CN-122010562-A - Lead zirconate titanate template and preparation method thereof

CN122010562ACN 122010562 ACN122010562 ACN 122010562ACN-122010562-A

Abstract

The invention discloses a lead zirconate titanate template and a preparation method thereof, comprising the steps of taking a lead source solution, an acidic zirconium source solution and a tetrabutyl titanate ethanol solution, dripping the tetrabutyl titanate ethanol solution into the zirconium source solution under the stirring condition, and continuously and uniformly stirring to obtain a zirconium-titanium mixed solution; the method comprises the steps of adding a zirconium source solution into a zirconium-titanium mixed solution in a dropwise manner, adding a complexing agent into the zirconium-titanium mixed solution, stirring to obtain a uniform precursor solution, adding a mineralizer into the precursor solution, stirring until the mineralizer is completely dissolved, regulating the pH value of a hydrothermal reaction system to be alkaline to obtain a hydrothermal reaction solution, placing the hydrothermal reaction solution into a high-pressure reaction kettle for hydrothermal reaction, naturally cooling to room temperature after the hydrothermal reaction is completed, washing and drying the obtained product to obtain a lead zirconate titanate template primary product, and roasting and cooling the lead zirconate titanate template primary product to obtain the lead zirconate titanate template.

Inventors

YANG SHUAI
FU MINGLI
WANG MINGWEN
LI FEI
XIAO YIZHOU
YANG WEIHONG
LI CHUNCHUN
ZHANG JINJING
LI JINGLEI
ZHUO RAN
YANG CHEN

Assignees

西安交通大学
中国南方电网有限责任公司
南方电网科学研究院有限责任公司

Dates

Publication Date: 20260512
Application Date: 20251118

Claims (10)

1. The preparation method of the lead zirconate titanate template is characterized by comprising the following steps of: taking a lead source solution, a zirconium source solution and a tetrabutyl titanate ethanol solution according to a Zr/Ti molar ratio of 0.45-0.65:0.55-0.35 and a Pb/(Zr+Ti) molar ratio of 1.05-1.2:1, dripping the tetrabutyl titanate ethanol solution into the zirconium source solution, and keeping stirring and continuing stirring until the zirconium source solution is transparent and clear in the dripping process to obtain a zirconium-titanium mixed solution, wherein the zirconium source solution is acidic; dropwise adding a lead source solution into the zirconium-titanium mixed solution, and simultaneously adding a complexing agent and stirring to a yellow transparent state to obtain a uniform precursor solution; Adding a mineralizer into the precursor solution, stirring until the mineralizer is completely dissolved, and then adjusting the pH value of the hydrothermal reaction system to be alkaline to obtain a hydrothermal reaction solution; placing the hydrothermal reaction liquid in a high-pressure reaction kettle for hydrothermal reaction, wherein the filling degree of the reaction kettle is 60% -80%, preserving heat for 8-16 hours at 180-220 ℃, continuously stirring in the reaction kettle in the hydrothermal reaction process, and naturally cooling to room temperature after the hydrothermal reaction is completed; washing and drying the hydrothermal reaction product to obtain a lead zirconate titanate template primary product; Roasting the lead zirconate titanate template initial product at 400-600 ℃ for 2-4 hours, and cooling to obtain the high-purity lead zirconate titanate template.
2. The method for preparing a lead zirconate titanate template according to claim 1, wherein lead nitrate, zirconium oxychloride and tetrabutyl titanate are taken according to the proportion, and lead source solution, zirconium source solution and tetrabutyl titanate ethanol solution are prepared by using the lead nitrate, zirconium oxychloride and tetrabutyl titanate respectively.
3. The method for preparing lead zirconate titanate template according to claim 1, wherein the zirconium source solution is obtained by dissolving zirconium oxychloride in deionized water, adding hydrochloric acid solution with the concentration of 1mol/L to adjust the pH value to 1-2, and stirring uniformly.
4. The method for preparing lead zirconate titanate template according to claim 1, wherein the complexing agent is citric acid or disodium edetate.
5. The method for preparing a lead zirconate titanate template according to claim 1, wherein the dripping speed of the tetrabutyl titanate ethanol solution is 50-100mL/min, and the stirring speed in the dripping process is 300-500r/min.
6. The method for producing a lead zirconate titanate template according to claim 1, wherein the drop rate of the lead source solution is 10-20mL/min, the molar ratio of the complexing agent to the metal ions is 1-1.5:1, and the metal ions include Pb 2+ 、Zr 4+ and Ti 4+ .
7. The method for preparing lead zirconate titanate template according to claim 1, wherein the mineralizer is a mixed system of potassium hydroxide and potassium fluoride, the volume ratio is 1:0.5-5, the KOH concentration is 2mol/L-4mol/L, and the KF concentration is 0.5mol/L-1.5mol/L.
8. The method for preparing lead zirconate titanate template according to claim 1, wherein the pH value of the hydrothermal reaction system is 12-14, and the stirring speed of the reaction kettle in the hydrothermal reaction process is 50-100r/min.
9. The method for preparing a lead zirconate titanate template according to claim 1, wherein washing and drying the hydrothermal reaction product comprises repeatedly washing with deionized water until the pH of the washing solution is 7-8, washing with absolute ethanol, and drying.
10. A lead zirconate titanate template obtained by the method according to any one of claims 1 to 9, having a sheet shape with a thickness of 0.1 to 0.9 μm, a length of 2 to 11 μm, and a d 33 of not less than 730pC/N.

