CN105198410A - Preparation method of core-shell-structured dielectric medium ceramic with high energy storage density - Google Patents
Preparation method of core-shell-structured dielectric medium ceramic with high energy storage density Download PDFInfo
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Abstract
The invention discloses a preparation method of core-shell-structured dielectric medium ceramic with high energy storage density. The method comprises the following steps: firstly, preparing Ba0.4Sr0.6TiO3 powder through a sol-gel method; secondly, covering the Ba0.4Sr0.6TiO3 powder with SiO2 prepared by hydrolyzing tetraethoxysilane; secondly, filling the prepared powder into a mold, and sintering by using a discharging plasma sintering system in a vacuum environment at the temperature of 1000 DEG C to 1050 DEG C to prepare a ceramic sintered body; finally, treating the ceramic sintered body at the temperature of 1100 DEG C to 1150 DEG C under an air atmosphere for 1 to 5 hours to prepare the core-shell-structured dielectric medium ceramic with the high energy storage density. The energy storage density of the core-shell-structured dielectric medium ceramic with the high energy storage density, which is prepared by the preparation method, can be up to more than 1.60J/cm<3> at a room temperature; compared with Ba0.4Sr0.6TiO3 dielectric medium ceramic which is not covered by SiO2 under the same condition, the energy storage density of the dielectric medium ceramic is improved by 0.40J/cm<3>.
Description
Technical field
The present invention relates to energy storage capacitor dielectric material technical field, particularly relate to a kind of preparation method of nucleocapsid structure high energy storage density dielectric ceramics.
Background technology
Dielectric capacitor energy storage mode is stored with the form of the enrichment charge voltage field between couple capacitors pole plate by electric energy.Compared with traditional fuel cell, lithium cell, the feature of dielectric medium energy storage capacitor is fast response time, power density is high, long service life, all solid state safeguard construction, use temperature scope are wide, has a very wide range of applications in high-power and Pulsed power device.For linear dielectric medium, its energy storage density is directly proportional to specific inductivity, to square being directly proportional of dielectric breakdown field intensity, therefore exploring the dielectric materials with high-k, high dielectric breakdown field intensity and low-dielectric loss, is the key improving energy storage density, realize device miniaturization.Barium-strontium titanate ceramic is widely used in the fields such as microelectronics, photoelectron, integrated optics and microelectromechanical systems because having good ferroelectricity, piezoelectricity, non-linear optical property etc.In energy storage, lower dielectric loss, higher specific inductivity and breaking down field strength, also make barium-strontium titanate ceramic obtain and pay close attention to.
Application number be 201110046717.6 Chinese patent disclose a kind of preparation method of barium strontium titanate-based energy storage dielectric ceramic, its step is as follows: the preparation of (1) BST pottery fine powder; (2) preparation of frit; (3) by percent by volume shared by each raw material be: BST pottery fine powder 80 ~ 99%, frit 1 ~ 20%, choose above-mentioned BST pottery fine powder and frit; Add frit in BST pottery fine powder, with zirconium white and dehydrated alcohol ball milling 24 ~ 36h, dry obtained ceramics-glass mixed powder, add binding agent granulation, the add-on of binding agent is 3 ~ 5% of ceramics-glass mixed powder quality, and compressing tablet obtains green sheet; Green sheet is incubated 2h binder removal at 600 DEG C, is cooled to room temperature, is finally 2 ~ 4 DEG C/min at temperature rise rate, is incubated 2 ~ 4h, obtains barium strontium titanate-based energy storage dielectric ceramic at 1050 ~ 1280 DEG C.Energy-storing dielectric ceramic prepared by the method, recording specific inductivity is 380, disruptive strength 28.0kV/mm, and effective energy storage density is 1.50J/cm
3.
