CN109704762B - Strontium niobate-based antiferroelectric ceramic and preparation method and application thereof - Google Patents
Strontium niobate-based antiferroelectric ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides strontium niobate antiferroelectric ceramic and a preparation method and application thereof, and relates to strontium niobate antiferroelectric ceramic material, wherein the chemical components of the ceramic material conform to the chemical general formula: (Sr)1‑xPbx)2Nb2O7Wherein x is more than or equal to 0.01 and less than or equal to 0.05, and x is mole percent.
Description
Technical Field
The invention belongs to the field of energy storage ceramics, and relates to an antiferroelectric ceramic material with a strontium niobate-based perovskite layered structure and a preparation method thereof.
Background
With the development of pulse technology, three energy storage modes, namely mechanical energy storage, electrochemical energy storage and capacitor energy storage, become core technologies of an energy storage system of a pulse power device. Among them, the dielectric energy storage capacitor plays a crucial role in pulse power application because of its advantages of high energy storage density, rapid energy release, high stability and miniaturization. Dielectric storage capacitors are divided into linear dielectrics, ferroelectric dielectrics, relaxor dielectrics and antiferroelectric dielectrics. Because the antiferroelectric material has double ferroelectric hysteresis loops, the energy storage density obtained by integral calculation is the highest among the four dielectric materials, and in recent years, antiferroelectric ceramic materials are rapidly developed in the field of dielectric energy storage.
At present, antiferroelectric energy storage materials are concentrated at home and abroad on lead zirconate titanate lanthanum stannate (PLZST) ceramics, sodium bismuth titanate (BNT) ceramics and silver niobate ceramics with high energy storage density. However, the antiferroelectric ceramic materials currently available have poor temperature stability, and the materials cannot be used at high temperatures. Xu et al found a sharp drop in the storage density as the temperature increased from room temperature to 140 ℃ by the investigated PLZST antiferroelectric ceramic material (j.am.center.soc., 99,2016: 2984-.Zhao et al in AgNbO3The energy density is improved by doping Ta in the ceramic, but the temperature stability range is only 20-120 ℃ (adv.Mater.,29,2017: 1701824). The perovskite structure has a rich phase structure, and structural phase change easily occurs when the temperature is raised, so that an antiferroelectric phase is converted into a ferroelectric phase or a paraelectric phase. Therefore, it is necessary to develop some antiferroelectric materials having a non-perovskite structure with a high curie temperature and a single phase structure.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a strontium niobate-based ceramic material having an antiferroelectric-like effect and excellent temperature stability, and a method for preparing the same and an application thereof.
On one hand, the invention provides a strontium niobate-based antiferroelectric ceramic material, which has chemical components according to the chemical general formula: (Sr)1-xPbx)2Nb2O7Wherein x is more than or equal to 0.01 and less than or equal to 0.05, and x is mole percent.
According to the invention, divalent lead ions are used to replace strontium niobate (Sr)2Nb2O7) The A site strontium ions in the perovskite layered structure adjust the displacement of metal atoms in the perovskite layered structure to form local antiparallel spontaneous polarization, so as to obtain the antiferroelectric effect. Measuring the double hysteresis loop, the four current peaks and the residual polarization value PrAnd the highest polarization value PmRespectively can be 0.2 mu C/cm2(0.1～0.3μC/cm2) And 2.6. mu.C/cm2(2.4～2.8μC/cm2) The highest applied electric field can reach 28 kV/mm. Meanwhile, the phenomena of double electric hysteresis loops and four current peaks can be stabilized from room temperature to 200 ℃, and the antiferroelectric-like behavior at wide temperature is beneficial to the development and application in dielectric energy storage capacitors.
In a second aspect, the present invention provides a method for preparing the strontium niobate-based antiferroelectric ceramic material, comprising the following steps: uniformly mixing a strontium source, a niobium source and a lead source according to a stoichiometric ratio, and calcining to synthesize ceramic powder;
and forming and sintering the ceramic powder to obtain the ceramic material.
The antiferroelectric ceramic with the divalent lead ion modified strontium-calcium-titanium niobate laminar structure is prepared by a solid-phase reaction process, and has the advantages of simple process, easily controlled parameters, low cost and easy industrial production.
