阅读说明：本技术 一种使kio3铁电材料获得低介电损耗的方法 (KiO3Method for obtaining low dielectric loss of ferroelectric material ) 是由 韩永昊 李娟� 赵星星 马秋 高春晓 于 2021-09-02 设计创作，主要内容包括：本发明的一种使KIO-(3)铁电材料获得低介电损耗的方法,属于功能材料的技术领域。步骤包括：在室温条件下,将KIO-(3)铁电材料在金刚石对顶砧中先加压至1.9GPa～20.56GPa再卸压至常压,得到介电损耗降低的KIO-(3)铁电材料。本发明提供了一种使KIO-(3)材料获得低介电损耗的新方法,通过压力改善KIO-(3)的介电性,为KIO-(3)材料的应用提供了新的方向和思路。(One kind of KIO of the invention 3 A method for obtaining low dielectric loss from ferroelectric material belongs to the technical field of functional materials. The method comprises the following steps: reacting KIO at room temperature 3 The ferroelectric material is firstly pressurized to 1.9 GPa-20.56 GPa in the diamond anvil cell and then is decompressed to normal pressure, and the KIO with reduced dielectric loss is obtained 3 A ferroelectric material. The invention provides a KIO 3 Novel method for obtaining materials with low dielectric loss, KIO improvement by pressure 3 The dielectric property of (A) is KIO 3 The application of the material provides a new direction and idea.)

1. KiO₃A method for obtaining low dielectric loss from ferroelectric material comprises subjecting KIO to room temperature₃The ferroelectric material is firstly pressurized to 1.9 GPa-20.56 GPa in the diamond anvil cell and then is decompressed to normal pressure, and the KIO with reduced dielectric loss is obtained₃A ferroelectric material.

2. A KIO according to claim 1₃The method for obtaining low dielectric loss from ferroelectric material is characterized by comprising the following steps:

assembling a diamond anvil cell, leveling and centering the assembled diamond anvil cell, distributing parallel plate electrodes on an upper anvil cell surface and a lower anvil cell surface of a diamond, punching a hole in the center of a composite insulating gasket to serve as a sample cavity, resetting the manufactured insulating gasket, enabling the center of the sample cavity to coincide with the center of the diamond anvil cell surface, and placing a sample and ruby in the sealed sample cavity for marking;

secondly, performing in-situ impedance spectrum measurement, connecting the electrode lead with a frequency response analyzer, applying alternating voltage to a sample to be measured, selecting a measurement frequency range, and obtaining a relation graph of a real part and an imaginary part of impedance under different pressures;

thirdly, processing the data, fitting the data measured in the second step to obtain the KIO₃The resistance of the dielectric ceramic is changed along with the pressure, and then the relative dielectric constant epsilon under different pressures is obtained according to an electromagnetic calculation formula related to the dielectric property_rDielectric loss tan theta, finally obtaining the KIO with low dielectric loss₃A ferroelectric material.

3. A kit according to claim 2, wherein the kit is administered to a patient in need thereof₃The method for obtaining low dielectric loss of ferroelectric material is characterized in that in the first step, the parallel plate electrode is made by cutting a platinum sheet into a slender strip shape with the width of 1/3 anvil faces, adhering a metal wire with silver paste, and respectively distributing the platinum sheet on the upper anvil face and the lower anvil face of a pressing anvil.

4. A kit according to claim 2, wherein the kit is administered to a patient in need thereof₃The method for obtaining the low dielectric loss from the ferroelectric material is characterized in that the first step of the manufacturing process of the composite insulating gasket is as follows: prepressing a T301 steel sheet to be used as a gasket, and reserving anvil surface impressions, chamfer impressions and side edge impressions of a diamond anvil block from the center to the outside on the steel sheet, wherein the thickness of the impressions is 60 mu m; punching a hole with the diameter of 180 mu m in the center of the anvil surface indentation of the prepressed insulating gasket; mixing aluminum oxide and epoxy resin according to the mass ratio of 6:1,after grinding uniformly, filling the holes of the gasket and all the imprints, pressurizing the anvil by using diamond, and punching the concentric circles at the centers of the imprints to form sample cavities, wherein the diameter of each hole is 130 mu m.

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to a KIO₃A method for obtaining low dielectric loss from ferroelectric materials.

Background

The ferroelectric material is a very important dielectric material, and has a wide application prospect in the aspects of solar cells, photoelectric switches, data storage devices and the like due to the characteristics of good ferroelectricity, piezoelectricity, pyroelectric property, nonlinear optics and the like. At present, lead-based piezoelectric ceramics dominate in electronic device preparation and commercial application due to excellent ferroelectric piezoelectric performance and a systematic research system, but lead element in the lead-based piezoelectric ceramics accounts for more than 60% of the total weight of raw materials, so that lead poisoning is caused and body health is affected in the process of using the products for a long time. In addition, during the production, use and subsequent disposal of lead-containing materials, severe damage is caused to the ecological environment. With the increasing emergence of environmental problems, many countries and regions have made it clear that the use of lead-containing harmful substances in electronic devices is prohibited, so that the search for materials which do not contain lead and have excellent piezoelectric, ferroelectric properties has been reluctant. Under such circumstances, perovskite-type ferroelectric materials are becoming hot of research.

