CN113735161A - Preparation method of perovskite phase PbTiO3 ferroelectric nano material - Google Patents

Preparation method of perovskite phase PbTiO3 ferroelectric nano material Download PDF

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CN113735161A
CN113735161A CN202111049868.7A CN202111049868A CN113735161A CN 113735161 A CN113735161 A CN 113735161A CN 202111049868 A CN202111049868 A CN 202111049868A CN 113735161 A CN113735161 A CN 113735161A
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perovskite phase
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pbtio
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杨光远
彭三文
吴昊天
李赞
李世建
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China Tobacco Hubei Industrial LLC
Hubei Zhongyan Cigarette Materials Factory
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Hubei Zhongyan Cigarette Materials Factory
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Abstract

The invention discloses a preparation method of a perovskite phase PbTiO3 ferroelectric nano material, which comprises the following steps: s1, dispersing titanium and lead salt in di (2-hydroxypropionic acid) ammonium dihydrogen oxide to obtain a mixed solution; s2, adding a mineralizer into the mixed solution, stirring at room temperature, and filtering to obtain hydroxide precipitate; s3, dispersing the hydroxide precipitate into a solvent, adding a mineralizer, and stirring for reaction to obtain a Pb-Ti precursor; s4, carrying out hydrothermal reaction on the Pb-Ti precursor in a closed state to obtain a crude product; s5, cooling the crude product to room temperature and filtering to obtain the perovskite phase PbTiO3Ferroelectric nanomaterial, ferroelectric PbTiO prepared therefrom3The nano sheet has regular morphology, good crystallinity and good ferroelectric property.

