CN116514547B - Lead ytterbium niobate-based antiferroelectric ceramic material and preparation method and application thereof - Google Patents
Lead ytterbium niobate-based antiferroelectric ceramic material and preparation method and application thereof Download PDFInfo
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- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 46
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910010293 ceramic material Inorganic materials 0.000 title claims description 49
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000004146 energy storage Methods 0.000 claims abstract description 70
- 239000000919 ceramic Substances 0.000 claims abstract description 62
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000010955 niobium Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 5
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 29
- 230000015556 catabolic process Effects 0.000 description 22
- 230000005684 electric field Effects 0.000 description 18
- 230000010287 polarization Effects 0.000 description 14
- 230000007704 transition Effects 0.000 description 13
- 230000008859 change Effects 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910001427 strontium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005620 antiferroelectricity Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
Compared with the prior art, the invention adopts A, B-site codoped component design and process optimization at the same time, can prepare the lead ytterbium niobate based antiferroelectric ceramic with excellent energy storage density (13.39J/cm 3) and high energy storage efficiency (76.17%), and can still maintain the ultrahigh energy storage density (9.52J/cm 3) and excellent energy storage efficiency (86.39%) at 150 ℃, thereby having important extremely high reference significance and practical value for further developing novel antiferroelectric ceramic capacitors with high energy storage performance.
Description
Technical Field
The invention relates to the technical field of functional ceramics, in particular to a lead ytterbium niobate-based antiferroelectric ceramic material and a preparation method and application thereof.
Background
The great demand for energy has led to great attention in the industry and academia for energy storage devices. Ceramic dielectric capacitors are known for their ultra-high power density, which means that stored energy can be released at ultra-high speeds, making them widely used in pulsed power systems. However, ceramic dielectric capacitors have a limited amount of power that can be released in one pass compared to electrochemical capacitors and other energy storage devices, which limits their further applications. In order to break through the miniaturization and weight reduction of the pulse power system, it is highly demanded to increase the energy storage density of the ceramic dielectric capacitor. The evaluation of its energy storage performance is based mainly on total energy storage density, recoverable energy storage density and energy storage efficiency, depending on the maximum polarization, remnant polarization and applied electric field. It can be seen that the maximum polarization and breakdown strength are critical to improve the energy storage properties of the ceramic. Adjacent dipoles in the antiferroelectric material are arranged in antiparallel, and electric dipole moments cancel each other out, so that macroscopic polarization is zero. When the applied voltage reaches a certain value, the dipole is reversed and the polarization increases significantly, while the material undergoes a transition from the antiferroelectric phase to the ferroelectric phase. These characteristics are unique advantages of antiferroelectric materials, making them more efficient in energy storage than ferroelectric and linear dielectric materials, and more suitable for practical applications.
