weighing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5And performing ball milling, drying, pre-sintering, tabletting and sintering on the powder to obtain the barium titanate-based high-energy-storage-density electronic ceramic.
In step one, x is 0.10 and y is 0.35.
The ball milling and drying method comprises the following specific steps:
mixing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5Putting the powder into a ball milling tank, adding absolute ethyl alcohol, carrying out ball milling on a planetary ball mill for 24 hours, and then drying.
The pre-sintering comprises the following specific steps:
placing the powder after ball milling and drying in a high-purity alumina crucible, and presintering the powder in a high-temperature sintering furnace at the temperature of 1100 ℃.
The presintering time is 2 h.
The tabletting method comprises the following specific steps:
and ball-milling the pre-sintered powder for 24 hours again, drying, adding 7 wt% of PVA for granulation, applying a pressure of 15MPa on a tablet press, and die-pressing to obtain a wafer with the diameter of 12mm and the thickness of 1.5 mm.
The sintering method comprises the following specific steps:
and (3) preserving the heat of the pressed wafer at 600 ℃ for 4h to remove the glue, sintering the wafer in a high-temperature sintering furnace at 1320 ℃, and cooling the wafer to room temperature along with the furnace to obtain the barium titanate-based high-energy-density electronic ceramic.
The sintering time is 5 h.
The barium titanate-based high energy storage density electronic ceramic prepared by the method.
The invention has the following advantages:
the method introduces electric domain engineering, Landau free energy calculation and the like in the component design process, skillfully finds out the cross region, greatly improves the energy storage performance of the ceramic prepared by the solid phase method compared with the existing product, has simple process flow, and ensures that the prepared sample has uniform grain size, high chemical uniformity and high electrical uniformity, thereby showing high energy storage density and efficiency.
Drawings
FIG. 1 is a schematic diagram of electric domain structure, dielectric and ferroelectric characteristics of a design cross region using electric domain engineering and Landau free energy calculation in the present disclosure;
FIG. 2 is an X-ray diffraction pattern of the barium titanate-based energy storage ceramic of example 1;
FIG. 3 is a surface scanning electron micrograph of the barium titanate-based energy storage ceramic of example 1.
FIG. 4 is a dielectric property spectrum of barium titanate-based energy storage ceramics of examples 1,2 and 3, (1) Ba of example 20.65Sr0.35TiO3Dielectric Properties of ceramics, (2) Ba in example 10.65Sr0.35TiO3-0.10Bi(Mg2/3Nb1/3)O3Dielectric Properties of ceramics, (3) Ba in example 30.65Sr0.35TiO3-0.20Bi(Mg2/3Nb1/3)O3Dielectric properties of the ceramic.
FIG. 5 is a graph comparing unipolar polarization curves for barium titanate-based energy storage ceramics of examples 1,2, and 3.
FIG. 6 is a graph comparing the energy storage density, energy storage efficiency, and breakdown field strength of barium titanate-based energy storage ceramics of examples 1,2, and 3.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method of barium titanate-based high-energy-storage-density electronic ceramic, which takes barium titanate ceramic as an object, is composed according to an electric domain engineering design formula and adopts a solid phase method to prepare the barium titanate-based electronic energy storage ceramic. The prepared sample has high energy storage density and efficiency and good temperature stability. The method specifically comprises the following steps:
the method comprises the following steps: sr is2+,Bi3+,Mg2+,Nb5+Ion doping into barium titanate ceramic to form (1-x) Ba(1-y)SryTiO3-xBi(Mg2/3Nb1/3)03So that it is within the crossover region;
step two: calculating the chemical proportion of the formula components obtained in the step one, and weighing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5And performing ball milling, drying, pre-sintering, tabletting and sintering on the powder to obtain the barium titanate-based high-energy-storage-density electronic ceramic.
In step one, x is 0.10 and y is 0.35.
The ball milling and drying method comprises the following specific steps:
mixing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5Putting the powder into a ball milling tank, adding absolute ethyl alcohol, ball milling for 24 hours on a planetary ball mill, and then dryingAnd (5) drying.
The pre-sintering comprises the following specific steps:
and placing the powder subjected to ball milling and drying in a high-purity alumina crucible, and presintering for 2 hours at 1100 ℃ in a high-temperature sintering furnace. The presintering time is 2 h.
The tabletting method comprises the following specific steps:
and ball-milling the pre-sintered powder for 24 hours again, drying, adding 7 wt% of PVA for granulation, applying a pressure of 15MPa on a tablet press, and die-pressing to obtain a wafer with the diameter of 12mm and the thickness of 1.5 mm.
