CN105272217B - A kind of barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density and preparation method thereof - Google Patents

A kind of barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density and preparation method thereof Download PDF

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CN105272217B
CN105272217B CN201510694450.XA CN201510694450A CN105272217B CN 105272217 B CN105272217 B CN 105272217B CN 201510694450 A CN201510694450 A CN 201510694450A CN 105272217 B CN105272217 B CN 105272217B
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barium
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CN105272217A (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 kind of preparation method of the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density, the method is first by raw material BaCO3, SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, dries after grinding, sieving, after 1150 DEG C are calcined 3 hours, Ba is obtained0.4Sr0.6TiO3Powder;Secondly by Ba0.4Sr0.6TiO3Powder and Al2O3Powder (100 x) in mass ratio:X carries out dispensing, wherein x=1~5, and drying after grinding, sieving is obtained ceramic powder;Ceramic powder is loaded into mould, is sintered for 1000 DEG C in vacuum environment using discharge plasma sintering system, ceramic sintered bodies are obtained;Under air atmosphere, by ceramic sintered bodies, 1100 DEG C are heat-treated 3 hours, and high energy storage density barium strontium titanate complex phase ceramic is obtained.The present invention prepare complex phase ceramic at room temperature dielectric breakdown field intensity up to 300kV/cm, energy storage density is up to 1.69J/cm at room temperature3, the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density prepared by the present invention can be used for the components such as high density energy-storage capacitor, have great application value in high-power and pulse power field.

