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CN-118479871-B - Five-membered BF-BT-based leadless piezoelectric ceramic with high-temperature stability and high-voltage electrical property and preparation method thereof

CN118479871BCN 118479871 BCN118479871 BCN 118479871BCN-118479871-B

Abstract

The invention discloses five-membered BF-BT based leadless piezoelectric ceramics with high temperature stability and high voltage performance and a preparation method thereof, wherein the composition general formula is ：(1-y)[(1-x)BiFeO 3 -xBaTiO 3 )]-y[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-zBi(Zn 0.5 Ti 0.5 )O 3 +uMnO 2 +vLi 2 CO 3 ,x、y、z、u, v represents mole fraction, x is more than or equal to 0.30 and less than or equal to 0.40, y is more than or equal to 0.05, z is more than or equal to 0 and less than or equal to 0.05, u is more than or equal to 0 and less than or equal to 0.01, and v is more than or equal to 0.01. The invention utilizes the phase structure and the domain structure to regulate and control the temperature stability and the piezoelectric performance simultaneously, designs the leadless piezoelectric ceramic with the piezoelectric performance still kept above 680 pC/N at the real-time depolarization temperature of 395.6 ℃, and the ceramic material has excellent piezoelectric temperature stability and is expected to be applied to the field of high temperature.

Inventors

  • YANG HUABIN
  • ZHU JIAMING
  • CHEN QIAOHONG
  • WANG XUETING
  • LUO QIULING
  • QIU SHAOHONG
  • PAN XIAOHUI

Assignees

  • 桂林电子科技大学

Dates

Publication Date
20260512
Application Date
20240611

Claims (10)

