CN112142466A - Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof - Google Patents
Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lead ytterbium niobate-based antiferroelectric ceramic material and a preparation method thereof, wherein the lead ytterbium niobate-based antiferroelectric ceramic material has the following general formula: pb ((Yb)1/2Nb1/2)1‑xSnx)O3‑ySnO2‑zTiO2Wherein x, y and z are molar ratio, x is more than 0.00 and less than 0.10, y is more than 0.00 and less than 0.20, and z is more than or equal to 0.00 and less than 0.20.
Description
Technical Field
The invention relates to a lead ytterbium niobate-based antiferroelectric ceramic material with high energy storage density at high temperature and a preparation method thereof, belonging to the technical field of functional ceramic materials.
Background
The pulse power technology is widely applied to the fields of military equipment, medical equipment, environmental management, civil power systems, automobiles, miniature electronic equipment and the like[1]. With the development of social economy and science and technology, pulse power devices are miniaturized, high in power and high in efficiencyThis requires the energy storage unit to have high energy storage density, high energy storage efficiency and fast charge and discharge speed. The ceramic capacitor has the characteristics of good high-frequency characteristic, high compressive strength, small loss, easy chip formation and the like, thereby becoming one of the main basic materials of the energy storage unit of the pulse power device[2]. In the ceramic capacitor, relative to linear ceramics and ferroelectric ceramics, dipoles of the antiferroelectric ceramics are antiparallel, the total electric moment is zero, the residual polarization is zero, and when an external electric field is increased to be close to a phase-change electric field, the polarization intensity is suddenly increased to generate a peak value, so that the requirements of high energy storage density, high energy storage efficiency and rapid charge and discharge are more easily met. Therefore, the antiferroelectric ceramic has wide application prospect in pulse power devices as an energy storage capacitor.
In order to obtain antiferroelectric ceramic materials with high energy storage density and high energy storage efficiency, researchers have conducted a great deal of research in recent years. The prior antiferroelectric ceramic with high performance is mostly lead zirconate (PbZrO)3) On the basis of (2) doping modification[3-4]. But due to lead zirconate (PbZrO)3) The Curie temperature of the lead zirconate-based antiferroelectric material is only 230 ℃, and the introduction of the doping ions further reduces the phase transition temperature from the antiferroelectric phase to the paraelectric phase, so that the antiferroelectric performance of the lead zirconate-based antiferroelectric material is very weak near 200 ℃, even the antiferroelectric property is completely lost, and the lead zirconate-based antiferroelectric material cannot be stably applied at a high temperature end (150-200 ℃). Lead ytterbium niobate (Pb (Yb)0.5Nb0.5)O3) Is an antiferroelectric material with Curie temperature as high as 302 ℃, and is expected to be applied in high-temperature environment. Lead ytterbium niobate (Pb (Yb) has been studied by researchers0.5Nb0.5)O3) In which Zr is introduced4+、Sr2+、Sc3+、Ba2+In which Zr4+、Sr2+Double hysteresis loops not obtained by doping[5-6]，Sc3+、Ba2+The introduction of (A) shows an unstable double hysteresis loop below the Curie temperature, which is believed to be caused by the presence of a metastable phase in the first-order phase transition, rather than the antiferroelectric phase[7-8]The Curie temperature is less than 100 ℃, and the energy storage density is less than 0.5J/cm3And the requirement of high energy storage density at high temperature cannot be met.
Reference documents:
[1] research on perovskite antiferroelectric oxides has progressed [ J ] physics, 2017(5).
[2] Xuchenghong, research on antiferroelectric ceramic design for pulse capacitor and charge and discharge behaviors thereof [ D ]. university of chinese academy of sciences (shanghai silicate institute of chinese academy of sciences), 2018.
[3]Wang H,Liu Y,Yang T,et al.Ultrahigh Energy-Storage Density in Antiferroelectric Ceramics with Field-Induced Multiphase Transitions[J].Advanced Functional Materials,2019,29(7):1807321.
[4]Liu Z,Lu T,Ye J,et al.Antiferroelectrics for energy storage applications:A review[J].Advanced Materials Technologies,2018,3(9):1800111.
[5]Kim J H,Im K V,Choo W K.Dielectric Properties and X-Ray Study of Zr-Sbustituted Pb(Yb1/2Nb1/2)O3Ceramics[J].Japanese Journal of Applied Physics,1999,38(9):5474-5477.