Preferably, the strontium source is SrCO3The niobium source is Nb2O5The lead source is PbO and/or Pb3O4。
Preferably, the calcining temperature is 1000-1300 ℃, and the heat preservation time is 0-24 hours.
Preferably, the sintering temperature is 1300-1450 ℃, and the heat preservation time is 0-24 hours.
In a third aspect, the present invention provides a strontium niobate-based antiferroelectric ceramic element produced using any of the above strontium niobate-based antiferroelectric ceramic materials.
Preferably, the ceramic element is made by processing the ceramic material to a desired size and then silver firing.
In a fourth aspect, the present invention provides a dielectric energy storage capacitor comprising any one of the above strontium niobate-based antiferroelectric ceramic materials.
According to the present invention, a strontium niobate-based ceramic material having an antiferroelectric-like effect and excellent temperature stability can be provided.
Drawings
FIG. 1 shows the temperature at 10Hz (Sr) at room temperature1-xPbx)2Nb2O7(x ═ 0.01,0.05) hysteresis loop (P-E) and current loop (I-E), where x is 0.01 on the left and 0.05 on the right.
FIG. 2 shows the temperature at 200 ℃ and 10Hz (Sr)1-xPbx)2Nb2O7(x ═ 0.01,0.05) hysteresis loop (P-E) and current loop (I-E), where x is 0.01 on the left and 0.05 on the right.
Fig. 3 is an XRD pattern of the ceramic material obtained in example 1 and example 2.
FIG. 4 shows the hysteresis loop (P-E) and the current loop (I-E) of the ceramic material obtained in comparative example 1 at room temperature and 200 ℃ respectively, wherein the left graph is room temperature and the right graph is 200 ℃.
FIG. 5 shows the hysteresis loop (P-E) and the current loop (I-E) at room temperature and 200 ℃ respectively for the ceramic material obtained in comparative example 2, wherein the left graph is room temperature and the right graph is 200 ℃.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Disclosed herein is a strontium niobate-based ceramic material having a chemical formula of (Sr)1-xPbx)2Nb2O7Wherein x is more than or equal to 0.01 and less than or equal to 0.05, and x is mole percent.
The strontium niobate-based ceramic material can be in a perovskite layered structure, and is structurally characterized by a structural unit consisting of discontinuous perovskite layers. By doping divalent lead ions to regulate the microstructure, the antiferroelectric effect can be obtained in the strontium niobate ferroelectric body with the perovskite layered structure. The term "antiferroelectric-like effect" refers to an effect having an intermediate state between antiferroelectric and ferroelectric properties, with an antiferroelectric-ferroelectric phase transition in the field, but with a non-zero remanent polarization (Acta mater, 154,2018: 190-198).
Under the test conditions of room temperature of 25 ℃ and 10Hz, the P-E curve (polarization intensity-electric field curve) shows an obvious double-hysteresis-line phenomenon along with the improvement of an applied electric field, and the I-E curve (current-electric field curve) shows an obvious four-current peak. The residual polarization value P of the strontium niobate-based ceramic materialrAnd the highest polarization value PmRespectively is-0.2 mu C/cm2And 2.6. mu.C/cm2The highest applied electric field reaches 28 kV/mm. Meanwhile, the phenomena of double hysteresis loop and four current peaks can be stabilized from room temperature to 200 ℃. Compared with the existing antiferroelectric ceramic material, the strontium niobate-based ceramic material remarkably improves the temperature stability, and the temperature stability range is 20-200 ℃. The antiferroelectric-like behavior at wide temperature is beneficial to the development and application in dielectric energy storage capacitors.
Regarding the doping amount of the divalent lead ions, if x is less than 0.01, the antiferroelectric-like phenomenon having a double hysteresis loop and four current peaks cannot be measured; if x is greater than 0.05, the antiferroelectric-like phenomenon with a double hysteresis loop and a four-current peak becomes less pronounced.
The preparation method of the strontium niobate-based ceramic material disclosed by the present disclosure is not limited, and the strontium niobate-based ceramic material can be prepared by a conventional solid phase reaction process, and for example, the preparation method can comprise the steps of batching, mixing, synthesizing, finely grinding, forming, plastic discharging, sintering and the like. Hereinafter, a method for producing the strontium niobate-based ceramic material will be exemplified.
