CN108358630B - High-energy-storage-density antiferroelectric ceramic material and preparation method thereof - Google Patents

High-energy-storage-density antiferroelectric ceramic material and preparation method thereof Download PDF

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CN108358630B
CN108358630B CN201810214293.1A CN201810214293A CN108358630B CN 108358630 B CN108358630 B CN 108358630B CN 201810214293 A CN201810214293 A CN 201810214293A CN 108358630 B CN108358630 B CN 108358630B
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王根水
边峰
闫世光
徐晨洪
毛朝梁
董显林
曹菲
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention provides an antiferroelectric ceramic material with high energy storage density and a preparation method thereof, wherein the antiferroelectric ceramic material has a chemical general formula of Pb0.97La0.02[(Zr0.375Sn0.625)1‑xTix]O3+a SiO2(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.15, a is SiO2With Pb0.97La0.02[(Zr0.375Sn0.625)1‑xTix]O3The a is more than or equal to 3 percent and less than or equal to 5 percent.

Description

High-energy-storage-density antiferroelectric ceramic material and preparation method thereof
Technical Field
The invention relates to an antiferroelectric ceramic material with high energy storage density and a preparation method thereof, belonging to the technical field of functional ceramic materials.
Background
The pulse power technology refers to an electro-physical technology (Science, 313: 334-. The basic system of pulsed power consists of two parts: an energy storage system, a portion of which is a low power level; another part is the generation and efficient delivery of high power pulses to the load. Energy storage systems are important components of pulse power devices, and currently provide primary energy sources mainly in the form of capacitance, inductance, mechanical energy, chemical energy, and the like. The capacitor has the advantages of high energy storage energy release speed, large output power, flexible combination, mature technology and low price, and becomes the most widely applied energy storage device at present.
As an important energy storage element of a pulse power device, a capacitor accounts for a great proportion in the pulse power device, and the development of a pulse capacitor (Journal of the American Ceramic Society 73, 323-595 (1990); Applied physics letters 72,593-595 (1998)) with high energy storage density, large discharge current, fast discharge speed and long charge-discharge life (103 times) has become a key and urgent task for the research in the field of pulse power technology at present.
The dielectric materials used as the pulse capacitor are mainly classified into linear ceramics, ferroelectric ceramics and antiferroelectric ceramics. The dielectric constant of the linear ceramic hardly changes with the electric field, and the linear ceramic has the advantages of low field linearity reversibility, repeated charge and discharge and the like, but the energy storage density is only 0.01J/cm in the safe electric field range3An order of magnitude. The ferroelectric ceramic has spontaneous polarization and a very high dielectric constant in the absence of an external electric field, and under the action of the electric field, the dielectric constant of the ferroelectric ceramic decreases with the increase of the electric field, and the breakdown field strength of the ferroelectric ceramic is usually not high, so that the energy storage density of the ferroelectric ceramic under the high field is not large and is not more than 0.2J/cm3. The antiferroelectric ceramic is characterized by having a double hysteresis loop, the antiferroelectric ceramic is the same as a linear ceramic when an external electric field is low, the polarization strength (P) and the electric field (E) are in a linear relation, when the electric field is increased to a certain value, partial dipoles in antiferroelectric unit cells, which are opposite to the direction of the electric field, begin to invert under the action of the electric field, antiferroelectric-ferroelectric phase transition (AFE-FE) occurs, the polarization strength of the material is suddenly increased, and the dielectric constant (epsilon-FE) is obtainedr) Reaches a peak value when the ceramic is in a charged state, the stored energy density (W)st) Is the integral of the forward hysteresis line with respect to the polarization. The theoretical energy storage density of the antiferroelectric ceramic is higher (W) because the dielectric constant is increased along with the increase of an electric field under a certain electric fieldre～J/cm3Order of magnitude) of the current, are important candidates for pulsed capacitor applications.