[6]Park S B,Choo W K,Park J W.Crystal structure and dielectric properties of Pb 1–x Sr x(Yb1/2Nb 1/2)O 3system[J].Journal of the European Ceramic Society,2001,21(10):1661-1664.
[7]Kim,J.H.；Koh,K.S.；Choo,W.K.,Phase transition behavior of Sc-substituted Pb(Yb1/2N1/2)O-3ceramics.Integr Ferroelectr 2002,47,11-18.
[8]Kim,J.H.；Kim,H.S.；Koh,K.S.；Shim,I.W.；Choo,W.K.,Structural and dielectric behavior or Ba-substituted Pb(Yb1/2Nb1/2)O-3ceramics.Integr Ferroelectr 2002,47,3-10.。
Disclosure of Invention
In order to solve the problems of limited energy storage density, low energy storage efficiency, low breakdown field strength, low application temperature and the like in the conventional antiferroelectric ceramic, the invention aims to provide a lead ytterbium niobate-based antiferroelectric ceramic material and a preparation method thereof.
In one aspect, the invention provides a lead ytterbium niobate-based antiferroelectric ceramic material, wherein niobium isThe general formula of the lead ytterbium acid based antiferroelectric ceramic material is as follows: pb ((Yb)1/2Nb1/2)1-xSnx)O3-ySnO2-zTiO2Wherein x, y and z are molar ratio, x is more than 0.00 and less than 0.10, y is more than 0.00 and less than 0.20, and z is more than or equal to 0.00 and less than 0.20.
In the present disclosure, the lead niobate ytterbate-based antiferroelectric ceramic material has typical antiferroelectric performance characteristics, namely, antiferroelectric superlattice diffraction peak and dual hysteresis loop, and simultaneously has high breakdown strength, high energy storage density and high energy storage efficiency. Wherein SnO2The internal doping can reduce the Curie temperature of the lead niobate ytterbate-based antiferroelectric ceramic, and is beneficial to adjusting the field phase transition to be in a controllable temperature range. SnO2The external doping can improve the energy storage efficiency, improve the breakdown field strength and reduce the antiferroelectric-ferroelectric phase transition electric field of the lead niobate-ytterbium base ceramic. Furthermore, TiO2The external doping can improve the field polarization strength of the lead niobate ytterbate-based antiferroelectric ceramic and improve the energy storage density. Therefore, under the synergistic effect of the three components, the antiferroelectric energy storage ceramic material with high breakdown strength, high energy storage efficiency and high energy storage density at high temperature can be obtained.
Preferably, z is more than or equal to 0.02 and less than or equal to 0.10.
Preferably, under the test conditions of 180-200 ℃ and 10Hz, the effective energy storage density of the lead niobate ytterbate-based antiferroelectric ceramic material is 1.26-2.79J/cm3And the energy storage efficiency is 53.73-88.54%.
On the other hand, the invention provides a preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material, which comprises the following steps:
(1) using niobate YbNbO4Powder, Pb3O4Powder and SnO2Powder and TiO2The powder is taken as a raw material, and is weighed and mixed according to the general formula of the lead ytterbium niobate-based antiferroelectric ceramic material to obtain mixed powder;
(2) pre-burning the obtained mixed powder at 800-900 ℃ to obtain pre-burned powder;
(3) mixing the pre-sintered powder and a binder, granulating, and performing compression molding to obtain a biscuit;
(4) and (3) removing the glue from the obtained biscuit, and sintering at 1000-1200 ℃ for 2-4 hours to obtain the lead ytterbium niobate-based antiferroelectric ceramic material.
Preferably Yb2O3Powder and Nb2O5The powder is prepared according to the niobate YbNbO4The niobate YbNbO is obtained by calcining for 2 to 4 hours at the temperature of 1000 to 1200 ℃ after being weighed and mixed according to the stoichiometric ratio4。
Preferably, the Pb is3O4The molar content of the powder needs to be excessive by 0.3-1.3%, and the preferable content is 1%.
Preferably, the pre-sintering time is 2 to 3 hours, preferably 2 hours.
Preferably, the temperature of the rubber discharge is 550-600 ℃, and the time is 3-4 hours; preferably, the temperature of the binder removal is 550 ℃.
Preferably, the sintering atmosphere is a Pb atmosphere.