First, a ceramic powder is prepared by a solid phase method. Specifically, a strontium source, a niobium source and a lead source are mixed as a mixed solution (Sr)1-xPbx)2Nb2O7The stoichiometric ratio is mixed evenly, and the ceramic powder is synthesized by calcination.
The strontium source may be selected from SrCO3. The niobium source may be selected from Nb2O5. The lead source is selected from PbO and Pb3O4And the like.
The raw materials can be uniformly mixed by adopting a wet ball milling method. The mass ratio of the raw materials, namely the ball to the alcohol can be 1:2 (1.8-2.0). The ball milling medium can be agate balls and the like. The ball milling time may be 2 to 8 hours (e.g., 4 hours), and the rotation speed may be 240 to 480 revolutions per minute (e.g., 360 revolutions per minute).
The synthesis temperature can be 1000-1300 ℃. Preferably, the temperature is raised to the synthesis temperature at a temperature rise rate of not more than 2 ℃/min, so that the reaction can be fully carried out, Pb2+The a bit is easily entered. The incubation time at the synthesis temperature may be less than 24 hours, for example 1 to 3 hours. After calcination, the mixture can be cooled to room temperature along with the furnace.
The ceramic powder may then be finely ground. The fine milling method may be a wet ball milling method. The mass ratio of the raw materials, namely the ball to the alcohol can be 1:2 (1.6-1.8). The ball milling medium can be agate balls and the like. The ball milling time may be 2 to 8 hours (e.g., 4 hours), and the rotation speed may be 240 to 480 revolutions per minute (e.g., 360 revolutions per minute). After fine grinding, drying and granulating. The binder used for granulation may be, for example, polyvinyl alcohol (PVA). The addition amount of the binder can be 5-7 wt% of the weight of the ceramic powder. The pellets may be aged for a period of time.
Then, the ceramic particles can be pressed and molded, and then the temperature is raised for plastic removal, so that a ceramic blank is obtained. The pressing pressure can be 1-3 MPa. The plastic removal conditions can be as follows: heating to 700-800 ℃ at a heating rate of not higher than 2 ℃/min, and preserving heat for 1-3 hours.
And sintering the ceramic blank to obtain the ceramic material. The ceramic green body may be coated with a ceramic powder having the same composition as the above ceramic powder at the time of sintering. The sintering temperature may be 1300-1450 deg.C, such as 1350-1400 deg.C. Preferably, the temperature is raised to the sintering temperature at a temperature raising rate of not more than 2 ℃/min, so that the ceramics can be easily made to be porcelain without the occurrence of composition segregation. The holding time at the sintering temperature may be 24 hours or less, for example, 1 to 3 hours. After sintering, the mixture can be cooled to room temperature along with the furnace.
Also disclosed herein is a strontium niobate-based antiferroelectric ceramic element produced using the above strontium niobate-based antiferroelectric ceramic material. In one example, the strontium niobate-based antiferroelectric ceramic element is obtained by processing a ceramic material into a desired size, ultrasonically cleaning, screen-printing silver, drying, and firing the silver. The silver firing condition can be heat preservation for 5-40 minutes at 700-800 ℃.
Also disclosed herein is a dielectric energy storage capacitor comprising the above strontium niobate-based antiferroelectric ceramic material. Other portions of the dielectric storage capacitor may take on structures commonly used in the art.
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
(1) The lead oxide-doped A-site perovskite layered structure (Sr) is prepared by adopting a solid-phase reaction method1-xPbx)2Nb2O7A ceramic. Wherein the molar ratio of Pb is 0.01, and SrCO3、Nb2O5And PbO powder as raw material, prepared according to stoichiometric ratio by wet planetary ballMixing by grinding, and mixing for 4 hours according to the mass ratio of the raw materials, namely ball and alcohol, of 1:2:1.8 to uniformly mix the components. After drying, sieving the mixture by a 40-mesh sieve, pressing the mixture into blocks under the pressure of 5MPa, raising the temperature to 1200 ℃ at the temperature rise rate of not higher than 2 ℃/min, and preserving the heat for 2 hours to synthesize the ceramic powder.
