CN109400153B

CN109400153B - Quaternary ceramic material with high transduction coefficient applied to piezoelectric energy collection and preparation

Info

Publication number: CN109400153B
Application number: CN201811183788.9A
Authority: CN
Inventors: 侯育冬; 闫晶; 于肖乐; 郑木鹏; 朱满康
Original assignee: Beijing University of Technology
Current assignee: Beijing University of Technology
Priority date: 2018-10-11
Filing date: 2018-10-11
Publication date: 2021-05-25
Anticipated expiration: 2038-10-11
Also published as: CN109400153A

Abstract

A quaternary ceramic material with high transduction coefficient for collecting piezoelectric energy and a preparation method thereof belong to the field of piezoelectric ceramic materials. The basic chemical composition of the ceramic material is (0.2-x) PZN-xPIN-0.8PZT, and x is 0.000-0.100. With ZnO and In₂O₃、Nb₂O₅、Pb₃O₄、ZrO₂、TiO₂The raw materials are subjected to wet grinding, drying, granulation, compression molding and sintering. The invention realizes the non-cooperative change trend of the piezoelectric charge constant and the dielectric constant, provides a brand new design idea for further developing high-performance piezoelectric energy collecting materials, and has great promotion effect on greatly enhancing the electromechanical conversion performance and the industrial application of the piezoelectric energy collecting device.

Description

Quaternary ceramic material with high transduction coefficient applied to piezoelectric energy collection and preparation

Technical Field

The invention belongs to the field of piezoelectric ceramic materials, and particularly relates to a quaternary piezoelectric ceramic material with high transduction coefficient and applied to piezoelectric energy collection and a preparation method thereof.

Background

In recent years, wireless sensor networks have been rapidly developed, and are widely applied to environmental control monitoring systems, embedded systems, military security application systems, field animal tracking devices and the like. Because the traditional method for supplying power by wiring or replacing a battery of the wireless sensor is too high in cost, how to realize self-power supply of the wireless sensor is a hot spot of research in all countries of the world. However, new energy sources such as solar energy and wind energy are too dependent on the environment, and cannot be well applied to the self-power supply of the wireless sensor. The piezoelectric energy collection technology converts mechanical energy in the environment into electric energy by utilizing the positive piezoelectric effect of the piezoelectric material, and has the advantages of high electromechanical conversion efficiency, high output voltage, no electromagnetic interference, no need of additional bias and the like, thereby having wide application prospect in the field of wireless sensing.

At present, materials applied to piezoelectric energy collecting devices mainly comprise piezoelectric single crystals, but the materials are high in preparation cost, complex in manufacturability and poor in processability, so that the materials cannot be applied on a large scale. Compared with the former, the conventional piezoelectric ceramic material has the advantages of low preparation cost, simple manufacturability, large-scale production and the like, so that the large-scale application requirement of an energy collecting device can be met.

In order to meet the practical application requirements of the piezoelectric energy collector, the piezoelectric ceramic material must have a high transduction coefficient (d)₃₃·g₃₃)：

d₃₃: piezoelectric charge constant g₃₃: constant of piezoelectric field

ε_r: relative dielectric constant ε₀: vacuum dielectric constant, 8.854X 10^-12F/m As can be seen from the formula (1-1), the high transduction coefficient (d) is observed for the piezoelectric ceramic material₃₃·g₃₃) By a high piezoelectric charge constant (d)₃₃) And a low relative dielectric constant (. epsilon.)_r) To obtain the final product.