Preferably, the obtained biscuit is placed on a crucible plate before sintering, the small crucible is covered after the biscuit is embedded by using the pre-sintering powder, the gap between the small crucible and the crucible plate is sealed by using the pre-sintering powder, and the large crucible is covered again, so that a Pb atmosphere environment is created in the sintering process, and Pb volatilization is reduced.
Preferably, the obtained pre-sintered powder is subjected to high-energy ball milling treatment, wherein the rotation speed of the high-energy ball milling treatment is 800-1200 r/min (for example, 1000r/min), and the time is 1-2 hours. Wherein, the high-energy ball milling can refine the granularity of the powder and then lead the sintering to be more compact in the subsequent sintering atmosphere.
Preferably, the binder is at least one of polyvinyl alcohol PVA and polyvinyl butyral PVB.
The invention is realized by adding Pb ((Yb)1/2Nb1/2)1-xSnx)O3Medium and external doped SnO2、TiO2The high-energy ball milling process is combined to reduce the field-induced phase transition electric field to be below the breakdown field intensity, so as to successfully obtain Pb (Yb)1/2Nb1/2)O3A double hysteresis loop of a base ceramic material. Moreover, the obtained lead ytterbium niobate-based antiferroelectric ceramic material is 10Hz and 235kV/cm at 180 DEG CUnder the test condition, the effective energy storage density can reach 2.38J/cm3The energy storage efficiency can reach 67.8%, and the pulse energy storage device is suitable for energy storage capacitors and high-power pulsers applied to high-temperature working environments.
Drawings
FIG. 1 is an XRD spectrum of a sample of antiferroelectric ceramic made in example 1;
FIG. 2 is a hysteresis loop of a sample of antiferroelectric ceramic prepared in example 1 at 200 ℃ and 10 Hz;
FIG. 3 is a graph of the effective energy storage density of antiferroelectric ceramic samples prepared in example 1 under different electric fields;
FIG. 4 is a hysteresis loop of a sample of antiferroelectric ceramic prepared in example 2 at 180 ℃ and 10 Hz;
FIG. 5 is a graph of the effective energy storage density of antiferroelectric ceramic samples prepared in example 2 under different electric fields;
FIG. 6 is a hysteresis loop of a sample of antiferroelectric ceramic prepared in example 4 at 200 ℃ and 10 Hz;
FIG. 7 is a hysteresis loop of the ceramic material prepared in comparative example 1 at 200 ℃ and 10 Hz.
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 general formula of the composition of the lead ytterbium niobate-based antiferroelectric ceramic material with high energy storage density at high temperature can be: pb ((Yb)1/2Nb1/2)1-xSnx)O3-ySnO2(PYNS for short), wherein x and y are molar ratio and satisfy 0.00 < x < 0.10, 0.00 < y < 0.20, and 0.00 < z < 0.20. Wherein, the content of x, y and z is excessive, so that the impure phase is increased, and the performance is stably reduced. If only TiO is doped2The energy storage density can be improved to a certain degree, but the dielectric loss under an electric field is large, and the energy storage efficiency is low. If it is only SnO2The internal doping can be realized, the Curie temperature can be reduced, but the AFE-FE phase transformation electric field can not be adjusted to be below the breakdown field intensity, a double-electric hysteresis loop can not be obtained, and the improvement of the energy storage density and the energy storage efficiency can not be realized. In alternative embodimentsIn the formula, under the test conditions of 180-200 ℃ and 10Hz, the effective energy storage density of the lead ytterbium niobate-based antiferroelectric ceramic material is 1.26-2.79J/cm3And the energy storage efficiency is 53.73-88.54%.
In one embodiment of the present invention, Pb ((Yb) is synthesized by a solid phase method1/2Nb1/2)1-xSnx)O3-ySnO2-zTiO2(PYNSZ for short) and then sintering to obtain the lead ytterbium niobate-based antiferroelectric ceramic material. The preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material provided by the invention is exemplarily described as follows.
Presynthesized ytterbium niobate (YbNbO)4) And (3) powder. Specifically, Yb2O3Powder and Nb2O5The powder is prepared according to the niobate YbNbO4The niobate YbNbO is obtained by calcining for 2 to 4 hours at the temperature of 1000 to 1200 ℃ after being weighed and mixed according to the stoichiometric ratio4. As a preparation method of ytterbium niobate (YbNbO)4) Example of the powder Yb2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Then the temperature is kept for 2 to 4 hours at the temperature of 1000 ℃ and 1200 ℃ to synthesize the ytterbium niobate powder.