Among antiferroelectric ceramics, PLZST antiferroelectric ceramics have the advantages that the initial peak value of discharge exceeds 1kA, more than 80% of charges are released within one hundred nanoseconds, and the performance does not deteriorate obviously after the PLZST antiferroelectric ceramics are subjected to charge and discharge for more than 2000 times (Journal of Applied Physics 106,034105, (2009); Journal of the American Ceramic Society 93, 4015-. For the same anti-ferroelectric dielectric material, the energy storage density is greatly influenced by improving the electric strength to achieve higher polarization strength. Furthermore, the pulse capacitor itself operates at a relatively high voltage, which also puts certain demands on the electrical strength of the ceramic material. Therefore, the improvement of the breakdown strength has important significance for the application of the antiferroelectric ceramic material in the pulse capacitor technology. With respect to the mechanism of breakdown, the weak point breakdown theory, which is currently generally accepted, for polycrystalline ceramic materials, grains, grain boundaries, pores, cracks, and the second phase all may initiate breakdown. Through earlier researches on the breakdown performance of the PZT-based ceramic under a direct-current electric field, the method comprises the following steps: the electrical breakdown path of the ceramic develops along the grain boundaries and the breakdown strength is largely influenced by porosity and grain size. The porosity and grain size of the ceramic are mainly influenced by the particle size of the powder, the activity of the powder, the synthesis conditions and the like. The surface modification is adopted to increase the reactivity of the powder, so that the porosity of the ceramic is improved, and the effect of increasing the electric strength of the ceramic is achieved, which provides a certain theoretical basis for regulating and controlling the microstructure of the ceramic to enhance the breakdown strength of the PLZST antiferroelectric ceramic.
At present, the method for improving the electric strength of ceramics mainly adopts a method of adding a sintering aid. CdO-Bi doping by Chen, S, et al2O3–PbO–ZnO–Al2O3–B2O3–SiO2The glass powder is used as a sintering aid and sintered at 1130 ℃ to synthesize the PLZST ceramic, the grain size of the ceramic is obviously reduced, the electric strength is improved by 2kV, and the energy conversion efficiency is also improved. Hao, X, and the like utilize glass powder as a sintering aid, and the electric strength resistance of an antiferroelectric film prepared from another PLZST material with higher energy storage density is improved from 450kV/cm to 581 kV/cm. However, since the glass powder is segregated in the ceramic, the incorporation of the glass powder rather reduces the polarization strength of the antiferroelectric ceramic, thereby affecting the releasable energy storage density under a fixed working electric field.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a high energy storage density antiferroelectric ceramic material sintered by chemically modified powder for an energy storage capacitor and a preparation method thereof.
In one aspect, the invention provides an antiferroelectric ceramic material with high energy storage density, wherein the chemical general formula of the antiferroelectric ceramic material is Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3+a SiO2(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.15, a is SiO2With Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The a is more than or equal to 3 percent and less than or equal to 5 percent.
Preferably, the antiferroelectric ceramic material has a releasable energy storage density of 2.32-2.68J/cm under a working electric field of 21.6-23.6 kV/mm3And the energy storage efficiency is 73-81%. Preferably, the antiferroelectric ceramic material has the releasable energy storage density of 2.68J/cm under the working electric field of 23.5kV/mm3The energy storage efficiency was 78%.
Preferably, the antiferroelectric ceramic material has a relative dielectric constant of 754 to 803 at room temperature, a dielectric loss of 0.001 to 0.002, and an AFE-FE phase-change electric field of 3.97 to 4.88 kV/mm; preferably, the antiferroelectric ceramic material has a relative dielectric constant of 791 at room temperature, a dielectric loss of 0.002, and an AFE-FE phase-change electric field of 4.68 kV/mm.
Preferably, the antiferroelectric ceramic material can be sintered at 1150-1200 ℃.
