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CN-121990825-A - Multi-element aliovalent ion co-doped AgNbO3Leadless antiferroelectric energy storage ceramic material and preparation method and application thereof

CN121990825ACN 121990825 ACN121990825 ACN 121990825ACN-121990825-A

Abstract

The invention discloses a multielement aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material, a preparation method and application thereof, wherein the chemical formula of the energy storage ceramic material is Ag 0.7‑ 3x Bi 0.1 Tm x Nb 0.9 Ta 0.1 O 3 , x is more than 0 and less than or equal to 0.05, and based on the Ag 0.7 Bi 0.1 Nb 0.9 Ta 0.1 O 3 antiferroelectric energy storage ceramic material, tm 3+ is introduced again at the A position to form a Bi 3+ and Tm 3+ at the A position, and Ta 5+ is co-doped with AgNbO 3 at the B position. According to the invention, under the synergistic effect of improving the stability of the antiferroelectric phase and the dielectric breakdown strength and the relaxation, the prepared Ag 0.655 Bi 0.1 Tm 0.015 Nb 0.9 Ta 0.1 O 3 energy storage ceramic material can obtain the energy storage density of 11.04J/cm 3 and the conversion efficiency of 79.62% under the action of 428kV/cm, which is about 4 times that of the AgNbO 3 ceramic material.

Inventors

  • SONG GUILIN
  • PAN QIANXI
  • ZHANG XIAOMING
  • SU JIAN
  • ZHANG NA
  • LI QIANKUN
  • ZHANG XINXIN
  • PAN HUAYING
  • Shang Pengyi

Assignees

  • 河南师范大学

Dates

Publication Date
20260508
Application Date
20260126

Claims (10)

  1. 1. A multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material is characterized in that the chemical formula of the energy storage ceramic material is Ag 0.7-3x Bi 0.1 Tm x Nb 0.9 Ta 0.1 O 3 , wherein x is 0< x and is less than or equal to 0.05, tm 3+ is introduced into the A site on the basis of the Ag 0.7 Bi 0.1 Nb 0.9 Ta 0.1 O 3 antiferroelectric energy storage ceramic material again, bi 3+ and Tm 3+ are formed at the A site, and Ta 5+ is co-doped with AgNbO 3 leadless antiferroelectric energy storage ceramic material at the B site.
  2. 2. The multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to claim 1, wherein the energy storage ceramic material has a single perovskite structure of Pbcm space group, two diffraction peaks (020) and (114) near 2θ=32 o are combined into one diffraction peak (114), the symmetry of the energy storage ceramic material is enhanced, the antiferroelectric phase of AgNbO 3 material is stabilized, the energy storage ceramic material has a compact microstructure, the porosity is extremely low, the crystal grains are uniformly distributed, the crystal grain boundary is clear, and the grain size is 2-4 mu m.
  3. 3. The multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to claim 1, wherein the chemical formula of the energy storage ceramic material is Ag 0.655 Bi 0.1 Tm 0.015 Nb 0.9 Ta 0.1 O 3 , the energy storage density is as high as 11.04J/cm 3 , the conversion efficiency is 79.62%, and the breakdown field strength is 428kV/cm.
  4. 4. A method for preparing the multielement aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to any one of claims 1-3, which is characterized by comprising the following specific preparation steps: Step S1, respectively weighing raw materials Ag 2 O、Bi 2 O 3 、Tm 2 O 3 、Nb 2 O 5 and Ta 2 O 5 according to the stoichiometric ratio of Ag 0.7-3x Bi 0.1 Tm x Nb 0.9 Ta 0.1 O 3 , wherein x is more than 0 and less than or equal to 0.05; s2, putting the weighed raw materials into a star ball mill, adding absolute ethyl alcohol as a medium for ball milling and drying to prepare mixed powder; Step 3, heating the mixed powder to 850-900 ℃ at a heating rate of 2-5 ℃ per minute under an oxygen atmosphere, presintering for 4-8 hours, performing secondary ball milling and drying on the presintered powder, and sieving the presintered powder; s4, adding an adhesive into the pre-sintered powder subjected to sieving treatment for granulation, and then carrying out isostatic pressing treatment to press the pre-sintered powder into a cylindrical blank; And S5, heating the cylindrical blank to 1050-1140 ℃ at a heating rate of 2-5 ℃ per minute under an oxygen atmosphere, sintering for 4-8 hours, cooling to 600 ℃ at a cooling rate of 2-5 ℃ per minute, and cooling to room temperature along with a furnace to obtain the Ag 0.7- 3x Bi 0.1 Tm x Nb 0.9 Ta 0.1 O 3 energy-storage ceramic material.
  5. 5. The method of preparing a multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to claim 4, wherein the purity of raw Ag 2 O in step S1 is higher than 99.7%, the purity of Bi 2 O 3 is higher than 99.9%, the purity of Tm 2 O 3 is higher than 99.9%, the purity of Nb 2 O 5 is higher than 99.99%, and the purity of Ta 2 O 5 is higher than 99.99%.
  6. 6. The preparation method of the multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material is characterized in that the ball milling process in the step S2 is ball milling at the rotating speed of 300-600 r/min for 18-24 h, and the sieving process in the step S3 is sieving by using a sieve with 100-200 meshes.
  7. 7. The preparation method of the multi-element aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to claim 4, wherein the binder in the step S4 is 4-6 wt.% polyvinyl alcohol aqueous solution, and the addition amount of the binder is 3-8 wt.% of the mass of the presintered powder.
  8. 8. The preparation method of the multielement aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material according to claim 4, wherein the pressing process in the step S4 is that a cylindrical blank with the diameter of 8mm and the thickness of 1mm is pressed under the isostatic pressure of 200-250 MPa.
  9. 9. Use of a multi-element aliovalent ion co-doped AgNbO 3 lead-free antiferroelectric energy storage ceramic material according to any one of claims 1-3 in the preparation of ceramic capacitors.
  10. 10. Use of a multi-element aliovalent ion co-doped AgNbO 3 lead-free antiferroelectric energy storage ceramic material according to any one of claims 1-3 in the preparation of a pulsed power capacitor.