Description

A kind of barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density and preparation method thereof
Technical field
It is situated between the present invention relates to energy-storage capacitor dielectric material technical field, more particularly to a kind of high energy storage density complex phase electricity Matter ceramics and preparation method thereof.
Background technology
Dielectric capacitor has ultra high power density, is very suitable for the fast and unstable application field of power swing, and There are the advantages such as fast response time, power density are high, service life cycle is more long, all solid state safeguard construction, have in energy storage field Wide prospect, barium-strontium titanate ceramic is typical dielectric material therein.But its relatively low energy storage density, limitation The broader applications of dielectric capacitor.Explore being hit with high-k, dielectric high with barium-strontium titanate ceramic as matrix Wear the new dielectric substance and its research emphasis in the new preparation process always field of field intensity and low-dielectric loss.
Reported according to existing document, although barium strontium titanate/Toughened Alumina Ceramics prepared by conventional solid sintering process are one Determine to improve ceramic breakdown strength in degree, but due to using conventional solid sintering process, there is bubble, dislocation etc. to lack at phase boundary Sunken aggregation causes its polarization to substantially reduce and breakdown strength improves less, adds conventional sintering method defect in itself, energy storage density Still it is very low.The Chinese patent of Application No. 201310681668.2 discloses a kind of system of high energy storage density barium-strontium titanate ceramic Preparation Method, its step is as follows:(1) by raw material BaCO3, SrCO3And TiO2By Ba1-xSrxTiO3Chemical formula dispensing, dries after grinding, Sieving;(2) after powder obtained in step (1) is calcined 1~5 hour in 1100~1250 DEG C, sieving;(3) step (2) is obtained Powder load mould, be sintered for 900~1050 DEG C in vacuum environment using discharge plasma sintering system, be obtained ceramics Sintered body;(4) under air atmosphere, described ceramic sintered bodies are heat-treated 1~5 hour in 800~1100 DEG C, the titanium is obtained Sour strontium titanate ceramicses.Pure Ba prepared by the method0.4Sr0.6TiO3Ceramic highest energy storage density can reach 1.20J/cm3
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of barium-strontium titanate-based aluminum oxide of high energy storage density Complex phase ceramic and preparation method thereof, energy storage density can reach 1.69J/cm to the complex phase ceramic of preparation at room temperature3
The purpose of the present invention is achieved through the following technical solutions:A kind of barium-strontium titanate-based aluminum oxide of high energy storage density Complex phase ceramic, the ceramics are by Ba0.4Sr0.6TiO3And Al2O3In mass ratio (100-x):X is constituted, wherein x=1,2,5;It is described Ba0.4Sr0.6TiO3The raw material of powder is barium carbonate, strontium carbonate and titania powder.
A kind of preparation method of the barium-strontium titanate-based Toughened Alumina Ceramics of high energy storage density, comprises the following steps:
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, be ground to particle diameter for 100nm~ Dried after 500nm, sieving;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) by Ba obtained in step (2)0.4Sr0.6TiO3Powder and Al2O3Powder (100-x) in mass ratio:X is matched somebody with somebody Material, wherein x=1~5, dry after grinding, and sieving is obtained ceramic powder;
(4) ceramic powder obtained in step (3) is loaded into mould, using discharge plasma sintering system in vacuum environment 1000 DEG C are sintered, and ceramic sintered bodies are obtained;
(5) under air atmosphere, by ceramic sintered bodies obtained in step (4), 1100 DEG C are heat-treated 3 hours, and the storage high is obtained Can density barium strontium titanate Toughened Alumina Ceramics.
Further, Ba0.4Sr0.6TiO3Powder and Al2O3The 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, zirconia ball and nothing is added Water-ethanol carries out ball milling.
The present invention improves the dielectric breakdown strength of complex phase ceramic, so as to improve by using discharge plasma sintering method The energy storage density of complex phase ceramic.
Compared with prior art, the beneficial effects of the present invention are:Using preparation method of the invention, when Ba0.4Sr0.6TiO3Powder and Al2O3Powder in mass ratio 99:1 when carrying out dispensing, and the complex phase ceramic of preparation at room temperature hit by dielectric Wear field intensity and reach 300kV/cm, and use the pure Ba of discharge plasma sintering method preparation0.4Sr0.6TiO3Jie of dielectric ceramics Electric breakdown field strength is only 210kV/cm, and dielectric breakdown field intensity improves more than 43%;Meanwhile, energy storage density reaches at room temperature 1.69J/cm3, and use the pure Ba of discharge plasma sintering method preparation0.4Sr0.6TiO3The energy storage density of dielectric ceramics is only 1.20J/cm3Left and right, energy storage density improves more than 41%.The barium-strontium titanate-based aluminum oxide of high energy storage density prepared by the present invention is answered Phase ceramics, can be used for the components such as high density energy-storage capacitor, have in high-power and pulse power field and greatly apply valency Value.
Brief description of the drawings
Fig. 1 is SPS sintering theories;
Fig. 2 is barium-strontium titanate-based Toughened Alumina Ceramics sample XRD diffracting spectrums:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 99wt.%Ba0.4Sr0.6TiO3- 1wt.%Al2O3(embodiment 1);(c) 98wt.%Ba0.4Sr0.6TiO3- 2wt.% Al2O3(embodiment 2);(d) 95wt.%Ba0.4Sr0.6TiO3- 5wt.%Al2O3(embodiment 3);
Fig. 3 is the stereoscan photograph on the polishing heat erosion surface of barium-strontium titanate-based Toughened Alumina Ceramics sample, is amplified Multiple is 20k:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 99wt.%Ba0.4Sr0.6TiO3- 1wt.%Al2O3(embodiment 1);(c) 98wt.%Ba0.4Sr0.6TiO3- 2wt.%Al2O3(embodiment 2);(d) 95wt.%Ba0.4Sr0.6TiO3- 5wt.% Al2O3(embodiment 3);
Fig. 4-7 be barium-strontium titanate-based Toughened Alumina Ceramics sample at different frequencies dielectric constant and dielectric loss with temperature The change curve of degree:Fig. 4 is Ba0.4Sr0.6TiO3(comparative example 1);Fig. 5 is 99wt.%Ba0.4Sr0.6TiO3- 1wt.%Al2O3 (embodiment 1);Fig. 6 is 98wt.%Ba0.4Sr0.6TiO3- 2wt.%Al2O3(embodiment 2);Fig. 7 is 95wt.% Ba0.4Sr0.6TiO3- 5wt.%Al2O3(embodiment 3);
Fig. 8 be barium-strontium titanate-based Toughened Alumina Ceramics sample at room temperature 60Hz when maximum field intensity under electric hysteresis return Line:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 99wt.%Ba0.4Sr0.6TiO3- 1wt.%Al2O3(embodiment 1);(c) 98wt.%Ba0.4Sr0.6TiO3- 2wt.%Al2O3(embodiment 2);(d) 95wt.%Ba0.4Sr0.6TiO3- 5wt.%Al2O3It is (real Apply example 3).
Specific embodiment
The present invention is further explained with reference to specific embodiment.
Embodiment 1
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, be ground to particle diameter for 100nm~ Dried after 500nm, sieving;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) by Ba obtained in step (2)0.4Sr0.6TiO3Powder and Al2O3Powder in mass ratio 100:1 carries out dispensing, grinds Dried after mill, sieving is obtained ceramic powder;
(4) ceramic powder obtained in step (3) is loaded into mould, using discharge plasma sintering system in vacuum environment 1000 DEG C are sintered, and ceramic sintered bodies are obtained;
(5) under air atmosphere, by ceramic sintered bodies obtained in step (4), 1100 DEG C are heat-treated 3 hours, energy storage high are obtained close Degree 98wt.%Ba0.4Sr0.6TiO3- 1wt.%Al2O3Complex phase ceramic.
SPS sintering theories are:SPS directly carries out energization pressure sintering using DC pulse current, by adjusting direct current arteries and veins The watt level of electric current is rushed to control heating rate.Whole sintering process can both be carried out under vacuum conditions, also with protection gas Carried out in atmosphere.Pulse current is directly acted on sample and mould, fast heating, and flash heat transfer is rapidly heated, and significantly shortens sample Product sintering time.
Embodiment 2
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, be ground to particle diameter for 100nm~ Dried after 500nm, sieving;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) by Ba obtained in step (2)0.4Sr0.6TiO3Powder and Al2O3Powder in mass ratio 100:2 carry out dispensing, grind Dried after mill, sieving is obtained ceramic powder;
(4) ceramic powder obtained in step (3) is loaded into mould, using discharge plasma sintering system in vacuum environment 1000 DEG C are sintered, and ceramic sintered bodies are obtained;
(5) under air atmosphere, by ceramic sintered bodies obtained in step (4), 1100 DEG C are heat-treated 3 hours, energy storage high are obtained close Degree 98wt.%Ba0.4Sr0.6TiO3- 2wt.%Al2O3Complex phase ceramic.
Embodiment 3
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, be ground to particle diameter for 100nm~ Dried after 500nm, sieving;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) by Ba obtained in step (2)0.4Sr0.6TiO3Powder and Al2O3Powder in mass ratio 100:5 carry out dispensing, grind Dried after mill, sieving is obtained ceramic powder;
(4) ceramic powder obtained in step (3) is loaded into mould, using discharge plasma sintering system in vacuum environment 1000 DEG C are sintered, and ceramic sintered bodies are obtained;
(5) under air atmosphere, by ceramic sintered bodies obtained in step (4), 1100 DEG C are heat-treated 3 hours, energy storage high are obtained close Degree 98wt.%Ba0.4Sr0.6TiO3- 5wt.%Al2O3Complex phase ceramic.
Comparative example 1
Pure Ba is provided0.4Sr0.6TiO3The discharge plasma sintering preparation process of ceramics:
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, be ground to particle diameter for 100nm~ Dried after 500nm, sieving;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) ceramic powder obtained in step (2) is loaded into mould, using discharge plasma sintering system in vacuum environment 1000 DEG C are sintered, and ceramic sintered bodies are obtained;
(4) under air atmosphere, by ceramic sintered bodies obtained in step (3), 1100 DEG C are heat-treated 3 hours, energy storage high are obtained close Spend pure Ba0.4Sr0.6TiO3Ceramics.
It is thick that the cylindrical dielectric ceramics sample sand paper that embodiment 1~3 and comparative example 1 are prepared is milled to 0.20mm Degree, after gold electrode is sprayed on surface, the ferroelectric hysteresis loop under its 60Hz frequency is measured using ferroelectricity analyzer, and it is calculated using integration method Energy storage density.
Table 1
Table 1 is shown using (100-x) wt.%Ba obtained in preparation method of the invention0.4Sr0.6TiO3- x wt.% Al2O3(x=1,2,5) complex phase ceramic and the Ba prepared using discharge plasma sintering method0.4Sr0.6TiO3Ceramics room temperature, Dielectric breakdown strength and energy storage density under 60Hz frequencies.Fig. 2, Fig. 3, Fig. 4-7, Fig. 8 illustrate sample phase composition, micro-structural and Dielectric, Ferroelectric performance.From test data, the obtained barium-strontium titanate-based glass complex phase ceramic of high energy storage density of the present invention is in room The lower highest energy storage density of temperature is 1.69J/cm3, and utilize the pure Ba of discharge plasma sintering method preparation0.4Sr0.6TiO3Ceramics Energy storage density is only 1.20J/cm at room temperature3