In another aspect, the present invention provides a method for preparing the high energy storage density antiferroelectric ceramic material, comprising:
(1) preparation of Pb by solid-phase reaction method0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Powder;
(2) the obtained Pb is0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Mixing the powder, tetraethyl silicate, water and alcohol, adjusting the pH value to 7.5-8.0, then carrying out hydrolysis reaction, filtering and washing to obtain coated powder (coated raw material powder);
(3) repeating the step (2) for 3-5 times, performing heat treatment at 450-500 ℃ for 2-4 hours, adding a binder for granulation, and performing compression molding to obtain a biscuit;
(4) and (3) after plastic removal, sintering the biscuit at 1150-1200 ℃ for 1-3 hours to obtain the high energy storage density antiferroelectric ceramic.
The invention uses a chemical method to prepare Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The breakdown-resistant substance is coated on the surface of the powder, so that the internal components of the ceramic are more uniform, and the reduction of the polarization strength of the ceramic is avoided to a certain extent. Specifically, the invention uses Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Mixing the powder, tetraethyl silicate, water and alcohol, adjusting the pH value to 7.5-8.0, and then carrying out hydrolysis reaction. Wherein, the product SiO of tetraethyl silicate hydrolysis2Coating with Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3And (3) carrying out heat treatment on the surface of the powder in a crucible at 450-500 ℃ for 2-4 hours to remove residual organic matters, and then carrying out plastic removal and sintering. In addition, the chemical method is used for preparing the lead-free copper alloy at Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3After the surface of the powder is modified, the activity of the powder is improved to a certain extent, and meanwhile, a liquid phase component is generated in the sintering process, so that the sintering temperature of the powder in the subsequent sintering process is reduced. And chemically reacting at Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3After the surface of the powder is modified, the volatilization of heavy metal Pb in the sintering process is also inhibited, so that the deviation of the final material components and the design is avoided, and the final excellent performance of the ceramic is ensured.
Preferably, the solid-phase reaction method is according to Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Weighing Pb source, La source, Zr source, Sn source,Mixing Ti sources, drying and calcining to obtain Pb0.97La0.02[(Zr0.375Sn0.625)1- xTix]O3Powder; preferably, in the above formula, x is 0.12, and the Pb source is Pb3O4The La source is La2O3The Zr source is ZrO2The Sn source is SnO2The Ti source is TiO2。
Preferably, the calcination temperature is 800-850 ℃ and the calcination time is 1-3 hours.
Preferably, the Pb is0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The mol ratio of the powder to the tetraethyl silicate is 100: (0.95-1.05), the volume ratio of the tetraethyl silicate to the alcohol solvent is 1 (150-160), and the molar ratio of the water to the tetraethyl silicate is 1 (1.5-2). Preferably, the alcohol is at least one of ethanol, ethylene glycol and butanol.
Preferably, the temperature of the hydrolysis reaction is 70-80 ℃ and the time is 3-5 hours; preferably, the temperature of the hydrolysis reaction is 80 ℃ and the time is 3-3.5 hours.
Preferably, the binder is at least one of polyvinyl butyral (PVB) and polyvinyl alcohol (PVA), and the addition amount is Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O38-10 wt% of the powder.
Preferably, the temperature of the plastic discharge is 400-600 ℃, and the time is 1-3 hours.
Preferably, the temperature rise rate of the sintering is 2-5 ℃/min.
The invention improves the powder activity by chemical modification, and can also reduce the sintering temperature of the ceramic to a certain extent, on one hand, the ceramic can be applied to low temperature co-firing (LTCC) of the ceramic and the inner electrode in the multilayer capacitor; on the other hand, the volatilization of heavy metal Pb can be inhibited, so that the deviation of the final material components and the design is avoided, and the final excellent performance of the ceramic is ensured. The invention carries out the transformation of the ceramic powderThe PLZST antiferroelectric energy storage ceramic material which can be sintered at 1150-1200 ℃ is obtained by chemical surface modification. The relative dielectric constant of the ceramic material at room temperature is 791, the dielectric loss is 0.002, and the AFE-FE phase-change electric field is 4.68 kV/mm. The releasable energy storage density of the ceramic material is 2.68J/cm under the working electric field of 23.5kV/mm3The energy storage efficiency was 78%. The material has the characteristics of high energy storage density and high energy storage efficiency. The antiferroelectric ceramic material can be used for manufacturing energy storage multilayer ceramic capacitors and has good application prospect.
