CN117602933A - Barium titanate-based energy storage ceramic and preparation method and application thereof - Google Patents
Barium titanate-based energy storage ceramic and preparation method and application thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 160
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 115
- 239000000919 ceramic Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 91
- 238000001354 calcination Methods 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 239000012700 ceramic precursor Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
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- 238000004891 communication Methods 0.000 claims description 4
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
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- 229920001778 nylon Polymers 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a barium titanate-based energy storage ceramic, and a preparation method and application thereof. The chemical composition of the barium titanate-based energy storage ceramic comprises (Ba 0.47‑2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68‑ y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10. The barium titanate-based energy storage ceramic not only has high energy storage density, but also maintains high energy storage efficiency, and can meet the use requirement to a greater extent, and particularly, the energy storage density of the barium titanate-based energy storage ceramic is 8J/cm at room temperature of 100Hz 3 ～10J/cm 3 The energy storage efficiency is 85% -93.5%.
Description
Technical Field
The invention belongs to the field of dielectric energy storage ceramic materials, and particularly relates to a barium titanate-based energy storage ceramic, and a preparation method and application thereof.
Background
With the rapid development of microwave communication, the automotive industry and aerospace technology, the demand for high-performance energy storage capacitors in the power industry has grown. Compared with various batteries and electrochemical capacitors, dielectric capacitors have become core components for avionics, automotive industry, military applications, and the like due to their ultra-high charge-discharge rates and extremely high power densities. However, dielectric capacitors have a relatively low energy storage density, which limits their further application. How to improve the energy storage properties of dielectric capacitors is a research hotspot in this field.
The energy storage density of the dielectric capacitor is determined by the applied electric field and the dielectric polarization, effectively increasing the polarization intensity difference (P m -P r ) And enhanced breakdown field strength (E b ) Is two important ways to improve the energy storage property of dielectric materials. BaTiO 3 Is the earliest discovered ABO 3 Perovskite ferroelectric materials have developed a great deal of work from discovery to date by researchers, however, it is often difficult to achieve both high energy storage densities and energy storage efficiencies. This is mainly because a significant increase in energy storage density is usually achieved at high electric fields, but the energy storage efficiency is reduced due to an increase in conduction loss and the growth of nano domains. Therefore, the preparation of the ceramic with high energy storage density and high energy storage efficiency has very important application value.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the invention is to provide a barium titanate-based energy storage ceramic, and a preparation method and application thereof. The barium titanate-based energy storage ceramic not only has high strengthBut also maintains high energy storage efficiency, can meet the use requirement to a greater extent, and particularly, the energy storage density of the barium titanate-based energy storage ceramic is 8J/cm at room temperature of 100Hz 3 ～10J/cm 3 The energy storage efficiency is 85% -93.5%.
In one aspect of the invention, a barium titanate-based energy storage ceramic is provided. According to an embodiment of the present invention, the chemical composition of the barium titanate-based energy storage ceramic includes (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68- y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10.
The barium titanate-based energy storage ceramic according to the above embodiment of the present invention has a chemical composition comprising (Ba 0.47- 2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10. The calculation formula of the configuration entropy of the barium titanate-based energy storage ceramic is as follows:where R is the ideal gas constant, x i Is the percentage of the element occupying the cationic site, x j The high entropy is the percentage of the element occupying the anion position, the configuration entropy S is required to be larger than 1.5R, the high entropy design is realized by adjusting the doping content of Sm, na and/or Zr ions, the high entropy design is helpful for enhancing electron scattering, causing large lattice distortion and smaller grain size, thereby reducing conduction loss and improving resistivity, which is helpful for greatly improving breakdown strength and further improving the energy storage density of the ceramic material. Meanwhile, the introduced Sm, na and/or Zr ions with different ionic radiuses, valence states and electronegativity convert the micro domains into nano domains, inhibit the further growth of the nano domains under a high electric field and ensure the high energy storage efficiency of the ceramic material under the high electric field. Therefore, the barium titanate-based energy storage ceramic not only has high energy storage density, but also maintains high energy storage efficiency, and can meet the use requirement to a greater extent.
