CN111825451B - Rare earth element Tm doped silver niobate antiferroelectric ceramic material and preparation method thereof - Google Patents

Rare earth element Tm doped silver niobate antiferroelectric ceramic material and preparation method thereof Download PDF

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CN111825451B
CN111825451B CN201910305422.2A CN201910305422A CN111825451B CN 111825451 B CN111825451 B CN 111825451B CN 201910305422 A CN201910305422 A CN 201910305422A CN 111825451 B CN111825451 B CN 111825451B
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毛朝梁
马江雷
王根水
闫世光
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a rare earth element Tm doped silver niobate antiferroelectric ceramic material and a preparation method thereof1‑3xTmxNbO3Wherein x is more than or equal to 0.01 and less than or equal to 0.08.

Description

Rare earth element Tm doped silver niobate antiferroelectric ceramic material and preparation method thereof
Technical Field
The invention relates to a silver niobate-based antiferroelectric ceramic material and a preparation method thereof, in particular to a rare earth element Tm doped silver niobate antiferroelectric ceramic material and a preparation method thereof and application of the silver niobate antiferroelectric ceramic material in an energy storage dielectric capacitor, belonging to the technical field of functional ceramic materials.
Background
Due to the increasing attention on energy, economy and social sustainable development, energy storage materials have received great attention and research interest, which are also the core of efficient energy storage devices. In the currently used electric energy storage devices, the pulse power capacitor has the advantages of fast charge and discharge capacity and high power density, and is increasingly widely applied in the pulse power technology. Such as electromagnetic pulse guns, particle accelerators, geological exploration, medical instruments, electrostatic precipitation, and the like. But the energy density is lower, typically an order of magnitude lower than electrochemical capacitors, batteries. In addition, capacitors are large in pulsed power devices. Pulsed power capacitors are reported to account for more than 25% of the volume and weight of the power electronics. Therefore, development of a pulse power device having high energy storage performance and high power density with miniaturization, weight reduction, and integration is moving forward in the future.
The dielectric materials used as capacitors are generally classified into organic and inorganic materials. The inorganic ceramic capacitor has the advantages of wide use temperature range, low loss, high discharge speed and the like, and is widely applied to pulse capacitors. It is mainly classified into linear dielectric ceramics, ferroelectric dielectric ceramics and antiferroelectric dielectric ceramics. The antiferroelectric ceramic material has higher energy storage density and faster discharge speed compared with linear ceramics and ferroelectric ceramics because of having electric field induced antiferroelectric-ferroelectric phase transition and being capable of returning to antiferroelectric phase in a very short time after the electric field is removed, thereby releasing a large amount of energy.
The most studied antiferroelectric ceramics are currently lead-containing material systems. Mainly comprises the following steps: pb (La, Zr, Ti) O3Base ceramic and Pb (La, Zr, Sn, Ti) O3A base ceramic. However, because of the environmental pollution and the harm to the health of human life caused by lead, researchers are looking for an alternative lead-free antiferroelectric material, in which silver niobate (AgNbO) having a perovskite structure is used3) Ceramics, which is one of the antiferroelectric energy storage materials having high saturation polarization and high energy storage density, is regarded as one of the very promising antiferroelectric energy storage materials. In fact, AgNbO3Materials have been widely studied as microwave ceramics and photocatalytic materials. Until recently, silver niobate (AgNbO)3) The material is focused as an energy storage material and becomes a research hotspot in the field of energy storage.
2016 Tian et al first treated AgNbO3Ceramic materials are used in the field of energy storage. Reports pure AgNbO under the electric field condition of 175kV/cm3Energy storage density W of ceramicrecUp to 2.1J/cm3. But pure AgNbO3The ceramic has a ferrielectric phase (M) at room temperature1) The improvement of the energy storage performance is influenced, and the bending electric field and the breakdown field strength are to be improved. In the prior art, AgNbO is generally realized by doping and modifying components3Energy storage characteristics of ceramicsThe method is greatly improved, and shows that AgNbO3The ceramic has wide application prospect in the field of energy storage.