The sintering method comprises the following specific steps:
and (3) preserving the heat of the pressed wafer at 600 ℃ for 4h to remove the glue, sintering the wafer in a high-temperature sintering furnace at 1320 ℃, and cooling the wafer to room temperature along with the furnace to obtain the barium titanate-based high-energy-density electronic ceramic. The sintering time is 5 h.
1. Domain structure design
The pure barium titanate bulk ceramic is a normal ferroelectric, has a wide electric domain structure, forms large polarization strength and high residual polarization strength under the action of an external electric field, has low breakdown electric field strength, and cannot store electric energy efficiently. Through ion doping, ions with similar solid solution radius and valence enter the crystal lattice, and the ferroelectric state is converted into the relaxation state. When the ion doping amount exceeds a certain value, an over-relaxation state is formed, the long-range ordered structure is destroyed at the moment, a plurality of nano domain structures with extremely small sizes are generated, and under the action of an external electric field, small polarization intensity is formed, but the residual polarization intensity is moderate, so that the energy storage density and the energy storage efficiency are not high. However, in the crossing region, the ion doping amount is moderate, the system is completely of a nano domain structure, and the large nano domains and the small nano domains are staggered, so that high polarization strength, low residual polarization strength and large breakdown electric field strength are easy to obtain, and the maximum energy storage density and the maximum energy storage efficiency can be obtained in the crossing region.
2. Design of relaxation state
In order to obtain the ceramic material with high energy storage performance, the material has certain relaxation property, and the energy storage density and the energy storage efficiency of the material are greatly improved. According to a dielectric property and temperature corresponding relation graph and corrected Landau free energy analysis, results show that a barium titanate ceramic system with a high relaxation factor has good energy storage characteristics, theoretical calculation and analysis find that the barium titanate ceramic system has the minimum free energy in a cross region, and the electric domain can be deflected when energy barrier difference is applied with driving force more easily. Therefore, a material system with a high relaxation factor designed by tolerance factors, Landau free energy calculation and the like can more easily obtain large energy storage density and high energy storage efficiency.
3. Preparation by solid phase reaction
Firstly, weighing raw materials according to a stoichiometric ratio (accurate to 0.001g) and putting the raw materials into a ball milling tank, adding an absolute ethyl alcohol solution into the ball milling tank, and putting the ball milling tank on a ball mill for ball milling for 24 hours. And secondly, drying the uniformly mixed raw materials in the first step, placing the dried raw materials in an alumina crucible for presintering, wherein the sintering temperature of the electronic ceramic of the system is usually 1100 ℃, and preserving heat for 2 hours. Thirdly, ball milling the presintered powder for 24 hours again. And fourthly, drying and sieving the powder obtained by secondary ball milling, adding a certain amount of polyvinyl alcohol solution (PVA, the concentration of 5 percent) to grind the powder uniformly in a mortar, and then molding the powder into wafers with the diameter of 12mm and the thickness of 1.5mm by using a tablet machine. And fifthly, sintering the ceramic material by adopting a crucible reversing method, placing the pressed ceramic slice on an alumina plate, reversing a small crucible above the ceramic slice, placing the ceramic slice in a high-temperature muffle furnace, heating to 1320 ℃ at a heating rate of 3 ℃/min, sintering and keeping the temperature for 5 hours to obtain the required sample.
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％)、SrCO3(99％)、Bi2O3(99％)、MgO (99.99％)、TiO2(99%) and Nb2O5(99.99%) were purchased from the national pharmaceutical group chemical reagents, Inc. The energy density and energy efficiency calculation data related to the invention are from a unipolar polarization curve measured by an Agilent ferroelectric comprehensive analyzer in the United states.
Example 1
Chemical composition of Ba0.65Sr0.35TiO3-0.10Bi(Mg2/3Nb1/3)O3The formula comprises the steps of weighing raw materials according to chemical proportion, carrying out ball milling for 24 hours, drying, tabletting and pressingSintering the good columnar block in a sintering furnace, pre-sintering for 2h at 1100 ℃, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, tabletting, placing the pressed wafer into a sintering furnace for sintering, keeping the temperature at 600 ℃ for two hours to remove glue, raising the temperature to 1320 ℃ at the rate of 3 ℃/min, keeping the temperature for 5 hours, and finishing sintering. And naturally cooling to room temperature to obtain the barium titanate-based energy storage ceramic.