In addition, the barium titanate-based energy storage ceramic according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, 0.04.ltoreq.x.ltoreq.0.10, 0.02.ltoreq.y.ltoreq.0.08. Therefore, the energy storage density and the energy storage efficiency of the barium titanate-based energy storage ceramic can be improved.
In some embodiments of the invention, the barium titanate-based energy storage ceramic has a breakdown field strength of 540kV/cm to 550kV/cm at 1050 ℃ to 1100 ℃.
In some embodiments of the invention, the barium titanate-based energy storage ceramic has an energy storage density of 8J/cm at room temperature of 100Hz 3 ～10J/cm 3 The energy storage efficiency is 85% -93.5%.
In a second aspect of the present invention, the present invention provides a method for preparing the barium titanate-based energy storage ceramic. According to an embodiment of the invention, the method comprises:
(1) According to chemical composition (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Weighing a Ba source, a Bi source, a Ca source, a Sm source, a Na source, a Sr source, a Ti source, a Fe source and/or a Zr source according to stoichiometric ratio, mixing, grinding and drying to obtain mixed material powder;
(2) Calcining the mixture powder to obtain barium titanate-based energy storage ceramic precursor powder;
(3) Mixing the barium titanate-based energy storage ceramic precursor powder with an adhesive, and pressing into a sheet and discharging glue to obtain a barium titanate-based energy storage ceramic green body;
(4) And sintering the barium titanate-based energy storage ceramic green body so as to obtain the barium titanate-based energy storage ceramic.
According to the method for preparing barium titanate-based energy storage ceramics of the above embodiment of the present invention, first, according to the chemical composition (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Stoichiometric ratio of Ba source, bi source, ca source, sm source, na source and Sr sourceMixing and grinding the Ti source, the Fe source and/or the Zr source, and then drying to obtain mixed powder, wherein grinding ensures that all raw materials are uniformly mixed, and particles become smaller, thereby being beneficial to the subsequent calcination reaction. And then calcining the mixed powder, wherein the calcination promotes the solid-phase chemical reaction of the raw materials to be more fully and uniformly, so as to obtain a solid solution with fixed composition, form a main crystalline phase, reduce carbon dioxide, water and the like in the raw materials, reduce shrinkage and deformation of a blank in the sintering process, avoid cracking of the product and better control the external dimension. And mixing the barium titanate-based energy storage ceramic precursor powder obtained by calcination with an adhesive, and pressing into a sheet and discharging glue to obtain the barium titanate-based energy storage ceramic green body. And finally sintering the barium titanate-based energy storage ceramic green body to obtain the barium titanate-based energy storage ceramic with excellent compactness and good strength. Therefore, the barium titanate-based energy storage ceramic with high energy storage density and energy storage efficiency can be prepared by adopting the method, and meanwhile, the preparation process is simple, the repeatability is good, the requirements on production equipment and places are low, the large-scale and industrial production is facilitated, and the prepared ceramic has stable performance.
In addition, the method for preparing the barium titanate-based energy storage ceramic according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the Ba source comprises BaCO 3 And at least one of BaO.
In some embodiments of the invention, the Bi source comprises Bi 2 O 3 。
In some embodiments of the invention, the Ca source includes CaCO 3 。
In some embodiments of the invention, the Sm source comprises Sm 2 O 3 。
In some embodiments of the invention, the Na source comprises Na 2 CO 3 。
In some embodiments of the invention, the Sr source comprises SrCO 3 。
In some embodiments of the invention, the Ti source comprises TiO 2 。
In some embodiments of the inventionWherein the Fe source comprises Fe 2 O 3 。
In some embodiments of the invention, the Zr source comprises ZrO 2 。
In some embodiments of the invention, in step (1), the rotational speed of the grinding is 260r/min to 300r/min, and the grinding time is 12h to 24h. Therefore, the mixture can be uniformly mixed and the proper particle diameter of the particles can be controlled.
In some embodiments of the invention, in step (1), the temperature of the drying is 68-72 ℃, and the time of the drying is 6-12 hours.
In some embodiments of the invention, in step (2), the calcination is performed at a temperature of 600 ℃ to 800 ℃ for a time of 2 hours to 3 hours. Thus, the progress of the solid phase chemical reaction of each raw material can be promoted, and a semi-phase precursor powder can be obtained.