Claims (3)

1. the preparation method of the barium-strontium titanate-based Toughened Alumina Ceramics of a kind of high energy storage density, it is characterised in that including following step Suddenly:
(1) by raw material BaCO3、SrCO3And TiO2By Ba0.4Sr0.6TiO3Chemical formula dispensing, is ground to particle diameter for 100nm~500nm After dry, sieve;
(2) after by the calcining 3 hours of 1150 DEG C of powder obtained in step (1), sieving is obtained Ba0.4Sr0.6TiO3Powder;
(3) by Ba obtained in step (2)0.4Sr0.6TiO3Powder and Al2O3Powder (100-x) in mass ratio:X carries out dispensing, its Middle x=1~5, dry after grinding, and sieving is obtained ceramic powder;
(4) ceramic powder obtained in step (3) is loaded into mould, using discharge plasma sintering system 1000 in vacuum environment DEG C it is sintered, ceramic sintered bodies is obtained;
(5) under air atmosphere, by ceramic sintered bodies obtained in step (4), 1100 DEG C are heat-treated 3 hours, the energy storage high are obtained close Degree barium strontium titanate Toughened Alumina Ceramics.
2. preparation method as claimed in claim 1, it is characterised in that Ba0.4Sr0.6TiO3Powder and Al2O3The mass ratio of powder (100-x):X, wherein x=1,2,5.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), (3), the method for grinding is:By raw material Ball grinder is put into, adds zirconia ball and absolute ethyl alcohol to carry out ball milling.
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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

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* Cited by examiner, † Cited by third party
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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

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