CN105198410B - A kind of preparation method of core shell structure high energy storage density dielectric ceramics - Google Patents

A kind of preparation method of core shell structure high energy storage density dielectric ceramics Download PDF

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CN105198410B
CN105198410B CN201510695891.1A CN201510695891A CN105198410B CN 105198410 B CN105198410 B CN 105198410B CN 201510695891 A CN201510695891 A CN 201510695891A CN 105198410 B CN105198410 B CN 105198410B
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citric acid
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CN105198410A (en
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吴勇军
黄玉辉
陈湘明
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of preparation method of core shell structure high energy storage density dielectric ceramics, this method prepares Ba by sol-gal process first0.4Sr0.6TiO3Powder;Secondly SiO is prepared using teos hydrolysis2Coat Ba0.4Sr0.6TiO3Powder;Then obtained powder is loaded into mould, be sintered for 1000 DEG C~1050 DEG C in vacuum environment using discharge plasma sintering system, ceramic sintered bodies are made;In air atmosphere, by the processing 1~5 hour of 1100 DEG C~1150 DEG C of ceramic sintered bodies, core shell structure high energy storage density dielectric ceramics is made finally.Using the present invention preparation method prepare core shell structure high energy storage density dielectric ceramics at room temperature energy storage density up to 1.60J/cm3More than, the uncoated SiO prepared than similarity condition2Ba0.4Sr0.6TiO3The energy storage density of dielectric ceramics improves 0.40J/cm3

Description

A kind of preparation method of core shell structure high energy storage density dielectric ceramics
Technical field
The present invention relates to energy-storage capacitor dielectric material technical field, more particularly to a kind of core shell structure high energy storage density The preparation method of dielectric ceramics.
Background technology
Dielectric capacitor energy storage mode is to store up electric energy in the form of capacitor is the enrichment charge potential pole plate Deposit.Be in response to that speed is fast, power density is high compared with traditional fuel cell, lithium battery, the characteristics of dielectric energy-storage capacitor, Service life length, all solid state safeguard construction, temperature in use scope are wide etc., have very wide in high-power and Pulsed power device General application.For linear dielectric, its energy storage density is directly proportional to dielectric constant, with dielectric breakdown field strength square into just Than, therefore the dielectric material with high-k, high dielectric breakdown field strength and low-dielectric loss is explored, it is that raising energy storage is close Spend, realize the key of device miniaturization.Barium-strontium titanate ceramic is because with good ferroelectricity, piezoelectricity, non-linear optical property Etc. being widely used in the fields such as microelectronics, photoelectron, integrated optics and microelectromechanical systems.It is relatively low in terms of energy storage Dielectric loss, higher dielectric constant and disruptive field intensity, also make it that barium-strontium titanate ceramic is paid close attention to.
The Chinese patent of Application No. 201110046717.6 discloses a kind of system of barium strontium titanate-based energy storage dielectric ceramic Preparation Method, its step is as follows:(1) preparation of the ceramic fine powders of BST;(2) preparation of frit;(3) volume hundred as shared by each raw material Fraction is:BST ceramics fine powder 80~99%, frit 1~20%, choose the ceramic fine powders of above-mentioned BST and frit;BST ceramics Frit is added in fine powder, with zirconium oxide and absolute ethyl alcohol 24~36h of ball milling, ceramics-glass mixed-powder is made in drying, adds Binding agent is granulated, and the addition of binding agent is the 3~5% of ceramics-glass mixed-powder quality, and tabletting obtains green sheet;Green compact Piece is incubated 2h dumpings at 600 DEG C, is cooled to room temperature, is finally protected in the case where heating rate is 2~4 DEG C/min, 1050~1280 DEG C 2~4h of temperature, obtains barium strontium titanate-based energy storage dielectric ceramic.Energy-storing dielectric ceramic prepared by this method, measuring dielectric constant is 380, breakdown strength 28.0kV/mm, effective energy storage density are 1.50J/cm3
Above-mentioned patent improves the dielectric breakdown strength of ceramics by adding glass phase in barium-strontium titanate ceramic, so that Obtain higher energy storage density.But substantially, therefore the dielectric constant that with the addition of the barium strontium titanate complex phase ceramic of glass phase declines How by being formulated adjustment and process modification, while the dielectric breakdown strength of ceramics is increased substantially, remain on moderate Dielectric constant, be the key for preparing high density capacitors.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of core shell structure high energy storage density dielectric The preparation method of ceramics, passes through SiO2Coat Ba0.4Sr0.6TiO3Nanometer powder and discharge plasma sintering method, improve dielectric The dielectric breakdown strength of ceramics, so as to improve the energy storage density of dielectric ceramics.