Above-mentioned patent, by adding glassy phase in barium-strontium titanate ceramic, makes the dielectric breakdown strength of pottery improve, thus obtains higher energy storage density.But the specific inductivity that with the addition of the strontium-barium titanate complex phase ceramic of glassy phase declines obviously, therefore how by formula adjustment and process modification, while the dielectric breakdown strength increasing substantially pottery, still keeping moderate specific inductivity, is the key preparing high density capacitors.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of nucleocapsid structure high energy storage density dielectric ceramics is provided, passes through SiO
2coated Ba
0.4sr
0.6tiO
3nanometer powder and discharge plasma sintering method, improve the dielectric breakdown strength of dielectric ceramics, thus improve the energy storage density of dielectric ceramics.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of nucleocapsid structure high energy storage density dielectric ceramics, the method comprises the following steps:
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify; Add citric acid, continue to stir to clarify; Add BaCO again
3and SrCO
3powder, dripping mass concentration is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in stirred in water bath to yellowish brown vitreosol subsequently baking oven dry, until colloidal sol color becomes dark-brown; Finally calcining obtains Ba
0.4sr
0.6tiO
3nanometer powder;
(2) tetraethoxy (TEOS) is utilized to be hydrolyzed preparation SiO
2coated Ba
0.4sr
0.6tiO
3powder: by Ba
0.4sr
0.6tiO
3powder carries out surface treatment, is specially: by Ba
0.4sr
0.6tiO
3powder joins the HNO of dilution
3in solution, leave standstill after sonic oscillation, remove supernatant liquid, deionized water wash for several times; The Ba that nitric acid treatment is crossed
0.4sr
0.6tiO
3powder joins in citric acid solution, leaves standstill after sonic oscillation, removes supernatant liquid; Ba after citric acid treatment
0.4sr
0.6tiO
3powder dispersion, in the mixed solution of ethanol/deionized water/ammoniacal liquor, after sonic oscillation, stirs and slowly drips tetraethoxy (TEOS), and the amount adding tetraethoxy makes the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x; Then heated and stirred is all evaporated to solvent, and residual powder is calcined after drying, and obtains the Ba with nucleocapsid structure
0.4sr
0.6tiO
3siO
2powder;
(3) powder obtained for step (2) is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C ~ 1050 DEG C sinter, obtained ceramic sintered bodies;
(4) under air atmosphere, ceramic sintered bodies 1100 DEG C ~ 1150 DEG C obtained for step (3) is processed 1 ~ 5 hour, obtained described nucleocapsid structure high energy storage density dielectric ceramics.
Further, in step (2), the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x, wherein x=5 ~ 12.5.
Further, the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x, wherein, x=5,8 or 12.5.
Further, in step (1), sol-gel method prepares Ba
0.4sr
0.6tiO
3during powder, Ti (C
4h
9o)
4compare for 1:15 ~ 1:25, Ti (C with the molar fraction of ethylene glycol
4h
9o)
4compare for 1:1 ~ 1:4 with the molar fraction of citric acid; Water bath heating temperature is 50 ~ 80 DEG C; Bake out temperature is 100 DEG C ~ 150 DEG C; Powder calcining temperature is 850 DEG C ~ 1150 DEG C, and calcination time is 2 ~ 5 hours.
Further, in step (1), sol-gel method prepares Ba
0.4sr
0.6tiO
3during powder, Ti (C
4h
9o)
4compare for 1:20, Ti (C with the molar fraction of ethylene glycol
4h
9o)
4compare for 1:2 with the molar fraction of citric acid; Water bath heating temperature is 70 DEG C; Bake out temperature is 120 DEG C; Powder calcining temperature is 1050 DEG C, and the time is 3 hours.
Further, in step (2), preparation SiO
2coated Ba
0.4sr
0.6tiO
3during powder, Ba
0.4sr
0.6tiO
3the concentration of nitric acid of the dilution used in powder surface process is 0.5 ~ 2mol/L; The concentration of the citric acid solution used is 0.005mol/L ~ 0.02mol/L; In the mixed solution of ethanol/deionized water/ammoniacal liquor that dispersion uses, ethanol, deionized water, ammoniacal liquor by volume mark mix than 50:10:1; SiO
2coated Ba
0.4sr
0.6tiO
3the calcining temperature of powder is 800 DEG C ~ 900 DEG C, and the time is 1 ~ 4 hour.