(2) Grinding the ceramic powder in the step (1), and sieving with a 40-mesh sieve. And mixing according to a wet planetary ball milling method, finely milling for 4 hours according to the mass ratio of the raw materials, namely ball and alcohol being 1:2:1.6, and drying the finely milled ceramic powder. And then adding 6 wt.% of PVA binder, granulating, briquetting and aging for 24 hours, sieving with a 30-mesh sieve, performing compression molding under the pressure of 1.4-1.6 MPa, and then heating to 800 ℃ for heat preservation for 2 hours to remove plastic, thereby obtaining the ceramic biscuit.
(3) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1350 ℃ at the heating rate of 2 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the ceramic wafer.
(4) Grinding the sintered ceramic wafer to 0.2mm, cleaning, drying, screen printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 30 minutes to burn silver to obtain the antiferroelectric ceramic material (Sr)0.99Pb0.01)2Nb2O7。
Example 2
The difference from example 1 is that the molar ratio of Pb is 0.05, and an antiferroelectric-like ceramic material (Sr)0.95Pb0.05)2Nb2O7。
The ceramics obtained in examples 1 and 2 were tested for ferroelectric properties by the following methods: a ferroelectric Analyzer TF Analyzer 2000 produced by German aixACCT company is adopted to measure the electric hysteresis loop and the current loop of the ceramic sample, and the test conditions are 25-200 ℃ and 10 Hz. The results are shown in FIGS. 1 and 2. As can be seen from FIGS. 1 and 2, under the test conditions of 25 ℃ and 10Hz, the P-E curve shows obvious double-hysteresis loop phenomenon, the I-E curve shows obvious four-current peak and the remanent polarization value PrAnd the highest polarization value PmRespectively is 0.2 mu C/cm2And 2.6. mu.C/cm2(examples 1 and 2 use at least 3 tests, respectively, and the obtained data are similar, and the remanent polarization value P isrAt 0.2 to 0.3 μ C/cm2Middle, highest polarization value PmAt 2.6 to 2.7 μ C/cm2In the middle), the highest applied electric field reaches 28kV/mm, and the antiferroelectric effect still has double hysteresis loops and four current peaks at 200 ℃, and shows excellent temperature stability.
The ceramics obtained in examples 1 and 2 were subjected to XRD testing, which was as follows: the phase structure analysis of the ceramic sample was performed by using an X-ray diffractometer model D/max-2550V of Rigaku, japan, which uses a K α line (λ: 0.15405nm) of a Cu target in a step scan with a step size of 0.02 °. The structure is shown in fig. 3, wherein (a) is embodiment 1, and (b) is embodiment 2. As can be seen from the fit of fig. 3, the ceramic exhibits a distinct single phase perovskite layered structure with no second phase generation.
Comparative example 1
The difference from example 1 is that x is 0, i.e., Sr2Nb2O7Is a ferroelectric ceramic material.
The ferroelectric property test result of the ceramic material obtained in comparative example 1 is shown in fig. 4, and it can be seen that the P-E curve is elliptical, no double hysteresis loop appears, and no current peak is detected in the I-E curve under the test conditions of 25 ℃ and 10 Hz. At 200 ℃ and 10Hz, the P-E curve shows a ferroelectric loop, and the I-E curve shows two current peaks, which are typical ferroelectric properties.
Comparative example 2
The difference from example 1 is that x is 0.15 and the molar ratio of Pb is 0.15, and an antiferroelectric-like ceramic material (Sr) is obtained0.85Pb0.15)2Nb2O7。
The results of the ferroelectric property test of the ceramic material obtained in comparative example 1 are shown in fig. 5, and it can be seen that under the test conditions of 25 ℃ and 10Hz, the electric field is increased to 16kV/mm at most, the double hysteresis loop phenomenon of the P-E curve becomes very weak, and the I-E loop also shows only two current peaks. The phenomenon of double hysteresis loop disappears at 200 ℃, which shows that the Pb-rich component no longer has the anti-ferroelectric effect at high temperature.
Claims (10)
1. The strontium niobate-based antiferroelectric ceramic material is characterized by being prepared from a strontium niobate-based antiferroelectric ceramic materialThe chemical components of (A) conform to the chemical general formula: (Sr)1-xPbx)2Nb2O7Wherein x is more than or equal to 0.01 and less than or equal to 0.05, and x is mole percent.