Description

Multi-element aliovalent ion co-doped AgNbO 3 lead-free antiferroelectric energy storage ceramic material and preparation method and application thereof Technical Field The invention belongs to the technical field of dielectric ceramic materials, and particularly relates to a multielement aliovalent ion co-doped AgNbO 3 leadless antiferroelectric energy storage ceramic material, and a preparation method and application thereof. Background With the steady promotion of the national 'double carbon' strategy and the rapid development of high-end electronic equipment such as new energy power systems, electric automobiles, pulse power weapons, industrial frequency converters and the like, unprecedented urgent demands are placed on high-performance, high-reliability, miniaturized and light-weight energy storage capacitors. The performance of the dielectric material, which is the core component of the capacitor, directly determines the volume, efficiency and lifetime of the capacitor device and equipment. Currently, dielectric materials can be classified into two major classes, linear dielectric materials and nonlinear dielectric materials, wherein the linear dielectric materials, although having a higher breakdown electric field (E b) and lower dielectric loss, limit the space for increasing the energy storage density (W rec) due to their smaller maximum polarization intensity (P max). The ferroelectric in the nonlinear dielectric has higher P max, but the remnant polarization (P r) is larger, the energy loss is higher, the energy storage density (W rec) is smaller and the conversion efficiency (ƞ) is lower, so that the requirements of integration, light weight and miniaturization of the high-power pulse device cannot be met. Compared with other dielectric materials, the Antiferroelectric (AFE) material has a unique double P-E loop, shows larger P max and P r close to zero, has higher W rec and eta in theory, and has huge application potential in the field of energy storage. Currently, the dielectric energy storage materials used commercially rely heavily on lead-based (PbZrO 3) antiferroelectric materials, which pollute the environment and harm health due to the fact that lead element is volatile at high temperature, and violate the global environmental protection and sustainable development consensus. Therefore, the development of green and environment-friendly high-performance lead-free energy storage dielectric materials is urgent to adapt to future development, and is also a national important strategic requirement for supporting high-end manufacturing industry and energy strategic safety in China. AgNbO 3 (AN) is one of typical representatives of lead-free AFE materials, and in addition to the unique double P-E loop and larger P m（Pm～52μC/cm2 of AFM materials and the P r characteristic close to zero, it also has a higher breakdown field strength (E b) due to its wider band gap (E g =2.96 eV), indicating that this combination can achieve higher W rec and ƞ, which is one of the hot spots for energy storage material research. However, AN has a rich phase change process at room temperature, wherein Pmc2 1 present in M 1 phase (Pbcm) exhibits Ferroelectricity (FIE), resulting in a larger P r value, and under the action of AN electric field, energy loss is larger during the phase change from antiferroelectric phase (AFM) to ferroelectric phase (FM), resulting in lower conversion efficiency, thereby impeding its further commercial application. In the prior art, design strategies such as ion doping or multi-element solid solution are generally adopted to enhance the stability of AN antiferroelectric phase at room temperature, reduce P r, improve E b and further optimize the energy storage characteristic. In the prior art, patent document with the application number of CN 201910305422.2 discloses that Ag 1-3xTmxNbO3 (x is more than or equal to 0.01 and less than or equal to 0.08) antiferroelectric ceramic material is prepared by a solid phase reaction method, the energy storage density reaches 2.6-4.3J/cm 3, the conversion efficiency is only 38-77%, and the energy storage density and the conversion efficiency are relatively low. In the prior art, patent document with the application number of CN202211559128.2 discloses that an AgNbO 3 antiferroelectric energy storage ceramic is synthesized by a hydrothermal reaction method, the energy storage density reaches 3.8-4.5J/cm 3, the conversion efficiency is relatively low and is only 38.5-45.1%, the energy loss is large, the preparation process is relatively complex, the prepared product quantity is small, and the mass production is not facilitated. In the prior art, patent document with the application number of CN202111194580.9 discloses that a cosolvent 0.01BaCu (B 2O7) is added into an antiferroelectric energy storage ceramic system (1-x) AgNbO 3-x(Sr0.7Bi0.2)HfO3 to reduce the sintering temperature and increase the density of a ceramic material. Although the energy st