Disclosure of Invention
Aiming at AgNbO in the prior art3The invention aims to provide a silver niobate antiferroelectric ceramic material doped with a rare earth element Tm and a preparation method thereof, which are designed from the multi-angle consideration of tolerance factors, high polarizability and grain size influencing antiferroelectric performance and solve the problems of low energy storage density, improved energy storage efficiency, ferroelectricity at room temperature and the like in antiferroelectric energy storage ceramic materials.
On one hand, the invention provides a rare earth element Tm doped silver niobate antiferroelectric ceramic material which is of a single perovskite structure and has a general formula of Ag1-3xTmxNbO3Wherein x is more than or equal to 0.01 and less than or equal to 0.08.
In the invention, AgNbO is realized by doping rare earth elements Tm (introducing A-site small ions and vacancies) with smaller ionic radius3Suppression of the ferroelectrics phase (FIE) at room temperature in ceramic materials, in particular M1-M2The phase transition temperature of the phase, namely the ferrielectric phase-the antiferroelectric phase, is reduced to be below room temperature, so that the room temperature presents the antiferroelectric phase, namely the antiferroelectric is enhanced. Moreover, the introduction of the rare earth element Tm is also beneficial to refining grains (the granularity of the solid solution can be reduced by doping refractory metal oxide into a matrix with a low melting point), the compactness of the ceramic is improved, the forward turning electric field is improved, and the AgNbO is further enhanced3The energy storage performance of the antiferroelectric energy storage ceramic.
Preferably, x is more than or equal to 0.02 and less than or equal to 0.04. For example, when x is 0.03, the energy density of the rare earth element Tm doped silver niobate antiferroelectric ceramic is 4.3J/cm3The energy storage efficiency is 64%.
Preferably, at room temperature (20-25 ℃), the positive bending electric field of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 14-28 kV/mm, and the reverse bending electric field is 5-14 kV/mm.
Preferably, at room temperature (20-25 deg.C)) The energy storage density of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 2.6-4.3J/cm3And the energy storage efficiency is 38-77%.
In another aspect, the present invention provides a method for preparing a rare earth element Tm doped silver niobate antiferroelectric ceramic material, comprising:
(1) selecting Ag2O powder and Nb2O5Powder and Tm2O3The powder is used as raw material powder and has the composition formula of Ag1-3xTmxNbO3Preparing materials and mixing to obtain mixed powder;
(2 calcining the obtained mixed powder in an oxygen-containing atmosphere at 850-900 ℃ to obtain Ag1-3xTmxNbO3Powder;
(3) mixing the obtained Ag1-3xTmxNbO3Mixing the powder and the binder, granulating, and performing compression molding to obtain a ceramic biscuit;
(4) and (3) after the obtained ceramic biscuit is subjected to plastic removal, sintering the ceramic biscuit in an oxygen-containing atmosphere at 1000-1250 ℃ to obtain the rare earth element Tm doped silver niobate antiferroelectric ceramic material.
In the present invention, Ag is selected2O powder and Nb2O5Powder and Tm2O3The powder is used as raw material powder, and Tm is added3+Doping modification, and then preserving heat for 2-3 hours at 850-900 ℃ in an oxygen-containing atmosphere, wherein Tm is in the process3+Regulate and control M thereof1，M2Phase, which is made to present an antiferroelectric phase at room temperature, namely inhibiting the ferroelectricicity, enhancing the antiferroelectricity and reducing the residual polarization strength, and then grinding and drying are carried out to obtain the Ag with the perovskite structure1-3xTmxNbO3And (3) powder. Mixing the obtained Ag1-3xTmxNbO3Adding binder into the powder, granulating, molding, removing plastic and sintering. Due to addition of Tm3+And crystal grains can be refined in the process of re-sintering, and the density of the ceramic is improved.
Preferably, the binder is at least one of polyvinyl alcohol and polyvinyl butyral; the above-mentionedThe addition amount of the binder is Ag1-3xTmxNbO33-8 wt% of the powder.
Preferably, the oxygen-containing atmosphere is an air atmosphere or an oxygen atmosphere.
Preferably, the temperature of the plastic discharge is 700-900 ℃, and the time is 2-3 hours; preferably, the temperature rise rate of the plastic discharge is 1-3 ℃/min.