Drawings
FIG. 1 shows a TEM image of the surface of a coated powder sample prepared in example 1;
FIG. 2 is a surface SEM image of an antiferroelectric ceramic sample prepared in example 1 of the present invention;
FIG. 3 is a surface SEM image of an antiferroelectric ceramic sample prepared in example 2 of the present invention;
FIG. 4 is a surface SEM image of an antiferroelectric ceramic sample prepared in comparative example 1 of the present invention;
FIG. 5 is a surface SEM image of an antiferroelectric ceramic sample prepared in comparative example 2 of the present invention;
FIG. 6 is a graph showing the ferroelectric hysteresis loop of an antiferroelectric ceramic sample prepared in example 1 of the present invention;
FIG. 7 is a graph showing the ferroelectric hysteresis loop of an antiferroelectric ceramic sample prepared in example 2 of the present invention;
FIG. 8 is a graph showing the ferroelectric hysteresis loop of a sample of an antiferroelectric ceramic prepared in comparative example 1 of the present invention;
fig. 9 is a hysteresis chart of an antiferroelectric ceramic sample prepared by comparative example 2 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 invention, the chemical composition of the high energy storage density antiferroelectric ceramic material conforms to the chemical general formula Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3+a SiO2Wherein x is more than or equal to 0.1 and less than or equal to 0.15A is more than or equal to 3 percent and less than or equal to 5 percent. x is mole number, a is SiO2With Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Mole percent of (c). When the value a is lower than 3, the coating has no obvious effect; when the value of a is higher than 5, the antiferroelectric properties of the material will be affected, or even the antiferroelectric transition electric field will disappear.
Optionally, the antiferroelectric ceramic material can be sintered at 1150-1200 ℃, and the releasable energy storage density is 2.32-2.68J/cm under a working electric field of 21.6-23.6 kV/mm3And the energy storage efficiency is 73-81%.
Alternatively, the antiferroelectric ceramic material can have a relative dielectric constant of 754 to 803 at room temperature (20 ℃), a dielectric loss of 0.001 to 0.002, and an AFE-FE phase-change electric field of 3.97 to 4.88kV/mm (e.g., 4.73 kV/mm).
The preparation method of the high energy storage density antiferroelectric ceramic material prepared by the present invention is exemplarily described as follows.
Preparation of Pb by solid-phase reaction method0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Powder (ceramic powder). In particular, according to Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Calculating the mass of the required Pb source, La source, Zr source, Sn source and Ti source according to the chemical formula, mixing materials by adopting a wet ball milling method, drying and calcining to obtain Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3And (3) powder, wherein x is more than or equal to 0.1 and less than or equal to 0.15, and x is a mole number. Wherein the Pb source can be Pb3O4. The La source may be La2O3. The Zr source may be ZrO2. The Sn source may be SnO2. The Ti source may be TiO2. The calcining temperature is 800-850 ℃, and the heat preservation time is 1-3 hours. The drying temperature can be 90-110 ℃, and the drying time is 10-12 hours.