Further, in step (2), preparation SiO
2coated Ba
0.4sr
0.6tiO
3during powder, Ba
0.4sr
0.6tiO
3the dilution concentration of nitric acid used in powder surface process is 1mol/L; The concentration of the citric acid solution used is 0.01mol/Lmol/L; SiO
2coated Ba
0.4sr
0.6tiO
3the calcining temperature 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 thermal treatment temp is 1125 DEG C, and the time is 3 hours.
Compared with prior art, beneficial effect of the present invention is: adopt preparation method of the present invention, Ba prepared by discharge plasma sintering
0.4sr
0.6tiO
3siO
2pottery at room temperature energy storage density reaches and can arrive 1.60J/cm
3above, non-coated Si O prepared by similarity condition
2ba
0.4sr
0.6tiO
3the energy storage density of dielectric ceramics is only 1.20J/cm
3left and right, energy storage density improves 0.40J/cm
3.Nucleocapsid structure high energy storage density dielectric ceramics 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 figure;
Fig. 2 is Liquid preparation methods nucleocapsid structure (100-x) mol%Ba
0.4sr
0.6tiO
3+ xmol%SiO
2(x=0,5,8,12.5) ceramic powder transmission electron microscope photo: (a) Ba
0.4sr
0.6tiO
3(comparative example 1); (b) 95mol%Ba
0.4sr
0.6tiO
3+ 5mol%SiO
2(embodiment 1); (c) 92mol%Ba
0.4sr
0.6tiO
3+ 8mol%SiO
2(embodiment 2); (d) 87.5mol%Ba
0.4sr
0.6tiO
3+ 12.5mol%SiO
2(embodiment 3);
Fig. 3 is for putting plasma agglomeration preparation (100-x) mol%Ba
0.4sr
0.6tiO
3+ xmol%SiO
2(x=0,5,8,12.5) ceramic XRD diffracting spectrum: (a) Ba
0.4sr
0.6tiO
3(comparative example 1); (b) 95mol%Ba
0.4sr
0.6tiO
3+ 5mol%SiO
2(embodiment 1); (c) 92mol%Ba
0.4sr
0.6tiO
3+ 8mol%SiO
2(embodiment 2); (d) 87.5mol%Ba
0.4sr
0.6tiO
3+ 12.5mol%SiO
2(embodiment 3);
Fig. 4 is discharge plasma sintering preparation (100-x) mol%Ba
0.4sr
0.6tiO
3+ xmol%SiO
2the polishing thermal etching surface scan electromicroscopic photograph of (x=0,5,8,12.5) ceramics sample: (a) Ba
0.4sr
0.6tiO
3(comparative example 1); (b) 95mol%Ba
0.4sr
0.6tiO
3+ 5mol%SiO
2(embodiment 1); (c) 92mol%Ba
0.4sr
0.6tiO
3+ 8mol%SiO
2(embodiment 2); (d) 87.5mol%Ba
0.4sr
0.6tiO
3+ 12.5mol%SiO
2(embodiment 3);
Fig. 5 is discharge plasma sintering preparation (100-x) mol%Ba
0.4sr
0.6tiO
3+ xmol%SiO
2ferroelectric hysteresis loop during (x=0,5,8,12.5) ceramics sample room temperature 60Hz under maximum electric field intensity: (a) Ba
0.4sr
0.6tiO
3(comparative example 1); (b) 95mol%Ba
0.4sr
0.6tiO
3+ 5mol%SiO
2(embodiment 1); (c) 92mol%Ba
0.4sr
0.6tiO
3+ 8mol%SiO
2(embodiment 2); (d) 87.5mol%Ba
0.4sr
0.6tiO
3+ 12.5mol%SiO
2(embodiment 3);
Embodiment
The present invention is explained further below in conjunction with specific embodiment.