As a novel antiferroelectric material, lead niobate ytterbium acid has great advantages and potential in the aspect of developing dielectric materials with high energy storage performance by virtue of extremely high phase change electric fields. And its sintering temperature is extremely low (about 950 ℃) which is advantageous for saving the manufacturing costs. However, the problem of mismatch between the breakdown and phase change fields severely limits the energy storage performance. For this purpose, a high breakdown field strength is necessary for achieving its energy storage properties. At present, a part of work aiming at improving the breakdown field strength of the antiferroelectric ceramic has been reported, for example, chinese patent No. CN201910555610.0, which is an antiferroelectric ceramic material and a preparation method thereof (issued bulletin No. CN 110342925A), and the breakdown field strength is improved from 270 to kV/cm to about 340 kV/cm through component regulation. For example, the invention of China patent No. CN202211065993.1, a lead zirconate stannate-based antiferroelectric ceramic material, a preparation method and application thereof (grant bulletin No. CN 115611627A), in which the breakdown field strength is improved from 370 kV/cm to about 500 kV/cm by means of component regulation. The energy storage performance at high temperature is also an important factor for measuring the excellent performance of ceramic dielectric capacitors, and tin oxide is introduced into a lead ytterbium niobate system by Li et al, and finally, the energy storage density of 2.38J/cm 3 and the energy storage efficiency of 67.9% are obtained at 180 ℃. From the current report, the development of antiferroelectric ceramics with high breakdown field strength and good energy storage performance at high temperature is still a key to further develop the energy storage potential of antiferroelectric ceramics, and has important significance for promoting the development of pulse capacitors with high energy storage density and high discharge speed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lead ytterbium niobate based antiferroelectric ceramic material and a preparation method and application thereof, and simultaneously adopts A, B-bit codoped component design and process optimization, on the component design, the B-bit introduced Fe 3+ reduces the B-bit order of the lead ytterbium niobate ceramic, improves the energy storage efficiency, further reduces the sintering temperature, and the A-bit introduced Sr 2+ enhances the antiferroelectric property of the lead ytterbium niobate based antiferroelectric ceramic, thereby greatly improving the energy storage performance. In the preparation process, the microstructure of the ceramic material is improved by adopting hot-pressing sintering so as to improve the breakdown field intensity, the problem that the phase-change electric field of the lead ytterbium niobate antiferroelectric ceramic is not matched with the breakdown electric field is solved, and the prepared lead ytterbium niobate antiferroelectric ceramic has high energy storage performance at room temperature and high temperature.
The aim of the invention can be achieved by the following technical scheme:
The first object of the invention is to provide a preparation method of a lead ytterbium niobate based antiferroelectric ceramic material, which comprises the following steps:
Step1: mixing a lead source, a strontium source, an iron source, an ytterbium source and a niobium source to obtain a mixture;
Step 2: sequentially ball milling, discharging, drying and calcining the mixture obtained in the step 1 to obtain calcined powder;
Step 3: sequentially performing secondary ball milling and drying on the calcined powder obtained in the step 2 to obtain dry powder, mixing the dry powder with a polyvinyl alcohol solution, and sequentially performing granulation and compression molding to obtain a ceramic blank;
Step 4: and sequentially carrying out glue discharging and hot-pressing sintering on the ceramic blank to obtain the antiferroelectric ceramic material, wherein the chemical general formula of the antiferroelectric ceramic material is (Pb 1-xSrx)(Yb0.47Fe0.03Nb0.5)O3, wherein x is more than or equal to 0 and less than or equal to 0.12).
Further, in step 1, the lead source comprises Pb 3O4, the strontium source comprises SrCO 3, the iron source comprises Fe 2O3, the ytterbium source comprises Yb 2O3, and the niobium source comprises Nb 2O5.
Further, the Pb 3O4、SrCO3、Fe2O3、Yb2O3 and Nb 2O5 were weighed according to the chemical composition of (Pb 1-xSrx)(Yb0.47Fe0.03Nb0.5)O3), respectively.
Further, the purity of both Pb 3O4、SrCO3、Fe2O3、Yb2O3 and Nb 2O5 is greater than 99wt%.
Preferably, in the step 2, the time of the ball milling process is 14-16 h; the secondary ball milling time in the step 3 is 14-16 h.
Further preferably, in step 2, the ball milling time is 15 h; in the step 3, the time of the secondary ball milling is 15 h.
Preferably, the ball milling and the secondary ball milling are carried out by placing raw materials into a ball milling tank, adding ball milling medium which is absolute ethyl alcohol, and then placing into a planetary ball mill, wherein the rotating speed of the ball mill is 300 r/min.
Preferably, in step 2, the calcination temperature is 800 ℃ and the calcination time is 3 h.
Preferably, in step 2, the calcination is performed in a muffle furnace.
Preferably, in the step 3, the mass concentration of the polyvinyl alcohol solution is 6-10%.
Preferably, in step 3, the pressure used for the compression molding is 6-10 MPa.
