CN112521145B - Barium strontium titanate-based ceramic with high energy storage density and power density and preparation method thereof - Google Patents

Barium strontium titanate-based ceramic with high energy storage density and power density and preparation method thereof Download PDF

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CN112521145B
CN112521145B CN202011566061.6A CN202011566061A CN112521145B CN 112521145 B CN112521145 B CN 112521145B CN 202011566061 A CN202011566061 A CN 202011566061A CN 112521145 B CN112521145 B CN 112521145B
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energy storage
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strontium titanate
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郑鹏
李成伟
白王峰
郑梁
张阳
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Hangzhou Dianzi University
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Abstract

The invention relates to barium strontium titanate-based ceramic with high energy storage density and power density and a preparation method thereof, belonging to the field of electric energy storage materials. Adopting solid-phase synthesis method, using paraelectric material Ba0.6Sr0.4TiO3Based on the incorporation of a certain molar ratio of NaNbO3Antiferroelectric material to obtain a novel composite ceramic having the chemical formula (1-x) Ba0.6Sr0.4TiO3‑xNaNbO3Wherein x is more than or equal to 0.10 and less than or equal to 0.25. The main performance parameter of the energy storage ceramic material obtained by the invention can restore the energy storage density Wrec＝6.09J/cm3The energy storage efficiency eta is 87.4 percent, and the power density P is achieved in a 360kV/cm electric fieldD＝221.7MW/cm3The current density can reach 1231.42A/cm2And the energy storage performance is greatly improved compared with the existing product. In addition, the process flow is simple, the method is suitable for industrial production, and the method meets the current lead-free environment-friendly requirement.

Description

Barium strontium titanate-based ceramic with high energy storage density and power density and preparation method thereof
Technical Field
The invention relates to barium strontium titanate-based high energy storage density and power density ceramic and a preparation method thereof, in particular to a doped antiferroelectric NaNbO3The preparation of the barium strontium titanate-based ceramic belongs to the field of dielectric energy storage materials.
Background
At present, the main electrical energy storage devices are batteries, dielectric capacitors, electrochemical capacitors, and the like. These energy storage devices differ significantly in energy density and power density due to their different energy storage mechanisms and charging and discharging processes. Compared with other energy storage devices, the dielectric capacitor can release electric energy in a very short time period (nanosecond to microsecond level) and generate huge pulse current or voltage, and the dielectric capacitor has huge application potential in a pulse power electronic system. Also, unlike electrochemical capacitors and batteries, dielectric capacitors do not involve chemical reactions during charging and discharging, which allows the dielectric capacitors to have good thermal and chemical stability and to operate in a high voltage environment (several hundred to several thousand volts) for a long time.
The dielectric ceramic energy storage material in the dielectric capacitor has the characteristics of high power density, low cost, excellent thermal stability and the like, and is widely applied to high-power systems such as commerce, consumption, medical treatment, military and the like. At present, most of materials used for ceramic capacitors are lead-based ceramics, although the energy storage density is high, the systems contain a large amount of lead elements, which have great harm to human health and environment, and the development of lead-free materials to replace lead-containing system materials is an inevitable trend. However, the lead-free dielectric ceramic capacitor has a limitation in that the energy storage density is low and cannot be compared with the energy storage performance of a lead-based ceramic capacitor, which makes it difficult to meet the development requirements for miniaturization, multifunction and integration of devices, thereby limiting its application in portable electronic devices. If the energy storage density of the lead-free dielectric ceramic capacitor can be effectively improved, the lead-free dielectric ceramic capacitor can be more widely applied to the field of energy storage.