Hitherto, in order to increase the transduction coefficient (d) of piezoelectric ceramic materials₃₃·g₃₃) Workers in the relevant fields of various countries have carried out a great deal of research work, which mainly comprises quasi-construction of Morphotropic Phase Boundaries (MPBs), doping, regulation of grain sizes and the like, in order to obtain a material with a high transduction coefficient (d)₃₃·g₃₃) The piezoelectric ceramic material of (1). 2013, Zheng et al for 0.2Pb (Zn)_1/ ₃Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃The doping modification research of the system is carried out, and the result shows that: the introduction of NiO dopant makes the system reach 10050X 10 of optimal transduction coefficient^-15m²N (Journal of the European Ceramic Society, 2013, Vol.33, No. 8, pp.1447-1456). Yue etc. by using high energy ball milling and pressureless sintering technology to prepare 0.2Pb (Zn) with submicron grain size_1/3Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃Fine crystalline ceramics with a transduction coefficient of 7980X 10^-15m²N (Journal of the American Ceramic Society, 2017, Vol. 100, No. 11, p. 5211-5219). Piezoelectric charge constant (d) in the previous research work₃₃) And relative dielectric constant (. epsilon.)_r) Tend to show a trend of variation that increases or decreases simultaneously, and such a synergistic variation severely limits the transduction coefficient (d) according to the above formula (1-1)₃₃·g₃₃) Thereby making it difficult to obtain excellent piezoelectric ceramic materials to meet the application requirements of high performance piezoelectric energy collectors. Therefore, a new material design concept must be sought to greatly improve the transduction coefficient (d) of the piezoceramic material₃₃·g₃₃)。

In view of the above, in order to satisfy the requirement of high electromechanical transduction performance of piezoelectric energy collecting devices, in this patent, the low relative dielectric constant component is mainly introduced to Pb (Zn) which is widely used at present_1/3Nb_2/3)O₃-Pb(Zr_1/2Ti_1/2)O₃In the base (abbreviated as PZN-PZT) ternary system piezoelectric ceramic material, the piezoelectric charge constant (d) of the PZN-PZT base piezoelectric ceramic material is effectively regulated and controlled₃₃) And relative dielectric constant (. epsilon.)_r) Thereby greatly improving the transduction coefficient (d)₃₃·g₃₃)。

Disclosure of Invention

The invention aims to effectively regulate and control the piezoelectric charge constant (d) of the PZN-PZT-based ceramic material₃₃) And relative dielectric constant (. epsilon.)_r) Thereby greatly improving the transduction coefficient (d) of the material system₃₃·g₃₃). The invention adopts Pb (In) with low relative dielectric constant_1/2Nb_1/2)O₃(abbreviated as PIN) relaxor as composite component is introduced into PZN-PZT ternary system perovskite ferroelectric matrix to construct novel (0.2-x) Pb (Zn)_1/3Nb_2/3)O₃-xPb(In_1/2Nb_1/2)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviated as (0.2-x) PZN-xPIN-0.8PZT) quaternary system piezoelectric ceramic material, and is expected to be utilizedThe low relative dielectric constant of the PIN composite component greatly reduces the relative dielectric constant (epsilon) of the material system_r) Meanwhile, based on the disturbance of different electronic configurations of B-site cations to the random field, the domain state is optimized, and the piezoelectric charge constant (d) of the material system is further stabilized₃₃) So as to obtain a high transduction coefficient (d) at a specific composition₃₃·g₃₃) The quaternary system piezoelectric ceramic material of (1).

In order to achieve the purpose, the invention adopts the following technical scheme.

The invention provides a piezoelectric energy collector with high transduction coefficient (d)₃₃·g₃₃) The quaternary system piezoceramic material is characterized in that a relaxor PIN with low relative dielectric constant is taken as a composite component and introduced into a PZN-PZT ternary system perovskite ferroelectric matrix to construct the quaternary system piezoceramic material, and the basic chemical composition of the piezoceramic material is as follows: (0.2-x) Pb (Zn)_1/3Nb_2/3)O₃-xPb(In_1/2Nb_1/2)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviated as (0.2-x) PZN-xPIN-0.8PZT), wherein x has a value of greater than 0.000 and less than 0.100, preferably 0.008 to 0.075, more preferably 0.042.

