CN105272217A - Barium strontium titanate based aluminum oxide composite ceramic with high energy storage density and preparation method of barium strontium titanate based aluminum oxide composite ceramic - Google Patents

Barium strontium titanate based aluminum oxide composite ceramic with high energy storage density and preparation method of barium strontium titanate based aluminum oxide composite ceramic Download PDF

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CN105272217A
CN105272217A CN201510694450.XA CN201510694450A CN105272217A CN 105272217 A CN105272217 A CN 105272217A CN 201510694450 A CN201510694450 A CN 201510694450A CN 105272217 A CN105272217 A CN 105272217A
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energy storage
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CN105272217B (en
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吴勇军
蒋小超
陈湘明
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Zhejiang University ZJU
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Abstract

The invention discloses a preparation method of barium strontium titanate based aluminum oxide composite ceramic with high energy storage density. According to the method, firstly, raw materials, BaCO3, SrCO3 and TiO2 are prepared according to the chemical formula Ba0.4Sr0.6TiO 3, then ground, dried, sieved and calcined for 3 hours at the temperature of 1,150 DEG C, and Ba0.4Sr0.6TiO 3 powder is prepared; secondarily, the Ba0.4Sr0.6TiO 3 powder and Al2O3 powder are prepared in the mass ratio being (100-x):x, wherein x ranges from 1 to 5, the powder is ground, dried and sieved, and ceramic powder is prepared; the ceramic powder is put in a mold and sintered in a vacuum environment at the temperature of 1,000 DEG C through a discharge plasma sintering system, and a ceramic sintered body is prepared; the ceramic sintered body is subjected to thermal treatment for 3 hours at the temperature of 1,100 DEG C in the air atmosphere, and the barium strontium titanate based aluminum oxide composite ceramic with high energy storage density is prepared. The dielectric breakdown strength of the prepared composite ceramic can reach 300 kV/cm at the room temperature, and the energy storage density can reach 1.69 J/cm<3> at the room temperature. The prepared barium strontium titanate based aluminum oxide composite ceramic with high energy storage density can be used for components such as a high-density energy storage capacitor and the like and has great application value in the high-power and impulse-power fields.