According to the chemical formula Pb ((Yb)1/2Nb1/2)1-xSnx)O3-ySnO2-zTiO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4Powder and Pb3O4Powder and SnO2Powder, TiO2And mixing the powder to obtain mixed powder. Considering the volatilization of PbO, Pb3O4The content needs to be excessive by 1 percent. The mixing mode can be as follows: putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours. And mixing the powder by the fans, pouring out and drying to obtain mixed powder.
The mixed powder is synthesized at 800-900 ℃ for 2-3 hours (e.g., 2 hours) to obtain a calcined powder of a desired phase. In order to improve the mass transfer speed and the reaction efficiency among the mixed powder bodies, the uniformly mixed powder bodies can be sieved and pressed into blocks, then placed in a high-temperature furnace for presintering, and then crushed, ground and sieved to obtain presintered powder bodies. In an alternative embodiment, the obtained pre-sintered powder is put into a ball milling pot of a high-energy ball mill, a solvent (for example, absolute ethyl alcohol) is added, and the mixture is ball milled for 1 to 2 hours at the rotating speed of 800-. The method utilizes high-energy ball milling to refine the granularity of powder, and then sintering is carried out in a sintering atmosphere to compact the powder.
And adding a binder into the pre-sintered powder for granulation to obtain granulated powder. Wherein the binder can be polyvinyl alcohol PVA, polyvinyl butyral PVB and the like. The binder may be added in an amount of 8 to 15 wt%, for example 10 wt%, based on the mass of the calcined powder.
The green body is obtained by pressing and molding the granulated powder, wherein the pressing and molding can be dry pressing and molding, for example, pressing and molding at 200 MPa.
And (5) removing the glue from the biscuit. Wherein the temperature for removing the glue can be 550-600 ℃, and the time is 3-4 hours. For example, the press-formed biscuit is kept at a temperature of 550 ℃ for 3 hours to expel the organic components and solvents (mainly binders, water, etc.).
And sintering the biscuit after the glue removal at the temperature of 1000-1200 ℃ for 2-4 hours to obtain the lead ytterbium niobate-based antiferroelectric ceramic material. Preferably, the biscuit after the binder removal is placed on a crucible plate and embedded in the pre-synthesized powder with the same components, a small crucible is covered, the gap between the crucible and the crucible plate is sealed by the pre-synthesized powder, a large crucible is covered, the lead atmosphere is maintained, and then sintering treatment is carried out.
The lead niobate ytterbate-based antiferroelectric ceramic material has high breakdown strength and energy storage density at high temperature, belongs to a typical antiferroelectric material, has very important research value in the field of antiferroelectric energy storage, and is expected to be applied to the fields of high-density energy storage capacitors, high-power pulse power supplies and the like in high-temperature working environments.
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: pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.02SnO2
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.02SnO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4Powder and Pb3O4Powder and SnO2Powder and Pb3O4And (3) powder. Considering the volatilization of PbO, Pb3O4The powder content needs to be excessive by 1 percent. Putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours, pouring out and drying to obtain mixed powder;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA solution with the mass of 10 wt% of the powder mass and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000 plus materials and 1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material.
The obtained ceramic was ground into powder and subjected to phase analysis by a D/max2550V diffractometer, and the XRD spectrum obtained is shown in FIG. 1. As can be seen from fig. 1: the ceramic is in a perovskite structure of an orthorhombic phase and has a superlattice diffraction peak with lead ions in antiparallel displacement, which indicates that the ceramic has an antiferroelectric phase;
FIG. 2 shows the double hysteresis loop of the ceramic material prepared in this example at 200 ℃ and 10Hz, as can be seen from FIG. 2: the ceramic sample has antiferroelectric-ferroelectric phase transition under a strong external electric field, and the polarization strength can reach 16.90 mu C/cm under the field strength of 283kV/cm2；
FIG. 3 is a graph showing the effective energy storage density of the ceramic material prepared in this example under different electric fields at 200 deg.C and 10Hz, from which it can be seen that the effective energy storage density rapidly increases near the antiferroelectric-ferroelectric phase transition electric field, and reaches as high as 2.27J/cm at 283kV/cm3。
Example 2: pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.06SnO2
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.06SnO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4With Pb3O4、SnO2Considering the volatilization of PbO, Pb3O4The content needs to be excessive by 1 percent. Putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours, pouring out and drying;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA with the mass of 10 wt% of the powder and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000 plus materials and 1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material.