The invention has the high transduction coefficient (d)₃₃·g₃₃) The preparation method of the quaternary system piezoelectric ceramic material is characterized by being prepared by a traditional solid phase method, and specifically comprises the following steps:

(1) synthesizing (0.2-x) PZN-xPIN-0.8PZT ceramic powder, and weighing the following raw materials according to the corresponding stoichiometric molar ratio: ZnO and Nb₂O₅、Pb₃O₄、ZrO₂、TiO₂、In₂O₃Putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium for ball milling for 24 hours; drying the slurry obtained after ball milling, calcining for 2 hours at 850 ℃ in the air atmosphere, cooling along with a furnace, carrying out secondary ball milling on a product (0.2-x) PZN-xPIN-0.8PZT obtained after calcining, and drying the slurry obtained after ball milling to obtain (0.2-x) PZN-xPIN-0.8PZT ceramic powder;

(2) and (2) granulating by using a polyvinyl alcohol (PVA) aqueous solution as a binder, performing compression molding, removing the binder at 560 ℃, sintering at 950-1150 ℃, preferably 1000 ℃, and preserving heat for 2 hours to obtain the ceramic material.

Preferably: the amount of the binder used in the step (2) is preferably 1.2ml per 10g of the ceramic powder, and the mass concentration of the binder is 5%. The molding pressure is 100 MPa.

Polishing the sintered ceramic plate, coating silver electrode on the polished ceramic plate, and placing the polished ceramic plate in silicone oil at 120 ℃ at 40kV cm^-1Polarization for 30min, aging at room temperature for 24h, and then testing the electrical properties of the sample.

Among them, the best samples are: 0.158PZN-0.042PIN-0.8PZT, the performance can reach: d₃₃＝379pC/N，ε_r＝1009，d₃₃·g₃₃＝16081×10^-15m²and/N, the requirement of an energy collecting device can be met.

Compared with the prior art, the invention has the following beneficial effects:

(1) the design method for introducing the low relative dielectric constant composite component provided by the invention can effectively solve the problem of piezoelectric charge constant (d)₃₃) And relative dielectric constant (. epsilon.)_r) The problem of cooperative change can effectively resolve the piezoelectric charge constant (d)₃₃) And relative dielectric constant (. epsilon.)_r) I.e. in a large decrease of the relative permittivity (. epsilon.)_r) While maintaining the piezoelectric charge constant (d)₃₃) The stability of the piezoelectric energy collecting material is improved, and a brand new design idea is provided for further developing the high-performance piezoelectric energy collecting material.

(2) The invention has high transduction coefficient (d)₃₃·g₃₃) The piezoelectric ceramic material can effectively improve the electromechanical conversion efficiency of the energy collecting device, and is a potential piezoelectric ceramic material applied to the energy collecting device.

(3) The invention has high transduction coefficient (d)₃₃·g₃₃) The piezoelectric ceramic material has the advantages of simple preparation method, easy operation, low cost, stable structure, convenient industrial production, good industrial application prospect and obvious social and economic effectsIt is beneficial to.

Drawings

FIG. 1 is an XRD pattern for 0.042 x of the present invention, i.e., 0.158PZN-0.042PIN-0.8 PZT;

FIG. 2 is a Transmission Electron Microscope (TEM) image of (0.2-x) PZN-xPIN-0.8PZT according to the present invention (a) x is 0.000 and (b) x is 0.042;

FIG. 3 shows the piezoelectric charge constant (d) of the quaternary piezoelectric ceramic having the composition (0.2-x) PZN-xPIN-0.8PZT, wherein x is 0.000 to 0.100₃₃) Relative dielectric constant (. epsilon.)_r) Coefficient of transduction (d)₃₃·g₃₃) The data map of (1).

Detailed Description

The essential features and the significant advantages of the invention are further clarified by the following examples. It should be noted that the invention is in no way limited to the embodiments presented.