Description

Barium-strontium titanate-based Toughened Alumina Ceramics of a kind of high energy storage density and preparation method thereof
Technical field
The present invention relates to energy storage capacitor dielectric material technical field, particularly relate to a kind of high energy storage density complex phase dielectric ceramics and preparation method thereof.
Background technology
Dielectric capacitor has ultra high power density, fast and the Application Areas of instability of very applicable fluctuation of power, and have the advantages such as fast response time, power density are high, service life cycle is longer, all solid state safeguard construction, have wide prospect in energy storage field, barium-strontium titanate ceramic is typical dielectric material wherein.But its relatively low energy storage density, limit the broader applications of dielectric capacitor.The research emphasis in this field of exploring that to take barium-strontium titanate ceramic as the new dielectric substance with high-k, high dielectric breakdown field intensity and low-dielectric loss of matrix and new preparation process thereof be always.
According to existing bibliographical information, although strontium-barium titanate/Toughened Alumina Ceramics prepared by conventional solid sintering process improves the disruptive strength of pottery to a certain extent, but owing to adopting conventional solid sintering process, have at phase boundary place the defect such as bubble, dislocation assemble cause its polarization greatly reduce and disruptive strength improve less, add the defect of conventional sintering method itself, energy storage density is still very low.Application number be 201310681668.2 Chinese patent disclose a kind of preparation method of high energy storage density barium-strontium titanate ceramic, its step is as follows: (1) is by raw material BaCO 3, SrCO 3and TiO 2by Ba 1-xsr xtiO 3chemical formula is prepared burden, and grinding post-drying, sieves; (2) powder obtained for step (1), is sieved after 1 ~ 5 hour in 1100 ~ 1250 DEG C of calcinings; (3) powder obtained for step (2) is loaded mould, utilize discharge plasma sintering system in vacuum environment 900 ~ 1050 DEG C sinter, obtained ceramic sintered bodies; (4) under air atmosphere, by described ceramic sintered bodies in 800 ~ 1100 DEG C of thermal treatments 1 ~ 5 hour, obtained described barium-strontium titanate ceramic.Pure Ba prepared by the method 0.4sr 0.6tiO 3the most high energy storage density of pottery can reach 1.20J/cm 3.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide barium-strontium titanate-based Toughened Alumina Ceramics of a kind of high energy storage density and preparation method thereof, the complex phase ceramic of preparation at room temperature energy storage density can reach 1.69J/cm 3.
The object of the invention is to be achieved through the following technical solutions: the barium-strontium titanate-based Toughened Alumina Ceramics of a kind of high energy storage density, described pottery is by Ba 0.4sr 0.6tiO 3and Al 2o 3(100-x): x forms in mass ratio, wherein x=1,2,5; Described Ba 0.4sr 0.6tiO 3the raw material of powder is barium carbonate, Strontium carbonate powder and titania powder.
A preparation method for the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density, comprises the following steps:
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) by Ba obtained for step (2) 0.4sr 0.6tiO 3powder and Al 2o 3powder is (100-x) in mass ratio: x prepares burden, wherein x=1 ~ 5, and grinding post-drying, sieves, obtained ceramic powder;
(4) ceramic powder obtained for step (3) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(5) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (4) is obtained 3 hours, obtained described high energy storage density strontium-barium titanate Toughened Alumina Ceramics.
Further, Ba 0.4sr 0.6tiO 3powder and Al 2o 3the mass ratio (100-x) of powder: x, wherein x=1,2,5.
Further, in step (1), (3), the method for grinding is: raw material is put into ball grinder, adds zirconia ball and dehydrated alcohol carries out ball milling.
The present invention, by adopting discharge plasma sintering method, improves the dielectric breakdown strength of complex phase ceramic, thus improves the energy storage density of complex phase ceramic.
Compared with prior art, beneficial effect of the present invention is: adopt preparation method of the present invention, work as Ba 0.4sr 0.6tiO 3powder and Al 2o 3powder is when 99:1 prepares burden in mass ratio, and the complex phase ceramic of preparation at room temperature dielectric breakdown field intensity reaches 300kV/cm, and the pure Ba adopting discharge plasma sintering method to prepare 0.4sr 0.6tiO 3the dielectric breakdown field intensity of dielectric ceramics is only 210kV/cm, and dielectric breakdown field intensity improves more than 43%; Meanwhile, at room temperature energy storage density reaches 1.69J/cm 3, and the pure Ba adopting discharge plasma sintering method to prepare 0.4sr 0.6tiO 3the energy storage density of dielectric ceramics is only 1.20J/cm 3left and right, energy storage density improves more than 41%.The barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density prepared by the present invention, can be used for the components and parts such as high-density energy storage capacitor, has great using value in high-power and pulse power field.