The purpose of the present invention is achieved through the following technical solutions:A kind of core shell structure high energy storage density dielectric pottery The preparation method of porcelain, this method comprises the following steps:
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify;Plus Enter citric acid, continue to stir to clarify;Add BaCO3And SrCO3Powder, is added dropwise the HNO that mass concentration is 65%3Few drops, obtain To mixed solution;Mixed solution is placed in into stirred in water bath to dry into the subsequent baking oven of yellowish-brown vitreosol, until colloidal sol face Discoloration is dark-brown;Finally calcining obtains Ba0.4Sr0.6TiO3Nanometer powder;
(2) SiO is prepared using tetraethyl orthosilicate (TEOS) hydrolysis2Coat Ba0.4Sr0.6TiO3Powder:By Ba0.4Sr0.6TiO3 Powder is surface-treated, and is specially:By Ba0.4Sr0.6TiO3Powder is added to the HNO of dilution3It is quiet after sonic oscillation in solution Put, remove supernatant liquor, deionized water is washed for several times;The Ba that nitric acid treatment is crossed0.4Sr0.6TiO3Powder is added to citric acid solution In, stood after sonic oscillation, remove supernatant liquor;Ba after citric acid treatment0.4Sr0.6TiO3Powder be dispersed in ethanol/go from In the mixed liquor of sub- water/ammoniacal liquor, after sonic oscillation, stir while tetraethyl orthosilicate (TEOS) is slowly added dropwise, add positive silicon The amount of acetoacetic ester causes the Ba after citric acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be (100-x):x;Then heat Stirring is all evaporated to solvent, is calcined after residual powder drying, is obtained the Ba with core shell structure0.4Sr0.6TiO3@SiO2Powder;
(3) powder made from step (2) is loaded into mould, using discharge plasma sintering system 1000 in vacuum environment DEG C~1050 DEG C be sintered, be made ceramic sintered bodies;
(4) under air atmosphere, by ceramic sintered bodies made from step (3), 1100 DEG C~1150 DEG C are handled 1~5 hour, system Obtain the core shell structure high energy storage density dielectric ceramics.
Further, in step (2), the Ba after citric acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be (100- x):X, wherein x=5~12.5.
Further, the Ba after citric acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be (100-x):X, wherein, X=5,8 or 12.5.
Further, in step (1), sol-gal process prepares Ba0.4Sr0.6TiO3During powder, Ti (C4H9O)4With ethylene glycol Molar fraction ratio be 1:15~1:25, Ti (C4H9O)4Molar fraction ratio with citric acid is 1:1~1:4;Water bath heating temperature For 50~80 DEG C;Drying temperature is 100 DEG C~150 DEG C;Powder calcining heat is 850 DEG C~1150 DEG C, and calcination time is 2~5 Hour.
Further, in step (1), sol-gal process prepares Ba0.4Sr0.6TiO3During powder, Ti (C4H9O)4With ethylene glycol Molar fraction ratio be 1:20, Ti (C4H9O)4Molar fraction ratio with citric acid is 1:2;Water bath heating temperature is 70 DEG C;Dry Dry temperature is 120 DEG C;Powder calcining heat is 1050 DEG C, and the time is 3 hours.