FIG. 4 shows the double hysteresis loops of the ceramic material prepared in this example 2 at 180 ℃ and 10Hz, where the ceramic sample is increased with the applied electric field, the double hysteresis loops tend to saturate, and the polarization can reach 17.36 μ C/cm at a field strength with very small residual polarization of 268kV/cm2The remanent polarization is only 0.63 μ C/cm2；
FIG. 5 is a graph showing the effective energy storage density of the ceramic material prepared in this example 2 at 180 ℃ and 10Hz in different electric fields, which is as high as 2.38J/cm at 268kV/cm3。
Example 3: pb ((Yb)1/2Nb1/2)0.96Sn0.04)O3-0.02SnO2
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)0.96Sn0.04)O3-0.02SnO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4With Pb3O4、SnO2Taking into account the volatilization of PbO，Pb3O4The content needs to be excessive by 1 percent. Putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours, pouring out and drying;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA with the mass of 10 wt% of the powder and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000 plus materials and 1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material. The values of the withstand voltage and energy storage characteristics of the obtained ceramic samples are shown in table 1.
Example 4: pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.02SnO2-0.02TiO2
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.02SnO2-0.02TiO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4With Pb3O4、SnO2、TiO2Considering the volatilization of PbO, Pb3O4The content needs to be excessive by 1 percent. Putting all raw material powder into a planetary ball milling tank, and adding anhydrousMixing ethanol, ball milling for 4-6 hr, pouring out and drying;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA with the mass of 10 wt% of the powder and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the small crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000-1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material.
FIG. 6 shows the double hysteresis loop of the ceramic material prepared in this example 4 at 200 ℃ and 10Hz, as can be seen from the following graph: the AFE-FE phase transformation electric field is 127kV/cm, and the polarization intensity can reach 21.90 mu C/cm2Effective energy storage density of 1.78J/cm3The energy storage efficiency is up to 71.66%.
Example 5: pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.01SnO2-0.10TiO2
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)0.98Sn0.02)O3-0.01SnO2-0.10TiO2The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4With Pb3O4、SnO2、TiO2Considering the volatilization of PbO, Pb3O4The content needs to be excessive by 1 percent. Putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours, pouring out and drying;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA with the mass of 10 wt% of the powder and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the small crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000-1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material. The values of the withstand voltage and energy storage characteristics of the obtained ceramic samples are shown in table 1.
Comparative example 1: pb (Yb)1/2Nb1/2)O3
(a) Yb of2O3And Nb2O5According to YbNbO4The stoichiometric ratio of (A) is accurately weighed, the mixture is placed in a planetary ball milling tank, absolute ethyl alcohol is added, and the mixture is dried after being mixed for 4 to 6 hours. Insulating at 1000-;
(b) according to the chemical formula Pb ((Yb)1/2Nb1/2)O3The stoichiometric ratio of (A) to (B) accurately weigh the pre-synthesized niobate YbNbO4With Pb3O4Considering the volatilization of PbO, Pb3O4The content needs to be excessive by 1 percent. Putting all the raw material powder into a planetary ball milling tank, adding absolute ethyl alcohol, mixing and ball milling for 4-6 hours, pouring out and drying;
(c) sieving and briquetting the uniformly mixed powder, placing the powder in a high-temperature furnace, and synthesizing for 2 hours at the temperature of 800-;
(d) crushing, grinding and sieving the synthesized blocks, putting the blocks into a ball milling tank of a high-energy ball milling tank, adding absolute ethyl alcohol, ball milling for 1-2 hours at the rotating speed of 1000r/min, pouring out and drying;
(e) adding PVA with the mass of 10 wt% of the powder and the concentration of 5 wt% into the powder obtained after ball milling for granulation, performing compression molding under 200MPa, and performing heat preservation on the biscuit subjected to compression molding at the temperature of 550 ℃ for 3-4 hours to discharge organic components;
(f) and placing the biscuit subjected to gel removal on a crucible plate, embedding the biscuit in the pre-synthesized powder with the same components, covering a small crucible, sealing a gap between the crucible and the crucible plate by using the pre-synthesized powder, covering a large crucible, keeping a lead atmosphere, and sintering at the temperature of 1000 plus materials and 1200 ℃ for 2-4 hours to obtain the niobium ytterbium acid lead-based antiferroelectric ceramic material.
