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US-12620529-B1 - Ferroelectric-piezoelectric ceramic energy storage materials, hybrid process preparation methods, and use thereof

US12620529B1US 12620529 B1US12620529 B1US 12620529B1US-12620529-B1

Abstract

A ferroelectric-piezoelectric ceramic energy storage material and a hybrid process preparation method and use thereof are provided. The ferroelectric-piezoelectric ceramic energy storage material is prepared with micro-nano composite structured particles formed by uniformly mixing polycrystalline powder with sol followed by heat-treatment, the micro-nano composite structured particles including the polycrystalline powder and a nanoscale PLZS component layer distributed around the polycrystalline powder. The method includes preparing sol and polycrystalline powder; performing heat-treatment on the sol and the polycrystalline powder to obtain micro-nano composite structured particles; and obtaining a ferroelectric-piezoelectric ceramic energy storage material sample through a casting process and sintering. By mixing with sol components, the specific surface area and oxygen vacancy content are increased, which is beneficial for reducing the sintering temperature of ceramic materials and improving their dielectric energy storage performance.

Inventors

  • Manwen Yao
  • Cangjin Li
  • Xi Yao

Assignees

  • TONGJI UNIVERSITY

Dates

Publication Date
20260505
Application Date
20250518
Priority Date
20250108

Claims (8)