Further preferably, in step S3, the mass concentration of the polyvinyl alcohol solution is 8%.
Further preferably, in step S3, the pressure used for the compression molding is 6 MPa.
Preferably, in step 4, the temperature of the adhesive discharging is 600 ℃, and the adhesive discharging time is 10 h.
Preferably, in step 4, the glue discharging is performed in a muffle furnace.
Preferably, in the step 4, the sintering process is performed in a hot-pressing sintering furnace, the temperature of the sintering process is 900 ℃, the sintering pressure is 1.5 t, the diameter of an inner hole of a hot-pressing sintering mold is 20 mm, the heat-preserving and pressure-maintaining time is 2h, the rate of heating to the sintering temperature is 3-5 ℃/min, and the pressure-increasing rate is 0.04 t/min.
Further, polishing the lead ytterbium niobate-based antiferroelectric ceramic material obtained in the step 4 by using sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface.
A second object of the present invention is to provide a lead ytterbium niobate-based antiferroelectric ceramic material having a chemical formula of (Pb 1-xSrx)(Yb0.47Fe0.03Nb0.5)O3, wherein 0.ltoreq.x.ltoreq.0.12).
Preferably, x= 0,0.04,0.08 or 0.12.
Preferably, the lead ytterbium niobate based antiferroelectric ceramic material has excellent energy storage density (13.39J/cm 3) and high energy storage efficiency (76.17%) at room temperature while still maintaining ultra high energy storage density (9.52J/cm 3) and excellent energy storage efficiency (86.39%) at 150 ℃.
Further, by adopting a A, B-bit co-doped component design and process optimization, on the component design, the B-bit order of the lead ytterbium niobate ceramic is reduced by introducing Fe 3+ at the B-bit, the energy storage efficiency of the antiferroelectric ceramic material is improved, and the sintering temperature is further reduced; the anti-ferroelectricity of the lead ytterbium niobate-based anti-ferroelectric ceramic is enhanced by introducing Sr 2+ at the A site, so that the energy storage performance of the anti-ferroelectric ceramic material is greatly improved.
Further, the antiferroelectric ceramic material has high energy storage performance at both room temperature and high temperature.
The third object of the invention is to provide an application of the lead ytterbium niobate based antiferroelectric ceramic material, and the lead ytterbium niobate based antiferroelectric ceramic material is used in the field of ceramic capacitors.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention discloses a lead ytterbium niobate based antiferroelectric ceramic material, which is a novel energy storage material, has an extremely high phase change electric field, and shows that the lead ytterbium niobate based antiferroelectric ceramic material has extremely high energy storage potential, but at room temperature, the phase change electric field is higher than breakdown, so that the energy storage performance of the lead ytterbium niobate based antiferroelectric ceramic material cannot be fully shown, and the preparation process and element doping cooperative regulation are adopted to construct the lead ytterbium niobate based antiferroelectric ceramic material with high phase change electric field characteristics.
2) Compared with the traditional solid-phase sintering, the hot-press sintering has the effect of refining the grains, and the breakdown electric field of the ceramic can be greatly increased along with the refinement of the grains.
3) According to the invention, the iron ions are introduced into the B site, so that the sintering temperature can be further reduced, and the phase-change electric field and the breakdown field intensity of the ceramic are at proper levels, thereby being beneficial to full polarization of the ceramic. Strontium ions are selected to enhance the stability of the lead ytterbium niobate-based antiferroelectric ceramic, so that the phase change electric field and the breakdown field intensity are synchronously improved, and the energy storage performance of the ceramic is greatly improved. And the introduction of strontium ions makes the electric hysteresis loop of the ceramic finer, improves the energy storage density, and can realize the great improvement of the comprehensive energy storage performance of the lead ytterbium niobate antiferroelectric ceramic by reasonably controlling the doping amount of the strontium ions.