In the aspects of sustainable electric energy and electrification of other commercial, civil and military systems, energy storage technology needs to be developed, the magnitude of energy storage density is related to the dielectric constant and breakdown electric field of materials, and for energy storage devices, dielectric materials with high dielectric constant and high breakdown field strength must be selected as components. Some stored energy dissipation, usually dielectric losses and leakage currents due to charge transfer, is necessary for the study of the electrical transport of dielectric materials. An efficient dielectric minimizes the energy losses of the thermal form, and therefore a dielectric can only exhibit high efficiency with as low dielectric losses as possible.

KIO₃The perovskite type ferroelectric material is a classic perovskite type ferroelectric material, and has very wide application prospect due to excellent piezoelectric property and nonlinear optical effect. The traditional method for reducing the dielectric loss of the material mainly comprises a preparation process and a doping method, the doping concentration and the reaction time need to be controlled, the operation difficulty is high, the time consumption is long, and therefore a simple and effective way for reducing the KIO is needed₃Dielectric loss for better application thereof.

Disclosure of Invention

The invention aims to provide a KIO₃The method for obtaining the low dielectric loss from the ferroelectric material has the following specific technical scheme:

KiO₃Method for obtaining low dielectric loss of ferroelectric material, in-chamberUnder warm conditions, KIO is added₃The ferroelectric material is firstly pressurized to 1.9 GPa-20.56 GPa in the diamond anvil cell and then is decompressed to normal pressure, and the KIO with reduced dielectric loss is obtained₃A ferroelectric material.

The method comprises the following more specific steps:

assembling a diamond anvil cell, leveling and centering the assembled diamond anvil cell, distributing parallel plate electrodes on an upper anvil cell surface and a lower anvil cell surface of a diamond, punching a hole in the center of a composite insulating gasket to serve as a sample cavity, resetting the manufactured insulating gasket, enabling the center of the sample cavity to coincide with the center of the diamond anvil cell surface, and placing a sample and ruby in the sealed sample cavity for marking;

secondly, performing in-situ impedance spectrum measurement, connecting the electrode lead with a frequency response analyzer, applying alternating voltage to a sample to be measured, selecting a measurement frequency range, and obtaining a relation graph of a real part and an imaginary part of impedance under different pressures;

thirdly, processing the data, fitting the data measured in the second step to obtain the KIO₃The resistance of the dielectric ceramic is changed along with the pressure, and then the relative dielectric constant epsilon under different pressures is obtained according to an electromagnetic calculation formula related to the dielectric property_rDielectric loss tan theta, finally obtaining the KIO with low dielectric loss₃A ferroelectric material.

The parallel plate electrode is manufactured by cutting a platinum sheet into a slender strip shape, wherein the width of the strip is 1/3 of an anvil surface, and sticking silver paste to a metal lead, and the strip parallel plate electrode is respectively distributed on the upper anvil surface and the lower anvil surface of an anvil, namely the upper surface and the lower surface of a sample.

The manufacturing process of the composite insulating gasket comprises the following steps: prepressing a T301 steel sheet to be used as a gasket, and reserving anvil surface impressions, chamfer impressions and side edge impressions of a diamond anvil block from the center to the outside on the steel sheet, wherein the thickness of the impressions is 60 mu m; punching a hole with the diameter of 180 mu m in the center of the anvil surface indentation of the prepressed insulating gasket; mixing aluminum oxide and epoxy resin according to the mass ratio of 6:1, grinding uniformly, filling the mixture into holes of a gasket and all indentations, pressurizing an anvil by using diamond, and punching holes at concentric circles at the centers of the indentations to form sample cavities, wherein the diameters of the holes are 130 micrometers.

Has the advantages that:

KIO₃as a perovskite type ferroelectric material, the dielectric property has important influence on the application of the material in energy storage devices, piezoelectric devices and the like, the invention provides a KIO₃A new method for obtaining low dielectric loss is to meet the requirements of different devices on low dielectric loss of materials, namely KIO₃The application of the ferroelectric material is convenient, and the method has the characteristics of simple and controllable operation and the like.

Drawings

FIG. 1 shows KIO under a pressure of 0 to 3.74GPa in example 4₃High pressure in situ impedance mapping of materials.

FIG. 2 shows KIO under a pressure of 4.3 to 9.16GPa in example 4₃High pressure in situ impedance mapping of materials.

FIG. 3 shows KIO under a pressure of 10 to 14.5GPa in example 4₃High pressure in situ impedance mapping of materials.

FIG. 4 shows KIO under a pressure of 15.3 to 20.56GPa in example 4₃High pressure in situ impedance mapping of materials.

FIG. 5 is KIO under the conditions of example 5₃The resistance and relative dielectric constant of the material are shown as the change of pressure.

FIG. 6 is KIO under the conditions of example 5₃The dielectric loss of different materials under different pressures is plotted against frequency.

