CN114520114B - High-temperature-stability bismuth sodium titanate-based medium energy storage ceramic and preparation method thereof - Google Patents

High-temperature-stability bismuth sodium titanate-based medium energy storage ceramic and preparation method thereof Download PDF

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CN114520114B
CN114520114B CN202210171277.5A CN202210171277A CN114520114B CN 114520114 B CN114520114 B CN 114520114B CN 202210171277 A CN202210171277 A CN 202210171277A CN 114520114 B CN114520114 B CN 114520114B
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袁颖
蒋泽华
唐斌
钟朝位
张树人
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University of Electronic Science and Technology of China
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Abstract

High-grade steelA temperature-stable sodium bismuth titanate-based dielectric energy storage ceramic material belongs to the technical field of electronic information functional materials and devices. The ceramic material is Na 0.5 Bi 0.5 TiO 3 ‑xBaTiO 3 ‑ySrTiO 3 ‑zZnTa 2 O 6 Wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.2 and less than or equal to 0.5,0<z is less than or equal to 0.2. The dielectric ceramic material not only realizes high energy storage density, energy storage efficiency and power density, but also realizes the temperature stability at room temperature which does not exist in other sodium bismuth titanate-based energy storage ceramics and meets the X7R standard.

Description

High-temperature-stability bismuth sodium titanate-based medium energy storage ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic information functional materials and devices, and particularly relates to a sodium bismuth titanate-based dielectric energy storage ceramic material.
Background
Under the promotion of technology and industry upgrading, the pulse power supply technology is widely applied to modern power systems. Dielectric capacitors have higher power density, charge-discharge rate and cycle life than super-capacitors and electrochemical capacitors, which are critical for pulsed capacitors. Meanwhile, in the face of the development trend of integration and miniaturization of modern power systems, the application of the dielectric capacitor is limited by the relatively small energy storage density. Therefore, the development of the dielectric energy storage ceramic material with high energy storage density and power density has great application value.
The bismuth sodium titanate ceramic with high intrinsic polarization characteristics has great application potential in the field of medium energy storage. However, bismuth sodium titanate ceramics exhibit significant hysteresis during the redirection of ferroelectric domains, resulting in greater energy loss and lower breakdown strength. The bismuth sodium titanate is a typical ferroelectric, has larger remnant polarization intensity and coercive field, and can obtain proper energy storage density and energy storage efficiency by doping and multiphase compound regulation and control of the composition and structure of bismuth sodium titanate ceramic, reducing ferroelectricity and enhancing the relaxation property of bismuth sodium titanate ceramic. Meanwhile, temperature stability is a key index for measuring the reliability of the dielectric capacitor under different working environments. However, the studies on the sodium bismuth titanate-based ceramics known so far have been conducted to evaluate only the thermal stability at high temperatures [1,2 ]]. For example, zhang et al by incorporating Bi into a bismuth sodium titanate-based ceramic 0.1 Sr 0.85 TiO 3 Increases the dielectric strength of the ceramic, thereby obtaining a large energy storage density (3.72J/cm 3 ) And energy storage efficiency (90).7%) but does not pay attention to the temperature stability in the range below room temperature when the ceramic is used as a dielectric capacitor material. Also, for example, li et al doped Bi (Mg) into sodium bismuth titanate-based ceramics 0.5 Sn 0.5 )O 3 Effectively inhibit the early planned saturation phenomenon of the ceramic, and the energy storage density of the ceramic is 1.47J/cm 3 Increased to 3.76J/cm 3 But it is of interest to have a temperature stability at 150 c when the ceramic is used as a dielectric capacitor material. ([1]Zhang,X.,D.Hu,Z.Pan,X.Lv,Z.He,F.Yang,P.Li,J.Liu and J.Zhai.Enhancement of recoverable energy density and efficiency of lead-free relaxor-ferroelectric BNT-based ceramics.Chem.Eng.J.,2021.406:p.126818.[2]Li,X.,X.Dong,F.Wang,Z.Tan,Q.Zhang,H.Chen,J.Xi,J.Xing,H.Zhou and J.Zhu.Realizing excellent energy storage properties in Na 0.5 Bi 0.5 TiO 3 -based lead-free relay ferroelectrics.J.Eur.Ceram.Soc.2021.42 (5): 2221-2229.). At present, related technical achievements of sodium bismuth titanate-based energy storage ceramics with excellent energy storage performance and thermal stability under room temperature condition are not published.
Disclosure of Invention