4) The invention realizes that the sample can still maintain the ultrahigh energy storage performance at high temperature. As the temperature increases, the phase change electric field of the ceramic is slightly reduced, but sufficient polarization of the ceramic is facilitated. And the electric hysteresis loop is finer, and the energy storage density is greatly improved.
5) The ceramic matrix system selected by the invention is novel, provides a new direction for the selection of energy storage materials in the future, and digs the potential energy storage performance of the ceramic matrix system, thereby having extremely high research and application values.
Drawings
Fig. 1 shows the hysteresis loops of antiferroelectric ceramics prepared in the first, second, third, and fourth embodiments at room temperature, wherein the abscissa E represents the electric field intensity and the ordinate P represents the polarization intensity;
Fig. 2 is data of the antiferroelectric ceramics prepared in example one, example two, example three, and example four in terms of effective energy storage density and energy storage efficiency;
fig. 3 is data of antiferroelectric ceramics prepared in example one, example two, example three, and example four in terms of breakdown field strength, phase change electric field, and maximum polarization value;
Fig. 4 is an XRD pattern at room temperature of the antiferroelectric ceramics prepared in example one, example two, example three, and example four;
fig. 5 is an SEM photograph of the antiferroelectric ceramics prepared in the first, second, third, and fourth examples after the hot etching treatment;
Fig. 6 shows the hysteresis loop of the antiferroelectric ceramic prepared in example three at high temperature, with the abscissa E being the electric field strength and the ordinate P being the polarization strength;
fig. 7 is data on effective energy storage density and energy storage efficiency at high temperature for the antiferroelectric ceramic prepared in example three.
Fig. 8 is a photograph of TEM morphology at different temperatures of the antiferroelectric ceramic prepared in example three.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
Example 1
In this embodiment, a lead ytterbium niobate-based antiferroelectric ceramic material is provided, and the chemical general formula of the material is Pb (Yb 0.47Fe0.03Nb0.5)O3.
The preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material comprises the following steps:
(1) Pb 3O4、Fe2O3、Yb2O3 and Nb 2O5 with purity more than 99% are selected as raw materials of the antiferroelectric ceramic material, and are respectively weighed and mixed according to chemical compositions to obtain a mixture;
(2) Sequentially carrying out 15 h ball milling, discharging, drying and 800 ℃ calcining on the mixture for 3h to obtain calcined powder;
(3) Sequentially carrying out secondary ball milling and drying on the calcined powder to obtain dry powder;
(4) Mixing the dry powder with 8wt% polyvinyl alcohol solution (the mass volume ratio of the mixing process is 0.3mL polyvinyl alcohol solution/g dry powder), and then sequentially granulating and compacting under 6 MPa to obtain a ceramic blank;
(5) Placing the ceramic blank in a muffle furnace to perform 10 h glue discharging treatment at 600 ℃, sintering the ceramic blank in a hot-pressing sintering furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, heating to 900 ℃ at a heating rate of 3 ℃/min, heating up to 1.5t while heating up secondarily, and preserving heat for 2h to obtain the antiferroelectric ceramic material.
The ferroelectric hysteresis loop, energy storage density and energy storage efficiency, breakdown field strength and phase change, XRD pattern and SEM photograph of the antiferroelectric ceramic sample obtained in the first example are shown in fig. 1 to 5, respectively. From the electrical property test, it can be seen from FIGS. 1,2 and 3 that the sample in the first embodiment has the phase transition type of antiferroelectric-ferroelectric transition, the breakdown field strength of 490 kV/cm, the antiferroelectric-ferroelectric phase transition electric field of 420 kV/cm, the maximum polarization value of 35.79 μC/cm 2, and the energy storage density of 8.03J/cm 3 and the energy storage efficiency of 67.82%. In terms of structure, XRD patterns and SEM pictures in figures 4 and 5 show that the prepared sample has a pure orthorhombic perovskite structure and no impurity phase, the crystal crystallization performance is good, the structure is compact, and the average grain size after heat corrosion treatment is smaller (1.42 mu m).