Preferably, the calcining time is 2-3 hours; the sintering time is 2-3 hours; the temperature rise rate of the sintering is 1-3 ℃/min.
Preferably, after the obtained rare earth element Tm doped silver niobate antiferroelectric ceramic material is polished to a specified thickness, a silver electrode is coated on the surface of the rare earth element Tm doped silver niobate antiferroelectric ceramic material; preferably, the predetermined thickness is 0.15 to 0.20 mm.
Preferably, the pressing and forming mode is dry pressing and forming, and the pressure of the dry pressing and forming is 150-200 MPa.
The invention has the beneficial effects that:
in the invention, a novel AgNbO is developed through component design by considering from multiple angles of tolerance factors, high polarizability and grain size which influence the antiferroelectric performance3A base antiferroelectric ceramic. Rare earth elements Tm (A site small ions and vacancies are introduced) with smaller ionic radius are adopted to ensure that the tolerance factor is as small as possible (the reduction of the tolerance factor is beneficial to the stability of an antiferroelectric phase), and AgNbO is used3The ferroelectrics phase (FIE) of the ceramic is reduced to below room temperature, so that the ferroelectrics phase is presented at room temperature, and the antiferroelectricity phase area is enlarged. Moreover, the introduction of the rare earth element Tm can also refine grains (the granularity of the solid solution can be reduced by doping refractory metal oxide into a matrix with a low melting point), so that the compactness is improved, the forward turning electric field is improved, and the AgNbO of the composite material is enhanced3Energy storage density and energy storage efficiency of the ceramic. Thus, Ag of the present invention1-3xTmxNbO3The ceramic has high energy storage performance. The energy storage ceramic of the invention has energy storage density WrecUp to 4.3J/cm3The energy storage efficiency can reach 64 percent. The energy storage ceramics of the invention also disclose Tm doping of rare earth elements with smaller ionic radiusAgNbO3Ceramics hold great promise in applications of dielectric energy storage capacitors.
Drawings
FIG. 1 is an XRD diffractogram of ceramic samples prepared according to comparative example 1 and examples 1-3 of the present invention;
FIG. 2 is a surface SEM image of a ceramic sample prepared according to comparative example 1 of the present invention;
FIG. 3 is a surface SEM image of a ceramic sample prepared according to example 1 of the present invention;
FIG. 4 is a surface SEM image of a ceramic sample prepared according to example 2 of the present invention;
FIG. 5 is a surface SEM image of a ceramic sample prepared according to example 3 of the present invention;
FIG. 6 is a graph showing a dielectric thermogram and a dielectric spectrogram of ceramic samples prepared in comparative example 1 and examples 1 to 3 according to the present invention;
FIG. 7 is a hysteresis loop of ceramic samples prepared in comparative example and examples 1-3 of the present invention;
FIG. 8 is a graph of turning electric fields of ceramic samples prepared in comparative example and examples 1-3 according to the present invention;
FIG. 9 is a graph of the energy storage density and efficiency of ceramic samples prepared according to comparative examples and examples 1-3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the chemical formula of the rare earth element Tm doped silver niobate antiferroelectric ceramic material with high energy storage density can be represented as: ag1-3xTmxNbO3Wherein x is more than or equal to 0.01 and less than or equal to 0.08. The x is the molar weight, so that the energy storage performance of the catalyst is further improved. Wherein, the doping of the rare earth element Tm can inhibit AgNbO3The ferroelectricity in the ceramic material is enhanced, the antiferroelectricity is enhanced, and the AgNbO is improved3The electric field is positively turned in the ceramic material, so that the silver niobate-based antiferroelectric energy storage ceramic material with high energy storage density and energy storage efficiency is obtained. The invention can also adjust the Tm doping content to be more than or equal to 0.01 and less than or equal to 0.08, so that the rare earth element Tm doped silver niobate antiferroelectric ceramicThe porcelain material is in an antiferroelectric phase at room temperature. Meanwhile, the remanent polarization is reduced, the forward turning electric field is improved, and the energy storage ceramic material with high energy storage density and energy storage efficiency is obtained, so that the energy storage ceramic material has a good application prospect.