In some embodiments of the invention, the compressed tablet is at a pressure of 2MPa to 8MPa and a dwell time of 1min to 2min.
In some embodiments of the invention, the temperature of the adhesive discharge is 500-600 ℃, and the time of the adhesive discharge is 2-4 hours.
In some embodiments of the invention, the binder comprises at least one of 5wt% to 8wt% aqueous polyvinyl alcohol solution and 5wt% to 8wt% polyvinyl butyral ester ethanol solution.
In some embodiments of the invention, in step (4), the sintering temperature is 1000 ℃ to 1200 ℃ and the sintering time is 2 hours to 3 hours. Therefore, the compactness and the strength of the barium titanate-based energy storage ceramic can be improved.
In a third aspect of the present invention, the present invention provides an application of the barium titanate-based energy storage ceramic or the barium titanate-based energy storage ceramic prepared by the method in the communication field, the aviation field or the automobile manufacturing field.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is XRD patterns of barium titanate-based energy storage ceramics of examples 1-3 and comparative example 1 of the present invention;
FIG. 2 is a STEM diagram of a barium titanate-based energy storage ceramic of example 1 of the present invention;
FIG. 3 is a graph of PE measured at maximum breakdown strength of the barium titanate-based energy storage ceramic of example 1 of the present invention;
FIG. 4 is a graph of PE measured at maximum breakdown strength of the barium titanate-based energy storage ceramic of example 2 of the present invention;
FIG. 5 is a graph of PE measured at maximum breakdown strength of the barium titanate-based energy storage ceramic of example 3 of the present invention;
FIG. 6 is a graph of PE measured at the maximum breakdown strength of the barium titanate-based energy storage ceramic of comparative example 1 of the present invention;
fig. 7 is a graph of PE measured at the maximum breakdown strength of the barium titanate-based energy storage ceramic of comparative example 2 of the present invention.
Detailed Description
The following detailed description of the embodiments of the invention is intended to be illustrative of the invention and is not to be taken as limiting the invention.
In one aspect of the invention, a barium titanate-based energy storage ceramic is provided. According to an embodiment of the present invention, the chemical composition of the barium titanate-based energy storage ceramic includes (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10.
The barium titanate-based energy storage ceramic according to the above embodiment of the present invention has a chemical composition comprising (Ba 0.47- 2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10. The calculation formula of the configuration entropy of the barium titanate-based energy storage ceramic is as follows:where R is the ideal gas constant, x i Is the percentage of the element occupying the cationic site, x j The high entropy is the percentage of the element occupying the anion position, the configuration entropy S is required to be larger than 1.5R, the high entropy design is realized by adjusting the doping content of Sm, na and/or Zr ions, the high entropy design is helpful for enhancing electron scattering, causing large lattice distortion and smaller grain size, thereby reducing conduction loss and improving resistivity, which is helpful for greatly improving breakdown strength and further improving the energy storage density of the ceramic material. Meanwhile, the introduced Sm, na and/or Zr ions with different ionic radiuses, valence states and electronegativity convert the micro domains into nano domains, inhibit the further growth of the nano domains under a high electric field and ensure the high energy storage efficiency of the ceramic material under the high electric field. Therefore, the barium titanate-based energy storage ceramic not only has high energy storage density, but also maintains high energy storage efficiency, and can meet the use requirement to a greater extent.
According to the embodiment of the invention, the breakdown field intensity of the barium titanate-based energy storage ceramic is 540kV/cm-550kV/cm at 1050-1100 ℃.
According to the embodiment of the invention, x is more than or equal to 0.04 and less than or equal to 0.10, and y is more than or equal to 0.02 and less than or equal to 0.08. By controlling the values of x and y within the above range, the energy storage density and the energy storage efficiency of the barium titanate-based energy storage ceramic can be remarkably improved.