The invention provides a high transduction coefficient (d)₃₃·g₃₃) The quaternary system piezoelectric ceramic material comprises the following chemical components: (0.2-x) PZN-xPIN-0.8PZT, wherein x is 0.000-0.100. The piezoelectric ceramic material (0.2-x) PZN-xPIN-0.8PZT comprises the following raw materials: pb₃O₄、ZnO、Nb₂O₅、ZrO₂、TiO₂、In₂O₃. The specific preparation method comprises the following steps of firstly, synthesizing (0.2-x) PZN-xPIN-0.8PZT ceramic powder, and weighing the following raw materials according to the corresponding stoichiometric ratio: ZnO and In₂O₃、Nb₂O₅、Pb₃O₄、ZrO₂、TiO₂Putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium for ball milling for 24 hours; and drying the slurry obtained after ball milling, calcining for 2 hours at 850 ℃ in an air atmosphere, cooling along with a furnace, carrying out secondary ball milling on a product (0.2-x) PZN-xPIN-0.8PZT obtained after calcining, and drying the slurry obtained after ball milling to obtain corresponding ceramic powder. Then, using a polyvinyl alcohol (PVA) aqueous solution with a mass concentration of 2-8%, preferably 5% as a binder, granulating, molding under a pressure of 100MPa, pressing into a molding with a diameter of 11.5mm and a thickness of about 1.5mm, removing the binder at 560 ℃, and then removing the binderAnd sintering at 950-1150 ℃, preferably 1000 ℃, and keeping the temperature for 2 hours to obtain the ceramic material. Polishing the sintered ceramic plate, coating with silver electrode, and soaking in 120 deg.C silicone oil at 40 kV-cm^-1Polarized for 30min at voltage (v). The samples were then tested for electrical properties as follows:

(1) dielectric property test

The capacitance value C was measured using an LCR digital bridge (Agilent E4980A) and the relative dielectric constant was calculated according to equation (1-2).

In the formula

C is a capacitance value;

t-the thickness of the sample;

a-area of sample;

ε₀dielectric constant in vacuum (8.85X 10)^-12F/m)。

(2) Piezoelectric performance test

Adopts a quasi-static d of ZJ-2A type of a Chinese academy of Acoustics₃₃Tester for directly reading piezoelectric strain constant d₃₃。

Example 1 (i.e., comparative):

firstly, the chemical formula of the matrix is 0.2Pb (Zn)_1/3Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.2PZN-0.8PZT) Nb₂O₅、Pb₃O₄、ZrO₂、TiO₂And ZnO, and ball milled in ethanol for 24 hours. And calcining the dried mixture at 850 ℃ for 2 hours, and then performing ball milling and drying in ethanol to obtain 0.2PZN-0.8PZT ceramic powder. Then weighing 0.2PZN-0.8PZT powder, mixing according to the proportion of 10g powder and 1.2mL binder, pressing into a shaped object under 100MPa, removing the binder from the shaped object at 560 ℃, sintering at 950-1150 ℃, preferably 1Sintering for 2 hours at the temperature of 000 ℃ to obtain pure 0.2PZN-0.8PZT ceramic.

Example 2:

firstly, the chemical formula of the matrix is 0.192Pb (Zn)_1/3Nb_2/3)O₃-0.008Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.192PZN-0.008PIN-0.8PZT) Nb weight₂O₅、In₂O₃、Pb₃O₄、ZrO₂、TiO₂And ZnO, and ball milled in ethanol for 24 hours. The mixture is calcined for 2 hours at 850 ℃ after being dried, and is ball milled and dried in ethanol again to obtain 0.192PZN-0.008PIN-0.8PZT ceramic powder. And then weighing 0.192PZN-0.008PIN-0.8PZT powder, mixing the powder according to the proportion of 10g of powder to 1.2mL of binder, pressing the mixture into a molded object under 100MPa, removing the binder from the molded object at 560 ℃, and sintering the molded object at 950-1150 ℃, preferably 1000 ℃ for 2 hours to obtain 0.192PZN-0.008PIN-0.8PZT ceramic.

Example 3:

at 0.184Pb (Zn)_1/3Nb_2/3)O₃-0.016Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.184PZN-0.016PIN-0.8 PZT). The rest is the same as example 2.