In an alternative embodiment, at room temperature, the positive bending electric field of the rare earth element Tm doped silver niobate antiferroelectric ceramic material can be 14-28 kV/mm, and the reverse bending electric field can be 5-14 kV/mm.
In an optional embodiment, at room temperature, the energy storage density of the rare earth element Tm doped silver niobate antiferroelectric ceramic material can be 2.6-4.3J/cm3And the energy storage efficiency is 38-77%. For example, the rare earth element Tm doped silver niobate antiferroelectric energy storage ceramic material has the energy storage density W under the condition that x is 0.03molrecHeight of 4.6J/cm3The energy storage efficiency is as high as 69%.
In the disclosure, the rare earth element Tm doped silver niobate antiferroelectric ceramic material is prepared by a solid phase reaction method. Specifically, the synthesis of Ag by passing oxygen1-3xTmxNbO3Powder (x is more than or equal to 0.01 and less than or equal to 0.08). Mixing Ag with water1-3xTmxNbO3The powder is then granulated, pressed, molded and discharged, and sintered and compacted at a certain temperature to obtain Ag1-3xTmxNbO3Ceramic material (silver niobate antiferroelectric ceramic doped with rare earth element Tm).
Hereinafter, the method of preparing the rare earth element Tm doped silver niobate antiferroelectric ceramic of the present invention is exemplarily described.
Synthesis of Ag by oxygen introduction1-3xTmxNbO3Powder, wherein x is more than or equal to 0.01 and less than or equal to 0.08; x is mole percent. The rare earth element Tm doped silver niobate antiferroelectric ceramic material can adopt Ag2O powder and Nb2O5Powder and Tm2O3The powder is used as a starting material, and the starting materials are proportioned and mixed according to a stoichiometric ratio to obtain mixed powder. Keeping the mixed powder in an oxygen-containing atmosphere at 850-900 ℃ for 2-3 hours to obtain Ag1-3xTmxNbO3And (3) powder. As an example, a purity of 99.0% may be employed, for exampleAg on2O powder and Nb2O5Powder and Tm2O3The powder is used as raw material powder, then the materials are mixed according to the stoichiometric ratio, and the mixture is subjected to ball milling, drying and grinding, and then is subjected to heat preservation for 2-3 hours at 850-900 ℃ under the oxygen condition to synthesize the Ag with the perovskite structure1- 3xTmxNbO3And (3) powder. The polishing method of the present invention is not particularly limited, and known polishing methods such as wet ball milling and the like can be used. In the case of wet ball milling, the feed: ball: the mass ratio of the ethanol is (0.8-1.0): (4.0-4.5): 1.5-1.7), and the mixing time is 12 hours.
In Ag1-3xTmxNbO3And adding a binder into the powder, granulating, and performing compression molding to obtain a biscuit. Specifically, the synthesized Ag1-3xTmxNbO3And (3) grinding the powder, adding a binder for granulation, and performing compression molding to obtain a biscuit. The sanding may be performed by a sand mill. In this case, Ag may be used1-3xTmxNbO3Powder: ball: the sanding time may be 3 hours for absolute ethyl alcohol (0.8-1.0): (4.0-4.5): 1.0-1.2). For example, iron balls, agate balls, zirconia balls, or the like can be used as the grinding balls. The binder to be added may be polyvinyl alcohol (PVA), polyvinyl butyral (PVB), or the like. The addition amount of the binder is 3-8% of the mass of the ceramic powder. The pressure for the press molding may be 150 to 200 MPa. In the invention, the ball milling is carried out in a ball milling tank, the sand milling is carried out in a sand mill, and the ball milling is respectively carried out for 12 hours and 3 hours by adopting absolute ethyl alcohol as a medium. Is beneficial to the uniform dispersion of the raw materials so as to obtain the powder with uniform and refined components. Therefore, the energy storage performance of the rare earth element Tm doped silver niobate antiferroelectric ceramic material can be further improved.