Example two
In this embodiment, a lead ytterbium niobate-based antiferroelectric ceramic material is provided, and has a chemical formula (Pb 0.96Sr0.04) (Yb0.47Fe0.03Nb0.5)O3).
The preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material comprises the following steps:
(1) Pb 3O4、SrCO3、Fe2O3、Yb2O3 and Nb 2O5 with purity more than 99% are selected as raw materials of the antiferroelectric ceramic material, and are respectively weighed and mixed according to chemical compositions to obtain a mixture;
(2) Sequentially carrying out 15 h ball milling, discharging, drying and 800 ℃ calcining on the mixture for 3h to obtain calcined powder;
(3) Sequentially carrying out secondary ball milling and drying on the calcined powder to obtain dry powder;
(4) Mixing the dry powder with 8wt% polyvinyl alcohol solution (the mass volume ratio of the mixing process is 0.3mL polyvinyl alcohol solution/g dry powder), and then sequentially granulating and compacting under 6 MPa to obtain a ceramic blank;
(5) Placing the ceramic blank in a muffle furnace to perform 10 h glue discharging treatment at 600 ℃, sintering the ceramic blank in a hot-pressing sintering furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, heating to 900 ℃ at a heating rate of 3 ℃/min, heating up to 1.5t while heating up secondarily, and preserving heat for 2h to obtain the antiferroelectric ceramic material.
The ferroelectric hysteresis loop, energy storage density and energy storage efficiency, breakdown field strength and phase change, XRD pattern and SEM photograph of the antiferroelectric ceramic sample obtained in the second example are shown in fig. 1 to 5, respectively. From the electrical performance test, it can be seen from fig. 1,2 and 3 that the phase transition type of the sample in the second embodiment is antiferroelectric-ferroelectric transition, the breakdown field strength is obviously improved to 620 kV/cm compared with the first embodiment, the antiferroelectric-ferroelectric phase transition electric field is 575 kV/cm, the maximum polarization value is slightly improved to 36.71 μc/cm 2, and thus the better energy storage performance is obtained: the energy storage density is 11.39J/cm 3, and the energy storage efficiency is 73.01%. In terms of structure, XRD patterns and SEM pictures in figures 4 and 5 show that the prepared sample has a pure orthorhombic perovskite structure and no impurity phase, the crystal crystallization performance is good, the structure is compact, and the average grain size after heat corrosion treatment is smaller (1.40 mu m).
Example III
In this embodiment, a lead ytterbium niobate-based antiferroelectric ceramic material is provided, and has a chemical formula (Pb 0.92Sr0.08) (Yb0.47Fe0.03Nb0.5)O3).
The preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material comprises the following steps:
(1) Pb 3O4、SrCO3、Fe2O3、Yb2O3 and Nb 2O5 with purity more than 99% are selected as raw materials of the antiferroelectric ceramic material, and are respectively weighed and mixed according to chemical compositions to obtain a mixture;
(2) Sequentially carrying out 15 h ball milling, discharging, drying and 800 ℃ calcining on the mixture for 3h to obtain calcined powder;
(3) Sequentially carrying out secondary ball milling and drying on the calcined powder to obtain dry powder;
(4) Mixing the dry powder with 8wt% polyvinyl alcohol solution (the mass volume ratio of the mixing process is 0.3mL polyvinyl alcohol solution/g dry powder), and then sequentially granulating and compacting under 6 MPa to obtain a ceramic blank;
(5) Placing the ceramic blank in a muffle furnace to perform 10 h glue discharging treatment at 600 ℃, sintering the ceramic blank in a hot-pressing sintering furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, heating to 900 ℃ at a heating rate of 3 ℃/min, heating up to 1.5t while heating up secondarily, and preserving heat for 2h to obtain the antiferroelectric ceramic material.
