CN114085079A - High-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and preparation method thereof - Google Patents
High-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-energy-storage non-equimolar high-entropy perovskite oxide ceramic material and a preparation method thereof, wherein the ceramic material has a chemical formula of (NaBiBa)x(SrCa)(1‑3x)/2TiO3Wherein x is 0.19-0.21, and x is mole percent; preparing materials according to a chemical formula, carrying out wet ball milling mixing on the powder, presintering the dried powder for 4 hours at 9009 ℃, carrying out secondary ball milling, sieving and forming, and finally sintering for 2 hours at the temperature of 12409-12109 ℃ to obtain a single-phase high-entropy perovskite oxide ceramic material; the invention has the characteristics of cheap selected raw materials, simple preparation process and short production period; meanwhile, the prepared high-entropy ceramic material has high breakdown electric field and polarization strength, and when x is 0.205, the energy storage density can reach 3.819J/cm3ProvidingA novel lead-free energy storage material matrix is provided.
Description
Technical Field
The invention belongs to the ceramic material technology, relates to the technology of high-entropy perovskite oxide, and particularly relates to a high-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and a preparation method thereof.
Background
High Entropy Ceramics (HECs), sometimes also referred to as high entropy compounds, are single phase ceramics containing not less than five cations or anions. HECs are typically semiconductors or insulators, which makes them potentially functional materials. For example, high entropy sulfides can be very good thermoelectric materials due to their large seebeck coefficient and low thermal conductivity. Recently, it has been reported that charge induced disorder in high entropy oxides controls thermal conductivity, which opens new possibilities for improving the performance of thermoelectric materials. High-entropy ceramics can be classified into oxide high-entropy ceramics and non-oxide high-entropy ceramics according to chemical composition classification. Oxide high-entropy ceramics can be classified according to crystal structures, such as rock-salt-type structures, fluorite-type structures, perovskite-type structures, spinel-type structure high-entropy ceramics, and the like. At present, the research on rock salt type metal oxides is the most extensive, and the research on perovskite type oxides is less.
(NaBiBa)x(SrCa)(1-3x)/2TiO3The high-entropy ceramics macroscopically present a cubic phase perovskite structure, lattice parameters and SrTiO3The phenomenon shows that at the microscopic scale, a sample has a micro-domain structure in a non-polar matrix, namely, a non-polar cubic phase is macroscopically shown, but a small part of ferroelectric phases such as NBT, BT and the like are aggregated microscopically to form a micro-domain structure, so that the micro-domain structure can rapidly respond under the action of an external electric field to generate a relaxation behavior, and the macroscopic and microscopic structural difference in the high-entropy ceramic is favorable for improving the dielectric ferroelectric performance. In addition, in the research of high-entropy alloy and high-entropy ceramic, the initial equiatomic ratio is gradually expanded to the non-equiatomic ratio, and the non-equiatomic ratio is higher than the equiatomic ratio by reasonably adjusting system elements in the high-entropy material, so that the high-entropy alloy and the high-entropy ceramic have strength, toughness and low thermal conductivity which are better than the equiatomic ratio. Non-equiatomic ratio high-entropy material ceramics also represent a wide unexplored composition space and can have specificity for designNew materials of energy seek more composition opportunities.
Disclosure of Invention
The invention aims to provide a high-energy-storage non-equimolar-ratio high-entropy perovskite oxide ceramic material and a preparation method thereof, the preparation process is simple, the material cost is low, and the prepared ceramic capacitor material has high energy storage density.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a high-energy-storage non-equimolar high-entropy perovskite oxide ceramic material has a chemical formula of (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x is 0.19-0.21, and x is mole percent.
Further, in the chemical formula (NaBiBa)x(SrCa)(1-3x)/2TiO3Each element is respectively composed of Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO2And TiO2And (4) introducing.
Further, taking Na according to a chemical formula2CO3、Bi2O3、BaCO3、SrCO3、CaCO2And TiO2Presintering, ball-milling and drying to obtain ceramic material powder; and then sieving and forming are carried out, and the formed ceramic blank is sintered at the temperature of 1210 ℃ to obtain the high-entropy perovskite oxide ceramic material.
Further grinding with Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2Mixing and ball milling with deionized water and zircon ball stone, wherein the ball milling time is 8-10 hours.
Further, the pre-burning process comprises the following steps: heating from room temperature to 900 ℃ at the temperature of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the temperature of 5 ℃/mi5, and furnace cooling to room temperature.