The phase composition of the samples upon pre-firing was examined by an X-ray diffractometer (RINT 2000, Rigaku) and, as shown in FIG. 2, was of a typical pseudo-cubic structure without diffraction peaks of other hetero-phases. The surface scanning electron microscope image of the obtained barium titanate-based energy storage ceramic is shown in figure 3, the average grain size of the ceramic is 2-2.5 mu m, the structure is arranged compactly, and the crystallinity is good.
Example 2
Chemical composition of Ba0.65Sr0.35TiO3The formula of (1) comprises the following steps of weighing raw materials according to a chemical ratio, carrying out ball milling for 24h, drying, tabletting, placing the pressed columnar block in a sintering furnace for sintering, presintering for 2h at 1050 ℃, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, tabletting, placing the pressed wafer into a sintering furnace for sintering, performing heat preservation at 600 ℃ for 2h for binder removal, raising the temperature to 1280 ℃ at the heating rate of 3 ℃/min, performing heat preservation for 5h, and finishing sintering. And naturally cooling to room temperature to obtain the barium titanate-based energy storage ceramic.
Example 3
Chemical composition of Ba0.65Sr0.35TiO3-0.20Bi(Mg2/3Nb1/3)O3The formula of (1) comprises the following steps of weighing raw materials according to a chemical proportion, carrying out ball milling for 24 hours, drying, tabletting, placing the pressed columnar block in a sintering furnace for sintering, presintering for 2 hours at 1100 ℃, and naturally cooling; and performing secondary ball milling on the pre-sintered ceramic powder to obtain powder, tabletting, placing the pressed wafer into a sintering furnace for sintering, keeping the temperature at 600 ℃ for two hours to remove glue, raising the temperature to 1340 ℃ at a later heating rate of 3 ℃/min, keeping the temperature for 5 hours, and finishing sintering. And naturally cooling to room temperature to obtain the barium titanate-based energy storage ceramic.
Example 4
The multiferroic bismuth ferrite-based electronic functional ceramics prepared in examples 1,2 and 3 were subjected to performance tests.
The dielectric characteristics of the ferroelectric are measured by using an HP4980AL analyzer, the test frequencies are 1kHz, 10kHz, 100kHz and 1MHz respectively, the test temperature range is-150 ℃ to 150 ℃, and as can be seen from figure 4, the figure (1) is a normal ferroelectric dielectric temperature spectrum, the dielectric constant is maximum, but the frequency dispersion is small; and the graph (3) shows the relaxor ferroelectric body with the smallest dielectric constant and moderate relaxation factor due to the frequency dispersion exceeding the glassy phase region; fig. 2 shows a cross ferroelectric with moderate dielectric constant, significant frequency dispersion, minimal dielectric loss, and in the glassy phase region, with the largest relaxation factor. This is because doping with appropriate levels of ions can alter the microscopic electric domain structure of the system, further affecting its electrical properties.
The ferroelectric properties were measured using an Agilent ferroelectric analyzer at a test frequency of 10Hz, and as can be seen from fig. 5, the black curve represents the unipolar polarization curve of the sample of example 2, the red curve represents the unipolar polarization curve of the sample of example 2, and the green curve represents the unipolar polarization curve of the sample of example 2. The test result is consistent with the results of electric domain engineering and theoretical calculation, and the unipolar polarization curve obtained in the crossed ferroelectric body has the largest surrounding area with the Y axis, which indicates that the largest energy storage density is obtained.
Measuring the unipolar polarization curve by Agilent ferroelectric analyzer according to the formula (1)
(3) η -Wrec/W the energy storage characteristics of the samples of examples 1,2 and 3 are calculated as shown in FIG. 6. the maximum breakdown field strength obtained in the crossed ferroelectric (sample of example 1) is 400kV/cm and has the highest energy storage density and energy storage efficiency of 3.34J/cm, respectively3，86％。
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (9)
1. The preparation method of the barium titanate-based high energy storage density electronic ceramic is characterized by comprising the following steps:
the method comprises the following steps:
the method comprises the following steps: sr is2+, Bi3+, Mg2+, Nb5+Ion doping into barium titanate ceramic to form (1-x) Ba(1-y)SryTiO3-xBi(Mg2/3Nb1/3)03So that it is within the crossover region;
step two: calculating the chemical proportion of the formula components obtained in the step one, and weighing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5And performing ball milling, drying, pre-sintering, tabletting and sintering on the powder to obtain the barium titanate-based high-energy-storage-density electronic ceramic.
2. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 1, wherein:
in step one, x = 0.10 and y = 0.35.
3. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 2, wherein:
the ball milling and drying method comprises the following specific steps:
mixing high-purity BaCO3、SrCO3、Bi2O3、MgO、TiO2And Nb2O5Putting the powder into a ball milling tank, adding absolute ethyl alcohol, carrying out ball milling on a planetary ball mill for 24 hours, and then drying.
4. The method for preparing a barium titanate-based high energy storage density electronic ceramic according to claim 3, wherein:
the pre-sintering comprises the following specific steps:
placing the powder after ball milling and drying in a high-purity alumina crucible, and presintering the powder in a high-temperature sintering furnace at the junction temperature of 1100 DEG CoC。
5. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 4, wherein:
the presintering time is 2 h.
6. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 5, wherein:
the tabletting method comprises the following specific steps:
and ball-milling the pre-sintered powder for 24 hours again, drying, adding 7 wt% of PVA for granulation, applying a pressure of 15MPa on a tablet press, and die-pressing to obtain a wafer with the diameter of 12mm and the thickness of 1.5 mm.
7. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 6, wherein:
the sintering method comprises the following specific steps:
pressing the wafer at 600oC, keeping the temperature for 4h, discharging the glue, and placing the mixture in a high-temperature sintering furnace 1320oAnd C, sintering, and cooling to room temperature along with the furnace to obtain the barium titanate-based high-energy-storage-density electronic ceramic.
8. The method of preparing a barium titanate-based high energy storage density electronic ceramic according to claim 7, wherein:
the sintering time is 5 h.
9. The barium titanate-based high energy storage density electronic ceramic produced according to the method of claim 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293247A (en) * | 2018-10-25 | 2019-02-01 | 陕西科技大学 | A kind of high electroconductive glass powder and preparation method thereof, and based on its barium phthalate base glass ceramics and preparation method thereof |
| CN111484325A (en) * | 2020-04-23 | 2020-08-04 | 西安工业大学 | Barium strontium titanate-based ceramic material and preparation method and application thereof |
| CN114349497A (en) * | 2021-12-28 | 2022-04-15 | 摩比天线技术（深圳）有限公司 | Wide-temperature-range stable energy storage ceramic material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133915A (en) * | 2018-08-30 | 2019-01-04 | 武汉理工大学 | A kind of high energy storage barium phthalate base dielectric material and preparation method thereof |
| CN109180178A (en) * | 2018-10-10 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | A kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and preparation method thereof |
-
2019
- 2019-12-19 CN CN201911316654.4A patent/CN111018516A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133915A (en) * | 2018-08-30 | 2019-01-04 | 武汉理工大学 | A kind of high energy storage barium phthalate base dielectric material and preparation method thereof |
| CN109180178A (en) * | 2018-10-10 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | A kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| FIKADU ALEMA ET AL.: "Dielectric properties of BaMg1/3Nb2/3O3 doped Ba0.45Sr0.55TiO3 thin films for tunable microwave applications", 《JOURNAL OF ADVANCED DIELECTRICS》 * |
| TONG WANG ET AL.: "Relaxor Ferroelectric BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for Energy Storage Application", 《JJOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| WEI HUANG ET AL.: ""Ultrahigh recoverable energy storage density and efficiency in barium strontium titanate-based lead-free relaxor ferroelectric ceramics"", 《APPLIED PHYSICS LETTERS》 * |
| 伍媛婷等编著: "《大学生创新创业项目理论指导与实践》", 31 July 2018, 西安：西北工业大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293247A (en) * | 2018-10-25 | 2019-02-01 | 陕西科技大学 | A kind of high electroconductive glass powder and preparation method thereof, and based on its barium phthalate base glass ceramics and preparation method thereof |
| CN109293247B (en) * | 2018-10-25 | 2021-11-16 | 陕西科技大学 | High-conductivity glass powder and preparation method thereof, barium titanate-based glass ceramic based on high-conductivity glass powder and preparation method thereof |
| CN111484325A (en) * | 2020-04-23 | 2020-08-04 | 西安工业大学 | Barium strontium titanate-based ceramic material and preparation method and application thereof |
| CN114349497A (en) * | 2021-12-28 | 2022-04-15 | 摩比天线技术（深圳）有限公司 | Wide-temperature-range stable energy storage ceramic material and preparation method thereof |
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