Accompanying drawing explanation
Fig. 1 is SPS sintering theory;
Fig. 2 is barium-strontium titanate-based Toughened Alumina Ceramics sample XRD diffracting spectrum: (a) Ba 0.4sr 0.6tiO 3(comparative example 1); (b) 99wt.%Ba 0.4sr 0.6tiO 3– 1wt.%Al 2o 3(embodiment 1); (c) 98wt.%Ba 0.4sr 0.6tiO 3– 2wt.%Al 2o 3(embodiment 2); (d) 95wt.%Ba 0.4sr 0.6tiO 3– 5wt.%Al 2o 3(embodiment 3);
Fig. 3 is the stereoscan photograph on the polishing thermal etching surface of barium-strontium titanate-based Toughened Alumina Ceramics sample, and magnification is 20k:(a) Ba 0.4sr 0.6tiO 3(comparative example 1); (b) 99wt.%Ba 0.4sr 0.6tiO 3– 1wt.%Al 2o 3(embodiment 1); (c) 98wt.%Ba 0.4sr 0.6tiO 3– 2wt.%Al 2o 3(embodiment 2); (d) 95wt.%Ba 0.4sr 0.6tiO 3– 5wt.%Al 2o 3(embodiment 3);
For barium-strontium titanate-based Toughened Alumina Ceramics sample, specific inductivity and dielectric loss variation with temperature curve: Fig. 4 are Ba to Fig. 4-7 at different frequencies 0.4sr 0.6tiO 3(comparative example 1); Fig. 5 is 99wt.%Ba 0.4sr 0.6tiO 3– 1wt.%Al 2o 3(embodiment 1); Fig. 6 is 98wt.%Ba 0.4sr 0.6tiO 3– 2wt.%Al 2o 3(embodiment 2); Fig. 7 is 95wt.%Ba 0.4sr 0.6tiO 3– 5wt.%Al 2o 3(embodiment 3);
Fig. 8 be barium-strontium titanate-based Toughened Alumina Ceramics sample at room temperature 60Hz time maximum field intensity under ferroelectric hysteresis loop: (a) Ba 0.4sr 0.6tiO 3(comparative example 1); (b) 99wt.%Ba 0.4sr 0.6tiO 3– 1wt.%Al 2o 3(embodiment 1); (c) 98wt.%Ba 0.4sr 0.6tiO 3– 2wt.%Al 2o 3(embodiment 2); (d) 95wt.%Ba 0.4sr 0.6tiO 3– 5wt.%Al 2o 3(embodiment 3).
Embodiment
The present invention is explained further below in conjunction with specific embodiment.
Embodiment 1
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) by Ba obtained for step (2) 0.4sr 0.6tiO 3powder and Al 2o 3powder in mass ratio 100:1 is prepared burden, and grinding post-drying, sieves, obtained ceramic powder;
(4) ceramic powder obtained for step (3) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(5) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (4) is obtained 3 hours, obtained high energy storage density 98wt.%Ba 0.4sr 0.6tiO 3– 1wt.%Al 2o 3complex phase ceramic.
SPS sintering theory is: SPS utilizes DC pulse current directly to carry out energising pressure sintering, controls temperature rise rate by regulating the watt level of DC pulse current.Whole sintering process both can be carried out under vacuum conditions, also to carry out in protective atmosphere.Pulsed current directly acts on sample and mould, fast heating, and flash heat transfer, is rapidly heated, and significantly shortens sample sintering time.
Embodiment 2
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) by Ba obtained for step (2) 0.4sr 0.6tiO 3powder and Al 2o 3powder in mass ratio 100:2 is prepared burden, and grinding post-drying, sieves, obtained ceramic powder;
(4) ceramic powder obtained for step (3) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(5) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (4) is obtained 3 hours, obtained high energy storage density 98wt.%Ba 0.4sr 0.6tiO 3– 2wt.%Al 2o 3complex phase ceramic.
Embodiment 3
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) by Ba obtained for step (2) 0.4sr 0.6tiO 3powder and Al 2o 3powder in mass ratio 100:5 is prepared burden, and grinding post-drying, sieves, obtained ceramic powder;
(4) ceramic powder obtained for step (3) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(5) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (4) is obtained 3 hours, obtained high energy storage density 98wt.%Ba 0.4sr 0.6tiO 3– 5wt.%Al 2o 3complex phase ceramic.
Comparative example 1
Pure Ba is provided 0.4sr 0.6tiO 3the discharge plasma sintering preparation process of pottery:
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) ceramic powder obtained for step (2) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(4) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (3) is obtained 3 hours, the obtained pure Ba of high energy storage density 0.4sr 0.6tiO 3pottery.
Cylindrical dielectric ceramics sample sand paper embodiment 1 ~ 3 and comparative example 1 prepared is milled to 0.20mm thickness, and after gold electrode is sprayed on surface, the ferroelectric hysteresis loop under utilizing ferroelectric analyser to measure its 60Hz frequency, utilizes integration to calculate its energy storage density.
Table 1
Table 1 shows (100-x) wt.%Ba utilizing preparation method of the present invention to obtain 0.4sr 0.6tiO 3– xwt.%Al 2o 3(x=1,2,5) complex phase ceramic and the Ba utilizing discharge plasma sintering method to prepare 0.4sr 0.6tiO 3the dielectric breakdown strength of pottery under room temperature, 60Hz frequency and energy storage density.Fig. 2, Fig. 3, Fig. 4-7, Fig. 8 illustrates sample phase composite, microstructure and Dielectric, Ferroelectric performance.From test data, the barium-strontium titanate-based glass complex phase ceramic of the high energy storage density that the present invention obtains at room temperature most high energy storage density is 1.69J/cm 3, and the pure Ba utilizing discharge plasma sintering method to prepare 0.4sr 0.6tiO 3under the room temperature of pottery, energy storage density is only 1.20J/cm 3.