The ferroelectric hysteresis loop, energy storage density and energy storage efficiency, breakdown field strength and phase change, XRD pattern and SEM photograph of the antiferroelectric ceramic sample obtained in this example three are shown in fig. 1 to 5, respectively. From the electrical property test, it can be seen from fig. 1,2 and 3 that the sample phase transition type in the third embodiment is antiferroelectric-ferroelectric transition, the breakdown field strength is obviously improved compared with the second embodiment, namely 690 kV/cm, the antiferroelectric-ferroelectric phase transition electric field is 610 kV/cm, the maximum polarization value is slightly improved to 37.59 μc/cm 2, and the excellent energy storage performance is obtained by the method: the energy storage density is 13.39J/cm 3, and the energy storage efficiency is 76.17%. As can be seen from fig. 6 and 7, the samples in the third embodiment show good energy storage performance at high temperature, and high energy storage density of 10J/cm 3 and energy storage efficiency of 85% can be obtained at the temperature higher than 100 ℃. The sample in example three still maintained an ultra high energy storage density (9.52J/cm 3) and excellent energy storage efficiency (86.39%) at 150 ℃. In terms of structure, XRD patterns and SEM pictures in figures 4 and 5 show that the prepared sample has a pure orthorhombic perovskite structure and no impurity phase, the crystal crystallization performance is good, the structure is compact, and the average grain size after heat corrosion treatment is smaller (1.21 mu m). The TEM morphology photographs at different temperatures in fig. 8 show that at temperatures below 170 ℃ the domain morphology of the ceramic is a mixture of 180 ° domains with antiferroelectric features and 60 ° domains with orthorhombic features. It can be stated that the phase structure of the ceramic is quite stable from room temperature to 170 ℃, which further explains the reason that the ceramic has good temperature stability. When the temperature is raised to 220 ℃, the 60 ° domains disappear, leaving some 180 ° domains, and the ceramic is transformed into tetragonal phase at this time. As the temperature increases further, the 180 ° domains disappear, and at this point the ceramic has crossed the curie temperature and changed into the cis-electric phase.
Example IV
In this embodiment, a lead ytterbium niobate-based antiferroelectric ceramic material is provided, and has a chemical formula (Pb 0.88Sr0.12) (Yb0.47Fe0.03Nb0.5)O3).
The preparation method of the lead ytterbium niobate-based antiferroelectric ceramic material comprises the following steps:
(1) Pb 3O4、SrCO3、Fe2O3、Yb2O3 and Nb 2O5 with purity more than 99% are selected as raw materials of the antiferroelectric ceramic material, and are respectively weighed and mixed according to chemical compositions to obtain a mixture;
(2) Sequentially carrying out 15 h ball milling, discharging, drying and 800 ℃ calcining on the mixture for 3h to obtain calcined powder;
(3) Sequentially carrying out secondary ball milling and drying on the calcined powder to obtain dry powder;
(4) Mixing the dry powder with 8wt% polyvinyl alcohol solution (the mass volume ratio of the mixing process is 0.3mL polyvinyl alcohol solution/g dry powder), and then sequentially granulating and compacting under 6 MPa to obtain a ceramic blank;
(5) Placing the ceramic blank in a muffle furnace to perform 10 h glue discharging treatment at 600 ℃, sintering the ceramic blank in a hot-pressing sintering furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, heating to 900 ℃ at a heating rate of 3 ℃/min, heating up to 1.5t while heating up secondarily, and preserving heat for 2h to obtain the antiferroelectric ceramic material.