The barium strontium titanate ceramic can be regarded as a solid solution of barium titanate and strontium titanate and belongs to ABO3A perovskite structure. The barium strontium titanate ceramic integrates the advantages of high dielectric constant of barium titanate and low dielectric loss of strontium titanate, and particularly, the dielectric property of the barium strontium titanate ceramic can be changed by adjusting the ratio of barium to strontium so as to meet different practical applications, so that the barium strontium titanate ceramic has great potential for energy storage application. However, the barium strontium titanate ceramic has low breakdown strength due to defects (such as air holes, etc.), which results in low energy storage density, and this also limits the application of barium strontium titanate ceramic in high energy storage density capacitors. Researchers have conducted many studies on these problems. In order to improve the energy storage performance of the barium strontium titanate ceramic, one method is to enhance the breakdown field strength of the barium strontium titanate ceramic by adding glass; another method adopts doping other materialsThe element improves the energy storage performance in a mode of enhancing the relaxation characteristic of the barium strontium titanate ceramic. However, the energy storage density of most barium strontium titanate-based ceramics is still low (<2J/cm3) This still does not replace lead-based ceramic materials.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide barium strontium titanate-based ceramic with high energy storage density and power density and a preparation method thereof, wherein a solid-phase synthesis method is adopted to prepare a paraelectric material Ba0.6Sr0.4TiO3Based on the first time, the antiferroelectric material (NaNbO)3) Introducing the barium strontium titanate-based ceramic into the barium strontium titanate-based ceramic for doping modification to obtain a novel composite ceramic; inducing to form a polar nano micro area to obtain low remanent polarization; the compactness of the ceramic is improved, the grain size of the ceramic is reduced, the breakdown strength of the ceramic is improved, the research direction of doping modification is expanded, and the lead-free energy storage ceramic with application potential is prepared.
The invention can be realized by the following technical scheme:
the chemical composition of the barium strontium titanate-based ceramic with high energy storage density and power density is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Wherein x is more than or equal to 0.10 and less than or equal to 0.25.
Preferably, x is 0.15. This is primarily due to the smaller grain size of the component ceramic, which contributes to the increased breakdown strength. At the same time, the dielectric loss of this component is small at room temperature, which contributes to the improvement of the energy storage efficiency of the ceramic.
The preparation method of the barium strontium titanate-based ceramic with high energy storage density and power density uses a solid-phase reaction method to prepare the corresponding energy storage ceramic, and specifically comprises the following steps:
(1) selecting BaCO with purity of more than 98 percent3Powder and SrCO3Powder of TiO2Powder, NaCO3Powder and Nb2O5The powder is used as raw material and is prepared according to the general formula (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Weighing raw materials, wherein x is 0.10-0.25, adding absolute ethyl alcohol with the same amount as the powder, and performing one-time ball millingUniformly mixing the powder to form slurry;
(2) placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) placing the powder in a mold to be pre-pressed into a material block, pre-burning the material block at the temperature of 1000-1050 ℃ under the closed condition, and keeping the temperature for 3-4h to obtain pre-synthesized ceramic powder;
(4) grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding equal amount of absolute ethyl alcohol into the obtained powder, and performing secondary ball milling.
(5) Drying the obtained slurry at 90 ℃, granulating, sieving and carrying out compression molding to obtain a ceramic green body;
(6) carrying out glue discharging treatment on the ceramic blank at the temperature of 600-650 ℃ for 3-4h, sintering the ceramic blank after glue discharging, wherein the sintering temperature is 1350-1400 ℃, the heating rate is 3-4 ℃/min, the heat preservation time is 2-3h, and cooling to room temperature to obtain the barium strontium titanate-based ceramic with high energy storage density and power density
Furthermore, absolute ethyl alcohol and ZrO are adopted during primary ball milling and secondary ball milling2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 h.
Further, the pre-firing temperature is preferably 1050 ℃ and the holding time is preferably 4 hours.
Furthermore, polyvinyl alcohol (PVA) with the concentration of 8% is used as a binder to be mixed into the powder during granulation, the mass of the mixed binder is 5% of the mass of the powder, the mass of the mixed distilled water is 2.5% of the mass of the powder, the powder is uniformly mixed in a mortar and then placed in a mold, and the powder is pressed into powder blocks.
Furthermore, sieving with 80 mesh and 140 mesh sieves to obtain powder material in the middle layer of 80 mesh and 140 mesh sieves.
Further, the pressure at the time of press molding was controlled to 200 MPa.
Furthermore, when the green body is placed in a crucible for glue removal, a gap is reserved between a cover covered on the crucible and the crucible; during sintering, sealed sintering is adopted, and a crucible is inverted and sealed on the ceramic green body.
Furthermore, the heating rate is controlled at 4 ℃/min during sintering, and the heat preservation time is controlled at 3 h.