Claims (4)

1. the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density, is characterized in that, described pottery is by Ba 0.4sr 0.6tiO 3and Al 2o 3(100-x): x forms in mass ratio, wherein x=1,2,5; Described Ba 0.4sr 0.6tiO 3the raw material of powder is barium carbonate, Strontium carbonate powder and titania powder.
2. a preparation method for the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density described in claim 1, is characterized in that, comprise the following steps:
(1) by raw material BaCO 3, SrCO 3and TiO 2by Ba 0.4sr 0.6tiO 3chemical formula is prepared burden, and being ground to particle diameter is 100nm ~ 500nm post-drying, sieves;
(2) powder 1150 DEG C calcining obtained for step (1), after 3 hours, is sieved, obtained Ba 0.4sr 0.6tiO 3powder;
(3) by Ba obtained for step (2) 0.4sr 0.6tiO 3powder and Al 2o 3powder is (100-x) in mass ratio: x prepares burden, wherein x=1 ~ 5, and grinding post-drying, sieves, obtained ceramic powder;
(4) ceramic powder obtained for step (3) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C sinter, obtained ceramic sintered bodies;
(5) under air atmosphere, ceramic sintered bodies 1100 DEG C of thermal treatments that step (4) is obtained 3 hours, obtained described high energy storage density strontium-barium titanate Toughened Alumina Ceramics.
3. preparation method as claimed in claim 2, is characterized in that, Ba 0.4sr 0.6tiO 3powder and Al 2o 3the mass ratio (100-x) of powder: x, wherein x=1,2,5.
4. preparation method as claimed in claim 2, it is characterized in that, in step (1), (3), the method for grinding is: raw material is put into ball grinder, adds zirconia ball and dehydrated alcohol carries out ball milling.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106542821A (en) * 2016-10-18 2017-03-29 陕西科技大学 A kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof
CN105948737B (en) * 2016-05-11 2019-01-04 武汉理工大学 A kind of CaTiO3Baseline energy-storing dielectric ceramic material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844919A (en) * 2010-06-03 2010-09-29 西北工业大学 Composite barium strontium titanate ceramics and preparation method thereof
CN103951418A (en) * 2014-04-16 2014-07-30 中国科学院青海盐湖研究所 Method for preparing doped or composite barium strontium titanate ceramic powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844919A (en) * 2010-06-03 2010-09-29 西北工业大学 Composite barium strontium titanate ceramics and preparation method thereof
CN103951418A (en) * 2014-04-16 2014-07-30 中国科学院青海盐湖研究所 Method for preparing doped or composite barium strontium titanate ceramic powder

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948737B (en) * 2016-05-11 2019-01-04 武汉理工大学 A kind of CaTiO3Baseline energy-storing dielectric ceramic material and preparation method thereof
CN106542821A (en) * 2016-10-18 2017-03-29 陕西科技大学 A kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof

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