Embodiment 1
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:15 with the molar fraction of ethylene glycol; Add citric acid, continue to stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:1 with the molar fraction of citric acid; Add BaCO again
3and SrCO
3powder, dripping massfraction is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in 50 DEG C of stirred in water bath to 100 DEG C, the baking oven oven dry subsequently of yellowish brown vitreosol, until colloidal sol color becomes dark-brown; Last 850 DEG C of calcinings obtain Ba in 5 hours
0.4sr
0.6tiO
3nanometer powder;
(2) tetraethoxy (TEOS) is utilized to be hydrolyzed preparation SiO
2coated Ba
0.4sr
0.6tiO
3powder: by Ba
0.4sr
0.6tiO
3powder carries out surface treatment, is specially: by Ba
0.4sr
0.6tiO
3powder joins the HNO of dilution
3in solution (dilution concentration of nitric acid is 0.5mol/L), leave standstill after sonic oscillation, remove supernatant liquid, deionized water wash for several times; The Ba that nitric acid treatment is crossed
0.4sr
0.6tiO
3powder joins (concentration of citric acid solution is 0.005mol/L) in citric acid solution, leaves standstill after sonic oscillation, removes supernatant liquid; Ba after citric acid treatment
0.4sr
0.6tiO
3powder dispersion, in the mixed solution of ethanol/deionized water/ammoniacal liquor, after sonic oscillation, stirs and slowly drips tetraethoxy (TEOS), and the amount adding tetraethoxy makes the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be 95:5; Then heated and stirred is all evaporated to solvent, and residual powder dries rear 800 DEG C of calcinings 4 hours, obtains the Ba with nucleocapsid structure
0.4sr
0.6tiO
3siO
2powder;
(3) powder obtained for step (2) being loaded diameter is the graphite jig of 10mm, put into discharge plasma sintering system 1000 DEG C, sinter under 50MPa mechanical pressure, soaking time is 0min.Be 100 DEG C/min from room temperature to the temperature rise rate of 900 DEG C, from 900 DEG C to 980 DEG C, temperature rise rate is 40 DEG C/min, and 980 DEG C to 1000 DEG C temperature rise rates are 20 DEG C/min, 1000 DEG C of insulation 0min, after having sintered, sheds pressure and cold with stove.As shown in Figure 1, 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 is carried out under vacuum conditions; Pulsed current directly acts on sample and mould, fast heating, and flash heat transfer, is rapidly heated, and significantly shortens sample sintering time.
(4) by ceramics sample obtained for step (3) thermal treatment 5 hours at 1100 DEG C in atmosphere after grinding off the graphite paper of adhesion.From room temperature to the temperature rise rate of 1100 DEG C be 5 DEG C/min, 1100 DEG C insulation 5h, the rate of temperature fall of 1100 DEG C to 800 DEG C is 2 DEG C/min, cold with stove afterwards, obtains nucleocapsid structure high energy storage density dielectric ceramics.
Embodiment 2
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:20 with the molar fraction of ethylene glycol; Add citric acid, continue to stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:2 with the molar fraction of citric acid; Add BaCO again
3and SrCO
3powder, dripping massfraction is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in 70 DEG C of stirred in water bath to 120 DEG C, the baking oven oven dry subsequently of yellowish brown vitreosol, until colloidal sol color becomes dark-brown; Last 1050 DEG C of calcinings obtain Ba in 3 hours
0.4sr
0.6tiO
3nanometer powder;
(2) tetraethoxy (TEOS) is utilized to be hydrolyzed preparation SiO
2coated Ba
0.4sr
0.6tiO
3powder: by Ba
0.4sr
0.6tiO
3powder carries out surface treatment, is specially: by Ba
0.4sr
0.6tiO
3powder joins the HNO of dilution
3in solution (dilution concentration of nitric acid is 1mol/L), leave standstill after sonic oscillation, remove supernatant liquid, deionized water wash for several times; The Ba that nitric acid treatment is crossed
0.4sr
0.6tiO
3powder joins (concentration of citric acid solution is 0.01mol/L) in citric acid solution, leaves standstill after sonic oscillation, removes supernatant liquid; Ba after citric acid treatment
0.4sr
0.6tiO
3powder dispersion, in the mixed solution of ethanol/deionized water/ammoniacal liquor, after sonic oscillation, stirs and slowly drips tetraethoxy (TEOS), and the amount adding tetraethoxy makes the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be 92:8; Then heated and stirred is all evaporated to solvent, and residual powder dries rear 850 DEG C of calcinings 3 hours, obtains the Ba with nucleocapsid structure
0.4sr
0.6tiO
3siO
2powder;
(3) powder obtained for step (2) being loaded diameter is the graphite jig of 10mm, put into discharge plasma sintering system 1050 DEG C, sinter under 50MPa mechanical pressure, soaking time is 0min.Be 100 DEG C/min from room temperature to the temperature rise rate of 950 DEG C, from 950 DEG C to 1030 DEG C, temperature rise rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C temperature rise rates are 20 DEG C/min, 1050 DEG C of insulation 0min, after having sintered, sheds pressure and cold with stove.