Compared with the prior art, the (1-x) Ba prepared by the invention0.6Sr0.4TiO3-xNaNbO3The ceramic is prepared by doping NaNbO in barium strontium titanate ceramic3The average grain size of the barium strontium titanate ceramic is reduced from 41.10 mu m to about 0.22 mu m, the extremely small submicron grain size is achieved, the compactness of the ceramic is greatly improved, the breakdown electric field of the barium strontium titanate ceramic is further enhanced, and finally the energy storage density of the barium strontium titanate ceramic is improved. In addition, the invention introduces Na through A position+Introduction of Nb into B site5+The original long-range ordered dipole arrangement sequence in the barium strontium titanate ceramic is broken, and the polar nano micro-region is formed, so that the hysteresis phenomenon of the dipole under the electric field is reduced, and the high effective energy storage density of 6.09J/cm is obtained3And high power density 221.7MW/cm3The novel energy storage ceramic. Meanwhile, under the electric field intensity of 400kV/cm, the energy storage density of the ceramic material can be kept stable within the temperature range of 20-90 ℃ and the frequency range of 1-500 Hz.
In addition, the preparation process of the invention improves the energy storage performance of the barium strontium titanate-based ceramic by a simple and effective method, the prepared barium strontium titanate-based ceramic has long hysteresis loop, high energy storage density and energy storage efficiency, and high charging and discharging speed, has extremely high application value for realizing lead-free of pulse power devices, has great significance for replacing lead-based energy storage ceramic materials, and can be widely applied to pulse power systems such as high-power microwave weapons, laser weapons, electromagnetic transmitters, hybrid electric vehicles and the like.
Drawings
FIG. 1 is an SEM photograph of a barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2;
FIG. 2 is a graph showing the dielectric constant and dielectric loss versus temperature curves of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2;
FIG. 3 is a hysteresis loop of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2;
FIG. 4 is a graph showing the variation of the energy storage characteristics of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2 with the electric field;
FIG. 5 is a graph showing the variation of the energy storage characteristics of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2 with temperature;
FIG. 6 is a graph showing the variation of the energy storage characteristics of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2 with frequency;
FIG. 7 shows the peak discharge current (I) of the barium strontium titanate-based high energy storage density and power density ceramic prepared in example 2max) And discharge current density (I)maxS) and discharge power density (P)D) Curve with electric field strength.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples will assist the person skilled in the art to further understand the invention, but do not limit it in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
The chemical composition of the barium strontium titanate-based ceramic with high energy storage density and power density is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Wherein x is 0.10, and the following steps are adopted:
(1) selecting BaCO with purity of more than 98 percent3Powder of SrCO3Powder of TiO2Powder, NaCO3Powder and Nb2O5The powder is used as raw material and has a chemical formula of 0.90Ba0.6Sr0.4TiO3-0.10NaNbO3Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling2The ball being asThe ball milling medium is milled at the rotating speed of 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 1050 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding equal amount of absolute ethyl alcohol into the obtained ceramic powder, and performing secondary ball milling, wherein absolute ethyl alcohol and ZrO are still adopted in the process2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8 wt% of polyvinyl alcohol (PVA) as a binder into the powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green body. Wherein, in the granulation, the mass of the binder to be mixed is 5% of the mass of the powder, and the mass of the distilled water to be mixed is 2.5% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering the crucible with a cover and leaving a gap, performing glue discharging treatment for 3 hours at 650 ℃, then inverting the crucible on the ceramic blank subjected to glue discharging, performing closed sintering at 1400 ℃, heating up at a rate of 4 ℃/min, keeping the temperature for 3 hours, and cooling to room temperature to obtain the barium strontium titanate-based high energy storage density and power density ceramic.
The ceramic achieves the charging energy density (total energy density, W) of 4.27J/cm under the electric field of 350kV/cm through testing3Available energy storage density (available energy storage density, W)rec) Reach 3.33J/cm3And the energy storage efficiency (eta) reaches 78.2 percent.
Example 2
The chemical composition of the barium strontium titanate-based ceramic with high energy storage density and power density is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Wherein x is 0.15, and the following steps are adopted:
(1) selecting BaCO with purity of more than 98 percent3Powder of SrCO3Powder of TiO2Powder, NaCO3Powder and Nb2O5The powder is used as raw material and has a chemical formula of 0.85Ba0.6Sr0.4TiO3-0.15NaNbO3Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and uniformly mixing through a one-time ball milling process to uniformly mix the powder to form slurry. Wherein anhydrous ethanol and ZrO are adopted during primary ball milling2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 h.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) placing the powder in a mould to be pre-pressed into a material block, pre-burning the material block at 1050 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding anhydrous ethanol with the same amount into the obtained ceramic powder, and performing secondary ball milling, wherein the anhydrous ethanol and ZrO are still adopted in the process2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 h.