Adding Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Mixing the powder (ceramic powder), tetraethyl silicate, water and alcohol, adjusting the pH to 7.5-8.0, then carrying out hydrolysis reaction, filtering and washing to obtain the raw material powder. The temperature of the hydrolysis reaction can be 70-80 ℃, and the time can be 3-5 hours. The Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The molar ratio of the powder to the tetraethyl silicate can be 100: (0.95-1.05), the volume ratio of the tetraethyl silicate to the alcohol solvent is 1 (150-160), and the molar ratio of the water to the tetraethyl silicate is 1 (1.5-2). The alcohol may be at least one of ethanol, ethylene glycol, and butanol. In which Pb is0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The powder can also be finely ground (ball-milled and mixed) and then mixed with tetraethyl silicate, water and alcohol. According to the ceramic powder: ball: deionized water 1: (1.6-2): (0.5-0.7) and grinding for 24-48 hours, wherein the grinding balls are iron balls, agate balls or zirconia balls. Adjusting pH by adding acid or alkali, wherein the acid can be organic acid such as acetic acid, propionic acid, etc., and the alkali can be ammonia water (aqueous ammonium hydroxide solution). Pb as described above0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3The powder (ceramic powder), tetraethyl silicate, water and alcohol can be mixed by first mixing Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3After the powder (ceramic powder), tetraethyl silicate and alcohol were mixed, water was added dropwise. As an example, the ceramic powder after being finely ground is added to alcohol and ultrasonically dispersed, and then mixed with tetraethyl silicate to form a mixed solution. And dropwise adding deionized water into the solution obtained in the step, then adjusting the pH value to 7.5, stirring and reacting in a water bath heating container, filtering, and washing to obtain coated powder. According to the ceramic powder: and (3) mixing the tetraethyl silicate and the alcohol solvent at a molar ratio of (0.95-1.05) of 100 and a volume ratio of 1 (150-160). According to deionized water: the tetraethoxysilane is dripped in a molar ratio of 1 (1.5-2), the pH value is 7.5-8, and the reaction temperature isThe reaction time is 3-3.5 hours at 70-80 ℃.
Repeating the preparation steps of the raw material powder for 3-5 times to adjust SiO in the antiferroelectric ceramic material2Mixing the obtained raw material powder with tetraethyl silicate, water and alcohol, adjusting the pH to 7.5-8.0, then carrying out hydrolysis reaction, and filtering and washing for at least 2-5 times. The alcohol is at least one of ethanol, ethylene glycol and butanol. Then carrying out heat treatment, adding a binder for granulation, and carrying out compression molding to obtain a biscuit. The heat treatment temperature can be 450-500 ℃, and the heat preservation time can be 2-4 hours. The added binder can be at least one of polyvinyl butyral (PVB) and polyvinyl alcohol (PVA), and the addition amount is Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O38-10% of the powder mass.
And after plastic removal, sintering the biscuit at 1150-1200 ℃ for 1-3 hours to obtain the high energy storage density antiferroelectric ceramic. And removing organic substances in the biscuit at a certain temperature, wherein the temperature for removing the plastic can be 400-600 ℃, and the heat preservation time can be 1-3 hours. And placing the obtained ceramic sample subjected to plastic removal into an alumina crucible for closed sintering, wherein the sintering temperature is 1150-1200 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-3 hours.
And (3) grinding the antiferroelectric ceramic with high energy storage density, cleaning, drying, screen-printing silver paste, drying again, putting into a box-type electric furnace for silver burning, wherein the silver burning condition is 600-750 ℃, and preserving heat for 30-60 min to obtain a ceramic sample (ceramic element) covered with an electrode.