(4) by ceramics sample obtained for step (3) thermal treatment 3 hours at 1125 DEG C in atmosphere after grinding off the graphite paper of adhesion.From room temperature to the temperature rise rate of 1125 DEG C be 5 DEG C/min, 1125 DEG C insulation 3h, the rate of temperature fall of 1125 DEG C to 800 DEG C is 2 DEG C/min, cold with stove afterwards, obtains nucleocapsid structure high energy storage density dielectric ceramics.
Embodiment 3
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:25 with the molar fraction of ethylene glycol; Add citric acid, continue to stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:4 with the molar fraction of citric acid; Add BaCO again
3and SrCO
3powder, dripping massfraction is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in 80 DEG C of stirred in water bath to 150 DEG C, the baking oven oven dry subsequently of yellowish brown vitreosol, until colloidal sol color becomes dark-brown; Last 1150 DEG C of calcinings obtain Ba in 2 hours
0.4sr
0.6tiO
3nanometer powder;
(2) tetraethoxy (TEOS) is utilized to be hydrolyzed preparation SiO
2coated Ba
0.4sr
0.6tiO
3powder: by Ba
0.4sr
0.6tiO
3powder carries out surface treatment, is specially: by Ba
0.4sr
0.6tiO
3powder joins the HNO of dilution
3in solution (dilution concentration of nitric acid is 2mol/L), leave standstill after sonic oscillation, remove supernatant liquid, deionized water wash for several times; The Ba that nitric acid treatment is crossed
0.4sr
0.6tiO
3powder joins (concentration of citric acid solution is 0.02mol/L) in citric acid solution, leaves standstill after sonic oscillation, removes supernatant liquid; Ba after citric acid treatment
0.4sr
0.6tiO
3powder dispersion, in the mixed solution of ethanol/deionized water/ammoniacal liquor, after sonic oscillation, stirs and slowly drips tetraethoxy (TEOS), and the amount adding tetraethoxy makes the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be 87.5:12.5; Then heated and stirred is all evaporated to solvent, and residual powder dries rear 900 DEG C of calcinings 1 hour, obtains the Ba with nucleocapsid structure
0.4sr
0.6tiO
3siO
2powder;
(3) powder obtained for step (2) being loaded diameter is the graphite jig of 10mm, put into discharge plasma sintering system 1050 DEG C, sinter under 50MPa mechanical pressure, soaking time is 0min.Be 100 DEG C/min from room temperature to the temperature rise rate of 950 DEG C, from 950 DEG C to 1030 DEG C, temperature rise rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C temperature rise rates are 20 DEG C/min, 1050 DEG C of insulation 0min, after having sintered, sheds pressure and cold with stove.
(4) by ceramics sample obtained for step (3) thermal treatment 1 hour at 1150 DEG C in atmosphere after grinding off the graphite paper of adhesion.From room temperature to the temperature rise rate of 1150 DEG C be 5 DEG C/min, 1150 DEG C insulation 5h, the rate of temperature fall of 1150 DEG C to 800 DEG C is 2 DEG C/min, cold with stove afterwards, obtains nucleocapsid structure high energy storage density dielectric ceramics.