In a second aspect of the present invention, the present invention provides a method for preparing the barium titanate-based energy storage ceramic. According to an embodiment of the invention, the method comprises:
s100: preparing mixed material powder
In this step, according to the chemical composition (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Stoichiometric ratio of Ba source, bi source, ca source, sm source, na source, sr source, ti source, fe source and/or Zr source is weighed, mixed, ground and dried, grinding ensures that all raw materials are uniformly mixed, particles become smaller, and the subsequent calcination reaction is facilitated, thus obtaining the mixed powderA body. The Ba source, bi source, ca source, sm source, na source, sr source, ti source, fe source, zr source are compounds which are conventional in the art, and those skilled in the art can select, for example, ba source including BaCO 3 And at least one of BaO, the Bi source comprising Bi 2 O 3 The Ca source comprises CaCO 3 The Sm source comprises Sm 2 O 3 The Na source includes Na 2 CO 3 The Sr source comprises SrCO 3 The Ti source comprises TiO 2 The Fe source includes Fe 2 O 3 The Zr source comprises ZrO 2 。
According to the embodiment of the invention, the grinding rotating speed is 260-300 r/min, and the grinding time is 12-24 h. By controlling the grinding rotation speed and time within the above ranges, the materials can be mixed more uniformly, the granularity of the particles is ensured, and the curing reaction efficiency of calcination is improved. It will be appreciated by those skilled in the art that milling is a conventional operation in the art, using also conventional equipment, for example a ball mill, the milling medium being oxidized bright spheres. Further, the drying temperature is 68-72 ℃, and the drying time is 6-12 hours, so that the moisture in the mixture can be removed as much as possible.
S200: calcining the mixed material powder
In the step, the mixed powder is calcined, the solid phase chemical reaction of the raw materials is promoted to be more fully and uniformly carried out, a solid solution with fixed composition is obtained, a main crystal phase is formed, carbon dioxide, water and the like in the raw materials are reduced, shrinkage and deformation of a blank body in the sintering process are reduced, and cracking of the product and better control of the external dimension are avoided.
According to the embodiment of the invention, the calcination temperature is 600-800 ℃ and the calcination time is 2-3 h. The inventor finds that the sintering driving force is reduced due to overlarge crystal grains after the calcination when the calcination temperature is too high and the calcination time is too long, which is not beneficial to the sintering; if the calcination temperature is too low and the calcination time is too short, the main crystal phase is not obvious and a lot of impurity phases are generated. Therefore, the calcination temperature is 600-800 ℃ and the time is 2-3 h, so that volatile matters in the raw materials can be removed, cracks caused by overlarge shrinkage in the sintering process can be prevented, and meanwhile, a required crystal phase can be formed.
S300: mixing barium titanate-based energy storage ceramic precursor powder and binder, and pressing into tablet
In the step, the barium titanate-based energy storage ceramic precursor powder obtained by calcination and the adhesive are fully mixed and stirred in a mortar, aged for 2 hours, then pass through a 150-mesh screen, and are pressed into tablets in an automatic tablet press, wherein the pressure of the tablet press is 2-8 MPa, and the pressure maintaining time is 1-2 min. And finally, placing the pressed sheet into a muffle furnace, discharging glue for 2-4 hours at the temperature of 500-600 ℃ and removing the adhesive to obtain the barium titanate-based energy storage ceramic green body. Further, the binder comprises at least one of 5wt% to 8wt% of an aqueous polyvinyl alcohol solution and 5wt% to 8wt% of an ethanol polyvinyl butyral ester solution. Specifically, 1g of barium titanate-based energy storage ceramic precursor powder is mixed with 2 to 3 drops of the above binder.
S400: sintering the barium titanate-based energy storage ceramic green body
In the step, the barium titanate-based energy storage ceramic green body is placed into a muffle furnace for sintering, so that the barium titanate-based energy storage ceramic with excellent compactness and certain strength is obtained, and ceramic densification is realized.