The ferroelectric hysteresis loop, energy storage density and energy storage efficiency, breakdown field strength and phase change, XRD pattern and SEM photograph of the antiferroelectric ceramic sample obtained in the fourth example are shown in fig. 1 to 5, respectively. From the electrical property test, it can be seen from fig. 1,2 and 3 that the sample phase transition type in the fourth embodiment is antiferroelectric-ferroelectric transition, the breakdown field strength is slightly reduced to 670 kV/cm compared with the third embodiment, the antiferroelectric-ferroelectric phase transition electric field is obviously reduced to 545 kV/cm, the maximum polarization value is greatly reduced to 21.29 μC/cm 2, the performance is deteriorated, the energy storage density of the obtained sample is 6.93J/cm 3, and the energy storage efficiency is 78.57%. In terms of structure, XRD patterns and SEM pictures in figures 4 and 5 show that the prepared sample has a pure orthorhombic perovskite structure and no impurity phase, the crystal crystallization performance is good, the structure is compact, and the average grain size after heat corrosion treatment is smaller (1.05 mu m).
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. The preparation method of the lead ytterbium niobate based antiferroelectric ceramic material is characterized by comprising the following steps of:
Step 1: mixing a lead source, a strontium source, an iron source, an ytterbium source and a niobium source to obtain a mixture; in step 1, the lead source comprises Pb 3O4, the strontium source comprises SrCO 3, the iron source comprises Fe 2O3, the ytterbium source comprises Yb 2O3, and the niobium source comprises Nb 2O5;
Step 2: sequentially ball milling, discharging, drying and calcining the mixture obtained in the step 1 to obtain calcined powder;
Step 3: sequentially performing secondary ball milling and drying on the calcined powder obtained in the step 2 to obtain dry powder, mixing the dry powder with a polyvinyl alcohol solution, and sequentially performing granulation and compression molding to obtain a ceramic blank;
step 4: sequentially performing glue discharging and hot-pressing sintering on the ceramic blank to obtain an antiferroelectric ceramic material, wherein the chemical general formula of the antiferroelectric ceramic material is (Pb 1-xSrx)(Yb0.47Fe0.03Nb0.5)O3, wherein x is more than or equal to 0.04 and less than or equal to 0.08;
The prepared lead ytterbium niobate antiferroelectric ceramic has high energy storage performance at room temperature and high temperature;
In the step 4, the temperature in the sintering process is 900 ℃, the sintering pressure is 1.5 t, the diameter of the inner hole of the hot-pressing sintering die is 20mm, the heat preservation and pressure maintaining time is 2h, the rate of heating to the sintering temperature is 3-5 ℃/min, and the pressure increasing rate is 0.04 t/min.
2. The method for preparing a lead ytterbium niobate-based antiferroelectric ceramic material according to claim 1, wherein in step 2, the time of the ball milling process is 14-16 h;
The secondary ball milling time in the step 3 is 14-16 h.
3. The method for preparing a lead ytterbium niobate based antiferroelectric ceramic material according to claim 1, wherein in step 2, the temperature of the calcination process is 800 ℃ and the calcination time is3 h.
4. The method for preparing the lead ytterbium niobate-based antiferroelectric ceramic material according to claim 1, wherein in the step 3, the mass concentration of the polyvinyl alcohol solution is 6-10%;
In the step 3, the pressure adopted by the compression molding is 6-10 MPa.
5. The method for preparing the lead ytterbium niobate based antiferroelectric ceramic material according to claim 1, wherein in the step 4, the glue discharging temperature is 600 ℃ and the glue discharging time is 10 h.
6. The lead ytterbium niobate-based antiferroelectric ceramic material prepared by the preparation method according to any one of claims 1 to 5, wherein the antiferroelectric ceramic material has a chemical formula (Pb 1-xSrx)(Yb0.47Fe0.03Nb0.5)O3, wherein x is more than or equal to 0.04 and less than or equal to 0.08).
7. A lead ytterbium niobate based antiferroelectric ceramic material according to claim 6, wherein said x = 0.04 or 0.08.
8. Use of a lead ytterbium niobate-based antiferroelectric ceramic material obtained by the preparation process according to any one of claims 1 to 5 or according to any one of claims 6 to 7, characterized in that said antiferroelectric ceramic material is used in the field of ceramic capacitors.
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