And (3) performing plastic removal on the biscuit, namely removing the organic matter binder (such as PVA) at a certain temperature to obtain a green body of the raw material. Specifically, the temperature for plastic removal can be 700 ℃ -900 ℃ (preferably 850 ℃ -900 ℃), and the heat preservation time can be 2-3 hours. The temperature rise rate of the plastic discharge can be 1-3 ℃/min.
Removing plasticSintering the blank at a certain temperature. Specifically, the sintering process can be carried out in oxygen, the sintering temperature can be 1000-1250 ℃, and the heat preservation time can be 2-3 hours. In the invention, the temperature rise rate of sintering can be 1-3 ℃/min. Wherein, oxygen-filling sintering is favorable for improving the density and inhibiting Ag2The decomposition of O ensures that the exact stoichiometric ratio of the components is obtained.
In the invention, the obtained crude product of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is ground to be thin to be 0.15-0.20 mm thick (grinding and polishing treatment) on the upper surface and the lower surface, so that the energy storage density of the rare earth element Tm doped silver niobate antiferroelectric ceramic material can be further improved.
In the invention, an electrode (for example, a silver electrode) is coated on the surface of the rare earth element Tm doped silver niobate antiferroelectric ceramic material, and then the energy storage ceramic element is obtained. Specifically, the surface-coated electrode includes, for example, screen-printing silver, baking, firing silver (for example, sintering at 600 ℃ for 30 minutes in air), and the like.
In the invention, a TF Analyzer 2000 ferroelectric Analyzer is adopted to measure that the forward bending electric field of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 14-28 kV/mm, and the reverse bending electric field is 5-14 kV/mm.
In the invention, the energy storage density of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 2.6-4.3J/cm3And the energy storage efficiency is 38-77%.
In the invention, the rare earth element Tm doped silver niobate antiferroelectric ceramic material can be used for an energy storage capacitor, such as the manufacture of an energy storage ceramic capacitor, is beneficial to promoting the application and development of a high energy storage density ceramic technology, and has good application prospect.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
the energy storage ceramic material comprises the following components: ag0.94Tm0.02NbO3(Ag1-3xTmxNbO3；x＝0.02)
(1) The preparation method of the comparative example 1 is repeated according to the formula to obtain AgNbO3A base antiferroelectric ceramic;
(2) AgNbO obtained in example 13XRD test is carried out on the antiferroelectric ceramic, and the test result is shown in figure 1;
(3) AgNbO obtained in example 13The surface SEM test of the antiferroelectric ceramic is carried out, and a surface topography of a ceramic sample of the embodiment is shown in FIG. 3;
(4) the ceramic sample is subjected to the tests of a dielectric temperature spectrum and a dielectric frequency spectrum, and the test results are shown in figure 6;
(5) the ceramic samples of this example were subjected to hysteresis loop measurement at room temperature (20-25 deg.C), and the results of the measurements and the calculation of the breakover electric field and energy storage performance are shown in FIGS. 7-9. The forward bending electric field of the obtained ceramic sample is 18kV/mm, and the reverse bending electric field is 12 kV/mm. The energy storage density of the obtained ceramic sample is 4.0J/cm3The energy storage efficiency is 58%.
Example 2:
the energy storage ceramic material comprises the following components: ag0.91Tm0.03NbO3(Ag1-3xTmxNbO3；x＝0.03)
(1) The preparation method of the comparative example 1 is repeated according to the formula to obtain AgNbO3A base antiferroelectric ceramic;
(2) AgNbO obtained in example 23XRD test is carried out on the antiferroelectric ceramic, and the test result is shown in figure 1;
(3) AgNbO obtained in example 23The surface SEM test of the antiferroelectric ceramic is carried out, and FIG. 4 shows the surface topography of the ceramic sample of the embodiment;
(4) the ceramic sample is subjected to the tests of a dielectric temperature spectrum and a dielectric frequency spectrum, and the test results are shown in figure 6;
(5) the ceramic samples of this example were subjected to hysteresis loop measurement at room temperature (20-25 deg.C), and the results of the measurements and the calculation of the breakover electric field and energy storage performance are shown in FIGS. 7-9. The forward bending electric field of the obtained ceramic sample is 28kV/mm, and the reverse bending electric field is 14 kV/mm. The energy storage density of the obtained ceramic sample is 4.3J/cm3The energy storage efficiency is 64%.