According to the embodiment of the invention, the sintering temperature is 1000-1200 ℃ and the sintering time is 2-3 h. The inventor finds that the selection of the sintering temperature and the sintering time has an extremely important influence on the compactness and the grain size of the barium titanate-based energy storage ceramic, and further influences the energy storage property of the barium titanate-based energy storage ceramic. Specifically, if the sintering temperature is too high, the time is too long, the sample is easy to melt, abnormal grains are easy to occur, a large amount of impurity phases can be generated, air holes and the like are generated, and the sizes of the grains are uneven; if the sintering temperature is too low and the time is too short, the densification degree of the ceramic is insufficient, the ceramic strength is insufficient, and a foreign phase is liable to occur. Therefore, the sintering condition with the temperature of 1000-1200 ℃ and the time of 2-3 h is adopted, so that the compactness and the strength of the barium titanate-based energy storage ceramic can be improved, a pure phase structure can be obtained, and the energy storage performance of the barium titanate-based energy storage ceramic is improved.
Therefore, the barium titanate-based energy storage ceramic with high energy storage density and energy storage efficiency can be prepared by adopting the method, and meanwhile, the preparation process is simple, the repeatability is good, the requirements on production equipment and places are low, the large-scale and industrial production is facilitated, and the prepared ceramic has stable performance. It should be noted that the features and advantages described above for the barium titanate-based energy storage ceramic are equally applicable to the method, and are not described here again.
In a third aspect of the present invention, the present invention provides an application of the barium titanate-based energy storage ceramic or the barium titanate-based energy storage ceramic prepared by the method in the communication field, the aviation field or the automobile manufacturing field.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
(1) BaCO is carried out 3 Powder, bi 2 O 3 Powder, fe 2 O 3 Powder, tiO 2 Powder, srCO 3 Powder, sm 2 O 3 Powder, na 2 CO 3 Powder, caCO 3 Powder, zrO 2 The powder is used as raw material and then is processed according to (Ba 0.33 Bi 0.32 Ca 0.11 Sm 0.07 Na 0.07 Sr 0.1 )(Ti 0.63 Fe 0.32 Zr 0.05 )O 3 Weighing raw materials according to the stoichiometric ratio, loading the powder into a 250ml nylon ball milling tank, and mixing the raw materials according to the following steps: and pouring alcohol into the anhydrous ethanol with the mass ratio of 1:2, ball-milling at the speed of 260r/min for 18 hours, separating slurry, drying at 70 ℃ for 10 hours, and then placing the powder into a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and calcining for 3 hours to obtain the barium titanate-based energy storage ceramic precursor powder.
(2) The barium titanate-based energy storage ceramic precursor powder and a polyvinyl alcohol aqueous solution (PVA solution adhesive) with the concentration of 5 weight percent are fully mixed in an agate mortar, and the ratio of the precursor powder to the adhesive is as follows: 1g of precursor powder: 2 drops of a 5% by weight aqueous solution of polyvinyl alcohol. After aging for 2 hours, passing through a 150-mesh screen, pouring 0.4g of powder into a tabletting mold with the diameter of 10cm, and carrying out compression molding in an automatic tabletting machine under the pressure of 4Mpa for 1 minute. And (3) placing the pressed sheet into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to remove the adhesive, thereby obtaining the barium titanate-based energy storage ceramic green body.
(3) Slowly transferring the barium titanate-based energy storage ceramic green body into a muffle furnace, and raising the temperature to 1050 ℃ at a heating rate of 5 ℃/min for 3 hours to obtain the barium titanate-based energy storage ceramic.
Example 2
(1) BaCO is carried out 3 Powder, bi 2 O 3 Powder, fe 2 O 3 Powder, tiO 2 Powder, srCO 3 Powder, sm 2 O 3 Powder, na 2 CO 3 Powder, caCO 3 Powder, zrO 2 The powder is used as raw material and then is processed according to (Ba 0.39 Bi 0.32 Ca 0.11 Sm 0.04 Na 0.04 Sr 0.1 )(Ti 0.58 Fe 0.32 Zr 0.1 )O 3 Weighing raw materials according to the stoichiometric ratio, loading the powder into a 250ml nylon ball milling tank, and mixing the raw materials according to the following steps: and pouring alcohol into the anhydrous ethanol with the mass ratio of 1:2, ball-milling at the speed of 260r/min for 18 hours, separating slurry, drying at 70 ℃ for 10 hours, and then placing the powder into a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and calcining for 3 hours to obtain the barium titanate-based energy storage ceramic precursor powder.
