CN112876247B - Wide-temperature-stability high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic and preparation method thereof - Google Patents
Wide-temperature-stability high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density and a preparation method thereof 2 NaNb 5 O 15 On the basis of incorporating a certain amount of Ta 5+ Substitute for Nb 5+ Of the formula Sr 2 NaNb 5‑x Ta x O 15 Wherein x is more than or equal to 0.0 and less than or equal to 2.0. The pulse energy storage dielectric ceramic material obtained by the invention has higher recoverable energy storage density W rec ＝3.99J/cm 3 The higher energy storage efficiency eta is 91.7 percent, and the power density P is achieved under the electric field of 170kV/cm D ＝78.7MW/cm 3 The current density can reach 925.8A/cm 2 And the energy storage performance is greatly improved compared with the existing product. More importantly, the change rate of the energy storage density is less than 2.5 percent in a wider temperature range, and the excellent temperature stability is shown. The preparation method is simple in process flow, is suitable for industrial production, and simultaneously meets the current lead-free environment-friendly requirement.
Description
Technical Field
The invention relates to the technical field of electronic information functional materials and devices, in particular to a high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and a preparation method thereof.
Background
With the increase of energy demand and the consumption of fossil fuels, the problems of improving the utilization rate of traditional energy and widening the practical range of new energy are increasingly highlighted, which provides opportunities for the rapid development of energy storage devices. Among the energy storage elements, the dielectric capacitor has the advantages of ultra-fast charge-discharge speed and high power density, meets the requirements of new energy development and utilization, and is widely applied to the fields of electromagnetic pulse weapons, hybrid electric vehicles, biomedical devices and the like. In the face of the trend of complex environment and high integration informatization, higher requirements are put forward on integration, miniaturization and light weight of equipment, and people are eagerly expected to find a dielectric material with high energy storage density. Meanwhile, the capacitor needs to overcome the use limitation under various severe environments, and the temperature stability becomes an important evaluation index. Therefore, materials with broad temperature stability and high energy storage density have become a necessary choice for high performance pulsed energy storage capacitor applications.
Lead-based perovskite dielectric ceramics currently exhibit outstanding advantages in energy storage applications, such as PbZrO 3 A base ceramic having a tremendous energy density. However, the damage of lead element to ecosystem and human is very serious, which has prompted intensive research on alternative materials for lead-free dielectric ceramics. Among these lead-free ceramics, lead-free relaxation ferroelectric ceramics have attracted extensive research interest due to their large polarization and thin hysteresis loops. In recent years, there have been many reports on the research of lead-free relaxant ferroelectric ceramics for capacitor applications, mainly focusing on perovskite-based relaxant ceramics, and remarkable results have been obtained. However, only some ceramics exhibit energy storage properties comparable to lead-based ceramics. Under such circumstances, in order to satisfy commercialization of energy storage devices, development of a novel lead-free ceramic system having high energy storage performance is urgently required.
The tungsten bronze structure ceramic is one of the most important dielectric materials next to perovskite structures, and is widely applied to the fields of photoelectricity, nonlinear optics, piezoelectricity, pyroelectricity and the like because the complex and adjustable structure of the tungsten bronze structure ceramic shows unique and interesting dielectric and ferroelectric properties. The open structure of tungsten bronze allows for wide tunability of its performance, potentially with great potential in energy storage. The strontium sodium niobate is a typical filled tungsten bronze structure ceramic, has good dielectric property and ferroelectric property, and has great potential in improving energy storage property. However, pure strontium sodium niobate ceramic has a sintering difficulty and abnormal grain growth, which makes it withstand voltage lower than 200 kV/cm. In addition, the pure strontium sodium niobate ceramic has low relaxivity, which causes great residual polarization and low efficiency. These disadvantages limit its application in energy storage. Therefore, it is especially important to effectively improve the energy storage density of the strontium sodium niobate ceramic.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density and the preparation method thereof. According to the invention, Ta ions are introduced into the strontium sodium niobate-based ceramic for the first time to replace Nb ions for doping modification, so that a long-range ferroelectric ordered structure is broken, a polar nano micro-region is formed by induction, and low remanent polarization is obtained; the compactness of the ceramic is improved, the grain size of the ceramic is reduced, and the breakdown strength of the ceramic is improved. The ceramic has the advantages of high energy storage density, environmental friendliness and high practicability, can be applied to energy storage capacitors with high requirements on temperature stability, and has great economic value.
In order to achieve the purpose, the invention can be realized by the following technical scheme:
the chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is more than or equal to 0.0 and less than or equal to 2.0.