  1. 1. A five-membered BF-BT based leadless piezoelectric ceramic with high temperature stability and high piezoelectric property is characterized in that the ceramic has the following general formula: (1-y)[(1-x)BiFeO 3 -xBaTiO 3 )]-y[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-zBi(Zn 0.5 Ti 0.5 )O 3 +uMnO 2 +vLi 2 CO 3 , Wherein x, y, z, u, v represents the molar fraction of the components, and 0.30≤x≤ 0.40,0 < y≤0.05, 0 < z≤0.05, 0 < u≤ 0.01,0 < v≤0.01.
  2. 2. The five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.98(0.7BiFeO 3 -0.3BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  3. 3. the five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.98(0.68BiFeO 3 -0.32BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  4. 4. The five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.98(0.67BiFeO 3 -0.33BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  5. 5. The five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.97(0.68BiFeO 3 -0.32BaTiO 3 )-0.03[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  6. 6. the five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.96(0.68BiFeO 3 -0.32BaTiO 3 )-0.04[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  7. 7. the five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.98(0.68BiFeO 3 -0.32BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.02Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  8. 8. The five-membered BF-BT based leadless piezoelectric ceramic having both high temperature stability and high piezoelectric property according to claim 1, wherein the chemical formula of the ceramic is: 0.98(0.68BiFeO 3 -0.32BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.03Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 .
  9. 9. The preparation method of the five-membered BF-BT based leadless piezoelectric ceramics with high temperature stability and high piezoelectric property as claimed in claim 1, which is characterized by comprising the following steps: 1) Preparing analytically pure Bi 2 O 3 、TiO 2 、Na 2 CO 3 and K 2 CO 3 serving as raw materials according to the proportion of 0.8 (Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ), ball-milling the uniformly mixed powder with absolute ethyl alcohol serving as a medium for 24 hours, taking out, drying at 80 ℃ in an oven for 12 hours, sieving with a 200-mesh sieve, putting into a high-alumina crucible, compacting and capping, putting into a muffle furnace, presintering at the temperature rising rate of 2 ℃ per min to 800 ℃, preserving heat for 6 hours, cooling to below 200 ℃, taking out, and synthesizing into 0.8 (Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 powder for later use; 2) Weighing and proportioning analytically pure Bi 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 、ZnO、MnO 2 and Li 2 CO 3 serving as raw materials, taking the Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 presintering powder synthesized in the step 1) according to a proportion of (1-y)[(1-x)BiFeO 3 -xBaTiO 3 )]-y[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-zBi(Zn 0.5 Ti 0.5 )O 3 +uMnO 2 +vLi 2 CO 3 , wherein x, y, z, u and v represent the mole fraction of the components, x is more than or equal to 0.30 and less than or equal to 0.40,0, y is more than or equal to 0.05, z is more than or equal to 0.05, u is more than or equal to 0 and less than or equal to 0.01,0, v is less than or equal to 0.01, wherein the excessive 4.0% mol of Bi element is used for making up volatilization of bismuth element in the sintering process, ball-milling the mixed powder for 24 hours by taking absolute ethyl alcohol as a medium, taking out, drying for 12 hours at 80 ℃ in an oven, sieving with a 200-mesh sieve, compacting and capping in a high-aluminum crucible, presintering at 780 ℃ in a muffle furnace, and preserving heat for 6 hours; 3) Fully grinding the presintered powder, adding 8% PVA solution for granulation, and performing compression molding in a powder tablet press under the pressure of 12 MPa; 4) Slowly heating the formed plain sheet to 600 ℃ at a heating rate of 30 ℃ per hour in a muffle furnace, preserving heat for 3 hours, discharging glue, heating to 950-1000 ℃ at a heating rate of2 ℃ per minute, sintering, preserving heat for 240 minutes, and cooling to room temperature along with the furnace; 5) Polishing the sintered ceramic wafer, plating silver paste on the surface of a sample, and burning silver for 30min at 450 ℃; 6) Polarizing the ceramic plate plated with silver electrode in silicone oil at 6000V/mm polarization electric field and 110 deg.c for 5-15min, maintaining the voltage unchanged, cooling to room temperature and taking out.
  10. 10. The method for preparing the five-membered BF-BT based leadless piezoelectric ceramics having both high temperature stability and high piezoelectric property as claimed in claim 9, comprising the steps of: (1) Preparing analytically pure Bi 2 O 3 、TiO 2 、Na 2 CO 3 and K 2 CO 3 serving as raw materials according to the proportion of 0.8 (Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ), ball-milling the uniformly mixed powder with absolute ethyl alcohol serving as a medium for 24 hours, taking out, drying at 80 ℃ in an oven for 12 hours, sieving with a 200-mesh sieve, putting into a high-alumina crucible, compacting and capping, putting into a muffle furnace, presintering at the temperature rising rate of 2 ℃ per min to 800 ℃, preserving heat for 6 hours, cooling to below 200 ℃, taking out, and synthesizing into 0.8 (Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 powder for later use; (2) Taking analytically pure Bi 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 、MnO 2 、Li 2 CO 3 and ZnO as raw materials, weighing and proportioning 0.8 (Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 presintering powder synthesized in the step (1) according to the proportion of 0.98(0.7BiFeO 3 -0.3BaTiO 3 )-0.02[0.8(Bi 0.5 Na 0.5 )TiO 3 -0.2(Bi 0.5 K 0.5 )TiO 3 ]-0.04Bi(Zn 0.5 Ti 0.5 )O 3 +0.01MnO 2 +0.01Li 2 CO 3 , wherein the excessive 4.0 mol% of Bi element is used for compensating volatilization of Bi element in the sintering process, ball-milling the mixed powder with absolute ethyl alcohol as a medium for 24 hours, taking out, drying in an oven at 80 ℃ for 12 hours, sieving with a 200-mesh sieve, putting into a high-aluminum crucible, compacting and capping, putting into a muffle furnace for presintering at 780 ℃, and preserving heat for 6 hours; (3) Fully grinding the presintered powder, adding 8% PVA solution for granulation, and performing compression molding in a powder tablet press under the pressure of 12 MPa; (4) Slowly heating the formed plain sheet to 600 ℃ at a heating rate of 30 ℃ per hour in a muffle furnace, preserving heat for 3 hours, discharging glue, heating to 1000 ℃ at a heating rate of 2 ℃ per minute, sintering, preserving heat for 240 minutes, and cooling to room temperature along with the furnace; (5) Polishing the sintered ceramic wafer, plating silver paste on the surface of a sample, and burning silver for 30min at 450 ℃; (6) Polarizing the ceramic plate plated with silver electrode in silicone oil at 6000V/mm polarization electric field and 110 deg.c for 5-15min, maintaining the voltage unchanged, cooling to room temperature and taking out.