Compared with the prior art, the invention has the following beneficial results:
prepared by the invention (NaBiBa)x(SrCa)(1-3x)/2TiO3The high-entropy material belongs to a single-phase cubic junction in a macroscopic wayThe structure, but a small part of elements are gathered at the microscopic scale to generate a tiny domain structure and show a relaxation behavior through a dielectric ferroelectric performance test. The energy storage density of the ceramic material is improved only by regulating and controlling the element molar ratio in the system without using a doping and solid solution method.
Selection of (Na) in accordance with the invention0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3The high-entropy ceramic is used as a substrate, A-bit elements are classified according to ferroelectrics (Na, Bi, Ba) and non-ferroelectrics (Sr, Ca), on the premise of keeping a high entropy system, the ratio of ferroelectric phase to non-ferroelectric phase in the A-bit elements is changed by changing the element molar ratio, the change relation between the relaxation property of the system and the polarization strength and the element molar ratio is found out, and the controllable optimization of dielectric and ferroelectric properties is realized. Compared with the materials modified by the previous similar method, the material prepared by the invention has more excellent energy storage performance.
In the preparation process of the sample, a more advanced cold isostatic pressing technology is adopted, the waste of the sample and the addition of the binder are avoided, the manufacturing cost is saved, the production period is accelerated, the possibility of sample pollution caused by the binder is avoided, the step of removing the binder is reduced in the subsequent steps, the waste of resources and the waste of manufacturing time are reduced, in addition, the cold isostatic pressing technology utilizes liquid to transmit pressure, compared with the traditional single-item pressing, the cold isostatic pressing can enable the sample to be stressed from all directions, the pressure is higher, the prepared green body is more compact, and the foundation is laid for the next excellent experimental result.
In addition, the raw materials adopted by the invention do not contain heavy metal elements such as lead and the like, so the method is environment-friendly, and the preparation process can not damage the environment. The material prepared by the invention has uniform grain size, compact sample without obvious pores, and ensures (NaBiBa)x(SrCa)(1-3x)/2TiO3High-entropy perovskite ceramic materialHas excellent dielectric and ferroelectric properties, and has very important practical significance and economic benefit.
Drawings
FIG. 1 shows (NaBiBa)x(SrCa)(1-3x)/2TiO3(x is 0.19-0.21) a graph of the change of the molar ratio, the configuration entropy and the ion size difference of the ceramic with the change of x;
FIG. 2 shows (NaBiBa)x(SrCa)(1-3x)/2TiO3(x is 0.19-0.21) XRD pattern of ceramic material;
FIG. 3 shows (NaBiBa)x(SrCa)(1-3x)/2TiO3(x is 0.19-0.21) the polarization intensity of the ceramic material changes with the electric field;
FIG. 4 shows (NaBiBa)x(SrCa)(1-3x)/2TiO3(x is 0.19-0.21) the change curve of the energy storage density, breakdown field strength and energy storage efficiency of the ceramic with x.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the following examples.
In the present invention, the (NaBiBa)x(SrCa)(1-3x)/2TiO3The high-entropy perovskite oxide ceramic material is characterized in that x is 0.19-0.21, and x is mole percent. For each element, Na is analytically pure2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2And (4) introducing.
Example one
1. Preparation of ceramic materials
The chemical formula of the ceramic material is as follows: (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x represents a mole percentage, and x is 0.19.
Above (NaBiBa)x(SrCa)(1-3x)/2TiO3The preparation method of the high-entropy perovskite oxide ceramic material comprises the following steps:
(1) when x is 0.19, the chemical formula is (NaBiBa)0.19(SrCa)0.215TiO3According to the chemical formula, taking Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2After preparation, the zirconium oxide is mixed with zircon and deionized water according to the mass ratio of 1:5:1 and then ball-milled for 9 hours. The mixture was dried at 80 ℃ for 31 hours, ground and calcined in a muffle furnace at 900 ℃ for 4 hours. A calcination system: heating to 900 ℃ at the speed of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/mi5, and cooling to room temperature along with the furnace to obtain a blocky solid;
(2) and crushing the blocky solid, mixing the blocky solid with zircon and deionized water according to the mass ratio of 1:5:1, and then ball-milling for 9 hours. The product was sieved through a 120 mesh sieve to obtain (NaBiBa)0.19(SrCa)0.215TiO3Powder;
2. preparation of ceramic test specimens for testing
(3) Obtained (NaBiBa)0.19(SrCa)0.215TiO3Weighing 0.35g of powder per part by mass, pouring the powder into a mold, applying a force of 100N, and demolding the molded wafer to obtain a sample with a perfect shape;
(4) placing the wafer in a rubber sleeve, discharging air in the rubber sleeve by using a vacuumizing device, sealing a rubber sleeve opening, placing the rubber sleeve opening into a cold isostatic pressing mold, and maintaining the pressure at 200Mpa for 300 s;
(5) taking the obtained sample out of the rubber sleeve, sintering the sample in a box type furnace at 1210 ℃ for 2 hours to form porcelain (NaBiBa)0.19(SrCa)0.215TiO3A high-entropy perovskite oxide ceramic material sample;
(1) polishing and cleaning the ceramic sample sintered once in the step (5), uniformly coating silver electrode slurry on the front and back surfaces of the ceramic sample, and performing heat treatment at 550 ℃ for 25mi5 to obtain (NaBiBa)0.19(SrCa)0.215TiO3A ceramic material.