  1. 1 . A ferroelectric-piezoelectric ceramic energy storage material, comprising micro-nano composite structured particles formed by uniformly mixing polycrystalline powder with sol followed by heat treatment, wherein the micro-nano composite structured particles comprise the polycrystalline powder and a nanoscale PLZS component layer distributed around the polycrystalline powder, wherein a chemical formula of the polycrystalline powder is (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O 3 .
  2. 2 . The ferroelectric-piezoelectric ceramic energy storage material of claim 1 , wherein a weight ratio of the sol to the polycrystalline powder is (1-3):5.
  3. 3 . The ferroelectric-piezoelectric ceramic energy storage material of claim 2 , wherein a chemical formula of the nanoscale PLZS component layer is (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O 3 .
  4. 4 . A hybrid process preparation method for the ferroelectric-piezoelectric ceramic energy storage material as claimed in claim 3 , comprising: S 1 , preparing the sol and the polycrystalline powder, respectively; S 2 , mixing the sol and the polycrystalline powder and removing organic matter by heat treatment to obtain the micro-nano composite structured particles; S 3 , mixing the micro-nano composite structured particles with a solvent, a binder, a dispersant, and a plasticizer to obtain a casting slurry; wherein the solvent is a mixture of ethanol and trichloroethylene, the binder is polyvinyl butyral, the dispersant is triethyl phosphate, the plasticizer is dibutyl phthalate; and a mass ratio of the micro-nano composite structured particles to the solvent, the binder, the dispersant, and the plasticizer is 20:20:2:0.4:0.8; S 4 , obtaining a thick film by defoaming and casting the casting slurry; S 5 , obtaining a ceramic green body by shearing, stacking, and hot pressing the thick film; and S 6 , obtaining a ferroelectric-piezoelectric ceramic energy storage material sample by performing binder removal and sintering on the ceramic green body.
  5. 5 . The method of claim 4 , wherein in S 1 , the sol is prepared by a process including: S 111 , weighing lead acetate, lanthanum acetate, zirconium n-propanol, and tin isopropanol according to a stoichiometric ratio; S 112 , dissolving the lead acetate and the lanthanum acetate in acetic acid, heating to 110° C. while stirring, and cooling to obtain a solution A; dissolving the zirconium n-propanol and the tin dioxide in ethylene glycol monomethyl ether, followed by mixing and stirring to obtain a mixture, introducing acetylacetone to the mixture and stirring uniformly to obtain a solution B, wherein a molar ratio of the acetylacetone to PLZS in the sol is 1.1:1; and S 113 , introducing the solution B into the solution A, and mixing and stirring uniformly to obtain a mixed solution, and adjusting a concentration, a pH, and a viscosity of the mixed solution by adding deionized water, the acetic acid, and the ethylene glycol sequentially, and after stirring, adjusting a volume of the mixed solution with the acetic acid to obtain the sol, wherein the concentration of the mixed solution is in a range of 0.027 g/mL to 0.08 g/mL, the pH of the mixed solution is in a range of 3 to 5, and the viscosity of the mixed solution is in a range of 7 cP to 9 cP.
  6. 6 . The method of claim 4 , wherein in S 1 , the polycrystalline powder is prepared by a process including: S 121 , mixing lead tetroxide, lanthanum trioxide, zirconium dioxide, tin dioxide, hafnium dioxide, and titanium dioxide according to a stoichiometric ratio and performing a first ball milling to obtain a first mixture, wherein a time of the first ball milling is in a range of 20 h to 30 h; S 122 , drying the first mixture, and pre-sintering the first mixture at a temperature of 900° C. with a holding time of 1 h to 3 h, and cooling the first mixture to room temperature in a furnace to obtain a pre-sintered mixture; and S 123 , performing a second ball milling on the pre-sintered mixture to obtain a second mixture, and drying the second mixture to obtain the polycrystalline powder, wherein a time of the second ball milling is in a range of 20 h to 30 h.
  7. 7 . The method of claim 4 , wherein in S 2 , a temperature of the heat treatment is 600° C., a holding time of the heat treatment is in a range of 5 h to 7 h, and the micro-nano composite structured particles are cooled to room temperature in a furnace.
  8. 8 . The method of claim 4 , wherein in S 6 , a temperature of the binder removal is 600° C., a holding time of the binder removal is in a range of 7 h to 10 h, a debinded ceramic green body is cooled to room temperature in a furnace, a temperature of the sintering is in a range of 1100° C. to 1130° C., a holding time of the sintering is 3 h, and a sintered ceramic green body is cooled to room temperature in a furnace.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Chinese Patent Application No. 202510033909.5, filed on Jan. 8, 2025, the contents of which are hereby incorporated by reference to its entirety. TECHNICAL FIELD The present disclosure relates to the technical field of ferroelectric-piezoelectric ceramic material, and in particular, to a ferroelectric-piezoelectric ceramic energy storage material, a hybrid process preparation method, and use thereof. BACKGROUND With the development of electronic information technology, ceramic capacitors, as an important electronic component, play an irreplaceable role in the electronics industry. Dielectric energy storage is an important application of ceramic capacitors, which places new demands on the performance of dielectric ceramic materials. Lead zirconate-based ferroelectric-piezoelectric ceramic energy storage materials have advantages such as high power density, fast discharge rate, and long service life, making them important candidate materials for pulse power electronic components. However, their application in electronic energy storage devices is limited by relatively low energy storage density and high sintering temperature, which results from the co-sintering process of dielectric ceramic materials with internal electrodes in multilayer ceramic capacitors requiring the ceramic materials to have sufficiently low sintering temperature. Taking the 70/30 palladium-silver electrode as an example, its annealing temperature is 1150° C., while the sintering temperature of lead zirconate-based energy storage ceramics is generally around 1300° C. Therefore, it is necessary to reduce the sintering temperature of lead zirconate-based ceramic materials. At present, it is generally recognized that the addition of glass is an effective means of reducing the sintering temperature. In Chinese Patent Application No. 202010798450.5, the sintering temperature of lead-barium-lanthanum-zirconium-Tin ceramic doped with barium-borosilicate glass phase is reduced to 1050° C., and the energy storage density is increased to 6.3 J/cm3. In Chinese Patent Application No. 202211297267.2, by adding BaCO3—B2O3—SiO2—K2CO3 glass phase, the sintering temperature of the ceramic material with a chemical formula of Pb0.95 La0.02Sr0.02 (Zr0.5Sn0.4Ti0.1)O3 is reduced from 1300° C. to 960° C., but its energy storage density is only 3.2 J/cm3. In these disclosures, the addition of glass is not very effective for the enhancement of energy storage properties, even reducing the dielectric constant of the materials. For ferroelectric-piezoelectric ceramic energy storage materials or other functional ceramic materials, it is conducive to saving energy and lowering the production cost by reducing the sintering temperature. Therefore, it is an urgent technical problem about how to improve the performance of energy storage materials while reducing the sintering temperature. SUMMARY The purpose of the present disclosure is to provide a ferroelectric-piezoelectric ceramic energy storage material, a hybrid process preparation method, and use thereof. By mixing and calcining polycrystalline powder with sol, micro-nano composite structured particles are formed, which increases the specific surface area and oxygen vacancy content, thereby reducing the sintering temperature of the ceramic material and improving the dielectric energy storage performance of ceramic materials. In order to realize the above purpose, the present disclosure provides a ferroelectric-piezoelectric ceramic energy storage material, comprising micro-nano composite structured particles formed by uniformly mixing polycrystalline powder with sol followed by heat-treatment, the micro-nano composite structured particles including the polycrystalline powder and a nanoscale PLZS component layer distributed around the polycrystalline powder. In some embodiments, a weight ratio of the sol to the polycrystalline powder is (1-3):5. In some embodiments, a chemical formula of the nanoscale PLZS component layer is (Pb0.97La0.02)(Zr0.6Sn0.4)O3. In some embodiments, a chemical formula of the polycrystalline powder is (Pb0.94La0.04)(Zr0.51Sn0.47Hf0.06Ti0.01)O3. In some embodiments, a hybrid process preparation method for a ferroelectric-piezoelectric ceramic energy storage material comprises: S1, preparing sol and polycrystalline powder, respectively; S2, mixing the sol and the polycrystalline powder, and removing organic matter by heat treatment to obtain micro-nano composite structured particles; S3, mixing the micro-nano composite structured particles with a solvent, a binder, a dispersant, and a plasticizer to obtain a casting slurry; S4, obtaining a thick film by defoaming and casting the casting slurry; S5, obtaining a ceramic green body by shearing, stacking, and hot pressing the thick film; and S6, obtaining a ferroelectric-piezoelectric ceramic energy storage material sample by performing binder removal and sintering on the c