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 antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3+5％SiO2
(1) Calculating required Pb according to the composition of the chemical formula3O4、La2O3、ZrO2、SnO2、TiO2Quality, adopting a wet ball milling method to mix materials, and mixing the raw materials according to the following ratio: ball: and (3) mixing deionized water in a mass ratio of 1:1.5:0.8 for 6-8 hours to uniformly mix the components. Drying, sieving with 30 mesh sieve, briquetting in air atmosphere, heating to 850 deg.C at a temperature rise rate of 2 deg.C/min, maintaining for 3 hr, and synthesizing to obtain Pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3The powder (ceramic powder) of (4);
(2) finely grinding Pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3Adding ethanol (C) into the powder2H5OH) ultrasonic dispersion, mixing with tetraethyl silicate to form a mixed solution, and mixing according to the weight ratio of ceramic powder: mixing tetraethyl silicate and an ethanol solvent at a molar ratio of (0.95-1.05) of 100 and a volume ratio of 1 (150-160);
(3) dropwise adding deionized water into the solution obtained in the step (2), wherein the molar ratio of the water to the tetraethyl silicate is 1:1.5, then adjusting the pH value to 7.5, reacting in a water bath heating container at 80 ℃ for 3-3.5 hours, filtering and washing. Repeating the steps (2) and (3) for 4 times. Then carrying out heat treatment in a crucible, and preserving heat for 3 hours at 550 ℃ to obtain coated powder; (4) and (4) adding a binding agent PVB into the powder obtained in the step (3), granulating, and performing compression molding to obtain a biscuit. Specifically, the powder obtained in the step (3) is prepared by the following steps: ball: finely grinding the mixture for 24 hours by using a wet method according to the proportion of deionized water to 1:2:0.6, discharging and drying the mixture, sieving the mixture by using a 40-mesh sieve, adding 8-10 wt% of PVB (polyvinyl butyral) for granulation, and pressing and molding the powder under the pressure of 150MPa to obtain a biscuit;
(5) and (3) preserving the biscuit obtained in the step (4) at 400-600 ℃ for 1-3 hours, removing organic substances in the biscuit, and enabling the plastic removal rate not to exceed 3 ℃/min. Placing the sample subjected to plastic removal into an alumina crucible for closed sintering, covering the blank with ceramic powder with components to prevent volatilization of lead components, covering a ground cover, raising the temperature to 1200 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling along with the furnace to obtain an antiferroelectric ceramic material;
(6) and (3) grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning, wherein the silver burning condition is 750 ℃ and the heat preservation is 30 min. An antiferroelectric ceramic sample coated with an electrode was obtained.
TEM observation is performed on the coated powder sample, and a surface micro-topography structure diagram of the powder sample prepared in the example 1 is shown in FIG. 1. The surface SEM observation of the antiferroelectric ceramic sample prepared in this example 1 was performed, and fig. 2 shows a structure diagram of the surface morphology of the antiferroelectric ceramic sample prepared in this example 1, from fig. 2, it can be seen that the surface composition is uniform, the pores are few, the coating is distributed at the grain boundary, and there are no other impurity phases.
The ferroelectric hysteresis loop measurement at room temperature (25 ℃) was performed on the antiferroelectric ceramic sample prepared in this example 1, and the test result is shown in fig. 6, from which it can be seen that the ceramic has good antiferroelectric property, and the AFE-FE phase transition electric field is 4.68 kV/mm; the releasable energy storage density is 2.68J/cm under the working electric field of 23.5kV/mm3. And the anti-ferroelectric ceramic sample sintered at 1200 ℃ is subjected to dielectric property and energy storage property tests. The relative dielectric constant at room temperature was 791 and the dielectric loss was 0.002, as detailed in Table 1.
Example 2
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3+3％SiO2
The preparation process of example 1 was repeated according to the above formulation except that the steps (2) and (3) were repeated 2 times and then heat-treated. And then adding a binder for granulation and preparing a biscuit, sintering the obtained blank at 1220 ℃, and preserving heat for 2 hours to obtain the antiferroelectric ceramic sample. And (3) grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning, wherein the silver burning condition is 750 ℃ and the heat preservation is 30 min. An antiferroelectric ceramic sample coated with an electrode was obtained.
TEM observation is performed on the coated powder sample, and a surface micro-topography structure diagram of the powder sample prepared in the example 2 is shown in FIG. 3. Surface SEM observation is performed on the antiferroelectric ceramic sample prepared in this example 2, fig. 3 shows a surface morphology structure diagram of the antiferroelectric ceramic sample prepared in this example 2, and it can be seen from fig. 3 that the surface components are uniform, the pores are few, the coating is distributed at the grain boundary, but it is not obvious, and there are no other impurity phases.