Comparative example 1
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:20 with the molar fraction of ethylene glycol; Add citric acid, continue to stir to clarify, wherein Ti (C
4h
9o)
4compare for 1:2 with the molar fraction of citric acid; Add BaCO again
3and SrCO
3powder, dripping massfraction is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in 70 DEG C of stirred in water bath to 120 DEG C, the baking oven oven dry subsequently of yellowish brown vitreosol, until colloidal sol color becomes dark-brown; Last 1050 DEG C of calcinings obtain Ba in 3 hours
0.4sr
0.6tiO
3nanometer powder;
(3) powder obtained for step (1) being loaded diameter is the graphite jig of 10mm, put into discharge plasma sintering system 1050 DEG C, sinter under 50MPa mechanical pressure, soaking time is 0min.Be 100 DEG C/min from room temperature to the temperature rise rate of 950 DEG C, from 950 DEG C to 1030 DEG C, temperature rise rate is 40 DEG C/min, and 1030 DEG C to 1050 DEG C temperature rise rates are 20 DEG C/min, 1050 DEG C of insulation 0min, after having sintered, sheds pressure and cold with stove.
(4) by ceramics sample obtained for step (3) thermal treatment 3 hours at 1125 DEG C in atmosphere after grinding off the graphite paper of adhesion.From room temperature to the temperature rise rate of 1125 DEG C be 5 DEG C/min, 1125 DEG C insulation 3h, the rate of temperature fall of 1125 DEG C to 800 DEG C is 2 DEG C/min, cold with stove afterwards.
Cylindrical dielectric ceramics sample sand paper embodiment 1 ~ 3 and comparative example 1 prepared is milled to 0.18 ~ 0.22mm thickness, after gold electrode is sprayed on surface, ferroelectric hysteresis loop under utilizing ferroelectric analyser to measure its 60Hz frequency, utilizes integration to calculate its energy storage density.
Table 1
Sample | Dielectric breakdown strength (kV/cm) | Energy storage density (J/cm 3) |
BSTSiO 2-5 (embodiments 1) | 230 | 1.20 |
BSTSiO 2-8 (embodiments 2) | 400 | 1.60 |
BSTSiO 2-12.5 (embodiments 3) | 400 | 1.30 |
BST (comparative example 1) | 230 | 1.20 |
Table 1 (100-x) mol%Ba for utilizing preparation method of the present invention to obtain
0.4sr
0.6tiO
3+ xmol%SiO
2(x=5,8,12.5) pottery and without SiO
2coated Ba
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, Fig. 5 illustrate sample microstructure, phase composite and ferroelectric properties; From test data, the high energy storage density dielectric ceramics that the present invention obtains at room temperature energy storage density reaches as high as 1.60J/cm
3, and non-coated Si O prepared by discharge plasma sintering
2ba
0.4sr
0.6tiO
3the energy storage density of dielectric ceramics is only 1.20J/cm
3left and right, energy storage density improves 0.40J/cm
3.
Claims (9)
1. a preparation method for nucleocapsid structure high energy storage density dielectric ceramics, is characterized in that, comprises the following steps:
(1) sol-gel method prepares Ba
0.4sr
0.6tiO
3powder: by Ti (C
4h
9o)
4be dissolved in ethylene glycol, stir to clarify; Add citric acid, continue to stir to clarify; Add BaCO again
3and SrCO
3powder, dripping mass concentration is the HNO of 65%
3several, obtain mixing solutions; Mixing solutions is placed in stirred in water bath to yellowish brown vitreosol subsequently baking oven dry, until colloidal sol color becomes dark-brown; Finally calcining obtains Ba
0.4sr
0.6tiO
3nanometer powder;
(2) tetraethoxy (TEOS) is utilized to be hydrolyzed preparation SiO
2coated Ba
0.4sr
0.6tiO
3powder: by Ba
0.4sr
0.6tiO
3powder carries out surface treatment, is specially: by Ba
0.4sr
0.6tiO
3powder joins the HNO of dilution
3in solution, leave standstill after sonic oscillation, remove supernatant liquid, deionized water wash for several times; The Ba that nitric acid treatment is crossed
0.4sr
0.6tiO
3powder joins in citric acid solution, leaves standstill after sonic oscillation, removes supernatant liquid; Ba after citric acid treatment
0.4sr
0.6tiO
3powder dispersion, in the mixed solution of ethanol/deionized water/ammoniacal liquor, after sonic oscillation, stirs and slowly drips tetraethoxy (TEOS), and the amount adding tetraethoxy makes the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x; Then heated and stirred is all evaporated to solvent, and residual powder is calcined after drying, and obtains the Ba with nucleocapsid structure
0.4sr
0.6tiO
3siO
2powder;
(3) powder obtained for step 2 is loaded mould, utilize discharge plasma sintering system in vacuum environment 1000 DEG C ~ 1050 DEG C sinter, obtained ceramic sintered bodies;
(4) under air atmosphere, ceramic sintered bodies 1100 DEG C ~ 1150 DEG C obtained for step 3 is processed 1 ~ 5 hour, obtained described nucleocapsid structure high energy storage density dielectric ceramics.