2. The strontium niobate-based antiferroelectric ceramic material of claim 1, wherein a P-E curve of the ceramic material shows a double hysteresis curve phenomenon, an I-E curve of the ceramic material shows four current peaks, and a remanent polarization value P is measured at 25 ℃ and 10Hzr0.1 to 0.3 μ C/cm2Maximum polarization value Pm2.4 to 2.8 mu C/cm2The maximum applied electric field was 28 kV/mm.
3. The strontium niobate-based antiferroelectric ceramic material of claim 1 or 2, wherein the ceramic material has an antiferroelectric-like effect with a double hysteresis loop and four current peaks at 200 ℃.
4. A method for preparing the strontium niobate-based antiferroelectric ceramic material of any one of claims 1 to 3, comprising the steps of:
uniformly mixing a strontium source, a niobium source and a lead source according to a stoichiometric ratio, and calcining to synthesize ceramic powder;
and forming and sintering the ceramic powder to obtain the ceramic material.
5. The method of claim 4, wherein the strontium source is SrCO3The niobium source is Nb2O5The lead source is PbO and/or Pb3O4。
6. The preparation method according to claim 4, wherein the calcination temperature is 1000 to 1300 ℃ and the holding time is 0 to 24 hours.
7. The preparation method according to any one of claims 4 to 6, wherein the sintering temperature is 1300-1450 ℃, and the holding time is 0-24 hours.
8. A strontium niobate-based antiferroelectric ceramic element produced using the strontium niobate-based antiferroelectric ceramic material according to any one of claims 1 to 3.
9. The strontium niobate-based antiferroelectric ceramic element according to claim 8, wherein the ceramic element is made by processing the ceramic material into a desired size and then silver firing.
10. A dielectric energy storage capacitor comprising the strontium niobate-based antiferroelectric ceramic material according to any one of claims 1 to 3.
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| CN111517787A (en) * | 2020-04-17 | 2020-08-11 | 上海工程技术大学 | Silver niobate-based antiferroelectric ceramic material and preparation method and application thereof |
| CN115959906A (en) * | 2021-10-13 | 2023-04-14 | 中国科学院上海硅酸盐研究所 | Strontium niobate-based perovskite layered structure lead-free piezoelectric ceramic and preparation method thereof |
| CN116514547A (en) * | 2023-04-27 | 2023-08-01 | 同济大学 | Lead ytterbium niobate-based antiferroelectric ceramic material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS545800B2 (en) * | 1974-04-19 | 1979-03-20 | ||
| JPS5453298A (en) * | 1978-06-26 | 1979-04-26 | Tdk Corp | Ferrodielectric piezo-electric porcelain material |
| CN1295047A (en) * | 2000-12-15 | 2001-05-16 | 上海联能科技有限公司 | Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure |
| CN106960726A (en) * | 2015-10-06 | 2017-07-18 | Tdk株式会社 | Dielectric composition and electronic component |
-
2019
- 2019-02-22 CN CN201910133466.1A patent/CN109704762B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS545800B2 (en) * | 1974-04-19 | 1979-03-20 | ||
| JPS5453298A (en) * | 1978-06-26 | 1979-04-26 | Tdk Corp | Ferrodielectric piezo-electric porcelain material |
| CN1295047A (en) * | 2000-12-15 | 2001-05-16 | 上海联能科技有限公司 | Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure |
| CN106960726A (en) * | 2015-10-06 | 2017-07-18 | Tdk株式会社 | Dielectric composition and electronic component |
Non-Patent Citations (2)
| Title |
|---|
| Crystallographic and Dielectric Properties of Ferroelectric A2B2O7 (A=Sr,B=Ta,Nb) crystals and their solid solutions;Satoshi Nanamatsu;《Journal of the physical society of Japan》;19750331;第38卷(第3期);第817-824页 * |
| INVESTIGATION OF s, p, d-ELEMENT NIOBATES AND;V. M. Zhukovsky等人;《Journal of Thermal Analysis and Calorimetry》;20000531;第60卷;第523-534页 * |
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