(5) Drying the obtained slurry at 90 ℃, adding 8 wt% of polyvinyl alcohol (PVA) as a binder to be doped into the powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the binder to be mixed is 5% of the mass of the powder, and the mass of the distilled water to be mixed is 2.5% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment at 650 ℃ for 3h, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering at 1375 ℃ at a heating rate of 4 ℃/min for 3h, and cooling to room temperature to obtain the barium strontium titanate-based high energy storage density and power density ceramic.
Fig. 1 is an SEM micrograph of the prepared barium strontium titanate-based ceramic with high energy storage density and power density. As can be seen, the ceramic grain size is around 0.22 microns, which helps to improve the breakdown strength of the ceramic.
FIG. 2 is a graph showing the dielectric constant and dielectric loss of the prepared barium strontium titanate-based ceramic with high energy storage density and power density along with the temperature variation at 100Hz-100kHz, wherein the testing temperature is-250 ℃ and 130 ℃. It can be seen that the temperature corresponding to the dielectric peak of the ceramic is far lower than room temperature, and in addition, the dielectric loss is well maintained below 0.1 within the range of-250-130 ℃.
Fig. 3 is a unidirectional hysteresis loop of the prepared barium strontium titanate-based ceramic with high energy storage density and power density at room temperature and 10Hz, and it can be seen from the figure that the hysteresis loop of the ceramic is relatively long and thin, and the highest electric field strength can reach 520 kV/cm.
FIG. 4 shows the energy storage performance of the prepared barium strontium titanate-based ceramic with high energy storage density and power density in the electric field of 120-520kV/cm, and it can be seen from the figure that the charging energy density (total energy density, W) reaches 6.97J/cm under the electric field of 520kV/cm3Available energy storage density (available energy storage density, W)rec) Reaches 6.09J/cm3And the energy storage efficiency (eta) reaches 87.4 percent.
FIG. 5 is a curve of the energy storage performance of the prepared barium strontium titanate-based ceramic with high energy storage density and power density along with the temperature change under the electric field intensity of 10Hz and 400 kV/cm. As can be seen from the figure, the ceramic material can maintain better temperature stability within 20-90 ℃. The total energy density is kept at 3.64J/cm3In the above way, the change rate of the available energy storage density is less than 12%, and the energy storage efficiency is maintained to be more than 82.0%.
FIG. 6 is a curve of the energy storage performance of the prepared barium strontium titanate-based ceramic with high energy storage density and power density along with the frequency change at room temperature and at an electric field strength of 400 kV/cm. As can be seen from the figure, the ceramic shows excellent frequency stability, the total energy density is kept above 4.01J/cm3 within the test frequency of 1-500Hz, the change rate of the available energy storage density is less than 8%, and the energy storage efficiency is maintained above 80.9%.
Fig. 7 shows the undamped discharge current peak, discharge current density and discharge power density of the prepared barium strontium titanate-based ceramic with high energy storage density and power density. As can be seen from the figure, the ceramic has the discharge current peak value of 38.67A and the discharge current density of 1231.42A/cm under the electric field strength of 360kV/cm2The discharge power density reaches 221.7MW/cm3. Therefore, the ceramic has certain commercial application prospect.
Example 3
The chemical composition of the barium strontium titanate-based ceramic with high energy storage density and power density is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Wherein x is 0.20, and the following steps are adopted:
(1) selecting BaCO with purity of more than 98%3Powder and SrCO3Powder, TiO2Powder, NaCO3Powder and Nb2O5The powder is used as raw material and has a chemical formula of 0.80Ba0.6Sr0.4TiO3-0.20NaNbO3Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 1050 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding anhydrous ethanol with the same amount into the obtained ceramic powder, and performing secondary ball milling, wherein the anhydrous ethanol and ZrO are still adopted in the process2The ball is used as a ball milling medium, the rotating speed is 225r/min, and the ball milling is carried out at intervalsThe running direction is adjusted once in half an hour, and the ball milling time is 12 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8 wt% of polyvinyl alcohol (PVA) as a binder to be doped into the powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the mixed binder is 5% of the mass of the powder, and the mass of the mixed distilled water is 2.5% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment at 650 ℃ for 3h, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering at 1350 ℃, keeping the temperature for 3h at the temperature rise rate of 4 ℃/min, and cooling to room temperature to obtain the barium strontium titanate-based high energy storage density and power density ceramic.
The ceramic achieves 4.38J/cm charging energy density (total energy density, W) under 440kV/cm electric field through testing3Available energy storage density (available energy storage density, W)rec) Reaching 4.08J/cm3And the energy storage efficiency (eta) reaches 93.2 percent.