Description

Lead zirconate titanate template and preparation method thereof Technical Field The invention belongs to the technical field of functional material preparation, and particularly relates to a lead zirconate titanate template and a preparation method thereof. Background PZT-based ceramics are the main stream core materials in the current commercial piezoelectric ceramic field due to their excellent piezoelectric properties, high phase transition temperature and component adjustability. For half a century, the formulation and piezoelectric properties of PZT-based commercial ceramics remained similar to that of the 70 s of the last century, with no obvious breakthrough. In recent years, the successful preparation of textured piezoelectric ceramics greatly improves the piezoelectric performance of the ceramics, but the common barium titanate and strontium titanate templates can have serious chemical reaction with a PZT matrix, so that the PZT matrix ceramics are not textured. Even though some papers report that PZT ceramics are textured, their special preparation methods are not satisfactory for engineering, mass production and applications. The successful preparation of the PZT template can overcome the chemical reaction of the template and the PZT matrix, so that the commercial PZT-based ceramic is successfully textured, the piezoelectric performance of the PZT ceramic is greatly improved, and the urgent requirements of the fields of piezoelectric sensors, ferroelectric memories, ultrasonic transducers and the like on high-performance piezoelectric materials are met. At present, the PZT template is prepared mainly by a molten salt method, the Zr content in the PZT template prepared by the method is lower (less than 10%), the chemical stability is still insufficient, and the commercial PZT ceramic component cannot be textured. In addition, the patent with the prior art publication number of CN108622931A discloses a preparation method of micron-sized lamellar lead zirconate titanate crystals, which adopts a molten salt method to prepare lamellar <001> preferred orientation bismuth titanate crystals as precursors, the precursor crystals are mixed with PbO and ZrO2 according to a set molar ratio through topological chemical reaction, then mixed powder and NaCl according to a set mass ratio, the mixed powder is insulated at 850-1050 ℃, finally the NaCl and Bi 2O3 in the baked products are removed through washing and acid washing by hot deionized water, so as to obtain micron-sized lamellar lead zirconate titanate (Pb (Zr 0.5Ti0.5)O3) crystals, the microscopic morphology is lamellar, the micron-sized lamellar lead zirconate titanate crystals have larger diameter-thickness ratio and high orientation degree, the micron-sized lamellar lead zirconate titanate crystals are used as seed crystals of high-orientation lead zirconate titanate textured ceramics, and the molten salt (KCl and/or NaCl) is used as fluxing agent for preparing the precursors through the molten salt method, so that the reaction conditions are more severe. Therefore, developing a PZT template preparation method with mild reaction conditions, uniform product morphology, high orientation degree, high preparation efficiency and controllable stoichiometric ratio becomes a technical problem to be solved in the field. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a preparation method of a lead zirconate titanate (Pb (Zr, ti) O 3, PZT for short) template based on a hydrothermal method, which is suitable for preparing a PZT template with high orientation and high crystallization quality. In order to achieve the above purpose, the technical scheme adopted by the invention is that the preparation method of the lead zirconate titanate template comprises the following steps: taking a lead source solution, a zirconium source solution and a tetrabutyl titanate ethanol solution according to a Zr/Ti molar ratio of 0.45-0.65:0.55-0.35 and a Pb/(Zr+Ti) molar ratio of 1.05-1.2:1, dripping the tetrabutyl titanate ethanol solution into the zirconium source solution, and keeping stirring and continuing stirring until the zirconium source solution is transparent and clear in the dripping process to obtain a zirconium-titanium mixed solution, wherein the zirconium source solution is acidic; dropwise adding a lead source solution into the zirconium-titanium mixed solution, and simultaneously adding a complexing agent and stirring to a yellow transparent state to obtain a uniform precursor solution; Adding a mineralizer into the precursor solution, stirring until the mineralizer is completely dissolved, and then adjusting the pH value of the hydrothermal reaction system to be alkaline to obtain a hydrothermal reaction solution; Placing the hydrothermal reaction liquid in a high-pressure reaction kettle for hydrothermal reaction, wherein the filling degree of the reaction kettle is 60% -80%180-220 ℃, preserving heat for 8-16 hou