Description

Five-membered BF-BT-based leadless piezoelectric ceramic with high-temperature stability and high-voltage electrical property and preparation method thereof Technical Field The invention relates to a lead-free piezoelectric ceramic, in particular to a bismuth ferrite-barium titanate-based high-temperature lead-free piezoelectric ceramic with high-temperature stability and high-voltage performance and a preparation method thereof. Background The high-temperature piezoelectric ceramic is a core element in a high-temperature piezoelectric vibration sensor, has important requirements in the fields of aerospace, nuclear energy, petroleum exploration and the like, and is characterized by harsh use conditions, high working temperature and long service life, and is widely applied due to excellent electrical performance and temperature stability of Pb (Zr, ti) O 3 (PZT) piezoelectric ceramic which occupies important position in the market, wherein the T C is generally less than 360 ℃ and the piezoelectric coefficient (d 33) is generally less than 400 pC/N. However, the toxic lead content in PZT ceramic exceeds 60 wt%, and the use of PZT ceramic as an electronic product in a large-scale use or scrapping recovery process causes serious physical health and ecological problems for human beings and the environment due to the excessive content of harmful substances. Therefore, there is an urgent need to develop a lead-free piezoelectric ceramic having both high piezoelectric response and high use temperature. In BiFeO 3-BaTiO3 (BF-BT) ceramics, one of the most obvious breakthroughs of performance is to utilize a relaxation ferroelectric to regulate and control a micro-electric domain structure near a quasi-homotype phase boundary (MPB) component, the disordered distribution of complex valence cations of the relaxation component can damage the long-range order of the ferroelectric, so that domains are thinned and local polar nano micro-domains are constructed, and the obtained nano domains and polar nano micro-domains (PNRs) have faster switching response speed than micro domains. Meanwhile, the temperature stability of BF-BT-based ceramics is related to a phase structure and a composite domain structure, the temperature stability and the tetragonality of the structure are positively correlated, and the larger the tetragonality is, the higher the temperature stability is. The existing research shows that the single regulation means, such as doping modification, A, B substitution and other technologies, cannot break through the current research bottleneck, and the structure of the ternary system cannot make the piezoelectric performance and the thermal stability of the system to be broken through more greatly, so that the research thought needs to be further widened to obtain the aim of improving the piezoelectric activity and the temperature stability of the ceramic. Disclosure of Invention In order to solve the limitation of d 33-Td conflict, the invention aims to provide five-membered BF-BT based leadless piezoelectric ceramics with high temperature stability and high piezoelectric performance and a preparation method thereof, and particularly relates to BiFeO3-BaTiO3-(Bi0.5Na0.5)TiO3-(Bi0.5K0.5)TiO3-Bi(Zn0.5Ti0.5)O3（BF-BT-BNT-BKT-BZT） leadless piezoelectric ceramics with high temperature stability and high piezoelectric performance and a preparation method thereof. The piezoelectric ceramic prepared by the technology of the invention has Curie temperature of T C = 491.9 ℃, and the piezoelectric constant d 33 can be still kept above 680 pC/N when the real-time depolarization temperature is 395.6 ℃, and the ceramic is expected to be applied to the field of high temperature. The technical scheme for realizing the aim of the invention is as follows: a five-membered BF-BT based leadless piezoelectric ceramics with high temperature stability and high piezoelectric performance comprises (1) Selecting (1-x) BiFeO 3-xBaTiO3 with high Curie temperature and component proportion near an MPB structure where R-T phases coexist as a matrix material, wherein x is more than or equal to 0.30 and less than or equal to 0.40; (2) Selecting 0.8 near MPB (Bi 0.5Na0.5)TiO3-0.2(Bi0.5K0.5)TiO3 is a relaxation component solid solution to regulate domain structure and domain size, and regulating stability of phase ferroelectric phase by using high tetragonal Bi (Zn 0.5Ti0.5)O3; (3) Design of (1-y)[(1-x)BiFeO3-xBaTiO3)]-y[0.8(Bi0.5Na0.5)TiO3-0.2(Bi0.5K0.5)TiO3]-zBi(Zn0.5Ti0.5)O3 The formulation is constructed into five-membered BF-BT-BNT-BKT-BZT. Specifically, a five-membered BF-BT based leadless piezoelectric ceramic with high temperature stability and high piezoelectric performance has the following composition general formula: (1-y)[(1-x)BiFeO3-xBaTiO3)]-y[0.8(Bi0.5Na0.5)TiO3-0.2(Bi0.5K0.5)TiO3]-zBi(Zn0.5Ti0.5)O3+uMnO2+vLi2CO3, Wherein x, y, z, u and v represent the mole fractions of the components, and 0.30≤x≤ 0.40,0 < y≤0.05, 0 < z≤0.05, 0 < u