Example 3:
the energy storage ceramic material comprises the following components: ag0.88Tm0.04NbO3(Ag1-3xTmxNbO3；x＝0.04)
(1) The preparation method of the comparative example 1 is repeated according to the formula to obtain AgNbO3A base antiferroelectric ceramic;
(2) AgNbO obtained in example 33XRD test is carried out on the antiferroelectric ceramic, and the test result is shown in figure 1;
(3) AgNbO obtained in example 33The surface SEM test of the antiferroelectric ceramic is carried out, and FIG. 5 shows a surface topography of the ceramic sample of the embodiment;
(4) the ceramic sample is subjected to the tests of a dielectric temperature spectrum and a dielectric frequency spectrum, and the test results are shown in figure 6;
(5) the ceramic samples of this example were subjected to hysteresis loop measurement at room temperature (20-25 deg.C), and the results of the measurements and the calculation of the breakover electric field and energy storage performance are shown in FIGS. 7-9. The energy storage density of the obtained ceramic sample is 4.1J/cm3The energy storage efficiency was 77%.
Comparative example 1:
the energy storage ceramic material comprises the following components: AgNbO3(Ag1-3xTmxNbO3；x＝0)
(1) Calculating the required Ag according to the chemical formula2O、Nb2O5，(Tm2O3) Mixing materials by adopting a wet ball milling method according to the following raw materials: ball: the anhydrous ethanol was mixed at a mass ratio of 1:4.5:1.7 for 12 hours to uniformly mix the components. Drying, sieving with 40 mesh sieve, briquetting under oxygen atmosphere, heating to 850 deg.C for 8 hr, maintaining for 2 hr, and synthesizing AgNbO3The powder of (4);
(2) and (2) adding the powder synthesized in the step (1). According to the raw materials: ball: the absolute ethyl alcohol is ground by a wet method (a sand mill) for 3 hours in a ratio of 1:4.5:1.2, then discharged and dried, and is sieved by a 40-mesh sieve, 3 wt% of PVA is added for granulation, and the mixture is formed into a green body with the diameter of 13mm and the thickness of about 2mm by dry pressing;
(3) keeping the temperature of the green body obtained in the step (2) at 800 ℃ for 2 hours, removing organic substances in the biscuit, discharging plastic, raising the temperature at the speed of 2 ℃/min, and discharging plastic to obtain a raw material green body;
(4) putting the raw material blank obtained in the step (3) into a muffle furnace, raising the temperature to 1000-1250 ℃ for 7 hours, and preserving the temperature for 2 hours to obtain the AgNbO3A base antiferroelectric ceramic;
(5) the AgNbO obtained in the step (4) is3XRD test is carried out on the antiferroelectric ceramic, and the test result is shown in figure 1;
(6) for the obtained AgNbO3The surface SEM observation of the antiferroelectric ceramic is carried out, and the AgNbO is shown in figure 23A surface topography of the energy storage ceramic material;
(7) the sintered AgNbO3Grinding the two sides of the energy storage ceramic material to be 0.15mm in thickness, cleaning, drying, performing screen printing of silver paste, drying again, and putting into a box type electric furnace for silver firing under the silver firing condition of 600 ℃ for 30 min. The heating rate is 2 ℃/min, and a ceramic sample covered with the electrode is obtained;
(8) the ceramic sample coated with the electrode is subjected to dielectric temperature spectrum and dielectric frequency spectrum tests, and the test results are shown in figure 6;
(9) the measurement of the hysteresis loop, the calculation of the breakover electric field and the energy storage performance were performed at room temperature (20 to 25 ℃) on the ceramic sample coated with the electrode of this comparative example, and the results are shown in FIGS. 7 to 9. The forward turning electric field of the obtained ceramic sample is 14kV/mm, and the reverse turning electric field is 5 kV/mm. The energy storage density of the obtained ceramic sample is 2.6J/cm3The energy storage efficiency is 38%.