Example 4
The chemical composition of the barium strontium titanate-based ceramic with high energy storage density and power density is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Wherein x is 0.25, and the following steps are adopted:
(1) selecting BaCO with purity of more than 98%3Powder of SrCO3Powder, TiO2Powder, NaCO3Powder and Nb2O5The powder is used as raw material and has a chemical formula of 0.75Ba0.6Sr0.4TiO3-0.25NaNbO3Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and uniformly mixing through a one-time ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 h.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) placing the powder in a mould to be pre-pressed into a material block, pre-burning the material block at 1050 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding equal amount of absolute ethyl alcohol into the obtained ceramic powder, and performing secondary ball milling, wherein absolute ethyl alcohol and ZrO are still adopted in the process2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8 wt% of polyvinyl alcohol (PVA) as a binder to be doped into the powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the binder to be mixed is 5% of the mass of the powder, and the mass of the distilled water to be mixed is 2.5% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment at 650 ℃ for 3h, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering at 1350 ℃, keeping the temperature for 3h at the temperature rise rate of 4 ℃/min, and cooling to room temperature to obtain the barium strontium titanate-based high energy storage density and power density ceramic.
The ceramic achieves 4.26J/cm charging energy density (total energy density, W) under 400kV/cm electric field through testing3Available energy storage density (available energy storage density, W)rec) Reach 3.86J/cm3And the energy storage efficiency (eta) reaches 90.7 percent.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. The barium strontium titanate-based ceramic with high energy storage density and power density is characterized in that the chemical composition of the ceramic is (1-x) Ba0.6Sr0.4TiO3-xNaNbO3In the above chemical composition, x is 0.15.
2. The preparation method of the barium strontium titanate-based ceramic with high energy storage density and power density is characterized in that the corresponding energy storage ceramic is prepared by a solid-phase reaction method, and the method specifically comprises the following steps:
selecting BaCO with purity of more than 98%3Powder of SrCO3Powder of TiO2Powder, Na2CO3Powder and Nb2O5The powder is used as raw material and is prepared according to the general formula (1-x) Ba0.6Sr0.4TiO3-xNaNbO3Weighing raw materials, wherein x =0.15, adding absolute ethyl alcohol with the same amount as that of the powder, and uniformly mixing the raw materials through a primary ball milling process to uniformly mix the powder to form slurry;
placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
placing the powder in a mold to be pre-pressed into a material block, pre-burning the material block under the closed condition at 1050 ℃ with the temperature being 1000-;
crushing and grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding equal amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling;
drying the obtained slurry at 90 ℃, granulating, sieving and carrying out compression molding to obtain a ceramic green body;
and carrying out glue discharging treatment on the ceramic blank at 600-650 ℃ for 3-4h, sintering the ceramic blank after glue discharging, wherein the sintering temperature is 1350-1400 ℃, the heating rate is 3-4 ℃/min, the heat preservation time is 2-3h, and cooling to room temperature to obtain the barium strontium titanate-based high energy storage density and power density ceramic.
3. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density as claimed in claim 2, wherein the anhydrous ethanol and ZrO are adopted for the primary ball milling and the secondary ball milling2The ball is used as a ball milling medium, the rotating speed is 225r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
4. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density according to claim 2, wherein the pre-sintering temperature is 1050 ℃ and the holding time is 4 hours.
5. The method of claim 2, wherein the polyvinyl alcohol with a concentration of 8% is used as a binder to be mixed into the powder during the granulation, the mass of the mixed binder is 5% of the mass of the powder, the mass of the mixed distilled water is 2.5% of the mass of the powder, and the powder is uniformly mixed in a mortar, placed in a mold, and pressed into a powder block.
6. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density according to claim 2, wherein 80 mesh and 140 mesh sieves are used for sieving, and powder materials in the middle layers of the 80 mesh and 140 mesh sieves are taken.
7. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density according to claim 2, wherein the pressure during compression molding is controlled to 200 MPa.
8. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density as claimed in claim 2, wherein when the green body is placed in a crucible for binder removal, a gap is left between a cover covering the crucible and the crucible; during sintering, sealed sintering is adopted, and a crucible is inverted and sealed on the ceramic green body.
9. The method for preparing barium strontium titanate-based ceramic with high energy storage density and power density according to claim 2, wherein the temperature rise rate during sintering is 4 ℃/min, and the heat preservation time is 3 h.
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