Description

Preparation method of perovskite phase PbTiO3 ferroelectric nano material
Technical Field
The invention relates to the field of ferroelectric nano material preparation, in particular to a perovskite phase PbTiO3A preparation method of ferroelectric nano material.
Technical Field
Lead titanate (PbTiO)3) The material is a typical perovskite structure ferroelectric oxide, has excellent ferroelectric, piezoelectric and dielectric properties, and higher Curie temperature (490)oC) And unique photocatalytic performance, are the hot materials of people's attention. In recent years, with the progress of manufacturing technology and the rapid development of microelectronic integration technology, miniaturization, integration and functionalization of ferroelectric devices have become development trends, and research on ferroelectric nanomaterials and nanoscale ferroelectric properties has become a hot spot for internationally researching novel functional materials. Therefore, the synthesis and performance research of materials with new morphology and structure have attracted extensive interest.
In the prior art, PbTiO3The preparation method of the nano material comprises a sol-gel method, a solid-phase reaction method, a molten salt method, a hydrothermal method and the like, and for example, Chinese patent with the publication number of CN200710177077.6 discloses an in-situ preparation method of PbTiO by utilizing the hydrothermal method3The method for preparing nano tube array film uses phosphoric acid, hydrofluoric acid, lead acetate and deionized water as main raw material, and firstly prepares TiO on titanium foil by anode oxidation method2Nanotube array film, and TiO 2 in the presence of aqueous solution of aluminum acetate in the molar concentration of 0.00001-10 mol/L as medium2The nano tube array film is taken as a template, a hydrothermal reaction solution with the volume percentage of 20-90 percent, namely a lead acetate water solution is added, and the temperature is kept at 300 ℃ for 0.5-50 hours at 150 DEG to obtain PbTiO3Nanotube array films, but PbTiO prepared therefrom3The nanotube has irregular appearance and poor ferroelectric property.
Disclosure of Invention
In order to solve the above problems, the present invention provides a perovskite phase PbTiO3Preparation method of ferroelectric nano material and prepared ferroelectric PbTiO3The nano-sheet has regular shape and is crystallizedGood performance and good ferroelectric property.
The technical scheme of the invention is to provide a perovskite phase PbTiO3The preparation method of the ferroelectric nano material is characterized by comprising the following steps:
s1, dispersing titanium and lead salt in di (2-hydroxypropionic acid) ammonium dihydrogen oxide to obtain a mixed solution;
s2, adding a mineralizer into the mixed solution, stirring at room temperature, and filtering to obtain hydroxide precipitate;
s3, dispersing the hydroxide precipitate into a solvent, adding a mineralizer, and stirring for reaction to obtain a Pb-Ti precursor;
s4, carrying out hydrothermal reaction on the Pb-Ti precursor in a closed state to obtain a crude product;
s5, cooling the crude product to room temperature and filtering to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial;
through the steps, a two-step hydrothermal reaction method is adopted, the titanium and lead salts of the di (2-hydroxypropionic acid) ammonium dihydroxide are used as reactant raw materials, ammonia water is used as a mineralizer, and Ti is fully precipitated4+And Pb2+Then, Pb-Ti hydroxide precipitate is synthesized, and then the precipitate product is dispersed into a mixed solution of a solvent and ammonia water to carry out hydrothermal synthesis in a reaction kettle;
preferably, the mineralizer is ammonia water to overcome PbTiO3The problem of alkali metal pollution of nano materials;
preferably, the lead salt comprises one or more of lead acetate, lead nitrate, lead citrate and lead acetate, so that the lead salt is Pb2+Form, providing conditions for the subsequent hydrothermal reaction;
preferably, the molar ratio of the lead salt to titanium bis (2-hydroxypropionic acid) ammonium dihydroxide is (0.8-1.2): 1;
preferably, in step S3, the solvent is one or more selected from deionized water, methanol, ethanol, ethylene glycol methyl ether, propanol, and propylene glycol, and the shape rules such as particles, squares, rods are grown by controlling different reaction pressures caused by different effects of the functional groups of the organic alcohol and different boiling points of the organic alcoholFlaky perovskite phase PbTiO3A nanomaterial;
preferably, the ratio of the molar amount of the mineralizer to the molar amount of the lead salt in the step S2 is (10-100): 1, so as to sufficiently precipitate Ti4+And Pb2+；
Preferably, in the step S4, the temperature of the hydrothermal reaction is 100-280 ℃, and the reaction time of the hydrothermal reaction is 1-72 h;
preferably, the ratio of the molar amount of the mineralizer to the molar amount of the lead salt in the step S3 is (10-100): 1;
preferably, the purity of the titanium bis (2-hydroxypropionate) ammonium dihydroxide is greater than 99%;
preferably, in the steps S2 and S3, the adding speed of the mineralizer is 1-2 drops/min.
In the traditional hydrothermal synthesis of PbTiO3In the nanometer material process, people often use NaOH or KOH as a mineralizer, but K ions and Na ions easily enter the crystal lattice of lead titanate, and the two alkali metal ions belong to conductive ions and enter the crystal lattice structure of the lead titanate, so that the insulativity of the lead titanate is reduced, the ferroelectric and piezoelectric properties of the lead titanate are damaged, and the alkali metal ions can inevitably bring about PbTiO pair3The scheme adopts a two-step hydrothermal reaction method, adopts di (2-hydroxypropionic acid) ammonium dihydroxide titanium and lead salt as reactant raw materials, adopts ammonia water as a mineralizer, and fully precipitates Ti4+And Pb2+Synthesizing Pb-Ti hydroxide precipitate, dispersing the precipitate into a mixed solution of a solvent and ammonia water, and carrying out hydrothermal synthesis in a reaction kettle, so that on one hand, the pollution of alkali metal ions to the product is avoided, on the other hand, the reaction environment is a liquid phase, which is very favorable for uniform nucleation and diffusion of crystallization reaction, the product with good crystallization performance is obtained, and then, the reaction pressure caused by different functional group effects of organic alcohol and different boiling points of organic alcohol is controlled, so that perovskite phase PbTiO with regular shapes such as particles, squares, rods and sheets is grown3The nano material has good ferroelectric property.
The invention has the beneficial effects that:
1. the scheme uses ammonia water as a mineralizer to prepare PbTiO3The nano material has no alkali metal pollution problem;
2. the reaction environment of the scheme is a liquid phase, which is beneficial to uniform nucleation and diffusion of crystallization reaction, and the product with good crystallization performance is obtained, and the perovskite phase PbTiO with regular appearance such as granular, square, rod and sheet can be grown by adjusting different reaction solvents3A nanomaterial;
3. the invention has simple process flow, and the prepared ferroelectric PbTiO is3The nano sheet has regular appearance, good crystallinity and good ferroelectric property.
Drawings
FIG. 1 is a crystal diagram of the product obtained in example 1;
FIG. 2 is an SEM photograph of the product obtained in example 1;
FIG. 3 is a TEM image of the product obtained in example 1;
FIG. 4 shows the results of PFM measurements on the product obtained in example 1;
FIG. 5 is a crystal diagram of the product obtained in example 4;
FIG. 6 is a TEM image of the product obtained in example 4;
FIG. 7 shows the results of PFM measurements on the product obtained in example 4;
FIG. 8 shows comparative results of electrical property tests.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments are not indicated by manufacturers, and are conventional products available by purchase
Example 1
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 10mol of ammonia water into the mixed solution at the speed of 1 drop/minute under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 20mL of ethylene glycol solvent, adding 10mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