Detailed Description

In the embodiment of the invention, in-situ impedance spectrum test is carried out under the experiment condition of room temperature, the experimental instrument is a Solartron1260/1296 impedance spectrum measuring instrument, alternating current with the voltage of 1V is selected, and the frequency range is selected to be 0.001-10⁷Hz。

Example 1 Assembly of a Diamond anvil device

Firstly, respectively putting the diamond and a cushion block of a press into a mixed solution of ethanol and acetone for ultrasonic cleaning for about 15 minutes, and wiping the diamond and the cushion block of the press clean to remove dirt on the surface of the diamond.

And secondly, putting the cleaned diamond into a public package, so that the anvil surface of the diamond and the central through hole of the cushion block are concentric circles, and bonding the anvil surface and the central through hole by using black glue.

And thirdly, placing the cushion block adhered with the diamond into a press, fixing the cushion block by using screws, and leveling and centering. The upper anvil surface and the lower anvil surface are completely superposed or form a concentric circle as centering, and the upper anvil surface and the lower anvil surface are lightly attached without color stripes for leveling.

EXAMPLE 2 fabrication of composite insulating gasket

Firstly, prepressing a T301 steel sheet as a gasket, and reserving anvil surface impressions, chamfer impressions and side edge impressions of the diamond anvil from the center to the outside on the steel sheet, wherein the thickness of the anvil surface impressions, the chamfer impressions and the side edge impressions is about 60 mu m.

And secondly, punching a hole with the diameter of 180 mu m in the center of the anvil surface indentation of the pre-pressed insulating gasket.

And thirdly, mixing the aluminum oxide and the epoxy resin according to the mass ratio of 6:1, uniformly grinding, filling the mixture into holes of the gasket and all indentations, and pressurizing the anvil by using diamond.

And fourthly, punching holes with the diameter of 130 mu m at the concentric circles of the centers of the anvil surface indentations in the third step to serve as sample cavities.

EXAMPLE 3 laying electrodes on Diamond anvil cells and assembling composite insulating gaskets

In the first step, parallel plate electrodes are disposed above and below the diamond anvil, the electrodes being disposed intermediate the anvil faces, the electrodes having a width of about 1/3 and a length of about 1/2.

And secondly, resetting the manufactured insulating gasket to ensure that the anvil surface indentation of the gasket is completely attached to the upper and lower diamond anvil surfaces, and the electrode is positioned in the center of the punched hole of the composite insulating gasket.

Third, fully grinding the KIO₃And (3) powder, namely adding the ground sample into a diamond anvil sealed sample cavity, and marking with ruby. After the assembly is completed, whether the electrode is attached to the sample or not is observed from a test observation window of the press, and the test can be performed only if the electrode is attached to the sample.

Example 4

And (4) applying pressure to the inside of the sample cavity of the anvil device by the diamond, and carrying out in-situ high-voltage impedance spectrum testing. Firstly, the pressure in a sample cavity of a diamond anvil cell device is changed within the range of 0-3.74 GPa, and an in-situ high-voltage impedance spectroscopy test is carried out. The specific in situ impedance spectroscopy test results are shown in figure 1. Secondly, the pressure is slowly increased from 4.3GPa to 9.16GPa, and the specific test result is shown in figure 2. Then, the slow pressurization is continued, and the pressure is increased from 10.0GPa to 14.5GPa, and the specific in-situ impedance spectrum is shown in figure 3. Finally, the pressure is slowly increased to 20.56GPa from 15.3GPa, and the specific in-situ impedance spectrum is shown in figure 4.

Example 5

The resistance values were obtained by fitting the experimental data of the in situ impedance spectroscopy measured in example 4 using the Zview software (see FIG. 5 a). And according to the formula ∈_r＝σ/2πε₀f_bThe relative dielectric constant was found to vary with pressure (see FIG. 5 b). The variation of dielectric loss with frequency at different pressures can be obtained according to the formula tan δ ═ epsilon "/epsilon' (see fig. 6).

As can be seen from fig. 5a, the resistance gradually increases after decreasing with increasing pressure. As can be seen from FIG. 5b, the dielectric constant increased to a maximum 5392 at 3.74GPa, and decreased sharply between 4.3GPa and 9.16 GPa. As can be seen from fig. 6, the dielectric loss does not change significantly in the high frequency region, and in the low frequency region, the dielectric loss gradually decreases with the increase of the pressure, and the decrease of the dielectric loss value is large. Then, the invention compares the dielectric loss value tan delta of 7.8GPa in the pressurizing process with the dielectric loss value tan delta of 7.6GPa in the pressure relief process, and finds that the frequency response interval of the dielectric loss after pressure relief is widened, and the dielectric loss in a low-frequency region is obviously reduced, which indicates that KIO is under high pressure₃The dielectric properties of (a) are changed. Thus, KIO can be produced by high pressure₃Dielectric loss reduction of ferroelectric materials to give KIO with lower dielectric loss₃The method can also be used for researching dielectric loss of other dielectric materials.