The invention overcomes the defects and shortcomings of the sodium bismuth titanate based dielectric energy storage ceramic in the prior art, and meets the EIA X7R standard (the capacitor takes the capacitance value of 25 ℃ as a reference, and the temperature change rate of the capacitor in the temperature range of minus 55 ℃ to 125 ℃ is not more than +/-15%) while obtaining high energy storage density, energy storage efficiency and power density.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a high-temperature-stability sodium bismuth titanate-based dielectric energy storage ceramic is characterized in that the ceramic material is Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 Wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.2 and less than or equal to 0.5,0<z≤0.2。
Further, the dielectric ceramic material adopts Na with purity of more than 98 weight percent 2 CO 3 、Bi 2 O 3 、BaCO 3 、SrCO 3 、TiO 2 、ZnO、Ta 2 O 5 The raw materials are prepared by ball milling and calcining according to the chemical formula, wherein the chemical formula is calculated according to the molar ratio, and the sintering temperature is 1000-1300 ℃.
Further, the dielectric energy storage ceramic material has a relative dielectric constant epsilon r Between 800 and 3000, dielectric loss is 5 multiplied by 10 -4 ～6×10 -3 Between more than 3J/cm 3 The energy storage density of the energy storage system can reach 95 percent at most, and the power density is 60MW/cm 3 The above.
The preparation method of the sodium bismuth titanate-based medium energy storage ceramic with high temperature stability is characterized by comprising the following steps of:
step 1, selecting Na with purity more than 98% 2 CO 3 、Bi 2 O 3 、BaCO 3 、SrCO 3 、TiO 2 、ZnO、Ta 2 O 5 Powder according to the chemical formula Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 ，0≤x≤0.1，0.2≤y≤0.5，0<z is less than or equal to 0.2;
step 2, filling the powder prepared in the step 1 into a nylon ball milling tank, taking zirconium balls and absolute ethyl alcohol as ball milling media, and mixing according to the following steps: grinding ball: the mass ratio of the absolute ethyl alcohol is 1 (4-8), the ratio of (1-3) is ball-milled for 3-10 hours to obtain uniformly mixed ceramic powder, then the ceramic powder is dried at the temperature of 60-120 ℃, and the ceramic powder is calcined for 2-6 hours at the temperature of 700-1000 ℃ after being sieved by a 80-120 mesh screen to obtain a presintered material;
step 3, pre-sintering the pre-sintering material obtained in the step 2 to obtain a pre-sintering material: grinding ball: ball milling for 3-10 h according to the mass ratio of (4-8) to (1-3), taking out and drying, granulating by taking 2% -10% concentration polyvinyl alcohol solution as adhesive, and pressing and forming under 10-20 MPa for 10-30 s to obtain green compact;
and 4, sintering the green body obtained in the step 3 at the temperature of 1000-1300 ℃ for 3-6 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
In general, compared with the prior art, the medium energy storage ceramic designed by the invention mainly has the following innovation points:
strontium and barium are introduced into the A site of bismuth sodium titanate, the ceramic is mainly converted from a three-phase to a four-phase, the ferroelectricity of the ceramic is greatly weakened, meanwhile, the non-uniformity of ceramic components and structures can enhance the relaxation characteristics of the ceramic, and the conversion from ferroelectric to relaxor ferroelectric is realized. By regulating the ratio of strontium and barium, a reduction in the remnant polarization can be achieved while maintaining a sufficiently large maximum polarization to achieve a strong energy storage capacity.
ZnTa 2 O 6 The introduction of the ceramic changes the structure of the ceramic, weakens the strength of the B-O bond, and reduces the energy required by the phase change of the ceramic. Therefore, the Curie temperature of the ceramic is reduced, so that the temperature stabilization area of the ceramic moves from high temperature to low temperature, the temperature stabilization characteristic at room temperature is obtained, and the EIA X7R standard is met.
By adjusting the values of X, y and z, the dielectric energy storage ceramic meeting the EIA X7R standard and the relative dielectric constant epsilon can be realized r Between 800 and 3000, dielectric loss is 5 multiplied by 10 -4 ～6×10 -3 Between more than 3J/cm 3 The energy storage density of the energy storage system can reach 95 percent at most, and the power density is 60MW/cm 3 The above.
The high-temperature-stability bismuth sodium titanate-based dielectric energy storage ceramic material provided by the invention does not contain Pb and other volatile toxic metals, can be widely applied to various energy storage components, and is environment-friendly and pollution-free.
In the preparation process, the invention realizes excellent performance by adopting simple components, and has convenient process and good application prospect by adopting a one-time synthesis method.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The material composition of the invention is shown as the chemical formula Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 (0≤x≤0.1,0.2≤y≤0.5，0<z is less than or equal to 0.2), and the material is prepared by solid phase reaction, wherein the raw materials are selected from Na 2 CO 3 、Bi 2 O 3 、BaCO 3 、SrCO 3 、TiO 2 、ZnO、Ta 2 O 5 Ceramic powder.