(2) The barium titanate-based energy storage ceramic precursor powder and a polyvinyl alcohol aqueous solution (PVA solution adhesive) with the concentration of 5 weight percent are fully mixed in an agate mortar, and the ratio of the precursor powder to the adhesive is as follows: 1g of precursor powder: 2 drops of a 5% by weight aqueous solution of polyvinyl alcohol. After aging for 2 hours, passing through a 150-mesh screen, pouring 0.4g of powder into a tabletting mold with the diameter of 10cm, and carrying out compression molding in an automatic tabletting machine under the pressure of 4Mpa for 1 minute. And (3) placing the pressed sheet into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to remove the adhesive, thereby obtaining the barium titanate-based energy storage ceramic green body.
(3) Slowly transferring the barium titanate-based energy storage ceramic green body into a muffle furnace, and raising the temperature to 1100 ℃ at a heating rate of 5 ℃/min for 3 hours to obtain the barium titanate-based energy storage ceramic.
Example 3
(1) BaC is carried outO 3 Powder, bi 2 O 3 Powder, fe 2 O 3 Powder, tiO 2 Powder, srCO 3 Powder, sm 2 O 3 Powder, na 2 CO 3 Powder, caCO 3 The powder is used as raw material and then is processed according to (Ba 0.27 Bi 0.32 Ca 0.11 Sm 0.1 Na 0.1 Sr 0.1 )(Ti 0.68 Fe 0.32 )O 3 Weighing raw materials according to the stoichiometric ratio, loading the powder into a 250ml nylon ball milling tank, and mixing the raw materials according to the following steps: and pouring alcohol into the anhydrous ethanol with the mass ratio of 1:2, ball-milling at the speed of 260r/min for 18 hours, separating slurry, drying at 70 ℃ for 10 hours, and then placing the powder into a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and calcining for 3 hours to obtain the barium titanate-based energy storage ceramic precursor powder.
(2) The barium titanate-based energy storage ceramic precursor powder and a polyvinyl alcohol aqueous solution (PVA solution adhesive) with the concentration of 5 weight percent are fully mixed in an agate mortar, and the ratio of the precursor powder to the adhesive is as follows: 1g of precursor powder: 2 drops of a 5% by weight aqueous solution of polyvinyl alcohol. After aging for 2 hours, passing through a 150-mesh screen, pouring 0.4g of powder into a tabletting mold with the diameter of 10cm, and carrying out compression molding in an automatic tabletting machine under the pressure of 4Mpa for 1 minute. And (3) placing the pressed sheet into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to remove the adhesive, thereby obtaining the barium titanate-based energy storage ceramic green body.
(3) Slowly transferring the barium titanate-based energy storage ceramic green body into a muffle furnace, and raising the temperature to 1075 ℃ at a heating rate of 5 ℃/min for 3 hours to obtain the barium titanate-based energy storage ceramic.
Comparative example 1
(1) BaCO is carried out 3 Powder, bi 2 O 3 Powder, fe 2 O 3 Powder, tiO 2 Powder, srCO 3 Powder, caCO 3 The powder is used as raw material and then is processed according to (Ba 0.47 Bi 0.32 Ca 0.11 Sr 0.1 )(Ti 0.68 Fe 0.32 )O 3 Weighing raw materials according to the stoichiometric ratio, loading the powder into a 250ml nylon ball milling tank, and mixing the raw materials according to the following steps: absolute ethanol with the mass ratio of 1:2 is poured into alcohol, ball milling is carried out for 18 hours at the speed of 260r/min, slurry is separated,and (3) drying at 70 ℃ for 10 hours, and then placing the powder in a muffle furnace, and heating to 750 ℃ at a heating rate of 5 ℃/min to calcine for 3 hours to obtain the barium titanate-based energy storage ceramic precursor powder.
(2) The barium titanate-based energy storage ceramic precursor powder and a polyvinyl alcohol aqueous solution (PVA solution adhesive) with the concentration of 5 weight percent are fully mixed in an agate mortar, and the ratio of the precursor powder to the adhesive is as follows: 1g of precursor powder: 2 drops of a 5% by weight aqueous solution of polyvinyl alcohol. After aging for 2 hours, passing through a 150-mesh screen, pouring 0.4g of powder into a tabletting mold with the diameter of 10cm, and carrying out compression molding in an automatic tabletting machine under the pressure of 4Mpa for 1 minute. And (3) placing the pressed sheet into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to remove the adhesive, thereby obtaining the barium titanate-based energy storage ceramic green body.