As a preferred embodiment, x is 0.15. This is primarily due to the smaller grain size of the component ceramic, which contributes to the improved breakdown strength. Meanwhile, the dielectric constant of the component is moderate, the residual polarization is low, the dielectric constant and the residual polarization reach a good balance state, and the high recoverable energy storage density is favorably obtained.
The preparation method of the high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 5-x Ta x O 15 Weighing raw materials, wherein x is 0.0-2.0, adding absolute ethyl alcohol with the same amount as that of the powder, and uniformly mixing the powder through primary ball milling to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050-;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue removal treatment on the ceramic blank in the third step at the temperature of 600-650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1275-1350 ℃, the heating rate is 3-4 ℃/min, the heat preservation time is 2-3 hours, and cooling to room temperature to obtain the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density.
Further, in the step one, the SrCO 3 、Nb 2 O 5 The purity of the raw material is more than 99.5 percent, and the NaCO is 3 The purity of the raw material is more than 99.8 percent, and the Ta 2 O 5 The purity of the raw material is more than 99.99 percent.
Further, in the ball milling processes in the first step and the third step, the ball milling time is 12 hours.
And further, sieving by using 80-mesh and 140-mesh sieves in the sieving process in the third step, and taking powder in the middle layers of the 80-mesh and 140-mesh sieves.
Further, in the third granulation step, polyvinyl alcohol (PVA) with the concentration of 5% is used as a binder, and the powder is uniformly mixed in a mortar and then placed in a mold to be pressed into a billet.
Further, the pre-sintering temperature in the second step is preferably 1050 ℃, and the holding time is preferably 4 hours.
Furthermore, in the fourth step, the sintering temperature is preferably 1325 ℃, and the heat preservation time is preferably 3 hours.
Furthermore, polishing and grinding the sintered ceramic wafer to the thickness of 0.1-0.15mm, and spraying gold electrodes on the two sides.
Sr prepared by the invention 2 NaNb 5-x Ta x O 15 The average grain size of the strontium sodium niobate ceramic is reduced from 13.15 mu m to about 1.03 mu m by using an ion doping modification method, so that the compactness of the ceramic is greatly improved, the breakdown electric field of the strontium sodium niobate ceramic is enhanced, and the energy storage density of the strontium sodium niobate-based ceramic is finally improved. In addition, the invention introduces Ta to the B site of the strontium sodium niobate 5+ To replace original Nb 5+ Causing NbO in the strontium sodium niobate based tungsten bronze ceramic 6 The octahedron inclination breaks through the long-range ordered dipole arrangement sequence, a polar nano micro-region is formed, the relaxation of the strontium sodium niobate is obviously enhanced, and the novel energy storage ceramic with high effective energy storage density and high energy storage efficiency is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) the energy storage medium ceramic material provided by the invention realizes great improvement on the performance. The energy storage density of the tungsten bronze system prepared by the prior art is mostly 2J/cm 3 Left and right. Compared with the energy storage density of the energy storage dielectric ceramic material reported previously, the energy storage density of the energy storage dielectric ceramic material provided by the invention is about twice that of the energy storage dielectric ceramic material reported previously, and 3.99J/cm is realized 3 High energy storage density and high energy storage efficiency of 91.7%.
(2) The invention utilizes a simple and effective method to improve the energy storage performance of the strontium sodium niobate-based tungsten bronze ceramic, and the obtained strontium sodium niobate-based ceramic has strong relaxation, a gentle dielectric peak and a wide application temperature range. Under the electric field intensity of 250kV/cm, the energy storage density of the ceramic material can be kept stable within the temperature range of 25-120 ℃, the change rate is less than 2.5 percent, and the ceramic material has wide application prospect.
(3) The tungsten bronze structure energy storage ceramic obtained by the invention has high charging and discharging speed, has extremely high application value for realizing lead-free of a pulse power device, and can be widely applied to various energy storage components.
(4) The ceramic dielectric material is obtained by a traditional solid-phase reaction method, has low preparation cost, simple process and easy operation, is suitable for large-scale industrial production, and is expected to be used as a new-generation environment-friendly energy storage ceramic dielectric material.
Drawings
FIG. 1 is an XRD diffraction analysis spectrum of a high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability prepared in example 4;
FIG. 2 is an SEM microstructure picture of a high-energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability prepared in example 4;
FIG. 3 is a graph showing the temperature dependence of dielectric constant and dielectric loss of a high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability prepared in example 4;
FIG. 4 is the hysteresis loop of a high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability prepared in example 4;
FIG. 5 is a curve of the energy storage characteristics of the high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability according to the electric field variation prepared in example 4;
FIG. 6 is a graph showing the variation of the energy storage characteristics with temperature of a strontium sodium niobate-based tungsten bronze ceramic with high energy storage density and wide temperature stability prepared in example 4;
FIG. 7 shows the peak discharge current (I) of a high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability obtained in example 4 max ) Discharge current density (I) max S) 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 those skilled in the art in further understanding the invention, but are not intended to limit the invention 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 present invention.