Further, in step (2), SiO is prepared2Coat Ba0.4Sr0.6TiO3During powder, Ba0.4Sr0.6TiO3Powder surface The concentration of nitric acid of the dilution used in processing is 0.5~2mol/L;The concentration of the citric acid solution used be 0.005mol/L~ 0.02mol/L;In the mixed liquor of the scattered ethanol/deionized water/ammoniacal liquor used, ethanol, deionized water, ammoniacal liquor press volume fraction Than 50:10:1 mixing;SiO2Coat Ba0.4Sr0.6TiO3The calcining heat of powder is 800 DEG C~900 DEG C, and the time is 1~4 hour.
Further, in step (2), SiO is prepared2Coat Ba0.4Sr0.6TiO3During powder, Ba0.4Sr0.6TiO3Powder surface The dilution concentration of nitric acid used in processing is 1mol/L;The concentration of the citric acid solution used is 0.01mol/L mol/L;SiO2 Coat Ba0.4Sr0.6TiO3The calcining heat of powder is 850 DEG C, and the time is 3 hours.
Further, in step (3), described sintering temperature is 1050 DEG C, and soaking time is 0min.
Further, in step (4), described heat treatment temperature is 1125 DEG C, and the time is 3 hours.
Compared with prior art, the beneficial effects of the present invention are:Using the preparation method of the present invention, plasma discharging burns Tie the Ba prepared0.4Sr0.6TiO3@SiO2Ceramic energy storage density at room temperature, which reaches, can arrive 1.60J/cm3More than, and similarity condition system Standby uncoated SiO2Ba0.4Sr0.6TiO3The energy storage density of dielectric ceramics is only 1.20J/cm3Left and right, energy storage density is improved 0.40J/cm3.Core shell structure high energy storage density dielectric ceramics prepared by the present invention, available for high density energy-storage capacitor etc. Component, has great application value in high-power and pulse power field.
Brief description of the drawings
Fig. 1 is SPS sintering theory figures;
Fig. 2 is that liquid phase method prepares core shell structure (100-x) mol%Ba0.4Sr0.6TiO3+ x mol%SiO2(x=0,5,8, 12.5) ceramic powders transmission electron microscope photo:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 95mol%Ba0.4Sr0.6TiO3+ 5mol%SiO2(embodiment 1);(c) 92mol%Ba0.4Sr0.6TiO3+ 8mol%SiO2(embodiment 2);(d) 87.5mol% Ba0.4Sr0.6TiO3+ 12.5mol%SiO2(embodiment 3);
Fig. 3 prepares (100-x) mol%Ba to put a plasma agglomeration0.4Sr0.6TiO3+ x mol%SiO2(x=0,5,8, 12.5) ceramics XRD diffracting spectrums:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 95mol%Ba0.4Sr0.6TiO3+ 5mol% SiO2(embodiment 1);(c) 92mol%Ba0.4Sr0.6TiO3+ 8mol%SiO2(embodiment 2);(d) 87.5mol% Ba0.4Sr0.6TiO3+ 12.5mol%SiO2(embodiment 3);
Fig. 4 is that discharge plasma sintering prepares (100-x) mol%Ba0.4Sr0.6TiO3+ x mol%SiO2(x=0,5,8, 12.5) the polishing heat erosion surface scan electromicroscopic photograph of ceramics sample:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 95mol% Ba0.4Sr0.6TiO3+ 5mol%SiO2(embodiment 1);(c) 92mol%Ba0.4Sr0.6TiO3+ 8mol%SiO2(embodiment 2); (d) 87.5mol%Ba0.4Sr0.6TiO3+ 12.5mol%SiO2(embodiment 3);
Fig. 5 is that discharge plasma sintering prepares (100-x) mol%Ba0.4Sr0.6TiO3+ x mol%SiO2(x=0,5,8, 12.5) ferroelectric hysteresis loop during ceramics sample room temperature 60Hz under maximum electric field intensity:(a)Ba0.4Sr0.6TiO3(comparative example 1);(b) 95mol%Ba0.4Sr0.6TiO3+ 5mol%SiO2(embodiment 1);(c) 92mol%Ba0.4Sr0.6TiO3+ 8mol%SiO2(implement Example 2);(d) 87.5mol%Ba0.4Sr0.6TiO3+ 12.5mol%SiO2(embodiment 3);
Embodiment
The present invention is further explained with reference to specific embodiment.