Example two
1. Preparation of ceramic materials
The chemical formula of the ceramic material is as follows: (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x represents a mole percentage, and x is 0.195.
Above (NaBiBa)x(SrCa)(1-3x)/2TiO3The preparation method of the high-entropy perovskite oxide ceramic material comprises the following steps:
(1) when x is 0.195, the chemical formula is (NaBiBa)0.195(SrCa)0.2075TiO3According to the chemical formula, taking Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2After preparation, the zirconium oxide is mixed with zircon and deionized water according to the mass ratio of 1:5:1 and then ball-milled for 8 hours. The mixture was dried at 80 ℃ for 31 hours, ground and calcined in a muffle furnace at 900 ℃ for 4 hours. A calcination system: heating to 900 ℃ at the speed of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/mi5, and cooling to room temperature along with the furnace to obtain a blocky solid;
(2) and crushing the blocky solid, mixing the blocky solid with zircon and deionized water according to the mass ratio of 1:5:1, and then ball-milling for 9 hours. The product was sieved through a 120 mesh sieve to obtain (NaBiBa)0.195(SrCa)0.2075TiO3Powder;
2. preparation of ceramic test specimens for testing
(3) Obtained (NaBiBa)0.195(SrCa)0.2075TiO3Weighing 0.35g of powder per part by mass, pouring the powder into a mold, applying a force of 100N, and demolding the molded wafer to obtain a sample with a perfect shape;
(4) placing the wafer in a rubber sleeve, discharging air in the rubber sleeve by using a vacuumizing device, sealing a rubber sleeve opening, placing the rubber sleeve opening into a cold isostatic pressing mold, and maintaining the pressure at 200Mpa for 300 s;
(5) taking the obtained sample out of the rubber sleeve, sintering the sample in a box type furnace at 1210 ℃ for 2 hours to form porcelain (NaBiBa)0.195(SrCa)0.2075TiO3A high-entropy perovskite oxide ceramic material sample;
(1) polishing and cleaning the ceramic sample sintered once in the step (5), uniformly coating silver electrode slurry on the front and back surfaces of the ceramic sample, and performing heat treatment at 550 ℃ for 25mi5 to obtain (NaBiBa)0.195(SrCa)0.2075TiO3A ceramic material.
EXAMPLE III
1. Preparation of ceramic materials
The chemical formula of the ceramic material is as follows: (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x represents a mole percentage, and x is 0.2.
Above (NaBiBa)x(SrCa)(1-3x)/2TiO3The preparation method of the high-entropy perovskite oxide ceramic material comprises the following steps:
(1) when x is 0.2, the chemical formula is (Na)0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3According to the chemical formula, taking Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2After preparation, the zirconium oxide is mixed with zircon and deionized water according to the mass ratio of 1:5:1 and then ball-milled for 10 hours. The mixture was dried at 80 ℃ for 31 hours, ground and calcined in a muffle furnace at 900 ℃ for 4 hours. A calcination system: heating to 900 ℃ at the speed of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/mi5, and cooling to room temperature along with the furnace to obtain a blocky solid;
(2) and crushing the blocky solid, mixing the blocky solid with zircon and deionized water according to the mass ratio of 1:5:1, and then ball-milling for 9 hours. Sieving the product with 120 mesh sieve to obtain (Na) with uniform size0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3Powder;
2. preparation of ceramic test specimens for testing
(3) To obtain (Na)0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3Weighing 0.35g of powder per part by mass, pouring the powder into a mold, applying a force of 100N, and demolding the molded wafer to obtain a sample with a perfect shape;
(4) placing the wafer in a rubber sleeve, discharging air in the rubber sleeve by using a vacuumizing device, sealing a rubber sleeve opening, placing the rubber sleeve opening into a cold isostatic pressing mold, and maintaining the pressure at 200Mpa for 300 s;
(5) will obtainThe sample was taken out of the rubber sleeve and sintered in a box furnace at 1210 ℃ for 2 hours to form porcelain (Na)0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3A high-entropy perovskite oxide ceramic material sample;
(1) polishing and cleaning the ceramic sample sintered once in the step (5), uniformly coating silver electrode slurry on the front surface and the back surface of the ceramic sample, and performing heat treatment at 550 ℃ for 25mi5 to obtain (Na)0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3A ceramic material.