The ferroelectric hysteresis loop measurement at room temperature (25 ℃) was performed on the antiferroelectric ceramic sample prepared in this example 2, and the test result is shown in fig. 7, from which it can be seen that the ceramic has good antiferroelectric property, and the AFE-FE phase transition electric field is 4.68 kV/mm; the releasable energy storage density is 2.32J/cm under the working electric field of 20.5kV/mm3. And the anti-ferroelectric ceramic sample sintered at 1200 ℃ is subjected to dielectric property and energy storage property tests. The relative dielectric constant at room temperature was 776, the dielectric loss was 0.002, as detailed in Table 1.
Comparative example 1
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3+0％SiO2
The preparation method of example 1 is repeated according to the formula except that no tetraethyl silicate is added, then a binder is added for granulation and biscuit preparation, and the obtained green body is sintered at 1260 ℃, and the temperature is kept for 2 hours to obtain an antiferroelectric ceramic sample. And (3) grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning, wherein the silver burning condition is 750 ℃ and the heat preservation is 30 min. An antiferroelectric ceramic sample coated with an electrode was obtained.
Surface SEM observation is carried out on the ceramic sample prepared in the comparative example 1, and a surface topography structure chart of the ceramic sample of the embodiment is shown in FIG. 4, so that the surface composition is uniform, but some holes are formed and a certain amount of impurity phase appears. The ceramic sample prepared in comparative example 1 was subjected to room temperatureThe lower hysteresis loop is measured, the test result is shown in figure 8, the graph shows that the ceramics have antiferroelectric property, and the AFE-FE phase change electric field is 5.36 kV/mm. The releasable energy storage density is 1.76J/cm under the working electric field of 12.2kV/mm3. The ceramic sample prepared in comparative example 1 was subjected to dielectric property and energy storage property tests. The relative dielectric constant at room temperature was 690 and the dielectric loss was 0.005, as detailed in Table 1.
Comparative example 2
The antiferroelectric ceramic material comprises the following components: pb0.97La0.02(Zr0.33Sn0.55Ti0.12)O3+6％SiO2
The preparation process of example 1 was repeated according to the above formulation except that the steps (2) and (3) were repeated 6 to 7 times and then heat-treated. And then adding a binder for granulation, preparing a biscuit, sintering the obtained blank at 1200 ℃, and preserving heat for 2 hours to obtain a ceramic sample.
Surface SEM observation of the ceramic sample prepared in comparative example 2 was performed, and FIG. 5 shows a surface morphology structure chart of the ceramic sample of this example, from which it was found that the surface composition distribution was not uniform, there were many pores, and a large amount of impurity phases occurred due to excessive SiO2Caused by the incorporation. The hysteresis loop measurement at room temperature was performed on the ceramic sample prepared in comparative example 2, and the test result is shown in fig. 9, from which it is understood that the ceramic does not have antiferroelectric properties and cannot exhibit AFE-FE phase transition electric field. The releasable energy storage density is 0.68J/cm under the working electric field of 10.8kV/mm3. The ceramic sample prepared in comparative example 1 was subjected to dielectric property and energy storage property tests. The relative dielectric constant at room temperature was 532 and the dielectric loss was 0.032, as detailed in Table 1.
Table 1 shows the dielectric properties and energy storage characteristics at room temperature of the antiferroelectric ceramic materials prepared in examples 1-2 and comparative examples 1-2:
Figure BDA0001598162400000081
Figure BDA0001598162400000091

Claims (15)

1. the antiferroelectric ceramic material with high energy storage density is characterized in that the antiferroelectric ceramic material has a chemical general formula of Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3 + a SiO2(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.15, a is SiO2With Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3A is more than or equal to 3 percent and less than or equal to 5 percent; SiO 22The source is tetraethyl silicate, and SiO is obtained through hydrolysis reaction2Said SiO2Exists as a second phase and is uniformly covered on Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Of (2) is provided.