Embodiment 1
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify, its Middle Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:15;Citric acid is added, continues to stir to clarify, wherein Ti (C4H9O)4 Molar fraction ratio with citric acid is 1:1;Add BaCO3And SrCO3Powder, is added dropwise the HNO that mass fraction is 65%3Few drops, Obtain mixed solution;Mixed solution is placed in 50 DEG C of stirred in water bath, 100 DEG C of drying into the subsequent baking oven of yellowish-brown vitreosol, Until colloidal sol color is changed into dark-brown;Last 850 DEG C of calcinings obtain Ba in 5 hours0.4Sr0.6TiO3Nanometer powder;
(2) SiO is prepared using tetraethyl orthosilicate (TEOS) hydrolysis2Coat Ba0.4Sr0.6TiO3Powder:By Ba0.4Sr0.6TiO3 Powder is surface-treated, and is specially:By Ba0.4Sr0.6TiO3Powder is added to the HNO of dilution3(dilution concentration of nitric acid in solution For 0.5mol/L), stand after sonic oscillation, remove supernatant liquor, deionized water is washed for several times;What nitric acid treatment was crossed Ba0.4Sr0.6TiO3Powder is added in citric acid solution quiet after (concentration of citric acid solution is 0.005mol/L), sonic oscillation Put, remove supernatant liquor;Ba after citric acid treatment0.4Sr0.6TiO3Powder is dispersed in the mixing of ethanol/deionized water/ammoniacal liquor In liquid, after sonic oscillation, stir while tetraethyl orthosilicate (TEOS) is slowly added dropwise, the amount for adding tetraethyl orthosilicate causes lemon Ba after lemon acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be 95:5;Then heating stirring is all evaporated to solvent, is remained Calcined 4 hours for 800 DEG C after remaining powder drying, obtain the Ba with core shell structure0.4Sr0.6TiO3@SiO2Powder;
(3) powder made from step (2) is loaded to a diameter of 10mm graphite jig, discharge plasma sintering system is put into Sintered under 1000 DEG C, 50MPa mechanical pressures, soaking time is 0min.From room temperature to 900 DEG C of heating rate be 100 DEG C/ Min, from 900 DEG C to 980 DEG C, heating rate is 40 DEG C/min, and 980 DEG C to 1000 DEG C heating rates are 20 DEG C/min, 1000 DEG C of guarantors After the completion of warm 0min, sintering, pressure is shed and cold with stove.As shown in figure 1, SPS sintering theories are:SPS utilizes DC-pulse Stream directly carries out energization pressure sintering, and heating rate is controlled by adjusting the watt level of DC pulse current.Whole sintering Process is carried out under vacuum conditions;Pulse current is directly acted on sample and mould, fast heating, flash heat transfer, quick to rise Temperature, significantly shortens sample sintering time.
(4) ceramics sample made from step (3) is being heat-treated 5 at 1100 DEG C in atmosphere after grinding off the graphite paper of adhesion Hour.It is 5 DEG C/min from room temperature to 1100 DEG C of heating rate, 1100 DEG C are incubated 5h, and 1100 DEG C to 800 DEG C of rate of temperature fall is It is 2 DEG C/min, cold with stove afterwards, obtain core shell structure high energy storage density dielectric ceramics.