(3) Slowly transferring the barium titanate-based energy storage ceramic green body into a muffle furnace, and raising the temperature to 1050 ℃ at a heating rate of 5 ℃/min for 3 hours to obtain the barium titanate-based energy storage ceramic.
Comparative example 2
(1) BaCO is carried out 3 Powder, bi 2 O 3 Powder, fe 2 O 3 Powder, tiO 2 Powder, srCO 3 Powder, sm 2 O 3 Powder, na 2 CO 3 Powder, caCO 3 Powder, zrO 2 The powder is used as raw material and then is processed according to (Ba 0.15 Bi 0.32 Ca 0.11 Sm 0.16 Na 0.16 Sr 0.1 )(Ti 0.53 Fe 0.32 Zr 0.15 )O 3 Weighing raw materials according to the stoichiometric ratio, loading the powder into a 250ml nylon ball milling tank, and mixing the raw materials according to the following steps: and pouring alcohol into the anhydrous ethanol with the mass ratio of 1:2, ball-milling at the speed of 260r/min for 18 hours, separating slurry, drying at 70 ℃ for 10 hours, and then placing the powder into a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and calcining for 3 hours to obtain the barium titanate-based energy storage ceramic precursor powder.
(2) The barium titanate-based energy storage ceramic precursor powder and a polyvinyl alcohol aqueous solution (PVA solution adhesive) with the concentration of 5 weight percent are fully mixed in an agate mortar, and the ratio of the precursor powder to the adhesive is as follows: 1g of precursor powder: 2 drops of a 5% by weight aqueous solution of polyvinyl alcohol. After aging for 2 hours, passing through a 150-mesh screen, pouring 0.4g of powder into a tabletting mold with the diameter of 10cm, and carrying out compression molding in an automatic tabletting machine under the pressure of 4Mpa for 1 minute. And (3) placing the pressed sheet into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to remove the adhesive, thereby obtaining the barium titanate-based energy storage ceramic green body.
(3) Slowly transferring the barium titanate-based energy storage ceramic green body into a muffle furnace, and raising the temperature to 1100 ℃ at a heating rate of 5 ℃/min for 3 hours to obtain the barium titanate-based energy storage ceramic.
The barium titanate-based energy storage ceramics of examples 1 to 3 and comparative examples 1 to 2 were subjected to performance measurement as follows:
(1) XRD analysis was performed on the barium titanate-based energy storage ceramics of examples 1 to 3 and comparative example 1, and the results are shown in FIG. 1. As can be seen from fig. 1, the high-entropy barium titanate-based energy storage ceramic samples of examples 1 to 3 and comparative example 1 each have a single perovskite structure, and no significant impurity phase is seen.
(2) STEM analysis was performed on the barium titanate-based energy storage ceramic of example 1, and the results are shown in fig. 2. It can be seen from fig. 2 that in the example 1 sample, both tetragonal domains (fig. 2B) and rhombohedral domains Fang Xiangchou (fig. 2C) were present, while the transition regions of tetragonal domains and rhombohedral domains (fig. 2D) were observed, which was beneficial in reducing the polarization anisotropy and domain inversion barrier, thereby improving efficiency.