As can be seen from fig. 1, the energy storage ceramic materials prepared in examples 1 to 3 do not have a second phase generated therein and have a single perovskite structure.
As can be seen from fig. 2 to 5, the ceramic materials of comparative example 1 and examples 1 to 3 have a relatively dense surface morphology, and the grain size gradually decreases as the Tm content increases. This is beneficial to the improvement of the breakdown field strength of the ceramic, thereby further improving the energy storage density;
FIG. 6 shows the temperature and frequency spectra of the energy-storing ceramic materials of comparative example 1 and examples 1 to 3, in which the ferrous electric phase (M) can be seen1) Is inhibited so that M1-M2Phase transition, namely phase transition from a ferrielectric phase to an antiferroelectric phase, namely 20-temperature point is reduced to be lower than room temperature, an antiferroelectric phase area is increased, and the antiferroelectric property is enhanced along with the increase of Tm content;
as shown in the hysteresis loop diagram (FIG. 7), the breakover electric field diagram (FIG. 8) and the results of the test and calculation of the energy storage performance (FIG. 9) of comparative example 1 and examples 1 to 3, it can be seen that the hysteresis loop becomes more narrow and the energy storage density W thereof becomes narrower as the Tm content increasesrecAnd the energy storage efficiency η are both gradually increased. When the Tm content reaches 0.03mol, the forward bending electric field and the reverse bending electric field are obviously improved, and the obtained energy storage density WrecReaching 4.3J/cm3The energy storage efficiency reaches 64 percent.

Claims (10)

1. The rare earth element Tm doped silver niobate antiferroelectric ceramic material is characterized by being of a single perovskite structure and having a general formula of Ag1-3xTmxNbO3Wherein x is more than or equal to 0.02 and less than or equal to 0.04; the energy storage density of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 4.0-4.3J/cm3And the energy storage efficiency is 58-77%.
2. The rare earth element Tm doped silver niobate antiferroelectric ceramic material according to claim 1, wherein the positive breakover electric field of the rare earth element Tm doped silver niobate antiferroelectric ceramic material is 18 to 28kV/mm and the negative breakover electric field is 12 to 14kV/mm at room temperature.
3. A method for preparing a rare earth element Tm doped silver niobate antiferroelectric ceramic material according to claim 1 or 2, comprising:
(1) selecting Ag2O powder and Nb2O5Powder and Tm2O3The powder is used as raw material powder and has the composition formula of Ag1-3xTmxNbO3Preparing materials and mixing to obtain mixed powder;
(2) calcining the obtained mixed powder in an oxygen-containing atmosphere at 850-900 ℃ to obtain Ag1-3xTmxNbO3Powder;
(3) mixing the obtained Ag1-3xTmxNbO3Mixing the powder and the binder, granulating, and performing compression molding to obtain a ceramic biscuit;
(4) and (3) after the obtained ceramic biscuit is subjected to plastic removal, sintering the ceramic biscuit in an oxygen-containing atmosphere at 1000-1250 ℃ to obtain the rare earth element Tm doped silver niobate antiferroelectric ceramic material.
4. The production method according to claim 3, wherein the binder is at least one of polyvinyl alcohol and polyvinyl butyral; the addition amount of the binder is Ag1-3xTmxNbO33-8 wt% of the powder.
5. The production method according to claim 3, wherein the oxygen-containing atmosphere is an air atmosphere or an oxygen atmosphere.
6. The preparation method according to claim 3, wherein the temperature of the plastic discharge is 700-900 ℃ and the time is 2-3 hours.
7. The preparation method according to claim 6, wherein the temperature rise rate of the plastic discharge is 1-3 ℃/min.
8. The method according to claim 3, wherein the calcination is carried out for 2 to 3 hours; the sintering time is 2-3 hours; the temperature rise rate of the sintering is 1-3 ℃/min.
9. The production method according to any one of claims 3 to 8, characterized in that the obtained rare earth element Tm doped silver niobate antiferroelectric ceramic material is polished to a prescribed thickness and then coated with a silver electrode on the surface thereof.
10. The method according to claim 9, wherein the predetermined thickness is 0.15 to 0.20 mm.
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