Embodiment 2
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify, its Middle Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:20;Citric acid is added, continues to stir to clarify, wherein Ti (C4H9O)4 Molar fraction ratio with citric acid is 1:2;Add BaCO3And SrCO3Powder, is added dropwise the HNO that mass fraction is 65%3Few drops, Obtain mixed solution;Mixed solution is placed in 70 DEG C of stirred in water bath, 120 DEG C of drying into the subsequent baking oven of yellowish-brown vitreosol, Until colloidal sol color is changed into dark-brown;Last 1050 DEG C of calcinings obtain Ba in 3 hours0.4Sr0.6TiO3Nanometer powder;
(2) SiO is prepared using tetraethyl orthosilicate (TEOS) hydrolysis2Coat Ba0.4Sr0.6TiO3Powder:By Ba0.4Sr0.6TiO3 Powder is surface-treated, and is specially:By Ba0.4Sr0.6TiO3Powder is added to the HNO of dilution3(dilution concentration of nitric acid in solution For 1mol/L), stand after sonic oscillation, remove supernatant liquor, deionized water is washed for several times;What nitric acid treatment was crossed Ba0.4Sr0.6TiO3Powder is added in citric acid solution quiet after (concentration of citric acid solution is 0.01mol/L), sonic oscillation Put, remove supernatant liquor;Ba after citric acid treatment0.4Sr0.6TiO3Powder is dispersed in the mixing of ethanol/deionized water/ammoniacal liquor In liquid, after sonic oscillation, stir while tetraethyl orthosilicate (TEOS) is slowly added dropwise, the amount for adding tetraethyl orthosilicate causes lemon Ba after lemon acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be 92:8;Then heating stirring is all evaporated to solvent, is remained Calcined 3 hours for 850 DEG C after remaining powder drying, obtain the Ba with core shell structure0.4Sr0.6TiO3@SiO2Powder;
(3) powder made from step (2) is loaded to a diameter of 10mm graphite jig, discharge plasma sintering system is put into Sintered under 1050 DEG C, 50MPa mechanical pressures, soaking time is 0min.From room temperature to 950 DEG C of heating rate be 100 DEG C/ Min, from 950 DEG C to 1030 DEG C, heating rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C heating rates are 20 DEG C/min, 1050 DEG C It is incubated after the completion of 0min, sintering, sheds pressure and cold with stove.
(4) ceramics sample made from step (3) is being heat-treated 3 at 1125 DEG C in atmosphere after grinding off the graphite paper of adhesion Hour.It is 5 DEG C/min from room temperature to 1125 DEG C of heating rate, 1125 DEG C are incubated 3h, and 1125 DEG C to 800 DEG C of rate of temperature fall is It is 2 DEG C/min, cold with stove afterwards, obtain core shell structure high energy storage density dielectric ceramics.
Embodiment 3
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify, Wherein Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:25;Citric acid is added, continues to stir to clarify, wherein Ti (C4H9O)4Molar fraction ratio with citric acid is 1:4;Add BaCO3And SrCO3Powder, it is 65% that mass fraction, which is added dropwise, HNO3Few drops, obtain mixed solution;Mixed solution is placed in 80 DEG C of stirred in water bath into the subsequent baking oven of yellowish-brown vitreosol 150 DEG C of drying, until colloidal sol color is changed into dark-brown;Last 1150 DEG C of calcinings obtain Ba in 2 hours0.4Sr0.6TiO3Nanometer powder;
(2) SiO is prepared using tetraethyl orthosilicate (TEOS) hydrolysis2Coat Ba0.4Sr0.6TiO3Powder:By Ba0.4Sr0.6TiO3 Powder is surface-treated, and is specially:By Ba0.4Sr0.6TiO3Powder is added to the HNO of dilution3(dilution concentration of nitric acid in solution For 2mol/L), stand after sonic oscillation, remove supernatant liquor, deionized water is washed for several times;What nitric acid treatment was crossed Ba0.4Sr0.6TiO3Powder is added in citric acid solution quiet after (concentration of citric acid solution is 0.02mol/L), sonic oscillation Put, remove supernatant liquor;Ba after citric acid treatment0.4Sr0.6TiO3Powder is dispersed in the mixing of ethanol/deionized water/ammoniacal liquor In liquid, after sonic oscillation, stir while tetraethyl orthosilicate (TEOS) is slowly added dropwise, the amount for adding tetraethyl orthosilicate causes lemon Ba after lemon acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be 87.5:12.5;Then heating stirring is all steamed to solvent Hair, calcines 1 hour for 900 DEG C after residual powder drying, obtains the Ba with core shell structure0.4Sr0.6TiO3@SiO2Powder;
(3) powder made from step (2) is loaded to a diameter of 10mm graphite jig, discharge plasma sintering system is put into Sintered under 1050 DEG C, 50MPa mechanical pressures, soaking time is 0min.From room temperature to 950 DEG C of heating rate be 100 DEG C/ Min, from 950 DEG C to 1030 DEG C, heating rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C heating rates are 20 DEG C/min, 1050 DEG C It is incubated after the completion of 0min, sintering, sheds pressure and cold with stove.