XRD test is carried out on the obtained product, and the crystal pattern is shown in figure 1; the microstructure of the product is characterized, the SEM image is shown in figure 2, the TEM image is shown in figure 3, and the product is square-block-shaped PbTiO3Nanocrystals having an edge length of about 90 nm; PbTiO in the form of square block3PFM test is carried out on the nano crystal, and the result is shown in figure 4, ferroelectric domains can be observed to exist, and the ferroelectric properties are proved.
Example 2
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 1.2mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2. atWhile stirring, 100mol of ammonia water was added to the mixture at a rate of 1 drop/min, and after stirring at room temperature, Ti was completely precipitated4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 10mL of ethanol solvent, adding 10mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 280 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Example 3
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.9mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 20mol of ammonia water into the mixed solution at the speed of 1 drop/minute under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions into 10mL of ethylene glycol monomethyl ether solvent, adding 15mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 100 ℃, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Example 4
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 10mol of ammonia water into the mixed solution at the speed of 1.5 drops/min under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 10mL of deionized water, adding 15mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 4h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
XRD testing was carried out on the obtained product, and the crystal pattern thereof is shown in FIG. 5; the microscopic morphology of the product is characterized, a TEM image is shown in FIG. 6, and the product is flaky PbTiO3A nanocrystal; for flake PbTiO3Nanocrystals ofBy performing PFM tests, and the results are shown in FIG. 7, ferroelectric domains can be observed to demonstrate ferroelectric properties.
Example 5
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 10mol of ammonia water into the mixed solution at the speed of 1 drop/minute under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 10mL of propanol, adding 100mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Example 6
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 2 drops per minute into the mixed solution under the stirring stateAdding 10mol ammonia water, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 10mL of propanol, adding 15mol of ammonia water, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Comparative example 1
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 10mol of NaOH into the mixed solution at the speed of 1 drop/minute under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions into 20mL of ethylene glycol solvent, adding 10mol of NaOH, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Comparative example 2
Perovskite phase PbTiO3The preparation method of the ferroelectric nano material comprises the following steps:
s1, dispersing 1mol of titanium ammonium dihydrogen di (2-hydroxypropionic acid) and 0.8mol of lead acetate in 20ml of deionized water, and uniformly stirring to obtain a mixed solution, wherein the purity of the titanium ammonium dihydrogen di (2-hydroxypropionic acid) is more than 99%, and the CAS number is 65104-06-5;
s2, adding 10mol of KOH into the mixed solution at the speed of 1 drop/minute under the stirring state, stirring at room temperature, and completely precipitating Ti4+And Pb2+Obtaining a suspension, filtering the suspension, and taking the precipitate to obtain hydroxide precipitate containing Pb and Ti ions;
s3, dispersing the hydroxide precipitate containing Pb and Ti ions in 20mL of deionized water, adding 10mol of KOH, and stirring at 20 ℃ and 100rpm for 3h to obtain a Pb-Ti precursor;
s4, transferring the Pb-Ti precursor into a 50mL reaction kettle lining, sealing the reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 800rpm after sealing, keeping the temperature of the hydrothermal reaction at 200 ℃, keeping the reaction time of the hydrothermal reaction at 1h, keeping the temperature for 20h, and finishing the hydrothermal reaction to obtain a crude product;
s5, cooling the crude product to room temperature, washing and filtering the crude product by using deionized water and absolute ethyl alcohol, and taking a precipitate to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
Test method
The electrical property test of the nano-material products obtained in examples 1-6 and comparative examples 1-2 is carried out according to GB/T1409-2006, and the result is shown in FIG. 8, which shows that the ferroelectric nano-material prepared by the scheme has good performance.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. Perovskite phase PbTiO3The preparation method of the ferroelectric nano material is characterized by comprising the following steps:
s1, dispersing titanium and lead salt in di (2-hydroxypropionic acid) ammonium dihydrogen oxide to obtain a mixed solution;
s2, adding a mineralizer into the mixed solution, stirring at room temperature, and filtering to obtain hydroxide precipitate;
s3, dispersing the hydroxide precipitate into a solvent, adding a mineralizer, and uniformly stirring to obtain a Pb-Ti precursor;
s4, carrying out hydrothermal reaction on the Pb-Ti precursor in a closed state to obtain a crude product;
s5, cooling the crude product to room temperature and filtering to obtain the perovskite phase PbTiO3A ferroelectric nanomaterial.
2. The perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that the mineralizer is ammonia water.
3. The perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that the lead salt comprises one or more of lead acetate, lead nitrate, lead citrate and lead acetate.
4. The perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that the molar ratio of the lead salt to the bis (2-hydroxypropionic acid) ammonium dihydroxide titanium is (0.8-1.2): 1.
5. the perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that in the step S3, the solvent is one or more of deionized water, methanol, ethanol, ethylene glycol monomethyl ether, propanol and propylene glycol.
6. A perovskite phase PbTiO according to claim 23The preparation method of the ferroelectric nano material is characterized in that the ratio of the molar weight of the mineralizer to the molar weight of the lead salt in the step S2 is (10-100): 1.
7. the perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that in the step S4, the temperature of the hydrothermal reaction is 100-280 ℃, and the reaction time of the hydrothermal reaction is 1-72 h.
8. The perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that the ratio of the molar weight of the mineralizer to the molar weight of the lead salt in the step S3 is (10-100): 1.
9. the perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that the purity of the bis (2-hydroxypropionic acid) ammonium dihydroxide titanium dioxide is more than 99%.
10. The perovskite phase PbTiO of claim 13The preparation method of the ferroelectric nano material is characterized in that in the step S2 and the step S3, the speed of adding the mineralizer is 1-2 drops/minute.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115140764A (en) * 2022-06-08 2022-10-04 浙江理工大学 Perovskite phase lead titanate with hierarchical structure, hydrothermal synthesis method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09286617A (en) * 1996-04-19 1997-11-04 Taiyo Yuden Co Ltd Production of lead titanate powder
CN102674446A (en) * 2012-05-10 2012-09-19 浙江大学 Preparation method for lead titanate powder having laminated structure
CN102674444A (en) * 2012-05-10 2012-09-19 浙江大学 Preparation method of pyrochlore-structured lead titanate powder
US20130044175A1 (en) * 2011-08-17 2013-02-21 University Of Washington Through Its Center For Commercialization Method and System of Fabricating PZT Nanoparticle Ink Based Piezoelectric Sensor
CN104018226A (en) * 2013-06-21 2014-09-03 浙江大学 Method for preparing nano-particle self-assembled square perovskite phase PbTiO3 micron piece