2. preparation method as claimed in claim 1, is characterized in that, in step 2, and the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x, wherein x=5 ~ 12.5.
3. preparation method as claimed in claim 2, is characterized in that, in step 2, and the Ba after citric acid treatment
0.4sr
0.6tiO
3powder and SiO
2mol ratio be (100-x): x, wherein, x=5,8 or 12.5.
4. preparation method as claimed in claim 1, it is characterized in that, in step 1, sol-gel method prepares Ba
0.4sr
0.6tiO
3during powder, Ti (C
4h
9o)
4compare for 1:15 ~ 1:25, Ti (C with the molar fraction of ethylene glycol
4h
9o)
4compare for 1:1 ~ 1:4 with the molar fraction of citric acid; Water bath heating temperature is 50 ~ 80 DEG C; Bake out temperature is 100 DEG C ~ 150 DEG C; Powder calcining temperature is 850 DEG C ~ 1150 DEG C, and calcination time is 2 ~ 5 hours.
5. preparation method as claimed in claim 4, it is characterized in that, in step 1, sol-gel method prepares Ba
0.4sr
0.6tiO
3during powder, Ti (C
4h
9o)
4compare for 1:20, Ti (C with the molar fraction of ethylene glycol
4h
9o)
4compare for 1:2 with the molar fraction of citric acid; Water bath heating temperature is 70 DEG C; Bake out temperature is 120 DEG C; Powder calcining temperature is 1050 DEG C, and the time is 3 hours.
6. preparation method as claimed in claim 1, is characterized in that, in step 2, and preparation SiO
2coated Ba
0.4sr
0.6tiO
3during powder, Ba
0.4sr
0.6tiO
3the concentration of nitric acid of the dilution used in powder surface process is 0.5 ~ 2mol/L; The concentration of the citric acid solution used is 0.005mol/L ~ 0.02mol/L; In the mixed solution of ethanol/deionized water/ammoniacal liquor that dispersion uses, ethanol, deionized water, ammoniacal liquor by volume mark mix than 50:10:1; SiO
2coated Ba
0.4sr
0.6tiO
3the calcining temperature of powder is 800 DEG C ~ 900 DEG C, and the time is 1 ~ 4 hour.
7. preparation method as claimed in claim 6, is characterized in that, in step 2, and preparation SiO
2coated Ba
0.4sr
0.6tiO
3during powder, Ba
0.4sr
0.6tiO
3the dilution concentration of nitric acid used in powder surface process is 1mol/L; The concentration of the citric acid solution used is 0.01mol/Lmol/L; SiO
2coated Ba
0.4sr
0.6tiO
3the calcining temperature of powder is 850 DEG C, and the time is 3 hours.
8. preparation method as claimed in claim 1, it is characterized in that, in step 3, described sintering temperature is 1050 DEG C, and soaking time is 0min.
9. preparation method as claimed in claim 1, it is characterized in that, in step 4, described thermal treatment temp is 1125 DEG C, and the time is 3 hours.
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CN111302789A (en) * | 2020-03-17 | 2020-06-19 | 华南理工大学 | Pulse energy storage dielectric material with sandwich structure and preparation method and application thereof |
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