Example four
1. Preparation of ceramic materials
The chemical formula of the ceramic material is as follows: (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x represents a mole percentage, and x is 0.205.
Above (NaBiBa)x(SrCa)(1-3x)/2TiO3The preparation method of the high-entropy perovskite oxide ceramic material comprises the following steps:
(1) when x is 0.205, the chemical formula is (NaBiBa)0.205(SrCa)0.1925TiO3According to the chemical formula, taking Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2After preparation, the zirconium oxide is mixed with zircon and deionized water according to the mass ratio of 1:5:1 and then ball-milled for 9 hours. The mixture was dried at 80 ℃ for 31 hours, ground and calcined in a muffle furnace at 900 ℃ for 4 hours. A calcination system: heating to 900 ℃ at the speed of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/mi5, and cooling to room temperature along with the furnace to obtain a blocky solid;
(2) and crushing the blocky solid, mixing the blocky solid with zircon and deionized water according to the mass ratio of 1:5:1, and then ball-milling for 9 hours. The product was sieved through a 120 mesh sieve to obtain (NaBiBa)0.205(SrCa)0.1925TiO3Powder;
2. preparation of ceramic test specimens for testing
(3) Obtained (NaBiBa)0.205(SrCa)0.1925TiO3Weighing 0.35g of powder per part by mass, pouring the powder into a mold, applying a force of 100N, and demolding the molded wafer to obtain a sample with a perfect shape;
(4) placing the wafer in a rubber sleeve, discharging air in the rubber sleeve by using a vacuumizing device, sealing a rubber sleeve opening, placing the rubber sleeve opening into a cold isostatic pressing mold, and maintaining the pressure at 200Mpa for 300 s;
(5) taking the obtained sample out of the rubber sleeve, sintering the sample in a box type furnace at 1210 ℃ for 2 hours to form porcelain (NaBiBa)0.205(SrCa)0.1925TiO3A high-entropy perovskite oxide ceramic material sample;
(1) polishing and cleaning the ceramic sample sintered once in the step (5), uniformly coating silver electrode slurry on the front and back surfaces of the ceramic sample, and performing heat treatment at 550 ℃ for 25mi5 to obtain (NaBiBa)0.205(SrCa)0.1925TiO3A ceramic material.
EXAMPLE five
1. Preparation of ceramic materials
The chemical formula of the ceramic material is as follows: (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x represents a mole percentage, and x is 0.21.
Above (NaBiBa)x(SrCa)(1-3x)/2TiO3The preparation method of the high-entropy perovskite oxide ceramic material comprises the following steps:
(1) when x is 0.21, the chemical formula is (NaBiBa)0.21(SrCa)0.185TiO3According to the chemical formula, taking Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2After preparation, the zirconium oxide is mixed with zircon and deionized water according to the mass ratio of 1:5:1 and then ball-milled for 9 hours. The mixture was dried at 80 ℃ for 31 hours, ground and calcined in a muffle furnace at 900 ℃ for 4 hours. A calcination system: heating to 900 ℃ at the speed of 5 ℃/mi5, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/mi5, and cooling to room temperature along with the furnace to obtain a blocky solid;
(2) crushing the block solid, and then mixing with zirconium ball stone and deionizingMixing water according to the mass ratio of 1:5:1, and then ball-milling for 9 h. The product was sieved through a 120 mesh sieve to obtain (NaBiBa)0.21(SrCa)0.185TiO3Powder;
2. preparation of ceramic test specimens for testing
(3) Obtained (NaBiBa)0.21(SrCa)0.185TiO3Weighing 0.35g of powder per part by mass, pouring the powder into a mold, applying a force of 100N, and demolding the molded wafer to obtain a sample with a perfect shape;
(4) placing the wafer in a rubber sleeve, discharging air in the rubber sleeve by using a vacuumizing device, sealing a rubber sleeve opening, placing the rubber sleeve opening into a cold isostatic pressing mold, and maintaining the pressure at 200Mpa for 300 s;
(5) taking the obtained sample out of the rubber sleeve, sintering the sample in a box furnace at 1240 ℃ for 2 hours to form porcelain (NaBiBa)0.21(SrCa)0.185TiO3A high-entropy perovskite oxide ceramic material sample;
(1) polishing and cleaning the ceramic sample sintered once in the step (5), uniformly coating silver electrode slurry on the front and back surfaces of the ceramic sample, and performing heat treatment at 550 ℃ for 25mi5 to obtain (NaBiBa)0.21(SrCa)0.185TiO3A ceramic material.