(4) ceramics sample made from step (3) is being heat-treated 1 at 1150 DEG C in atmosphere after grinding off the graphite paper of adhesion Hour.It is 5 DEG C/min from room temperature to 1150 DEG C of heating rate, 1150 DEG C are incubated 5h, and 1150 DEG C to 800 DEG C of rate of temperature fall is It is 2 DEG C/min, cold with stove afterwards, obtain core shell structure high energy storage density dielectric ceramics.
Comparative example 1
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify, its Middle Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:20;Citric acid is added, continues to stir to clarify, wherein Ti (C4H9O)4 Molar fraction ratio with citric acid is 1:2;Add BaCO3And SrCO3Powder, is added dropwise the HNO that mass fraction is 65%3Few drops, Obtain mixed solution;Mixed solution is placed in 70 DEG C of stirred in water bath, 120 DEG C of drying into the subsequent baking oven of yellowish-brown vitreosol, Until colloidal sol color is changed into dark-brown;Last 1050 DEG C of calcinings obtain Ba in 3 hours0.4Sr0.6TiO3Nanometer powder;
(3) powder made from step (1) is loaded to a diameter of 10mm graphite jig, discharge plasma sintering system is put into System is sintered under 1050 DEG C, 50MPa mechanical pressures, and soaking time is 0min.From room temperature to 950 DEG C of heating rate be 100 DEG C/ Min, from 950 DEG C to 1030 DEG C, heating rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C heating rates are 20 DEG C/min, 1050 DEG C It is incubated after the completion of 0min, sintering, sheds pressure and cold with stove.
(4) ceramics sample made from step (3) is being heat-treated 3 at 1125 DEG C in atmosphere after grinding off the graphite paper of adhesion Hour.It is 5 DEG C/min from room temperature to 1125 DEG C of heating rate, 1125 DEG C are incubated 3h, and 1125 DEG C to 800 DEG C of rate of temperature fall is It is 2 DEG C/min, cold with stove afterwards.
The cylindrical dielectric ceramics sample that embodiment 1~3 and comparative example 1 are prepared is milled to 0.18 with sand paper~ 0.22mm thickness, surface is sprayed after gold electrode, is measured the ferroelectric hysteresis loop under its 60Hz frequency using ferroelectricity analyzer, is utilized integration Method calculates its energy storage density.
Table 1
Sample Dielectric breakdown strength (kV/cm) Energy storage density (J/cm3)
BST@SiO2- 5 (embodiments 1) 230 1.20
BST@SiO2- 8 (embodiments 2) 400 1.60
BST@SiO2- 12.5 (embodiments 3) 400 1.30
BST (comparative example 1) 230 1.20
Table 1 is to utilize (100-x) mol%Ba made from the preparation method of the present invention0.4Sr0.6TiO3+ x mol%SiO2(x =5,8,12.5) ceramics and without SiO2The Ba of cladding0.4Sr0.6TiO3Dielectric breakdown strength of the ceramics under room temperature, 60Hz frequencies And energy storage density.Fig. 2, Fig. 3, Fig. 4, Fig. 5 illustrate sample micro-structural, phase composition and ferroelectric properties;From test data, sheet Energy storage density reaches as high as 1.60J/cm to the obtained high energy storage density dielectric ceramics of invention at room temperature3, and plasma discharging Sinter the uncoated SiO prepared2Ba0.4Sr0.6TiO3The energy storage density of dielectric ceramics is only 1.20J/cm3Left and right, energy storage is close Degree improves 0.40J/cm3

Claims (5)

1. a kind of preparation method of core shell structure high energy storage density dielectric ceramics, it is characterised in that comprise the following steps:
(1) sol-gal process prepares Ba0.4Sr0.6TiO3Powder:By Ti (C4H9O)4Ethylene glycol is dissolved in, is stirred to clarify, Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:15~1:25;Citric acid is added, continues to stir to clarify, Ti (C4H9O)4With The molar fraction ratio of citric acid is 1:1~1:4;Add BaCO3And SrCO3Powder, is added dropwise the HNO that mass concentration is 65%3Number Drop, obtains mixed solution;Mixed solution is placed in into stirred in water bath to dry into the subsequent baking oven of yellowish-brown vitreosol, until molten Glue color is changed into dark-brown;Finally calcining obtains Ba0.4Sr0.6TiO3Nanometer powder;Water bath heating temperature is 50~80 DEG C, drying Temperature is 100 DEG C~150 DEG C, and powder calcining heat is 850 DEG C~1150 DEG C, and calcination time is 2~5 hours;
(2) SiO is prepared using teos hydrolysis2Coat Ba0.4Sr0.6TiO3Powder:By Ba0.4Sr0.6TiO3Powder carries out table Face is handled, and is specially:By Ba0.4Sr0.6TiO3Powder is added to the HNO of dilution3In solution, concentration of nitric acid is 0.5~2mol/L, Stood after sonic oscillation, remove supernatant liquor, deionized water is washed for several times;The Ba that nitric acid treatment is crossed0.4Sr0.6TiO3Powder is added Into citric acid solution, the concentration of citric acid solution is in standing after 0.005mol/L~0.02mol/L, sonic oscillation, removal Layer clear liquid;Ba after citric acid treatment0.4Sr0.6TiO3Powder is dispersed in the mixed liquor of ethanol/deionized water/ammoniacal liquor, ethanol, Deionized water, ammoniacal liquor press Volume fraction 50:10:1, after sonic oscillation, stir while tetraethyl orthosilicate is slowly added dropwise, plus Enter the amount of tetraethyl orthosilicate so that Ba after citric acid treatment0.4Sr0.6TiO3Powder and SiO2Mol ratio be (100-x):X, its Middle x=5~12.5;Then heating stirring to solvent all evaporate, residual powder drying after calcine, calcining heat be 800 DEG C~ 900 DEG C, the time is 1~4 hour, obtains the Ba with core shell structure0.4Sr0.6TiO3@SiO2Powder;
(3) by made from step (2) powder load mould, using discharge plasma sintering system 1000 DEG C in vacuum environment~ 1050 DEG C are sintered, and ceramic sintered bodies are made;
(4) under air atmosphere, by ceramic sintered bodies made from step (3), 1100 DEG C~1150 DEG C are heat-treated 1~5 hour, are made The core shell structure high energy storage density dielectric ceramics.
2. preparation method as claimed in claim 1, it is characterised in that in step (2), after citric acid treatment Ba0.4Sr0.6TiO3Powder and SiO2Mol ratio be (100-x):X, wherein, x=5,8 or 12.5.
3. it is prepared by preparation method as claimed in claim 1, it is characterised in that in step (1), sol-gal process Ba0.4Sr0.6TiO3During powder, Ti (C4H9O)4Molar fraction ratio with ethylene glycol is 1:20, Ti (C4H9O)4With rubbing for citric acid Your score ratio is 1:2, water bath heating temperature is 70 DEG C, and drying temperature is 120 DEG C;Powder calcining heat is 1050 DEG C, and the time is 3 Hour.
4. preparation method as claimed in claim 1, it is characterised in that in step (2), prepares SiO2Coat Ba0.4Sr0.6TiO3 During powder, Ba0.4Sr0.6TiO3The dilution concentration of nitric acid used in powder surface treatment is 1mol/L, the citric acid solution used Concentration be 0.01mol/L;SiO2Coat Ba0.4Sr0.6TiO3The calcining heat of powder is 850 DEG C, and the time is 3 hours.
5. preparation method as claimed in claim 1, it is characterised in that in step (4), described heat treatment temperature is 1125 DEG C, the time is 3 hours.
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