FIG. 7 is a graph showing the hysteresis loop of the ceramic material prepared in comparative example 1 at 200 ℃ and 10Hz, as seen from the following: pure phase Pb (Yb)1/2Nb1/2)O3Under high temperature and high electric field, the antiferroelectric ceramic has no AFE-FE phase transformation trend, and the phase transformation electric field is far higher than the breakdown field strength and can not meet the application requirements.
Table 1 shows the values of the relevant parameters of the dielectric breakdown characteristic and the energy storage characteristic of the ceramic sample obtained in the present invention:
as is clear from FIGS. 1 to 7 and Table 1, Pb ((Yb)1/2Nb1/2)1-xSnx)O3-ySnO2-zTiO2(0.00<x<0.10，0.00<y<0.20，0.00≤z<0.20) has high breakdown field strength and high energy storage density at high temperature (150-200 ℃), and the AFE-FE phase change electric field has the following Sn4+、Ti4+The doping amount is increased and reduced, so the method is expected to be applied to the fields of high-density energy storage capacitors, high-power pulse power supplies and the like in high-temperature working environments.
It is necessary to point out here: the above examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations of the present invention by those skilled in the art based on the foregoing descriptions are within the scope of the present invention.
Claims (9)
1. The lead niobate ytterbate-based antiferroelectric ceramic material is characterized by comprising the following components in a general formula: pb ((Yb)1/2Nb1/2)1-xSnx)O3-ySnO2-zTiO2Wherein x, y and z are molar ratio, x is more than 0.00 and less than 0.10, y is more than 0.00 and less than 0.20, and z is more than or equal to 0.00 and less than 0.20.
2. The lead niobate ytterbate-based antiferroelectric ceramic material as claimed in claim 1, wherein the effective energy storage density of the lead niobate ytterbate-based antiferroelectric ceramic material is 1.26-2.79J/cm under the test condition of 10Hz at 180-200 ℃3And the energy storage efficiency is 53.73-88.54%.
3. A method for preparing a lead niobate ytterbate-based antiferroelectric ceramic material according to claim 1 or 2, comprising:
(1) using niobate YbNbO4Powder, Pb3O4Powder and SnO2Powder and TiO2The powder is taken as a raw material, and is weighed and mixed according to the general formula of the lead ytterbium niobate-based antiferroelectric ceramic material to obtain mixed powder;
(2) pre-burning the obtained mixed powder at 800-900 ℃ to obtain pre-burned powder;
(3) mixing the pre-sintered powder and a binder, granulating, and performing compression molding to obtain a biscuit;
(4) and (3) removing the glue from the obtained biscuit, and sintering at 1000-1200 ℃ for 2-4 hours to obtain the lead ytterbium niobate-based antiferroelectric ceramic material.
4. The process according to claim 3, wherein Yb is prepared by mixing Yb with a solvent2O3Powder and Nb2O5Powder according toNiobate YbNbO4The niobate YbNbO is obtained by calcining for 2 to 4 hours at the temperature of 1000 to 1200 ℃ after being weighed and mixed according to the stoichiometric ratio4。
5. The method according to claim 3 or 4, wherein the Pb is3O4The molar content of the powder needs to be excessive by 0.3-1.3%, and the preferable content is 1%.
6. The production method according to any one of claims 3 to 5, wherein the pre-firing is performed for 2 to 3 hours, preferably 2 hours.
7. The preparation method according to any one of claims 3 to 6, wherein the temperature of the binder removal is 550 to 600 ℃ and the time is 3 to 4 hours; preferably, the temperature of the binder removal is 550 ℃.
8. The production method according to any one of claims 3 to 7, wherein the atmosphere for sintering is a Pb atmosphere.
9. The method according to claim 8, wherein, before sintering, the obtained green body is placed on a crucible plate and covered with a small crucible after being embedded with the pre-sintered powder, and then the gap between the small crucible and the crucible plate is sealed with the pre-sintered powder and covered with a large crucible again, thereby allowing a Pb atmosphere to be generated during sintering.
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