Example 4:

at 0.175Pb (Zn)_1/3Nb_2/3)O₃-0.025Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.175PZN-0.025PIN-0.8 PZT). The rest is the same as example 2.

Example 5:

at 0.158Pb (Zn)_1/3Nb_2/3)O₃-0.042Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.158PZN-0.042PIN-0.8 PZT). The rest is the same as example 2.

Example 6:

at 0.15Pb (Zn)_1/3Nb_2/3)O₃-0.05Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.150PZN-0.05PIN-0.8 PZT). The rest is the same as example 2.

Example 7:

at 0.125Pb (Zn)_1/3Nb_2/3)O₃-0.075Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.125PZN-0.075PIN-0.8 PZT). The rest is the same as example 2.

Example 8 (i.e., comparative):

at 0.1Pb (Zn)_1/3Nb_2/3)O₃-0.1Pb(In_1/2Nb_2/3)O₃-0.8Pb(Zr_1/2Ti_1/2)O₃(abbreviation 0.1PZN-0.1PIN-0.8 PZT). The rest is the same as example 2.

Table 1 comparative table of properties of the above examples

Claims

1. The quaternary system piezoelectric ceramic material with high transduction coefficient for piezoelectric energy collection is characterized by adopting Pb (In) with low relative dielectric constant_1/2Nb_1/2)O₃The relaxor is taken as a composite component and introduced into a PZN-PZT ternary system perovskite ferroelectric matrix to construct a quaternary system piezoelectric ceramic material, and the chemical composition of the quaternary system piezoelectric ceramic material is as follows: (0.2-x) Pb(Zn_1/3Nb_2/3)O₃-x Pb(In_1/2Nb_1/2)O₃-0.8 Pb(Zr_1/2Ti_1/2)O₃Abbreviated as (0.2-x)PZN-xPIN-0.8PZT, whereinxHas a value of greater than 0.000 and less than 0.100.

2. A quaternary piezoceramic material with high transduction coefficient for piezoelectric energy collection according to claim 1, wherein the quaternary piezoceramic material comprises a ceramic material,xthe value of (A) is 0.008 to 0.075.

3. A quaternary piezoceramic material with high transduction coefficient for piezoelectric energy collection according to claim 1, wherein the quaternary piezoceramic material comprises a ceramic material,xthe value of (A) is 0.042.

4. The method for preparing the piezoceramic material according to claim 1, which is prepared by a traditional solid-phase method, comprises the following steps:

(1) synthesis of (0.2-x)PZN- xThe preparation method comprises the following steps of weighing the following raw materials in a corresponding chemical molar ratio: ZnO and In₂O₃、Nb₂O₅、Pb₃O₄、ZrO₂、TiO₂Putting the weighed raw materials into a ball milling tank, and putting the raw materials into a horizontal ball mill by taking absolute ethyl alcohol as a medium for ball milling for 24 hours; drying the slurry obtained after ball milling, calcining for 2 hours at 850 ℃ in air atmosphere, cooling along with the furnace, and calcining the obtained product (0.2-x)PZN- xCarrying out secondary ball milling on the PIN-0.8PZT, and drying slurry obtained after ball milling to obtain corresponding ceramic powder;

(2) adopting a polyvinyl alcohol aqueous solution as a binder for granulation, compression molding, removing the binder, sintering at 950-1150 ℃, and preserving heat for 2 hours to obtain (0.2-x)PZN- xPIN-0.8PZT ceramic material.

5. The method according to claim 4, wherein the step (2) is carried out by using an aqueous polyvinyl alcohol solution having a mass concentration of 2% to 8% as a binder for granulation.

6. The method of claim 4, wherein the forming pressure of step (2) is 100MPa and the binder is removed at 560 ℃.

7. A method according to claim 4, characterized in that the amount of binder is 1.2ml per 10g of ceramic powder.

8. The method of claim 4, wherein the sintering temperature in step (2) is 1000 ℃.