2. The high energy storage density antiferroelectric ceramic material as claimed in claim 1, wherein the antiferroelectric ceramic material has a releasable energy storage density of 2.32-2.68J/cm under an operating electric field of 21.6-23.6 kV/mm3And the energy storage efficiency is 73-81%.
3. The high energy storage density antiferroelectric ceramic material as claimed in claim 2, wherein said antiferroelectric ceramic material has a releasable energy storage density of 2.68J/cm under an operating electric field of 23.5kV/mm3The energy storage efficiency was 78%.
4. The antiferroelectric ceramic material with high energy storage density as claimed in claim 1 or 2, wherein the antiferroelectric ceramic material has a relative dielectric constant of 754-803 at room temperature, a dielectric loss of 0.001-0.002, and an AFE-FE phase transition electric field of 3.97-4.88 kV/mm.
5. The high energy storage density antiferroelectric ceramic material according to claim 4, wherein said antiferroelectric ceramic material has a relative dielectric constant of 791 at room temperature, a dielectric loss of 0.002, and an AFE-FE phase transition electric field of 4.68 kV/mm.
6. A method for preparing a high energy storage density antiferroelectric ceramic material according to any of claims 1-5, comprising:
(1) preparation of Pb by solid-phase reaction method0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Powder;
(2) the obtained Pb is0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Mixing the powder, tetraethyl silicate, water and alcohol, adjusting the pH value to 7.5-8.0, then carrying out hydrolysis reaction, and filtering and washing to obtain coated powder;
(3) repeating the step (2) for 2-5 times, performing heat treatment at 450-500 ℃ for 2-4 hours, adding a binder for granulation, and performing compression molding to obtain a biscuit;
(4) and (3) after plastic removal, sintering the biscuit at 1150-1200 ℃ for 1-3 hours to obtain the high energy storage density antiferroelectric ceramic.
7. The method according to claim 6, wherein the solid phase reaction is performed according to Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3Weighing Pb source, La source, Zr source, Sn source and Ti source according to the stoichiometric ratio, mixing, drying and calcining to obtain Pb0.97La0.02[(Zr0.375Sn0.625)1-xTix]O3And (3) powder.
8. The production method according to claim 7, wherein the Pb source is Pb3O4The La source is La2O3The Zr source is ZrO2The Sn source is SnO2The Ti source is TiO2。
9. The preparation method according to claim 7, wherein the calcination is carried out at a temperature of 800 ℃ to 850 ℃ for 1 hour to 3 hours.
10. The method according to claim 6, wherein the Pb is0.97La0.02[(Zr0.375Sn0.625)1- xTix]O3The mol ratio of the powder to the tetraethyl silicate is 100: (0.95-1.05), the volume ratio of the tetraethyl silicate to the alcohol solvent is 1 (150-160), and the molar ratio of the water to the tetraethyl silicate is 1 (1.5-2).
11. The production method according to claim 10, wherein the alcohol is at least one of ethanol, ethylene glycol and butanol.
12. The method according to claim 6, wherein the hydrolysis reaction is carried out at a temperature of 70 to 80 ℃ for 3 to 5 hours.
13. The method according to claim 12, wherein the hydrolysis reaction is carried out at 80 ℃ for 3 to 3.5 hours.
14. The method of claim 6, wherein the binder is at least one of polyvinyl butyral (PVB) and polyvinyl alcohol (PVA) added in Pb amount0.97La0.02[(Zr0.375Sn0.625)1-xTix]O38-10 wt% of the powder.
15. The method according to any one of claims 6 to 14, wherein the temperature of the plastic discharge is 400 to 600 ℃ and the time is 1 to 3 hours.
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