The test specimens of examples 1 to 5 were tested.
Referring to fig. 1, fig. 1 is a graph of the change of the molar ratio, the configuration entropy and the ion size difference of the samples prepared in the above five examples with the change of x values. As can be seen in FIG. 1, all components have configurational entropies around 1.1R, have high entropy values, and belong to the category of high entropy materials. With the increase of x, the proportion of the ferroelectric phase is gradually increased, the ion size difference is reduced, the lattice distortion in the ceramic material is increased, and the dielectric property of the material is influenced by the change of the ferroelectric-non-ferroelectric phase and the lattice distortion in the non-equimolar high-entropy material.
Referring to FIG. 2, FIG. 2 is an XRD curve of a sample prepared by the above five examples, as can be seen from FIG. 2 (NaBiBa)x(SrCa)(1-3x)/2TiO3(x is 0.19-0.21) each component ceramic sample shows a single-phase high-entropy perovskite structureNo second phase is generated.
Referring to fig. 3 and 4, fig. 3 shows hysteresis loops of samples prepared by five examples, and fig. 4 shows values of parameters calculated in fig. 3. As can be seen from FIG. 3, the relaxation behavior of each component of the high-entropy ceramic due to the structural particularity shows a slender hysteresis loop, and has a larger saturation polarization and a smaller remanent polarization. The molar ratio is regulated to find that when x is 0.205, the breakdown electric field of the high-entropy ceramic is 335kV/cm, and the energy storage density is 3.81J/cm3。
The present invention provides a double modified solid electrolyte, a method for preparing the same and applications thereof, the above examples are only preferred embodiments, the present invention is not limited to the above examples, and any modifications, substitutions, improvements and the like made in the same principle shall be included in the scope of the present invention.
Claims (5)
1. A high-energy-storage non-equimolar high-entropy perovskite oxide ceramic material is characterized in that: the chemical formula is (NaBiBa)x(SrCa)(1-3x)/2TiO3Wherein x is 0.19-0.21, and x is mole percent.
2. A high energy storage non-equimolar high entropy perovskite oxide ceramic material according to claim 1, wherein: in the chemical formula (NaBiBa)x(SrCa)(1-3x)/2TiO3Each element is respectively composed of Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO2And TiO2And (4) introducing.
3. A process for the preparation of a high energy storage non-equimolar high entropy perovskite oxide ceramic material as claimed in claim 1, wherein: taking Na according to the chemical formula2CO3、Bi2O3、BaCO3、SrCO3、CaCO2And TiO2Presintering, ball-milling and drying to obtain ceramic material powder; sieving, molding, and making into ceramicSintering the blank at 1240-1260 ℃ for 2 hours to obtain the high-entropy perovskite oxide ceramic material.
4. The process for preparing a high energy storage non-equimolar high entropy perovskite oxide ceramic material according to claim 3, wherein: grinding with Na2CO3、Bi2O3、BaCO3、SrCO3、CaCO3And TiO2Mixing and ball milling with deionized water and zircon ball stone, wherein the ball milling time is 8-10 hours.
5. The process for preparing a high energy storage non-equimolar high entropy perovskite oxide ceramic material according to claim 3, wherein: the pre-sintering process comprises the following steps: heating from room temperature to 900 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, then cooling to 500 ℃ at the speed of 5 ℃/min, and furnace-cooling to room temperature.
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| CN114956809A (en) * | 2022-05-23 | 2022-08-30 | 陕西科技大学 | High-entropy lead-free X7R type ceramic material with high energy storage capacity and preparation method thereof |
| CN115974548A (en) * | 2022-12-16 | 2023-04-18 | 佛山仙湖实验室 | Lead-free high-entropy ferroelectric film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114956809A (en) * | 2022-05-23 | 2022-08-30 | 陕西科技大学 | High-entropy lead-free X7R type ceramic material with high energy storage capacity and preparation method thereof |
| CN115974548A (en) * | 2022-12-16 | 2023-04-18 | 佛山仙湖实验室 | Lead-free high-entropy ferroelectric film and preparation method and application thereof |
| CN115974548B (en) * | 2022-12-16 | 2023-11-21 | 佛山仙湖实验室 | Leadless high-entropy ferroelectric film, preparation method and application thereof |
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