Example 1
The chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 0.5. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 4.5 Ta 0.5 O 15 Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and performing primary ball milling to uniformly mix the powder to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The ceramic reaches 1.38J/cm in charging energy density (total energy density, W) under the electric field of 160kV/cm through testing 3 Available energy storage density (available energy storage density, W) rec ) Reaches 0.9J/cm 3 And the energy storage efficiency (eta) reaches 65.3 percent.
Example 2
The chemical composition of the wide-temperature-stability high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 1.0. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 4.0 Ta 1.0 O 15 Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and performing primary ball milling to uniformly mix the powder to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The test shows that the charging energy density (total energy density, W) of the ceramic reaches 1.20J/cm under the electric field of 160kV/cm 3 Available energy storage density (available energy storage density, W) rec ) Reaching 1.05J/cm 3 And the energy storage efficiency (eta) reaches 87.7 percent.
Example 3
The chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 1.25. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 3.75 Ta 1.25 O 15 Weighing raw materials, and addingThe powder is uniformly mixed to form slurry through primary ball milling by using anhydrous ethanol with the same amount as the powder;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The ceramic achieves the charging energy density (total energy density, W) of 1.22J/cm under the electric field of 160kV/cm through testing 3 Available energy storage density (available energy storage density, W) rec ) Reach 1.08J/cm 3 And the energy storage efficiency (eta) reaches 88.9 percent.
Example 4
The chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 1.5. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 3.5 Ta 1.5 O 15 Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and performing primary ball milling to uniformly mix the powder to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The test shows that the charging energy density (total energy density, W) of the ceramic reaches 1.22J/cm under the electric field of 160kV/cm 3 Available energy storage density (available energy storage density, W) rec ) Reaching 1.14J/cm 3 And the energy storage efficiency (eta) reaches 93.1 percent. The energy storage performance of x ═ 1.5 components is better compared under a low electric field, and the best component is preferred.
FIG. 1 is an XRD diffraction analysis spectrum of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density. As can be seen, the ceramic is a typical tungsten bronze structure.
FIG. 2 is an SEM microstructure picture of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density. As can be seen, the ceramic grain size is around 1 micron, which helps to improve the breakdown strength of the ceramic.
FIG. 3 is the dielectric constant and dielectric loss variation curve with temperature of 100Hz-1MHz of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density, and the testing temperature is 25-400 ℃. It can be seen from the figure that the temperature corresponding to the dielectric peak of the ceramic is not higher than room temperature, and the dielectric constant at room temperature is about 1200.
FIG. 4 shows the unidirectional hysteresis loop of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density at room temperature and 10Hz, and it can be seen from the figure that the hysteresis loop of the ceramic is relatively thin and long, and the highest electric field strength can reach 380 kV/cm.
FIG. 5 shows the energy storage performance of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density in a 380kV/cm electric field of 160-charge, and it can be seen from the figure that the charging energy density (total energy density, W) reaches 4.35J/cm under the 380kV/cm electric field 3 Available energy storage density (available energy storage density, W) rec ) Reaching 3.99J/cm 3 And the energy storage efficiency (eta) reaches 91.7 percent.
FIG. 6 is a curve of the energy storage performance of the prepared high energy storage density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability along with the temperature change at the electric field intensity of 10Hz and 250 kV/cm. As can be seen from the figure, the ceramic material can maintain better temperature stability within 25-120 ℃, and the change rate of the available energy storage density is less than 2.5%.
FIG. 7 shows the undamped discharge current peak value, the discharge current density and the discharge power density of the prepared strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density. As can be seen from the figure, the ceramic has the discharge current peak value of 29.1A under the electric field strength of 170kV/cm and the discharge current density of 925.8A/cm 2 The discharge power density reaches 78.7MW/cm 3 . Therefore, the ceramic has certain commercial application prospect.
Example 5
The chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 1.75. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 3.25 Ta 1.75 O 15 Weighing raw materials, and adding the same amount of the powderThe anhydrous ethanol is subjected to primary ball milling to uniformly mix the powder to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The test shows that the charging energy density (total energy density, W) of the ceramic reaches 1.16J/cm under the electric field of 160kV/cm 3 Available energy storage density (available energy storage density, W) rec ) Reaching 1.10J/cm 3 And the energy storage efficiency (eta) reaches 94.6 percent.