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09286617A (en) * 1996-04-19 1997-11-04 Taiyo Yuden Co Ltd Production of lead titanate powder
US20130044175A1 (en) * 2011-08-17 2013-02-21 University Of Washington Through Its Center For Commercialization Method and System of Fabricating PZT Nanoparticle Ink Based Piezoelectric Sensor
CN102674446A (en) * 2012-05-10 2012-09-19 浙江大学 Preparation method for lead titanate powder having laminated structure
CN102674444A (en) * 2012-05-10 2012-09-19 浙江大学 Preparation method of pyrochlore-structured lead titanate powder
CN104018226A (en) * 2013-06-21 2014-09-03 浙江大学 Method for preparing nano-particle self-assembled square perovskite phase PbTiO3 micron piece

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XINYI LI等: "Hydrothermal Synthesis of PbTiO3 Nanocrystals with a pH‑Adjusting Agent of Ammonia Solution", 《ELECTRONIC MATERIALS LETTERS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115140764A (en) * 2022-06-08 2022-10-04 浙江理工大学 Perovskite phase lead titanate with hierarchical structure, hydrothermal synthesis method and application
CN115140764B (en) * 2022-06-08 2023-08-11 浙江理工大学 Perovskite-phase lead titanate with hierarchical structure, hydrothermal synthesis method and application

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