The preparation method of the ceramic material comprises the following steps:
step 1: selected from Na with purity of more than 98% 2 CO 3 、Bi 2 O 3 、BaCO 3 、SrCO 3 、TiO 2 、ZnO、Ta 2 O 5 Powder according to the chemical formula Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 ，0≤x≤0.1，0.2≤y≤0.5，0<z is less than or equal to 0.2;
step 2: filling the powder prepared in the step 1 into a nylon ball milling tank, taking zirconium balls and absolute ethyl alcohol as ball milling media, and mixing according to the following steps: grinding ball: the mass ratio of the absolute ethyl alcohol is 1 (4-8), the ratio of (1-3) is ball-milled for 3-10 hours to obtain uniformly mixed ceramic powder, then the ceramic powder is dried at the temperature of 60-120 ℃, and the ceramic powder is calcined for 2-6 hours at the temperature of 700-1000 ℃ after being sieved by a 80-120 mesh screen to obtain a presintered material;
step 3: and (3) pre-sintering the pre-sintering material obtained in the step (2) to obtain a pre-sintering material: grinding ball: ball milling for 3-10 h according to the mass ratio of (4-8) to (1-3), taking out and drying, granulating by taking 2% -10% concentration polyvinyl alcohol solution as an adhesive, and pressing and forming under the pressure of 10-20 MPa for 10-30 s to obtain a green body;
step 4: sintering the green body obtained in the step 3 at the temperature of 1000-1300 ℃ for 3-6 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 1
And 3, weighing.5012g of Na 2 CO 3 15.6220g Bi 2 O 3 0g of BaCO 3 13.8642g SrCO 3 18.0018g of TiO 2 0.7643g ZnO and 4.1499g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 2
3.3891g of Na 2 CO 3 15.1219g Bi 2 O 3 0g of BaCO 3 13.6644g SrCO 3 17.5575g of TiO 2 0.9415g ZnO and 5.1126g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 3
3.4931g of Na 2 CO 3 15.5956g Bi 2 O 3 0.4622g of BaCO 3 13.4861g SrCO 3 17.9598g of TiO 2 0.7625g ZnO and 4.1403g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 4
3.0589g of Na 2 CO 3 13.6484g Bi 2 O 3 2.7201g of BaCO 3 13.2270g SrCO 3 17.4313g of TiO 2 0.9348g ZnO and 5.0759g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 5
3.1463g of Na 2 CO 3 14.0382g Bi 2 O 3 1.7596g of BaCO 3 11.8474g SrCO 3 16.5582g of TiO 2 1.2699g ZnO and 6.8955g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 6
3.1324g of Na 2 CO 3 13.9763g Bi 2 O 3 2.6278g of BaCO 3 11.1399g SrCO 3 16.4851g of TiO 2 1.2643g ZnO and 6.8651g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 7
3.2581g of Na 2 CO 3 14.5371g Bi 2 O 3 1.3413g of BaCO 3 12.3758g SrCO 3 17.0101g of TiO 2 1.1063g ZnO and 6.0071g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 8
3.3736g of Na 2 CO 3 15.0527g Bi 2 O 3 0.9091g of BaCO 3 、12.9217g SrCO 3 17.4771g of TiO 2 0.9372g ZnO and 5.0892g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 9
3.0119g of Na 2 CO 3 13.4386g Bi 2 O 3 2.6783g of BaCO 3 12.6897g SrCO 3 16.9827g of TiO 2 1.1045g ZnO and 5.9974g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
Example 10
Weigh 3.3582g of Na 2 CO 3 14.9840g Bi 2 O 3 1.8099g of BaCO 3 12.1856g SrCO 3 17.3974g of TiO 2 0.9330g ZnO and 5.0660g Ta 2 O 5 Obtaining a mixture;
taking zirconium dioxide balls as ball milling media of the obtained mixture, and according to the mixture: grinding ball: ball milling is carried out on the anhydrous ethanol with the mass ratio of 1:5:2 to obtain evenly mixed ceramic powder, then the ceramic powder is dried at the temperature of 70 ℃, sieved by a 100-mesh screen, and calcined at the temperature of 900 ℃ for 4 hours to obtain a presintered material;
crushing the obtained presintered material, taking zirconium dioxide balls as ball milling media, and mixing according to the following steps: grinding ball: ball milling is carried out for 6 hours by the mass ratio of absolute ethyl alcohol being 1:5:2, drying is carried out at the temperature of 70 ℃, then polyvinyl alcohol solution with the concentration of 2% -10% is taken as adhesive for granulation, and the mixture is kept for 10s under the pressure of 10MPa for compression molding, thus obtaining green bodies;
and sintering the obtained green body at the temperature of 1200 ℃ for 5 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
TABLE 1 Performance parameters of microwave dielectric ceramic materials prepared in accordance with the examples of this invention
Figure GDA0004197501890000081
Figure GDA0004197501890000091
As can be seen from Table 1, the dielectric energy storage ceramic material prepared by the invention has a dielectric energy storage capacity of more than 3J/cm 3 The energy storage density of the energy storage system can reach 93 percent, and the power density is 60MW/cm 3 The above has the outstanding advantage of having the temperature stability at room temperature which is not available in other sodium bismuth titanate based energy storage ceramics and which meets the X7R standard.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.