(3) The barium titanate-based energy storage ceramics of examples 1 to 3 and comparative examples 1 to 2 were subjected to P-E curve test as shown in fig. 3 to 7, respectively. As can be seen from FIGS. 3 to 5, the breakdown field strength of the barium titanate-based energy storage ceramics of examples 1 to 3 can reach 540kV/cm to 550kV/cm, and the energy storage density under the maximum electric field is 8.42J/cm 3 ～10.00J/cm 3 As is clear from FIGS. 6 and 7, the breakdown field strength of the barium titanate-based energy storage ceramics of comparative examples 1 and 2 is significantly reduced to 320kV/cm to 390kV/cm, and thus the energy storage density thereof is reduced to 4.07J/cm 3 ～5.16J/cm 3 The efficiency is 90.9-92.0%. The specific performance test results of the barium titanate-based energy storage ceramics of examples 1 to 3 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
As can be seen from Table 1, the barium titanate-based energy storage ceramics of examples 1 to 3 have high breakdown field strengths (540 kV/cm to 550 kV/cm) while maintaining extremely high maximum polarization strength, and can meet the use requirements to a greater extent. The barium titanate-based energy storage ceramics of examples 1 to 3 have not only a high energy storage density but also excellent energy storage efficiency, compared to comparative examples 1 to 2.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A barium titanate-based energy storage ceramic is characterized in that the chemical composition of the barium titanate-based energy storage ceramic comprises (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Wherein x is more than 0 and less than or equal to 0.14,0, y is more than or equal to 0.10.
2. The barium titanate-based energy storage ceramic of claim 1, wherein 0.04 +.x +.0.10, 0.02 +.y +.0.08.
3. The barium titanate-based energy storage ceramic of claim 1, wherein the barium titanate-based energy storage ceramic has a breakdown field strength of 540kV/cm to 550kV/cm at 1050 ℃ to 1100 ℃.
4. A barium titanate-based energy storage ceramic according to claim 1 or 3, wherein the energy storage density of the barium titanate-based energy storage ceramic is 8J/cm at room temperature of 100Hz 3 ～10J/cm 3 The energy storage efficiency is 85% -93.5%.
5. A method of preparing the barium titanate-based energy storage ceramic of any one of claims 1-4, comprising:
(1) According to chemical composition (Ba 0.47-2x Bi 0.32 Ca 0.11 Sm x Na x Sr 0.1 )(Ti 0.68-y Fe 0.32 Zr y )O 3 Weighing a Ba source, a Bi source, a Ca source, a Sm source, a Na source, a Sr source, a Ti source, a Fe source and/or a Zr source according to stoichiometric ratio, mixing, grinding and drying to obtain mixed material powder;
(2) Calcining the mixture powder to obtain barium titanate-based energy storage ceramic precursor powder;
(3) Mixing the barium titanate-based energy storage ceramic precursor powder with an adhesive, and pressing into a sheet and discharging glue to obtain a barium titanate-based energy storage ceramic green body;
(4) And sintering the barium titanate-based energy storage ceramic green body so as to obtain the barium titanate-based energy storage ceramic.
6. The method of claim 5, wherein in step (1), the Ba source comprises BaCO 3 And BaO;
optionally, the Bi source comprises Bi 2 O 3 ；
Optionally, the Ca source comprises CaCO 3 ；
Optionally, the Sm source comprises Sm 2 O 3 ；
Optionally, the Na source comprises Na 2 CO 3 ；
Optionally, the Sr source comprises SrCO 3 ；
Optionally, the Ti source comprises TiO 2 ；
Optionally, the Fe source comprises Fe 2 O 3 ；
Optionally, the Zr source comprises ZrO 2 ；
Optionally, the grinding rotating speed is 260 r/min-300 r/min, and the grinding time is 12 h-24 h;
optionally, the temperature of the drying is 68-72 ℃, and the time of the drying is 6-12 h.
7. The method according to claim 5, wherein in the step (2), the calcination is performed at 600 to 800 ℃ for 2 to 3 hours.
8. The method according to claim 5, wherein in the step (3), the pressure of the compressed tablet is 2MPa to 8MPa and the dwell time is 1min to 2min;
optionally, the temperature of the glue discharging is 500-600 ℃, and the time of the glue discharging is 2-4 hours;
optionally, the binder comprises at least one of 5wt% to 8wt% aqueous polyvinyl alcohol solution and 5wt% to 8wt% polyvinyl butyral ester ethanol solution.
9. The method according to claim 5, wherein in the step (4), the sintering temperature is 1000 ℃ to 1200 ℃ and the sintering time is 2h to 3h.
10. Use of the barium titanate-based energy storage ceramic of any one of claims 1-4 or the barium titanate-based energy storage ceramic prepared by the method of any one of claims 5-9 in the field of communications, aviation or automotive manufacturing.
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