Example 6
The chemical composition of the high-energy-storage-density strontium sodium niobate tungsten bronze ceramic with wide temperature stability is Sr 2 NaNb 5- x Ta x O 15 Wherein x is 2.0. The method specifically comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, NaCO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 3.0 Ta 2.0 O 15 Weighing raw materials, adding absolute ethyl alcohol with the same amount as the powder, and performing primary ball milling to uniformly mix the powder to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050 ℃ under a closed condition, and preserving heat for 4 hours to obtain a presynthesized ceramic plate;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: and (3) carrying out glue discharging treatment on the ceramic body in the third step at 650 ℃ to remove PVA. And sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1325 ℃, the heating rate is 4 ℃/min, the heat preservation time is 3 hours, and cooling to room temperature to obtain the high-energy-storage-density strontium-sodium niobate-based tungsten bronze ceramic with wide temperature stability.
The test shows that the charging energy density (total energy density, W) of the ceramic reaches 1.08J/cm under the electric field of 160kV/cm 3 Available energy storage density (available energy storage density, W) rec ) Reaching 1.03J/cm 3 And the energy storage efficiency (eta) reaches 95.3 percent.
In conclusion, the strontium sodium niobate-based tungsten bronze ceramic is subjected to ion doping modification, so that on one hand, the sintering compactness of the ceramic is improved, and the grain size is reduced, so that the breakdown strength of the material is enhanced; on the other hand, the relaxation property of the ceramic is enhanced, a thin electric hysteresis line is obtained, high energy storage efficiency is facilitated to be obtained, ferroelectric response of the material is reduced, temperature stability of the material is improved, the novel energy storage dielectric ceramic with high energy storage performance, excellent charge and discharge performance and good temperature stability is obtained, the application prospect is good, and the industrial requirement of a high-performance pulse capacitor can be met.
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 strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density is characterized in that the chemical composition of the ceramic is Sr 2 NaNb 5-x Ta x O 15 Wherein x in the chemical composition is 1.5.
2. A preparation method of high-energy-storage-density strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability is characterized in that a corresponding energy storage ceramic is prepared by a solid-phase reaction method, and comprises the following steps:
the method comprises the following steps: selecting SrCO 3 Powder, Na 2 CO 3 Powder and Nb 2 O 5 Powder and Ta 2 O 5 The powder is taken as a raw material and has the general formula of Sr 2 NaNb 5- x Ta x O 15 Weighing raw materials, wherein x =1.5, adding absolute ethyl alcohol with the same amount as that of the powder, and uniformly mixing the powder through one-time ball milling to form slurry;
step two: placing the slurry obtained in the step one in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder; then placing the powder into a die to be pressed into a material block, presintering the material block at 1050-;
step three: crushing and grinding the ceramic wafer obtained in the step two in a mortar to obtain ceramic powder, adding the same amount of absolute ethyl alcohol into the obtained powder, and carrying out secondary ball milling; drying the slurry subjected to ball milling at 90 ℃, and performing granulation, sieving and compression molding to obtain a ceramic green body;
step four: carrying out glue removal treatment on the ceramic blank in the third step at the temperature of 600-650 ℃ to remove PVA; and sintering the ceramic blank after the binder removal, wherein the sintering temperature is 1275-1350 ℃, the heating rate is 3-4 ℃/min, the heat preservation time is 2-3 hours, and cooling to room temperature to obtain the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density.
3. The preparation method of the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, wherein the SrCO in the step one 3 、Nb 2 O 5 The purity of the raw material is more than 99.5 percent, and the Na 2 CO 3 The purity of the raw material is more than 99.8 percent, and the Ta 2 O 5 The purity of the raw material is more than 99.99 percent.
4. The preparation method of the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, wherein in the ball milling process in the first step and the third step, the ball milling time is 12 h.
5. The preparation method of the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, wherein in the third sieving step, 80-mesh and 140-mesh sieves are used for sieving, and powder in the middle layer of the 80-mesh and 140-mesh sieves is taken.
6. The preparation method of the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, wherein polyvinyl alcohol with concentration of 5% is used as a binder in the third granulation process, and the powder is uniformly mixed in a mortar and then placed in a mold to be pressed into a billet.
7. The preparation method of the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, wherein the pressure in the three-step compression molding process is controlled at 200 MPa.
8. The method for preparing the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 2, further comprising polishing and gold-plating electrodes.
9. The method for preparing the strontium sodium niobate-based tungsten bronze ceramic with wide temperature stability and high energy storage density as claimed in claim 8, wherein the polishing and gold-plating electrode is obtained by polishing the ceramic wafer obtained in the fourth step to a thickness of 0.1-0.15mm, and sputtering the gold electrode on both sides.
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