Claims (2)

1. Sodium bismuth titanate-based dielectric energy storage ceramic material with high temperature stability, wherein the ceramic material is Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 Wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.2 and less than or equal to 0.5,0<z≤0.2。
2. The preparation method of the sodium bismuth titanate-based dielectric energy storage ceramic material as claimed in claim 1, comprising the following specific steps:
step 1, selecting Na with purity more than 98% 2 CO 3 、Bi 2 O 3 、BaCO 3 、SrCO 3 、TiO 2 、ZnO、Ta 2 O 5 Powder according to the chemical formula Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 -ySrTiO 3 -zZnTa 2 O 6 ，0≤x≤0.1，0.2≤y≤0.5，0<z is less than or equal to 0.2;
step 2, transferring the powder prepared in the step 1 into a nylon ball milling tank, taking zirconium balls and absolute ethyl alcohol as ball milling media, and mixing according to the following steps: grinding ball: the mass ratio of the absolute ethyl alcohol is 1 (4-8), the ratio of (1-3) is ball-milled for 3-10 hours to obtain uniformly mixed ceramic powder, then the ceramic powder is dried at the temperature of 60-120 ℃, and the ceramic powder is calcined for 2-6 hours at the temperature of 700-1000 ℃ after being sieved by a 80-120 mesh screen to obtain a presintered material;
step 3, pre-sintering the pre-sintering material obtained in the step 2 to obtain a pre-sintering material: grinding ball: ball milling for 3-10 h according to the mass ratio of (4-8) to (1-3), taking out and drying, granulating by taking 2% -10% concentration polyvinyl alcohol solution as an adhesive, and pressing and forming under the pressure of 10-20 MPa for 10-30 s to obtain a green body;
and 4, sintering the green body obtained in the step 3 at the temperature of 1000-1300 ℃ for 3-6 hours, and naturally cooling to room temperature after the sintering is completed to obtain the dielectric energy storage ceramic material.
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